JP2012212089A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which can form a colored cured product with more excellent heat resistance and light resistance, and a color filter containing the same.SOLUTION: A colored photosensitive resin composition contains a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), in which the colorant (A) contains salt represented by formula (1).

Description

  The present invention relates to a colored photosensitive resin composition.

  A color filter used for a liquid crystal display element or a solid-state imaging element has a red pixel. It is known that the colored photosensitive resin composition forming the red pixel contains a dye as a colorant. For example, Patent Document 1 describes a colored photosensitive resin composition containing a cyanine dye, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

JP 2010-168531 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) more excellent in heat resistance and light resistance, and a color filter containing the same. .

［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、ニトロ基又は−ＳＯ_２Ｒ^２９を表す。
Ｒ^２９は、−ＯＨ、−ＮＨＲ^３０又は−Ｒ^３２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。
環Ｚ^１及び環Ｚ^２は、互いに独立に、置換基を有していてもよい芳香環を表し、Ｒ^２１及びＲ^２２は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表し、Ｒ^２３及びＲ^２４は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２３とＲ^２４が一緒になってアルカンジイル基を形成してもよく、Ｒ^２５及びＲ^２６は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２５とＲ^２６が一緒になってアルカンジイル基を形成してもよく、Ｒ^２７及びＲ^２８は、互いに独立に、置換基を有してもよい炭素数１〜１２の脂肪族炭化水素基又は水素原子を表すか、Ｒ^２７とＲ^２８が一緒になってアルカンジイル基を形成してもよい。Ｘ^１は、水素原子又は塩素原子を表す。]
［２］光重合開始剤が、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物、オキシム化合物及びビイミダゾール化合物からなる群から選ばれる少なくとも１種を含む光重合開始剤である［１］記載の着色感光性組成物。
［３］Ｍ^１が、Ｃｒである［１］記載の着色感光性組成物。
［４］［１］〜［３］のいずれか一項記載の着色感光性樹脂組成物により形成されるカラーフィルタ。
［５］［４］記載のカラーフィルタを含む表示装置。 The present invention provides the following [1] to [5].
[1] A colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the colorant (A) is represented by the formula (1). A colored photosensitive resin composition which is a colorant containing a salt.

Wherein ^(1), R 1 ^{to R 18,} independently of each other, represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group or a _-SO 2 ^{R 29.}
R ²⁹ represents —OH, —NHR ³⁰ or —R ³² .
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.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ may together form an alkanediyl group, and R ²⁵ and R ²⁶ are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Alternatively, it represents a hydrogen atom, or R ²⁵ and R ²⁶ may be combined to form an alkanediyl group, and R ²⁷ and R ²⁸ may each independently have a substituent having 1 to 1 carbon atoms. 12 aliphatic hydrocarbon groups or hydrogen atoms, or R ²⁷ and R ²⁸ together A lucandiyl group may be formed. X ¹ represents a hydrogen atom or a chlorine atom. ]
[2] The coloring according to [1], wherein the photopolymerization initiator is a photopolymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and biimidazole compounds. Photosensitive composition.
[3] The colored photosensitive composition according to [1], wherein M ¹ is Cr.
[4] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film or a pattern) excellent in light resistance and heat 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), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the colorant (A). Are an anion represented by the following formula (A1) (hereinafter sometimes referred to as “anion (A1)”) and a cation represented by the following formula (A2) (hereinafter sometimes referred to as “cation (A2)”): (Hereinafter sometimes referred to as “salt (1)”).

The anion (A1) can be selected according to the color of the target color filter. It is preferable that the salt containing an anion (A1) is sufficiently dissolved in a solvent. Furthermore, it is preferable that the salt containing an anion (A1) is dissolved in a developing solution used for pattern formation described below to such an extent that the pattern can be formed.

  Note that since the anion (A1) has a resonance structure, the anion in which the charge of the anion described in the formula (A1) is transferred is also included in the present invention.

  In the anion (A1), the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, decyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group and the like.

  In the anion (A1), 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.

  In the anion (A1), the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1 , 4-diyl group, 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 Etc.

  In the anion (A1), the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms includes a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, Examples include 2-butylcyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group and the like.

In the anion (A1), —R ³¹ —O—R ³² includes methoxymethyl group, ethoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxy A propyl group, 2-oxo-4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like can be mentioned.

In the anion (A1), —R ³¹ —CO—O—R ³² includes methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxycarbonylmethyl group, propoxycarbonylethyl group, butoxy Examples thereof include a carbonylmethyl group and a butoxycarbonylethyl group.

In the anion (A1), as —R ³¹ —O—CO—R ³² , acetyloxymethyl group, acetyloxyethyl group, ethylcarbonyloxymethyl group, ethylcarbonyloxyethyl group, propylcarbonyloxymethyl group, propylcarbonyloxy Examples thereof include an ethyl group, a butylcarbonyloxymethyl group, and a butylcarbonyloxyethyl group.

In the anion (A1), as —SO ₂ R ²⁹ , 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.

In the anion (A1), as —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-dimethylheptyl Examples include a sulfonyl group, a 2-ethylhexylsulfonyl 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 formed and further excellent pattern, one 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, —SO ₂ NHR ³⁰ or —SO ₂ R ³² , preferably —SO ₂ R ³² . Among them, preferred is _-SO 2 CH _3.
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.

  The cation (A2) can be selected according to the color of the target color filter. It is preferable that the salt containing a cation (A2) is sufficiently dissolved in a solvent. Furthermore, it is preferable that the salt containing a cation (A2) is dissolved in a developer used for pattern formation described later to such an extent that the pattern can be formed.

  In addition, since the cation (A2) has a resonance structure, a cation in which the charge of the cation described in the formula (A2) is transferred is also included in the present invention.

In the cation (A2), the ring Z ¹ and the ring Z ² each independently represent an aromatic ring which may have a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring.

Examples of the substituent on the benzene ring and the naphthalene ring include
Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl;
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Acyloxy groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group Alkylsulfamoyl groups such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group;
Alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Examples thereof include a nitro group and a cyano group.
When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group An aromatic hydrocarbon group such as a group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group; carboxy group; cyano group; nitro group;

From the viewpoint of solubility, the ring Z ¹ and the ring Z ² are each preferably a benzene ring that may be substituted, and more preferably an unsubstituted benzene ring.

In the cation (A2), X ¹ is preferably a hydrogen atom.

In the cation (A2), R ²¹ and R ²² are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and preferably has a substituent. An aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms having no substituent, and particularly preferably a methyl group. R ²¹ and R ²² are preferably the same group.

In the cation (A2), when R ²¹ and R ²² are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, the aliphatic hydrocarbon group includes, for example, a methyl group, Ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, Examples include isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group;
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.

In the cation (A2), when R ^{23 to} R ²⁸ are an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, the aliphatic hydrocarbon group includes, for example, a methyl group, Ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, Examples include isohexyl group, 5-methylhexyl group, heptyl group, and octyl group.
Examples of the substituent in the aliphatic hydrocarbon group include:
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group.
Halogen groups such as fluoro, chloro, bromo and iodo groups;
Furthermore, a carboxy group, a nitro group, and a cyano group are mentioned.
Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group is mentioned.

In the cation (A2), when R ^{23 to} R ²⁸ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, preferably has a substituent. An alkyl group having 1 to 3 carbon atoms, more preferably a methyl group which may have a substituent, and particularly preferably a methyl group having no substituent. R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ are preferably the same group.

In the cation (A2), when R ²³ and R ²⁴ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

In the cation (A2), when R ²⁵ and R ²⁶ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms. More preferably a pentane-1,5-diyl group.

  Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include a lower alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Can be mentioned.

In the cation (A2), when R ²⁷ and R ²⁸ together form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms. More preferably a propane-1,5-diyl group.

Examples of the hydrocarbon ring formed from the alkanediyl group include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include a lower alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Can be mentioned.

  Among the salts (1), preferred examples of the pyrazole azo compound that serves as a ligand for the anion (A1) include compounds represented by the formulas (1-a1) to (1-a64).

  Among the salts (1), preferred examples of the anion (A1) include anions represented by the formulas (1-b1) to (1-b60).

  Among the salts (1), preferred examples of the cation (A2) include cations represented by the formula (1-c1) to the formula (1-c36).

  Next, the manufacturing method of the salt containing an anion (A1) is demonstrated. The anion (A1) can be produced by reacting the compound represented by (1d) (hereinafter sometimes referred to as “compound (1d)”) with a chromium compound or a cobalt compound in an organic solvent.

［式（１ｄ）中、Ｒ^１〜Ｒ^５、Ｒ^１１〜Ｒ^１４及びＲ^１９は、上記と同じ意味を表す。］

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

  Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, and acetonitrile.

  The compound (1d) which becomes a ligand of the complex anion of the salt (1) can be produced by a diazo coupling method of a diazonium salt and a pyrazole compound. For example, it is represented by the formula (1b) obtained by diazotizing an amine represented by the 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 described above. 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 -, C 6}} H 5 COO - , 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 described above. ]

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 at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and further 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 further stir at said 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.

The anion (A1) in which M ¹ in the formula (A1) is Cr can be produced by reacting the compound (1d) with a chromium compound at 70 to 100 ° C. in an aqueous solvent. 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.

［式（ｂ）中、Ｒ^２１〜Ｒ^２８及びXは、式（１）中のものと同じ意味を表す。Ａ⁻は、１価のアニオンを表す。］
１価のアニオンとしては、Ｃｌ⁻、Ｂｒ⁻、Ｉ⁻、ＣｌＯ_４ ⁻、ＰＦ_６ ⁻又はＢＦ_４ ⁻等が挙げられる。 Next, the manufacturing method of the salt which can manufacture the cation (A2) of salt (1) is demonstrated.
Examples of the salt containing a cation (A2) include the following structures.

[In formula (b), R ^{21 to} R ²⁸ and X 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 ⁻ .

The salt containing a cation (A2) can be produced by a known synthesis method.
For example, as described in J. Mater. Chem., 1999, 6 (4), 559-565, indole is reacted with an alkyl halide to give compound (b-0), which is then reacted with triethoxymethane in the presence of a base. By the reaction, cyanine (b-1) having a halide ion as a counter ion is obtained. The counter ion of (b-1) can be induced to the target counter ion by a salt exchange reaction with NaClO ₄ , NaPF ₆ , and NaBF ₄ .

Next, the manufacturing method of salt (1) is demonstrated.
The salt (1) can be produced by subjecting a salt containing an anion (A1) and a salt containing a cation (A2) to a salt exchange reaction in a solvent. The anion (A1) and the cation (A2) are preferably reacted at a molar ratio of 1: 1 to 1: 4.

When the anion (A1) 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 do. 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.

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

  The content of the salt (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 salt (1) together with the salt (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 together with the salt (1).
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, the transmission spectrum can be easily optimized and the chemical resistance is improved.
These pigments may be used alone or in combination of two or more.

If necessary, the 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. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When 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.

When a pigment is contained in the colorant (A), the content of the pigment is preferably 1 to 99% by mass, more preferably 10 to 97% by mass.
The content ratio (mass ratio) of the salt (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, salt (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] a monomer (a) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a)"), an unsaturated carboxylic acid and an unsaturated carboxylic acid A copolymer with at least one (b) selected from the group consisting of anhydrides (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) has, for example, a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (A) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

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

  (A1) 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. And monomer (a1-2) (hereinafter may be referred to as “(a1-2)”).

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

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

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

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

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

  (A) is preferably (a1) in that the reliability of the 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 0.002 with respect to the total amount of (a) to (c). 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 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, and for example, a polymerizable ethylenically unsaturated bond The compound etc. which have these are mentioned, Preferably a (meth) acrylic acid ester compound is mentioned.

  Among these, the photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. The photopolymerizable compound (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 superposition | 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.
The photopolymerization initiator (D) is preferably a compound that generates an active radical by the action of light, and is at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds, and biimidazole compounds. Is more preferable, and a photopolymerization initiator containing an oxime compound is more preferable.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl. Butan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- And oligomers of [4- (1-methylvinyl) phenyl] propan-1-one, etc. Examples thereof include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. It is done. Commercial products such as Irgacure 369, 907 (manufactured by Ciba Japan) may be used.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

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

  The 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 parts by mass, more preferably 1 to 100 parts by mass of the total amount of the resin (B) and the photopolymerizable compound (C). ˜20 parts by mass. When the content of the photopolymerization initiator is within the above range, 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 phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid -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 photopolymerization start adjuvant (D1), the usage-amount is preferably 0.01-50 mass parts with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), More preferably, it is 0.1-40 mass parts. Moreover, it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, relative to 1 mol of the photopolymerization initiator (D). When the amount of the polymerization initiation assistant (D1) is within this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

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, propylene glycol monomethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable. When these solvents are included, the flatness during application is excellent.

  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.

  The colored photosensitive resin composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc., as necessary. May be included.

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, and the like. .

  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 aqueous solutions of alkaline compounds (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.). The developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. Post baking is preferably in the range of 150 to 230 ° C. and 10 to 240 minutes, for example.

  According to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film, a pattern and a high quality color filter having good heat resistance and light resistance. Also, display devices including these color filters or patterns as a part of their components, for example, all known devices related to various colored images, such as liquid crystal display devices, organic EL devices, solid-state imaging devices, etc. It can be utilized in the form of.

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
65 parts of methyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 63 parts of 2,3,3-trimethyl-3H-indole (manufactured by Wako Pure Chemical Industries, Ltd.), followed by heating at 140 ° C. for 6 hours. After cooling, 120 parts of diethyl ether was added and the resulting precipitate was collected by filtration, washed with cold acetone, dried under reduced pressure, and 1-methyl-2,3,3-trimethyl-3H-indolium iodide. 102 parts were obtained (86%). Subsequently, 470 parts of pyridine, 64 parts of triethylamine, 100 parts of 1-methyl-2,3,3-trimethyl-3H-indolium iodide and 64 parts of ethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) are reacted at 120 ° C. for 1 hour. I let you. After cooling, a precipitate obtained by gradually adding 800 parts of diethyl ether is obtained by filtration. This solid was recrystallized using ethanol and then dried under reduced pressure at 60 ° C. for 24 hours to obtain 145 parts of cyanine compound (d-1) (90%).

Identification of compound represented by formula (d-1) (mass spectrometry) ionization mode = ESI +: m / z = 357.3 [M−I ⁻ ] ⁺
Exact Mass: 484.1

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) ( Yield 63%) was obtained.

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

  4 parts of the compound represented by the formula (z-2) were dissolved in 70 parts of N-methyl-2-pyrrolidone. A solution prepared by dissolving 2 parts of the compound represented by the formula (d-1) in 15 parts of N-methyl-2-pyrrolidone was added to this solution and stirred for 2 hours. After stirring, 300 parts of water was slowly added dropwise, and the precipitated red solid was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 4.5 parts of the compound represented by the formula (1-27) (yield 88 %).

Synthesis example 2
<Synthesis of Resin Solution B1>
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 140 parts of ethyl lactate, and the solution is added at 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., then cooled to room temperature, and the weight average molecular weight Mw, 1.3 × 10 ^4, a solid content 33 wt%, a solution acid value A resin B1 solution of 34 mg-KOH / g was obtained. Calculated from the solid content and the solution acid value, the solid content acid value of the resin B1 is 100 mg-KOH / g.

Synthesis example 3
<Synthesis of Resin Solution B2>
333 parts 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. Thereafter, the temperature of the solution in the flask was raised to 100 ° C., and then 18.7 parts of N-benzylmaleimide, 70.5 parts of benzyl methacrylate, 51.7 parts of methacrylic acid, 90.0 parts of methyl methacrylate, azobisisobutyro A mixture consisting of 5.2 parts of nitrile and 182 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours using a dropping funnel, and stirring was further continued at 100 ° C. for 5 hours after completion of the addition.
After the stirring was completed, 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 parts of trisdimethylaminomethylphenol and 0.165 parts of hydroquinone were added to the flask. The reaction was continued at 110 ° C. for 6 hours to obtain a resin B2 solution 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-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

Example 2
[Preparation of colored photosensitive resin composition]
(A) Salt (1): Compound represented by formula (1-27) 30 parts (B) Resin: Resin B1 (solid content conversion) 40 parts (C) Photopolymerizable compound: Dipentaerythritol pentaacrylate and di Mixture with pentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2 -Imine (Irgacure OXE 01; manufactured by BASF Japan) 12 parts (D) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; BASF Japan) 6 parts (D2) photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (EAB-F; Hodogaya Chemical) Ltd.)) 2 parts (E) Solvent: 528 parts of propylene glycol monomethyl ether acetate (E) Solvent: Propylene glycol monomethyl ether 69 parts
(F) Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.09 part was mixed to obtain a colored photosensitive resin composition.

[Formation of pattern]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then prebaked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 100 mJ / Light irradiation was performed with an exposure amount of cm ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. After the light irradiation, the 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 film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and found to be 2.0 μm.

[Heat resistance evaluation]
In the above pattern formation, the same operation was performed except that exposure was performed without using a photomask, and a coating film was prepared. After the obtained coating film was stored in an oven at 230 ° C. for 2 hours, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the color matching function of the C light source was determined. The xy chromaticity coordinates (Rx, Ry) (ie, chromaticity) and lightness RY before and after the heat resistance test were measured in the CIE XYZ color system, and the color difference ΔEab * before and after the heat resistance test was calculated. The smaller the color difference ΔEab *, the better the heat resistance. The results of the color difference ΔEab * are shown in Table 1.

(Light resistance evaluation)
In the above pattern formation, the same operation was performed except that exposure was performed without using a photomask, and a coating film was prepared. The obtained coating film was stored for 48 hours under irradiation of a xenon lamp (manufactured by Toyo Seiki Seisakusho Co., Ltd .: Suntest CPS +), and then spectroscopically analyzed using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). Measure xy chromaticity coordinates (Rx, Ry) (that is, chromaticity) and lightness RY before and after the heat test in the CIE XYZ color system using the color matching function of the C light source. The color difference ΔEab * was calculated. The smaller the color difference ΔEab *, the better the heat resistance. The results of the color difference ΔEab * are shown in Table 1.

Comparative Example 1
(A) Colorant: Compound represented by formula (d-1) 10.2 parts (B) Resin: Resin solution B1 (solid content conversion) 40 parts (C) Photopolymerizable compound: Dipentaerythritol pentaacrylate Mixture with dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts (D) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one- 2-imine (Irgacure OXE 01; manufactured by BASF Japan) 12 parts (D) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; BASF 6 parts (D2) photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (EAB-F; Hodogaya) 2 parts (E) Solvent: N, N-dimethylformamide 445 parts (E) Solvent: Propylene glycol monomethyl ether 60 parts (E) Solvent: Propylene glycol monomethyl ether acetate 8 parts (F) Surfactant : Megafac F475 (manufactured by DIC Corporation) 0.1 part was mixed to obtain a colored photosensitive resin composition. The colored photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  The coating film formed using the colored photosensitive resin composition of the present invention was confirmed to have good heat resistance and light resistance. This shows that it is possible to obtain a pattern exhibiting good heat resistance and light resistance and a high-quality color filter.

  According to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film, a pattern and a high quality color filter having good heat resistance and light resistance.

Claims (5)

A salt containing a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) is represented by the formula (1) The coloring photosensitive resin composition which is a coloring agent containing this.

Wherein ^(1), R 1 ^{to R 18,} independently of each other, represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group or a _-SO 2 ^{R 29.}
R ²⁹ represents —OH, —NHR ³⁰ or —R ³² .
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.
Ring Z ¹ and Ring Z ² each independently represent an optionally substituted aromatic ring, and R ²¹ and R ²² each independently represent a substituent having 1 to 1 carbon atoms. 12 represents an aliphatic hydrocarbon group or a hydrogen atom having 12 carbon atoms, and R ²³ and R ²⁴ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, R ²³ and R ²⁴ may together form an alkanediyl group, and R ²⁵ and R ²⁶ are each independently an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Alternatively, it represents a hydrogen atom, or R ²⁵ and R ²⁶ may be combined to form an alkanediyl group, and R ²⁷ and R ²⁸ may each independently have a substituent having 1 to 1 carbon atoms. 12 aliphatic hydrocarbon groups or hydrogen atoms, or R ²⁷ and R ²⁸ together A lucandiyl group may be formed. X ¹ represents a hydrogen atom or a chlorine atom. ]   The coloring according to claim 1, wherein the photopolymerization initiator (D) is a photopolymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and biimidazole compounds. Photosensitive composition. The colored photosensitive composition according to claim 1, wherein M ¹ is Cr.   The color filter formed with the coloring photosensitive resin composition as described in any one of Claims 1-3.   A display device comprising the color filter according to claim 4.