KR101786898B1 - Colored photosensitive resin composition - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) (Bb) having a polymerizable double bond with a carboxyl group is added to at least one kind (Ba) selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, (Bc) selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is reacted with a bisphenol A type epoxy resin and a bisphenol F type epoxy resin And a resin obtained by reacting a polyfunctional epoxy compound (Bd) comprising at least one selected from the group consisting of a polyfunctional epoxy compound (Bd) and a polyfunctional epoxy compound (Bd).

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The colored photosensitive resin composition is used for manufacturing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, and a plasma display panel. In this colored photosensitive resin composition, it is known to use a pigment or a dye as a colorant (Non-Patent Document 1).

[Non-Patent Document 1]

Suzuki Hachijuni, "Getting to Know LCD Display", First Edition, Daily Newspaper, March 2005, P. 112

It is an object of the present invention to provide a colored photosensitive resin composition capable of forming a coating film, a pattern and a color filter excellent in heat resistance.

 The present invention provides the following [1] to [12].

[1] A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) (Bb) having a polymerizable double bond with a carboxyl group is added to at least one kind (Ba) selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, (Bc) selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is reacted with a bisphenol A type epoxy resin and a bisphenol F type epoxy resin And a resin obtained by reacting a polyfunctional epoxy compound (Bd) containing at least one selected from the group consisting of a polyfunctional epoxy compound (Bd) and a polyfunctional epoxy compound (Bd).

[2] The colored photosensitive resin composition according to [1], wherein the dye is at least one dye selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a xanthene compound.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the dye is a dye containing a compound represented by formula (1).

: Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ Or -SO ₂ NR ⁸ R ⁹ .

R ⁵ represents -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

X represents a halogen atom.

a represents an integer of 0 or 1;

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, CO- or -NR < ⁷ > -.

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be -O- or - CO-. ≪ / RTI >

R ⁸ and R ⁹ each independently represent a linear or branched monovalent saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 30 carbon atoms, or -Q, and the saturated aliphatic hydrocarbon group and / The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with -OH, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ , and the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S-, -CO-, -NH- or -NR ⁶ -. R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring containing a nitrogen atom of 3 to 10-membered ring, and a hydrogen atom contained in the heterocyclic ring may be substituted with R ⁶ , -OH or -Q .

Q is a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and heterocyclic ^{group, -OH, R 6, -OR 6} , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ Or a halogen atom.

M represents a sodium atom or a potassium atom.

However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.]

[4] The resin composition according to any one of [1] to [4], wherein the binder resin (B) is at least one kind (Ba) selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin and a monomer (Bb) having a polymerizable double bond with a carboxyl group (Bc) selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is reacted with a bisphenol A-type epoxy resin and a bisphenol F-type epoxy resin (Bd) having at least one member selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is reacted with a polyfunctional epoxy compound (Bd) containing at least one compound The colored photosensitive resin composition according to any one of [1] to [3], which is a binder resin containing a resin.

[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the monomer (Bb) having a carboxyl group and a polymerizable double bond is at least one selected from the group consisting of acrylic acid and methacrylic acid.

[6] The toner according to any one of [1] to [5] above, wherein the content of the binder resin (B) is 20% by mass or more and 80% by mass or less based on the total amount of the binder resin (B) and the photopolymerizable compound (C) And the coloring photosensitive resin composition described above.

[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the content of the dye is 0.5% by mass to 60% by mass relative to the solid content of the colored photosensitive resin composition.

[8] The colored photosensitive resin composition according to any one of [1] to [7], wherein the colorant (A) is a colorant containing a pigment.

[9] A pigment according to any one of the items [ Pigment Blue 15: 6, C.I. Pigment Red 254, C.I. Pigment Red 242, C.I. Pigment Red 177, C.I. Pigment Green 58, C.I. Pigment Yellow 150 and C.I. Pigment Yellow 138. The colored photosensitive resin composition according to the above [8], wherein the coloring photosensitive resin composition is at least one selected from the group consisting of Pigment Yellow 138,

[10] A coating film formed by using the colored photosensitive resin composition according to any one of [1] to [9].

[11] A pattern formed by using the colored photosensitive resin composition according to any one of [1] to [9].

[12] The pattern according to [11], which is formed by photolithography.

[13] A color filter comprising at least one selected from the group consisting of the coating film described in [10] and the patterns described in [11] and [12].

1 is a schematic view for explaining a method of manufacturing a color filter of the present invention,
2 is a schematic view for explaining a method of manufacturing a color filter of the present invention,
3 is a schematic view for explaining a method of manufacturing a color filter of the present invention,
4 is a schematic view for explaining a manufacturing method of a color filter of the present invention.

The colored photosensitive resin composition of the present invention contains a colorant (A).

The colorant (A) used in the colored curable resin composition of the present invention is a colorant containing a dye. The dye contained in the colorant (A) is not particularly limited, and known dyes can be used. Examples thereof include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes.

Examples of the above-mentioned dyes include compounds classified as dyes in the color index (The Society of Dyers and Colourists) or known dyes described in dyeing notes (dyeing yarns). Specifically, C.I. 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Solvent Yellow 4 (hereinafter, the description of CI. Solvent Yellow is omitted.

C.I. Solvent Red 45, 49, 125, 130;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56;

C.I. Solvent Blue 35, 37, 59, 67;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like. C.I. As the acid dye, 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, 112, 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, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 382, 383, 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 Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, 340;

C.I. Acid Violet 6B, 7, 9, 17, 19;

C.I. Dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, C.I. As direct dyes, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 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, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 173, 181, 172, 173, 188, 189, 190, 192, 193, 163, 164, 166, 167, 170, 171, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

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. Dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82. Also, C.I. As a modern dye, C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern 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. 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. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Dyes such as 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53 can be cited.

Examples of the dyes contained in the colorant (A) include amine salts of the acidic dyes represented by the following formulas (i) to (vii), and sulfonamide derivatives of the acidic dyes represented by the formulas (viii) and (ix) .

In the formulas (i) to (ix), D represents a group derived from a dye.

v represents an integer of 1 or more and 20 or less, and w represents an integer of 1 or more and 20 or less.

e and f independently represent an integer of 1 or more and 10 or less.

Ph represents a phenyl group, and Py represents a group represented by the formula (I) following the C _w H _{2w + 1} as a nitrogen atom.

[In the formula (I), R ^a represents a methyl group. and ma represents an integer of 0 or 1.]

p represents an integer of 1 or more and 8 or less.

q represents an integer of 0 to 8 inclusive.

And L represents a hydrogen atom or a monovalent cation.

Specific examples of D in the formulas (i) to (ix) include groups derived from azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes.

m is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 8 or less.

n is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 8 or less.

e and f each independently represent an integer of preferably 1 or more and 8 or less, more preferably an integer of 1 or more and 6 or less.

Py preferably represents a group represented by formula (I-1).

p represents an integer of preferably 1 or more and 6 or less, more preferably an integer of 1 or more and 5 or less.

q represents an integer of preferably 0 or more and 6 or less, more preferably 0 or more and 5 or less.

Examples of the monovalent cation in L include a lithium ion, a sodium ion, a potassium ion, a quaternary ammonium ion such as (C ₂ H ₅ ) ₃ HN ⁺ , and the like. have.

Examples of the azo dye include dyes represented by the following formulas (a) to (d).

In formula (a), R ^z1 represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, an alkoxy group having 2 to 12 carbon atoms (A-1), an alkyloxycarbonylalkyl group represented by the formula (a-2), a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or a phenyl group Or an alkyl group having 1 to 20 carbon atoms.

L ^l - CO - O - L ² - (a-1)

L ³ -O-CO-L ⁴ - (a-2)

[In the formula (a-1), L ¹ represents an alkyl group having 2 to 12 carbon atoms. L ² represents an alkylene group having ² to 12 carbon atoms.

In the formula (a-2), L ³ represents an alkyl group having 2 to 12 carbon atoms. And L < ⁴ > represents an alkylene group having 2 to 12 carbon atoms.

In the formula (a), R ^z2 to R ^z5 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

Examples of the alkyl group having 2 to 20 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-hexyl group, a n-nonyl group, -Dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, and 1,1,3,3-tetramethylbutyl group.

Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a cyclohexylethyl group, a 3-cyclohexylpropyl group and an 8-cyclohexyloctyl group.

Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group and a 2- (n-butyl) cyclohexyl group.

Examples of the alkyl group having 2 to 12 carbon atoms substituted with an alkoxy group having 2 to 12 carbon atoms include a 3-ethoxy-n-propyl group, a propoxypropyl group, a 4-propoxy- Ethyl group and 3- (2-ethylhexyloxy) propyl group.

Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include o-isopropylphenyl group and the like.

Examples of the alkyl group having 1 to 20 carbon atoms substituted with a phenyl group include a DL-1-phenylethyl group, a benzyl group and a 3-phenyl-n-butyl group.

Examples of the alkyl group having 2 to 12 carbon atoms in L ¹ and L ³ include an ethyl group, a propyl group, an n-hexyl group, a n-nonyl group, a n-decyl group, Dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, and 1,1,3,3-tetramethylbutyl group.

Examples of the alkylene group having 2 to 12 carbon atoms in L ² and L ⁴ include an ethylene group and a hexanediyl group.

^Examples of R ^z2 to R ^z5 in the formula (a) include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec- An ethyl group, an n-propyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a fluorine atom or a bromine atom, Chlorine atom.

Among the dyes represented by the formula (a), preferred examples of the dye include compounds represented by the formula (e).

The dye having a group derived from an anthraquinone dye includes, for example, a compound represented by the formula (f).

The dye having a group derived from a triphenylmethane dye includes, for example, a compound represented by the formula (g).

The dye having a group derived from a xanthene dye includes, for example, a compound represented by the formula (h).

Examples of the dyes having a group derived from a phthalocyanine dye include compounds represented by the formula (j).

As the dye, a dye containing at least one selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a xanthene compound is preferable, and a compound represented by the following formulas (1) to (3) And a dye containing at least one species selected from the group consisting of As the dye, a dye dissolved in any one of the solvents described later used in the colored photosensitive resin composition of the present invention is preferable.

As the dye, a dye containing a xanthene compound is preferable, and a dye containing a compound represented by the following formula (1) is more preferable.

: Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ Or -SO ₂ NR ⁸ R ⁹ .

R ⁵ represents -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

X represents a halogen atom.

a represents an integer of 0 or 1;

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, CO- or -NR < ⁷ > -.

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be -O- or - CO-.

R ⁸ and R ⁹ each independently represent a linear or branched monovalent saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 30 carbon atoms, or -Q, and the saturated aliphatic hydrocarbon group and / The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with -OH, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ , and the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S-, -CO-, -NH- or -NR ⁶ -. R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring containing a nitrogen atom of 3 to 10-membered ring, and a hydrogen atom contained in the heterocyclic ring may be substituted with R ⁶ , -OH or -Q .

Q is a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and heterocyclic ^{group, -OH, R 6, -OR 6} , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ Or a halogen atom.

M represents a sodium atom or a potassium atom.

However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.]

R ¹ to R ⁴ in the compound represented by the formula (1) each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - may be replaced by -O-, -CO- or -NR ⁷ - (R ⁷ is, represents a monovalent saturated hydrocarbon group of 1 to 10 carbon atoms, hydrogen atoms contained groups corresponding saturated hydrocarbon group is optionally substituted with a halogen atom, -CH ₂ - is replaced by -O- or -CO- Which may be substituted).

Examples of -R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, A cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a nonyl group, a decanyl group, a tricyclodecanyl group, a methoxypropyl group, an ethoxypropyl group, a hexyloxypropyl group, a 2-ethylhexyl A methoxy group, an ethoxy propyl group, and the like.

R ¹ to R ⁴ And the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in Q include, for example, a phenyl group and a naphthyl group.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ Or -SO ₂ NR ⁸ R ⁹ .

R ⁶ has the same meaning as defined above.

Each of R ⁸ and R ⁹ independently represents a linear or branched monovalent saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 30 carbon atoms, or -Q (Q represents a hydrocarbon group having 6 to 10 carbon atoms a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group having a carbon number of 3 to 10 of the hydrogen atoms contained in ^{these, -OH, -R 6, -OR 6} , -NO 2, -CH = CH 2, -CH = CHR ⁶ Or a halogen atom).

The hydrogen atoms contained in the straight-chain or branched monovalent saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms and the monovalent alicyclic hydrocarbon group of 3 to 30 carbon atoms in R ⁸ and R ⁹ may be replaced by -OH, a halogen atom, -Q, -CH = CH ₂ Or -CH = CHR ⁶ , and -CH ₂ - may be substituted with -O-, -S-, -CO-, -NH- or -NR ⁶ -.

R ⁸ and R ⁹ may combine with each other to form a 3- to 10-membered heterocyclic ring. In this case, the hydrogen atom contained in the corresponding heterocycle may be substituted with -R ⁶ , -OH or -Q.

The above M represents a sodium atom or a potassium atom.

Examples of the halogen atom which may be substituted for the hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.

Examples of -OR ⁶ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, A siloxane group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, and a decyloxy group.

Examples of -CO ₂ R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentoxycarbonyl group, an isopentoxycarbonyl group, a neopentoxycarbonyl group, A cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cycloheptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a cyclooctyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, A methoxypropyloxycarbonyl group, an ethoxypropyloxycarbonyl group, a hexyloxypropyloxycarbonyl group, a 2-ethylhexyloxypropyloxycarbonyl group, a methoxyhexyloxycarbonyl group and the like.

In the -SO ₂ NR ⁸ R ⁹ , examples of the 3- to 10-membered heterocyclic ring formed by bonding R ⁸ and R ⁹ to each other include,

And the like. In addition, the above-mentioned heterocyclic ring binds to sulfur atoms with the bonding hands described in the above-mentioned drawings.

As the monovalent heterocyclic group having 3 to 10 carbon atoms in Q,

And the like. In addition, the coupling of the complex ventilation in Q can be arbitrarily set.

Examples of -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

Examples of -SO ₂ NHR ^8, N- methyl-sulfamoyl, N- ethyl sulfamoyl, N- propyl sulfamoyl, N- isopropyl-sulfamoyl, N- butyl sulfamoyl, N- isobutyl-sulfamoyl , N-pentylsulfamoyl group, N-isopentylsulfamoyl group, N-neopentylsulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsapamoyl group, (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N-cyclooctylsulfamoyl group, N-cycloheptylsulfamoyl group, N- N-nonylsulfamoyl group, N-decylsulfamoyl group, N-tricyclodecanylsulfamoyl group, N-methoxypropylsulfamoyl group, N-ethoxypropylsulfamoyl group, N-propoxypropylsulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl group, N-isopropoxypropylsulfamoyl group, N- (3-phenyl-1-methylpropyl) sulfamoyl group and the like Can.

Examples of -SO ₂ NHR ⁸ include groups represented by the following formulas.

In the above formula, X ¹ represents a halogen atom. Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom and a bromine atom.

In the above formula, X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, and perfluoromethyl.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a methoxy group, an ethoxy group and a propoxy group.

In the above formula, X < ³ >

In the above formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom contained in the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the halogen atom in X ² include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, and trifluoromethyl.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a methoxy group, an ethoxy group and a propoxy group.

Among them, preferable examples of -SO ₂ NHR ⁸ include those wherein R ⁸ is a branched saturated aliphatic hydrocarbon group having 6 to ⁸ carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, an aralkyl group having 8 to 10 carbon atoms, A saturated aliphatic hydrocarbon group having 2 to 8 carbon atoms and an allyl group or an alkoxy group containing saturated aliphatic hydrocarbon group or aryl group having 2 to 8 carbon atoms, and particularly preferably a 2-ethylhexyl group.

Examples of -SO ₂ NR ⁸ R ⁹ include groups represented by the following formulas.

In the above formula, X ² has the same meaning as described above.

Examples of R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ include a branched saturated aliphatic hydrocarbon group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms Containing saturated aliphatic hydrocarbon group having 2 to 8 carbon atoms and an aryl group or an alkoxy group containing saturated aliphatic hydrocarbon group or aryl group having 2 to 8 carbon atoms, and particularly preferably a 2-ethylhexyl group.

The substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ in the formula (1) is preferably an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, -SO ₃ R ⁶ or -SO ₂ NHR ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, a decanylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, , A dimethoxyphenyl group, an ethoxyphenyl group, a hexyloxyphenyl group, a decanyloxyphenyl group, and a trifluoromethylphenyl group.

In R ¹ to R ⁴ in the formula (1), at least one of R ¹ and R ² , or at least one of R ³ and R ⁴ , is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms or a substituted or unsubstituted carbon number Is preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.

At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted And more preferably at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

R ⁵ in the compound represented by formula (1) represents -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

In the formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

R ⁵ is preferably a carboxyl group, an ethyloxycarbonyl group, a sulfo group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- -Phenyl-1-methylpropyl) sulfamoyl group, and N- (isopropoxypropyl) sulfamoyl group.

In the formula (1), X represents a halogen atom, and a represents an integer of 0 or 1.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom and a bromine atom.

The compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) or (1-2).

[In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, ^{_{-CO 2 H, -CO 2 R 6}} , -SO 3 R 6, -SO 2 NH 2, -SO 2 NHR 8 Or -SO ₂ NR ⁸ R ⁹ .

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NH ₂ , -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NH ₂ , -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meanings as defined above.

Provided that the number of + electrons and the number of - electrons in the compound represented by formula (1-1) are the same.]

[In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ^26, or -SO ₂ NHR ²⁸ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or -SO ₂ NHR ²⁸ .

R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is -OR ²⁷ Or a halogen atom.

R ²⁷ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -R ²⁶ Or -OR < ^{26 &} gt ;.

m, X and a have the same meanings as defined above.

Provided that the number of positive charge and the number of negative charge of the compound represented by formula (1-2) are the same.]

The compound represented by the formula (1) is preferably a compound represented by the following formula (1-3).

Wherein R ³¹ and R ³² each independently represent a phenyl group and the hydrogen atom contained in the phenyl group is a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , SO ₃ R ^26, or -SO ₂ NHR ²⁸ .

R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

Provided that the number of positive charge and the number of negative charge of the compound represented by formula (1-3) are the same.]

Further, the compound represented by the formula (1) is more preferably the compound represented by the following formula (1-4).

[In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ .

R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

Provided that the number of + electrons and the number of - electrons in the compound represented by formula (1-4) are the same.]

Examples of the compound represented by the formula (1) include compounds represented by the following formulas (1a) to (1f).

[In the formula (1a), R ⁵¹ and R ⁵² each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -CO ₂ H or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents 2-ethylhexyl. X and a have the same meanings as defined above.

Provided that the number of + electrons and the number of electrons in the compound represented by formula (1a) are the same.]

[In the formula (1b), R ⁵¹ has the same meaning as defined above. Provided that the number of + electric charge and the number of - electric charge of the compound represented by formula (1b) are the same.]

The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

[In the formula (1b-1), R ⁵¹ , X and a have the same meanings as defined above. However, the number of + electrons and the number of electrons in the compound represented by formula (1b-1) are the same.]

In the formulas (1c) and (1d), R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents a 2-ethylhexyl group. Provided that the number of positive charge and the number of negative charge of the compound represented by formula (1c) and the compound represented by formula (1d) are the same, respectively.

In the formulas (1e) and (1f), R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents a 2-ethylhexyl group. However, the number of positive charge and the number of negative charge of the compound represented by formula (1e) and the compound represented by formula (1f) are the same, respectively.]

Specific examples of the compounds represented by formulas (1a) to (1f) include compounds obtained by sulfonating aminosulfonylamine B, -SO ₃ ^- or -SO ₃ H of sulfolodamine B, CI Solvent Red 49, CI Acid Red 289, -SO ₃ ^- or -SO ₃ H of CI Acid Red 289, a compound obtained by sulfonation of -SO ₃ ^- or -SO ₃ H of CI Acid Violet 102, Amidated compounds and the like. Among the dyes used in the colored photosensitive resin composition of the present invention, the compounds represented by formula (1e) or (1f) are preferable, and specifically, CI acid red 289, -SO ₃ ^- of CI acid red 289 A compound in which -SO ₃ H is sulfonamidated is preferable. Particularly, a compound represented by the formula (h) is preferable.

The compound represented by the formula (1) can be obtained by, for example, chlorinating a dye or a dye intermediate having -SO ₃ H by a method of preparation and converting the resulting dye or dye intermediate having -SO ₂ Cl into R ⁸ -NH ₂ Amine in the presence of a base. In addition, the dye prepared by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Laid-Open Publication No. 3-78702 can be produced by chlorination followed by reaction with an amine in the same manner as described above.

When the colorant (A) contains the compound represented by the formula (1), the content of the compound represented by the formula (1) in the colorant (A) is preferably 3 to 80% by mass, By mass to 70% by mass, and even more preferably 3% by mass to 50% by mass.

When the colorant (A) contains a dye different from the compound represented by the formula (1), the mixing ratio of the compound represented by the formula (1) and the dye different from the compound represented by the formula (1) .

A compound represented by the formula (1): 1 to 99 mass%

A dye different from the compound represented by the formula (1): 1 to 99 mass%

When the compounding ratio of the dye represented by the formula (1) and the dye different from the compound represented by the formula (1) is in the above-mentioned range, the objective spectroscopy can be obtained.

The dye is preferably a dye containing an azo compound, more preferably a dye containing a compound represented by formula (2).

[In the formula (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, or an acyl group of 2 to 18 carbon atoms which may have a substituent.

p1 represents 1 or 2; When p1 is 2, a plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different.

If p1 is 1, R ⁵² is, represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a hydrogen atom or a monovalent substituent, and when the p1 is 2, R is ⁵² carbon atoms which may have a substituent 1 to -CH ₂ - included in the monovalent aliphatic hydrocarbon group and the bivalent aliphatic hydrocarbon group is substituted with -O-, -S-, -CO-, and -NR'- do.

R 'represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The compound represented by the formula (2) is preferably a compound represented by the formula (2-1).

[In the formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent and is included in Z ¹ , Z ² and Z ³ -CH ₂ - may be substituted with -CO- or -O-.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, or an acyl group of 2 to 18 carbon atoms which may have a substituent.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. The number of carbon atoms of the substituent does not include the number of carbon atoms of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and the number thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include an alkanediyl group having 1 to 16 carbon atoms, and examples thereof include methylene, ethylene, propane di, , An octanediyl group, a decanediyl group, a tetradecanediyl group and a hexadecanediyl group.

-CH ₂ - included in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with -CO- or -O-. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain -O-, and more preferably an alkanediyl group having 5 to 7 carbon atoms which may contain -O-. Examples of preferred groups, _{e.g., - (CH 2) 3 -} , - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- ( CH ₂ ) ₂ - or -CH ₂ -CH (CH ₃ ) -.

Z ³ is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain -C (= C) -, more preferably an unsubstituted alkanediyl group having 1 to 8 carbon atoms, More preferably an unsubstituted alkanediyl group having 8 to 8 carbon atoms. Preferable groups include, for example, - (CH ₂ ) ₂ -, - (CH ₂ ) ₄ - or -CH ₂ -C (= CH ₂ ) -.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which represents R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be any of linear, branched or cyclic monovalent aliphatic hydrocarbon groups. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Ethylhexyl group (such as a 2-ethylhexyl group), a cyclopentyl group, a cyclohexyl group (e.g., a methyl group, an ethyl group, , A methylcyclohexyl group (such as a 2-methylcyclohexyl group), and a cyclohexylalkyl group.

The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group such as a 3- (isopropoxy) propyl group and an alkoxypropyl group such as 3- (2-ethylhexyloxy) And a propyl group). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with a carboxy group include a 2- (carboxy) ethyl group, a 3- (carboxy) propyl group and a 4- (carboxy) butyl group.

As the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and optionally having a substituent represented by R ⁵² ,

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R ⁵² include an alkanediyl group having 1 to 35 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propanediyl group, a butane diyl group, A diaryl group, a diaryl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group and a hexadecanediyl group.

-CH ₂ - contained in a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with -O-, -S-, -CO- and -NR'-. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms for R 'include methyl, ethyl, propyl, butyl, pentyl, hexyl and cyclohexyl.

The hydrogen atom contained in the acyl group having 2 to 18 carbon atoms representing R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted with an alkoxy group having 1 to 8 carbon atoms. The number of carbon atoms of the acyl group having 2 to 18 carbon atoms which may have a substituent group is preferably 6 to 10, inclusive of the carbon number of the substituent. Examples of the acyl group which may have a substituent include an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group and the like) and the like.

As R ⁵³ and R ⁵⁴ , a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms are preferable. Preferable groups include, for example, a hydrogen atom, an acetyl group or a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which represent A ⁰ , A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an oxo atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- , An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

Examples of the N-substituted sulfamoyl group include -SO ₂ NHR ⁵⁵ and -SO ₂ N (R ⁵⁵ ) R ^56. Specifically, -SO ₂ NHR ⁸ in the compound represented by the formula (1) A and ^{_{-SO 2 N (R 8) R}} 9 may be the same groups as either. Among them, R ⁵⁵ and R ⁵⁶ are each independently preferably an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or an N-substituted sulfamoyl group which is an acyl group having 2 to 18 carbon atoms and may have a substituent.

B ⁰ , B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group]

As the corresponding organic device, for example, the same group as R ⁵⁹ described later can be mentioned.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is preferably a hydroxyl group, an oxo group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a cyano group, And may be substituted with an N-substituted amino group.

As the N-substituted amino group, -NHR ⁵⁷ group or -NR ⁵⁷ R ⁵⁸ group is preferable. R ⁵⁷ and R ⁵⁸ each independently represent a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent or a monovalent heterocyclic group of 3 to 14 carbon atoms which may have a substituent. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

B ⁰ , B ¹ and B ² each independently represent a group represented by formula (2-1a).

[In the formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent.]

The pyridone ring of the group represented by the formula (2-1a) may be a keto or an enol form.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same groups as described above. R ⁵⁹ represents a methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), a methylhexyl group Ethylhexyl group and the like), a methylcyclohexyl group (such as a 2-methylcyclohexyl group) and an alkoxypropyl group (such as a 3- (2-ethylhexyloxy) propyl group and the like) ), And the like, which is preferably a branched chain aliphatic hydrocarbon group.

Examples of the substituent for R ⁵⁹ and R ⁶⁰ include a hydroxyl group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include the same ones as described above. Examples of the acyloxy group having 1 to 8 carbon atoms include an acetyloxy group, a propionyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a benzoyloxy group.

R ⁶⁰ is preferably a methyl group.

Examples of the compound represented by formula (2) include compounds represented by formulas (I-1) to (I-18). In the table, A ¹ , A ² , Z ^1, and Z ² represent the combined hand on the right hand side closer to Z ³ .

It is more preferable that B ¹ and B ² are groups of the same kind, and furthermore, it is more preferable that A ¹ and A ² , R ⁵³ and R ⁵⁴ , Z ¹ and Z ² are the same kind of groups. With these groups, it is easy to produce the compound represented by the formula (2-1).

The compound represented by the formula (2-1) is obtained by reacting the compound represented by the formula (IA) and the compound represented by the formula (I-A ') with the compound represented by the formula (IB) at 0 to 150 캜 Can be manufactured.

Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² in the formulas (IA), (I-A ' It represents meaning.

R ⁶⁷ and R ⁶⁸ each independently represent -OR ⁶⁹ or a halogen atom. And R ⁶⁹ represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms.

Examples of the compound represented by the formula (I-B) include dimethyl malonate, isobutyl succinate, dimethyl adipate, diethyl superate, malonate, succinate, adipic acid and superic acid.

The amount of the compound represented by the formula (I-B) is preferably 0.5 to 3 moles, for example, relative to 1 mole of the total amount of the compound represented by the formula (I-A) and the compound represented by the formula (I-A '). When water is contained in the solvent, it is preferable to use the compound represented by the formula (I-B) in excess of the amount described above.

When R ³¹ and R ³² of the compound represented by the formula (IB) are -OR ³³ , it is preferable to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid and para-toluenesulfonic acid. The amount of the acid catalyst to be used is preferably 0.01 to 2 mol, for example, relative to 1 mol of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ').

The reaction between the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') and the compound represented by the formula (I-B) is carried out in a solvent. As the solvent, for example, water; Ethers such as 1,4-dioxane (particularly, cyclic ethers); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichlorethylene, perchlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Carbon-based aromatic compounds such as benzene, toluene and xylene; And alkylamides such as N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferable and two or more kinds of solvents may be used in combination. The amount of the solvent to be used is preferably 1 to 20 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ' 10 parts by mass.

The reaction between the compound represented by the formula (IA) and the compound represented by the formula (IA ') and the compound represented by the formula (IB) is preferably carried out under a nitrogen atmosphere or an argon atmosphere, The reaction may be carried out under air.

The reaction temperature is, for example, preferably 0 to 150 占 폚, more preferably 10 to 130 占 폚. The reaction time is preferably, for example, 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A '), the compound represented by the formula (IB) and the solvent is not particularly limited, but the compound represented by the formula (IA) (IB) is added (added dropwise) to a solution comprising a compound represented by the formula (II) and a solvent. In the case of using an acid catalyst, it is preferable to add (drop) the compound represented by the formula (IB) to a solution comprising a compound represented by the formula (IA), a compound represented by the formula (I-A '), an acid catalyst and a solvent .

The method for obtaining the target compound represented by the formula (2-1) from the reaction mixture obtained as described above is not particularly limited, and various known methods can be adopted. For example, the reaction mixture is dissolved in an organic solvent And the like. If necessary, it may be further purified by a known method such as washing with an alkaline aqueous solution or an acidic aqueous solution, recrystallization or the like.

The compound represented by the formula (2-1) can be produced by subjecting a compound represented by the formula (IC), a compound represented by the formula (ID) and a compound represented by the formula (I-D ') to a coupling reaction . (2-1) by reacting a salt of the compound represented by the formula (IC) with a compound represented by the formula (ID) and a compound represented by the formula (I-D ') in an aqueous solvent at 20 to 60 ° C, ) Can be produced.

(In the formulas (IC) and (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² have the same meanings as defined above.

X ^- represents an inorganic or organic anion.)

Examples of inorganic or organic Anna Ian of the compound represented by the formula (IC), fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ^{_{ion, CH 3 -COO -, Ph-}} COO - , and the like, and may be mentioned ^-, preferably -COO chloride ion, bromide ion, CH _3.

The dye is preferably a dye containing a metal complex having an azo compound as a ligand, more preferably a dye containing a compound represented by the formula (3). The compound represented by the formula (3) is a salt of chromium anion or cobalt anion and cations.

R ^a1 to R ^a18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- represents a -COOR ^a30 or -SO ₂ R ^a30.

R ^a19 And R ^a20 each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

R ^a30 each independently represent a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted with -O- or -CO-.

M ¹ represents Cr or Co.

n ¹ represents an integer of ¹ to 5;

D ¹ represents a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^a1 to R ^a18 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- 1, 3-tetramethylbutyl group, 1, 5-dimethylhexyl group, 1, 6-dimethylhexyl group, -Methylhexyl group, a dimethylheptyl group, a 2-ethylhexyl group and a 1,1,5,5-tetramethylhexyl group.

As the monovalent hydrocarbon group having 1 to 10 carbon atoms representing R ^a30 , a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, And a group having 4 to 10 carbon atoms in combination. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include groups similar to those of Q in the compound represented by the formula (1). Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the hydrocarbon group substituted with -CH ₂ - by -O- or -CO- include -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , -R ^a32 -O-CO-R ^a33 have. R ^a32 is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^a33 is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ^a32 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, -1,3-diyl group, pentane-1, 5-diyl group, hexane-1, 6-diyl group, heptane-1, 7-diyl group and octane-1, 8-diyl group.

^Examples of -R ^a32 -OR ^a33 include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, 4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

^Examples of -R ^a32- CO-OR ^a33 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonyl Methyl group, and butoxycarbonyl ethyl group.

^Examples of -R ^a32 -O-CO-R ^a33 include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, Butylcarbonyloxyethyl group and the like.

Examples of -SO ₂ NHR ^a30 include a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2-methylpropyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Substituted with an aliphatic hydrocarbon group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- Sulpa Weather;

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ) -S (-O-lower alkyl) sulfamoyl group such as N- (2-ethylhexyloxypropyl) sulfamoyl group, N- ^{31 a} sulfamoyl group substituted with -OR ³² ;

(Methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (Propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) A sulfamoyl group substituted with -R ³¹ -CO-OR ^{32 such} as a sulfamoyl group;

N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (acetyloxymethyl) sulfamoyl group, N- (Propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group and the like A sulfamoyl group substituted with -R ³¹ -O-CO-R ³² ;

(2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- 4-butylcyclohexyl) sulfamoyl group and the like; a sulfamoyl group substituted with a cyclohexyl group having a substituent;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) Pamoyl group, and sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

^Examples of -COOR ^a30 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a decyloxycarbonyl group.

Examples of -SO ₂ R ^a30 include methanesulfonyl, ethanesulfonyl, propanesulfonyl, isopropanesulfonyl, n-butanesulfonyl, sec-butanesulfonyl, tert- Methylheptanesulfonyl group, a 1, 6-dimethylheptanesulfonyl group, a 2-ethylhexylsulfonyl group, an isobutylsulfonyl group, an isobutylsulfonyl group, Hexanesulfonyl group, and 1,1,5,5-tetramethylhexanesulfonyl group.

Heat resistance tends to be high. Therefore, R ^a1 to R ^a18 Is at least one nitro group.

Examples of R ^a30, a cyclohexyl group which is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, optionally substituted with an alkyl group having a carbon number of 1~4, -R -OR ^{a32 a33, a32} -R -CO-OR ^a33 and ^a32 -R - O-CO-R < ^a33 & gt ^; is preferred.

In the compound represented by the formula (3), preferred examples of the pyrazole compound to be the ligand of the complexing agent include compounds represented by the formulas (1-a1) to (1-a64).

In the compound represented by the formula (3), preferred examples of the anion are anions represented by the formulas (1-b1) to (1-b60).

D ¹ is a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton. Of these, monovalent cationic compounds derived from a compound having a xanthene skeleton are preferable in that the resulting color filter has a high brightness. Examples of the compound having a xanthene skeleton include a compound represented by the formula (1).

The compound represented by the formula (3) is preferably a compound represented by the formula (3-1) in view of solubility in an organic solvent.

[In the formula (3-1), R ^a41 ~R ^a58 are independently of each other, a monovalent aliphatic hydrocarbon group of a hydrogen atom, a halogen atom, having 1 to 8 carbon atoms, a nitro group, a sulfo group, -SO ₂ R ^a33 Or -SO ₂ NHR ^a34 .

R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , R ^a32 -O-CO-R ^a33 or an aralkyl group having 7 to 10 carbon atoms.

R ^a32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a33 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a59 And R ^a60 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ² represents Cr or Co.

R ^a21 to R ^a24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group May be substituted by a hydroxyl group, -OR ³² , a sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ^a25 And R ^a26 each independently represent a hydrogen atom or a methyl group.

R ^a27 represents an ethylene group, a propane-1,3- ^diyl group or a propane-1,2- ^diyl group.

R ^a28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R < ²⁷ > s may be the same or different.]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those shown above for R ^a1 to R ^a18 .

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those represented by R ^a32 .

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

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group and a naphthyl group; An aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group and a 3-phenylpropyl group.

Examples of the cyclohexyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms include a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-butylcyclohexyl group A 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4-isopropylcyclohexyl group, and a 4-butylcyclohexyl group.

Heat resistance tends to be high. Therefore, R ^a41 to R ^a58 Is at least one nitro group.

In addition, R ^a41 and R ^a46 ~R ^a50 ~R at least one at least one of the ^a45, sulfo, -SO ₂ NHR ^a34 or -SO ₂ R ^a33, and should preferably, -SO ₂ R ^a33, and is more preferably that the, -SO ₂ CH ₃ are still more preferred.

R ^a21 to R ^a24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group because the color density is high.

As R ^a27 , an ethylene group and a propane- ^1,2-diyl group are preferable, and an ethylene group is more preferable.

As R ^a28 , a hydrogen atom is preferable.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and still more preferably 3.

- (R ^a27 -O) n R ^a28 , 2- (2-hydroxyethoxy) ethyl group and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group are preferable in view of solubility in organic solvents And more preferred is 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group.

In the compound represented by the formula (3-1), preferred examples of the cation derived from the xanthene compound include a cation represented by the formula (1-c1) to (1-c48).

Specific examples of the compound represented by the formula (3-1) include compounds represented by the formulas (3a-1) to (3a-26).

(3a-1), (3a-3) to (3a-5) and (3a-7) in terms of solubility in an organic solvent among specific examples of the compound represented by the formula (3-1) (3a-9), (3a-11) to (3a-16), (3a-18) to (3a-21) and (3a-1), a compound represented by the formula (3a-3) and a compound represented by the formula (3a-23) are more preferable.

In order to produce the compound represented by the formula (3), the compound represented by the formula (3d) and the chromium compound are used to form the chromium complex, or the compound represented by the formula (3d) and the cobalt compound are used to form the cobalt complex . Thereafter, if necessary, the compound represented by the formula (3) can be prepared by subjecting the salt having the corresponding complex salt and D ¹ to a salt exchange reaction.

[In the formula (3d), R ^a1 to R ^a5 , R ^a11 to R ^a14 And R ^a19 have the same meanings as in formula (3).]

The compound represented by the formula (3d) can be produced by a method of diazo coupling of a diazonium salt and a pyrazole compound well known in the dye field.

The compound represented by the formula (3-1) is prepared by subjecting the complex salt to a salt exchange reaction with the xanthene compound represented by the formula (b).

In the formula (b), R ^a21 to R ^a28 and n have the same meanings as in the formula (3-1). A ^- represents a monovalent anion.]

Examples of univalent anions include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^- or BF ₄ ^- and the like.

The xanthene compound represented by the formula (b) can be produced by reacting the compound represented by the formula (b0) with the compound represented by the formula (b1) in an organic solvent.

[In the formulas (b0) and (b1), R ^a21 to R ^a28 And n have the same meanings as in the formula (2-1). A ^- has the same meaning as in formula (b).]

In the above reaction, the reaction temperature is preferably 15 ° C to 60 ° C, and the reaction time is preferably 1 hour to 12 hours. From the viewpoint of shortening the reaction time or improving the yield, it is preferable to use an acid catalyst and / or a dehydrating agent.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid and the like.

Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; Di-2-pyridyl carbonate, and the like. Among them, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent since post treatment and purification are easy.

Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, acetonitrile and the like.

The compound represented by the formula (3-1) can be produced by subjecting the complex salt and the xanthene compound represented by the formula (b) to a salt exchange reaction in a solvent. It is preferable to react the cobalt complex salt and the xanthene compound (b) in a molar ratio of 1: 1 to 1: 4.

These dyes are appropriately selected in accordance with the solubility in a solvent and the light discoloration resistance and spectral spectrum when a pattern of a color filter is formed using a photosensitive resin composition containing the dye.

The content of the dye is preferably 0.5 to 60 mass%, more preferably 0.7 to 50 mass%, and still more preferably 1 to 40 mass%, based on the solid content of the colored photosensitive resin composition. Here, the solid content refers to the total amount of the components excluding the solvent from the colored photosensitive resin composition.

Further, it is preferable that the colorant (A) contains a pigment in addition to the dye.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified in the color index (published by The Society of Dyers and Colourists) as pigments.

Specific examples of the organic pigment include 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, 194 and 214;

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. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 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, and 58;

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

C.I. Pigment black 1, pigment black 7, and the like.

Among them, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 209, 242, 254, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, 15: 6, and C.I. Pigment greens 7, 36 and 58 are preferred. As the pigment to be used in the colored photosensitive resin composition of the present invention, there may be mentioned C.I. Pigment Blue 15: 6, C.I. Pigment Red 254, C.I. Pigment Red 242, C.I. Pigment Red 177, C.I. Pigment Green 58, C.I. Pigment Yellow 150 and C.I. And Pigment Yellow 138 are more preferable.

The above-mentioned pigments may be subjected to a surface treatment using a pigment derivative or a pigment dispersing agent to which a rosin treatment, an acidic group or a basic group has been introduced, a graft treatment on the surface of a pigment with a polymer compound or the like, an atomization treatment with a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water to remove impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the pigment has a uniform particle diameter. By containing a pigment dispersant and carrying out a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

As the above-mentioned pigment dispersant, a commercially available surfactant can be used. For example, a surfactant such as a silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, And the like. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimines (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Material Electronics Co., Ltd.) ), Fluoride (manufactured by Sumitomo 3M Ltd.), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Sulfone (manufactured by AGC Seiyam Chemical Co., Ltd.) , EFKA (manufactured by CIBA), Adipa (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Big Chemical).

When a pigment dispersant is used, the amount thereof to be used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less, per 1 part by mass of the pigment. When the amount of the pigment dispersant is within the above range, it is preferable because a pigment dispersion in a uniformly dispersed state can be obtained.

These dyes and pigments may be used individually or in combination of two or more. The dyes and pigments may be mixed in an arbitrary ratio and used.

The content of the dye in the colorant (A) is 3 to 100% by mass, preferably 5 to 95% by mass, and more preferably 5 to 80% by mass.

The content of the pigment in the colorant (A) is 0 to 97% by mass, preferably 5 to 95% by mass, and more preferably 20 to 95% by mass.

When the content of the dye and the pigment is in the above-mentioned range, it is preferable that the object spectroscopy can be obtained, and both the excellent heat resistance and the light resistance can be obtained.

When a coating film and / or a pattern formed by using the colored photosensitive resin composition is used for a color filter provided in a liquid crystal display device or the like, the colored photosensitive resin composition contains a blue photosensitive resin composition, a green photosensitive resin composition and a red photosensitive resin Respectively.

The blue photosensitive resin composition preferably contains a compound represented by formula (1) as a dye. As the pigment, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, and 15: 6, and preferably at least one pigment selected from the group consisting of C.I. It is more preferable to contain Pigment Blue 15: 6.

When the pigment is C.I. Pigment Blue 15: 6, C.I. It is preferable that the mass ratio of Pigment Blue 15: 6 to the compound represented by Formula (1) is 97: 3 to 50: 50.

The green photosensitive resin composition preferably contains, as a dye, a compound represented by the formula (2). As the pigment, C.I. Pigment Green 36, 58, C.I. Pigment Yellow 138, and 150. It is preferable that at least one selected from the group consisting of Pigment Yellow 138 and Pigment Yellow 138 is contained.

The red photosensitive resin composition preferably contains, as a dye, a compound represented by the formula (3). As the pigment, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254, based on the total weight of the composition.

The content of the colorant (A) is preferably from 5 to 60 mass%, more preferably from 8 to 55 mass%, and still more preferably from 10 to 50 mass%, based on the solid content in the colored photosensitive resin composition. When the content of the colorant (A) is within the above range, the color density when the color filter is formed is sufficient, and since a necessary amount of the binder resin can be contained in the composition, a pattern having sufficient mechanical strength can be formed .

The colored photosensitive resin composition of the present invention contains a binder resin (B).

The binder resin (B) contained in the colored photosensitive resin composition of the present invention contains at least one (Ba) selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin with a polymerizable double bond (Bc) which is selected from the group consisting of anhydrous succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is allowed to react with the monomer (Bb) having an epoxy group, and the reaction is further carried out by reacting a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (Hereinafter sometimes referred to as " resin (BA) ") obtained by reacting a polyfunctional epoxy compound (Bd) containing at least one member selected from the group consisting of a polyfunctional epoxy compound (Bd)

(Ba) (hereinafter sometimes referred to as " epoxy resin (Ba) ") selected from the group consisting of bisphenol A epoxy resin and bisphenol F epoxy resin is represented by the following formula (Ba-1) / RTI >

In the formula (Ba-1), R represents a hydrogen atom or a methyl group. n represents an average value of the degree of polymerization and is 0 to 20, preferably 0 to 2, more preferably 0 to 1.

Specific examples of the monomer (Bb) having a carboxyl group and a polymerizable double bond (hereinafter sometimes referred to as "monomer (Bb)") include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, (Meth) acryloyloxyethyl], [omega] -carboxypolycaprolactone mono (meth) acrylate, and the like. Of these, acrylic acid and methacrylic acid are preferable, acrylic acid is particularly preferable because photopolymerization is high and sensitivity tends to be high.

In the present specification, the term "(meth) acryloyl" means at least one selected from the group consisting of acryloyl and methacryloyl. The term "(meth) acrylic acid" also has the same meaning.

(Bc) (hereinafter sometimes referred to as "acid anhydride (Bc)") selected from the group consisting of maleic anhydride, succinic anhydride, maleic anhydride, and anhydrous tetrahydrophthalic acid includes anhydride succinic anhydride, maleic anhydride, anhydrous tetrahydro Phthalic acid may be used alone, or two or more kinds of them may be used in combination. Among them, succinic anhydride is preferable.

Further, an acid anhydride different from the acid anhydride (Bc) (hereinafter sometimes referred to as "acid anhydride (Bc ')") may be used in combination. Examples of the acid anhydride (Bc ') include glutaric anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, 5,6-dicarboxybicyclo [2. 2,1] hepto-2-ene anhydride (hydroamic anhydride).

(Hereinafter sometimes referred to as a "polyfunctional epoxy compound (Bd)") containing at least one member selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, Bisphenol A type epoxy resin and bisphenol F type epoxy resin may be used alone, or two or more kinds of them may be used in combination. Examples of polyfunctional epoxy compounds containing these resins include bisphenol S type epoxy resins and bisphenol fluorene type epoxy resins.

The epoxy resin (Ba) as the starting material and the polyfunctional epoxy compound (Bd) to be reacted after the reaction of the acid anhydride (Bc) may be the same or different.

Resin (BA) can be obtained by the following reaction.

First, a reaction product is obtained in which a monomer (Bb) is reacted with an epoxy group in an epoxy resin (Ba) to introduce a (meth) acryloyl group, and a monomer (Bb) is added to the epoxy resin (Ba). Subsequently, an acid anhydride (Bc) is ester-bonded to a hydroxyl group generated by ring opening of the epoxy group in the obtained reaction product to introduce a carboxyl group. The resin (BA) can be obtained by reacting the thus obtained resin with a polyfunctional epoxy compound (Bd).

The reaction between the epoxy resin (Ba) and the monomer (Bb) is preferably carried out at a reaction rate of 0.8 to 1.1 chemical equivalents such that the carboxyl group in the monomer (Bb) is approximately equivalent to the 1.0 chemical equivalent of the epoxy group in the epoxy resin (Ba) .

The reaction between the epoxy resin (Ba) and the monomer (Bb) can be carried out, for example, by reacting a polymerization inhibitor such as hydroquinone, monomethylether hydroquinone or oxygen, and a tertiary amine, tertiary phosphine, lithium chloride, In the presence of a reaction catalyst such as a basic ammonium salt or a quaternary phosphonium salt, at 80 to 130 캜.

In the reaction of the reaction product obtained by the reaction of the epoxy resin (Ba) with the monomer (Bb) and the acid anhydride (Bc), 1.0 hydroxyl equivalent of the hydroxyl group formed by the reaction of the epoxy resin (Ba) and the monomer (Bb) To react with 0.1 to 1.9 chemical equivalents of the acid anhydride (Bc). When the acid anhydride (Bc) is in the above range, development tends to be good, which is preferable. When the acid anhydride (Bc ') is used in combination, it is preferable that the total amount of the acid anhydride (Bc) and the acid anhydride (Bc') is in the above range.

This reaction can be carried out in the presence of a polymerization inhibitor such as, for example, hydroquinone, monomethylether hydroquinone, oxygen, etc., in the presence of a catalyst, or a tertiary amine, a tertiary phosphine, a lithium chloride, a quaternary ammonium salt, It can be carried out at 50 to 130 占 폚 under the coexistence of a phosphonium salt and the like.

The reaction between the resin obtained by the reaction and the polyfunctional epoxy compound (Bd) is carried out in such a manner that the epoxy group in the polyfunctional epoxy compound (Bd) It is preferable to conduct the reaction so as to have a chemical equivalent of 0.8. When the epoxy group in the polyfunctional epoxy compound (Bd) is in the above-mentioned range, it is preferable because the developability and the mechanical strength tend to be good.

This reaction can be carried out in the presence of a polymerization inhibitor such as hydroquinone, monomethylether hydroquinone, oxygen, etc., in the presence of a tertiary amine, a tertiary phosphine, lithium chloride, a quaternary ammonium salt or a quaternary phosphonium salt In the presence of the reaction catalyst, at 80 to 130 占 폚.

The binder resin (BA) is obtained by reacting the resin obtained by the above reaction with a compound (Be) having at least one acid anhydride selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid Anhydride (Be) "in some cases). By carrying out the reaction, development tends to be good, which is preferable.

In this reaction, the acid anhydride (Be) which can be used is the same compound as the above-mentioned acid anhydride (Bc). The reaction conditions are the same as those in the reaction of the reaction product obtained by the reaction of the epoxy resin (Ba) with the monomer (Bb) and the acid anhydride (Bc).

The acid value of the resin (BA) is preferably 20 to 150, more preferably 25 to 130, and particularly preferably 30 to 110. When the acid value is in the above-mentioned range, the solubility in the developer is improved and the unexposed portion is liable to be dissolved, which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic acid-based polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The weight average molecular weight of the resin (BA) determined by gel permeation chromatography on the basis of polystyrene is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. When the weight average molecular weight is within the above range, the coating property tends to be good, and a high developing speed tends to be obtained while maintaining the residual film ratio at the time of development.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (BA) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the above-mentioned range, the developing property tends to be excellent.

The content of the resin (BA) is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, and particularly preferably 50 to 100 mass%, based on the mass of the binder resin (B). When the content of the resin (BA) is within the above-mentioned range, the solubility in the developer is sufficient and the heat resistance tends to be unlikely to cause development residue on the substrate of the non-pixel portion.

In addition to the resin (BA), a known resin may be used in combination with the binder resin (B).

The resin to be used as the binder resin (B) is preferably one having solubility in a developing solution used in the developing treatment step, particularly preferably an alkali developing solution, and is not particularly limited. Examples thereof include a carboxyl group, a phenolic hydroxyl group, A copolymer (BB) (hereinafter sometimes referred to as "resin (BB)") of a compound (B1) having an acidic functional group such as a sulfonic acid (hereinafter sometimes referred to as " . Among them, unsaturated compounds having a carboxyl group are preferable as (B1).

(B1) may be used alone or in combination of two or more.

Examples of the unsaturated compound having a carboxyl group include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids or unsaturated dicarboxylic acids. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, cinnamic acid, mono [2- (meth) acryloyloxyethyl] ? -carboxypolycaprolactone mono (meth) acrylate, 5-carboxy-5-methylbicyclo [2. 2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2. 2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2. 2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2. 2.1] hepto-2-ene. Among them, acrylic acid and methacrylic acid are preferable.

As the binder resin (BB), among the compounds copolymerizable with (B1), the reliability (heat resistance, light resistance, solvent resistance, mechanical properties, etc.) of the colored pattern formed by the colored photosensitive resin composition is improved, A resin containing a constituent unit derived from a compound (B0) (hereinafter occasionally referred to as " (B0) ") is preferable.

As the unsaturated compound (B0) having a curable group, for example, a compound having a carbon-carbon unsaturated double bond and a cyclic ether structure is preferably exemplified. The cyclic ether structure includes, for example, an epoxy structure (i.e., an oxirane structure), an oxetane structure, and a tetrahydrofuran structure, and an epoxy structure and an oxetane structure are particularly preferable.

The epoxy structure includes, for example, an aliphatic epoxy structure, an aliphatic monocyclic epoxy structure and an aliphatic polycyclic epoxy structure, and an aliphatic polycyclic epoxy structure is particularly preferable.

(B0) may be used alone or in combination of two or more.

Here, the aliphatic epoxy structure is a structure obtained by epoxidizing an alkene, and the aliphatic monocyclic epoxy structure is a structure obtained by epoxidizing a monocyclic cycloalkene. The aliphatic polycyclic epoxy structure is a structure obtained by epoxidizing a cycloalkene of a cross- to be. Examples of the above-mentioned monocyclic cycloalkane include cyclopentene, cyclohexene, and cycloheptene. Examples of the cycloalkene of the cross linking ring include norbornene, dicyclopentene and tricyclodecene.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic epoxy structure include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (Meth) acrylate, glycidyl vinyl ether, and compounds represented by the following formulas described in JP-A-7-248625.

In the present specification, (meth) acrylate refers to at least one kind selected from the group consisting of acrylate and methacrylate.

(Wherein R ^x1 to R ^x3 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and mx is an integer of 1 to 5)

Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl Methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidyloxymethyl) styrene, 2,4-bis (Glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, Tris (glycidyloxymethyl) styrene, 2, 3, 6-tris (glycidyloxymethyl) styrene, 3,4,5- 4, 6-tris (glycidyloxymethyl) styrene, and the like.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include, for example, vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; (Manufactured by Daicel Chemical Industries, Ltd.), 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, Cyclomer-A400; Manufactured by Daicel Chemical Industries, Ltd.), 3, 4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer-M100; (Manufactured by Daicel Chemical Industries, Ltd.).

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure include 3, 4-epoxy norbornyl acrylate, 3,4-epoxy norbornyl methacrylate, (B0-2), and preferably at least one compound selected from the group consisting of a compound represented by the formula (B0-1) and a compound represented by the formula (B0-2) Compounds.

[In the formulas (B0-1) and (B0-2), R ^y1 And R ^y2 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ^y1 And X < ^y2 > independently represent an alkylene group having 1 to 6 carbon atoms which may contain a single bond or a hetero atom.

Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- Propyl group, a 2-hydroxy-n-propyl group, a 3-hydroxy-n-propyl group, a 1-hydroxy-isopropyl group Butyl group, a 3-hydroxy-n-butyl group, a 4-hydroxy-n-butyl group and the like . Among them, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a methyl group is more preferable.

R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the hetero atom in the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom. The number of heteroatoms is not included in the number of carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an ethylene group, a propylene group, an oxymethylene group (i.e., -O-CH ₂ -), an oxyethylene group, an oxypropylene group, (I.e., -S-CH ₂ -), sulfanylethylene group, sulfanylpropylene group, iminomethylene group (i.e., -NH-CH ₂ -), iminoethylene group and iminoproylene group, A methylene group, an ethylene group, an oxymethylene group or an oxyethylene group can be mentioned, and an oxyethylene group is more preferable.

X ^y1 And X ^y2 are preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

Examples of the compound represented by the formula (B0-1) include compounds represented by the formulas (B0-1-1) to (B0-1-15), preferably the compounds represented by the formulas (B0-1-1) (B0-1-3), (B0-1-5), (B0-1-7), (B0-1-9), (B0-1-11) (B0-1-1), formula (B0-1-7), formula (B0-1-9), or formula (B0-1-15) And the like.

Examples of the compound represented by the formula (B0-2) include compounds represented by the formulas (B0-2-1) to (B0-2-15), preferably the compounds represented by the formulas (B02-1), (B02-5), (B02-7), (B02-9), and (B02-11) to (B0-2-15) More preferably, the compound represented by formula (B0-2-1), formula (B0-2-7), formula (B02-9) or formula (B02-15).

At least one kind of compound selected from the group consisting of the compound represented by the formula (B0-1) and the compound represented by the formula (B0-2) can be used alone. Further, they can be mixed at an arbitrary ratio. The mixing ratio thereof is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 10:90 to 90:10 in terms of the molar ratio of the formula (B0-1): formula (B0-2) 20:80 to 80:20.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an oxetane structure include 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3- (Meth) acryloyloxymethyloxetane, 3-methyl-3- [1- (meth) acryloxy] methyloxetane, 3- Ethyl-3- [1- (meth) acryloxy] ethyloxetane, 2-phenyl-3- (meth) acryloxy methyloxetane, 3- (Meth) acryloyloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl- (Meth) acryloxyethyloxetane, 2-phenyl-3- (meth) acryloxyethyloxetane, 2-trifluoromethyl-3- - pentafluoroethyl-3- (meth) acryloxyethyloxetane, 3-methacryloxy oxetane, and the like. The. Among them, 3-ethyl-3- (meth) acryloxymethyloxetane is preferable.

Specific examples of the compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure include tetrahydrofurfuryl (meth) acrylate, tetrahydrofuryl methoxyethyl (meth) acrylate, tetrahydrofuryl methoxypropyl (meth) Acrylate, and the like.

When the binder resin (BB) is a copolymer of (B1) and (B0), the ratio of the constituent unit derived from (B1) and the constituent unit derived from (B0) With respect to the total number of moles, in the range below, the storage stability, heat resistance and mechanical strength tend to be favorable.

(B1); 2 to 98 mol%

(B0); 2 to 98 mol%

The ratio of the above-mentioned structural units is preferably within the following range in terms of developability, residual film ratio and solvent resistance.

(B1); 15 to 60 mol%

(B0); 40 to 85 mol%

The above-mentioned binder resin (BB) can be produced, for example, by the method described in "Experimental Method of Polymer Synthesis" (issued by Otsu Chemical Co., Ltd., 1st Edition, 1st Edition, , Which is incorporated by reference herein.

Concretely, a copolymer is obtained by adding a compound such as (B1) and (B0), a polymerization initiator and a solvent into a reaction vessel, replacing oxygen by nitrogen, stirring, heating and keeping the temperature in the absence of oxygen . The resulting copolymer may be a solution obtained by concentrating or diluting the solution after the reaction as it is, or a solid (powder) extracted by re-precipitation or the like.

The binder resin (BB) includes, in addition to (B1) or (B1) and (B0), a compound (B2) copolymerizable with (B1) (excluding (B1) and (B0) (B2) "). ≪ / RTI > (B2) include, for example, carboxylic acid esters having olefinic double bonds, amide compounds having olefinic double bonds, aromatic compounds having a polymerizable carbon-carbon unsaturated bond, substituted vinyl compounds, dienes, N Substituted maleimide compounds, polycyclic unsaturated compounds, and the like.

(B2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl Acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5. ^2,1 ] ^2,6 ] decan-8-yl (meth) acrylate (also referred to in the art as dicyclopentanyl (meth) acrylate), dicyclopentoxyethyl (meth) Unsaturated carboxylic acid esters such as acrylate, phenyl (meth) acrylate, aminoethyl (meth) acrylate, diethyl maleate, diethyl fumarate and diethyl itaconate;

Carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate, polymerizable amides such as dimethyl (meth) acrylamide and isopropyl (meth) acrylamide;

Polymerizable aromatic compounds such as styrene,? -Methylstyrene or vinyltoluene;

Vinyl cyanide such as acrylonitrile, methacrylonitrile or? -Chloro (meth) acrylonitrile;

N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide;

Polymerizable aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Halogenated vinyl halides such as chloroethylene, dichloroethylene, trichlorethylene, fluoroethylene, difluoroethylene, trifluoroethylene and tetrafluoroethylene;

Dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

Bicyclo [2. 2.1] hepto-2-ene, 5-methylbicyclo [2. 2.1] hepto-2-ene, 5-ethylbicyclo [2.. 2.1] hepto-2-ene, 5-hydroxybicyclo [2. 2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.. 2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.. 2.1] hepto-2-ene, 5-methoxybicyclo [2. 2.1] hepto-2-ene, 5-ethoxybicyclo [2.. 2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.. 2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.. 2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [ 2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.. 2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.. 2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.. 2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.. 2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.. 2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.. 2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.. 2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2. 2,1] hepto-2-ene, and the like.

Of these, benzyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [ 2.1] hepto-2-ene and the like are preferable.

The above-mentioned (B2) may be used singly or in combination of two or more kinds.

When the binder resin (BB) is a copolymer of (B1) and (B2), the proportion of the constituent unit derived from (B1) and the constituent unit derived from (B2) With respect to the total molar number, if it is in the range below, storage stability and heat resistance tends to be good, which is preferable.

(B1); 2 to 98 mol%

(B2); 2 to 98 mol%

The ratio of the above-mentioned structural units is preferably within the following range in terms of developability and residual film ratio.

(B1); 15 to 60 mol%

(B2); 40 to 85 mol%

When the binder resin (BB) is a copolymer of (B1) and (B0) and (B2), the proportion of the constituent units derived from (B0) to (B2) When the number of moles is in the range below, the storage stability, heat resistance and mechanical strength tend to be favorable.

(B0); 2 to 97 mol%

(B1); 2 to 97 mol%

(B2); 1 to 96 mol%

The ratio of the above-mentioned structural units is preferably within the following range in terms of developability, residual film ratio and solvent resistance.

(B0); 20 to 80 mol%

(B1); 10 to 50 mol%

(B2); 10 to 70 mol%

The binder resin (BB) containing the structural units derived from the above-mentioned (B0) to (B2) can be produced by the same method as the above resin containing the structural units derived from (B1) and (B0) .

(B1) and (B2), the binder resin (BB) containing the structural unit derived from the photosensitive resin (B2) improves the heat resistance, the light resistance, the solvent resistance and the mechanical characteristics of the colored pattern formed from the colored photosensitive resin composition. B0) and (B2).

Examples of the constituent unit in the above-mentioned binder resin (BB) include macromonomers having a monoacryloyl group or monomethacryloyl group at the end, a unit represented by the following formula (21) and a unit represented by the formula (22) It is more preferable in terms of pattern adhesion, solvent resistance and sensitivity.

[In the formulas (21) and (22), R ^y3 , R ^y4 , R ^y5 And R ^y6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The binder resin (BB) having the constituent unit represented by the formula (21) is preferably a constituent unit (B1a) derived from an unsaturated compound having a carboxyl group or an unsaturated compound having a carboxylic anhydride (hereinafter sometimes referred to as (B1a) For example, copolymers of (B1a) and (B0), copolymers of (B1a) and (B2), copolymers of (B1a) and (B0) and (B2) And a compound represented by the following formula (23) in a carboxylic acid moiety or a carboxylic anhydride moiety containing (B1a).

Examples of the unsaturated compound having a carboxyl group in the formula (B1a) include compounds as specific examples of the compound (B1), and specific examples of the unsaturated compound having a carboxylic acid anhydride include maleic anhydride, 5,6-dicarboxybicyclo [ . 2,1] hepto-2-ene anhydride (hydroamic anhydride). Among them, (meth) acrylic acid is preferable.

[In the formula (23), R ^y4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

The binder resin (BB) having the constituent unit represented by the formula (22) can be obtained by obtaining a copolymer in the same manner as described above, and reacting the obtained copolymer with the compound represented by the formula (24) In the same manner as described in the publication.

[In the formula (24), R ^y6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

The acid value of the resin (BB) is usually 50 to 150, preferably 60 to 135, and particularly preferably 70 to 135. When the acid value is in the above range, the solubility in a developing solution is improved and the unexposed portion is easily dissolved, which is preferable.

The weight average molecular weight of the resin (BB) determined by gel permeation chromatography on the basis of polystyrene is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. When the weight average molecular weight is within the above-mentioned range, the coating property tends to be good, and a high developing speed is preferably obtained while maintaining the residual film ratio at the time of development.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (BB) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the above-mentioned range, the developing property tends to be excellent.

When the binder resin (B) contains the resin (BA) and the resin (BB), the resin (BA) and the resin (BB) can be mixed and used at an arbitrary ratio. In this case, it is preferable that the mixing ratio of the resin (BA) and the resin (BB) is in the following range by mass ratio.

Resin (BA): 10 to 90 mass%

Resin (BB): 90 to 10 mass%

The content of the binder resin (B) is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, based on the solid content in the colored photosensitive resin composition.

The content of the binder resin (B) relative to the total amount of the binder resin (B) and the photopolymerizable compound (C) is preferably 20 to 80 mass%, particularly preferably 30 to 70 mass% And preferably 40 to 65 mass%. When the content of the binder resin (B) is in the above range, solubility in a developing solution is sufficient, development residue is not easily generated on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion occurs during development And it is preferable because the tendency that the dropout of the non-pixel portion becomes good. It is also preferable that the resolution and the residual film ratio tend to be improved.

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator (D) by irradiation with light, and includes, for example, a compound having a polymerizable carbon- .

The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more carbon-carbon unsaturated bonds. Examples of the polyfunctional photopolymerizable compound having three or more functional groups include pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass with respect to the solid content of the colored photosensitive resin composition Mass%. When the content of the photopolymerizable compound (C) is within the above-mentioned range, curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, and the undercut is hard to get into the pattern and the adhesion tends to be good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include an active radical generator and an acid generator.

The active radical generator generates active radicals by being irradiated with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2- Phenylpropane-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and the like, (4-methylthiophenyl) propane-1-one.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 1,2,4- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- - methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3,5 -Triazine, and the like.

Examples of the oxime compound include O-acyloxime compounds. Specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [ 3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- { } -9H-carbazol-3-yl] ethan-1-imine. Commercially available products such as Sigma Cure OXE-01, OXE-02 (manufactured by Chiba and Japan) and N-1919 (manufactured by ADEKA) may be used.

Examples of the active radical generator other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ' Methylphenylacrylate, methyl 5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, , A titanocene compound, or the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfone Nitro, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , And diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylates, and the like.

Among the compounds described above as the above-mentioned active radical generator, there are compounds which generate an acid at the same time as an active radical. For example, a triazine-based compound is also used as an acid generator.

The photopolymerization initiator (D) is preferably an active radical generator, more preferably a photopolymerization initiator comprising at least one selected from the group consisting of an acetophenone compound, a triazine compound and an oxime compound, and a photopolymerization initiator Is more preferable. With these photopolymerization initiators, a pattern can be formed with high sensitivity.

The content of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the binder resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above-mentioned range, it is preferable because a high sensitivity is obtained and the exposure time is shortened and the productivity is improved.

The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide and the like.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate , Anisole, Nitol, methyl anisole and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- Cyclopentanone, cyclohexanone, and the like.

The alcohols include, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, But are not limited to, methyl lactate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Firing may be mentioned acid methyl, 2-oxo-butanoic acid ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl γ- lactone ol.

Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Of these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use them in combination.

The solvent (E) may be used alone or in combination of two or more.

The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 90% by mass, based on the mass of the colored photosensitive resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good and the color characteristic is not insufficient when the color filter is formed, so that the display characteristic tends to be good.

The colored photosensitive resin composition of the present invention may contain a photopolymerization initiator (F). The photopolymerization initiator (F) is a compound or a sensitizer used in combination with the photopolymerization initiator (D) and used for promoting polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

Examples of the photopolymerization initiator (F) include an amine compound, an alkoxyanthracene compound, and a thioxanthone compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- , 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9-10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9 , 10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

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

The photopolymerization initiator (F) may be used alone or in combination of two or more. As a photopolymerization initiator (F), commercially available products such as "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.) and the like may be used.

Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiator (F) in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2- Methyl-2-methyl-1-phenylpropane (2-hydroxy-2-methylphenyl) (Diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4, 4'-bis (diethylamino) ) Oligomer of 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone.

When these photopolymerization initiators (F) are used, the amount thereof to be used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (D).

The colored photosensitive resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include at least one selected from the group consisting of a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Specific examples of the silicone oil include dodecyl silicone DC3PA, dodecyl silicone SH7PA, dodecyl silicone DC11PA, dodecyl silicone SH21PA, dodecyl silicone SH28PA, dodecyl silicone SH29PA, dodecyl silicone SH30PA, polyether-denatured silicone oil SH8400 (manufactured by Dole Silicone Co., Ltd.), KP321 and KP322 , KP323, KP324, KP326, KP340, KP341 [Shin-Etsu Chemical Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Momentive Performance Materials Japan] And the like.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of such a solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Trade name) S381, and Saphron S382 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), Megafac R30 [manufactured by DIC Corporation], EfTop EF301, Efopto EF303, Efopto EF351, , BM-1000 and BM-1100 (both trade names: manufactured by BM Chemie), and the like can be given as examples of commercially available products, which are commercially available from Sumitomo Chemical Co., Ltd. have.

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by DIC Corporation) and the like.

These surfactants may be used alone or in combination of two or more.

The content of the surfactant (G) is preferably 0.00001 to 0.1 mass%, more preferably 0.00005 to 0.01 mass%, based on the mass of the colored photosensitive resin composition. When the content of the surfactant (G) is within the above-mentioned range, the flatness tends to be good, which is preferable. However, the content of the surfactant (G) does not include the content of the pigment dispersant.

As a method for forming a pattern of a color filter using the colored photosensitive resin composition of the present invention, for example, a method of forming a colored photosensitive resin composition of the present invention on a substrate or a separate resin layer (for example, , A method of forming a colored layer by removing volatile components such as a solvent to expose and developing the colored layer through a photomask (that is, a photolithographic method), a photolithographic method And a method of using an ink jet apparatus that does not require a method.

In the above-described pattern formation method, the photomask of the present invention can be obtained by not using a photomask during the exposure and / or by not developing the photomask.

Specifically, a plurality of TFTs 22 are formed for each pixel on a glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). The TFT 22 includes a gate electrode 22a formed on the glass substrate 21 by, for example, molybdenum (Mo) and constituting a part of the gate line, and a gate electrode 22a formed on the gate electrode 22a nitride film (SiN _x) and the oxide layer a polycrystalline silicon film (22c) with, for example, an oxide film (SiO ₂₎ and a nitride film formed on the gate insulating film (22b) and a gate insulation film (22b) formed of a laminate film of (SiO ₂₎ And a protective film 22d formed of a laminated film of SiN _x . A region opposite to the gate electrode 22a of the polycrystalline silicon film 22c serves as a channel region of the TFT 22 and both regions of the channel region serve as a source region or a drain region. The source region of the polycrystalline silicon film 22c is electrically connected to a signal line 27 formed of, for example, aluminum (Al) through a connection hole (contact hole) provided in the protective film 22d. The drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as will be described later.

Alignment marks (not shown) are formed on the glass substrate 21 simultaneously with the TFTs 22 when a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel. This alignment mark serves as a reference for alignment in the process of forming the color filter layer 23, as will be described later. These alignment marks may also be used as a mark used as a reference for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same step by using at least one layer when forming a metal layer such as wiring or a polycrystalline silicon layer in the manufacturing process of the TFT 22. [

Next, a colored photosensitive resin composition layer 23A having a thickness of 0.5 to 5.0 mu m, for example, 1.0 mu m is formed on the TFT 22 and the glass substrate 21 on which the alignment marks are formed by spin coating or other methods. . This colored photosensitive resin composition layer 23A corresponds to the color filter of the present invention.

Subsequently, the colored photosensitive resin composition layer 23A is dried by performing heat treatment at a temperature in the range of 30 to 120 占 폚, for example, 60 to 110 占 폚. In order to dry the colored photosensitive composition layer 23A, the reduced-pressure drying may be performed in combination with heat drying. Next, ultraviolet rays are irradiated to the colored photosensitive resin composition layer 23A through a photomask (not shown), and unnecessary portions (unexposed portions) are selectively removed by a developing solution to remove the drain of the polycrystalline silicon film 22c (Contact hole) 201 reaching the region is formed and then cleaned with water. Thereafter, in order to re-flow (reflow) the colored photosensitive resin composition layer 23A and to cure the curable component contained in the colored photosensitive resin composition layer 23A, a temperature in the range of 100 to 300 DEG C, for example, And heated at 150 to 230 캜.

Thereby, the colored photosensitive resin composition layer 23A becomes the color filter layer 23 including the red filter 23a, the green filter 23b and the blue filter 23c corresponding to each pixel column (see FIG. 2). The region between the respective filters of the color filter layer 23 becomes a mixed region of adjacent colors, but this region is a shielding region opposed to the signal line 27, so that there is no particular problem in terms of quality. In addition, the area between the filters may not be colored.

Subsequently, for example, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 mu m is formed so as to cover the color filter layer 23 by a spin coating method (see Fig. 3). Subsequently, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and a region corresponding to the connection hole 201 and unnecessary portions are selectively removed by a developing solution, whereby the polycrystalline silicon film 22c, (Contact hole) 202 reaching the drain region of the semiconductor substrate 201, followed by cleaning with water. Thereafter, for reflow (reflow) of the photosensitive resin film 29, it is heated at a temperature in the range of 100 to 300 占 폚, for example, 200 占 폚. Then, in order to remove the residues and organic substances deposited in the contact hole 202, etching is performed by oxygen plasma, and etching is performed by, for example, dilute hydrofluoric acid in order to remove the oxide film formed by the oxygen plasma.

Next, a transparent conductive material, for example, ITO (Indium-Tin Oxide: an oxide mixed film of indium and tin) is formed on the photosensitive resin film 29 by, for example, a sputtering method, and this ITO film is subjected to photolithography Technique and etching to form a transparent pixel electrode 24 (see Fig. 4). The pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag), depending on the device to be manufactured. Thereafter, after the alignment film is formed by a conventional method, the liquid crystal display device can be manufactured by joining the driving substrate and the counter substrate.

According to the present invention, it is possible to obtain a coating film, a pattern and a color filter excellent in heat resistance, and the obtained color filter is suitably used for a liquid crystal display element or a solid-state image pickup element.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part " are by mass% and mass part, respectively, unless otherwise specified.

[Synthesis Example 1]

[Synthesis Example of Compound Represented by Formula (1)] [

A cooling tube and a stirrer were charged 15 parts of a mixture of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2), 150 parts of chloroform and 50 parts of N, N-dimethyl And 8.9 parts of formamide was added thereto, and 10.9 parts of thionyl chloride was added dropwise thereto while maintaining the temperature at 20 ° C or lower while stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, held at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine with stirring while maintaining the temperature at 20 ° C or lower. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added to the reaction mixture. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered and washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain a mixture (A1) of the compound represented by the formula (A1-a) and a compound represented by the formula (A1- -1) to a mixture of compounds represented by the formula (A1-8)].

R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or a 2-ethylhexylsulfanyl group, for example, in the formula (A1-a) .]

[Synthesis Example 2]

350 parts of a bisphenol A type epoxy resin (epoxy equivalent 187 g / eq) was added to the reaction vessel, and 1 part of p-methoxyphenol was added as a polymerization inhibitor. While bubbling nitrogen and oxygen mixed gas (oxygen concentration 5% , 138 parts of acrylic acid, 135 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) and 3.2 parts of triethylamine were added and reacted for 4 hours. The reaction product was cooled to 105 占 폚, 187 parts of succinic anhydride and 225 parts of PGMEA were added and reacted for 7 hours. Subsequently, 233 parts of a bisphenol A type epoxy resin (epoxy equivalent 187 g / eq), 1000 parts of PGMEA and 1 part of p-methoxyphenol as a polymerization inhibitor were added and reacted at 115 DEG C for 12 hours, 1.

The obtained resin solution 1 was measured for various physical properties and found to have a weight average molecular weight of 1.2 x 10 ⁴ , a solid content concentration of 40.0% obtained by drying at 160 ° C under vacuum, an acid value per solid fraction of 49 mg KOH / g .

[Synthesis Example 3]

350 parts of bisphenol A type epoxy resin (epoxy equivalent 187 g / eq) was added to a separable flask equipped with a cooling tube as a reaction tank, 1 part of p-methoxyphenol was added as a polymerization inhibitor, and a mixed gas of oxygen and oxygen %) Was heated to 115 DEG C while bubbling, and then 138 parts of acrylic acid, 135 parts of PGMEA and 3.2 parts of dimethylbenzylamine were added and reacted for 4 hours. The reaction product was cooled to 100 占 폚, 187 parts of succinic anhydride and 221 parts of PGMEA were added and reacted for 5 hours. Then, 262 parts of a bisphenol A type epoxy resin (epoxy equivalent 187 g / eq), 1040 parts of PGMEA and 1 part of p-methoxyphenol as a polymerization inhibitor were added and reacted at 115 DEG C for 10 hours. 9 parts by weight of succinic anhydride was added and reacted at 110 DEG C for 3 hours and then cooled to room temperature to obtain a resin solution 2. [

Various physical properties of the resulting resin solution 2 were measured in the same manner as in the case of the resin solution 1, the weight average molecular weight was 2.36 x 10 ⁴ , the solid content concentration was 41.4%, and the acid value per solid fraction was 44 mg KOH / g.

[Synthesis Example 4]

350 parts of bisphenol A type epoxy resin (epoxy equivalent 187 g / eq) was placed in a separable flask equipped with a cooling tube as a reaction tank, and 1 part of p-methoxyphenol was added as a polymerization inhibitor, %) Was heated to 115 DEG C while bubbling through the mixture. Then, 138 parts of acrylic acid, 135 parts of PGMEA and 3.2 parts of triethylamine were added and reacted for 4 hours. The reaction product was cooled to 100 占 폚, 187 parts of succinic anhydride and 220 parts of PGMEA were added and reacted for 3 hours. Subsequently, 583 parts of a bisphenol A type epoxy resin (epoxy equivalent 467 g / eq), 1500 parts of PGMEA and 1.3 parts of p-methoxyphenol as a polymerization inhibitor were added and reacted at 115 DEG C for 10 hours. 9 parts by weight of succinic anhydride was added and reacted at 110 DEG C for 3 hours and then cooled to room temperature to obtain a resin solution 3.

Various physical properties of the obtained resin solution 3 were measured in the same manner as in the case of the resin solution 1, and the weight average molecular weight was 1.82 x 10 ⁴ , the solid content concentration was 40.0%, and the acid value per solid fraction was 50 mg KOH / g.

[Synthesis Example 5]

340 parts of bisphenol A type epoxy resin (epoxy equivalent 187 g / eq) and 420 parts of PGMEA were placed in a separable flask equipped with a cooling tube as a reaction tank, 1 part of p-methoxyphenol was added as a polymerization inhibitor, (Oxygen concentration: 7%) was heated to 115 캜 while bubbling it, and then 135 parts of acrylic acid, 135 parts of PGMEA and 3.2 parts of triethylamine were added and reacted for 8 hours. The reaction product was cooled to 100 占 폚, and 160 parts of succinic anhydride was added thereto, followed by reaction for 3 hours. Then, 213 parts of a bisphenol A type epoxy resin (epoxy equivalent 187 g / eq) and 700 parts of PGMEA and 1 part of p-methoxyphenol as a polymerization inhibitor were added and reacted at 115 DEG C for 10 hours. 4 was obtained.

Various physical properties of the resulting Resin Solution 4 were measured in the same manner as in Resin Solution 1, and the weight average molecular weight was 9.0 × 10 ³ , the solid content concentration was 40.0%, and the acid value per solid fraction was 33 mg KOH / g.

[Synthesis Example 6]

A 1 L flask equipped with a reflux condenser, a dropping rod and a stirrer was purged with 0.02 L / min of nitrogen to make a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate , And the mixture was heated to 70 DEG C while stirring. Subsequently, 60 parts by mass of methacrylic acid, 30 parts by mass of 3,4-epoxytricyclo [5.0. 2,1] ^2,6 ] decyl acrylate [compound of the following formula (B1-1-1) and compound represented by the formula (B1-2-1) at a molar ratio of 50:50)] 240 And 140 parts by mass of 3-methoxybutyl acetate to prepare a solution. The solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping rod. On the other hand, a solution obtained by dissolving 30 parts by mass of 2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask / RTI > After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 占 폚 for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 1.3 占⁰⁴ , the dispersion degree (Mw / Mn) A resin solution H1 having a solid content of 33 mass% and an acid value of 34 mg-KOH / g was obtained.

The polystyrene reduced weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained Resins 1 to 4 and H1 were measured by the GPC method under the following conditions.

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μL

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

                      F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

[Example 1]

(Preparation of colored photosensitive resin composition 1)

(A) Colorant: C.I. Pigment Blue 15: 6 (pigment: PB 15: 6) 33 parts

             Acrylic pigment dispersant 5 parts

              Propylene glycol monomethyl ether acetate 137 parts

And the pigment was sufficiently dispersed using a bead mill, and then,

(A) Colorant: Dye A1 5 parts

(B) Resin: Resin solution 1 150 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

                     [KAYARAD DPHA; 50 parts (manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: 15 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01;

(E) Solvent: ethyl lactate 289 parts

To obtain a colored photosensitive resin composition 1.

The obtained colored photosensitive resin composition 1 was evaluated by the following method. The results are shown in Table 1.

≪ Formation of pattern &

The colored photosensitive resin composition 1 was applied on a glass substrate (Eagle 2000; Corning) having a 2-inch square by spin coating, and then pre-baked at 100 ° C for 3 minutes. After cooling, the space between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask having a pattern was set to 100 mu m, and exposure equipment (TME-150 RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm < 2 > (based on 365 nm) in an air atmosphere. After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water and then subjected to post-baking in an oven at 220 DEG C for 20 minutes Respectively. After cooling, the film thickness of the cured pattern thus obtained was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.) to find that it was 2.2 탆.

≪ Evaluation of heat resistance &

The obtained pattern on the glass substrate was measured with a colorimeter [OSP-SP-200; (X, y) and brightness (Y) in the XYZ color system of CIE were measured using an isochromatic function of C light source. The pattern was heated in an oven at 230 DEG C for 2 hours. After heating, the chromaticity coordinates were measured again, and the color difference (? Eab *) before and after heating was calculated. The results are shown in Table 22.

The smaller the color difference [Delta] Eab *, the better the heat resistance. If the heat resistance of the pattern is good, good heat resistance is exhibited also in the coating film as in the pattern.

[Examples 2 to 5]

A colored photosensitive resin composition and a pattern were obtained in the same manner as in Example 1 except that the resin was changed to have the composition shown in Table 22 or a combination of plural resins was used. The evaluation was carried out in the same manner as in Example 1. The results are shown in Table 22.

[Comparative Example 1]

(Preparation of colored photosensitive resin composition)

(A) Colorant: C.I. Pigment Blue 15: 6 (pigment: PB 15: 6) 33 parts

    Colorant: C.I. Pigment Violet 23 (pigment: PV 23) 5 parts

    Acrylic pigment dispersant 5 parts

    Propylene glycol monomethyl ether acetate 137 parts

And the pigment was sufficiently dispersed using a bead mill, and then,

(B) Resin: Resin solution H1 150 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

                     [KAYARAD DPHA; 50 parts (manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: Irgacure OXE 01 (manufactured by Chiba Japan) 15 parts

(E) Solvent: ethyl lactate 289 parts

To obtain a colored photosensitive resin composition. The obtained colored photosensitive resin composition was patterned in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 22.

1) PB 15: 6 is mixed with acrylic dispersant (5 parts) and PGMEA (137 parts) and dispersed.

2) PV 23 is mixed with acrylic dispersant (5 parts) and PGMEA (137 parts) together with PB 15: 6 (33 parts) and dispersed.

[Synthesis Example 7]

[Synthesis Example of Compound Represented by Formula (2)] [

After adding 200 parts of water to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to a pH of 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice-cooling. 11.1 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. And 10.1 parts of amide sulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

To 14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrido-2-one represented by the formula (c-2), 125 parts of water and N-methylpyrrolidone 25.0 And the mixture was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice-cooling.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% aqueous sodium hydroxide solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 21.4 parts (yield: 87%) of a compound represented by the formula (d-3).

0.35 g of Compound (d-3) was dissolved in N, N-dimethylformamide to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with water to make a volume of 100 cm 3 (concentration: 0.028 g / , And a spectrophotometer (quartz cell, cell length: 1 cm). This compound exhibited an absorbance of 2.9 (arbitrary unit) at? Max = 433 nm.

5.0 parts of the compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, and thionyl chloride 2.4 parts was added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling to 20 占 폚. The cooled reaction solution was poured into 150 parts of ice water while stirring, followed by stirring for 30 minutes. The precipitated yellow crystals were filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was separately prepared, 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were fed into the flask. While keeping the temperature below 20 ° C with stirring, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After 40 parts of methanol was added to the reaction solution and stirred, the mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield: 69%) of a compound represented by the formula (III-3).

0.35 g of Compound (III-3) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / L) Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.3 (arbitrary unit) at? Max = 431 nm.

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound (III-3) was added 4.0 parts of N-methylpyrrolidone, and the mixture was stirred for 30 minutes to adjust the reaction solution. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added and the mixture was stirred for 30 minutes. The organic phase was separated by using a separating rod, and then washed with 500 parts of water, 500 parts of 10% sodium carbonate aqueous solution, 500 parts of 10% acetic acid aqueous solution and 500 parts of ion exchange water. The separated organic phase was subjected to solvent distillation to obtain 2.0 parts of a compound represented by the formula (I-6) (dye A2). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. JMS-700 (manufactured by Japan Electronics Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of Compound (I-6) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.2 (arbitrary unit) at? Max = 431 nm.

[Synthesis Example 8]

[Synthesis Example of Compound Represented by Formula (3)] [

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added to dissolve. Under ice cooling, 6.1 parts of 35% aqueous solution of sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by dissolving 19.4 parts of 35% hydrochloric acid little by little and stirring for 2 hours to obtain a suspension containing the diazonium salt. Subsequently, an aqueous solution prepared by dissolving 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added to quench excess sodium nitrite.

Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of the dropwise addition, stirring was continued for another 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 11.7 parts (yield: 87%) of a compound represented by the formula (p-1).

10 parts of the compound of the formula (p-2) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.1 parts of ammonium chromate (III) sulfate (manufactured by Wako Pure Chemical Industries, And 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto, and the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the red-orange solid obtained after filtration was dried at 60 캜 to obtain 13.6 parts (63%) of a compound represented by the formula (z-1).

The structure of the compound represented by the formula (z-1) was identified using a mass spectrometer JMS-700 (manufactured by Nihon Denshi Co., Ltd.).

Identification of the compound represented by the formula (z-1)

(Mass spectrometry) Ionization mode = ESI-: m / z = 882.1 [M-Na ⁺ ] ^-

                         Exact Mass: 905.1

, 170 parts of anhydrous chloroform (manufactured by KANTO CHEMICAL CO., LTD.), 1.0 part of camphorsulfonic acid [manufactured by Aldrich Co., Ltd.], 4- (N, N-dimethylamino) , 1.4 parts of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred for about 30 minutes. Thereafter, a solution prepared by adding 47 parts of anhydrous chloroform to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added slowly, And stirred for 2 hours. The separation operation was performed twice with a 1N hydrochloric acid aqueous solution (150 parts), and then the organic layer was washed twice with 150 parts of 10% brine. Subsequently, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes. The drying agent was filtered off and the solvent was distilled off to obtain 20.6 parts (yield: 90%) of a compound represented by the formula (g-1).

Identification of the compound represented by the formula (g-1)

(Mass Spec.) Ionization mode = ESI +: m / z = 575.3 [M-Cl -] +

                         Exact Mass: 610.3

To 253 parts of the compound represented by the formula (z-1), 4030 parts of methanol was added to adjust the solution (s3). To 153 parts of the compound represented by the formula (g-1), 1080 parts of methanol was added to adjust the solution (t3). Thereafter, the solutions (s3) and (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 占 폚, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 占 폚 to obtain 263 parts (yield 65%) of a compound represented by the formula (3a-23) (dye A3).

The structure of the compound represented by the formula (3a-23) was determined by elemental analysis. The analytical instrument is an ICP emission analyzer [ICPS-8100; (Manufactured by Shimadzu Corporation) was used.

C 55.6 H 5.1 N 11.9 Cr 3.71

[Example 6]

(Preparation of colored photosensitive resin composition)

(A) Colorant: C.I. Pigment Green 58 (pigment: PG 58) 45 parts

(A) Colorant: C.I. Pigment Yellow 138 (pigment: PY 138) 10 parts

             Acrylic pigment dispersant 5 parts

             Propylene glycol monomethyl ether acetate 155 parts

And the pigment was sufficiently dispersed using a bead mill, and then,

(A) Colorant: Dye A2 10 parts

(B) Resin: Resin solution 1 150 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

                      [KAYARAD DPHA; 50 parts (manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: 15 parts of N-benzoyloxy-1- (4-phenylsulfanylphenylene) octan-1-one-2-imine (Irgacure OXE-01 manufactured by Chiba Japan)

(E) Solvent: 250 parts of ethyl lactate

To obtain a colored photosensitive resin composition.

A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 23.

[Examples 7 to 10]

A colored photosensitive resin composition was obtained in the same manner as in Example 6 except that the resin was changed to have the composition shown in Table 23 or a combination of plural resins was used. Further, a pattern was obtained in the same manner as in Example 1, and the evaluation was carried out. The results are shown in Table 23.

1) PG 58 and PY 138 are all mixed and dispersed with an acrylic dispersant (5 parts) and propylene glycol monomethyl ether acetate (155 parts).

[Example 11]

(Preparation of colored photosensitive resin composition)

(A) Colorant: C.I. Pigment Red 254 (pigment: PR 254) 40 parts

(A) Colorant: C.I. Pigment Red 177 (pigment: PR 177) 17 parts

             Acrylic pigment dispersant 6 parts

             Propylene glycol monomethyl ether acetate 148 parts

And the pigment was sufficiently dispersed using a bead mill, and then,

(A) Colorant: Dye A3 10 parts

(B) Resin: Resin solution 1 150 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

                      [KAYARAD DPHA; 50 parts (manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: 15 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE-01 manufactured by Chiba Japan)

(E) Solvent: 250 parts of ethyl lactate

To obtain a colored photosensitive resin composition.

A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 24.

[Examples 12 to 15]

A colored photosensitive resin composition was obtained in the same manner as in Example 11 except that the resin was changed to have the composition shown in Table 24 or a combination of plural resins was used. Further, a pattern was obtained in the same manner as in Example 1, and the evaluation was carried out. The results are shown in Table 24.

1) PR 254 and PR 177 are all mixed and dispersed with an acrylic dispersant (6 parts) and propylene glycol monomethyl ether acetate (148 parts).

In the pattern formed using the colored photosensitive resin composition of the examples,? Eab * exhibited a small value and high heat resistance was confirmed.

According to the present invention, a highly heat-resistant coating film, a pattern, and a color filter can be obtained.

21: glass substrate 22: TFT (switching element)
23: Color filter layer
23A: Colored photosensitive resin composition layer (color filter)
23a: Red filter 23b: Green filter
23c: blue filter 24: pixel electrode
27: Signal line 29: Photosensitive resin film (protective film)
201, 202: Connection holes

Claims (13)

1. A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) The binder resin (B) is obtained by adding a monomer (Bb) having a polymerizable double bond to a carboxyl group in at least one kind (Ba) selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (Bc) selected from the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid is reacted with the resulting resin, and then at least one selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (Bd) containing one kind of a polyfunctional epoxy compound (Bd) is further reacted with a polyfunctional epoxy compound (Bd) in the group consisting of succinic anhydride, maleic anhydride and anhydrous tetrahydrophthalic acid And a compound (Be) having at least one selected from the group consisting of a compound The method according to claim 1,
Wherein the dye is at least one dye selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a xanthene compound. The method according to claim 1,
A colored photosensitive resin composition wherein the dye is a dye containing a compound represented by formula (1).
[Chemical Formula 1]

: Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ may be substituted with NR ⁸ R ^9.
R ⁵ represents -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .
m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.
X represents a halogen atom.
a represents an integer of 0 or 1;
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, CO- or -NR < ⁷ > -.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, -CH ₂ - included in the saturated hydrocarbon group may be -O- or - CO-.
R ⁸ and R ⁹ each independently represent a linear or branched monovalent saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 30 carbon atoms, or -Q, and the saturated aliphatic hydrocarbon group and / The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with -OH, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ , and the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S-, -CO-, -NH- or -NR ⁶ -. R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring containing a nitrogen atom of 3 to 10-membered ring, and a hydrogen atom contained in the heterocyclic ring may be substituted with R ⁶ , -OH or -Q .
Q is a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group having a carbon number of 3 to 10 carbon atoms of 6 to 10, the hydrogen atoms contained in the aromatic hydrocarbon group and heterocyclic ^{group, -OH, R 6, -OR 6} , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ or a halogen atom.
M represents a sodium atom or a potassium atom.
However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.] delete The method according to claim 1,
Wherein the monomer (Bb) having a carboxyl group and a polymerizable double bond is at least one selected from the group consisting of acrylic acid and methacrylic acid. The method according to claim 1,
Wherein the content of the binder resin (B) is 20 mass% or more and 80 mass% or less with respect to the total amount of the binder resin (B) and the photopolymerizable compound (C). The method according to claim 1,
Wherein the content of the dye is 0.5% by mass or more and 60% by mass or less based on the solid content of the colored photosensitive resin composition. The method according to claim 1,
A colored photosensitive resin composition wherein the colorant (A) is a colorant further comprising a pigment. 9. The method of claim 8,
Wherein the pigment is selected from the group consisting of CI Pigment Blue 15: 6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, CI Pigment Green 58, CI Pigment Yellow 150 and CI Pigment Yellow 138 And at least one selected from the group consisting of a coloring agent and a coloring agent. A coating film formed using the colored photosensitive resin composition according to claim 1. A pattern formed using the colored photosensitive resin composition according to claim 1. 12. The method of claim 11,
A pattern formed by photolithography. A coating film according to claim 10, and a pattern according to any one of claims 11 to 12.

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