TWI566045B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is widely used in the production of color filters used in display devices such as liquid crystal display devices, organic electroluminescence display devices, and plasma displays. In such a colored photosensitive resin composition, a copolymer containing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate as a coloring property of a resin is known. Resin composition (Patent Document 1).

[Patent Document 1] JP-A-2010-211198

It is known that when the color-developing photosensitive resin composition described above is formed into a colored pattern by a lithography method, the unexposed portion is applied to the developer. Solubility still occurs when the demand is not adequately met.

The present invention provides the following items [1] to [6].

[1] A colored photosensitive resin composition comprising: a colorant, a binder resin, a polymerizable compound, and a polymerization initiator; the binder resin is a binder resin comprising a copolymer having the following structural unit: from methacrylic acid The structural unit, the structural unit derived from acrylic acid, and the structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid.

[2] The colored photosensitive resin composition according to [1], wherein the copolymer is a copolymer comprising a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.

[3] The colored photosensitive resin composition according to the above [1], wherein the content of the copolymer is 10% by mass or more and 100% by mass based on the content of the binder resin. the following.

[4] The colored photosensitive resin composition according to [1], [2] or [3], wherein the coloring agent is a coloring agent including a dye.

[5] A color filter formed of the colored photosensitive resin composition according to [1], [2], [3] or [4].

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

In the colored photosensitive resin composition of the present invention, when the colored pattern is formed, the unexposed portion can have high solubility to the developer.

The colored photosensitive resin composition of the present invention comprises a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D); and the binder resin (B) includes the following The binder resin of the copolymer of the structural unit: a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid.

The colored photosensitive resin composition of the present invention contains a coloring agent (A). The coloring agent (A) may, for example, be a dye (A1) or a pigment (A2), and is preferably a coloring agent containing the dye (A1). The dye (A1) may, for example, be a dye such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, for example, a color index (The Color Index, The The dyes described in the Society of Dyers and Colourists, that is, the compounds having a hue other than the pigment, and the known dyes described in the dyed NOTE. Further, depending on the chemical structure, for example, an azo dye, an anthraquinone dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, or the like can be given. The dyes of the above may be used singly or in combination of two or more. Among the above substances, an organic solvent-soluble dye is preferred.

Specifically, it can be exemplified as follows: C.I. solvent yellow 4 (hereinafter, C.I. description of solvent yellow is omitted, only numbers are listed), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI solvent red 45, 49, 111, 125, 130 , 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230; 245, 247; CI solvent orange 2, 7, 11, 15, 26, 56, 77, 86; solvent violet violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue (solvent Blue) 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 , 35 and so on CI solvent dye.

CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99 , 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 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 ;CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95 , 107, 108, 169, 173; CI acid violet 6B, 7, 9, 17, 19, 30, 34, 102; CI acid blue 1, 3, 9, 15, 18, 22 , 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92 , 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161 , 166, 167, 168, 170 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI acid green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106 , 109, etc. C.I. Acid dyes.

CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108 , 109, 129, 136, 138, 141; CI direct red (direct red) 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250; CI direct orange 34, 39 , 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct violet (direct violet) 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 40, 41 , 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114 , 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173 188, 189 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27 , 31, 32, 34, C.I. Direct dyes of 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.

CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60; CI basic red 1, 10; CI basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64 , 65, 66, 67, 68; CI basic green 1; etc. CI basic dye, CI reactive yellow 2, 76, 116; CI active orange 16; CI active red ( Reactive red) 36; etc. CI reactive dye, CI acid medium yellow (mordant yellow) 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 ; CI acid medium red (mordant red) 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36 , 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI acid orange (mordant orange) 3, 4 , 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI acidity Medium purple (mordant violet) 1,2,4,5,7,14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI acid blue (mordant blue) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI acid medium green (mord green) 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. CI acid medium dye, CI reduction green ( Vat green) 1 etc. CI vat dyes and the like.

In the case of the dye (Al), a xanthene dye (Aa) is preferred.

Xanthene dye (Aa) is a dye containing a compound having a xanthene backbone.

The xanthene dye (Aa) may, for example, be CI Acid Red 51, 52, 87, 92, 94, 289, 388; CI Acid Violet 9, 30, 102; CI Basic Red 1 (Rhodamine 6G, Rhodamin 6G), 2, 3, 4, 8; CI basic red 10 (Rhodamin B), 11; CI basic purple 10, 11, 25; CI solvent red 218; CI acid medium red 27; CI activity Red Bengal B; Sulforhodamine; the xanthene dye disclosed in Japanese Laid-Open Patent Publication No. 2010-32999, and the xanthene dye disclosed in Japanese Patent No. 4492760.

In the case of the xanthene dye (Aa), a dye containing a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)") is preferred. Compound (1) can also be a tautomer thereof. When the compound (1) is used, the content of the compound (1) relative to the total amount of the xanthene dye (Aa) is 50% by mass or more is preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. In particular, it is preferred to use only the compound (1) as the xanthene dye (Aa).

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and the aromatic hydrocarbon group contained in the aromatic hydrocarbon group; The hydrogen atom may be substituted with a functional group described later: a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, - CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 3 carbon atoms. It is substituted; -CH ₂ - contained in the above saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may simultaneously form a ring containing a nitrogen atom, and R ³ and R ⁴ may simultaneously form a ring containing a nitrogen atom.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

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

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

The M ⁺ system represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

X is a halogen atom.

a represents an integer of 0 or 1.

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

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms; and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom; the saturated aliphatic hydrocarbon group The contained -CH ₂ - may also be substituted with -O-, -CO-, -NH- or -NR ⁸ -; R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen atom-containing 3~ 10 rings of plural rings. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, and a C group. Base phenyl and butyl phenyl and the like.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ is selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ At least one of the groups consisting of NR ⁹ R ¹⁰ is preferable, and at least one of the groups consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ is more preferable. In the case of -SO ₃ ^- M ^{+ in this} case, it is preferred that -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferable. When R ¹ to R ⁴ are the above-mentioned functional groups, it is possible to form a color filter which is less likely to generate foreign matter and is excellent in heat resistance from the colored photosensitive resin composition of the present invention containing the compound (1).

The ring formed simultaneously with R ¹ and R ² and the ring formed by R ³ and R ⁴ at the same time may, for example, be listed below.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Carbon number of pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecyl, eicosyl, etc. An alkyl group of ~20; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

The -OR ⁸ may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group or a 2-ethylhexyloxy group. And eicosyloxy and the like.

The -CO ₂ R ⁸ may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a 3-butoxycarbonyl group, a hexyloxycarbonyl group or an eicosyloxycarbonyl group.

The -SR ⁸ may, for example, be a methylsulfanyl group, an ethylthio group, a butylthio group, a hexylthio group, a thiol group or an eicosylthio group.

Examples of the -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butasulfonyl group, a hexylsulfonyl group, a sulfonyl group, and an eicosylsulfonyl group.

The -SO ₃ R ⁸ may, for example, be methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 3-butoxysulfonyl, hexyloxysulfonyl and Decaloxysulfonyl.

The -SO ₂ NR ⁹ R ¹⁰ may, for example, be sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-butyl-2-butylsulfonyl, N-tert 3-butylsulfonate Sulfhydryl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1, 2-dimethylpropyl)sulfasulfonyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2 -Methylbutyl)Aminosulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3 - dimethyl butyl) amsulfoxonyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfonyl, N-(1-methylhexyl)sulfonate Sulfhydryl, N-(1,4-dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5 N-substituted sulfonamide of N-methyl)hexylsulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfamoyl; N,N-dimethyl Amisulphol, N,N-ethylmethylsulfamoyl, N,N-diethylsulfonate N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-3-butylmethylsulfamoyl, N,N-butyl N,N-2 substituted amisulphtyl, etc. of N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethylsulfamoyl, etc. .

In addition, as for the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ , the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom; and the saturated hydrocarbon group may contain - CH ₂ - may also be substituted with -O-, -CO-, -NH- or -NR ⁸ -.

R ⁹ and R ¹⁰ may be bonded to each other to form a complex ring of 3 to 10 rings containing a nitrogen atom. The plural ring may be, for example, the following list.

R ⁵ is preferably -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H or SO ₂ NHR ⁹ and is considered to be -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H or SO ₂ NHR ^{9 is more} preferred.

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

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ may, for example, be a group having 1 to 6 carbon atoms among the alkyl groups listed above.

The aralkyl group having 7 to 10 carbon atoms in R ¹¹ may, for example, be a benzyl group, a phenethyl group or a phenylbutyl group.

The M ⁺ system is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N(R ¹¹ ) ₄ .

In the case of ⁺ N(R ¹¹ ) ₄ , it is preferred that at least two of the four R ^{11 be} a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ¹¹ ) ₄ is present in the compound (1), and R ¹¹ is the above-mentioned group, the foreign color can be formed from the colored photosensitive resin composition of the present invention containing the compound (1). Very few color filters.

The compound (1) is preferably a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"), and a xanthene dye (Aa) is a compound (2). The dye is better. Compound (2) can also be a tautomer thereof. When the compound (2) is used, the content of the compound (2) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. In particular, it is particularly preferable to use the compound (2) alone as the xanthene dye (Aa).

In the formula (2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and the hydrogen atom contained in the aromatic hydrocarbon group may be described later. The functional group is substituted: -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

X ^a represents a halogen atom.

a ¹ represents an integer of 0 or 1.

M1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, the plural R ²⁵ is the same or different.

M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

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

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

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

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ may be, for example, the same as those exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ .

In particular, in the combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; The hydrogen atom contained may be substituted with -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . More preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and a hydrogen atom contained in the aromatic hydrocarbon group may also be -SO ₃ ^- M ⁺ or -SO ₂ NHR ²⁶ to replace. When R ²¹ to R ²⁴ are the above-mentioned functional groups, a color filter excellent in heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ may, for example, be the same as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably independently a hydrogen atom, a methyl group or an ethyl group.

In -SO ₃ R ^26, and in the -SO ₂ NHR ²⁶ R ^26, the line that branched chain alkyl group having 3 to 20 carbon atoms, preferably carbon atoms branched alkyl group having 6 to 12 more preferably, 2 - Ethylhexyl is particularly preferred. When R ²⁶ is a functional group such as the above, a color filter in which foreign matter is rarely generated can be formed from the coloring photosensitive resin composition containing the compound (2).

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and preferably ⁺ N(R ²⁷ ) ₄ .

In the case of ⁺ N(R ²⁷ ) ₄ , it is preferred that at least two of the four R ^{27 be} a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2), if R ²⁷ is a functional group such as the above, it can be formed from the colored photosensitive resin composition of the present invention containing the compound (2). A color filter that produces little foreign matter.

The compound (1) is, for example, a compound represented by the following formula (1-1) to formula (1-30). In the following formula, the Ra system represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably a branched chain alkyl group having 6 to 12 carbon atoms and a 2-ethylhexyl group. Among the above substances, C.I. A sulfonamide compound of acid red 289, a grade 4 ammonia salt of C.I. Acid Red 289, a sulfonamide compound of C.I. Acid Violet 102 or a grade 4 ammonia salt of C.I. Acid Violet 102 is preferred. The compound of the above-mentioned type may, for example, be a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).

In addition, it is more preferable that the dye containing the compound represented by the following formula (3) (hereinafter also referred to as "compound (3)") is more preferable. Compound (3) can also be a tautomer thereof. When the compound (3) is used, the content of the compound (3) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.

In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms or an alkyl sulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may also form a ring containing a nitrogen atom at the same time, and R ³² and R ³⁴ may simultaneously form a ring containing a nitrogen atom.

The p and q are each independently representing an integer from 0 to 5. When p is 2 or more, the plural R ³³ may be the same or different from each other; when q is 2 or more, the plural R ³⁴ may be the same or different from each other.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a 2-butyl group. Tertiary 3-butyl, hexyl, 2-ethylhexyl, decyl, decyl and the like. The alkyl group having 1 to 4 carbon atoms represented by R ³³ and R ³⁴ may, for example, be a functional group having a carbon number of 4 among the above-exemplified alkyl groups.

Examples of the alkyl sulfanyl group having 1 to 4 carbon atoms represented by R ³³ and R ³⁴ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group and an isopropylthio group.

The alkyl sulfonyl having 1 to 4 carbon atoms represented by R ³³ and R ³⁴ may, for example, be a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group or a sulfonyl group. Isopropyl sulfonyl.

R ³¹ and R ³² are each independently a methyl group, an ethyl group, a propyl group or an isopropyl group. R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

Preferably, p and q are each independently an integer of 0 to 2, and more preferably 1 or 2.

The compound (3) may, for example, be a compound represented by the formula (1-31) to the formula (1-43), respectively. In particular, a compound represented by formula (1-31) to formula (1-40) is preferred from the viewpoint of excellent solubility in an organic solvent.

For the xanthene dye (Aa), it is also possible to use a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Tokyo Chemical Industry Co., Ltd." Rhodamin 6G", etc.). Further, a commercially available xanthene dye can be used as a starting material, and the synthesis can be carried out in accordance with JP-A-2010-32999.

The colorant (A) may also contain a pigment (A2).

The pigment is not particularly limited, and a known raw material such as a color index (Color Index, published by The Society of Dyers and Colourists) classified as a pigment may be used, and for example, CI pigment yellow (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, Yellow pigments of 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64 , 65, 71, 73, etc. orange pigment; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Red pigment; CI pigment blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigment; CI pigment violet 1, Pigeon violet 1, 19, 23, 29, 32, Purple pigment of 36, 38, etc.; green pigment of CI pigment green 7, 36, 58; CI pigment brown 23, 25, etc. brown pigment; CI pigment black 1, 7 Wait for black pigments and so on.

Among them, the following pigments are preferred: CI Pigment Yellow 138, 139, 150; CI Pigment Red 177, 209, 242, 254; CI Pigment Violet 23; CI Pigment Blue 15:3, 15:6 and CI Pigment Green 7, 36, 58. The pigment used in the colored photosensitive resin composition of the present invention is preferably a pigment containing at least one of the group consisting of the following pigments: 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. By containing the above-described pigment, the optimization of the breakthrough spectrum can be facilitated, and the chemical resistance can be improved.

The above-mentioned pigments may be used singly or in combination of two or more.

The pigment may be subjected to a corresponding treatment if necessary: rosin treatment, use of a pigment derivative into which an acidic group or a basic group is introduced, or the like The treatment, the graft treatment of the surface of the pigment by a polymer compound or the like, the micronization treatment by a sulfuric acid micronization method, or the like, or the washing treatment or the use of an organic solvent or water for removing impurities. The removal treatment of ionic impurities and the like are removed by an ion exchange method or the like.

It is preferred that the pigment has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant described above include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and propylene. The above-mentioned pigment dispersing agents may be used singly or in combination of two or more kinds. In the case of the pigment dispersant, for example, the following trade names: KP (Shin-Etsu Chemical Co., Ltd.), Floren (Kyoei Chemical Co., Ltd.), Solspers (Zeneca (limited stock)), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.

When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less based on 100 parts by mass of the pigment (A2), and more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state can be obtained.

In the case of the colorant (A), it is preferred to contain both the dye (A1) and the pigment (A2). In this case, the content ratio ((A1): (A2)) of the dye (A1) and the pigment (A2) is preferably 1:99 to 99:1 and 3:97 to 90 on a mass basis. :10 is even better. By maintaining the above ratio, The optimization of the breakthrough spectrum becomes easy, and the obtained color filter also has an excellent tendency in terms of contrast, brightness, heat resistance, chemical resistance, and the like.

In particular, when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, the coloring agent (A) is a coloring agent containing a xanthene dye and a blue pigment. Preferably, a coloring agent containing xanthene dye and CI Pigment Blue 15:6 is more preferred. The ratio of the content of xanthene dye and blue pigment is preferably 3:97 to 90:10, more preferably 3:97 to 70:30, and 3:97 to 50:50. 5:95~30:70 is the best. By making the above-mentioned coloring agent contain the above-described content, a blue color filter of high brightness can be obtained.

The content of the coloring agent (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. ~30% by mass is the best. When the content of the colorant (A) falls within the above range, the desired spectral and color concentration can be obtained as a color filter, and a necessary amount of binder resin and polymerizability can be added to the composition. The compound can form a color filter having a very strong mechanical strength. The solid content described herein means the total amount of components other than the solvent in the colored photosensitive resin composition of the present invention. The content of each component in the solid component and the solid component can be measured using a known analytical means such as liquid chromatography or gas chromatography.

The colored photosensitive resin composition of the present invention comprises a binder resin (B), and the binder resin (B) is a copolymer comprising the following structural unit. (B1) (hereinafter also referred to as copolymer (B1)) binder resin: structural unit derived from methacrylic acid, structural unit derived from acrylic acid, and monomer (3) derived from copolymerizable with methacrylic acid and acrylic acid (hereinafter referred to as "monomer (x)") structural unit.

The monomer (x) is not particularly limited as long as it can be copolymerized with methacrylic acid and acrylic acid, and is not the same as methacrylic acid and acrylic acid, and for example, (a) has An unsaturated compound having a cyclic ether structure of 2 to 4 carbon atoms (hereinafter also referred to as "(a)"); (b) at least one selected from the group consisting of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride ( However, it is different from acrylic acid and methacrylic acid) (hereinafter also referred to as "(b)"); (c) other copolymerizable monomers (but different from acrylic acid, methacrylic acid, (a) and (b)) (hereinafter also referred to as "(c)").

The cyclic ether structure having 2 to 4 carbon atoms which is contained in (a) may, for example, be an oxirane ring, an oxetane ring or a tetrahydrofuran ring. In the case of (a), a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions of "(meth)acrylonitrile" and "(meth)acrylate" also mean the same meaning.

(a), for example, a monomer (a1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter also referred to as "(a1)"), having an oxetane Alkyl group and ethylenically unsaturated bonded monomer (a2) (hereinafter also referred to as "(a2)"), tetrahydroindenyl (Tetrahydrofurfuryl) and ethylenically unsaturated bonded monomer (a3) (below) Also known as "(a3)").

(a1), for example, a linear or branched aliphatic hydrocarbon having an epoxidized structure and a monomer (a1-1) having an ethylenically unsaturated bonding structure (hereinafter also referred to as "(a1-1) ))), and an alicyclic unsaturated hydrocarbon having an epoxidized structure and an ethylenically unsaturated bonded monomer (a1-2) (hereinafter also referred to as "(a1-2)").

In terms of (a1-1), for example, glycidyl (meth)acrylate, glycidyl β-methyl(meth)acrylate, and glycidyl β-ethyl(meth)acrylate , epoxidized propyl vinyl ether, o-vinylbenzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, α-methyl-o-vinyl Benzyl epoxidized ether, α-methyl-m-vinylbenzyl epoxidized propyl ether, α-methyl-p-vinylbenzyl epoxidized propyl ether, 2,3-bis(epoxypropyloxy) Methyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(epoxypropyl) Oxymethyl)styrene, 2,3,4-tris(epoxypropyloxymethyl)styrene, 2,3,5-tris(epoxypropyloxymethyl)styrene, 2,3,6 -Tris(epoxypropyloxymethyl)styrene, 3,4,5-tris(epoxypropyloxymethyl)styrene, 2,4,6-tris(epoxypropyloxymethyl)benzene Ethylene and the like.

In the case of (a1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example: CEL oxide 2000, Daicel Chemical Industry (limited shares) )), 3,4-epoxycyclohexyl (meth) acrylate methyl ester (for example: Cyclomer A400, Daicel Chemical Industry Co., Ltd. a limited amount), 3,4-epoxycyclohexyl (meth) acrylate (for example: Cyclomer M100, manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the following formula (I) and a formula ( II) Compounds and the like represented.

In the formulae (I) and (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be a hydroxyl group. Replace.

X ¹ and X ² each independently represent a single bond, -R ^C -, *-R ^C -O-, *-R ^C -S-, *-R ^C -NH-.

R ^C represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with an oxygen atom. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, and a 3-butyl group.

The alkyl group substituted with a hydroxyl group in a hydrogen atom may, for example, be a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group or a 3-hydroxypropyl group. , 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group; more preferably a hydrogen atom or a methyl group.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene-1,2-yl group, a propylene-1,3- group, a butylene-1,4-yl group, and a penta-1. 5-based, hexylene-1,6-yl and the like.

In the case of X ¹ and X ² , preferred are: single bond, methylene, ethylene, *-CH ₂ -O- (* is a bond to an oxygen atom), *-CH ₂ More preferably, CH ₂ -O- group; single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) may, for example, be a compound represented by the following formula (I-1) to formula (I-15). Preferred among them are: formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)~ I-15) The compound represented. More preferably, it is a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

The compound represented by the formula (II) may, for example, be: (II-1)~ A compound represented by the formula (II-15). Preferred among them are: formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~ Compounds represented by II-15). More preferably, it is a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the above formula (I) and the compound represented by the formula (II) can be used singly. Further, the above compounds may be used in combination at any ratio. When mixed, the mixing ratio is in the formula (I): formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20: 80~80:20 is especially good.

The monomer (a2) having an oxetane group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloxy group. In the case of (a2), for example, 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane , 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methyl Propylene oxiranyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane Alkane, 3-ethyl-3-propenyloxyethyloxetane, and the like.

The monomer (a3) having a tetrahydroindenyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydroindenyl group and a (meth)acryloxy group.

Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

In (a), (a1) is preferable from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of improving the storage stability of the colored photosensitive resin composition, (a1-2) is more preferable.

Specific examples of (b) include unsaturated monocarboxylic acids such as crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid; fumaric acid (maleic acid); Fumaric acid), citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid (4-vinyl) Phthalic acid), 3,4,5,6-tetrahydroanthracene An unsaturated dicarboxylic acid such as acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid or 1,4-cyclohexanedicarboxylic acid; methyl-5-protopane- 2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene a carboxyl group-containing bicyclic unsaturated compound such as 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4 -vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1 An unsaturated dicarboxylic anhydride such as hept-2-ene anhydride; succinic acid mono [2-[(2-(methyl)propenyl)oxy]ethyl]ester (mono-2-((meth)acryloyloxy) )ethyl succinate), 1,2-cyclohexanedicarboxylic acid mono[2[(2-(methyl)-1-oxo-2-propenyl)oxy]ethyl]ester (2-((meth)) Acrylyloxyethyl)ethyl hexahydrophthalate) an unsaturated mono[[(2-methylpropenyl)oxy]alkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more; like α-(hydroxymethyl) Acrylic, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule, and the like.

(c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, (methyl) 3rd butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] 癸-8-ester (in this The conventional name referred to in the technical field is: dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ]癸- 8-ester (common name referred to in the art: dicyclopentanyl (meth)acrylate), isobornyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid (meth) acrylates such as allyl ester, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate; (methyl) Hydroxy-containing (2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, etc. Acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; bicyclo [2.2.1] hept-2-ene, 5-methyl Bicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[ 2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5 -ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1] Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene , 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2. 2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2 - alkene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis (3rd butoxy Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-benzene N-phenyl maleimide, N-cyclohexyl maleic anhydride imide, N-benzyl maleic anhydride imide, N-ammonium imino-3- maleic anhydride N-succinimidyl-3-maleimidebenzoate, N-succinimide-4-maleic acid butylimide, N-succinimide-6-maleic anhydride Aminohexanoate, N-succinimide-3-maleic anhydride propylimide, N-(9-acridinyl)maleimide, N-(9-acridinyl)maleimide, etc. Dicarbonyl quinone imine derivatives; styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile ), methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene (isoprene), 2,3-dimethyl-1,3-butadiene, and the like.

Among the above-mentioned substances, from the viewpoints of copolymerization reactivity and heat resistance, the following are preferred: styrene, vinyl toluene, N-phenylmaleic anhydride, imine, N-cyclohexyl Anhydrous imide, N-benzyl maleic anhydride, bicyclo[2.2.1]hept-2-ene, and the like.

In the case of the copolymer (B1), if the color filter obtained is bright From the viewpoint of the degree, it is preferred to contain a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a copolymer (a).

In the copolymer (B1), the ratio of the structural unit derived from methacrylic acid, the structural unit derived from acrylic acid, and the structural unit derived from the monomer (x), which is possessed in the entire structural unit constituting the copolymer (B1) The ratio is preferably in the following ranges: structural unit derived from methacrylic acid: 1 to 54 mol% (more preferably 1 to 45 mol%); structural unit derived from acrylic acid: 1 to 54 mol % (more preferably 1 to 45 mol%); structural unit derived from monomer (x): 55 to 98 mol% (more preferably 60 to 90 mol%).

Further, the total amount of the structural unit derived from methacrylic acid and the structural unit derived from acrylic acid is 2 to 55 mol%, preferably 15 to 50 mol, in the entire structural unit constituting the copolymer (B1). % is better.

When the ratio of the structural unit of the copolymer (B1) is within the above range, the storage stability and developability of the colored photosensitive resin composition and the solvent resistance of the color filter tend to be improved.

For the copolymer (B1), for example, the document "Experimental method for polymer synthesis" (produced by Otsuka, the Institute of Chemicals, Ltd., the first edition of the first brush, issued on March 1, 1972) The method and the cited documents disclosed in the literature are used for manufacturing.

Specifically, a predetermined amount of methacrylic acid or acrylic acid and a monomer (x), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and for example, The method of replacing oxygen with nitrogen gas to form a deoxidizing atmosphere, and heating and holding while stirring. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and can be used in any general-purpose substance in the field. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.). And an organic peroxide (benzoquinone benzoate or the like); in the solvent, any solvent which can dissolve each monomer can be used, and a solvent (E) which is a coloring photosensitive resin composition of the present invention described later can also be used. Solvents, etc.

Further, the obtained copolymer may be used as it is, or may be used as a solid (powder) by a concentrated or diluted solution or by reprecipitation or the like. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent for polymerization, the solution after the reaction can be directly used for preparing the colored photosensitive resin composition of the present invention. Therefore, the manufacturing steps of the colored photosensitive resin composition of the present invention can be simplified.

The copolymer (B1) may contain a structural unit represented by the following formula (III) and/or a structural unit represented by the formula (IV) as a structural unit derived from the monomer (x).

In the formulae (III) and (IV), R ^d and R ^f each independently represent a hydrogen atom or a methyl group. R ^e and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The alkyl group having 1 to 6 carbon atoms in R ^e and R ^g may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. In terms of R ^e and R ^g , a hydrogen atom or a methyl group is preferred.

For example, when the copolymer (B1) is a structural unit represented by the formula (III), a homopolymer of methacrylic acid or a copolymer of methacrylic acid and a monomer (x) is obtained by the same method as described above. The copolymer (B1) containing the structural unit represented by the formula (III) can be obtained by adding a compound represented by the formula (IIIa) to a carboxyl group derived from methacrylic acid.

Further, when the copolymer (B1) is a structural unit represented by the formula (IV), a homopolymer of methacrylic acid or a copolymer of methacrylic acid and monomer (x) is obtained by the same method as above. The copolymer (B1) containing the structural unit represented by the formula (III) can be obtained by adding a compound represented by the formula (IVa) to a carboxyl group derived from methacrylic acid.

In the formulae (IIIa) and (IVa), R ^e and R ^g are the same as defined above. ]

Even when the copolymer (B1) contains a structural unit represented by the formula (III) and/or a structural unit represented by the formula (IV) as a structural unit derived from the monomer (x), the ratio from each structural unit It is preferred to be within the above range.

When the copolymer (B1) is a structural unit represented by the formula (III) and/or a structural unit represented by the formula (IV), the ratio of the above structural unit, It is preferably from 5 to 80 mol%, more preferably from 15 to 70 mols, in the total structural unit constituting the copolymer (B1).

When the content ratio of the structural unit represented by the formula (III) and/or the structural unit represented by the formula (IV) is within the above range, storage stability, developability, sensitivity, and color of the colored photosensitive resin composition The balance of the solvent resistance, heat resistance, and mechanical strength of the filter tends to be good.

Specific examples of the copolymer (B1) include 3,4-epoxycyclohexylmethyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, and 3,4-epoxy acrylate. Tricyclo[5.2.1.0 ^2,6 ]decyl ester/methacrylic acid/acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, (methyl ) Glycidyl acrylate / styrene / methacrylic acid / acrylic acid copolymer, 3,4-epoxytricycloacrylic acid [5.2.1.0 ^2,6 ] decyl ester / N-cyclohexyl maleic anhydride imide / Methacrylic acid/acrylic acid copolymer, 3-methyl-3-(methyl)propenyloxymethyloxetane/styrene/methacrylic acid/acrylic acid copolymer, benzyl (meth)acrylate/ A methacrylic acid/acrylic acid copolymer, a styrene/methacrylic acid/acrylic acid copolymer, a glycidyl (meth)acrylate, and an benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer are subjected to an addition reaction. A resin, a resin obtained by adding a reaction of a glycidyl (meth) acrylate with a tricyclodecyl (meth) acrylate/styrene/methacrylic acid/acrylic acid copolymer. A resin obtained by addition reaction of glycidyl methacrylate with tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer. Among them, benzyl (meth)acrylate/methacrylic acid/acrylic acid copolymer, styrene/methacrylic acid/acrylic acid copolymer, and 3,4-epoxytricycloacrylic acid [5.2.1.0 ^2,6 ] An oxime ester/methacrylic acid/acrylic acid copolymer is preferred.

The polystyrene-equivalent weight average molecular weight of the copolymer (B1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 30,000, particularly preferably 5,000 to 18,000, and most preferably 5,000 to 12,000. When the molecular weight is in the above range, the solubility of the unexposed portion in the developer is high, and the residual film ratio and hardness of the obtained colored pattern tend to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer (B1) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the copolymer (B1) is preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 170 mg-KOH/g, and particularly preferably from 100 to 150 mg-KOH/g. Here, the acid value is a measured value of the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The binder resin (B) may contain a resin other than the copolymer (B1) (hereinafter also referred to as "resin (B2)"). The resin (B2) is not particularly limited as long as it needs to be an alkali-soluble resin, and examples thereof include a copolymer of methacrylic acid and a monomer (x); a copolymer of acrylic acid and a monomer (x); a copolymer of methacrylic acid or acrylic acid and (a); a copolymer of (a) and (b); a copolymer of methacrylic acid or acrylic acid and (b); a copolymer of (b) and (c); And copolymers of (b) and (c); resins obtained by addition reaction of (meth)acrylic acid and/or (b) copolymers of (a) and (c); Methacrylic acid and And the copolymer of (b) and (c) is subjected to an addition reaction, and further, a resin which is reacted to form an acid anhydride or the like. Specifically, for example, a resin which is an alkali-soluble resin disclosed in JP-A-2010-224204, and the like can be mentioned.

Among them, preferred are: methacrylic acid or acrylic acid and (a) copolymer, (a) and (b) copolymer, (a) and (b) and (c) copolymer, methacrylic acid or Acrylic acid and copolymer of (c), and copolymer of (b) and (c); more preferably: copolymer of methacrylic acid or acrylic acid and (a), methacrylic acid or acrylic acid and (c) Things. The binder resin (B) can have the resin (B1) containing the above-mentioned resin at the same time, so that the unexposed portion has high solubility to the developer, and the shape of the obtained colored pattern is improved. Preferably.

The polystyrene-equivalent weight average molecular weight of the resin (B2) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 5,000 to 15,000.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B2) is preferably from 50 to 180 mg-KOH/g, more preferably from 60 to 170 mg-KOH/g, and particularly preferably from 90 to 160 mg-KOH/g.

When the resin (B2) is the above-mentioned resin, particularly when used in combination with the copolymer (B1), the solubility of the unexposed portion to the developer is high, and the residual film ratio and hardness of the obtained colored pattern are also There is a tendency to improve.

The content of the copolymer (B1) is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, particularly preferably from 30 to 70% by mass, based on the total amount of the binder resin (B). ~50% by mass is the best.

When the content of the copolymer (B1) is within the above range, the solubility of the unexposed portion in the developer is improved, so that the yield of the colored pattern is excellent. When the content of the copolymer (B1) is less than the above range, the developability of the effect of the present invention cannot be sufficiently obtained.

In particular, the binder resin (B) is preferably composed of a copolymer (B1), a copolymer of methacrylic acid or acrylic acid and (a), and a copolymer of methacrylic acid or acrylic acid and (c). . The content in this case is preferably as follows: copolymer (B1): 15 to 70% by mass, methacrylic acid or acrylic acid, and copolymer of (a): 15 to 70% by mass, methacrylic acid or acrylic acid. And (c) copolymer: 15 to 70% by mass; more preferably: copolymer (B1): 25 to 50% by mass, methacrylic acid or acrylic acid and (a) copolymer: 25 to 50% by mass, A A copolymer of acrylic acid or acrylic acid and (c): 25 to 50% by mass.

When the binder resin (B) is in the above combination, the solubility of the unexposed portion in the developer is improved, and a colored pattern having an excellent shape can be formed.

The colored photosensitive resin composition of the present invention includes a polymerizable compound (C). The polymerizable compound (C) is a compound obtained by polymerizing an active radical derived from a polymerization initiator (D), an acid, or the like, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. For example, a (meth) acrylate compound is preferred.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. This type of gathering The conjugated compound may, for example, be trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate. Ester, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, tris(2-(methyl) Propylene decyl oxyethyl) trimeric isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate Ester, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred. The above-mentioned polymerizable compounds may be used singly or in combination of two or more kinds.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and more preferably 17 to 55 mass%, based on the solid content of the coloring photosensitive resin composition. good. When the content of the polymerizable compound (C) is within the above range, the hardening is completed sufficiently, the residual film ratio during development is increased upward, and the undercut of the colored pattern is less likely to occur. Further, the adhesion tends to be good, so that it is preferable.

The colored photosensitive resin composition of the present invention includes a polymerization initiator (D).

In the above-mentioned polymerization initiator (D), any compound which can be polymerized by the action of light to generate an active radical and/or an acid to start polymerization of the polymerizable compound (C) can be used without particular limitation. A known polymerization initiator can be used.

In the case of the polymerization initiator (D), a compound which can generate an active radical by the action of light is preferred, and a compound containing an alkyl phenone or a triazine is preferably contained. More preferably, a polymerization initiator of at least one of the group consisting of an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound contains a ruthenium compound and an alkyl benzophenone. The polymerization initiator of the compound is particularly preferred.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the formula (d3). In some of the above structures, the benzene ring may have a substituent.

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one. 2-Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- ]]-1-[4-(4-morpholino)phenyl]butan-1-one. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (above, BASF Corporation) can also be used.

In the case of a compound having a partial structure represented by the formula (d3), For example: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1- Oligomers such as ketone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propan-1-one, α,α-diethoxybenzene Ethyl ketone, benzyl dimethyl ketal, and the like.

From the viewpoint of sensitivity, in the case of the above alkylphenone compound, a compound having a partial structure represented by the formula (d2) is preferred, and is considered to be 2-methyl-2-morpholino-1- (4-Methylthiophenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one are more preferred.

The above triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-double. (trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)ether]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Ether]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ether]-1 , 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ether]-1,3,5-triazine, and the like.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide or the like. A commercially available product such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

The above hydrazine compound is a compound having a partial structure represented by the following formula (d1). Hereinafter, * is used to indicate the bond.

The above hydrazine compound may, for example, be N-benzoic acid-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzoic acid-1-(4) -phenylthiophenyl)oct-1-one-2-imine, N-benzoic acid-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2 -imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]e-i-imine, N-acetoxy -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy)benzimidyl}-9H-oxime Zyrid-3-yl]e-i-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3 -cyclopentylpropan-1-imine, N-benzoic acid-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3- Cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE (registered trademark) OXE 01, OXE 02 (above, BASF), and N-1919 (made by Adeka) can also be used. Among them, the following are preferred: N-benzoic acid-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoic acid-1-(4) -phenylthiophenyl)oct-1-one-2-imine and N-benzoic acid-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2 - Imine. When the above-mentioned ruthenium compound is used, in particular, when the colored photosensitive resin composition of the present invention is prepared into a blue colored photosensitive resin composition, a high-brightness color filter can be obtained.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis (2, 3-Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2' - double (2- Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, see Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204) An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913). Preferred are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole Wait.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoin compound; benzophenone, methyl o-benzoquinone, 4-phenylbenzophenone, 4-phenylhydrazine-4'-methyldiphenyl sulfide, 3,3 a benzophenone compound such as ',4,4'-tetra (t-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone ( 9,10-phenanthrenequinone), 2-ethyl anthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone (10-butyl-2-chloro acridone) ), benzil, methyl phenylglyoxylate, titanium tetradecene compound, and the like. The above-mentioned materials are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

In the case of an acid generator which generates an acid by light, for example, 4-hydroxyl Phenyl dimethyl phthalate p-toluene sulfonate, 4-hydroxyphenyl dimethyl hydrazine hydrohexafluoro decanoate, 4-ethyl methoxy phenyl dimethyl phthalate p-toluene sulfonic acid Salt, 4-acetoxyphenylmethylbenzyl halide hydrogen hexafluoroantimonate, triphenyl telluride p-toluenesulfonate, triphenyl phosphonium hydrogen hexafluoroantimonate, diphenyl Onium salt of iodonium p-toluenesulfonate, diphenyliodonium hydrogen hexafluoroantimonate, nitrobenzyl tosylate, p-toluenesulfonate Benzoate (benzoin tosylate) and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total of the binder resin (B) and the polymerizable compound (C). It is better. When the content of the polymerization initiator (D) is within the above range, the colored pattern can be formed with high sensitivity, so that the exposure time can be shortened and the yield can be improved.

The colored photosensitive resin composition of the present invention may further include a polymerization initiation aid (D1). In the case where the polymerization initiating aid (D1) is contained, it is usually used in combination with the polymerization initiator (D). The polymerization initiating aid (D1) is a compound for promoting polymerization of a polymerizable compound which initiates polymerization by a polymerization initiator, or a sensitizer.

The polymerization initiation aid (D1) may, for example, be an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound or the like, wherein a thioxanthone compound is used. good.

The above amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Isoamyl methylaminobenzoate, benzoic acid 2-Dimethylaminoethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl Ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The above alkoxy fluorene compound may, for example, be 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 above thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthene. Ketone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxy. Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl Glycine, naphthyloxyacetic acid, and the like.

The polymerization initiation aid (D1) may be used singly or in combination of two or more.

When the above-mentioned polymerization initiation aid (D1) is used, the amount thereof is 0.1 to 30 parts by mass based on 100 parts by mass of the total of the binder resin (B) and the polymerizable compound (C). Good, 1~20 parts by mass is better. When the amount of the polymerization initiation aid (D1) is within the above range, the colored pattern can be formed with high sensitivity, so that the yield of the colored pattern can be improved.

The colored photosensitive resin composition of the present invention preferably contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be selected from the solvents listed below: an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (containing -O- in the molecule, but not containing a solvent of -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule but not containing -COO-), an alcohol solvent ( A solvent containing OH in the molecule but not containing -O-, -CO-, and -COO-, an aromatic hydrocarbon solvent, a guanamine solvent, or a dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and acetic acid. Isoamyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate Ester, cyclohexanol acetate, γ-butyrolactum, and the like.

The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol. Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl Butanol, tetrahydrofuran, tetrahydropyran (tetrahydropyran), 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, two Ethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxyl. Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate , 2-ethoxy-2-methylpropionic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Butyl ether acetate and the like.

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

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

In the case of a decylamine solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide (N,N- Dimethylacetamide), N-methylpyrrolidone, and the like.

The solvent of the above may be used singly or in combination of two or more.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C or more and 180 ° C or less at 1 atm is preferred from the viewpoints of coatability and drying properties. Among them, preferred are: propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethyl group More preferred are: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy 1-butanol, ethyl 3-ethoxypropionate, and the like.

The content of the solvent (E) in the coloring photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored photosensitive resin composition of the present invention. good. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when the color filter is formed, since the color density is not insufficient, the display is performed. The features will get better.

In the colored photosensitive resin composition of the present invention, a surfactant (F) may be further included. Examples of the surfactant (F) include a ruthenium-based surfactant, a fluorine-based surfactant, and a ruthenium-based surfactant having a fluorine atom. The above substances may also be those having a polymerizable group in the side chain.

The lanthanoid surfactant may, for example, be a surfactant having a siloxane coupling. Specifically, for example, TORAY SILICON (trade name) DC3PA, the same series SH7PA, the same series DC11PA, the same series SH21PA, the same series SH28PA, the same series SH29PA, the same series SH30PA, the same series 8400 (Toray Dow Corning (limited shares) )); KP321, 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 Co., Ltd.).

The fluorine-based surfactant described above may, for example, be a surfactant having a fluorocarbon chain. Specifically, for example, FLUORAD (registered trademark) FC430, the same series FC431 (Sumitomo 3M (share limited) system); MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177 , the same series F183, the same series F554, the same series R30, the same series RS-718-K (DIC (share limited) system); FTOP (registered trademark) EF301, the same series EF303, the same series EF351, the same series EF352 (Mitsubishi Materials) E-Chemical (trademark) system; SURFLON (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (Asahi Glass (share limited) system); E5844 ((share limited) Daikin Fine Chemical Research Institute), etc. .

The above-mentioned fluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a siloxane coupling or a fluorocarbon chain. Specifically, for example, MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, and the same series F433 (DIC (stock limited) system) can be mentioned.

The above-mentioned surfactants may be used singly or in combination of two or more.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and 0.002% by mass or more and 0.1% by mass based on the total amount of the coloring photosensitive resin composition of the present invention. More preferably, it is particularly preferably 0.01% by mass or more and 0.05% by mass or less. Further, the content of the pigment dispersant is not included in the above content. When the content of the surfactant (F) is within the above range, the flatness of the color filter becomes good.

In the colored photosensitive resin composition of the present invention, various additives (hereinafter also referred to as "other components") known in the art, which are exemplified below, may be added as needed: a filler, other polymer compound, Adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, chain transfer agent, and the like.

The colored photosensitive resin composition of the present invention includes, for example, a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), and may be used in combination if necessary. The polymerization initiation aid (D1), the solvent (E), the surfactant (F), and other components are used for preparation.

When the pigment (A2) is contained, the pigment (A2) is previously mixed with a part or all of the solvent (E) until the average particle diameter of the pigment is 0.2 μm or less, and then the bead mill is used. It is better to disperse (beads-mill). At this time, a part or all of the above-mentioned pigment dispersant and binder resin (B) may be added in combination as necessary. In the obtained pigment dispersion liquid, the remaining components and the like are mixed according to a predetermined concentration to be converted. The colored photosensitive resin composition for the purpose of the present invention can be prepared.

When the dye (A1) is contained, the dye (A1) is preferably prepared by dissolving a part or all of the solvent (E) in advance. This solution is preferably filtered by using a filter having a pore diameter of about 0.01 to 1 μm.

The colored photosensitive resin composition prepared and mixed as described above is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

The method of forming the colored pattern of the color filter using the colored photosensitive resin composition of the present invention may, for example, be a lithography method or an inkjet method. The method of forming a colored pattern by a lithography method is to apply the colored photosensitive resin composition of the present invention to a substrate or another resin layer (for example, a different colored photosensitive resin composition is formed on the substrate). On the layer or the like, the volatile component such as a solvent is removed (dried) to form a dried coating film, and the colored layer is exposed and developed by a photomask. In the above lithography method, if a mask is not used at the time of exposure, and/or development is not performed, a cured product which is a dried coating film of the colored coating film can be formed. The above-mentioned colored pattern and colored coating film can be used to form a color filter.

The film thickness of the produced color filter is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.5 to 20 μm, preferably 0.5 to 6 μm. Better.

The colored photosensitive resin composition is applied onto a substrate, and then dried by heating (pre-bake) and/or under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth drying. Coating film.

For the substrate, quartz glass, borosilicate glass, alumina silicate glass, soda-lime coated with cerium oxide can be used. a glass substrate such as glass; a resin substrate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate; and aluminum, silver, silver/copper formed on the substrate / Palladium alloy film and the like. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates described above.

The coating method may, for example, be a spin coating method, a slit coating method, a slit or a spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, in terms of heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

When the drying under reduced pressure is carried out, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature of from 20 to 25 °C.

The film thickness of the coating film after drying is not particularly limited and may be appropriately adjusted depending on the materials to be used, the use, and the like.

The film is applied after drying, and exposure is performed by a mask for forming a target pattern. At this time, the shape of the pattern on the photomask is not particularly limited, and a graphic shape corresponding to the intended use can be used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm can be taken out by using a filter capable of extracting the above-mentioned wavelength range, or light having a wavelength of about 435 nm, around 408 nm, and around 365 nm can be used to filter out the bands of the above-mentioned wavelength domains. A band-pass filter is selectively filtered out. Specifically, for example, a mercury lamp or a light-emitting lamp A polar body, a metal halide lamp, a halogen lamp, or the like.

In order to uniformly illuminate the entire exposed surface of the exposure surface, and to position the reticle in the correct position with the substrate on which the dried coating film has been formed, a mask aligner and a stepper are used. A device such as a stepper is preferred.

After the exposure, the exposed portion is brought into contact with the developer, and the unexposed portion is dissolved and removed (i.e., developed) to obtain a colored pattern. The developing solution may, for example, be an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the above-mentioned basic compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The development method may also use puddle development, dipping, spray, or the like. Further, the substrate can be tilted at an arbitrary angle during development.

After development, it is preferred to perform a water wash.

Furthermore, post-bake processing may be performed correspondingly if necessary. The temperature after the post-baking treatment is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The time for post-baking treatment is preferably from 1 to 120 minutes, preferably from 10 to 60 minutes.

According to the colored photosensitive resin composition of the present invention, in particular, a color filter can be produced with high yield. The color filter is very advantageous for use as a color filter for a display device (for example, a liquid crystal display device, an organic electroluminescence device, an electronic paper, etc.) and a solid-state imaging device.

[Examples]

The present invention will be more specifically described below by way of examples. In the examples, "%" and "parts" refer to both mass % and mass parts unless otherwise stated.

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (manufactured by a method of external chemical conversion), 15 parts of chloroform, and 150 parts of chloroform and N were added. 8.9 parts of N-dimethylformamide, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C or lower while stirring. After the completion of the dropwise addition, the temperature was raised to 50 ° C, maintained at the same temperature for 5 hours to cause a reaction, and then cooled to 20 ° C. After the cooled reaction solution was maintained at 20 ° C or lower with stirring, a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Next, the obtained reaction mixture was distilled off by a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. The mixture was stirred and added to a mixed liquid of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals are separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain dye A1 (dye A1) (formula (A1-1) to formula (A1- 8) A mixture of the indicated compounds) 11.3 parts.

[Synthesis Example 2]

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under a light-shielding condition, and the obtained solution was at 110 ° C. Stir under 6 hours. After cooling the obtained reaction liquid to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The residue obtained by suction filtration of the precipitated crystals is dried to obtain 24 parts of the compound represented by the formula (1-31). The yield was 80%.

The structure of the compound represented by the formula (1-31) was confirmed by mass spectrometry (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4 Exact Mass: 602.2

[Synthesis Example 3]

Except that N-ethyl-o-toluidine was changed to N-propyl-2,6-dimethylaniline, the other steps were the same as in Synthesis Example 1, and the formula (1-39) was obtained. Compound.

Identification of the compound represented by formula (1-39): (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9 Exact Mass: 658.9

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 72 parts of methacrylic acid, 7 parts of acrylic acid, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II) were prepared. -1) The compound represented by mixing 50:50 at a molar ratio) 250 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. Inside.

On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 7.0 × 10 ³ , a molecular weight distribution of 2.5, a solid content of 42%, and a solid component. A resin B1 solution having an acid value of 138 mg-KOH/g. The resin B1 has the structural unit shown below.

[Synthesis Example 5]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 10 parts of methacrylic acid, 58 parts of acrylic acid, and 3,4-epoxytricyclo[ ^{5.2.1.0 2,6} ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II) were prepared. -1) the compound represented by mixing at a molar ratio of 50:50) 254 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. Inside. On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 7.0 × 10 ³ , a molecular weight distribution of 2.5, a solid content of 41%, and a solid component. A resin B2 solution having an acid value of 136 mg-KOH/g. The resin B2 has the structural unit shown below.

[Synthesis Example 6]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Next, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1) were prepared. The compound shown was mixed at a molar ratio of 50:50. 336 parts of a solution dissolved in 140 parts of ethyl lactate, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel to 4 The hour was dripped into the flask. After the solution of the polymerization initiator was completed, it was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 8.0 × 10 ³ , a molecular weight distribution of 2.5, a solid content of 48%, and a solution acid. A resin B3 solution having a value of 50 mg-KOH/g. When the solid component acid value is calculated from the above solid content and the acid value of the solution, it is 104 mg-KOH/g. Resin B3 has the structural unit shown below.

[Synthesis Example 7]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at a rate of 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 100 ° C while stirring. Next, a solution in which 90 parts by mass of methacrylic acid and 210 parts by mass of benzyl methacrylate were dissolved in 140 parts by mass of ethyl lactate was prepared, and the solution was dropped into a flask kept at 100 ° C for 4 hours using a dropping funnel. Inside. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate, and using another dropping funnel It was dropped into the flask over 4 hours. After the solution of the polymerization initiator was dropped, it was maintained at 100 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.2 × 10 ⁴ , a molecular weight distribution of 2.2, a solid content of 30% by mass, and solid form. A resin B4 solution having an acid value of 154 mg-KOH/g. Resin B4 has the structural unit shown below.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was carried out by the following conditions using the GPC method.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Toray (share limited) system)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight converted from the polyethylene obtained above was used as the molecular weight distribution.

[Examples 1 to 6 and Comparative Example 1]

According to the composition shown in Table 1, each component was mixed, and the colored photosensitive resin composition was obtained.

In addition, each component in Table 1 shows the following each substance. Further, the binder resin (B) is represented by parts by mass in terms of solid content.

Colorant (A): (A-1); C.I. Pigment Blue 15:6

Colorant (A): (A-2); dye A1

Colorant (A): (A-3); a compound represented by formula (1-39)

Adhesive resin (B): (B-1); resin B1

Adhesive resin (B): (B-2); resin B2

Adhesive Resin (B): (B-3); Resin B3

Adhesive Resin (B): (B-4); Resin B4

Polymerizable compound (C): (C-1); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kay (Pharmaceutical Co., Ltd.)

Polymerization initiator (D): (D-1); N-benzoic acid-1-(4-phenylthiophenyl)oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF company)

Polymerization initiator (D): (D-2); 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one (IRGACURE 907; manufactured by BASF Corporation)

Polymerization initiation aid (D1): 2,4-diethylthioxanthone (KAYACURE DETX-S; manufactured by Nippon Kayaku Co., Ltd.)

Solvent (E): (E-1); propylene glycol monomethyl ether acetate

Solvent (E): (E-2); propylene glycol monomethyl ether

Solvent (E): (E-3); ethyl lactate

Surfactant (F): (F-1); Polyether modified eucalyptus oil (TORAY SILICON SH8400; Toray Dow Corning (limited by shares))

<Solubility evaluation>

A glass substrate (Eagle 2000; manufactured by Corning) having an angle of 2 inches was sequentially washed with a neutral detergent, water, and ethanol, and then dried. Further, the colored photosensitive resin composition was applied onto the glass substrate by a spin coating method, and then placed in a clean oven, and prebaked at 100 ° C for 3 minutes.

Next, the developing solution immersed in a liquid temperature of 25 ° C (in terms of mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalene sulfonate, respectively) was developed in the center of the substrate. The end time of the dissolution of the 10 mm portion was started as the dissolution time. When the dissolution time is 20 seconds or less, the solubility is good. The aforementioned colored photosensitive resin composition is even in When the development time is short, it is possible to suppress the development failure of the residue or the like and to produce a colored pattern, so that the yield is extremely high. The results are shown in Table 2.

<Production of coloring graphics>

The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning) having a 5 cm angle, and then pre-baked at 100 ° C for 3 minutes to form a dry film. After the film. After cooling, the substrate having the dried coating film and the quartz glass mask were separated by 80 μm, and exposed to an atmosphere of 60 mJ/cm using an exposure machine (TME-150RSK; Topcon). The exposure amount of ² (365 nm reference) was irradiated with light. In the case of a photomask, a line and space pattern which can form 100 μm is used. After the light irradiation, the coating film was immersed in a developing solution (in an amount of a mass fraction, an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfon, respectively) at 25 ° C for 60 seconds. After development, washing with water, and then baking at 230 ° C for 30 minutes in an oven, a colored pattern can be obtained.

<Measurement of film thickness>

With respect to the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

<Coloring shape shape evaluation>

The shape of the obtained coloring pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High Technology Co., Ltd.). If it is the shape shown in the following (p1) (so-called straight tapered shape) ○ If it is the shape shown by (p2), it will be △, and if it is the shape shown by (p3), it will be ×. In the case of the shape shown by (p1), when an inorganic film is deposited on the colored pattern, cracking and peeling of the inorganic film are less likely to occur. The results are shown in Table 2.

<Color Evaluation>

For the obtained coloring pattern, a color measuring machine (OSP-SP-200; Olympus Co., Ltd.) was used to measure the splitting, and the characteristic function of the C light source was used to measure the xy chromaticity coordinates in the XYZ color system of the CIE. (x, y) and tristimulus value Y. If the value of Y is larger, it means that the brightness is higher. The results are shown in Table 2.

[Examples 7 to 9]

The same procedure as in Examples 1 to 3 was carried out except that the dye A1 was changed to the compound represented by the formula (1-31), and a colored photosensitive resin composition was obtained. The same operation as described above was carried out, and it was confirmed that the solubility was extremely excellent. Further, a colored pattern excellent in both brightness and shape is obtained.

From the above results, it is confirmed that the colored photosensitive resin composition of the present invention has excellent color properties and pattern shapes on the one hand, and coloring on the other hand. When the pattern is formed, the solubility to the developer is also very high. Therefore, it is understood that the colored filter can be produced in a high yield by the colored photosensitive resin composition of the present invention.

[Industrial availability]

According to the colored photosensitive resin composition of the present invention, the unexposed portion can have high solubility to the developer when the colored pattern is formed.

Claims (5)

A colored photosensitive resin composition comprising: a colorant, a binder resin, a polymerizable compound, and a polymerization initiator; the binder resin is a binder resin including a copolymer having the following structural unit: a structure derived from methacrylic acid a unit, a structural unit derived from acrylic acid, and a structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid, and a structural unit derived from methacrylic acid of 1 to 54 mol%, which is derived from methacrylic acid and The structural unit of the acrylic acid-copolymerized monomer is a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms. The colored photosensitive resin composition according to the first aspect of the invention, wherein the content of the copolymer is 10% by mass or more and 100% by mass or less based on the binder resin. The colored photosensitive resin composition according to claim 1, wherein the coloring agent is a coloring agent including a dye. A color filter comprising the colored photosensitive resin composition as described in claim 1, 2 or 3. A display device comprising the color filter of claim 4 of the patent application.