JP5510152B2 - 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.

  In a colored photosensitive resin composition that forms a red pixel of a color filter, it is known to use a dye as a colorant in the colored photosensitive resin composition in order to increase the contrast of the color filter. For example, Patent Document 1 describes a colored photosensitive resin composition containing Orasol Red G as a red dye.

JP 2009-163226 A

  The objective of this invention is providing the colored photosensitive resin composition which can obtain the colored hardened | cured material (for example, coating film, pattern) with higher solvent resistance, and the color filter containing it.

［１］着色剤、樹脂、光重合性化合物、光重合開始剤及び溶剤を含み、着色剤が、式（１）で表される化合物を含む着色剤である着色感光性樹脂組成物。

［式（１）中、Ｒ^１〜Ｒ^１８は、互いに独立に、水素原子、ハロゲン原子、炭素数１〜８の１価の脂肪族炭化水素基、ニトロ基、−ＳＯ_２Ｒ^２９又は−ＳＯ_２Ｒ^３２を表す。
Ｒ^２９は、−ＯＨ又は−ＮＨＲ^３０を表す。
Ｒ^３０は、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基、−Ｒ^３１−Ｏ−Ｒ^３２、−Ｒ^３１−ＣＯ−Ｏ−Ｒ^３２、−Ｒ^３１−Ｏ−ＣＯ−Ｒ^３２、又は炭素数７〜１０のアラルキル基を表す。
Ｒ^３１は、炭素数１〜８の２価の脂肪族炭化水素基を表す。
Ｒ^３２は、炭素数１〜８の１価の脂肪族炭化水素基を表す。
Ｒ^１９及びＲ^２０は、互いに独立に、水素原子、メチル基、エチル基又はアミノ基を表す。
Ｍ^１は、Ｃｒ又はＣｏを表す。
Ｒ^２１〜Ｒ^２４は、互いに独立に、水素原子、炭素数１〜８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、−ＯＲ^３２、スルホ基、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ又はハロゲン原子で置換されていてもよい。
Ｒ^２５及びＲ^２６は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^２７は、エチレン基、プロパン−１，３−ジイル基又はプロパン−１，２−ジイル基を表す。
Ｒ^２８は、水素原子又は炭素数１〜４のアルキル基を表す。
ｎは、１〜４の整数を表す。ｎが２以上の整数である場合、複数のＲ^２７は互いに同一であっても異なっていてもよい。］ The present invention is the following inventions.

[1] A colored photosensitive resin composition comprising a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant is a colorant containing a compound represented by formula (1).

[In the formula (1), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group.
R ²⁷ represents an ethylene group, propane-1,3-diyl or propane-1,2-diyl group.
R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 4. When n is an integer greater than or equal to 2, several R < ²⁷ > may mutually be same or different. ]

[2] The colored photosensitive composition according to [1], wherein the colorant further contains a pigment.
[3] The pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The colored photosensitive resin composition according to [2], which is at least one selected from the group consisting of CI Pigment Red 254.
[4] The resin is selected from the group consisting of a structural unit derived from a cyclic ether having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated double bond, and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. The colored photosensitive resin composition according to any one of [1] to [3], which is a resin containing a copolymer having a structural unit derived from at least one kind.
[5] A colored pattern formed using the colored photosensitive resin composition according to any one of [1] to [4].
[6] A color filter including the coloring pattern according to [5].

［式（２）中、Ｒ^１〜Ｒ^１８は、互いに独立に、水素原子、ハロゲン原子、炭素数１〜８の１価の脂肪族炭化水素基、ニトロ基、−ＳＯ_２Ｒ^２９又は−ＳＯ_２Ｒ^３２を表す。
Ｒ^２９は、−ＯＨ又は−ＮＨＲ^３０を表す。
Ｒ^３０は、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数１〜４のアルキル基で置換されていてもよいシクロヘキシル基、−Ｒ^３１−Ｏ−Ｒ^３２、−Ｒ^３１−ＣＯ−Ｏ−Ｒ^３２、−Ｒ^３１−Ｏ−ＣＯ−Ｒ^３２、又は炭素数７〜１０のアラルキル基を表す。
Ｒ^３１は、炭素数１〜８の２価の脂肪族炭化水素基を表す。
Ｒ^３２は、炭素数１〜８の１価の脂肪族炭化水素基を表す。
Ｒ^１９及びＲ^２０は、互いに独立に、水素原子、メチル基、エチル基又はアミノ基を表す。
Ｍ^１は、Ｃｒ又はＣｏを表す。
Ｒ^２１〜Ｒ^２４は、互いに独立に、水素原子、炭素数１〜８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、−ＯＲ^３２、スルホ基、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ又はハロゲン原子で置換されていてもよい。
Ｒ^２５及びＲ^２６は、それぞれ独立に、水素原子又はメチル基を表す。］ [7] A compound represented by formula (2).

[In the formula (2), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. ]

[8] The compound according to [7], wherein M ¹ is Cr.
[9] The compound according to [7] or [8], wherein at least one of R ^{1 to} R ¹⁸ is a nitro group.

  According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film or a pattern) having high solvent resistance can be formed, and a high-quality color filter including the same can be obtained.

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), and a solvent (E). A) is a colorant containing a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).
Compound (1) is a salt of a chromium complex anion or a cobalt complex anion and a cation derived from a xanthene compound.

[In the formula (1), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group.
R ²⁷ represents an ethylene group, propane-1,3-diyl or propane-1,2-diyl group.
R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 4. When n is an integer greater than or equal to 2, several R < ²⁷ > may mutually be same or different. ]

  Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, dexyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethyl A heptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group, etc. are mentioned.

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

  Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, Examples include butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.

  Examples of monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl groups, methylphenyl groups, dimethylphenyl groups, trimethylphenyl groups, ethylphenyl groups, propylphenyl groups, butylphenyl groups, and naphthyl groups. An aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group;

  Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-butylcyclohexyl group, Examples include 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group and the like.

As —R ³¹ —O—R ³² , methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, 2-oxo Examples include -4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group, and the like.

—R ³¹ —CO—O—R ³² includes methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxycarbonylmethyl group, butoxycarbonyl. An ethyl group etc. are mentioned.

—R ³¹ —O—CO—R ³² includes acetyloxymethyl, acetyloxyethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxymethyl, propylcarbonyloxyethyl, butylcarbonyloxy Examples thereof include a methyl group and a butylcarbonyloxyethyl group.

—SO ₂ R ²⁹ includes a sulfo group; a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group, sulfamoyl group substituted with an aliphatic hydrocarbon group such as N-allylsulfamoyl group;

N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-methoxypropylsulfamoyl) group, N- (3- Ethoxypropyl) sulfamoyl group, N- (3-propoxypropyl) sulfamoyl group, N- (3-isopropoxypropyl) sulfamoyl group, N- (3-hexyloxypropylsulf) famoyl group, N- (2-ethylhexyloxypropyl) A sulfamoyl group substituted with —R ³¹ —O—R ³² such as a sulfamoyl group, an N- (3-tert-butoxypropyl) sulfamoyl group, an N- (4-octyloxybutyl) sulfamoyl group;
N- (methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylmethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (propoxycarbonylmethyl) sulfamoyl group, A sulfamoyl group substituted with —R ³¹ —CO—O—R ³² such as N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) sulfamoyl group;
N- (acetyloxymethyl) sulfamoyl group, N- (acetyloxyethyl) sulfamoyl group, N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (propylcarbonyloxymethyl) Substituted with —R ³¹ —O—CO—R ³² such as sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group, etc. Sulfamoyl groups;

N-cyclohexylsulfamoyl group, N- (2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- (4-butylcyclohexyl) sulfamoyl A sulfamoyl group substituted with a cyclohexyl group having a substituent such as a group, etc .;
N-benzylsulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl Group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfamoyl group, N- ( And a sulfamoyl group substituted with an aralkyl group such as a 3-phenyl-1-methylpropyl) sulfamoyl group.

The -SO ₂ R ^32, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n- butylsulfonyl group, sec- butylsulfonyl group, tert- butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, Heptylsulfonyl group, octylsulfonyl group, 1-methylbutylsulfonyl group, 1,1,3,3-tetramethylbutylsulfonyl group, 1,5-dimethylhexylsulfonyl group, 1,6-dimethylheptylsulfonyl group, 2-ethylhexyl Examples include a sulfonyl group and a 1,1,5,5-tetramethylhexylsulfonyl group. Of these, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

Since the heat resistance tends to be higher, of R ¹ to R ^18, is preferably at least one nitro group.
Further, at least one of R ^{1 to} R ⁵ and at least one of R ^{6 to} R ¹⁰ are preferably —SO ₂ R ²⁹ . When a plurality of —SO ₂ R ²⁹ are contained, the plurality of R ²⁹ may be the same as or different from each other.
—SO ₂ R ²⁹ is —SO ₂ H or —SO ₂ NHR ³⁰ , preferably —SO ₂ NHR ³⁰ . Among these, a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a 2-ethylhexyl group is more preferable.
When compounds of the present invention have a _-SO 2 ^{R 32,} it is preferable that at least one of the at least one and ^R 15 ^{to R 18} of R 11 ^{to R 14} is _-SO 2 ^{R 32.} In the case of having a plurality of —SO ₂ R ³² , the plurality of R ³² may be the same as or different from each other.

R ^{21 to} R ²⁴ are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, since the color density increases. Or it is more preferable that it is an ethyl group.

R ²⁷ is preferably an ethylene group or a propane-1,2-diyl group, and more preferably an ethylene group.
R ²⁸ is preferably a hydrogen atom.
n is an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 3 or 4.
- The ^{(R 27 -O) n-R} 28, since there is a tendency to increase the solubility in an organic solvent of the compound (1), 2- (2-hydroxyethoxy) ethyl and 2- [2- A (2-hydroxyethoxy) ethoxy] ethyl group is preferred, and a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group is more preferred.

  Among the compounds (1), preferable examples of the pyrazole azo compound serving as a ligand for the complex anion include compounds represented by the formulas (1-a1) to (1-a64).

  Among compounds (1), preferred examples of the complex anion include anions represented by the formulas (1-b1) to (1-b60).

  Among the compounds (1), preferred examples of the cation derived from the xanthene compound include cations represented by the formula (1-c1) to the formula (1-c48).

  Compound (1) is formed by using a compound represented by formula (1d) (hereinafter sometimes referred to as “compound (1d)”) and a chromium compound to form a chromium complex salt, and then the chromium complex salt and the xanthene compound. Or a cobalt complex salt is formed using the compound (1d) and a cobalt compound, and then the cobalt complex salt and the xanthene compound (b) are subjected to a salt exchange reaction.

[In formula (a4), R ^{1 to} R ⁵ , R ^{11 to} R ¹⁴ and R ¹⁹ represent the same meaning as in formula (1). ]

[In formula (b), R ^{21 to} R ²⁸ and n represent the same meaning as in formula (1). A ⁻ represents a monovalent anion. ]
Examples of the monovalent anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ^{− and} BF ₄ ⁻ .

［式（ｂ０）及び式（ｂ１）中、Ｒ^２１〜Ｒ^２８及びｎは、式（１）におけるものと同じ意味を表す。Ａ⁻は、式（ｂ）におけるものと同じ意味を表す。］
前記反応において、反応温度は１５℃〜６０℃が好ましく、反応時間は１時間〜１２時間が好ましい。また、反応時間短縮や収率向上の点で、酸触媒及び／又は脱水剤を用いることが好ましい。
酸触媒としては、硫酸、ｐ−トルエンスルホン酸などが挙げられる。
脱水剤としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩等のカルボジイミド類；１−アルキル−２−ハロピリジウム塩類；１，１’−カルボニルジイミダゾール；ビス（２−オキソ−3−オキサゾリジニル）ホスフィン酸塩化物；ジ−２−ピリジル炭酸塩などが挙げられる。中でも、脱水剤としては、後処理及び精製が容易であることから、1-エチル-3-（3-ジメチルアミノプロピル）カルボジイミド塩酸塩が好ましい。
前記反応に用いられる有機溶媒としては、ジクロロメタン、クロロホルム、テトラヒドロフラン、トルエン、アセトニトリルなどが挙げられる。 The xanthene compound (b) can be produced by reacting the compound represented by the formula (b0) and the compound represented by the formula (b1) in an organic solvent.

[In formula (b0) and formula (b1), R ^{21 to} R ²⁸ and n represent the same meaning as in formula (1). A ⁻ represents the same meaning as in formula (b). ]
In the above reaction, the reaction temperature is preferably 15 ° C. to 60 ° C., and the reaction time is preferably 1 hour to 12 hours. Moreover, it is preferable to use an acid catalyst and / or a dehydrating agent in terms of shortening the reaction time and improving the yield.
Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid.
Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1′-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; di-2-pyridyl carbonate and the like can be mentioned. Among these, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent because of easy post-treatment and purification.
Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, and acetonitrile.

  The compound (1d) serving as a ligand for the complex anion of the compound (1) can be produced by a diazo coupling method of a diazonium salt and a pyrazole compound, which is well known in the dye field. For example, the formula (1b) obtained by diazotizing an amine (diazo component) represented by formula (1a) (hereinafter sometimes referred to as “amine (1a)”) with nitrous acid, nitrite or nitrite. ) Can be used as the diazonium salt.

[In formula (1a) and formula (1b), R ^{11 to} R ¹⁴ represent the same meaning as in formula (1). A ¹ represents an inorganic or organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like.
Examples of the organic anion, for _example, CH ³ COO ^_-, PhCOO -, and the like.
Preferably, chloride ion, bromide _ion, CH 3 COO ^-, and the like.

  The compound represented by the formula (1d) and the compound represented by the formula (1c) are subjected to diazo coupling in an aqueous solvent, whereby the compound represented by the formula (1d) (hereinafter referred to as “compound (1d)”). Can be manufactured). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

[In formula (1c), R ^{1 to} R ⁵ and R ¹⁹ represent the same meaning as in formula (1). ]

When compound (1d) has —SO ₂ R ²⁹ and —SO ₂ R ²⁹ is —SO ₂ NHR ³⁰ , it can also be produced by using amine (1a) having —SO ₂ NHR ³⁰ , but sulfo It is preferable to carry out the coupling reaction using the amine (1a) having a group and then sulfonamid the sulfo group. For example, an azo compound having a sulfo group in the compound (1d) (hereinafter referred to as “compound (1s)”) is synthesized, and the sulfo group (—SO ₃ H) is converted to a sulfonyl halide (—SO ₂ ) with a thionyl halide compound. X; X is a halogen atom) to obtain a sulfonyl halide compound, and then reacting the sulfonyl halide compound with an amine (R ³⁰ NH ₂ ) to sulfonamid the sulfo group to produce the compound (1d) Can do.

  Specific examples of the compound (1s) include compounds represented by the formula (1-a1), the formula (1-a2), and the formulas (1-a5) to (1-a20). Examples thereof include compounds represented by 1-a5), (1-a6), (1-a15) and (1-a16). Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide and the like, preferably thionyl chloride and thionyl bromide, and particularly preferably thionyl chloride. It is preferable that the usage-amount of thionyl halide is 1-10 mol with respect to 1 mol of compounds (1s). When water is brought into the reaction system, it is preferable to use an excessive amount of the thionyl halide compound.

  The sulfonyl halide is carried out in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly preferably cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane can be used. The usage-amount of a solvent is 3 mass parts or more (preferably 5 mass parts or more) with respect to 1 mass part of compound (1s), and is 10 mass parts or less (preferably 8 mass parts or less).

  In sulfonyl halide formation, it is preferable to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide, etc.) in combination. When N, N-dialkylformamide is used, the amount used is, for example, 0.05 to 1 mol with respect to 1 mol of the thionyl halide compound. When compound (1s) and N, N-dialkylformamide are mixed in advance in a solvent and then a thionyl halide compound is added, heat generation can be suppressed.

  The reaction temperature in the sulfonyl halide formation is, for example, 0 ° C. or higher, preferably 30 ° C. or higher and 70 ° C. or lower, preferably 60 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 3 hours or more and 8 hours or less, preferably 5 hours or less.

Sulfonyl halide compound prepared as described above may be reacted with an amine (R ^{30 NH} ₂₎ from isolated, remains an amine of the reaction mixture without isolation (R ^{30 NH} ₂₎ reacting You may let them. In the case of isolation, for example, the reaction mixture and water may be mixed, and the precipitated crystals may be collected by filtration. The obtained crystals of the sulfonyl halide compound may be washed with water and dried as necessary before the reaction with the amine (R ³⁰ NH ₂ ).

Examples of the amine (R ³⁰ NH ₂ ) include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine and the like), tetramethylbutylamine (1,1,3,3- Tetramethylbutylamine and the like), ethylhexylamine (such as 2-ethylhexylamine), aminophenylbutane (such as 3-amino-1-phenylbutane), and isopropoxypropylamine. The amount of amine ^(R 30 NH _2), to the sulfonyl halide compound to 1 mole, 2 moles or more, 10 mol or less, preferably 7 mol or less.

The order of addition of the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is not particularly limited, but it is preferable to add (drop) the amine (R ³⁰ NH ₂ ) to the sulfonyl halide compound. The reaction between the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is preferably performed in a solvent. As the solvent, the same solvent as that used for preparing the sulfonyl halide compound can be used.

The reaction between the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is preferably performed in the presence of a basic catalyst. Examples of basic catalysts include tertiary amines (aliphatic tertiary amines such as triethylamine and triethanolamine; aromatic tertiary amines such as pyridine), and secondary amines (aliphatic secondary amines such as diethylamine; piperidine, etc. And cycloaliphatic secondary amines). Among these, tertiary amines, particularly aliphatic tertiary amines such as triethylamine are preferable. The amount of basic catalyst, relative to the amine ^(R 30 NH _2), 1.1 mol or more, 6 mol or less, preferably 1.1 mol or more and 5 mol or less.

When an amine (R ³⁰ NH ₂ ) and a basic catalyst are added to the sulfonyl halide compound, the timing of addition of the basic catalyst is not particularly limited, either before or after the addition of the amine (R ³⁰ NH ₂ ). Alternatively, it may be added at the same timing as the amine (R ³⁰ NH ₂ ). Further, it may be added after mixing with a reactive amine in advance, or may be added separately from the amine (R ³⁰ NH ₂ ).

The reaction temperature between the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is, for example, 0 ° C. or higher and 50 ° C. or lower, preferably 0 ° C. or higher and 30 ° C. or lower. The reaction time is 1 to 5 hours.

  The method for obtaining the target compound (1d) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture is preferably mixed with an acid (for example, acetic acid and the like) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature when adding the reaction mixture is 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

When the anion part of the compound (1) is a chromium complex anion (M ¹ in the formula (1) is Cr), the compound (1d) and the chromium compound are reacted in an aqueous solvent at 70 to 100 ° C. Can be manufactured. It is preferable to react the compound (1d) and the chromium compound in a molar ratio of 2: 1 to 4: 1.

  As said chromium compound, chromium formate, chromium acetate, chromium chloride, chromium fluoride, etc. are mentioned, Preferably chromium formate, chromium acetate, etc. are mentioned.

  Compound (1) can be produced by subjecting a chromium complex salt and a xanthene compound (b) to a salt exchange reaction in a solvent. It is preferable that the chromium complex salt and the xanthene compound (b) are reacted at a molar ratio of 1: 1 to 1: 4.

When the anion part of the compound (1) is a cobalt complex anion (M ¹ in the formula (1) is Co), the compound (1d) and the cobalt compound are reacted at 70 to 100 ° C. in an aqueous solvent. Can be manufactured. It is preferable to react the compound (1d) and the cobalt compound in a molar ratio of 2: 1 to 4: 1.

  Examples of the cobalt compound include cobalt chloride, cobalt acetate, cobalt sulfate, tris (2,4-pentanedionato) cobalt (III), and preferably tris (2,4-pentadionato) cobalt (III). Can be mentioned.

  Compound (1) can be produced by subjecting a cobalt complex salt and a xanthene compound (b) to a salt exchange reaction in a solvent. The cobalt complex salt and the xanthene compound (b) are preferably reacted at a molar ratio of 1: 1 to 1: 4.

  Specific examples of the compound (1) include compounds represented by formula (1-1) to formula (1-26).

  Of the compounds (1), a compound represented by the formula (2) (hereinafter sometimes referred to as “compound (2)”) is preferable in that it has high solubility in an organic solvent.

[In the formula (2), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. ]

M ¹ is preferably Cr.
In addition, at least one of R ^{1 to} R ¹⁸ is preferably a nitro group. By having a nitro group, the heat resistance tends to increase.
It is preferable that at least one of R ^{1 to} R ⁵ and at least one of R ^{6 to} R ¹⁰ are —SO ₂ R ²⁹ , and among them, —SO ₂ H (ie, R ²⁹ is —OH) and —SO ₂ More preferably, it is at least one selected from the group consisting of NHR ³³ (ie, R ²⁹ is —NHR ³³ ).
When the compound (2) has —SO ₂ R ³² , it is preferable that at least one of R ^{11 to} R ¹⁴ and at least one of R ^{15 to} R ¹⁸ are —SO ₂ R ³² .

R ³³ is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms are the same as those listed above. Has a -SO ₂ R ^29, and compounds ^{R 29} is -NHR ^33, except replacing the amine with ^(R 30 NH ₂₎ to the amine ^(R 33 NH ₂₎ The same method as Compound (1) And can be manufactured.

  Specific examples of the compound (2) include formula (1-1), formula (1-3) to formula (1-5), formula (1-7) to formula (1-9), formula (1-11). ) To Formula (1-16), Formula (1-18) to Formula (1-21), and Formula (1-23) to Formula (1-26). -1) to formula (1-3), formula (1-21), and compounds represented by formula (1-23) to formula (1-26) are preferable.

  The content of the compound (1) is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 80% by mass or less, and further preferably 3% by mass or more and 70% by mass or less in the colorant (A). .

  The colorant (A) may contain a dye different from the compound (1). Examples of the dye include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, the dyes are classified as dyes by the Color Index (published by The Society of Dyers and Colorists). And known dyes described in Dyeing Notes (Color Dyeing).

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; I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 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 Violet 6B, 7, 9, 17, 19; I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; I. Direct dyes,
C. 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 Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; I. Examples include modern dyes.

The colorant (A) may further contain a pigment.
Examples of the pigment include organic pigments such as C.I. I. Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; 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; I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Is mentioned. Especially, C.I. I. Pigment yellow 138, 139, 150, C.I. I. It is preferable to contain at least one selected from CI Pigment Red 177, 242, and 254. By including the pigment, it is easy to optimize the transmission spectrum of the red photosensitive resin composition, and the chemical resistance is improved.
These pigments may be used alone or in combination of two or more.

If necessary, the organic pigment is 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. Or a cleaning process using an organic solvent or water for removing impurities, an ionic impurity removing process using an ion exchange method, 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. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When a pigment dispersant is used, the amount used is preferably 100% by mass, more preferably 5% by mass or more and 50% by mass or less with respect to the pigment (A2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

The content of the pigment in the colorant (A) is preferably 1 to 99% by mass, more preferably 10 to 97% by mass.
The content ratio (mass ratio) of the compound (1) and the pigment is preferably 1:99 to 99: 1, and more preferably 3:97 to 90:10. 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, compound (1) and C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The mass ratio with at least one selected from the group consisting of CI Pigment Red 254 is preferably 3:97 to 90:10, and more preferably 3:97 to 70:30.

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

The colored photosensitive resin composition of the present invention contains a resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin.
Examples of the resin (B) include the following resins [K1] to [K4].
[K1] selected from the group consisting of a monomer having a cyclic ether having 2 to 4 carbon atoms (a) (hereinafter sometimes referred to as “(a)”), an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride A copolymer with at least one (b) (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) [K3] Copolymer of (b) and (c) [K4] A resin obtained by reacting (a) with a copolymer of (b) and (c).
When resin (B) contains the structural unit derived from (a), reliability, such as heat resistance of the obtained colored pattern and chemical resistance, can be made higher.

(A) includes, for example, a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and a polymerizable group other than the cyclic ether. The polymerizable compound which has. (A) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenic carbon-carbon double bond, and a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group. More preferred are monomers having
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (a) include a monomer having an oxiranyl group (a1) (hereinafter sometimes referred to as “(a1)”), a monomer having an oxetanyl group (a2) (hereinafter referred to as “(a2)”) And a monomer (a3) having a tetrahydrofuryl group (hereinafter sometimes referred to as “(a3)”). Among them, the monomer (a1) having an oxiranyl group is preferable, and the monomer (a1-2) having a structure obtained by epoxidizing a cyclic olefin (hereinafter sometimes referred to as “(a1-2)”) is more preferable. .

The monomer (a1) having an oxiranyl group refers to a polymerizable compound having an oxiranyl group and a polymerizable group other than the oxiranyl group. (A1) has, for example, a monomer (a1-1) having a structure obtained by epoxidizing a chain olefin (hereinafter sometimes referred to as “(a1-1)”), and a structure obtained by epoxidizing a cyclic olefin. A monomer (a1-2) is mentioned.
(A1) is preferably a monomer having an oxiranyl group and an ethylenic carbon-carbon double bond, and more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group.

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

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

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ¹ and X ² each independently represent a single bond, —R ^c —, * —R ^c —O—, * —R ^c —S—, or * —R ^c —NH—.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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

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

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

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

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. 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, particularly preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  The monomer (a2) having an oxetanyl group refers to a polymerizable compound having an oxetanyl group and a polymerizable group other than the oxetanyl group. (A2) is preferably a monomer having an oxetanyl group and an ethylenic carbon-carbon double bond, and more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. As (a2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

The monomer (a3) having a tetrahydrofuryl group refers to a polymerizable compound having a tetrahydrofuryl group and a polymerizable group other than the tetrahydrofuryl group. (A3) is preferably a monomer having a tetrahydrofuryl group and an ethylenic carbon-carbon double bond, and more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.
Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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

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

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

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

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

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

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

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 60 to 98 mol% (more preferably 65 to 95 mol%)
Structural unit derived from (b); 2 to 40 mol% (more preferably 5 to 35 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the cured pattern tend to be good.

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

  Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and oxygen is substituted with nitrogen, thereby deoxidizing, stirring, heating, and keeping warm. Is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as a solvent for the photosensitive resin composition.

  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 (D) 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 the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (b); 2 to 40 mol% (more preferably 5 to 35 mol%)
Structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, storage stability, developability, solvent resistance of the cured pattern, heat resistance, and mechanical strength tend to be improved.

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

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(B) 2 to 40 mol%, more preferably 5 to 35 mol%
(C) 60-98 mol%, more preferably 65-95 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

The resin [K4] is obtained by obtaining a copolymer of (b) and (c) and adding the carboxy group of (c) to the cyclic ether having 2 to 4 carbon atoms of (a). Can do.
First, a copolymer of (b) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (b) and (c).
(B) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%
Next, the carboxy group and / or part of the carboxylic acid anhydride contained in the structural unit derived from (c) in the copolymer is reacted with a C2-C4 cyclic ether of (a). .
Subsequent to the production of the copolymer of (b) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (a) a reaction catalyst of a carboxy group and a cyclic ether (for example, tris (dimethylaminomethyl) phenol Etc.) is 0.001 to 5% by mass with respect to the total amount of (a) to (c), and a polymerization inhibitor (for example, hydroquinone and the like) is 0. The resin [K4] can be obtained by placing 001 to 5 mass% in a flask and reacting at 60 to 130 ° C for 1 to 10 hours, for example. The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the amount of (a) used is preferably from 5 to 80 mol%, more preferably from 10 to 75 mol%, and even more preferably from 15 to 70 mol%, based on (b). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin with glycidyl (meth) acrylate added to resin tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid Examples thereof include resin [K4] such as a resin obtained by adding glycidyl (meth) acrylate to a copolymer. Among them, resin [K1] and resin [K2] are preferable, resin [K1] is more preferable, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid co-polymer. More preferred are polymers.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 35,000. Particularly preferred is 6,000 to 30,000, and particularly preferred is 7,000 to 28,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 150, more preferably 60 to 135, and still more 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 resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the solid content of the colored photosensitive resin composition. %. When the content of the resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film rate tend to be improved.

  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. For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

  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. 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 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), if it is a compound which generate | occur | produces an active radical, an acid, etc. by the effect | action of light, and starts polymerization, it will not specifically limit, A well-known polymerization initiator can be used. . The photopolymerization initiator (D) may contain a photopolymerization initiation assistant (D1) together with a compound that generates an active radical, an acid, and the like by the action of light. The photopolymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the photopolymerizable compound that has been polymerized by the photopolymerization initiator.
As a photoinitiator (D), the compound which generate | occur | produces an active radical by the effect | action of light is preferable, and an acetophenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-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- [ 4- (1-methylvinyl) phenyl] propan-1-one oligomers and the like are preferred. Or 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907 (manufactured by Ciba Japan) may be used.

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

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

  Examples of oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and 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-carbazol-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 the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxypheny ) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), an imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group And compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Furthermore, as the polymerization initiator (C), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a photopolymerization initiation assistant (C1) (particularly amines) described later.

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

  The photopolymerization initiator (D) may be a compound that simultaneously generates an active radical and an acid by light, such as a triazine compound.

Examples of the photopolymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the total amount of the resin (B) and the photopolymerizable compound (C). %. 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 (D1). The photopolymerization initiation assistant (D1) is usually used in combination with the photopolymerization initiator (D), and is a compound used for accelerating the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator, Or it is a sensitizer.
Examples of the photopolymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
The photopolymerization initiation assistant (D1) may be used alone or in combination of two or more.

  When using these photoinitiator adjuvant (D1), the usage-amount is with respect to 1 mol of photoinitiators (D), Preferably it is 0.01-10 mol, More preferably, it is 0.01-5 mol It is.

The colored photosensitive resin composition of the present invention contains a solvent (E).
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used.

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

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

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

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

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

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

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

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N , N-dimethylformamide, N-methylpyrrolidone and the like are preferable, and propylene glycol monomethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

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

The colored photosensitive resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: 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) Manufactured) and the like.

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

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass with respect to the colored photosensitive resin composition. Below, more preferably 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.
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 ), A colored pattern having excellent coatability and excellent solvent resistance and spectroscopy can be obtained.

As a method for forming a colored pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is first formed on a substrate or another resin layer (for example, on the substrate). Applied to another colored photosensitive resin composition layer, etc.), removing / drying volatile components such as a solvent to form a colored layer, exposing the colored layer through a photomask, and developing And a method using an inkjet apparatus that does not require a photolithographic method.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material to be used, application, etc., and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, more preferably 1 to 6 μm. .

  Examples of the method of 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).

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

The dried coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc., which can be cut using a filter that cuts a specific wavelength range, or selectively extracted using a bandpass filter that extracts a specific wavelength range. And may be exposed.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the substrate can be performed.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. Examples of the developer include an aqueous solution of an alkaline compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.) that may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. Post baking is preferably in the range of 150 to 230 ° C. and 10 to 240 minutes, for example.

  The colored photosensitive resin composition of the present invention can provide a good color pattern and color filter such as color density, brightness, contrast, sensitivity, resolution, and heat resistance. In addition, a display device provided with these color filters or colored patterns as a part of its constituent parts, for example, a known liquid crystal display device, an organic EL device, a solid-state imaging device, etc. It can be utilized in a known manner.

Hereinafter, the colored photosensitive resin composition 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 parts by mass.

(Synthesis Example 1)
<Synthesis of Compound (1-1)>
After adding 75 parts of water to 7.7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of sodium hydroxide was added and dissolved. Under ice cooling, 9.5 parts of 35% aqueous sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was added, then 30.0 parts of 35% hydrochloric acid was added little by little to dissolve, and the mixture was stirred for 2 hours. A suspension containing was obtained. Then, an aqueous solution in which 8.9 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 36 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 13 parts of 3-methyl-1- (3′-sulfamoylphenyl) -5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 100 parts of water, and the pH was adjusted using sodium hydroxide. Was adjusted to 8.0. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 17.9 parts (yield 85%) of the compound represented by the formula (p-1).

  10 parts of the compound of formula (p-1) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved in ammonium sulfate chromium (III) 12 water (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1. After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 12.8 parts of the compound represented by the formula (z-1) ( 60%).

  18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), 1.0 part of camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 4- (N, N-dimethyl) Amino) pyridine (Tokyo Chemical Industry Co., Ltd.) 1.4 parts and triethylene glycol (Wako Pure Chemical Industries Co., Ltd.) 18 parts were added and stirred for about 30 minutes. Thereafter, 47 parts of anhydrous chloroform was added to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and a solution dissolved beforehand was slowly added. Thereafter, the mixture was stirred at room temperature for about 2 hours. The liquid separation operation was performed twice with 150 parts of a 1N hydrochloric acid aqueous solution, and then the organic layer was washed twice with 150 parts of 10% saline. Next, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 20.6 parts (yield 90%) of the compound represented by the formula (g-1). It was.

Identification of compound represented by formula (g-1) (mass spectrometry) ionization mode = ESI +: m / z = 575.3 [M-Cl ⁻ ] ⁺
Exact Mass: 610.3

4025 parts of methanol was added to 253 parts of the compound represented by the formula (z-1) to prepare a solution (s1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t1). Thereafter, the solution (s1) and the solution (t1) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried at 60 ° C. under reduced pressure, washed with 3500 parts of water, filtered, and dried at 60 ° C. under reduced pressure to obtain 263 parts (yield) of the compound (dye A1) represented by the formula (1-1). 65%) was obtained.
The structure of the compound represented by Formula (1-1) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C55.6 H4.7 N12.0 Cr3.57

(Synthesis Example 2)
<Synthesis of Compound (1-2)>
Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 parts, anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.) 40 parts, camphorsulfonic acid (manufactured by Aldrich Co., Ltd.) 0.3 parts, 4- (N, N -Dimethylamino) pyridine (Tokyo Chemical Industry Co., Ltd.) 0.3 part and diethylene glycol (Wako Pure Chemical Industries Co., Ltd. 3.9 part) were added and it stirred for about 30 minutes. Thereafter, 10 parts of anhydrous chloroform was added to 2.9 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and a solution dissolved beforehand was slowly added. Thereafter, the mixture was stirred at room temperature for about 2 hours. After performing the liquid separation operation twice with 100 parts of 1N aqueous hydrochloric acid, the organic layer was washed twice with 100 parts of 10% saline. Next, 12 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 5.0 parts of the compound represented by the formula (g-2) (yield 85%). It was.

Identification of compound represented by formula (g-2) (mass spectrometry) ionization mode = ESI +: m / z = 531.3 [M-Cl ⁻ ] ⁺
Exact Mass: 566.3

To 10 parts of the compound represented by the formula (z-1), 100 parts of N-methylpyrrolidone was added to prepare a solution (s2). Further, 50 parts of N-methylpyrrolidone was added to 5.6 parts of the compound represented by the formula (g-2) to prepare a solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature, stirred for about 1 hour, and poured into 500 parts of water. The resulting red solid was filtered and dried at 60 ° C. under reduced pressure to obtain 15 parts (yield 95%) of the compound represented by formula (1-2) (dye A2).
The structure of the compound represented by Formula (1-1) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C56.0 H4.9 N12.2 Cr3.47

(Synthesis Example 3)
<Synthesis of Compound (1-3)>
By the same method as in Synthesis Example 1, a compound represented by formula (g-3) is obtained from a compound represented by formula (rh-1). Furthermore, the compound (Dye A3) represented by Formula (1-3) is obtained by the same method as in Synthesis Example 1.

(Synthesis Example 4)
<Synthesis of Resin Solution B1>
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 305 parts by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (in the compound represented by the following formula (I-1) and the formula (II-1) The compound represented is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution is added over 4 hours using a dropping funnel. And dropped in a flask kept at 70 ° C. On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of dropping of the polymerization initiator solution, the solution 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 solid content was 33% by mass, and the acid value was 34 mg. A resin solution B1 of -KOH / g (solution) was obtained.

(Synthesis Example 5)
<Synthesis of Resin Solution B2>
300 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the temperature of the solution in the flask was raised to 100 ° C., and then 176.2 parts by mass of benzyl methacrylate, 30.2 parts by mass of methacrylic acid, 3.6 parts by mass of azobisisobutyronitrile, and 197 masses of propylene glycol monomethyl ether acetate. The mixture consisting of 1 part was dropped into the flask over 2 hours using a dropping funnel, and stirring was further continued at 100 ° C. for 2.5 hours after completion of the dropping. The weight average molecular weight Mw was 9.8 × 10 ³ , solid. A resin solution B2 having a mass of 34% by mass and an acid value of 102 mg-KOH / g (in terms of solid content) was obtained.

(Synthesis Example 6)
<Synthesis of Resin Solution B3>
333 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 gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Then, after heating the solution in a flask to 100 degreeC, N-benzyl maleimide 18.7g, benzyl methacrylate 70.5g, methacrylic acid 51.7g, methyl methacrylate 90.0g, azobisisobutyronitrile 5.2g A mixture of 182 g of propylene glycol monomethyl ether acetate was dropped into the flask over 2 hours using a dropping funnel, and stirring was further continued at 100 ° C. for 5 hours after the completion of the dropping.
After the completion of stirring, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with air. Then, 28.5 g of glycidyl methacrylate, 1.3 g of trisdimethylaminomethylphenol and 0.165 g of hydroquinone were placed in the flask. Then, the reaction was continued at 110 ° C. for 6 hours to obtain a resin solution B3 having a weight average molecular weight Mw of 16 × 10 ³ , a solid content of 31%, and an acid value of 80 mg-KOH / g (in terms of solid content).

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%
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) Pigment: C.I. I. Pigment Red 242 22 parts Acrylic Pigment Dispersant 6.7 parts (B) Resin: Resin Solution B2 27 parts Propylene Glycol Monomethyl Ether Acetate 131 parts, thoroughly disperse the pigment using a bead mill,
(A) Compound (1): Dye A1 7.1 parts (B) Resin: Resin solution B1 37 parts (C) Photopolymerizable compound: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 32 parts (D) Photopolymerization initiator: Oxime ester compound (N-1919; manufactured by ADEKA Co., Ltd.) 9.5 parts (D1) Photopolymerization initiation assistant: 4, 4'- Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 1.6 parts (E) Solvent: propylene glycol monomethyl ether 172 parts (E) Solvent: propylene glycol monomethyl ether acetate 33 parts (E) Solvent: Ethyl 3-ethoxypropionate 22 parts (F) Surfactant: Megafac F554 (manufactured by DIC Corporation) 0.1 To obtain a colored photosensitive resin composition 1 were mixed.

[Formation of pattern]
The colored photosensitive resin composition 1 was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition 1 and the photomask made of quartz glass is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 80 mJ. Light was irradiated with an exposure amount of / cm ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. After the light irradiation, the substrate was developed by immersing in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and then in an oven at 230 ° C. For 30 minutes. After standing to cool, the thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.0 μm.

(Solvent resistance evaluation)
In the above pattern formation, the same operation was performed except that exposure was performed without using a photomask, and a colored coating film was prepared. The obtained coating film was immersed in N-methyl-2-pyrrolidone at 23 ° C. for 30 minutes, and the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The color difference ΔEab * before and after immersion was calculated by measuring the xy chromaticity coordinates (Rx, Ry) (that is, chromaticity) and brightness RY before and after immersion in the CIE XYZ color system using the color matching function. If ΔEab * is 2 or less, it can be judged that the solvent resistance is good. The results are shown in Table 1.

(Example 2)
A colored photosensitive resin composition 2 was obtained in the same manner as in Example 1 except that the dye A1 was replaced with the dye A2. The colored photosensitive resin composition 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
A colored photosensitive resin composition 3 is obtained in the same manner as in Example 1 except that the dye A1 is replaced with the dye A3. When the colored photosensitive resin composition 3 is evaluated in the same manner as in Example 1, a good solvent resistance result is obtained.

Example 4
(A) Pigment: C.I. I. Pigment Red 242 23 parts Acrylic Pigment Dispersant 6.8 parts (B) Resin: Resin Solution B2 27 parts Propylene Glycol Monomethyl Ether Acetate 132 parts are mixed sufficiently using a bead mill to disperse the pigment a Got.
(A) Pigment: C.I. I. Pigment Red 177 5.1 parts Acrylic pigment dispersant 2.0 parts (B) Resin: Resin solution B2 5.3 parts Propylene glycol monomethyl ether acetate 24 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. And then mixing with dispersion a,
(A) Compound (1): Dye A3 6.4 parts (B) Resin: Resin solution B1 25 parts (C) Photopolymerizable compound: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 29 parts (D) Photopolymerization initiator: Oxime ester compound (N-1919; ADEKA Co., Ltd.) 8.6 parts (D1) Photopolymerization initiation assistant: 4, 4′- Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part (E) Solvent: Propylene glycol monomethyl ether 180 parts (E) Solvent: Propylene glycol monomethyl ether acetate 20 parts (E) Solvent: Ethyl 3-ethoxypropionate 6 parts (F) Surfactant: Megafac F554 (manufactured by DIC Corporation) 0.1 part Mixture to obtain a colored photosensitive resin composition 4. The colored photosensitive resin composition 4 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
(A) Pigment: C.I. I. Pigment Red 242 22 parts Acrylic Pigment Dispersant 6.7 parts (B) Resin: Resin Solution B2 27 parts Propylene Glycol Monomethyl Ether Acetate 131 parts, thoroughly disperse the pigment using a bead mill,
(A) Compound (1): Dye A1 7.1 parts (B) Resin: Resin solution B1 37 parts (C) Photopolymerizable compound: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 32 parts (D) Photopolymerization initiator: Oxime ester compound (N-1919; ADEKA Co., Ltd.) 6.3 parts (D) Photopolymerization initiator: 2,4-bis ( (Trichloromethyl) -6-piperonyl-1,3,5-triazine (compound represented by the following formula (Dt)) (TAZ-PP; manufactured by Siber Hegner, Japan) 3.2 parts (D1) Agent: 4,4′-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 1.6 parts (E) Solvent: 172 parts of propylene glycol monomethyl ether (E) Solvent: Propylene glycol monomethyl ether acetate 33 parts (E) Solvent: Ethyl 3-ethoxypropionate 22 parts (F) Surfactant: Megafac F554 (manufactured by DIC Corporation) 0.1 part A colored photosensitive resin composition 5 was obtained. The colored photosensitive resin composition 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
(A) Pigment: C.I. I. Pigment Red 254 12 parts Acrylic pigment dispersant 6.9 parts (A) Compound (1): Dye A2 8.1 parts Propylene glycol monomethyl ether acetate 81 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. Dispersion b was obtained.
(A) Pigment: C.I. I. Pigment Red 242 11 parts Acrylic Pigment Dispersant 3.3 parts (B) Resin: Resin Solution B2 13 parts Propylene Glycol Monomethyl Ether Acetate 65 parts, thoroughly disperse the pigment using a bead mill, then dispersion b and then
(A) Compound (1): Dye A3 7.0 parts (C) Photopolymerizable compound: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 30 parts (B) Resin: Resin solution B1 39 parts (D) Photopolymerization initiator: Oxime ester compound (N-1919; manufactured by ADEKA Corporation) 8.9 parts (D1) Photopolymerization initiation assistant: 4, 4′- Bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part (E) Solvent: Propylene glycol monomethyl ether 160 parts (E) Solvent: Propylene glycol monomethyl ether acetate 48 parts (E) Solvent: Ethyl 3-ethoxypropionate 6 parts (F) Surfactant: Megafac F554 (manufactured by DIC Corporation) 0.1 part Mixture to obtain a colored photosensitive resin composition 6. The colored photosensitive resin composition 6 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
(A) Colorant: Orasol Red G (manufactured by Ciba Japan Co., Ltd.) 47.5 parts (B) Resin: Resin solution B3 16 parts (C) Photopolymerizable compound: Dipentaerythritol pentaacrylate and dipentaerythritol hexa Mixture with acrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 23.9 parts (D) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907: manufactured by Ciba Japan Co., Ltd.) 3.6 parts (D) Photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; 2.8 parts (D1) photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (EAB-F; Hodogaya) 1.2 parts (E) Solvent: Propylene glycol monomethyl ether 267 parts (E) Solvent: Propylene glycol monomethyl ether acetate 138 parts (F) Surfactant: Megafac F475 (manufactured by DIC Corporation) 0.1 part was mixed and the colored photosensitive resin composition 7 was obtained. The colored photosensitive resin composition 7 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
(A) Colorant: Orasol Red G (manufactured by Ciba Japan Co., Ltd.) 47.5 parts (B) Resin: Resin solution B3 13 parts (C) Photopolymerizable compound: Dipentaerythritol pentaacrylate and dipentaerythritol hexa Mixture with acrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 19 parts (D) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907: manufactured by Ciba Japan Co., Ltd.) 2.9 parts (D) photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP; Nippon Siber Hegner) 2.2 parts (D1) Photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (EAB-F; Hodogaya Chemical Co., Ltd.) ) 1.0 part (E) Solvent: propylene glycol monomethyl ether 203 parts (E) Solvent: propylene glycol monomethyl ether acetate 203 parts (F) Surfactant: MegaFuck F475 (manufactured by DIC Corporation) 0.1 part Epoxy Compound: 9.6 parts of Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.) were mixed to obtain a colored photosensitive resin composition 8. The colored photosensitive resin composition 8 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

＊）Ｎ−メチル−２−ピロリドン浸漬中に着色塗膜がガラス基板から剥離したため、色差△Ｅａｂ＊を測定することができなかった。

*) Since the colored coating film was peeled off from the glass substrate during the immersion in N-methyl-2-pyrrolidone, the color difference ΔEab * could not be measured.

(Synthesis Example 7)
<Synthesis of Compound (1-23)>
After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-4-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% aqueous sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours. A suspension containing was obtained. Subsequently, an aqueous solution in which 5.6 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 70 parts of water, and the pH is adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.7 parts (yield 87%) of the compound represented by the formula (p-2).

  10 parts of the compound of the formula (p-2) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved in ammonium sulfate (III) 12 water (made by Wako Pure Chemical Industries, Ltd.) 3.1. After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by formula (z-2) ( 63%).

Identification of compound represented by formula (z-2) (mass spectrometry) ionization mode = ESI−: m / z = 882.1 [M−Na ⁺ ] ⁻
Exact Mass: 905.1

4025 parts of methanol was added to 253 parts of the compound represented by the formula (z-2) to prepare a solution (s3). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried at 60 ° C. under reduced pressure, washed with 3500 parts of water, filtered, and dried under reduced pressure at 60 ° C. to obtain 263 parts (yield of the compound represented by formula (1-23) (Dye A4)). 65%) was obtained.
The structure of the compound represented by formula (1-23) was determined by elemental analysis. As an analytical instrument, an ICP emission analyzer (ICPS-8100; manufactured by Shimadzu Corporation) was used.
C55.6 H5.1 N11.9 Cr3.71

(Example 7)
A colored photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the dye A1 was replaced with the dye A3. As a result of evaluating the colored photosensitive resin composition 7 in the same manner as in Example 1, the xy chromaticity coordinates (Rx, Ry) (chromaticity) of the obtained colored coating film were (0.641, 0. 326) and the lightness RY was 20.3. In the solvent resistance test, the color difference ΔEab * before and after immersion was as good as 0.7.

  Good solvent resistance was confirmed for the colored coating films formed using the colored photosensitive resin compositions of Examples 1, 2, and 4-7. This shows that it is possible to obtain a colored pattern exhibiting good solvent resistance and a high-quality color filter.

  According to the colored photosensitive resin composition of the present invention, a colored coating film, a colored pattern, and a high-quality color filter with good solvent resistance can be obtained.

Claims (9)

A colored photosensitive resin composition comprising a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant is a colorant containing a compound represented by formula (1).

[In the formula (1), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group.
R ²⁷ represents an ethylene group, propane-1,3-diyl or propane-1,2-diyl group.
R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 4. When n is an integer greater than or equal to 2, several R < ²⁷ > may mutually be same or different. ]   The colored photosensitive composition according to claim 1, wherein the colorant further comprises a pigment.   The pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The colored photosensitive resin composition according to claim 2, which is at least one selected from the group consisting of CI Pigment Red 254.   The resin is a structural unit derived from a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenically unsaturated double bond, and at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. The colored photosensitive resin composition according to claim 1, which is a resin containing a copolymer having a structural unit derived from a seed.   The coloring pattern formed using the coloring photosensitive resin composition in any one of Claims 1-4.   A color filter comprising the colored pattern according to claim 5. A compound represented by formula (2).

[In the formula (2), R ^{1 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ R ²⁹ or —SO. It represents a ₂ R ^32.
R ²⁹ represents —OH or —NHR ³⁰ .
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -O-R ³² ,- R ³¹ —CO—O—R ³² , —R ³¹ —O—CO—R ³² , or an aralkyl group having 7 to 10 carbon atoms is represented.
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group may be substituted with a hydroxy group, —OR ³² , a sulfo group, —SO ₃ Na, —SO ₃ K, or a halogen atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. ] The compound according to claim 7, wherein M ¹ is Cr. The compound according to claim 7 or 8, wherein at least one of R ^{1 to} R ¹⁸ is a nitro group.