JP6115005B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition.

  Colored photosensitive resin compositions are used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As this colored photosensitive resin composition, a colored photosensitive resin composition containing only N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine as a polymerization initiator is known. (Patent Document 1).

JP 2010-224204 A

  Conventionally known colored photosensitive resin compositions described above may not always have sufficient sensitivity. If the sensitivity is low, the exposure through the photomask takes a long time, which may reduce the productivity.

The present invention provides the following [1] to [6].
[1] includes a colorant, a binder resin, a polymerizable compound, and a polymerization initiator,
The colorant is a colorant containing a dye,
A colored photosensitive resin composition, wherein the polymerization initiator is a polymerization initiator containing an oxime compound and an alkylphenone compound.
[2] The colored photosensitive resin composition according to [1], further comprising a thioxanthone compound.
[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of the oxime compound is 20% by mass to 98% by mass with respect to the content of the polymerization initiator.
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the colorant is a colorant containing a pigment and 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].

  Since the colored photosensitive resin composition of the present invention has high sensitivity, a pattern can be formed with a small exposure amount.

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 colorant (A) is a colorant containing a dye (A1),
It is a colored photosensitive resin composition whose polymerization initiator is a polymerization initiator containing an oxime compound and an alkylphenone compound.
The colorant (A) preferably further contains the pigment (A2) together with the dye (A1).
The colored photosensitive resin composition of the present invention preferably contains at least one selected from the group consisting of a polymerization initiation assistant (D1) and a solvent (E).
Further, the colored photosensitive resin composition of the present invention may contain a surfactant (F).

  The colorant (A) contains a dye (A1). 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 other than pigments and known dyes described in dyeing notes (Color Dyeing). 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.

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, 99 162;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. 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, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 22,426;
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, etc. 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, 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, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Examples include vat dyes.

As the dye (A1), a xanthene dye is preferable.
A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule.
Examples of xanthene dyes include C.I. I. Acid Red 51, 52, 87, 91, 92, 94, 95, 98, 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.

  Among these, as the xanthene dye, 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 a compound (1), content of the compound (1) in a xanthene dye becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only the compound (1) as the xanthene dye.

[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 an integer of 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 ^{8 to} R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, and 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, cyclohexyl group, cycloheptyl C3-C20 cycloalkyl groups, such as a group, a cyclooctyl group, and a tricyclodecyl group.

Examples of —OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an 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, and the saturated —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 more preferably a dye containing a compound represented by the formula (2) (hereinafter sometimes referred to as “compound (2)”). Compound (2) may be a tautomer thereof. When using the compound (2), the content of the compound (2) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

[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 +, -SO 3 H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} 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 may be substituted with _-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, a color filter with less generation of foreign matters can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).

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.

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

  Preferable xanthene dyes include, for example, dyes mainly composed of compounds represented by formulas (1-1) to (1-29). 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), and formula (1-12).

  Moreover, as a xanthene dye, 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 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 (1-30) to formula (1-42), respectively. Especially, the compound represented by Formula (1-30)-Formula (1-39) is preferable at the point which is excellent in the solubility to an organic solvent.

  As the xanthene dye, 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 Industry Co., Ltd., etc.) can also be used. . 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 pigment (A2) is not particularly limited, and a known pigment 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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, 80; 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. As the pigment dispersant, 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), 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 in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  When the pigment (A2) is contained, the content ratio of the dye (A1) and the pigment (A2) is preferably from 1:99 to 99: 1, more preferably from 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 from 3:97 to 90:10, more preferably from 3:97 to 70:30, and even more preferably from 3:97 to 50:50 on a mass basis.

  Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a colored photosensitive resin composition, More preferably, it is 8-55 mass%, More preferably, it is 10-10. 50% by mass. Here, solid content means the sum total of the component except a solvent in a coloring photosensitive resin composition. 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 pattern with sufficient mechanical strength can be formed.

The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the binder resin (B) include the following resins [K1] to [K6].
[K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) [K3] Copolymer of (a) and (c) [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
[K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
[K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-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 (hymic acid 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.
Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether 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 (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) may be, for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) ), A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), 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 (b1-2) 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 ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the 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 alkanediyl groups 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 ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O) group, 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 (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 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 (b3) 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 (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored photosensitive resin composition is excellent.

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 called dicyclopentanyl (meth) acrylate as a common name), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (Meta Acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) (meth) acrylic acid esters such as 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.
Of these, styrene, 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.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is within the above range, the colored photosensitive resin composition tends to be excellent in storage stability, developability, and solvent resistance of the resulting pattern.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen in the atmosphere with nitrogen to form a deoxygenated atmosphere, A method of heating and keeping warm while stirring is mentioned. 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.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is within the above range, the colored photosensitive resin composition is excellent in storage stability, developability, and solvent resistance, heat resistance and mechanical strength of the resulting pattern. Tend.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator and a solvent are placed in a reaction vessel, and, for example, oxygen in the atmosphere is replaced with nitrogen, thereby removing a deoxygenated atmosphere. Then, a method of heating and keeping warm while stirring can be mentioned. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has a carboxy group and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms. It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the carboxy group and / or part of the carboxylic acid anhydride contained in the structural unit derived from (a) in the copolymer is reacted with a C2-C4 cyclic ether of (b). .
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and 5 to 80 mol% of (b), carboxylic acid or 0.001 to 5% by mass of a polymerization catalyst of carboxylic acid anhydride and cyclic ether (for example, tris (dimethylaminomethyl) phenol) with respect to the total amount of (a), (b) and (c), and polymerization An inhibitor (for example, hydroquinone etc.) etc. is put into a flask 0.001-5 mass% with respect to the total amount of (a), (b), and (c), for example, at 60-130 degreeC, 1- Resin [K4] can be obtained by reacting for 10 hours. The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of a colored photosensitive resin composition, developability, and the solvent resistance of a color filter, heat resistance, mechanical strength, and a sensitivity to become favorable.
Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following ranges with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

Specific examples of the binder resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.02 ^{. 6} ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / ( (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylic Relate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer resin [K3]; glycidyl (meth) acrylate added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meta ) Resin such as resin obtained by adding glycidyl (meth) acrylate to acrylic acid copolymer [K4]; Reacting (meth) acrylic acid to dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin, dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) a Resin such as a resin obtained by reacting a copolymer of relate with (meth) acrylic acid [K5]; reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid And resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin.
These resins may be used alone or in combination of two or more.

Among these, as the binder resin (B), the resin [K1] and the resin [K2] are preferable, the resin [K1] is more preferable, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. An acrylate / (meth) acrylic acid copolymer is more preferable.

The polystyrene-reduced weight average molecular weight of the binder resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. is there. When the molecular weight is in the above range, the solubility of the unexposed portion in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the binder resin (B) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 170 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.

  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, the solubility of the unexposed area in the developer tends to be high.

  The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or acid generated from the polymerization initiator (D) by the action of light, and has, for example, a compound having a polymerizable ethylenically unsaturated bond Etc., preferably (meth) acrylic acid ester compounds.

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, and 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 within the above range, the curing is sufficiently performed, the film thickness ratio before and after the development is improved, the pattern is less likely to be undercut, and the adhesion is good. It is preferable because it tends to become.

  The polymerization initiator (D) contains an oxime compound and an alkylphenone compound.

具体的には、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、オキシム化合物は、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−イミンからなる群から選ばれる少なくとも１種が好ましく、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−イミンがより好ましい。これらのオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 Examples of the oxime compound include an O-acyl oxime compound, and the O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Specifically, 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-dioxacyclopenta] Nylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylben Yl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one- At least one selected from the group consisting of 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy-1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these oxime compounds are used, a high brightness color filter tends to be obtained.

で表される部分構造を有する化合物であり、具体的には、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−１−（４−モルホリノフェニル）−２−（４−メチルフェニルメチル）ブタン−１−オン等が挙げられる。市販品としては、イルガキュア（登録商標）３６９、３７９、９０７（以上、ＢＡＳＦ社製）等が挙げられる。
α−アルコキシアルキルフェノン化合物は、式（ｄ３）

［式（ｄ３）中、Ｒ^ｚは、アルキル基を表す。］
で表される部分構造を有する化合物であり、具体的には、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。
α−ヒドロキシアルキルフェノン化合物としては、式（ｄ４）

で表される部分構造を有する化合物であり、具体的には、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−（１−メチルビニル）フェニル〕プロパン−１−オンのオリゴマー等が挙げられる。 Examples of the alkylphenone compounds include α-aminoalkylphenone compounds, α-alkoxyalkylphenone compounds, and α-hydroxyalkylphenone compounds.
The α-aminoalkylphenone compound has the formula (d2)

Specifically, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like. Examples of commercially available products include Irgacure (registered trademark) 369, 379, and 907 (above, manufactured by BASF).
The α-alkoxyalkylphenone compound has the formula (d3)

[In the formula (d3), R ^z represents an alkyl group. ]
And specific examples include diethoxyacetophenone, benzyldimethyl ketal, and the like.
The α-hydroxyalkylphenone compound includes a compound represented by the formula (d4)

Specifically, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2- Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer, and the like. .

  As the alkylphenone compound, α-aminoalkylphenone compounds are preferable, and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) are preferred. ) -2-Benzylbutan-1-one is more preferred.

  The polymerization initiator (D) may contain a polymerization initiator other than those described above, but is preferably substantially free from the viewpoint of sensitivity. The polymerization initiator other than the above is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (C), and a known polymerization initiator can be used. Examples of polymerization initiators other than the above include triazine compounds, acylphosphine oxide compounds, biimidazole compounds, and the like.

  As triazine compounds, 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-methyl) Phenyl) ethenyl 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 (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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 (trialkoxypheny ) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), an imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group And 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.

In the polymerization initiator (D), the content of the oxime compound is preferably 20 to 98% by mass, more preferably 40 to 95% by mass, and further preferably 60 to 95% by mass.
In the polymerization initiator (D), the content of the alkylphenone compound is preferably 2 to 80% by mass, more preferably 5 to 60% by mass, and further preferably 5 to 40% by mass.

  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 in the above range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

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. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
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 thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl 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, and 4,4′-bis (diethylamino) benzophenone is preferred. 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

These polymerization initiation assistants may be used alone or in combination of two or more.
Moreover, when using a polymerization start adjuvant (D1), the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and polymeric compound (C), More preferably, it is 1-20 mass parts. Moreover, Preferably it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

  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, ethyleneglycol monomethyl ether acetate, ethyleneglycol 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 in the above range, the flatness at the time of application of the colored photosensitive resin composition becomes good, and the color density is not insufficient when the color filter is formed, so that the display characteristics are good. There is a tendency to be good.

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 DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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) Can be 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, R183, 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 or more and 0.1% by mass with respect to the colored photosensitive resin composition. Below, more preferably 0.01 mass% or more and 0.05 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 may 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 resin (B) as needed. In the obtained pigment dispersion, the dye (A1), the remainder of the resin (B), the polymerizable compound (C) and the polymerization initiator (D), and a polymerization initiation assistant (D1) used as necessary The desired colored photosensitive resin composition can be prepared by mixing the remainder of the solvent (E), the surfactant (F), and other components so as to have a predetermined concentration.
The dye (A1) is preferably prepared in advance by dissolving in part or all of the solvent (E). Moreover, it is preferable to filter this solution with a filter having a pore diameter 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 color filter pattern using the colored photosensitive resin composition of the present invention include a photolithographic method and an inkjet method. In order to form a pattern by the photolithographic method, it is applied onto a substrate or another resin layer (for example, another colored photosensitive resin composition layer previously formed on the substrate), and a volatile component such as a solvent. Is removed (dried) to form a colored layer, and the colored layer is exposed through a photomask and developed. In the photolithography method described above, a coating film having no pattern can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern to be produced is not particularly limited, and can be appropriately adjusted depending on the material used, application, and the like.

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, a resin layer, a transistor, a circuit, and the like may be formed.
Examples of the coating method include spin coating, slit coating, and slit-and-spin coating.

  As a method of forming each color pixel by the photolithography method, a known or commonly used method can be used. For example, it can be produced as follows.

A colored photosensitive resin composition is applied onto a substrate and dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored layer.
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 shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application 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 the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the colored layer can be performed.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. 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 sensitivity. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, etc.) 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 (1a) 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 residue of suction filtration and then dried to obtain 24 parts of a compound represented by the formula (1-30). The yield was 80%.

Identification of compound represented by formula (1-30) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３４）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]^＋ ６３０．３
Ｅｘａｃｔ Ｍａｓｓ： ６３０．３ [Synthesis Example 3]
A compound represented by the formula (1-34) was obtained in the same manner as in Synthesis Example 2 except that N-ethyl-o-toluidine was replaced with N-ethyl-2,6-dimethylaniline.

Identification of compound represented by formula (1-34) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 630.3
Exact Mass: 630.3

式（１−３５）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]^＋ ６３０．３
Ｅｘａｃｔ Ｍａｓｓ： ６３０．３ [Synthesis Example 4]
A compound represented by the formula (1-35) was obtained in the same manner as in Synthesis Example 2 except that N-ethyl-o-toluidine was replaced with N-isopropyl-o-toluidine.

Identification of compound represented by formula (1-35) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 630.3
Exact Mass: 630.3

式（１−３８）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]^＋ ６５９．４
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 5]
A compound represented by the formula (1-38) was obtained in the same manner as in Synthesis Example 2 except that N-ethyl-o-toluidine was replaced with N-propyl-2,6-dimethylaniline.

Identification of compound represented by formula (1-38) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4
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質量部を乳酸エチル２２５質量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は、９．１×１０^３、分子量分布は２．１、固形分２６質量％、固形分酸価１２０ｍｇ−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 6]
Into 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. Next, 60 parts by mass of acrylic 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) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution is added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC.

On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate 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 temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 9.1 × 10 ³ , the molecular weight distribution was 2.1, and the solid content A resin B1 solution having 26% by mass and a solid content acid value of 120 mg-KOH / g was obtained. Resin B1 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, 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 obtained 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 B2 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 B2 has the structural units shown below.

[Synthesis Example 8]
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 obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate 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 B3 solution having 30% by mass and a solid content acid value of 154 mg-KOH / g was obtained. Resin B3 has the structural units shown below.

[Synthesis Example 9]
133 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. The temperature was raised to 100 ° C., 82.8 g (0.47 mol) of benzyl methacrylate, 37.0 g (0.43 mol) of methacrylic acid, monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22 A solution prepared by adding 3.6 g of 2,2′-azobisisobutyronitrile to a mixture consisting of 0.0 g (0.10 mol) and 164 g of propylene glycol monomethyl ether acetate was added dropwise, and stirring was continued at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, 21.5 g of glycidyl methacrylate [0.15 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol,. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin B4 solution (solid content: 38%) having a solid content acid value of 97 mgKOH / g. 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 1-8 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 (pigment)
Colorant (A); (A-2); Dye A1
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 Corp .; Oxime Compound)
Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corp .; alkylphenone compound )
Polymerization initiator (D); (D-3); 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure (registered trademark) 369; manufactured by BASF Corp .; alkylphenone compound )
Polymerization initiation aid (D1); (D1-1); 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd .; thioxanthone compound)
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.)

Example 9
Colorant (A); C.I. I. Pigment Blue 15: 6 (pigment) 16 parts,
6.2 parts of acrylic pigment dispersant,
Solvent (E); 85 parts of propylene glycol monomethyl ether acetate, and solvent (E); 25 parts of ethyl lactate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Colorant (A); 4.5 parts of compound represented by formula (1-30),
Binder resin (B); 40 parts of resin B1
Polymerizable compound (C): 60 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF) 11 parts,
Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF) 5.4 Part,
Polymerization initiation aid (D1); 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.) 9 parts,
Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts,
Solvent (E): 15 parts of propylene glycol monomethyl ether acetate and solvent (E); 571 parts of ethyl lactate were mixed to obtain a colored photosensitive resin composition.

Example 10
A colored photosensitive resin composition was obtained in the same manner as in Example 9, except that the compound represented by the formula (1-30) was replaced with the compound represented by the formula (1-34).

Example 11
A colored photosensitive resin composition was obtained in the same manner as in Example 9 except that the compound represented by the formula (1-30) was replaced with the compound represented by the formula (1-35).

Example 12
A colored photosensitive resin composition was obtained in the same manner as in Example 9, except that the compound represented by the formula (1-30) was replaced with the compound represented by the formula (1-38).

<Pattern preparation>
A colored photosensitive resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes. After standing to cool, the distance between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask was set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corp.) was used in an air atmosphere at 60 mJ. Light was irradiated with an exposure amount of / cm ² (based on 365 nm). A photomask having a 50 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. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a pattern.

<Film thickness measurement>
About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 2 and 3.

<Chromaticity evaluation>
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE (Characteristic function of C light source) x, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Tables 2 and 3.

<Pattern shape evaluation>
About the obtained 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 it is the shape shown by (p1), when an inorganic film is laminated on the pattern, there is a tendency that cracks and peeling do not easily occur. The results are shown in Tables 2 and 3.

<Sensitivity evaluation>
About the obtained pattern, the line | wire width was measured using the scanning electron microscope (S-4000; Hitachi High-Technologies Corporation make). It can be determined that the higher the line width, the higher the sensitivity.

  From the above results, it was confirmed that the colored photosensitive resin composition of the present invention can form a pattern with high sensitivity. 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.

  Since the colored photosensitive resin composition of the present invention has high sensitivity, a pattern can be formed with a small exposure amount.

Claims (4)

Including a colorant, a binder resin, a polymerizable compound, a polymerization initiator and a thioxanthone compound,
The colorant is a colorant containing a dye,
The dye contains a compound represented by the formula (2),
The polymerization initiator is a polymerization initiator containing an oxime compound and an alkylphenone compound ,
Content of a polymerization initiator (D) is 1-20 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and polymeric compound (C),
The content of the oxime compound in the polymerization initiator (D) is 60 to 95% by mass, and the content of the alkylphenone compound is 5 to 40% by mass,
The coloring photosensitive resin composition whose content of a thioxanthone compound is 30-80 mass parts with respect to 100 mass parts of polymerization initiators (D) .

[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. The hydrogen atom to be substituted may be substituted with —SO ₃ ^— , —SO ₃ ^— Ma ⁺ , —SO ₃ H, —SO ₃ R ^26, or —SO ₂ NHR ²⁶ .
X ^a represents a halogen atom.
a ¹ represents an integer of 0 or 1.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
Ma ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁵ _is, ^-SO 3 _- represents a Ma +, -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. ] Colorants, colored photosensitive resin composition of claim 1 Symbol mounting a colorant comprising a pigment and a dye. A color filter formed by claims 1 or 2 colored photosensitive resin composition. A display device comprising the color filter according to claim 3 .