JP2010244027A - Colored photosensitive resin composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition capable of further improving lightness and flatness of a coating film, and to provide a color filter. <P>SOLUTION: The resin composition contains a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), a solvent (E) and a surfactant (F), wherein the colorant (A) contains both of a dye (A-1) containing a compound expressed by formula (1) and a pigment (A-2); the surfactant (F) is a F and/or Si-containing surfactant, and the content of the surfactant (F) is 0.0005 to 0.3 pt.mass in 100 pts.mass of the whole composition. In the formula (1), R<SP>1</SP>to R<SP>4</SP>each represent an aromatic hydrocarbon group or the like; R<SP>5</SP>represents -SO<SB>3</SB>-, -SO<SB>2</SB>N(R<SP>8</SP>)R<SP>9</SP>or the like; m represents an integer of 0 to 5; X represents a halogen atom; a represents 0 or 1; R<SP>8</SP>and R<SP>9</SP>each represent a 1-10C alkyl group or the like; and the number of positive charges and the number of negative charges in the compound of formula (1) are the same. <P>COPYRIGHT: (C)2011,JPO&INPIT

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.

A conventional photosensitive resin composition includes a pyrazole-based squarylium compound as a dye and a blue pigment Pigment Blue (P.B) 15: 6 as a pigment (for example, Patent Document 1).
However, in the coating film obtained using this photosensitive resin composition, the brightness and flatness may not be sufficient.

JP 2006-79012 A

  This invention is made | formed in view of the said subject, Furthermore, it aims at providing the colored photosensitive resin composition and color filter which can improve the brightness and the flatness of a coating film.

The present invention performs the following inventions.
[1] A coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F) are included.
The colorant (A) contains both a dye (A-1) and a pigment (A-2) containing a compound represented by the formula (1),
The surfactant (F) is a surfactant having fluorine atoms and / or silicon atoms, and the content of the surfactant (F) is 0.0005 parts by mass in 100 parts by mass of the colored photosensitive resin composition. The amount is 0.3 parts by mass or less.

(In the formula (1),
R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group having 6 to 10 carbon atoms. 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 or it may be substituted by _{^{-SO 2 N (R 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, or —SO ₂ N (R ⁸ ) R ⁹ .
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. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. —CH ₂ — contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —O—, —CO— or —NR ⁷ —.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.
R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. The hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with a halogen atom, —OH, —Q, —CH═CH ₂ or —CH═CHR ⁶ . —CH ₂ — contained in the alkyl group and the cycloalkyl group may be substituted with —O—, —CO—, —NH— or —NR ⁶ —. The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with —R ⁶ , —OH or —Q.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having a 5- to 10-membered ring, and the aromatic hydrocarbon group and the aromatic heterocyclic group The hydrogen atom contained in may be substituted with a halogen atom, —OH, —R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ or —CH═CHR ⁶ .
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. )

[2] The colored photosensitive resin composition according to [1], wherein the ratio of the content of the dye (A-1) and the content of the pigment (A-2) is 1:99 to 99: 1.
[3] The pigment (A-2) is C.I. I. The colored photosensitive resin composition according to [1] or [2], which is a pigment containing CI Pigment Blue 15: 6.
[4] A colored pattern formed using the colored photosensitive resin composition according to any one of [1] to [3].
[5] A color filter comprising the colored pattern according to [4].
[6] The color filter according to [5], which is formed by a photolithography method.
[7] A liquid crystal display device comprising the color filter according to [5] or [6].
[8] Use of the colored photosensitive resin composition according to any one of [1] to [3] for producing a color filter.

  According to the present invention, it is possible to provide a colored photosensitive resin composition and a color filter that can further improve brightness and flatness of a coating film.

The colored photosensitive resin composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and a surfactant (F )including.
In the present specification, although different depending on the number of carbon atoms, the substituents described later are exemplified in any chemical structural formulas unless otherwise specified. Moreover, the thing which can take both a linear or branched includes both.

As a coloring agent (A), both the dye (A-1) containing the compound represented by Formula (1) and a pigment (A-2) are included.

(In the formula (1),
R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group having 6 to 10 carbon atoms. 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 or it may be substituted by _{^{-SO 2 N (R 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, or —SO ₂ N (R ⁸ ) R ⁹ .
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. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. Is, -O - - _-CH 2 contained in a saturated hydrocarbon group of carbon number 1 to 10, - CO- or -NR ⁷ - may be substituted with.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.
R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. The hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with a halogen atom, —OH, —Q, —CH═CH ₂ or —CH═CHR ⁶ . —CH ₂ — contained in the alkyl group and the cycloalkyl group may be substituted with —O—, —CO—, —NH— or —NR ⁶ —. The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with —R ⁶ , —OH or —Q.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having a 5- to 10-membered ring, and the aromatic hydrocarbon group and the aromatic heterocyclic group The hydrogen atom contained in may be substituted with a halogen atom, —OH, —R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ or —CH═CHR ⁶ .
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. )

Here, examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an aryl group substituted with an alkyl group.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group and the like.
Examples of the aryl group substituted with an alkyl group include those obtained by arbitrarily combining the above-described aryl group and the following alkyl groups.

Examples of the halogen atom include fluorine, chlorine, bromine and the like.
The saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group that is an arbitrary combination of these substituents, or an alkyl group substituted with a cycloalkyl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 1-methylpropyl group, and 2-methyl. Propyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, 1-dimethyl-n-propyl group, 1,2-dimethylpropyl group, 2,2- A dimethylpropyl group etc. are mentioned.
Examples of the cycloalkyl group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecanyl group.

  As the alkoxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 1-methylpropoxy group 2-methylpropoxy group, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 1,1-dimethylpropoxy group, 1,2-dimethyl Examples thereof include a propoxy group and a 2,2-dimethylpropoxy group.

The heterocyclic group may be aromatic or may not have aromaticity.
As an aromatic heterocyclic group,

等が挙げられる。なお、複素環基の結合手は上に記載した位置でＳＯ_２と結合する。 As a heterocyclic ring having no aromaticity,

Etc. In addition, the bond of the heterocyclic group is bonded to SO ₂ at the position described above.

Examples of —OR ⁶ include alkoxy groups such as a methoxy group, an ethoxypropoxy group, a butoxy group, a hexyloxy group, and a 2-ethylhexyloxy group.
The -CO ₂ R ^6, a methyl group, an ethyloxycarbonyl group, a propyl group, an isopropyloxycarbonyl group, butyloxycarbonyl group, isobutyloxycarbonyl group, pentyloxycarbonyl group, iso-pentyloxy group, neo Pentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl, 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxy Carbonyl group, decanyloxycarbonyl group, tricyclodecanyloxycarbonyl group, methoxypropyloxycarbonyl group Ethoxypropyl oxycarbonyl group, hexyloxy propyloxy group, 2-ethylhexyloxy propyloxy carbonyl group, such as methoxy hexyloxycarbonyl group.

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

The _-SO 2 ^N R ⁹ is a hydrogen atom ^(R 8) R ^{9 (i.e.} _-SO 2 NHR ^8), a sulfamoyl group, N- (methyl) sulfamoyl, N- (ethyl) sulphamoyl group, N- ( Propyl) sulfamoyl group, N- (isopropyl) sulfamoyl group, N- (butyl) sulfamoyl group, N- (isobutyl) sulfamoyl group, N- (pentyl) sulfamoyl group, N- (isopentyl) sulfamoyl group, N- (neopentyl) Sulfamoyl group, N- (cyclopentyl) sulfamoyl group, N- (hexyl) sulfamoyl group, N- (cyclohexyl) sulfamoyl group, N- (heptyl) sulfamoyl group, N- (cycloheptyl) sulfamoyl group, N- (octyl) sulfamoyl Group N- (2-ethylhexyl) Sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (cyclooctyl) sulfamoyl group, N- (nonanesulfamoyl group, N- (decyl) sulfamoyl group, N- (tricyclodecyl) sulfamoyl Group, N- (methoxypropyl) sulfamoyl group, N- (ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group, N- (isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl, N- (2-Ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl group, N- (3-phenyl-1-methylpropyl) sulfamoyl group and the like can be mentioned.

Furthermore, examples of —SO ₂ N (R ⁸ ) R ^{9 in} which R ⁹ is a hydrogen atom include groups represented by the following formulae. However, in the following formulas, X ¹ represents a halogen atom. X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. .
Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include perfluoromethyl in addition to the alkyl group described above.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include the above-described alkyl groups, particularly a methoxy group, an ethoxy group, and a propoxy group.

Examples of —SO ₂ N (R ⁸ ) R ⁹ in which R ⁸ and R ⁹ are other than a hydrogen atom include the following groups.

Examples of the heterocyclic ring formed by combining R ⁸ and R ⁹ with each other include groups represented by the following formulae.

Among them, as R ⁸ and R ⁹ , a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, carbon A hydroxy group-containing alkyl and aryl group having 2 to 8 carbon atoms, an alkoxyl group-containing alkyl and aryl group having 2 to 8 carbon atoms are preferable, and a branched alkyl group having 6 to 8 carbon atoms is more preferable.

Examples of the substituent for the aromatic hydrocarbon group having 6 to 10 carbon atoms include ethyl group, propyl group, phenyl group, dimethylphenyl group, —SO ₂ R ⁶ or —SO ₂ N (R ⁸ wherein R ⁹ or R ⁹ is a hydrogen atom. ) R ⁹ is preferred. ^{_{Here, -SO 2 N (R 8)}} R 9 is a hydrogen atom as the ^{R 8} in ^{R 9,} in particular, having 1 to 10 carbon atoms linear or branched alkyl groups and cycloalkyl of 3 to 30 carbon atoms Group is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, a branched alkyl group having 6 to 8 carbon atoms is more preferable, and 2-ethylhexyl is particularly preferable.

Examples of the optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, hexylphenyl group, decanylphenyl group, fluorophenyl group, and chlorophenyl. Group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, hexyloxyphenyl group, decanyloxyphenyl group, trifluoromethylphenyl group, etc., and -SO ₂ N ^(R 8) or the like ^{groups R 9} is substituted and the like.

At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted aromatic carbon atom having 6 to 10 carbon atoms. A hydrogen group is preferred.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted aromatic carbon atom having 6 to 10 carbon atoms. A hydrogen group is preferred.
More preferably, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ⁵ is a carboxy group, an ethoxycarbonyl group, a sulfo group, N-(2-ethyl-hexyloxy-propyl) sulfamoyl group, N-(1,5-dimethyl-hexyl) sulfamoyl group, N-(3- phenyl-1-methyl Propyl) sulfamoyl group and N- (isopropoxypropyl) sulfamoyl group are preferable.

  The compound represented by formula (1) is preferably at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-4), for example.

(In the formulas (1-1) to (1-4),
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO _It may be substituted with ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, or —SO ₂ N (R ⁸ ) R ⁹ .
R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, or —SO ₂ N (R ⁸ ) R ⁹ .
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Hydrogen atoms contained in the aromatic hydrocarbon group of carbon number 6-10, a halogen _{^{atom, -R 26, -OH, -OR 26}} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO ₂ R _{^26, -SO} 3 _H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 28.}
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ₂ NHR ²⁸ .
R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom.
R ²⁸ represents a hydrogen atom, —R ²⁶ , —CO ₂ R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms. The atom may be substituted with -R ²⁶ or -OR ²⁶ .
R ³¹ and R ³² each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group. Hydrogen atoms contained in the aromatic hydrocarbon group, a halogen _{^{atom, -R 26, -OR 26, -CO}} 2 R 26, optionally substituted with -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 ⁴¹ and R ⁴² each independently represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group. A hydrogen atom contained in the aromatic hydrocarbon group may be substituted with —R ²⁶ or —SO ₂ NHR ²⁸ .
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meaning as described above. )
Of these, formula (1-4) is preferred.

（式中、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＣＯ_２Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。
Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。
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−ＳＯ_２ＮＨＲ^ａを表す。
Ｒ^ａは、１〜１０のアルキル基、好ましくは、２−エチルヘキシル基を表す。
Ｘ及びａは、上記と同じ意味を表す。）
式（１ｂ）で表される化合物は、式（１ｂ−１）で表される化合物の互変異性体である。
なかでも、式（１ｅ）及び式（１ｆ）が好ましい。 As a compound represented by Formula (1), the compound represented by Formula (1a)-Formula (1f) is mentioned, for example. However, the number of + charges and the number of − charges in the compound represented by the formula (1) are the same.

(In the formula, R ^b and R ^c each independently represent a hydrogen atom, —SO ₃ ^— , —CO ₂ H, or —SO ₂ NHR ^a .
R ^d , R ^e and R ^f each independently represent —SO ₃ ^— , —SO ₃ Na or —SO ₂ NHR ^a .
R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, —SO ₃ ^— , —SO ₃ H or —SO ₂ NHR ^a .
^Ra represents a 1 to 10 alkyl group, preferably a 2-ethylhexyl group.
X and a represent the same meaning as described above. )
The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).
Of these, the formula (1e) and the formula (1f) are 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.

  Examples of the pigment (A-2) contained in the colorant (A) include organic pigments such as C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. And violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38. Especially, C.I. I. Pigment red violet 23, C.I. I. Preferably at least one pigment selected from CI Pigment Blue 15: 3 and 15: 6; I. It is particularly preferable that pigment blue 15: 6 is contained. These pigments may be used alone or in combination of two or more.

If necessary, the organic pigment can be finely divided by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc. 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 organic pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more.
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 (A-2). When the amount of the pigment dispersant used is within this range, it is preferable because a pigment dispersion in a uniform dispersion state tends to be obtained.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a colored photosensitive resin composition, More preferably, it is 8-55 mass%, More preferably, it is 10-10. 50% by mass. Here, solid content means the sum total of the components except a solvent in a coloring photosensitive resin composition.
When the content of the colorant (A) is in the above range, the color density when a color filter is obtained is sufficient, and a necessary amount of the binder polymer can be contained in the composition. It is preferable because a sufficient pattern can be formed.
Content of dye (A-1) in a coloring agent (A) is 3-80 mass%, Preferably it is 3-70 mass%, More preferably, it is 3-50 mass%.
Content of the pigment (A-2) in a coloring agent (A) is 20-97 mass%, Preferably it is 30-97 mass%, More preferably, it is 50-97 mass%.
The content ratio (mass ratio) of the dye (A-1) and the pigment (A-2) is suitably 1:99 to 99: 1, and 1:99 to 60:40. Preferably, it is 5: 95-40: 60. By setting such a ratio, it is easy to optimize the transmission spectrum, which is favorable for obtaining high contrast and high brightness. Furthermore, heat resistance and chemical resistance are improved.

  In particular, C.I. I. The mass ratio of Pigment Blue 15: 6 to Dye (A-1) is preferably 97: 3 to 50:50, and more preferably 97: 3 to 70:30.

  The colored photosensitive resin composition of the present invention contains an alkali-soluble resin (B). The alkali-soluble resin (B) is not particularly limited, and any resin may be used. For example, the alkali-soluble resin (B) contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 mol% or more and 38 in all the structural units constituting the alkali-soluble resin (B). It is less than mol%. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is improved during development. Moreover, there is a tendency that a residue hardly remains in a non-pixel portion after development, which is preferable.

  Examples of other monomers that derive structural units other than the structural units derived from (meth) acrylic acid constituting the alkali-soluble resin (B) include aromatic vinyl compounds, unsaturated carboxylic acid esters, and unsaturated carboxylic acid amino acids. Alkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, polymer molecular chain ends Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group, units represented by the formula (II), and units represented by the formula (III).

（式（ＩＩ）及び式（ＩＩＩ）中、Ｒ^５３及びＲ^５５は、それぞれ独立に、水素原子又はメチル基を表す。Ｒ^５４及びＲ^５６は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。）

(In Formula (II) and Formula (III), R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom or a methyl group. R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or a C 1-6 carbon atom. Represents an alkyl group of

Specific examples of the alkali-soluble resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid. / Styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (II) (wherein, in formula (II), R ⁵³ represents a methyl group, R ⁵⁴ represents Represents a hydrogen atom) / benzyl methacrylate copolymer, a constituent represented by the formula (II) (wherein, in the formula (II), R ⁵³ represents a methyl group, and R ⁵⁴ represents a hydrogen atom) .) / Benzyl methacrylate copolymer, methacrylic acid / component represented by formula (III) Here, in formula (III), R ⁵⁵ represents a methyl group, and R ⁵⁶ represents a hydrogen atom.) / Styrene copolymer / Tricyclodecanyl methacrylate copolymer and the like are preferable.

In particular, the alkali-soluble resin (B) represented by the formula (IV) is preferable in terms of curability and developability.

Formula (II) an alkali-soluble resin having a constituent represented by (B), for example, configuration component represented by methacrylic acid / Formula (II) (However, in this case, in formula ^{(II), R 53} is methyl R ⁵⁴ represents a hydrogen atom.) / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer and formula (V ) (Wherein, in formula (V), R ⁵⁷ represents a hydrogen atom).

（式（Ｖ）中、Ｒ^５７は、水素原子又は炭素数１〜６のアルキル基を表す。）

(In the formula (V), R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Methacrylic acid / constituent component represented by formula (III) (wherein, in formula (III), R ⁵⁵ represents a methyl group and R ⁵⁶ represents a hydrogen atom) / styrene copolymer / tricyclo The decanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

The copolymerization is generally performed in a solvent using a polymerization initiator.
Examples of the polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. A peroxide such as is used.
The solvent only needs to dissolve each monomer. For example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, which will be described later. Solvents exemplified as the solvent (E) to be used are used.

The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer.
The side chain of the copolymer thus obtained can be modified with a compound having a polymerizable group to form a photosensitive alkali-soluble resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added.
Examples of the catalyst include trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

Examples of the alkali-soluble resin (B) include the following copolymers [K1] to [K4].
[K1] A unit having an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (B1) (hereinafter sometimes simply referred to as “(B1)”) and a group having a cyclic ether having 2 to 4 carbon atoms. A copolymer obtained by polymerizing a monomer (B2) (hereinafter sometimes simply referred to as “(B2)”).
[K2] A copolymer obtained by polymerizing (B1), (B2) and the monomer (B3). Here, the monomer (B3) (hereinafter sometimes simply referred to as “(B3)”) is a monomer copolymerizable with (B1) and / or (B2), and (B1) And / or a monomer that is not (B2).
[K3] In the copolymer of (B1) and (B3), a part of the carboxy group derived from (B1) is reacted with a group having a C2-C4 cyclic ether derived from (B2). The copolymer obtained by this.
[K4] A copolymer of (B1) and (B3).
Especially, it is preferable that it is a copolymer formed by polymerizing at least (B1) and (B2).

Examples of (B1) include aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid anhydride. In particular,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itacone, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydro Unsaturated dicarboxylic acids such as phthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
You may use these individually or in combination of 2 or more types. In the present specification, unless otherwise specified, the exemplified compounds, components, agents and the like can be used alone or in combination of two or more.

  (B2) may have, for example, at least one group selected from the group consisting of a group having a cyclic ether having 2 to 4 carbon atoms (for example, an oxiranyl group, an oxetanyl group, and a tetrahydrofuryl group), Furthermore, it is preferable that it is a monomer which has an unsaturated bond.

  Examples of (B2) include a monomer having an oxiranyl group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

The monomer having an oxiranyl group refers to a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group, for example.
The monomer having an oxiranyl group is preferably a compound having at least one group selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group and having an unsaturated bond, A monomer having a (meth) acryloyloxy group is more preferable.

（式（VI)中、Ｒ^６１〜Ｒ^６３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍ^１は１〜５の整数である。）。 An aliphatic oxiranyl group refers to a structure obtained by epoxidizing an aliphatic olefin.
Specific examples of the compound having an aliphatic oxiranyl group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples thereof include compounds represented by the following formula (VI).

(In formula (VI), R ^{61 to} R ⁶³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m ¹ is an integer of ¹ to 5).

  Examples of the compound represented by the formula (VI) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl. -M-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2 , 6-Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5 -Triglycidyloxymethylstyrene 2,4,6-glycidyloxy-methylstyrene and the like.

An alicyclic oxiranyl group refers to a structure obtained by epoxidizing an alicyclic olefin.
Examples of the monomer having an alicyclic oxiranyl group include a monomer having an aliphatic monocyclic oxiranyl group and a monomer having an aliphatic polycyclic oxiranyl group. The monomer having an aliphatic monocyclic oxiranyl group refers to a polymerizable compound having a structure obtained by epoxidizing a monocyclic aliphatic olefin. Moreover, the monomer which has an aliphatic polycyclic oxiranyl group means the polymeric compound which has the structure which epoxidized the polycyclic aliphatic olefin.
The monomer having an oxiranyl group preferably has a structure obtained by epoxidizing an alicyclic olefin and has an unsaturated bond, and has a structure obtained by epoxidizing an alicyclic olefin and (meth) acryloyl. A compound having a group is preferable.

Examples of the monocyclic aliphatic olefin include cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Especially, a C5-C7 compound is preferable.
Specific examples of the monomer having an aliphatic monocyclic oxiranyl group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3 , 4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and the like. It is done.

Examples of the polycyclic aliphatic olefin include dicyclopentene, tricyclodecene, norbornane, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, bicyclododecene, and tricyclododecene. It is done.
Especially, a C8-C12 compound is preferable.

式（VII）及び式（VIII）において、Ｒ⁷¹及びＲ⁷²は、それぞれ独立に、水素原子又はヒドロキシ基で置換されていてもよい炭素数１〜４のアルキル基を表す。
Ｘ⁷¹及びＸ⁷²は、それぞれ独立に、単結合、炭素数１〜６のアルカンジイル基又は＊−（ＣＨ_２）_ｓ−Ｘ'−（ＣＨ_２）_ｔ−、Ｘ'は−Ｓ−、−Ｏ−又は−ＮＨ−、ｓは１〜６の整数を表し、ｔは、０〜６の整数を表す。ただしｓ＋ｔ≦６を表す。＊はＯとの結合手を表す。］ Examples of the monomer having an aliphatic polycyclic oxiranyl group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by formula (VII), and a formula And compounds represented by (VIII).

In formula (VII) and formula (VIII), R ⁷¹ and R ⁷² each independently represent a C 1-4 alkyl group which may be substituted with a hydrogen atom or a hydroxy group.
X ⁷¹ and X ⁷² are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms or * — (CH ₂ ) _s —X ′ — (CH ₂ ) _t —, wherein X ′ is —S—, — O- or -NH-, s represents an integer of 1 to 6, and t represents an integer of 0 to 6. However, it represents s + t ≦ 6. * Represents a bond with O. ]

Specific examples of R ⁷¹ and R ⁷² include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a 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- Examples thereof include hydroxy-substituted alkyl groups such as methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group.
Of these, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable. More preferably, they are a hydrogen atom and a methyl group.

Specific examples of the alkanediyl group having 1 to 6 carbon atoms include a single bond; methylene group, ethylene group, 1,2-propanediyl group, 1,3-propanediyl group, 1,4-butanediyl group, 1 , 5-pentanediyl group and 1,6-hexanediyl group.
Of these, a single bond, a methylene group, an ethylene group, —O—CH ₂ —, and —O— (CH ₂ ) ₂ — are preferable. More preferably a single bond, -O- _{(CH 2)} 2 - is.

式（VII’）及び式（VIII’）において、Ｒ⁷¹’及びＲ⁷²’は、それぞれ前記Ｒ⁷¹及びＲ⁷²と同義である。 At least one compound selected from the group consisting of a compound represented by formula (VII) and a compound represented by formula (VIII) is a compound represented by the following formula (VII ′) and formula (VIII ′): It is preferable that it is at least 1 type of compound chosen from the group which consists of a compound represented by these.

In formula (VII ′) and formula (VIII ′), R ⁷¹ ′ and R ⁷² ′ have the same meanings as R ⁷¹ and R ⁷² , respectively.

Examples of the compound represented by the formula (VII) include compounds represented by the formula (VII-1) to the formula (VII-15). Preferably Formula (VII-1), Formula (VII-3), Formula (VII-5)
), Formula (VII-7), formula (VII-9), formula (VII-11) to formula (VII-15). More preferred are formula (VII-1), formula (VII-7), formula (VII-9), and formula (VII-15).

Examples of the compound represented by the formula (VIII) include compounds represented by the formula (VIII-1) to the formula (VIII-15). Preferably formula (VIII-1), formula (VIII-3), formula (VIII
−5), Formula (VIII-7), Formula (VIII-9), Formula (VIII-11) to Formula (VIII-15). More preferably, Formula (VIII-1), Formula (VIII-7), Formula (VIII-9), Formula (VIII-15)
It is.

  The compound represented by the formula (VII) and the compound represented by the formula (VIII) can be used alone. Moreover, it can mix in arbitrary ratios. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to Formula (VII): Formula (VIII). 80:20.

The monomer having an oxetanyl group refers to a polymerizable compound having an oxetanyl group, for example. The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and an unsaturated bond, and more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3- Ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3-acryloxy And ethyl oxetane.

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

As the copolymerizable monomer (B3), for example,
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta (Meth) acrylate cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide;
N-cycloalkylmaleimides such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide;
N-bridged carbocyclic group-substituted maleimides such as N-adamantyl maleimide, N-norbornyl maleimide;

N-arylmaleimides such as N-phenylmaleimide;
N-aralkylmaleimides such as N-benzylmaleimide;
N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, etc. Dicarbonylimide derivatives of

  Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.

  Copolymers [K1] to [K4] are described, for example, in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Edition, issued on March 1, 1972). Can be produced with reference to the published methods and the cited references described in the literature.

  Specifically, monomers (B1) and (B2) constituting the copolymer, and optionally a predetermined amount of (B3), a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. In the absence of oxygen, the polymer is obtained by stirring, heating, and keeping the temperature. Polymerization conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization, and the like.

As the polymerization initiator and the solvent used here, any of those usually used in the art can be used. For example, a polymerization initiator and a solvent described later can be used.
In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used.
In particular, by using a solvent described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In copolymer [K1], the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting copolymer [K1].
(B1) 5 to 95 mol%, more preferably 10 to 90 mol%, still more preferably 10 to 50 mol%,
(B2) 5 to 95 mol%, more preferably 10 to 90 mol%, still more preferably 50 to 90 mol%.

Moreover, it is preferable that copolymer [K2] has the ratio of each monomer in the following ranges with respect to the total mole number of the monomer which comprises copolymer [K2].
(B1) 2 to 40 mol%, more preferably 5 to 35 mol%
(B2) 2 to 95 mol%, more preferably 5 to 80 mol%
(B3) 1 to 65 mol%, more preferably 1 to 60 mol%.

The copolymer [K3] can be produced through a two-step process.
First, (B1) and (B3) are copolymerized in the same manner as described above to obtain a copolymer.
In this case, the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting the resin.
(B1) 5-50 mol%, preferably 10-45 mol%
(B3) 50 to 95 mol%, preferably 55 to 90 mol%.

Next, a part of the carboxylic acid and / or carboxylic anhydride of (B1) derived from the copolymer of (B1) and (B3) is converted to an oxiranyl group, oxetanyl group or tetrahydrofuryl group derived from (B2). React.
Therefore, the atmosphere in the flask is subsequently replaced with nitrogen to air, and (B2), a reaction catalyst, a polymerization inhibitor and the like are placed in the flask, and the reaction is continued, for example, at 60 to 130 ° C. for 1 to 10 hours. The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.
In this case, the number of moles of (B2) is suitably from 5 to 80 mole%, preferably from 10 to 75 mole%, more preferably from 15 to 70 mole%, based on the number of moles of (B1). is there.

The reaction catalyst is preferably, for example, one used as a reaction catalyst between a carboxy group and an oxiranyl group, an oxetanyl group, or a tetrahydrofuryl group. Specific examples include tris (dimethylaminomethyl) phenol.
As for the usage-amount of a reaction catalyst, about 0.001-5 mass% is illustrated with respect to the total amount of (B1)-(B3), for example.
Examples of the polymerization inhibitor include hydroquinone.
As for the usage-amount of a polymerization inhibitor, about 0.001-5 mass% is illustrated with respect to the total amount of (B1)-(B3), for example.

In copolymer [K4], the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting copolymer [K4].
(B1) 2 to 40 mol%, more preferably 5 to 35 mol%
(B2) 60 to 98 mol%, more preferably 65 to 95 mol%.

The weight average molecular weight in terms of polystyrene of the copolymers [K1] to [K4] is preferably 3,000 to 100,000, more preferably 5,000 to 50,000.
The dispersity (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymers [K1] to [K4] are preferably 1.1 to 6.0, more preferably 1.2 to 4.0.

  The polystyrene-converted weight average molecular weight of the alkali-soluble resin (B) is 5,000 to 35,000, preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The acid value of the alkali-soluble resin (B) is 50 to 150, preferably 60 to 135, and particularly preferably 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the alkali-soluble resin (B), and can be determined by titration using an aqueous potassium hydroxide solution. it can.

  Content of alkali-soluble resin (B) is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 13-60 mass%, More preferably, it is 17-55 mass%. It is. When the content of the alkali-soluble resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved, which is preferable.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is not particularly limited as long as it 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 polymerizable carbon-carbon unsaturated bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.

  The content of the photopolymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably based on the solid content of the colored photosensitive resin composition. It is 17-55 mass%. When the content of the photopolymerizable compound (C) is within the above range, curing is sufficiently performed, the film thickness ratio before and after the development is improved, and the pattern is less likely to be undercut and adhesion is improved. It is preferable because it tends to be good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D).
As said photoinitiator (D), an active radical generator, an acid generator, etc. are mentioned. An active radical generator generates an active radical when irradiated with light. The acid generator generates acid when irradiated with light.
Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl). 2-benzylbutan-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, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, preferably 2-Methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1 On and the like.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) 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-methoxynaphthyl) -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 (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds 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-carbazole-3- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl}- 9H-carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator 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 and the like may be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl 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. For example, a triazine photopolymerization initiator is also used as an acid generator.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass and more preferably 1 to 30% by mass with respect to the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). 20% by mass. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (G). The photopolymerization initiation assistant (G) is a compound that is usually used in combination with the photopolymerization initiator (D), and is used to accelerate the polymerization of the photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there.
Examples of the photopolymerization initiation aid (G) 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, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

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

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

  The photopolymerization initiation assistant (G) may be used alone or in combination of two or more. Moreover, as a photoinitiation adjuvant (G), a commercially available thing can also be used, and as a commercially available photoinitiation assistant (G), for example, brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (G) 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-methylsulfanylphenyl) 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] propane-1- ON / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl Nyl ketone / 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-methylsulfanylphenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photopolymerization initiation assistants (G), the amount used is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles per mole of the photopolymerization initiator (D). .

The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, The solvent normally used in the said field | area can be used.
For example, esters (solvents containing —COO—), ethers other than esters (solvents containing —O—), ketones other than esters (solvents containing —CO—), alcohols, aromatic hydrocarbons And amides, N-methylpyrrolidone, dimethyl sulfoxide and the like.

  Examples of the esters include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyric acid. Ethyl, butyl butyrate, methyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl lupropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3- Examples include methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, cyclohexanol acetate, and γ-butyrolactone.

  Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol,

  Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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 Examples include acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, anisole, phenetole, and methyl anisole.

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

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

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

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

  Especially, it is preferable that 1 type of hydroxy group containing solvent is included. Examples of the hydroxy group-containing solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Content of the solvent (E) in a colored photosensitive resin composition is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, it is suitable to adjust the content of the solvent (E) so that the solid content is 5 to 30% by mass, preferably 8 to 25% by mass with respect to the colored photosensitive resin composition. If the content of the solvent (E) is in the above range, the flatness at the time of application is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. preferable.

As the surfactant (F) contained in the colored photosensitive resin composition of the present invention, a surfactant having a fluorine atom or a silicon atom is suitable. Specific examples include at least one selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: Tole Silicone; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan GK)).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFac (trade name) F142D, F171, F172, F173, F177, F183, F183, F489, F554, R30 (manufactured by DIC Corporation), Ftop (trade name) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratories 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.

  The content of the surfactant (F) is preferably 0.0005 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the colored photosensitive resin composition. . By making content of surfactant (F) into this range, there exists a tendency for flatness to become favorable and is preferable.

The colored photosensitive resin composition of the present invention is preferably a negative colored photosensitive resin composition.
The colored photosensitive resin composition of the present invention can be suitably used for forming a color filter or a colored pattern, and has a good colored pattern and color such as color density, brightness, contrast, sensitivity, resolution, and heat resistance. A filter can be obtained. Further, an optical film, an array substrate or the like provided with these color filters or colored patterns as a part of its constituent parts, and a display device including these color filters or colored patterns, an optical film or an array substrate, for example, known The liquid crystal display device, the organic EL device, the solid-state imaging device, and the like can be used in a known manner for all devices related to various colored images.

As a method of forming a color filter or a pattern thereof 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 the substrate). The colored layer is applied on another colored photosensitive resin composition layer formed in advance, and a volatile component such as a solvent is removed / dried to form a colored layer, and the colored layer is exposed through a photomask. And a developing method and a method using an ink jet apparatus which does not require a photolithography method.
The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material used, application, etc. For example, about 0.1-30 μm, preferably about 1-20 μm, more preferably 1-6 μm. The degree is illustrated.

  Examples of the method for applying the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, you may apply | coat using coaters, such as a dip coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater (it may also be called a die coater, a curtain flow coater, and a spinless coater). Especially, it is preferable to apply using a spin coater.

Examples of the solvent removal / drying include natural drying, ventilation drying, and drying under reduced pressure. The specific heating temperature is suitably about 10 to 120 ° C, and preferably about 25 to 100 ° C. The heating time is suitably about 10 seconds to 60 minutes, preferably about 30 seconds to 30 minutes.
It is exemplified that the drying under reduced pressure is performed in a temperature range of about 20 to 25 ° C. under a pressure of about 50 to 150 Pa.

  The colored photosensitive resin composition of the present invention can be suitably used for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state imaging device.

  Hereinafter, the colored photosensitive resin composition and the color filter of 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 part by mass.

Synthesis Example 1: Synthesis of Dye A1 In a flask equipped with a cooling tube and a stirrer, 15 parts of a dye represented by Formula A0-1 (manufactured by Chugai Kasei), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide 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 the mixture was 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. Subsequently, the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added, and the mixture was vigorously stirred. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 11.3 parts of dye A1 (mixed dye of dye A1-1 to dye A1-8).

(In the formula (A1),
R _c independently represents —SO ₂ NH—R _a , —SO ₃ H, —SO ₃ ^— or —H.
R _a represents a 2-ethylhexyl group. )

Synthesis Example 2: Synthesis of Resin B1 210 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen. Thereafter, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) A solution prepared by adding 3.6 g of 2,2′-azobisisobutyronitrile to a mixture of 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 215 g was added dropwise, and further stirring was continued at 100 ° C. It was.

Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin solution B1 having a solid content acid value of 79 mgKOH / g.
The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 × 10 ⁴ .

About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
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)

Example 1
[Preparation of colored photosensitive resin composition 1]
(A-2) Pigment: C.I. I. Pigment Blue 15: 6 3.0 parts Acrylic Pigment Dispersant 1.0 part Propylene Glycol Monomethyl Ether Acetate 23 parts is mixed and the pigment is sufficiently dispersed using a bead mill,
(A-1) Dye: Dye A1 0.5 part (B) Resin: Resin solution B1 16 part (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 6 parts (D) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by Ciba Japan) 1.4 parts ( E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts (F) Surfactant: Polyether-modified silicone oil (SH8400, manufactured by Toray Dow Corning Co., Ltd.) Resin composition 1 was obtained.

[Formation of coating film for evaluation]
The colored photosensitive resin composition was applied by spin coating on a 3-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes in a clean oven. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), the sample was irradiated with light at an exposure dose (365 nm) of 150 mJ / cm ^{2 in} an air atmosphere and heated at 220 ° C. for 20 minutes for evaluation. A coating film was prepared. It was 2.8 micrometers when the film thickness of the coating film was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

[Evaluation of flatness]
The obtained coating film surface was confirmed visually. The results are shown in Table 3.

[Brightness evaluation]
About the coating film on the obtained glass substrate, spectroscopy was measured using a colorimeter (OSP-SP-200; Olympus Co., Ltd.), and xy chromaticity in the XYZ color system of CIE using a C light source. Coordinates (Bx, By) and brightness were measured. The results are shown in Table 3.

Examples 2-3
In the colored photosensitive resin composition 1, colored photosensitive resin compositions 2 and 3 were obtained in the same manner as in Example 1 except that (F) was changed to the number of parts shown in Table 1. Further, in the same manner as in Example 1, a coating film for evaluation was prepared and evaluated. The results are shown in Table 3.

Example 4
[Preparation of colored photosensitive resin composition 4]
(A-2) Pigment: C.I. I. Pigment Blue 15: 6 3.0 parts Acrylic Pigment Dispersant 1.0 part Propylene Glycol Monomethyl Ether Acetate 23 parts is mixed and the pigment is sufficiently dispersed using a bead mill,
(A-1) Dye: Dye A1 0.5 part (B) Resin: Resin solution B1 16 part (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 6 parts (D) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by Ciba Japan) 1.4 parts ( E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts (F) Surfactant: Megafac F554
(Product made by DIC Corporation) 0.003 part was mixed and the colored photosensitive resin composition 4 was obtained.

[Evaluation]
A coating film for evaluation was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

なお、表３においては、界面活性剤の含有量は、着色感光性樹脂組成物１００質量部に対する含有量を示す。 Examples 5-6
In the colored photosensitive resin composition 4, a colored photosensitive resin composition was obtained in the same manner as in Example 4 except that the components (B) to (F) were changed to the number of parts shown in Table 2. Further, in the same manner as in Example 4, a coating film for evaluation was prepared and evaluated. The results are shown in Table 3.

In Table 3, the content of the surfactant indicates the content relative to 100 parts by mass of the colored photosensitive resin composition.

  In Examples 1 to 6, a coating film with good flatness without unevenness was obtained, and excellent brightness was confirmed.

  According to the colored photosensitive resin composition of the present invention, a coating film and a color filter having high brightness and excellent flatness can be obtained.

Claims (8)

A colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F);
The colorant (A) contains both a dye (A-1) and a pigment (A-2) containing a compound represented by the formula (1),
The surfactant (F) is a surfactant having fluorine atoms and / or silicon atoms, and the content of the surfactant (F) is 0.0005 parts by mass in 100 parts by mass of the colored photosensitive resin composition. A colored photosensitive resin composition having a content of 0.3 parts by mass or less.

(In the formula (1),
R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group having 6 to 10 carbon atoms. 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 or it may be substituted by _{^{-SO 2 N (R 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, or —SO ₂ N (R ⁸ ) R ⁹ .
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. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. —CH ₂ — contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —O—, —CO— or —NR ⁷ —.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.
R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. Hydrogen atoms contained in the alkyl group and the cycloalkyl group, a halogen atom, -OH, -Q, which may be substituted with at -CH = CH ₂ or -CH = CHR ^6. —CH ₂ — contained in the alkyl group and the cycloalkyl group may be substituted with —O—, —CO—, —NH— or —NR ⁶ —. The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with —R ⁶ , —OH or —Q.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having a 5- to 10-membered ring, and the aromatic hydrocarbon group and the aromatic heterocyclic group The hydrogen atom contained in may be substituted with a halogen atom, —OH, —R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ or —CH═CHR ⁶ .
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. )   The colored photosensitive resin composition according to claim 1, wherein the ratio of the content of the dye (A-1) and the content of the pigment (A-2) is 1:99 to 99: 1.   The pigment (A-2) is C.I. I. The colored photosensitive resin composition according to claim 1 or 2, which is a pigment containing CI Pigment Blue 15: 6.   The coloring pattern formed using the coloring photosensitive resin composition in any one of Claims 1-3.   A color filter comprising the colored pattern according to claim 4.   The color filter according to claim 5, which is formed by a photolithographic method.   A liquid crystal display device comprising the color filter according to claim 5.   Use for manufacturing the color filter of the colored photosensitive resin composition in any one of Claims 1-3.