JP5742165B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state imaging device, and a color filter using the 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. In this colored photosensitive resin composition, it is known to use a pigment or a dye as a colorant (Non-patent Document 1).

Suzuki Hachioji, “Until the creation of a well-understood liquid crystal display”, first edition, Nikkan Kogyo Shimbun, March 2005, p. 112

  The contrast of a coating film formed using a conventional colored photosensitive resin composition is not always satisfactory.

The present invention provides the following [1] to [14].
[1] A colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a typical metal compound, the colorant is a colorant containing a dye, the typical metal compound contains a carbon atom, and A colored photosensitive resin composition, which is a typical metal compound in which the maximum value of the molar extinction coefficient in the visible light region of the typical metal compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the dye.
[2] The colored photosensitive resin composition according to the above [1], wherein the maximum value of the molar extinction coefficient in the visible light region of the typical metal compound is 0 or more and 1000 or less.
[3] The above [1] or [2], wherein the typical metal compound is a compound containing at least one selected from the group consisting of magnesium, aluminum, calcium, zinc, gallium, rubidium, strontium, indium, cesium and barium. Colored photosensitive resin composition.
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the typical metal compound is a compound containing at least one selected from the group consisting of aluminum, zinc, indium, and barium.
[5] Any one of [1] to [4], wherein the typical metal compound is a compound containing at least one group selected from the group consisting of —C (═O) — and —C (═S) —. The colored photosensitive resin composition as described.
[6] The above-mentioned [1] to [1], wherein the typical metal compound is at least one selected from the group consisting of a compound represented by the formula (F1), a compound represented by the formula (F2), and a hydrate thereof. 5] The colored photosensitive resin composition according to any one of [5].

[In Formula (F1) and Formula (F2), W ¹ and W ² are each independently a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic carbon group having 6 to 10 carbon atoms. Represents a hydrogen group, and a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. .
M ¹ and M ² represent typical metal atoms.
x and y represent an integer of 1 to 3, and when x is an integer of 2 or more, the plurality of W ¹ and W ² may be the same or different from each other, and y is an integer of 2 or more. In some cases, the plurality of W ³ and W ⁴ may be the same as or different from each other. ]
[7] Any of [1] to [6], wherein the content of the typical metal compound is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin and the photopolymerizable compound. The colored photosensitive resin composition described in 1.

[8] The colored photosensitive resin composition according to any one of [1] to [7], wherein the dye is a compound represented by the formula (1).

[In Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. The hydrogen atom is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , It may be substituted with —SO ₂ NH ₂ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . Represent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom.
a represents an integer of 0 or 1.
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and is contained in the saturated hydrocarbon group. —CH ₂ — may be replaced by —O—, —CO— or —NR ⁷ —.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and is contained in the saturated hydrocarbon group. —CH ₂ — may be replaced by —O— or —CO—.
R ⁸ and R ⁹ are each independently a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or -Q The hydrogen atom contained in the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group is substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ^6. The —CH ₂ — contained in the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced with —O—, —S—, —CO—, —NH— or —NR ⁶ —. It may be. R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring containing a 3- to 10-membered nitrogen atom, and the hydrogen atom contained in the heterocyclic ring is R ⁶ , —OH or —Q May be substituted.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 5 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group and the heterocyclic group is , —OH, R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶ or a halogen atom.
M represents a sodium atom or a potassium atom.
However, the number of + charges and the number of −charges of the compound represented by the formula (1) are the same. ]

[9] The colored photosensitive resin composition according to any one of [1] to [8], wherein the colorant is a colorant containing a pigment.
[10] The pigment is C.I. I. The colored photosensitive resin composition according to [9], which is a pigment containing CI Pigment Blue 15: 6.
[11] C.I. I. The colored photosensitive resin composition according to [10], wherein the mass ratio of the pigment containing Pigment Blue 15: 6 and the dye containing the compound represented by Formula (1) is 97: 3 to 50:50.
[12] A coating film formed by applying and drying the colored photosensitive resin composition according to any one of [1] to [11].
[13] A pattern formed by applying and drying the colored photosensitive resin composition according to any one of [1] to [11].
[14] A color filter comprising at least one selected from the group consisting of the coating film according to [12] and the pattern according to [13].

  According to the colored photosensitive resin composition of the present invention, a coating film excellent in contrast can be formed.

It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention.

Hereinafter, the present invention will be described in detail.
The colored photosensitive resin composition of the present invention contains a colorant (A).

The colorant (A) used in the colored curable resin composition of the present invention is a colorant containing a dye. It does not specifically limit as a dye contained in a coloring agent (A), A well-known dye can be used. Examples thereof include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes.
The dye species can be selected in accordance with the target spectrum.

Examples of the dyes include compounds classified as dyes by Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color dyeing company). 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 Blue 35, 37, 59, 67;
C. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. 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, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Violet 6B, 7, 9, 17, 19;
C. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109. In addition, C.I. I. As a direct dye, C.I. 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 Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. 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 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 violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

  Examples of the dye contained in the colorant (A) include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, squarylium dyes, and phthalocyanine dyes. Etc.

  Especially, as a dye which a coloring agent (A) contains, a xanthene dye is preferable and the dye containing the compound represented by following formula (1) is more preferable.

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

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. In addition, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and —CH ₂ — represents —O—, —CO—, or —NR ⁷ — (R ⁷ represents 1 carbon atom). Represents a saturated hydrocarbon group having 10 to 10 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — represents —O— or —CO It may be replaced with-.

-R ⁶ includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group Octyl group, 2-ethylhexyl group, cyclooctyl group, nonyl group, decanyl group, tricyclodecanyl group, methoxypropyl group, ethoxypropyl group, hexyloxypropyl group, 2-ethylhexyloxypropyl group, methoxyhexyl group, An ethoxypropyl group etc. are mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ and Q include a phenyl group and a naphthyl group.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO. _{3 H, -SO 3 M, -CO} 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NH 2, optionally substituted with -SO 2 NHR ⁸ or _-SO 2 ^NR 8 ^{R 9} Good.

R ⁶ represents the same meaning as described above.
R ⁸ and R ⁹ are each independently a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or — Q (Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 3 to 10 carbon atoms, and the hydrogen atoms contained therein are —OH, —R ⁶ , -OR ^6, represents an _{-NO 2,} -CH = CH _2, may be substituted by -CH = CHR ^6, or a halogen atom.).
In R ⁸ and R ⁹ , a hydrogen atom contained in a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ⁶ may be substituted, and —CH ₂ — may be —O—, —S—, —CO—, —NH— or It may be substituted with —NR ⁶ —.
R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring containing a 3- to 10-membered nitrogen atom. In this case, the hydrogen atom contained in the heterocyclic ring may be substituted with —R ⁶ , —OH or —Q, and M represents a sodium atom or a potassium atom.

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

-OR ⁶ includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, Examples include heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group and the like.

Examples of —CO ₂ R ⁶ include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxy Carbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl Group, decyloxycarbonyl group, tricyclodecanyloxycarbonyl group, methoxypropyloxycarbonyl group, ethoxypropoxy group Oxycarbonyl group, hexyloxy propyloxy group, 2-ethylhexyloxy propyloxy carbonyl group, and methoxy hexyloxy carbonyl group.

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

等が挙げられる。なお、上記の複素環は、上図に記載される結合手で、硫黄原子と結合する。 In —SO ₂ NR ⁸ R ⁹ , a heterocyclic ring containing a 3- to 10-membered nitrogen atom formed by combining R ⁸ and R ⁹ with each other

Etc. In addition, said heterocyclic ring couple | bonds with a sulfur atom with the bond described in the above figure.

等が挙げられる。なお、Ｑにおける複素環基の結合手は、任意の位置とすることができる。 As the monovalent heterocyclic group having 3 to 10 carbon atoms in Q,

Etc. The bond of the heterocyclic group in Q can be at any position.

—SO ₂ NHR ⁸ includes N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N— Isobutylsulfamoyl group, N-pentylsulfamoyl group, N-isopentylsulfamoyl group, N-neopentylsulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- Cyclohexylsulfamoyl group, N-heptylsulfamoyl group, N-cycloheptylsulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) ) Sulfamoyl group, N-cyclooctylsulfamoyl group, N-nonylsulfamoyl group, N Decanylsulfamoyl group, N-tricyclodecanylsulfamoyl group, N-methoxypropylsulfamoyl group, N-ethoxypropylsulfamoyl group, N-propoxypropylsulfamoyl group, N-isopropoxypropylsulfa Moyl group, N-hexyloxypropyl sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl group, N- (3-phenyl-1-methylpropyl) sulfamoyl group, etc. Is mentioned.

Furthermore, examples of —SO ₂ NHR ⁸ include groups represented by the following formulae.

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

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

In the above formula, X ³ represents the same meaning as described above.
In the above formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and a hydrogen atom contained in the alkyl group and the alkoxy group is a halogen atom. May be substituted.
Examples of the halogen atom for X ² include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 3 carbon atoms that may be substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a trifluoromethyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a methoxy group, an ethoxy group and a propoxy group.

Among them, as —SO ₂ NHR ⁸ , R ⁸ is a branched saturated aliphatic hydrocarbon group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, a phenyl group, carbon Those which are an aralkyl group having 8 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 2 to 8 carbon atoms and an aryl group, or an alkoxy group-containing saturated aliphatic hydrocarbon group or aryl group having 2 to 8 carbon atoms are preferable. Particularly preferred is a 2-ethylhexyl group.

Examples of —SO ₂ NR ⁸ R ⁹ include a group represented by the following formula.

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

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

Examples of the substituent for the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ in the formula (1) include an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, —SO ₃ R ⁶ or — SO ₂ NHR ⁸ is preferred.

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

In R ^{1 to} R ⁴ in the formula (1), at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is monovalent saturation having 1 to 4 carbon atoms. It is preferably a hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.
In addition, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms or an optionally substituted carbon number. 6-10 aromatic hydrocarbon groups are preferred, in particular at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is optionally substituted carbon A monovalent aromatic hydrocarbon group of several 6 to 10 is more preferable.

R ⁵ in the compound represented by the formula (1) is —SO ₃ —, —SO ₃ H, SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ^8. or an _-SO 2 ^NR 8 ^{R 9.}
In formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.

R ⁵ is preferably a carboxy group, an ethyloxycarbonyl group, a sulfo group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- (1,5-dimethylhexyl) sulfamoyl group, or N- (3-phenyl). -1-methylpropyl) sulfamoyl group and N-isopropoxypropylsulfamoyl group.

In formula (1), X represents a halogen atom, and a represents an integer of 0 or 1.
Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom and a bromine atom.

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

［式（１−１）中、Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子、−Ｒ^６又は炭素数６〜１０の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^６、−ＯＨ、−ＯＲ^６、−ＳＯ_３−、−ＳＯ_３Ｈ、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^６、−ＳＯ_３Ｒ^６、−ＳＯ_２ＮＨ_２、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２ＮＲ^８Ｒ^９で置換されていてもよい。
Ｒ^１５は、水素原子、−ＳＯ_３−、−ＳＯ_３Ｈ、−ＳＯ_２ＮＨ_２、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２ＮＲ^８Ｒ^９を表す。
Ｒ^１６は、−ＳＯ_３−、−ＳＯ_３Ｈ、−ＳＯ_２ＮＨ_２、−ＳＯ_２ＮＨＲ^８又は−ＳＯ_２ＮＲ^８Ｒ^９を表す。
Ｒ^６、Ｒ^８、Ｒ^９、ｍ、Ｘ及びａは、前記と同じ意味を表す。
ただし、式（１−１）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In Formula (1-1), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. hydrogen atom, a halogen _{^{atom, -R 6, -OH, -OR 6}} , -SO 3 -, - SO 3 H, -SO 3 Na, -CO 2 H, -CO 2 R 6, -SO 3 R 6, It may be substituted with —SO ₂ NH ₂ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen _{atom, -SO 3 -, - SO 3} H, -SO 2 NH 2, represents a -SO 2 NHR ⁸ or _-SO 2 ^NR 8 ^{R 9.}
R ¹⁶ _{is, -SO 3 -, - SO 3} H, -SO 2 NH 2, represents a -SO 2 NHR ⁸ or _-SO 2 ^NR 8 ^{R 9.}
R ⁶ , R ⁸ , R ⁹ , m, X and a represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-1) are the same. ]

［式（１−２）中、Ｒ^２１〜Ｒ^２４は、それぞれ独立に、水素原子、−Ｒ^２６又は炭素数６〜１０の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^２６、−ＯＨ、−ＯＲ^２６、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^２６、−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^２６又は−ＳＯ_２ＮＨＲ^２８で置換されていてもよい。
Ｒ^２５は、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^２６、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^２８を表す。
Ｒ^２６は、炭素数１〜１０の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、−ＯＲ^２７又はハロゲン原子で置換されていてもよい。
Ｒ^２７は、炭素数１〜１０の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^２８は、水素原子、−Ｒ^２６、−ＣＯ_２Ｒ^２６又は炭素数６〜１０の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、−Ｒ^２６又は−ＯＲ^２６で置換されていてもよい。
ｍ、Ｘ及びａは、前記と同じ意味を表す。
ただし、式（１−２）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In Formula (1-2), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, —R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. The hydrogen atom is a halogen atom, —R ²⁶ , —OH, —OR ²⁶ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H, —SO ₃ R ²⁶ or It may be substituted with —SO ₂ NHR ²⁸ .
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or —SO ₂ NHR ²⁸ .
R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OR ²⁷ or a halogen atom.
R ²⁷ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ²⁸ is a hydrogen ^atom, -R _26, an aromatic hydrocarbon group -CO ^{2 R 26} or a C 6-10, hydrogen atom contained in the aromatic hydrocarbon group, ^{-R 26} or -OR ²⁶ may be substituted.
m, X, and a represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-2) are the same. ]

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

［式（１−３）中、Ｒ^３１及びＲ^３２は、それぞれ独立に、フェニル基を表し、該フェニル基に含まれる水素原子は、ハロゲン原子、−Ｒ^２６、−ＯＲ^２６、−ＣＯ_２Ｒ^２６、−ＳＯ_３Ｒ^２６又は−ＳＯ_２ＮＨＲ^２８で置換されていてもよい。
Ｒ^３３は、−ＳＯ_３ ⁻又は−ＳＯ_２ＮＨＲ^２８を表す。
Ｒ^３４は、水素原子、−ＳＯ_３ ⁻又は−ＳＯ_２ＮＨＲ^２８を表す。
Ｒ^２６、Ｒ^２８、Ｘ及びａは、前記と同じ意味を表す。
ただし、式（１−３）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In Formula (1-3), R ³¹ and R ³² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group is a halogen atom, —R ²⁶ , —OR ²⁶ , —CO ₂ R ^26, may be substituted by _-SO 3 ^{R 26} or _-SO 2 ^{NHR 28.}
R ³³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ³⁴ represents a hydrogen atom, —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a have the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-3) are the same. ]

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

［式（１−４）中、Ｒ^４１及びＲ^４２は、それぞれ独立に、フェニル基を表し、該フェニル基に含まれる水素原子は、−Ｒ^２６又は−ＳＯ_２ＮＨＲ^２８で置換されていてもよい。
Ｒ^４３は、−ＳＯ_３ ⁻又は−ＳＯ_２ＮＨＲ^２８を表す。
Ｒ^２６、Ｒ^２８、Ｘ及びａは、前記と同じ意味を表す。
ただし、式（１−４）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In Formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group may be substituted with —R ²⁶ or —SO ₂ NHR ^28. Good.
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a have the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1-4) are the same. ]

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

［式（１ａ）中、Ｒ^５１及びＲ^５２は、それぞれ独立に、水素原子、−ＳＯ_３−、−ＳＯ_３Ｈ、−ＣＯ_２Ｈ又は−ＳＯ_２ＮＨＲ^５０を表す。Ｒ^５０は、２−エチルヘキシルを表す。Ｘ及びａは、上記と同じ意味を表す。
ただし、式（１ａ）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In formula (1a), R ⁵¹ and R ⁵² each independently represent a hydrogen atom, —SO ₃ —, —SO ₃ H, —CO ₂ H, or —SO ₂ NHR ⁵⁰ . R ⁵⁰ represents 2-ethylhexyl. X and a represent the same meaning as described above.
However, the number of + charges and the number of −charges of the compound represented by the formula (1a) are the same. ]

［式（１ｂ）中、Ｒ^５１は、上記と同じ意味を表す。ただし、式（１ｂ）で表される化合物の＋電荷数と−電荷数とが同一である。］

[In formula (1b), R ⁵¹ represents the same meaning as described above. However, the number of + charges and the number of −charges of the compound represented by the formula (1b) are the same. ]

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

［式（１ｂ−１）中、Ｒ^５１、Ｘ及びａは、上記と同じ意味を表す。ただし、式（１ｂ−１）で表される化合物の＋電荷数と−電荷数とが同一である。]

[In formula (1b-1), R ⁵¹ , X and a represent the same meaning as described above. However, the number of + charges and the number of −charges of the compound represented by the formula (1b-1) are the same. ]

[式（１ｃ）及び式（１ｄ）中、Ｒ^５３、Ｒ^５４及びＲ^５５は、それぞれ独立に、−ＳＯ_３−、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^５０を表す。Ｒ^５０は、２−エチルヘキシル基を表す。ただし、式（１ｃ）で表される化合物及び式（１ｄ）で表される化合物の＋電荷数と−電荷数とがそれぞれ同一である。]

[In Formula (1c) and Formula (1d), R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent —SO ₃ —, —SO ₃ Na or —SO ₂ NHR ⁵⁰ . R ⁵⁰ represents a 2-ethylhexyl group. However, the + charge number and the -charge number of the compound represented by the formula (1c) and the compound represented by the formula (1d) are the same. ]

[式（１ｅ）及び式（１ｆ）中、Ｒ^５６、Ｒ^５７及びＲ^５８は、それぞれ独立に、水素原子、−ＳＯ_３−、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^５０を表す。Ｒ^５０は、２−エチルヘキシル基を表す。ただし、式（１ｅ）で表される化合物及び式（１ｆ）で表される化合物の＋電荷数と−電荷数とがそれぞれ同一である。］

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

Specific examples of the compound represented by the formula (1a) to the formula (1f) include a compound obtained by sulfonamidating sulforhodamine B, —SO ₃ — of sulforhodamine B, or —SO ₃ H; I. Solvent Red 49, Rhodamine B, C.I. I. Acid Violet 102, C.I. I. A compound obtained by sulfonamidation of —SO ₃ — or —SO ₃ H of Acid Violet 102, C.I. I. Acid Red 289, C.I. I. And compounds obtained by sulfonamidating Acid Red 289 —SO ₃ — or —SO ₃ H. As the dye used in the colored photosensitive resin composition of the present invention, a compound represented by the formula (1e) or the formula (1f) is particularly preferable. I. Acid Red 289, C.I. I. A compound obtained by sulfonamidating Acid Red 289 —SO ₃ — or —SO ₃ H is preferred. In particular, a compound represented by the formula (AI) is preferable.

The compound represented by formula (1) is obtained by, for example, chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method, and converting the obtained dye or dye intermediate having —SO ₂ Cl into R ⁸ —NH. It can manufacture by making it react with the amine represented by ₂ . Moreover, it can manufacture by making the pigment | dye manufactured by the method of Unexamined-Japanese-Patent No. 3-78702 page 3 right upper column-lower left column react with an amine after chlorination like the above.

As the colorant (A), a dye may be selected according to the color of the target color filter, and a plurality of dyes may be combined and used.
When the colorant (A) includes a compound represented by the formula (1), the content of the compound represented by the formula (1) in the colorant (A) is 3 to 80 with respect to the colorant (A). It is preferable that it is mass%, Especially preferably, it is 3-70 mass%, More preferably, it is 3-50 mass%.

When the colorant (A) contains a dye different from the compound represented by the formula (1) and the compound represented by the formula (1), the compound represented by the formula (1) and the formula (1) The mixing ratio of the dye different from the compound to be formed is preferably in the following range by mass ratio.
Compound represented by formula (1): 1 to 99% by mass
Dyes different from the compound represented by the formula (1): 1 to 99% by mass
If the compounding ratio of the compound represented by the formula (1) and the dye represented by the formula (1) is in the above range, the desired spectrum can be obtained.

  Furthermore, it is preferable that content of dye is 0.5-60 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 0.7-50 mass%, More preferably, it is 1- 40% by mass. Here, solid content means the total amount of the component remove | excluding the solvent from the coloring photosensitive resin composition.

  Furthermore, the colorant (A) can contain a pigment in addition to the above dye.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. These pigments may be used alone or in admixture of two or more.

  If necessary, the pigment may be rosin treatment, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, a graft treatment on the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for 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.

  As the pigment dispersant, commercially available surfactants can be used, for example, silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. These surfactants can be used, and each can be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Materials Electronic Chemicals Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Sumitomo 3M Co., Ltd.), Asahi Guard (Asahi Glass Co., Ltd.), Surflon (AGC Seimi Chemical Co., Ltd.), Solsperse (Geneca Co., Ltd.), EFKA (CIBA Co.), Ajispur (Ajinomoto Fine Techno) Dispersbyk (by Big Chemie) And the like.

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

  The dye and the pigment can be used alone or in combination of two or more. Moreover, dye and a pigment can be mixed and used for arbitrary ratios.

The content of the dye in the colorant (A) is 1 to 100% by mass, preferably 3 to 95% by mass, and more preferably 5 to 80% by mass.
Content of the pigment in a coloring agent (A) is 0-99 mass%, Preferably it is 5-97 mass%, More preferably, it is 20-95 mass%.
When the content of the dye and the pigment is in the above-mentioned range, the desired spectrum can be obtained, and excellent heat resistance and light resistance tend to be combined, which is preferable.

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

  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. When the content of the colorant (A) is in the above range, the color density when the color filter is obtained is sufficient, and the resin can be contained in the composition in a required amount, so that the mechanical strength is sufficient. It is preferable that a simple pattern can be formed.

The colored photosensitive resin composition of the present invention contains a resin (B).
The resin (B) is preferably a resin that is soluble in a developer (particularly an alkali developer) used in the photolithography method, and more preferably an acidic functional group (such as a carboxy group, a phenolic hydroxyl group, or a sulfo group) ( More preferably, it is a resin having a carboxy group.
A preferred resin (B) includes at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; an ethylenically unsaturated bond, and the monomer (a) And a different monomer (x) (hereinafter abbreviated as “monomer (x)”); As the monomer (a) and the monomer (x), one type may be used alone, or two or more types may be used in combination.

As the monomer (a), for example,
(Meth) acrylic acid, crotonic acid, cinnamic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2 2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2 -Unsaturated monocarboxylic acids such as ene;
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, 1,4-cyclohexene dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid;
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);
Etc. Among these, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  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.

  The monomer (x) is preferably a monomer having an ethylenically unsaturated bond and a curable group, more preferably a monomer having an ethylenically unsaturated bond and a cyclic ether having 2 to 4 carbon atoms (b (Hereinafter abbreviated as “monomer (b)”). If a resin having a monomer having a curable group is used as the resin (B), the reliability of the resulting colored pattern (heat resistance, light resistance, solvent resistance, mechanical properties, etc.) tends to improve. Yes, it is preferable.

  The monomer (b) having an ethylenically unsaturated bond and a cyclic ether having 2 to 4 carbon atoms may be used alone or in combination of two or more. As the monomer (b), a monomer (b1) having an ethylenically unsaturated bond and an oxirane ring, a monomer (b2) having an ethylenically unsaturated bond and an oxetane ring, and an ethylenically unsaturated bond and And a monomer (b3) having a tetrahydrofuran ring. Among these, the monomer (b1) having an ethylenically unsaturated bond and an oxirane ring and the monomer (b2) having an ethylenically unsaturated bond and an oxetane ring are preferable, and have an ethylenically unsaturated bond and an oxirane ring. The monomer (b1) is more preferable.

  As the monomer (b1) having an ethylenically unsaturated bond and an oxirane ring, a monomer (b1-1) having an ethylenically unsaturated bond and a structure obtained by epoxidizing an alkene (that is, a monocyclic oxirane ring) ( (Hereinafter abbreviated as “monomer (b1-1)”), and a structure obtained by epoxidizing an ethylenically unsaturated bond and a cycloalkene (that is, a structure in which an aliphatic hydrocarbon ring and an oxirane ring are condensed). Monomer (b1-2) (hereinafter abbreviated as “monomer (b1-2)”). Among these, the monomer (b1-2) is preferable. Examples of the cycloalkene include monocyclic cycloalkenes such as cyclopentene, cyclohexene and cycloheptene; and bridged cycloalkenes such as norbornene, dicyclopentene and tricyclodecene.

  The ethylenically unsaturated bond preferably has an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an allyloxy group, or a styryl group, and more preferably has an acryloyloxy group or a methacryloyloxy group. .

  Examples of the monomer (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples thereof include a compound represented by formula (b1-3).

In formula (b1-1a), R ^{60 to} R ⁶² each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. m1 represents an integer of 1 to 5.

  Examples of the monomer (b1-1a) include 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- Squirrel (glycidyloxy) styrene, and 2,4,6-tris (glycidyloxy-methyl) styrene and the like.

  Examples of the monomer (b1-2) include 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 2,3-epoxycyclohexylmethyl ( (Meth) acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries) Etc.).

  Among the monomers (b1-2), a monomer (b1-3) having a structure obtained by epoxidizing an ethylenically unsaturated bond and a bridged ring cycloalkene (hereinafter referred to as “monomer (b1-3)”. ) "), For example, epoxy norbornyl (meth) acrylate {for example, 3,4-epoxynorbornyl (meth) acrylate}, a compound represented by formula (b1-3a), and formula ( and a compound represented by b1-3b).

In formulas (b1-3a) and (b1-3b), R ^b1 represents a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and is included in the saturated aliphatic hydrocarbon group. The hydrogen atom may be substituted with a hydroxy group.
L ¹ represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and —CH ₂ — of the saturated aliphatic hydrocarbon group is —O—, —S— or —NR ^b2. -May be replaced by-, and R ^b2 represents a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Examples of the saturated aliphatic hydrocarbon group which may be substituted with the hydroxy group of R ^b1 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hydroxymethyl Group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl Group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like. R ¹ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the divalent saturated aliphatic hydrocarbon group that may be substituted with L ¹ —O—, —S—, —NR ^b2 — or the like include a methylene group, an ethylene group, a propanediyl group, a methyleneoxy group (— CH ₂ —O—), ethyleneoxy group {— (CH ₂ ) ₂ —O—}, propanediyloxy group {— (CH ₂ ) ₃ —O— etc.}, methylenesulfanediyl group (—CH ₂ —S) -), ethylene sulfanediyl group _{{- (CH 2) 2 -S-} }, propanediyl sulfanediyl group {- (CH _{2) 3} -S-, etc.}, Mechiren'imino group (-CH ₂ -NH-) , Ethyleneimino group {— (CH ₂ ) ₂ —NH—}, propanediylimino group {— (CH ₂ ) ₃ —NH— etc.} and the like. L ¹ is preferably a single bond, a methylene group, an ethylene group, a methyleneoxy group, an ethyleneoxy group, an ethylenesulfanediyl group, or an ethyleneimino group, and more preferably a single bond or an ethyleneoxy group.

  The compound represented by the formula (b1-3a) and the compound represented by the formula (b1-3b) may be used singly or in combination of two or more. Further, a mixture of a compound represented by the formula (b1-3a) and a compound represented by the formula (b1-3b) may be used. When these mixtures are used, the molar ratio of the compound represented by the formula (b1-3a): the compound represented by the formula (b1-3b) is preferably 5:95 to 95: 5, more preferably 10 : 90 to 90:10, more preferably 20:80 to 80:20.

  Of the compounds represented by formula (b1-3a), formula (b1-1-1) to formula (b1-1-15) are preferable. Among these, monomer (b1-1-1), monomer (b1-1-3), monomer (b1-1-5), monomer (b1-1-7), single amount Body (b1-1-9) and monomer (b1-1-11) to monomer (b1-1-15) are more preferable, monomer (b1-1-1), monomer ( More preferred are b1-1-7), monomer (b1-1-9), and monomer (b1-1-15).

  The compound represented by Formula (b1-3b) is preferably Formula (b1-2-1) to Formula (b1-2-15). Among these, monomer (b1-2-1), monomer (b1-2-3), monomer (b1-2-5), monomer (b1-2-7), single amount Body (b1-2-9) and monomer (b1-2-11) to monomer (b1-2-15) are more preferable, and monomer (b1-2-1), monomer ( More preferred are b1-2-7), monomer (b1-2-9), and monomer (b1-2-15).

  Examples of the monomer (b2) having an ethylenically unsaturated bond and an oxetane ring include 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, and 3-ethyl-3. -(Meth) acryloxymethyloxetane, 3-methyl-3- [1- (meth) acryloxy] methyloxetane, 3-ethyl-3- [1- (meth) acryloxy] methyloxetane, 3-methyl-3- [ 1- (meth) acryloxy] ethyl oxetane, 3-ethyl-3- [1- (meth) acryloxy] ethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- ( (Meth) acryloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyl oxetane, 3 Methyl-3- (meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) ) Acryloxyethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloxyethyl oxetane, 3- (meth) acryloxy oxetane, and the like. Among these, 3-ethyl-3- (meth) acryloxymethyl oxetane is preferable.

  Examples of the monomer (b3) having an ethylenically unsaturated bond and a tetrahydrofuran ring include tetrahydrofurfuryl (meth) acrylate, tetrahydrofurylmethoxyethyl (meth) acrylate, tetrahydrofurylmethoxypropyl (meth) acrylate, and the like. .

  The monomer (x) may contain a monomer (c) different from the monomer (a) and the monomer (b). Examples of the monomer (c) include carboxylic acid esters having an ethylenically unsaturated bond, amides having an ethylenically unsaturated bond, and a polymerizable unsaturated bond (particularly an ethylenically unsaturated bond) in the side chain. Aromatic compounds, substituted vinyl compounds, N-substituted maleimides, dienes, polycyclic unsaturated compounds, and the like. A monomer (c) may be used individually by 1 type, and may use 2 or more types together.

As the monomer (c), more specifically,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl ( Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (sometimes referred to by the common name “dicyclopentanyl (meth) acrylate” in the art) 4-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, 5-tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate , Phenyl (meth) acrylate, aminoethyl (meth) acrylate, diethyl maleate, fumaric acid Ethyl, carboxylic acid esters having an ethylenically unsaturated bond such as itaconic acid diethyl;
Amides having an ethylenically unsaturated bond such as dimethyl (meth) acrylamide and isopropyl (meth) acrylamide;
An aromatic compound having a polymerizable unsaturated bond in the side chain, such as styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloro (meth) acrylonitrile;
Halogenated vinyl compounds such as chloroethylene, dichloroethylene, trichloroethylene, fluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene;
N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide;
Dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene;
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 [2.2 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-cyclohexyloxycarbonylbicyclo [2] 2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2 -Polycyclic unsaturated compounds such as ene;
Etc.

Among monomers (c), benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, styrene, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

  As the monomer (x), only one of the monomer (b) and the monomer (c) may be used, or both of them may be used. The monomer (x) preferably contains the monomer (b). That is, the monomer (x) is preferably only the monomer (b) or both the monomer (b) and the monomer (c), more preferably only the monomer (b). . If the copolymer containing the monomer (b) is used, the heat resistance, light resistance, solvent resistance and mechanical properties of the coating film and pattern are improved.

  When the resin (B) is a copolymer of the monomer (a) and the monomer (b), the structural unit derived from the monomer (a) in all the structural units of the copolymer is: Preferably it is 2-98 mol%, More preferably, it is 15-60 mol%, The structural unit derived from a monomer (b) becomes like this. Preferably it is 2-98 mol%, More preferably, it is 40-85 mol%. . If the ratio of the monomer (a) to the monomer (b) is within the above preferred range, the storage stability, heat resistance and mechanical strength tend to be good, and within the above preferred range. If present, the developability, the remaining film rate and the solvent resistance are further improved.

  When the resin (B) is a copolymer of the monomer (a) and the monomer (c), the structural unit derived from the monomer (a) among all the structural units of the copolymer is: Preferably it is 2 to 98 mol%, more preferably 15 to 60 mol%, and the structural unit derived from the monomer (c) is preferably 2 to 98 mol%, more preferably 40 to 85 mol%. . If the ratio of the monomer (a) and the monomer (c) is within the above preferred range, the storage stability and heat resistance tend to be good, and if within the above preferred range, Further, the developability and the remaining film rate are improved.

  When the resin (B) is a copolymer of the monomer (a), the monomer (b), and the monomer (c), in all the structural units of the copolymer, the monomer (a) The derived structural unit is preferably 2-97 mol%, more preferably 20-80 mol%, and the structural unit derived from the monomer (b) is preferably 2-97 mol%, more preferably 10 The structural unit derived from the monomer (c) is preferably 1 to 96 mol%, more preferably 10 to 70 mol%. If the ratio of the monomer (a) to the monomer (c) is within the above preferred range, the storage stability, heat resistance and mechanical strength tend to be good, and within the above preferred range. For example, the developability, the remaining film rate, and the solvent resistance are further improved.

  Resin (B) 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 by polymerizing monomers with reference to the literature cited in the above. More specifically, a predetermined amount of monomer (a), monomer (b) and / or monomer (c), a polymerization initiator and a solvent are charged into a reaction vessel, and in the absence of nitrogen-substituted oxygen. The copolymer can be produced by stirring, heating and keeping warm. What is necessary is just to adjust suitably the preparation method and reaction temperature of this copolymerization, considering the production equipment, the calorific value by superposition | polymerization, etc.

  For the obtained copolymer, the solution after the reaction may be used as it is. In particular, if the solvent (G) described later is used as the polymerization solvent, it can be used as it is in the resin composition without removing the solvent from the copolymer solution after polymerization, and the production process can be simplified. Further, the copolymer solution may be concentrated or diluted. Further, a copolymer taken out as a solid (powder) by a method such as reprecipitation may be used.

  The resin (B) may further contain a structural unit represented by the formula (d1) or the formula (d2). If the resin (B) containing a structural unit is used, pattern adhesion, solvent resistance and sensitivity can be improved.

In formula (d1) and formula (d2), R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably a hydrogen atom or a methyl group).

  The structural unit represented by the formula (d1) is derived from the monomer (a) after copolymerizing the monomer (a) and the monomer (b) and / or the monomer (c). A monomer represented by the formula (b1-4) is added to a carboxy group or a carbonyloxycarbonyl group (carboxylic anhydride structure), for example, in the same manner as described in JP-A-2005-189574. Can be formed. The structural unit represented by the formula (d2) can be formed using the monomer represented by the formula (b1-4) in the same manner as described above.

［式（ｂ１−４）又は式（ｂ１−５）中、Ｒ^６５は前記と同じ意味である。］

[In Formula (b1-4) or Formula (b1-5), R ⁶⁵ has the same meaning as described above. ]

The acid value of the resin (B) is preferably 50 to 150 mgKOH / g, more preferably 60 to 135 mgKOH / g, and still more preferably 70 to 135 mgKOH / g. If it is this range, the solubility with respect to a developing solution will improve, and it will become easy to melt | dissolve an unexposed part.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acidic group such as a carboxy group, and is usually determined by titration using an aqueous potassium hydroxide solution. Can be sought.

The weight average molecular weight of the resin (B) is preferably 2,000 to 100,000 (more preferably 2,000 to 50,000, still more preferably 3,000 to 30,000).
If it is this range, the applicability | paintability of a composition will be favorable and there exists a tendency for a high developing speed to be obtained, maintaining the residual film rate at the time of image development. The weight average molecular weight is determined by gel permeation chromatography using polystyrene as a standard.

  The molecular weight distribution {namely, weight average molecular weight (Mw) / number average molecular weight (Mn)} of the resin (B) is preferably 1.1 to 6.0 (more preferably 1.2 to 4.0). Within this range, the developability tends to be excellent.

  The content of the resin (B) is preferably 10 to 35% by mass (more preferably 15 to 30% by mass) with respect to the solid content of the composition; of the resin (B) and the polymerizable compound (B) Preferably it is 30-85 mass% (more preferably 35-75 mass%, still more preferably 40-65 mass%) with respect to the total amount. When the content of the resin (B) is within the above range, the solubility in the developer is sufficient, and there is a tendency that development residues are hardly generated on the substrate in the non-exposed part (non-pixel part). Further, the film thickness of the exposed portion (pixel portion) hardly occurs during development, and the non-exposed portion (non-pixel portion) tends to be easily removed, and the resolution and the remaining film ratio tend to be improved.

  In the present specification, the “solid content of the composition” refers to “the total of each component of the composition excluding the solvent”. This solid content can be measured by known means such as gas chromatography or liquid chromatography.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light. Examples thereof include compounds having a saturated bond as a polymerizable group. Especially, as a photopolymerizable compound (C), the compound which has a (meth) acryloyl group is preferable, and the compound which has a 3 or more (meth) acryloyl group is more preferable.

  The photopolymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate and the like, and dipentaerythritol hexaacrylate is preferable. You may use a photopolymerizable compound (C) individually or in combination of 2 or more types.

  The content of the photopolymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably based on the solid content of the colored photosensitive resin composition. 17-55 mass%. When the content of the photopolymerizable compound (C) is in the above range, 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 improved. It tends to be preferable.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). As a photoinitiator (D), an active radical generator, an acid generator, etc. are mentioned, for example.
An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include alkylphenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds. Of these, oxime compounds are preferable in terms of sensitivity.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one. , Benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [ An oligomer of 4- (1-methylvinyl) phenyl] propan-1-one and the like are preferable, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like are preferable.

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

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6 Such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyl oxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy. -1- (4-phenylsulfanylphenyl) octane-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-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole- 3-yl] ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (manufactured by Ciba Japan), and N-1919 (manufactured by ADEKA) may be used.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl. -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. may be used. it can.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-
Onium salts such as acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitro Examples thereof include benzyl tosylate and benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical, and for example, a triazine compound is also used as an acid generator.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass of the total amount of the resin (B) and the photopolymerizable compound (C). ˜20 parts by mass. When the content of the photopolymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity tends to be improved.

  Furthermore, the colored photosensitive resin composition of the present invention may contain a photopolymerization initiation assistant (E). The photopolymerization initiation assistant (E) is usually used in combination with the photopolymerization initiator (D), and a compound used for promoting the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator, Or it is a sensitizer.

  Examples of the photopolymerization initiation assistant (E) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.

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

  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-. Examples include dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

  The photopolymerization initiation assistant (E) may be used alone or in combination of two or more. In addition, as the photopolymerization initiation aid (E), for example, a commercial product such as a trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (E) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylke / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiator adjuvant (E), the usage-amount is preferably 0.01-10 mol per 1 mol of photoinitiators (D), More preferably, it is 0.01-5 mol. .

The colored photosensitive resin composition of the present invention contains a typical metal compound (F). A typical metal compound refers to a compound containing an atom of an element in which a simple element is metallic among typical elements (hereinafter sometimes referred to as “typical metal atom”). The typical metal compound (F) contains a carbon atom, and the maximum value of the molar extinction coefficient in the visible light region of the typical metal compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the dye. By containing the typical metal compound, the contrast, heat resistance and light resistance of the coating film can be improved.
Examples of the typical metal compound (F) include typical metal complexes and typical metal salts, and those that are soluble in an organic solvent are preferable.

The maximum value of the molar extinction coefficient ε in the visible light region (wavelength 380 nm to 780 nm) was adjusted by diluting 0.1 g of a typical metal compound (F) to 0.250 L with ethyl lactate, and the solution was subjected to UV-visible spectroscopy. The absorption spectrum in the visible light region is measured with a photometer and is calculated by using Lambert-Beer's law.
The maximum value of the molar extinction coefficient ε in the visible light region of the typical metal compound (F) is smaller than the maximum value of the molar extinction coefficient ε in the visible light region of the dye contained in the colored photosensitive resin composition of the present invention, preferably It is 0 or more and 1000 or less, more preferably 0 or more and 500 or less, further preferably 0 or more and 100 or less, still more preferably 20 or more and 80 or less, and particularly preferably 30 or more and 60 or less.
It is preferable that the maximum value of the molar extinction coefficient ε in the visible light region is 1000 or less because the brightness of the coating film tends to increase.

As typical metal atoms contained in the typical metal compound (F), for example, group 1A (alkali metal), group 2A (alkaline earth metal), group 2B (zinc group), group 3B (boron group) of the periodic table, Atoms of metal elements included in Group 4B (carbon group) and Group 5B (nitrogen group) can be given.
Specifically, for example, beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), rubidium (Rb), strontium (Sr), cadmium (Cd) , Indium (In), tin (Sn), cesium (Cs), barium (Ba), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), francium (Fr), radium (Ra) And the like.
Among them, magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), rubidium (Rb), strontium (Sr), indium (In), cesium (Cs), barium (Ba) Atoms of aluminum (Al), zinc (Zn), indium (In), and barium (Ba) are more preferable, and atoms of aluminum (Al), zinc (Zn), and indium (In) are more preferable.
By using the typical metal compound (F) for the colored photosensitive resin composition, the contrast, heat resistance and light resistance of the coating film obtained from the colored photosensitive resin composition tend to be high, which is preferable.

Further, the typical metal compound (F) is preferably a compound containing a typical metal atom and at least one group selected from the group consisting of —C (═O) — and —C (═S) —. At least one selected from the group consisting of a compound represented by F1), a compound represented by formula (F2), and hydrates thereof is more preferred.
When the typical metal compound (F) is the above-mentioned compound, the coating film obtained from the colored photosensitive resin composition tends to have high contrast, heat resistance and light resistance, and solubility in organic solvents. Tends to be improved, which is preferable.

［式（Ｆ１）及び式（Ｆ２）中、Ｗ^１及びＷ^２は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｗ^３及びＷ^４は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｍ^１及びＭ^２は、典型金属原子を表す。
ｘ及びｙは、１〜３の整数を表し、ｘが２以上の整数である場合、複数のＷ^１及びＷ^２は互いに同一であっても異なっていてもよく、ｙが２以上の整数である場合、複数のＷ^３及びＷ^４は互いに同一であっても異なっていてもよい。］

[In Formula (F1) and Formula (F2), W ¹ and W ² are each independently a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic carbon group having 6 to 10 carbon atoms. Represents a hydrogen group, and a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. .
M ¹ and M ² represent typical metal atoms.
x and y represent an integer of 1 to 3, and when x is an integer of 2 or more, the plurality of W ¹ and W ² may be the same or different from each other, and y is an integer of 2 or more. In some cases, the plurality of W ³ and W ⁴ may be the same as or different from each other. ]

W ¹ and W ² are each a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a hydroxy group, or carbon atoms in which a hydrogen atom may be substituted with a hydroxy group. To 10 monovalent aromatic hydrocarbon groups.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which the hydrogen atom may be substituted with a hydroxy group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a sec-butyl group. Tert-butyl group, pentyl group, hexyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy- Examples include 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, preferably ethyl group, butyl Group, 2-hydroxyethyl group.

  Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom may be substituted with a hydroxy group include a phenyl group, a toluyl group, a xylyl group, a benzyl group, a propylphenyl group, and a butylphenyl group. , Hydroxyphenyl group, hydroxymethylphenyl group and the like, preferably phenyl group and benzyl group.

W ³ and W ⁴ are monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms in which hydrogen atoms may be substituted with halogen atoms.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a fluorine atom.

  Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom may be substituted with a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a sec-butyl group. Tert-butyl group, pentyl group, hexyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, chloromethyl group, chloroethyl group, dichloroethyl group, chloropropyl group, chlorobutyl group, bromobutyl group And an iodobutyl group, and a methyl group, a tert-butyl group, and a trifluoromethyl group are preferable.

Preferable typical metal compounds (F) include, for example, tris (2,4-pentandionato) aluminum (III), tris (trifluoro-2,4-pentandionato) aluminum (III), tris ( Aluminum compounds such as 2-hydroxypropanoic acid) aluminum and bis (2-ethylhexanoato) hydroxyaluminum:
Bis (2-sulfanylpyridine-N-oxide) zinc, bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc, bis (N, N-dimethyldithiocarbamate) zinc, bis (N, N-diethyl) Dithiocarbamate) zinc, bis (N, N-dibutyldithiocarbamate) zinc, bis (N-ethyl-N-phenyldithiocarbamate) zinc, bis (N, N-dibenzyldithiocarbamate) zinc, bis (thiocyanate) zinc And zinc compounds such as bis (2-hydroxypropanoic acid) zinc:
Tris (2,4-pentanedionato) indium (III), tris (2,2,6,6-tetramethyl-3,5-heptaneedionato) indium (III), tris (trifluoro-2,4-pentanedio Nato) Indium compounds such as indium (III):
Bis (2,4-pentanedionato) barium, bis (hexafluoro-2,4-pentandedionato) barium, bis (2,2,6,6-tetramethyl-3,5-heptanedionato) barium, bis ( Barium compounds such as 2-hydroxypropanoic acid) barium, bis (thiocyanate) barium, bis (stearic acid) barium, barium arsenate, barium oxalate, etc .:
And hydrates of the above compounds, preferably bis (N, N-dibutyldithiocarbamate) zinc, bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc, tris (2 , 4-pentanedionato) indium (III), tris (2,4-pentandionato) aluminum (III) or a hydrate thereof.
The use of the above-mentioned typical metal compound is preferable because the solubility in an organic solvent and the contrast of the coating film tend to be high.

  The content of the typical metal compound (F) is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the photopolymerizable compound (C), and 0.5 mass. The amount is more preferably no less than 15 parts by mass and even more preferably no greater than 1 part by mass and no greater than 10 parts by mass. When the content of the typical metal compound is in the above range, the contrast of the coating film tends to be high while maintaining good developability, which is preferable.

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

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

Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. Etc.
Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2 -Methyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxy Examples include butyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

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

Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use these in combination.
Furthermore, you may use a solvent (G) individually or in combination of 2 or more types.

  Content of the solvent (G) in a colored photosensitive resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-90 mass%. When the content of the solvent (G) is in the above range, the flatness at the time of application is good, and when the color filter is formed, the color density is not insufficient, and the display characteristics tend to be good. preferable.

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

  Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (trade name) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC) ), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass) Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (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.

  Content of surfactant (H) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 0.00001-0.1 mass%, More preferably, it is 0.00005-0.01 mass%. It is. When the content of the surfactant (H) is in the above range, the flatness tends to be good, which is preferable. However, the content of the surfactant (H) does not include the content of the pigment dispersant.

  As a method for forming a color filter pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, on a substrate). And a colored layer is formed by removing volatile components such as a solvent, and exposing the colored layer through a photomask and developing the layer. (That is, a photolithographic method) and a method using an inkjet apparatus that does not require a photolithographic method. In the above photolithographic method, the coating film of the present invention can be obtained by not using a photomask and / or not developing during exposure.

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

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

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

  Subsequently, the colored photosensitive resin composition layer 23 </ b> A is dried by performing heat treatment at a temperature in the range of 30 to 120 ° C., preferably 60 to 110 ° C. In order to dry the colored photosensitive composition layer 23A, vacuum drying may be performed in combination with heat drying. Next, the colored photosensitive resin composition layer 23A is irradiated with ultraviolet rays through a photomask (not shown), and unnecessary portions (unexposed portions) are selectively removed with a developing solution, so that After forming a connection hole (contact hole) 201 reaching the drain region of the crystalline silicon film 22c, it is washed with water. Thereafter, in order to reflow (reflow) the colored photosensitive resin composition layer 23A and to cure the curable component contained in the colored photosensitive composition layer 23A, a temperature in the range of 100 to 300 ° C., for example, 150 Heat at ~ 230 ° C.

  Thereby, the colored photosensitive resin composition layer 23A becomes the color filter layer 23 including the red filter 23a, the green filter 23b, and the blue filter 23c corresponding to each pixel column (see FIG. 2). A region between the filters of the color filter layer 23 is a mixed region of adjacent colors. Since this region is a light-shielding region facing the signal line 27, there is no particular problem in quality. Note that the region between the filters may not be colored.

  Subsequently, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 μm, for example, is formed so as to cover the color filter layer 23 by, for example, a spin coating method. Next, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the regions corresponding to the connection holes 201 and unnecessary portions are selectively removed with a developer, thereby polycrystal After a connection hole (contact hole) 202 reaching the drain region of the silicon film 22c is formed, it is washed with water. Thereafter, in order to reflow (reflow) the photosensitive resin film 29, heating is performed at a temperature in the range of 100 to 300 ° C., for example, 200 ° C. Next, in order to remove residues such as dyes and organic substances deposited in the contact hole 202, etching with oxygen plasma is performed, and further, for example, etching with dilute hydrofluoric acid is performed to remove the oxide film formed by oxygen plasma. To do.

  Next, a transparent conductive material, for example, ITO (Indium-Tin Oxide) is formed on the photosensitive resin film 29 by sputtering, for example, and this ITO film is formed by photolithography and etching. Patterning is performed to form a transparent pixel electrode 24 (see FIG. 3). The pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on a device to be manufactured. After that, after forming an alignment film by a known method, a liquid crystal display device can be manufactured by bonding the drive substrate and the counter substrate.

  According to the colored photosensitive resin composition of this invention, it becomes possible to obtain the coating film, pattern, and color filter excellent in contrast.

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

[Synthesis Example 1]
(Synthesis example of the compound represented by the formula (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 filtered off, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and a mixture of a compound represented by formula (A1-a) and a compound represented by formula (A1-b) ( 11.3 parts of dye A1) (mixture of compounds represented by formula (A1-1) to formula (A1-8)) were obtained.

［式（Ａ１−ａ）及び式（Ａ１−ｂ）中、Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３−、−ＳＯ_３Ｈ又はＮ−（２−エチルヘキシル）スルファモイル基を表す。］

[In formula (A1-a) and formula (A1-b), R ^g , R ^h and R ⁱ are each independently a hydrogen atom, —SO ₃ —, —SO ₃ H or N- (2-ethylhexyl). Represents a sulfamoyl group. ]

[Synthesis Example 2]
(Resin synthesis)
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (B1-1-1) and a formula (B1-2) -1) 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 3-methoxybutyl acetate, and the solution is added to a dropping funnel. Was added dropwise to the flask kept at 70 ° C. over 4 hours. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. 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 1.3 × 10 ⁴ , the molecular weight distribution was 2.5, and the solid content. A resin solution 1 having 33% by mass and a solution acid value of 34 mg-KOH / g was obtained.

The polystyrene-converted weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the resin obtained in Synthesis Example 2 were measured using the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-1, A-2500, A-500
(Manufactured by Tosoh Corporation)

Examples 1-4
(Preparation of colored photosensitive resin composition 1)
(A) Colorant: C.I. I. Pigment Blue 15: 6 (PB15: 6) 33 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
(A) Colorant: Dye A1 5 parts (B) Resin: Resin solution 1 150 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 50 parts (D ) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by Ciba Japan) 15 parts (E) Solvent: ethyl lactate 289 Part (F) Typical metal compounds: Typical metal compounds described in Table 2
A colored photosensitive resin composition was obtained by mixing a mass part corresponding to 1.5 molar equivalents with respect to the dye A1.
The molecular weight of the formula (A1-1) was used as the molecular weight of the dye A1.

[Calculation of molar extinction coefficient]
In a measuring flask, 0.1 g of each compound shown in Table 1 was weighed and then diluted to 0.250 L with ethyl lactate. With respect to this solution, an absorption spectrum was measured with an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), and the visible light region (Lambert-Beer's law was used). The maximum value of the molar extinction coefficient ε at 380 nm to 780 nm was calculated. The results are shown in Table 1.

  It can be seen that the maximum molar extinction coefficient of any typical metal compound is smaller than the maximum molar extinction coefficient of the dye.

[Formation of pattern]
On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), a colored photosensitive resin composition was applied by spin coating so that the chromaticity By after post-baking was 0.085, and then in a clean oven And prebaking at 100 ° C. for 3 minutes. After standing to cool, the substrate coated with the colored photosensitive resin composition 1 was exposed to 150 mJ / cm ^{2 in} an air atmosphere (365 nm standard) using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). And irradiated with light. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. Was post-baked for 20 minutes to obtain a pattern.

[Chromaticity evaluation]
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates (Bx, By in the XYZ color system of CIE using the C light source. ) And brightness were measured. If the brightness is 9.2 or higher, it can be determined that the brightness is good. The results are shown in Table 2.

[Contrast evaluation]
The same operation as described above was performed except that a photomask was not used at the time of light irradiation, and a coating film was prepared so that the chromaticity By after post-baking was 0.085. About the obtained coating film, contrast was measured using a contrast meter (color difference meter BM-5A; manufactured by Topcon Corporation, light source; F-10, polarizing film; manufactured by Keyakizaka Electric Co., Ltd.) with a blank value of 30000. did. If the contrast is 17000 or higher, it can be determined that the contrast is good. The results are shown in Table 2.

[Heat resistance evaluation]
The obtained coating film was measured for xy chromaticity coordinates (Bx, By) and brightness before and after heating in a clean oven at 230 ° C. for 2 hours, and a color difference ΔEab * before and after heating was calculated. If ΔEab * is 5 or less, it can be determined that the heat resistance is good. The results are shown in Table 2. Moreover, if the heat resistance of a coating film is favorable, it will show favorable heat resistance also in a pattern similarly to a coating film.

(Light resistance evaluation)
The obtained coating film was measured for xy chromaticity coordinates (Bx, By) and brightness before and after the treatment for 48 hours in a light resistance tester (Suntest CPS +; manufactured by Toyo Seiki Seisakusho). The color difference ΔEab * of was calculated. If ΔEab * is 5 or less, it can be determined that the light resistance is good. The results are shown in Table 2. Moreover, if the light resistance of a coating film is favorable, it will show favorable light resistance also in a pattern similarly to a coating film.

  High contrast was confirmed in the coating films formed using the colored photosensitive resin compositions of Examples 1 to 4. Moreover, since the brightness was high and ΔEab * was 5 or less, it was confirmed that the heat resistance and light resistance were also good.

According to the colored photosensitive resin composition of the present invention, a coating film having a high contrast can be obtained.

21 Glass substrate 22 TFT (switching element)
23 Color filter layer 23A Colored photosensitive resin composition layer (color filter film)
23a Red filter 23b Green filter 23c Blue filter 24 Pixel electrode 27 Signal line 29 Photosensitive resin film (protective film)
201, 202 connection hole

Claims (9)

Including colorants, resins, photopolymerizable compounds, photopolymerization initiators, solvents and typical metal compounds,
The colorant is a colorant containing a xanthene dye,
A colored photosensitive resin composition, wherein the typical metal compound is at least one selected from the group consisting of a compound represented by formula (F1), a compound represented by formula (F2), and a hydrate thereof.

[In Formula (F1) and Formula (F2), W ¹ and W ² are each independently a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic carbon group having 6 to 10 carbon atoms. Represents a hydrogen group, and a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. .
M ¹ and M ² represent at least one selected from the group consisting of aluminum, gallium, zinc and indium.
x and y represent an integer of 1 to 3, and when x is an integer of 2 or more, the plurality of W ¹ and W ² may be the same or different from each other, and y is an integer of 2 or more. In some cases, the plurality of W ³ and W ⁴ may be the same as or different from each other. ] The colored photosensitive resin composition according to claim 1 , wherein the content of the typical metal compound is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin and the photopolymerizable compound. The colored photosensitive resin composition according to claim 1 or 2, wherein the dye is a compound represented by the formula (1).

[In Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and are included in the aromatic hydrocarbon group. The hydrogen atom is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , It may be substituted with —SO ₂ NH ₂ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . Represent.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom.
a represents an integer of 0 or 1.
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and is contained in the saturated hydrocarbon group. —CH ₂ — may be replaced by —O—, —CO— or —NR ⁷ —.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and is contained in the saturated hydrocarbon group. —CH ₂ — may be replaced by —O— or —CO—.
R ⁸ and R ⁹ are each independently a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or -Q The hydrogen atom contained in the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group is substituted with —OH, a halogen atom, —Q, —CH═CH ₂ or —CH═CHR ^6. The —CH ₂ — contained in the saturated aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced with —O—, —S—, —CO—, —NH— or —NR ⁶ —. It may be. R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring containing a 3- to 10-membered nitrogen atom, and the hydrogen atom contained in the heterocyclic ring is R ⁶ , —OH or —Q May be substituted.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent heterocyclic group having 5 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group and the heterocyclic group is , —OH, R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶ or a halogen atom.
M represents a sodium atom or a potassium atom.
However, the number of + charges and the number of −charges of the compound represented by the formula (1) are the same. ] Colorants, colored photosensitive resin composition according to any one of claims 1 to 3, which is a colorant comprising a pigment. The pigment is C.I. I. The colored photosensitive resin composition according to claim 4, which is a pigment containing CI Pigment Blue 15: 6. C. I. The colored photosensitive resin composition according to claim 5 , wherein the mass ratio of the pigment containing Pigment Blue 15: 6 to the dye containing the compound represented by Formula (1) is 97: 3 to 50:50. The coating film formed by apply | coating the colored photosensitive resin composition in any one of Claims 1-6 , and drying. The pattern formed by apply | coating the colored photosensitive resin composition in any one of Claims 1-6 , and drying. A color filter containing at least one selected from the group consisting of coating and pattern of claim 8 according to claim 7 wherein.

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