JP2012198508A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition with high solubility to a developer.SOLUTION: A colored photosensitive resin composition contains a colorant, a binder resin, a polymerizable compound and a polymerization initiator, in which the binder resin contains a copolymer having 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.

Description

  The present invention relates to a colored photosensitive resin composition.

Colored photosensitive resin compositions are used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored photosensitive resin composition, a colored photosensitive resin containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin. Compositions are known (Patent Documents 1 and 2).

JP 2010-211198 A JP 2010-224204 A

  When forming a colored pattern by the photolithographic method from the conventionally known colored photosensitive resin composition, the solubility of the unexposed portion in the developer may not always be sufficiently satisfied.

The present invention provides the following [1] to [6].
[1] includes a colorant, a binder resin, a polymerizable compound, and a polymerization initiator,
A colored photosensitive resin in which the binder resin is a resin including a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a copolymer having a structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid. Resin composition.
[2] The colored photosensitive resin composition according to [1], wherein the copolymer is a copolymer having 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 [1] or [2], wherein the content of the copolymer is from 10% by mass to 100% by mass with respect to the total amount of the binder resin.
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the colorant is a colorant containing a dye.
[5] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

  The colored photosensitive resin composition of the present invention has high solubility in a developing solution in an unexposed portion when forming a colored pattern.

The colored photosensitive resin composition of the present invention includes a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The binder resin (B) is a resin containing a copolymer having 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. It is a certain colored photosensitive resin composition.

  The colored photosensitive resin composition of the present invention contains a colorant (A). Examples of the colorant (A) include a dye (A1) and a pigment (A2), and a colorant containing the dye (A1) is preferable. Examples of the dye (A1) include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, dyes in the color index (published by The Society of Dyers and Colorists), Examples include compounds classified as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of two or more. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 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;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 34, 102;
C. I. Acid Blue 1, 7, 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;
C. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109; I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 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;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Examples include vat dyes.

As the dye (A1), a xanthene dye (Aa) is preferable.
The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton.
Examples of the xanthene dye (Aa) include C.I. I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dye described in JP 2010-32999 A, xanthene dye described in Japanese Patent No. 4492760, and the like.

  As the xanthene dye (Aa), a dye containing a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) is preferable. Compound (1) may be a tautomer thereof. When using the compound (1), the content of the compound (1) with respect to the total amount of the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use substantially 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. It represents a hydrogen atom contained in the aromatic hydrocarbon group, 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, which may be substituted by _-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 has 1 carbon atom. May be substituted with ˜3 alkoxy groups, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O—, —CO— or —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -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 represents NR ⁹ R ¹⁰
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ are 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.
M ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
X represents 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 the 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 the hydrogen atom contained in the saturated hydrocarbon group is substituted with a hydroxy group or a halogen atom. And —CH ₂ — contained in the saturated aliphatic hydrocarbon group may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. ]

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, a propylphenyl group, and a butylphenyl group.

Monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ are, as a _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - M + and _-SO 2 ^NR 9 ^{R 10} it is preferable to have at least one selected from the group consisting of, _-SO ³ - and more preferably has a ^{M +} and at least one selected from the group consisting of _-SO 2 ^NR 9 ^{R 10} . _-SO ³ in this case - ^{M + _{Examples, -SO 3 - + N (R}} 11) 4 are preferred. When R ^{1 to} R ⁴ are these groups, a color filter with less generation of foreign matters and excellent heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (1).

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following.

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, an isobutyl group, a pentyl group, and an isopentyl group. Group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, etc. alkyl group having 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group , An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.

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

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

In the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁹ and R ¹⁰ , a hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom. —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO—, —NH— or —NR ⁸ —.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. Examples of the heterocyclic ring include the following.

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 includes SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , -SO ₃ H or _SO 2 NHR ⁹ is more preferable.
m is preferably 1 to 4, and more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

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

M ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
^{As +} N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four ^{R 11} is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1), when R ¹¹ is any of these groups, the color filter with less foreign matter from the colored photosensitive resin composition of the present invention containing the compound (1) Can be formed.

  The compound (1) is preferably a compound represented by the formula (2) (hereinafter sometimes referred to as “compound (2)”), and the xanthene dye (Aa) is more preferably a dye containing the compound (2). Compound (2) may be a tautomer thereof. When using the compound (2), 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 further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2) as the xanthene dye (Aa).

[In the formula (2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group. hydrogen atoms _{^{are, -SO 3 -, -SO 3 -}} M a +, -SO 3 H, optionally substituted by -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 the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
M ^{a +} represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁵ _is, ^-SO 3 _- represents a M a +, -SO ₃ H or _{^{SO 2 NHR 26 -, -SO 3}} .
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R < ²⁷ > represents a C1-C20 monovalent | monohydric saturated hydrocarbon group or benzyl group each independently. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ .
Among them, as a combination of R ^{21 to} R ²⁴ , preferably, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 -}} M +, in which -SO 3 _H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26} is there. More preferably, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups is, _-SO ³ - ^{M +} or those which may optionally be substituted by _-SO 2 ^{NHR 26.} When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
When R ^{21 to} R ²⁴ are —R ^26, it is preferable that —R ²⁶ is independently a hydrogen atom, a methyl group, or an ethyl group.
The ^{R 26} in -SO ₃ R ²⁶ and _-SO 2 ^{NHR 26,} preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, 2- More preferred is an ethylhexyl group. When R ²⁶ is these groups, the colored photosensitive resin composition containing the compound (2) can form a color filter with less generation of foreign matters.

M ^{a +} is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
^{As +} N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four ^{R 27} is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2), a color filter that generates less foreign matter from the colored photosensitive resin composition of the present invention containing the compound (2) in which R ²⁷ is any of these groups Can be formed.

  Examples of compound (1) include compounds represented by formula (1-1) to formula (1-30). In the following formulae, Ra represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).

  Moreover, as a xanthene dye (Aa), the dye containing the compound (henceforth "compound (3)") represented by Formula (3) is also more preferable. Compound (3) may be a tautomer thereof. When using the compound (3), 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 further preferably 90% by mass or more.

［式（３）中、Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜１０のアルキル基を表す。Ｒ³³及びＲ³⁴は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基または炭素数１〜４のアルキルスルホニル基を表す。Ｒ³¹及びＲ³³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ³²及びＲ³⁴は、一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ³³は同一であっても異なっていてもよく、ｑが２以上である場合、複数のＲ³⁴は同一であっても異なっていてもよい。］

Wherein (3), R ³¹ and R ^32, independently of each other, represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ^34, independently of one another, represent an alkyl group, an alkylsulfanyl group, or an alkylsulfonyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms having 1 to 4 carbon atoms. R ³¹ and R ³³ may be combined to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different. ]

Examples of the alkyl group having 1 to 10 carbon atoms representing R ³¹ and R ³² include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, 2 -An ethylhexyl group, a nonyl group, a decyl group, etc. are mentioned. Examples of the alkyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include groups having up to 4 carbon atoms.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ³¹ and R ³² are preferably 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.
p and q are each independently preferably an integer of 0 to 2, and more preferably 1 or 2.

  Examples of compound (3) include compounds represented by formula (1-31) to formula (1-43), respectively. Especially, the compound represented by Formula (1-31)-Formula (1-40) is preferable at the point which is excellent in the solubility to an organic solvent.

  As the xanthene dye (Aa), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Co., Ltd., etc.) is used. You can also. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

The colorant (A) may contain a pigment (A2).
The pigment is not particularly limited, and known pigments can be used, and compounds classified as pigments by the color index (published by The Society of Dyers and Colorists), such as C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as 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;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. Examples of the pigment used in the colored photosensitive resin composition of the present invention include C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment red 242, C.I. I. Pigment red 177, C.I. I. Pigment green 58, C.I. I. Pigment yellow 150 and C.I. I. A pigment containing at least one selected from the group consisting of CI Pigment Yellow 138 is more preferable. By including the pigment, the transmission spectrum can be easily optimized and the chemical resistance is improved.
These pigments may be used alone or in combination of two or more.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (A2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion having a uniform dispersion state tends to be obtained.

  The colorant (A) preferably contains 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, more preferably 3:97 to 90:10, based on mass. . By setting such a ratio, the transmission spectrum can be easily optimized, and the resulting color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

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

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% with respect to the solid content of the colored photosensitive resin composition. It is mass%, Most preferably, it is 12-30 mass%. When the content of the colorant (A) is in the above range, a desired spectrum and color density can be obtained when a color filter is used, and a necessary amount of a binder resin and a polymerizable compound are contained in the composition. Therefore, a color filter having sufficient mechanical strength can be formed. Here, solid content means the total amount of the component remove | excluding the solvent from the colored photosensitive resin composition of this invention. The solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  The colored photosensitive resin composition of the present invention contains a binder resin (B), and the binder resin (B) is a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and copolymerized with methacrylic acid and acrylic acid. A copolymer (B1) having a structural unit derived from a possible monomer (x) (hereinafter sometimes referred to as “monomer (x)”) (hereinafter referred to as “copolymer (B1)”). Resin).

The monomer (x) is not particularly limited as long as it is copolymerizable with methacrylic acid and acrylic acid and is a monomer different from methacrylic acid and acrylic acid.
(A) an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as “(a)”)
(B) At least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (but different from acrylic acid and methacrylic acid) (hereinafter sometimes referred to as “(b)”)
(C) Other copolymerizable monomer (however, different from acrylic acid, methacrylic acid, (a) and (b)) (hereinafter sometimes referred to as “(c)”)
Is mentioned.

As a C2-C4 cyclic ether structure which (a) has, an oxirane ring, an oxetane ring, and a tetrahydrofuran ring are mentioned, for example. (A) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (a) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (a2) (hereinafter sometimes referred to as “(a2)”), monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a3)”), and the like Can be mentioned.

  (A1) is, for example, a monomer (a1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, an ethylenically unsaturated bond and a structure (hereinafter referred to as “(a1 -1) "), and a monomer (a1-2) having an alicyclic unsaturated hydrocarbon epoxidized structure, an ethylenically unsaturated bond and a structure (hereinafter referred to as" (a1-2) ") ”).

  As (a1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (a1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (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 is a hydroxy group May be substituted.
X ¹ and X ² each independently represent a single bond, —R ^c —, * —R ^c —O—, * —R ^c —S—, or * —R ^c —NH—.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O), or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formula (I-11) to Formula (I-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (a2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (A) is preferably (a1) in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Furthermore, (a1-2) is more preferable in that the storage stability of the colored photosensitive resin composition is excellent.

Specific examples of (b) include unsaturated monocarboxylic acids such as crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 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- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is referred to as dicyclopentanyl (meth) acrylate as a common name), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2 (In the art, as trivial names are said dicyclopentenyl (meth) acrylate.) 1.0 ^2,6] decene-8-yl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) (Meth) acrylic esters such as acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

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

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

  The copolymer (B1) is preferably a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and (a) in terms of the brightness of the color filter to be obtained.

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) is the total structure constituting the copolymer (B1). In the unit, each is preferably in the following range.
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%)
Furthermore, it is preferable that the total amount of the structural unit derived from methacrylic acid and the structural unit derived from acrylic acid is 2 to 55 mol% in all the structural units constituting the copolymer (B1). More preferably, it is 50 mol%.
When the ratio of the structural unit of the copolymer (B1) is within the above range, the storage stability of the colored photosensitive resin composition, the developability, and the solvent resistance of the color filter tend to be good.

  The copolymer (B1) can be prepared by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, Kagaku Dojin Co., Ltd. It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a predetermined amount of methacrylic acid, acrylic acid and monomer (x), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, oxygen is replaced with nitrogen to obtain a deoxygenated atmosphere. In addition, there is a method of heating and keeping warm while stirring. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as the solvent (E) of the colored photosensitive resin composition of the present invention.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive resin composition of the present invention can be simplified.

  The copolymer (B1) may contain 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). .

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

Examples of the alkyl group having 1 to 6 carbon atoms in R ^e and R ^g include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. R ^e and R ^g are preferably a hydrogen atom or a methyl group.

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

[In formula (IIIa) and formula (IVa), R ^e and R ^g represent the same meaning as described above. ]

Even when the copolymer (B1) contains the structural unit represented by the formula (III) and / or the structural unit represented by the formula (IV) as a structural unit derived from the monomer (x), The ratio of the structural units derived from each is preferably in the above range.
When the copolymer (B1) includes the structural unit represented by the formula (III) and / or the structural unit represented by the formula (IV), the ratio of these structural units is determined by the copolymer (B1). 5-80 mol% is preferable in all the structural units to comprise, and 15-70 mol% is more preferable.
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, the storage stability, developability and sensitivity of the colored photosensitive resin composition. In addition, the color filter tends to have a good balance of solvent resistance, heat resistance and mechanical strength.

As the copolymer (B1), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / methacrylic acid / acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^{2 .6} ] Decyl acrylate / methacrylic acid / acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer, glycidyl (meth) acrylate / styrene / methacrylic acid / acrylic acid copolymer Polymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / N-cyclohexylmaleimide / methacrylic acid / acrylic acid copolymer, 3-methyl-3- (meth) acryloyl Oxymethyloxetane / styrene / methacrylic acid / acrylic acid copolymer, benzyl (meth) acrylate Relate / methacrylic acid / acrylic acid copolymer, styrene / methacrylic acid / acrylic acid copolymer, benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclo A resin obtained by adding glycidyl (meth) acrylate to a decyl (meth) acrylate / styrene / methacrylic acid / acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer And a resin obtained by adding glycidyl (meth) acrylate to the resin. Among them, benzyl (meth) acrylate / methacrylic acid / acrylic acid copolymer, styrene / methacrylic acid / acrylic acid copolymer, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / A 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, and further preferably 5,000 to 30,000. And particularly preferably 5,000 to 18,000, and particularly 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 remaining film ratio and hardness of the resulting colored pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer (B1) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the copolymer (B1) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 170 mg-KOH / g, and still more preferably 100 to 150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The binder resin (B) may contain a resin other than the copolymer (B1) (hereinafter sometimes referred to as “resin (B2)”). The resin (B2) is not particularly limited as long as it is an alkali-soluble resin, a copolymer of methacrylic acid and the monomer (x), a copolymer of acrylic acid and the monomer (x), methacrylic acid Or a copolymer of acrylic acid and (a), a copolymer of (a) and (b), a copolymer of methacrylic acid or acrylic acid and (b), and (b) and (c) (Meth) acrylic acid and / or (b) a copolymer, a copolymer of (a), (b) and (c), a copolymer of (a) and (c) A resin obtained by adding (a) to a copolymer of (meth) acrylic acid and / or a copolymer of (b) and (c) and further reacting with an acid anhydride. Specifically, the resin described as alkali-soluble resin in Unexamined-Japanese-Patent No. 2010-224204 is mentioned.
Among them, a copolymer of methacrylic acid or acrylic acid and (a), a copolymer of (a) and (b), a copolymer of (a), (b) and (c), methacrylic acid or A copolymer of acrylic acid and (c) and a copolymer of (b) and (c) are preferred, and a copolymer of methacrylic acid or acrylic acid and (a) and methacrylic acid or acrylic acid and (c And a copolymer thereof is more preferable. When the binder resin (B) contains these resins together with the copolymer (B1), there is a tendency that both high solubility in the developer in the unexposed area and good color pattern shape are obtained. Because there is, it is preferable.

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 further 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 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the resin (B2) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 170 mg-KOH / g, and still more preferably 90 to 160 mg-KOH / g.
When the resin (B2) is the above-mentioned resin, particularly when combined with the copolymer (B1), the solubility of the unexposed portion in the developer is high, and the remaining film ratio and hardness of the resulting colored pattern are also high. Tend.

The content of the copolymer (B1) is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and further preferably 30 to 70% by mass with respect to the total amount of the binder resin (B). %, Particularly preferably 30 to 50% by mass.
When the content of the copolymer (B1) is within the above range, the solubility of the unexposed area in the developer is high, and thus there is a tendency that the productivity of the colored pattern is excellent. When content of a copolymer (B1) is less than the said range, there exists a possibility that the effect of this invention concerning developability cannot fully be acquired.

In particular, the binder resin (B) preferably comprises 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 contents in this case are
Copolymer (B1); 15 to 70% by mass
Copolymer of methacrylic acid or acrylic acid and (a); 15 to 70% by mass
Copolymer of methacrylic acid or acrylic acid and (c); 15 to 70% by mass
Is preferred,
Copolymer (B1); 25-50% by mass
Copolymer of methacrylic acid or acrylic acid and (a); 25-50% by mass
Copolymer of methacrylic acid or acrylic acid and (c); 25-50% by mass
Is more preferable.
When the binder resin (B) has the above combination, a colored pattern having an excellent shape and high solubility in a developer in an unexposed area can be formed.

  Content of binder resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 13-55 mass%, More preferably, it is 17-50. % By mass. When the content of the binder resin (B) is in the above range, there is a tendency that a colored pattern having an excellent shape can be formed with high solubility in a developing solution in an unexposed portion.

  The colored photosensitive resin composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that can be polymerized by active radicals and acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. (Meth) acrylic acid ester compound is mentioned.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octane. (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified penta Erythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Le-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymerizable compounds may be used alone or in combination of two or more.
The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 based on the solid content of the colored photosensitive resin composition. It is -55 mass%. When the content of the polymerizable compound (C) is in the above range, curing is sufficiently performed, the remaining film ratio in development is improved, and the undercut is difficult to enter in the colored pattern, thereby improving the adhesion. It is preferable because of its tendency.

The colored photosensitive resin composition of the present invention contains a polymerization initiator (D).
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical and / or an acid by the action of light and initiating polymerization of the polymerizable compound (C). The polymerization initiator can be used.
The polymerization initiator (D) is preferably a compound that generates an active radical by the action of light, and includes at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds, and biimidazole compounds. The polymerization initiator containing is more preferable, and the polymerization initiator containing an oxime compound and an alkylphenone compound is more preferable.

式（ｄ２）で表される部分構造を有する化合物としては、例えば、２−メチル−２−モルホリノ−１−（４−メチルスルファニルフェニル）プロパン−１−オン、２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−ベンジルブタン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］ブタン−１−オン等が挙げられる。イルガキュア（登録商標）３６９、９０７及び３７９（以上、ＢＡＳＦ社製）等の市販品を用いてもよい。
式（ｄ３）で表される部分構造を有する化合物としては、例えば、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−〔４−（２−ヒドロキシエトキシ）フェニル〕プロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−（４−イソプロペニルフェニル）プロパン−１−オンのオリゴマー、α，α−ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
感度の点で、前記アルキルフェノン化合物としては、式（ｄ２）で表される部分構造を有する化合物が好ましく、２−メチル−２−モルホリノ−１−（４−メチルスルファニルフェニル）プロパン−１−オン及び２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−ベンジルブタン−１−オンがより好ましい。 The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2), such as 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one. And 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one is more preferred.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by BASF) may be used.

前記オキシム化合物としては、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンが好ましい。これらのオキシム化合物であると、特に、本発明の着色感光性樹脂組成物を青色着色感光性樹脂組成物として調製する場合に、高明度なカラーフィルタが得られる傾向にある。 The oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclo) Pentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- 2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred. When these oxime compounds are used, particularly when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, a color filter with high brightness tends to be obtained.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Nyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator that generates an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4 -Onium salts such as acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, Examples thereof include nitrobenzyl tosylate and benzoin tosylate.

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

The colored photosensitive resin composition of the present invention may further contain a polymerization initiation assistant (D1). When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like, and thioxanthone compounds are preferred.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
The polymerization initiation assistant (D1) may be used alone or in combination of two or more.

  When these polymerization initiation assistants (D1) are used, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). More preferably, it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the colored pattern tends to be improved.

The colored photosensitive resin composition of the present invention preferably contains a solvent (E).
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

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

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

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

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

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, More preferred are 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

  The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored photosensitive resin composition of the present invention. is there. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

The colored photosensitive resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone (trade name) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) Is mentioned.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone 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 preferably 0.002% by mass with respect to the total amount of the colored photosensitive resin composition of the present invention. The content is 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less. This content does not include the content of the pigment dispersant. When the content of the surfactant (F) is within the above range, the flatness of the color filter can be improved.

  The colored photosensitive resin composition of the present invention is used in the technical field as necessary, such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents and the like. Various known additives (hereinafter sometimes referred to as “other components”) may also be included.

The colored photosensitive resin composition of the present invention includes, for example, a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation assistant used as necessary. It can be prepared by mixing (D1), solvent (E), surfactant (F) and other components.
When the pigment (A2) is included, the pigment (A2) is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Is preferred. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and binder resin (B) as needed. The desired colored photosensitive resin composition can be prepared by mixing the remaining components and the like into the obtained pigment dispersion so as to have a predetermined concentration.
When the dye (A1) is included, it is preferable to prepare a solution by dissolving the dye (A1) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored photosensitive resin composition prepared by mixing as described above is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

Examples of a method for forming a colored pattern of a color filter using the colored photosensitive resin composition of the present invention include a photolithographic method and an inkjet method. In order to form a colored pattern by a photolithographic method, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, another colored photosensitive resin composition layer previously formed on the substrate, etc. ), Removing volatile components such as a solvent (drying) to form a coating film after drying, exposing the colored layer through a photomask, and developing. In the above photolithographic method, a colored coating film which is a cured product of the coating film after drying can be formed by not using a photomask and / or not developing during exposure. These colored patterns and colored coating films can be used as color filters.
The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the material used, the use, and the like. 6 μm.

A colored photosensitive resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (pre-baking) and / or drying under reduced pressure to obtain a smooth post-drying coating film.
As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, resin layer, transistor, circuit, or the like may be formed.
Examples of the coating method include spin coating, slit coating, and slit-and-spin coating.

30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coating film after drying is not particularly limited, and can be appropriately adjusted depending on the material used, application, and the like.

After drying, the coating film is exposed through a photomask for forming a target pattern. The pattern on the photomask at this time is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because it can irradiate parallel light uniformly over the entire exposure surface or perform accurate alignment between the mask and the substrate on which the coating film has been formed after drying. .

After exposure, a colored pattern can be obtained by bringing the unexposed portion into contact with a developing solution to remove it (that is, development). As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, tetramethylammonium hydroxide and the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored photosensitive resin composition of the present invention, a color filter can be produced with particularly high productivity. The color filter is useful as a color filter used for a display device (for example, electronic paper such as a liquid crystal display device or an organic EL device) or a solid-state image sensor.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

[Synthesis Example 1]
In a flask equipped with a condenser and a stirrer, 15 parts of a mixture of the compound represented by formula (A0-1) and the compound represented by formula (A0-2) (manufactured by Chugai Kasei), 150 parts of chloroform and N, 8.9 parts of N-dimethylformamide was added, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and dye A1 (dye A1) (compounds represented by formula (A1-1) to formula (A1-8)). 11.3 parts of a mixture were obtained.

[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 shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 24 parts of a 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; Agilent 1200 type, MASS; Agilent LC / MSD type).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３９）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 3]
A compound represented by the formula (1-39) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

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

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部を乳酸エチル９５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗが７．０×１０^３、分子量分布が２．５、固形分が４２％、固形分酸価が１３８ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は下記に示す構造単位を有する。 [Synthesis Example 4]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 72 parts of methacrylic acid, 7 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II- 1) The compound represented by 1) was mixed at a molar ratio of 50:50) 250 parts were dissolved in 140 parts of ethyl lactate to prepare a solution, and this solution was added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 7.0 × 10 ³ , the molecular weight distribution is 2.5, and the solid content is A resin B1 solution having 42% and a solid content acid value of 138 mg-KOH / g was obtained. Resin B1 has the structural units shown below.

[Synthesis Example 5]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Subsequently, 10 parts of methacrylic acid, 58 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II- The compound represented by 1) was mixed at a molar ratio of 50:50) 254 parts were dissolved in 140 parts of ethyl lactate to prepare a solution, and this solution was added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 7.0 × 10 ³ , the molecular weight distribution is 2.5, and the solid content is A resin B2 solution having 41% and a solid content acid value of 136 mg-KOH / g was obtained. Resin B2 has the structural units shown below.

[Synthesis Example 6]
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 336 parts in a molar ratio of 50:50) was dissolved in 140 parts of ethyl lactate to prepare a solution, and this solution was kept at 70 ° C. for 4 hours using a dropping funnel. The solution was dropped into the flask. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 8.0 × 10 ³ , the molecular weight distribution is 2.5, and the solid content is A resin B3 solution having a 48% solution acid value of 50 mg-KOH / g was obtained. The solid content acid value calculated from the solid content and the solution acid value is 104 mg-KOH / g. Resin B3 has the structural units shown below.

[Synthesis Example 7]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 305 parts by mass of ethyl lactate was added, and the mixture was heated to 100 ° C. with stirring. Next, a solution was prepared by dissolving in 90 parts by mass of methacrylic acid, 210 parts by mass of benzyl methacrylate and 140 parts by mass of ethyl lactate, and the solution was kept at 100 ° C. for 4 hours using a dropping funnel. It was dripped in. On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 100 ° C. for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 1.2 × 10 ⁴ , the molecular weight distribution was 2.2, and the solid content. A resin B4 solution having 30% by mass and a solid content acid value of 154 mg-KOH / g was obtained. Resin B4 has the structural units shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1 to 6 and Comparative Example 1
Each component was mixed so that it might become a composition shown in Table 1, and the colored photosensitive resin composition was obtained.

In Table 1, each component represents the following. Moreover, binder resin (B) showed the mass part of solid content conversion.
Colorant (A); (A-1); C.I. I. Pigment Blue 15: 6
Colorant (A); (A-2); Dye A1
Colorant (A); (A-3); compound represented by formula (1-39) Binder resin (B); (B-1); Resin B1
Binder resin (B); (B-2); Resin B2
Binder resin (B); (B-3); Resin B3
Binder resin (B); (B-4); Resin B4
Polymerizable compound (C); (C-1); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)
Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF)
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 silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Solubility evaluation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and ethanol and then dried. The colored photosensitive resin composition was spin-coated on this glass substrate, and then pre-baked at 100 ° C. for 3 minutes in a clean oven.
Next, development was performed by immersing in a developer at a liquid temperature of 25 ° C. (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction), and 10 mm from the center of the substrate. The time at which the portion was completely dissolved was defined as the dissolution time. If the dissolution time is 20 seconds or less, the solubility is good. Such a colored photosensitive resin composition can be said to have high productivity because it can produce a colored pattern in which development failure such as residue is suppressed even if the development time is short. The results are shown in Table 2.

<Preparation of colored pattern>
A colored photosensitive resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a coating film after drying. After allowing to cool, the distance between the substrate on which the coating film is formed after drying and the photomask made of quartz glass is set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corp.) is used in an air atmosphere at 60 mJ / Light irradiation was performed with an exposure amount of cm ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. After the light irradiation, the coating film was developed by immersing in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction) at 25 ° C. for 60 seconds, and washed with water. Then, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored pattern.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

<Colored pattern shape evaluation>
About the obtained coloring pattern, the shape was observed using the scanning electron microscope (S-4000; Hitachi High-Technologies Corporation make). The shape indicated by (p1) below (so-called forward tapered shape) was indicated by ◯, the shape indicated by (p2) was indicated by Δ, and the shape indicated by (p3) was indicated by ×. When the inorganic film is laminated on the colored pattern, the shape shown by (p1) tends to prevent cracking or peeling off of the inorganic film. The results are shown in Table 2.

<Chromaticity evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

Examples 7-9
A colored photosensitive resin composition is obtained in the same manner as in Examples 1 to 3, except that the compound represented by the formula (1-31) is used instead of the dye A1. The same operation as described above is performed, and it is confirmed that the solubility is excellent. Furthermore, a colored pattern having excellent brightness and shape is obtained.

  From the above results, it was confirmed that the colored photosensitive resin composition of the present invention has high solubility in a developer when forming a colored pattern while having excellent color performance and pattern shape. From this, it can be seen that according to the colored photosensitive resin composition of the present invention, a color filter can be produced with high productivity.

  According to the colored photosensitive resin composition of the present invention, the solubility of the unexposed portion in the developer is high when forming a colored pattern.

Claims (6)

Including a colorant, a binder resin, a polymerizable compound and a polymerization initiator,
A colored photosensitive resin in which the binder resin is a resin including a structural unit derived from methacrylic acid, a structural unit derived from acrylic acid, and a copolymer having a structural unit derived from a monomer copolymerizable with methacrylic acid and acrylic acid. Resin composition.   The colored photosensitive resin composition according to claim 1, wherein the copolymer is a copolymer containing 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 claim 1 or 2, wherein the content of the copolymer is 10% by mass or more and 100% by mass or less with respect to the total amount of the binder resin.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the colorant is a colorant containing a dye.   The color filter formed with the colored photosensitive resin composition as described in any one of Claims 1-4.   A display device comprising the color filter according to claim 5.