KR101734978B1 - Colored photosensitive resin composition - Google Patents

Abstract

A colored photosensitive resin composition comprising a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is a colorant comprising a pyridone azo metal complex compound.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

It is known to use a dye as a coloring agent in a colored photosensitive resin composition for enhancing the contrast of a color filter in a colored photosensitive resin composition forming a red pixel of a color filter. For example, Patent Document 1 describes a colored photosensitive resin composition containing Orasol Red G as a red dye.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 2009-163226

It is an object of the present invention to provide a colored photosensitive resin composition which is capable of obtaining a colored cured product having a higher solvent resistance (for example, a colored coating film, a colored pattern) and a color filter containing the same.

The present invention provides the following inventions [1] to [9].

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

[In the formula (1), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .

R ²⁹ represents -OH or -NHR ³⁰ .

R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ¹ represents Cr or Co.

R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

R ²⁷ represents an ethylene group, a propane-1,3-diyl group or a propane-1,2-diyl group.

And R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R < ²⁷ > s may be the same or different.]

[2] The colored photosensitive composition according to [1], wherein the colorant is also a colorant containing a pigment.

[3] The process according to [1], wherein the pigment is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment Red 254. The colored photosensitive resin composition according to < 2 >

[4] A resin composition comprising a structural unit derived from a monomer having a cyclic ether and an ethylenically unsaturated double bond having 2 to 4 carbon atoms, and a structure derived from at least one member selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride [1] to [3], wherein the resin is a resin containing a copolymer having a unit represented by the following formula (1).

[5] A coloring pattern formed using the colored photosensitive resin composition according to any one of [1] to [4].

[6] A color filter comprising a coloring pattern according to [5].

[7] A compound represented by formula (2).

[In the formula (2), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .

R ²⁹ represents -OH or -NHR ³⁰ .

R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ¹ represents Cr or Co.

R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

[8] The compound according to [7], wherein M ¹ is Cr.

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

The colored photosensitive resin composition of the present invention comprises a colorant (A), an alkali soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) (Hereinafter sometimes referred to as " compound (1) ").

Compound (1) is a salt with catechin derived from chromium complex ion or cobalt complex anion and xanthene compound.

[In the formula (1), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .

R ²⁹ represents -OH or -NHR ³⁰ .

R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ¹ represents Cr or Co.

R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

R ²⁷ represents an ethylene group, a propane-1,3-diyl group or a propane-1,2-diyl group.

And R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R < ²⁷ > s may be the same or different.]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group, an isobutyl group, a n-hexyl group, Ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.

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

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

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

Examples of the cyclohexyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms include a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-butylcyclohexyl group A 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4-isopropylcyclohexyl group, and a 4-butylcyclohexyl group.

-R ³¹ -OR ^{32 is preferably a} methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, 4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

Examples of -R ³¹ -CO-OR ³² include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonyl Methyl group, and butoxycarbonyl ethyl group.

-R ³¹ -O-CO-R ^{32 is preferably an} acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, Butylcarbonyloxyethyl group and the like.

Examples of -SO ₂ R ²⁹ include a sulfo group; Sulfamoyl group; N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Substituted with an aliphatic hydrocarbon group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- Sulfamoyl group;

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ), A sulfamoyl group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- (3-tert-butoxypropyl) sulfamoyl group, A sulfamoyl group substituted with R ³¹ -OR ³² ;

(Methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (Propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) A sulfamoyl group substituted with -R ³¹ -CO-OR ^{32 such} as a sulfamoyl group;

N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (acetyloxymethyl) sulfamoyl group, N- (Propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group and the like A sulfamoyl group substituted with -R ³¹ -O-CO-R ³² ;

(2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- 4-butylcyclohexyl) sulfamoyl group and the like; a sulfamoyl group substituted with a cyclohexyl group having a substituent;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) Pamoyl group, and sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

Examples of -SO ₂ R ³² include a methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert- Methylhexylsulfonyl group, 1,1,3,3-tetramethylbutylsulfonyl group, 1,5-dimethylhexylsulfonyl group, 1,6-dimethylheptylsulfonyl group, 2-ethyl Hexylsulfonyl group, and 1,1,5,5-tetramethylhexylsulfonyl group. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

It is preferable that at least one of R ¹ to R ¹⁸ is a nitro group.

It is preferable that at least one of R ¹ to R ⁵ and at least one of R ⁶ to R ¹⁰ is -SO ₂ R ²⁹ . When the -SO ₂ R ²⁹ having more than one, a plurality of R ²⁹ may be the same or different from each other.

-SO ₂ R ²⁹ is -SO ₃ H or -SO ₂ NHR ³⁰ , preferably -SO ₂ NHR ³⁰ . Among them, a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a 2-ethylhexyl group is more preferable.

If the compounds of the invention having a -SO ₂ R ^32, at least one of R ¹¹ and R 1 ~R at least ¹⁵ of the ¹⁴ ~R ¹⁸ is preferably -SO ₂ R ^32. When there are a plurality of -SO ₂ R ³² , a plurality of R ^{32 s} may be the same or different.

R ²¹ to R ²⁴ are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group because the color density is high.

As R ^{27, an} ethylene group and a propane-1,2-diyl group are preferable, and an ethylene group is more preferable.

As R ^{28, a} hydrogen atom is preferable.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4.

- (R ²⁷ -O) _n -R ²⁸ tends to improve the solubility of the compound (1) in an organic solvent, and therefore, a 2- (2-hydroxyethoxy) Hydroxyethoxy) ethoxy] ethyl group is preferable, and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group is more preferable.

Preferable examples of the pyrazole compound in the compound (1) to be the ligand of the complexing agent include compounds represented by the formulas (1-a1) to (1-a64).

In the compound (1), preferred examples of the anion are anions represented by the formulas (1-b1) to (1-b60).

In the compound (1), preferred examples of the catehene derived from the xanthene compound include cateens represented by the formulas (1-c1) to (1-c48).

The compound (1) can be obtained by forming a chromium complex salt using a compound represented by the formula (1d) (hereinafter sometimes referred to as "compound (1d)") and a chromium compound and then reacting the chromium complex salt with a xanthene compound (1d) and a cobalt compound to form a cobalt complex salt, and then subjecting the cobalt complex salt and the xanthene compound (b) to a salt-exchange reaction.

[In formula (a4), R ¹ to R ⁵ , R ¹¹ to R ¹⁴ and R ¹⁹ have the same meanings as in formula (1).]

[In the formula (b), R ²¹ to R ²⁸ and n have the same meanings as in the formula (1). A ^- represents a monovalent anionic.]

Examples of univalent anions include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^- or BF ₄ ^- and the like.

The xanthene compound (b) can be produced by reacting the compound represented by the formula (b0) with the compound represented by the formula (b1) in an organic solvent.

[In formulas (b0) and (b1), R ²¹ to R ²⁸ and n have the same meanings as in formula (1). A ^- has the same meaning as in formula (b).]

In the above-mentioned reaction, the reaction temperature is preferably 15 ° C to 60 ° C, and the reaction time is preferably 1 hour to 12 hours. In addition, from the viewpoint of shortening the reaction time or improving the yield, it is preferable to use an acid catalyst and / or a dehydrating agent.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid and the like.

Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; Di-2-pyridyl carbonate, and the like. Among them, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as a dehydrating agent since post treatment and purification are easy.

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

The compound (1d) which is a ligand of anions of the compound (1) can be prepared by a method of diazotizing a diazonium salt and a pyrazole compound well known in the dye field. (1b) obtained by diazotizing amino (diazo component) represented by the formula (1a) [hereinafter sometimes referred to as "amino (1a)") with nitrite, nitrite or nitrite ester The compound can be used as the diazonium salt.

[In formulas (1a) and (1b), R ¹¹ to R ¹⁴ have the same meanings as in formula (1). A ¹ represents an inorganic or organic anion.]

Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a hypochlorite ion, and the like.

Examples of the organic anion include CH ₃ COO ^- , PhCOO ^- and the like.

Preferred examples thereof include chloride ion, bromide ion, CH ₃ COO ^- and the like.

A compound represented by formula (1d) (hereinafter sometimes referred to as "compound (1d)") may be prepared by diazotizing a compound represented by formula (1b) and a compound represented by formula (1c) in an aqueous solvent . 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 the formula (1c), R ¹ to R ⁵ and R ¹⁹ have the same meanings as in the formula (1).]

When the compound (1d) has -SO ₂ R ²⁹ and -SO ₂ R ²⁹ is -SO ₂ NHR ³⁰ , it can also be prepared by using an amine (1a) having -SO ₂ NHR ³⁰ , After the coupling reaction is carried out using the amine (1a), the sulfone group is preferably sulfonated. For example, an azo compound having a sulfo group in the compound (1d) (hereinafter sometimes referred to as "compound (1s)") is synthesized and a sulfo group (-SO ₃ H) (1d) is obtained by sulfonylating the sulfo group by reacting a sulfonyl halide compound with an amine (R ³⁰ NH ₂ ) by sulfonyl halide (-SO ₂ X; X is a halogen atom) to obtain a sulfonyl halide compound, Can be produced.

Specific examples of the compound (1s) include a compound represented by the formula (1-a1), a formula (1-a2) and a formula (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. Particularly preferred thionyl chloride is thionyl chloride . The amount of the thionyl halide to be used is preferably 1 to 10 moles per 1 mole of the compound (1s). Further, when water is added to the reaction system, it is preferable to use a thionyl halide compound in excess.

The sulfonyl halide is carried out in a solvent. As the solvent, for example, ethers such as 1,4-dioxane (particularly preferably, cyclic ethers); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichlorethylene, tetrachlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane can be used. The amount of the solvent to be used is generally 3 parts by mass or more, preferably 5 parts by mass or more, and usually 10 parts by mass or less, preferably 8 parts by mass or less, based on 1 part by mass of the compound (1s).

N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide or the like) is preferably used in sulfonyl halide formation. When N, N-dialkylformamide is used, its amount to be used is usually 0.05 to 1 mol per 1 mol of thionyl halide compound. Compound (1s) and N, N-dialkylformamide are mixed in a solvent in advance, and thionyl halide compound is added to suppress heat generation.

In the case of sulfonyl halide formation, the reaction temperature is usually 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 hour or more, preferably 3 hours or more, usually 8 hours or less, preferably 5 hours or less.

The sulfonyl halide compound prepared as described above is separated (單離), and then they may be an amine (R ³⁰ NH ₂₎ and is be reacted, without isolation of the reaction mixture as the amine (R ³⁰ NH ₂₎ and reaction. In the case of separation, the reaction mixture and water may be mixed and the precipitated crystals may be filtered off. The crystals of the obtained sulfonyl halide compound may be washed and dried with water as needed 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 Tetramethylbutylamine), ethylhexylamine (2-ethylhexylamine, etc.), aminophenylbutane (3-amino-1-phenylbutane and the like), isopropoxypropylamine and the like. The amount of the amine (R ³⁰ NH ₂ ) to be used is usually 2 mol or more and 10 mol or less, preferably 2 mol or more and 7 mol or less per 1 mol of the sulfonyl halide compound.

The order of addition of the sulfonyl halide compound and 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. Further, the reaction between the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is preferably carried out in a solvent. As the solvent, a solvent such as a solvent for preparing a sulfonyl halide compound can be used.

Further, the reaction of the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is preferably carried out in the presence of a basic catalyst. Examples of the basic tackifier 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; And cyclic aliphatic secondary amine such as pyridine). Of these, tertiary amines, especially aliphatic tertiary amines such as triethylamine, are preferred. The amount of the basic catalyst to be used is usually 1.1 mol or more and 6 mol or less, preferably 1.1 mol or more and 5 mol or less, based on the amine (R ³⁰ NH ₂ ).

When the amine (R ³⁰ NH ₂ ) and the basic catalyst are added to the sulfonyl halide compound, the timing of adding the basic catalyst is not particularly limited, but may be either before or after the addition of the amine (R ³⁰ NH ₂ ) , it may be added to the amine at the same timing, and (R ³⁰ NH _2). Further, it may be added after mixing with the reactive amine in advance, or may be added separately from the amine (R ³⁰ NH ₂ ).

The reaction temperature of the sulfonyl halide compound and the amine (R ³⁰ NH ₂ ) is usually 0 ° C or more and 50 ° C or less, preferably 0 ° C or more and 30 ° C or less. The reaction time is usually 1 to 5 hours.

A method for obtaining the desired compound (1d) from the reaction mixture is not particularly limited, but various known methods may be employed. For example, it is preferable to mix the reaction mixture with an acid (for example, acetic acid) and water, and to filtrate the precipitated crystals. It is preferable that the acid is prepared in advance of an aqueous solution of an acid, and then the reaction mixture is added to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C or higher and 50 ° C or lower, preferably 20 ° C or higher and 50 ° C or lower, more preferably 20 ° C or higher and 30 ° C or lower. Further, it is preferable that the reaction mixture is added to an aqueous solution of an acid and stirred at the same temperature for about 0.5 to 2 hours. The filtered crystals are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

When the anion portion of the compound (1) is a chromium anion ion [when M ¹ in the formula (1) is Cr], by reacting the compound (1d) and a chromium compound in an aqueous solvent, usually at 70 to 100 ° C Can be manufactured. The compound (1d) and the chromium compound are preferably reacted at a molar ratio of 2: 1 to 4: 1.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride and the like, preferably chromium formate, chromium acetate and the like.

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

When the anion portion of the compound (1) is a cobalt anion ion [when M ¹ in the formula (1) is Co], by reacting the compound (1d) and the cobalt compound in an aqueous solvent at 70 to 100 ° C Can be manufactured. It is preferable to react the compound (1d) and the cobalt compound at a molar ratio of 2: 1 to 4: 1.

Examples of the cobalt compound include cobalt chloride, cobalt acetate, cobalt sulfate and tris (2,4-pentanedionato) cobalt (III), and preferably tris (2,4-pentanedionato) cobalt (III) And the like.

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

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

Among the compounds (1), compounds represented by the formula (2) (hereinafter sometimes referred to as "compounds (2)") are preferable in that the solubility in an organic solvent is high.

[In the formula (2), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .

R ²⁹ represents -OH or -NHR ³⁰ .

R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ¹ represents Cr or Co.

R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

M ¹ is preferably Cr.

It is preferable that at least one of R ¹ to R ¹⁸ is a nitro group. The presence of a nitro group tends to increase the heat resistance.

At least one of R ¹ to R ⁵ and at least one of R ⁶ to R ¹⁰ is preferably -SO ₂ R ²⁹ , and among them, -SO ₃ H (that is, R ²⁹ is -OH) and -SO ₂ NHR ³³ (That is, R ²⁹ is -NHR ³³ ).

When the compound (2) having a -SO ₂ R ^32, at least one of R ¹¹ and R 1 ~R at least ¹⁵ of the ¹⁴ ~R ¹⁸ is preferably -SO ₂ R ^32.

R ³³ is a hydrogen atom or a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include those exemplified above. Had have a -SO ₂ R ^29, R ²⁹ is -NHR ³³ also the compounds, except for changing the amine (R ³⁰ NH ₂₎ of the amine (R ³³ NH ₂₎ to be prepared in the same way as compound (1) .

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

The content of the compound (1) in the colorant (A) 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 still more preferably 3% by mass or less by mass.

The colorant (A) may contain a dye different from the compound (1). Examples of the dyes include useful dyes, acid dyes, dyes such as amine salts of acid dyes and sulfonamide derivatives of acid dyes, and for example, compounds classified as dyes in the Color Index (The Society of Dyers and Colourists) Or a known dye described in Dyeing Note (Shika Sensha).

Specifically, C.I. 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Solvent Yellow 4 (hereinafter, the description of C.I.Solvent Yellow is omitted and only the description is given);

C.I. Solvent Red 45, 49, 125, 130;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56; C.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, 112, 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, 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, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 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; C.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, 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, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct dyes,

C.I. As a modern dye, C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; C.I. And modern dyes.

The colorant (A) may also contain a pigment.

As the pigment, an organic pigment such as C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.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 , 147, 148, 150, 153, 154, 166, 173, 194 and 214; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, And the like. Among them, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254, in addition to the pigment. By including the above-mentioned pigment, the transmission spectrum of the red photosensitive resin composition can be easily optimized and the chemical resistance can be improved.

These pigments may be used singly or in combination of two or more kinds.

If necessary, the organic pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with a solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like.

The organic pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the above-mentioned pigment dispersant include surfactants such as caterpenic, 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.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), Sole Spares (manufactured by Zeneca), EFKA (Manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Beck Chemicals).

When a pigment dispersant is used, its amount to be used is preferably 100% by mass, more preferably 5% by mass or more and 50% by mass or less based on the pigment (A2). When the amount of the pigment dispersant is in the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

The content of the pigment in the colorant (A) is preferably from 1 to 99% by mass, and more preferably from 10 to 97% by mass.

The content ratio (mass ratio) of the compound (1) to the pigment is preferably 1: 99 to 99: 1, more preferably 3: 97 to 90: 10. Such a ratio is preferable because the transmission spectrum can be easily optimized and high contrast and high brightness can be obtained. Further, heat resistance and chemical resistance are improved.

Particularly, the compound (1) and C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment Red 254 is preferably 3: 97 to 90: 10, more preferably 3: 97 to 70: 30.

The content of the colorant (A) is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and still more preferably 10 to 50 mass%, based on the solid content in the colored photosensitive resin composition. Here, the solid content refers to the total of components in the colored photosensitive resin composition excluding the solvent. When the content of the colorant (A) is within the above range, it is possible to form a pattern having sufficient color density in a color filter, containing a required amount of a binder polymer in the composition, and sufficient mechanical strength.

The colored photosensitive resin composition of the present invention comprises the resin (B). The resin (B) is not particularly limited, but is preferably an alkali-soluble resin.

As the resin (B), for example, the following resins [K1] to [K4] and the like can be mentioned.

(K1) at least one monomer (b) selected from the group consisting of a monomer (a) having a cyclic ether having 2 to 4 carbon atoms (hereinafter sometimes referred to as "a") and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, (Hereinafter sometimes referred to as " b ").

(Hereinafter sometimes referred to as " (c) ") of the monomer (c) copolymerizable with [K2] (a) and (b) Copolymer.

[K3] Copolymer of (b) and (c).

[K4] Resin obtained by reacting (a) a copolymer of (b) and (c).

By including the structural unit derived from (a) in the resin (B), the reliability of heat resistance, chemical resistance, etc. of the resulting colored pattern can be further improved.

(a) is, for example, a cyclic ether having 2 to 4 carbon atoms (for example, at least one kind selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring (oxolane ring) Refers to a polymerizable compound having a polymerizable group other than a type ether. (a) is preferably a cyclic ether having 2 to 4 carbon atoms and a monomer having an ethylenic carbon-carbon double bond, more preferably a cyclic ether having 2 to 4 carbon atoms and a monomer having a (meth) acryloyloxy group Do.

In the present specification, "(meth) acrylic acid" represents at least one member selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(a1) having an oxiranyl group (hereinafter sometimes referred to as "(a1)"), a monomer (a2) having an oxetanyl group (hereinafter referred to as " , And a monomer (a3) having a tetrahydrofuryl group [hereinafter sometimes referred to as "(a3)"). Among them, the monomer (a1) having an oxiranyl group is preferable, and the monomer (a1-2) (hereinafter sometimes referred to as "(a1-2)") having a structure in which a cyclic olefin is epoxidized is preferable .

The monomer (a1) having an oxiranyl group indicates a polymerizable compound having a polymerizable group other than an oxiranyl group and an oxiranyl group. (a1) may be a monomer (a1-1) having a structure obtained by epoxidizing a chain olefin (hereinafter sometimes referred to as "(a1-1)"), a structure obtained by epoxidizing a cyclic olefin (A1-2).

(a1) is preferably a monomer having an oxiranyl group and an ethylenic carbon-carbon double bond, more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group.

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl- Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) have.

(a1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Sucoxide 2000; (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, CYRAMER A400; (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, Cyclomer M100; (Manufactured by Daicel Chemical Industries, Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II).

[In the formulas (I) and (II), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ¹ and X ² independently represent a single bond, -R ^c -, -R ^c -O-, -R ^c -S-, or -R ^c -NH.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Indicates a binding hand with O.]

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

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

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- A 6-diyl group and the like.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents a bond with O), * -CH ₂ CH ₂ -O- group , More preferably a single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15). (I-1), (I-3), (I-5), (I-7) ). (I-1), (I-7), (I-9) and (I-15) are more preferred.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula ). (II-1), formula (II-7), formula (II-9) and formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. They may be mixed at an arbitrary ratio. When mixed, the mixing ratio thereof is preferably in a molar ratio of 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 in formula (I): formula (II) ~ 80: 20.

The monomer (a2) having an oxetanyl group means a polymerizable compound having a polymerizable group other than an oxetanyl group and an oxetanyl group. (a2) is preferably a monomer having an oxetanyl group and an ethylenic carbon-carbon double bond, more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (a2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

The monomer (a3) having a tetrahydrofuryl group refers to a polymerizable compound having a polymerizable group other than a tetrahydrofuryl group and a tetrahydrofuryl group. (a3) is preferably a monomer having a tetrahydrofuryl group and an ethylenic carbon-carbon double bond, more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

Specific examples of the monomer (a3) include tetrahydrofurfuryl acrylate (for example, Viscont V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(a) is preferably (a1) in that the reliability of the obtained color pattern in heat resistance, chemical resistance and the like can be further enhanced. Furthermore, (a1-2) is more preferable in view of excellent storage stability of the colored photosensitive resin composition.

(b) include, for example, 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-vinyloctanoic acid, 4-vinyloctanoic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic acid anhydride, itaconic anhydride, 3-vinyl butanoic anhydride, 4-vinyl butanoic anhydride, 3,4,5,6-tetrahydrophotoic anhydride, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acid anhydrides such as phthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl (meth) acrylate] of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- ] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable in view of copolymerization reactivity and solubility in an aqueous alkali solution.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl -Cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate [which is conventionally referred to in the art as dicyclopentanyl (meth) acrylate) (Meth) acrylate, naphthyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, (Meth) 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, and diethyl itaconate;

Benzocyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] - ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [ 2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2- - ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the respective structural units derived from each of them is preferably in the following range in the total structural units constituting the resin [K1].

a structural unit derived from (a); 60 to 98 mol% (more preferably 65 to 95 mol%),

a 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 within the above range, the solvent stability of the storage stability, developability and curing pattern tends to be good.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis", published by Takeshi Otsu, 1st Ed., 1st Edition, published on March 1, 1972, Can be prepared by referring to the literature.

Concretely, there is exemplified a method in which a predetermined amount of (a) and (b), a polymerization initiator and a solvent are mixed in a reaction vessel, and oxygen is replaced by nitrogen, thereby stirring, heating and maintaining the oxygen under deoxygenation. The polymerization initiator and solvent used herein are not particularly limited, and any of those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (such as benzoyl peroxide) And the solvent may be any one obtained by dissolving the respective monomers, and as the solvent of the photosensitive resin composition, a solvent described later or the like may be used.

The solution obtained after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) extracted by re-precipitation or the like may be used. In particular, the solvent after the reaction can be used as it is by using the solvent (D) to be described later as a solvent in the polymerization, and the production process can be simplified.

In the resin [K2], the ratio of the structural units derived from each of them is preferably in the following range in the total structural units constituting the resin [K2].

a structural unit derived from (a); 2 to 95 mol% (more preferably 5 to 80 mol%)

a structural unit derived from (b); 2 to 40 mol% (more preferably 5 to 35 mol%)

a 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 within the above range, the storage stability, developability, solvent resistance of the cured pattern, heat resistance and mechanical strength tend to be good.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Specifically, there are a method of mixing predetermined amounts of (a), (b) and (c), a polymerization initiator and a solvent in a reaction vessel and substituting oxygen by nitrogen to stir, have. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used. Or may be used as a solid (powder) extracted by a method such as re-precipitation.

In the resin [K3], the ratio of the structural units derived from each of them is preferably in the following range in the total structural units constituting the resin [K3].

(b) 2 to 40 mol%, more preferably 5 to 35 mol%

(c) 60 to 98 mol%, more preferably 65 to 95 mol%

The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Resin [K4] can be obtained by obtaining a copolymer of (b) and (c) and adding (c) having a carboxy group to the cyclic ether (a) having 2 to 4 carbon atoms.

First, a copolymer of (b) and (c) is prepared in the same manner as described for the production of [K1]. In this case, the ratio of the respective structural units derived from each of them is preferably in the following range in the total 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%

Subsequently, a cyclic ether (a) having 2 to 4 carbon atoms is reacted with a part of the carboxyl group and / or the carboxylic anhydride contained in the structural unit derived from (c) in the copolymer.

(a), a reaction catalyst of a carboxy group and a cyclic ether (for example, a tris (dimethylaminomethyl) -tris (dimethylamino) methyl) Phenol and the like) is added to the total amount of (a) to (c) in an amount of usually 0.001 to 5 mass%, polymerization inhibitor (such as hydroquinone) Usually, 0.001 to 5 mass% is put into a flask, and the reaction is usually carried out at 60 to 130 캜 for 1 to 10 hours to obtain a resin [K4]. The reaction conditions such as the mixing method, the reaction temperature, and the time can be suitably adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization, as in the case of the polymerization conditions.

The amount of (a) in this case is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol% based on (b). When the content is in this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

Resin (B) Examples of specifically 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.O ^{2 .6]} decyl acrylate / ( A resin [K1] such as a methacrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / ) Resin, or a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) . Among them, the resin [K1] and the resin [K2] are preferable, the resin [K1] is more preferable, and the 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) desirable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, even more preferably from 5,000 to 35,000, still more preferably from 6,000 to 30,000, Is 7,000 to 28,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is increased, the solubility of the unexposed portion in the developing solution becomes better, 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 even more preferably 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous solution of potassium hydroxide.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on 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 residual film ratio tend to be improved.

The colored photosensitive resin composition of the present invention comprises a photopolymerizable compound (C). The photopolymerizable compound (C) is not particularly limited so long as it is a compound which can be polymerized by an active radical, an acid generated from the photopolymerization initiator (D) by irradiation of light. For example, a compound having a polymerizable carbon-carbon unsaturated bond.

The photopolymerizable compound (C) is preferably a multifunctional photopolymerizable compound having three or more functional groups. Examples of the polyfunctional photopolymerizable compound having three or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, 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 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the photopolymerizable compound (C) is within the above range, the curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, the undercut is difficult to get into the pattern, and the adhesion tends to be good.

The colored photosensitive resin composition of the present invention comprises a photopolymerization initiator (D).

As the photopolymerization initiator (D), any known initiator can be used as long as it is a compound that generates an active radical or an acid by the action of light and initiates polymerization. The photopolymerization initiator (D) may contain a photopolymerization initiator (D1) together with a compound which generates an active radical or an acid by the action of light. The photopolymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator.

As the photopolymerization initiator (D), compounds which generate an active radical by the action of light are preferable, and acetophenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and biimidazole compounds are more preferable.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone And oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and the like, -1- (4-methylsulfanylphenyl) propane-1-one, and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. And commercially available products such as Irgacure® 369 and 907 (manufactured by Chiba Japan Co., Ltd.) may be used.

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) 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- ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. And commercially available products such as Ilgare Cure 819 (manufactured by Chiba Japan) may be used.

As the oxime compounds, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1- (4-phenylsulfanylphenyl) -Imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- -6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- . Commercially available products such as Sigma Cure OXE-01, OXE-02 (manufactured by Chiba 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'-tetraphenylbaimidazole, 2,2'-bis (2,3- , 4 ', 5,5'-tetraphenylbaimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2.2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraphenylbaimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) bimidazole, 2,2'- 5'-tetra (trialkoxyphenyl) bimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-Open No. 62-174204) Imidazole compounds substituted with a haloalkoxy group (for example, see JP-A-7-10913). Preferred are 2,2'-bis (2-chlorophenyl) -4,4'5,5'-tetraphenylbimidazole, 2,2'-bis (2,3-dichlorophenyl) , 5,5'-tetraphenylbaimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbaimidazole and the like.

Examples of the photopolymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. They are preferably used in combination with a photopolymerization initiator (D1) (particularly, amines) described below.

Examples of the acid generator generating an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodide Onium salts such as p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates and benzoin tosylates.

The photopolymerization initiator (D) may be, for example, a compound which simultaneously generates an active radical of light and an acid such as a triazine compound.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the total amount of the resin (B) and the photopolymerizable compound (C).

When the content of the photopolymerization initiator is within the above range, high sensitivity is obtained and the exposure time is shortened and the productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiator (D1). The photopolymerization initiation auxiliary (D1) is a compound or a sensitizer used for promoting polymerization of a photopolymerizable compound initiated by polymerization with a photopolymerization initiator, usually used in combination with the photopolymerization initiator (D).

Examples of the photopolymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [generic, microclerketone], 4,4'-bis (diethylamino) benzophenone, '-Bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) or the like 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, 9,10- Anthracene, and 2-ethyl-9,10-dibutoxyanthracene.

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

The photopolymerization initiator auxiliary (D1) may be used alone or in combination of two or more.

When the photopolymerization initiator (D1) is used, the amount of the photopolymerization initiator (D) to be used is preferably 0.01 to 10 mol, and more preferably 0.01 to 5 mol based on 1 mol of the photopolymerization initiator (D).

The colored photosensitive resin composition of the present invention comprises a solvent (E).

The solvent (E) is not particularly limited, but solvents commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO-), an ether solvent (a solvent containing -O-) other than the ester solvent, an ether ester solvent (a solvent containing -COO- and -O-) Ketone solvents other than solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, Butyl, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butylolactone.

Examples of the ether solvent 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 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Tate, di, and the like ethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclohexanone, isophorone, and the like.

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

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

From the viewpoint of coatability and dryness in the above solvent, an organic solvent having a boiling point of 120 캜 or higher and 180 캜 or lower at 1 atm is preferable. Among these, 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, Methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone are preferable, and propylene glycol monomethyl ether acetate, ethyl lactate and ethyl 3-ethoxypropionate are more preferable .

The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed, so that 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 a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

As the silicone surfactant, a surfactant having a siloxane bond can be mentioned. Specific examples of the silicone oil include dodecyl silicone DC3PA, Dole silicone SH7PA, Dore silicone DC11PA, Dore silicone SH21PA, Dore silicone SH28PA, Dore silicone SH29PA, Dole silicone SH30PA, Polyether modified silicone oil SH8400 (trade name: KP321, KP323, KP324, KP326, KP340, KP341 [manufactured by Shin-Etsu Chemical Industry Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Momentive Performance Material Japan Joint-Venture Company].

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of such a solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Manufactured by Mitsubishi Chemical Corporation), Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], Epson EF301, Epson EF303, Epson EF351 and Epshot EF352 (Trade name) S381, Saphron S382, Saphron SC101, and Saphron SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by DIC Corporation) and the like.

These surfactants may be used alone or in combination of two or more.

The content of the surfactant (F) is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and still more preferably 0.01 mass% or more and 0.05 % Or less. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

When the colored photosensitive resin composition of the present invention is a composition composed of a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F) A coloring pattern excellent in solvent resistance and spectroscopy can be obtained.

As a method for forming a colored pattern using the colored photosensitive resin composition of the present invention, for example, a method of forming the colored photosensitive resin composition of the present invention by using a substrate or a separate resin layer (for example, a separate colored photosensitive resin A composition layer, etc.), removing volatile components such as a solvent to form a colored layer, exposing and developing the colored layer through a photomask, and a method of using an inkjet apparatus that does not require a photolithography And the like.

The thickness of the coating film in this case is not particularly limited, but it can be appropriately adjusted depending on the materials used and the application, and is usually 0.1 to 30 탆, preferably 1 to 20 탆, more preferably 1 to 6 탆.

Examples of the application method of the colored photosensitive resin composition include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, dye coating and the like. It is also possible to use a deep coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (dye coater), a curtain flow coater, , Or a spinless coater) may be used for the coating.

Examples of the removal / drying of the solvent include natural drying, air drying, vacuum drying, and heating and drying. The specific drying temperature is preferably 10 to 120 占 폚, more preferably 25 to 100 占 폚.

The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The reduced-pressure drying is preferably carried out at a pressure in the range of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The dried coating film is exposed through a photomask for forming a desired pattern. The pattern shape on the photomast at this time is not particularly limited, but a pattern shape according to the intended use can be used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. Specifically, examples include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp, and they may be selectively extracted using a band filter that cuts out a specific wavelength region or extracts a specific wavelength region .

It is preferable to use a mask aligner, a stepper, or the like in order to uniformly irradiate the entire surface of the exposure surface with a parallel light beam and align the precise position between the mask and the substrate.

After exposure, a pattern can be obtained by dissolving and developing a predetermined portion, for example, an unexposed portion contacting with a developing solution. As the developer, an aqueous solution of an alkaline compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.) which may also contain a surfactant may, for example, be mentioned.

The developing method may be any one of a paddle method, a dipping method and a spray method. Further, the substrate may be inclined at an arbitrary angle at the time of development. After development, it is preferable to rinse with water.

Furthermore, post-baking may be carried out if necessary. Post baking is preferably performed at a temperature of 150 to 230 캜 for 10 to 240 minutes.

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

The colored photosensitive resin composition of the present invention can obtain a good coloring pattern such as color density, brightness, contrast, sensitivity, resolution, heat resistance, and color filter. Further, all of the devices related to various kinds of colored images, such as display devices having these color filters or colored patterns as a part of the components thereof, for example, known liquid crystal display devices, organic EL devices, solid- In a known manner.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail. In the examples, "% " and " part " are by mass% and mass part, unless otherwise specified.

[Synthesis Example 1]

≪ Synthesis of Compound (1-1) >

After adding 75 parts of water to 7.7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of sodium hydroxide was added and dissolved. 9.5 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto under ice-cooling, and then 30.0 parts of 35% hydrochloric acid was added little by little to dissolve and stir for 2 hours to obtain a suspension containing the diazonium salt. Subsequently, an aqueous solution prepared by dissolving 8.9 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 36 parts of water was added slowly to quench excess sodium nitrite.

Subsequently, 13 parts of 3-methyl-1- (3'-sulfamoylphenyl) -5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 100 parts of water and sodium hydroxide was added to adjust the pH to 8.0 Respectively. The suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of dropwise addition, stirring was continued for 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 17.9 parts (yield: 85%) of the compound represented by the formula (p-1).

10 parts of the compound of the formula (p-1) was dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 3.1 parts of ammonium chromate (III) sulfate (manufactured by Wako Pure Chemical Industries, And 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto, and the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline. After filtration, the resulting red-orange solid was dried at 60 캜 to obtain 12.8 parts (yield: 60%) of a compound represented by the formula (z-1).

, 170 parts of anhydrous chloroform (manufactured by Kanto Kagaku KK), 1.0 part of camphorsulfonic acid [manufactured by Aldrich Co., Ltd.], 4- (N, N-dimethylamino ) 1.4 parts of pyridine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred for about 30 minutes. Subsequently, 47.5 parts of anhydrous chloroform was added to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and the previously dissolved solution was added slowly, Lt; / RTI > for about 2 hours. The separating operation was carried out twice with 150 parts of 1N hydrochloric acid aqueous solution, and then the organic layer was washed twice with 150 parts of 10% saline. Subsequently, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes. The drying agent was filtered off and the solvent was removed by evaporation to obtain 20.6 parts (yield: 90%) of the compound represented by the formula (g-1).

Identification of the compound represented by the formula (g-1)

(Mass Spec.) Ionization mode = ESI +: m / z = 575.3 [M-Cl -] +

Exact Mass: 610.3

To 253 parts of the compound represented by the formula (z-1), 4030 parts of methanol was added to prepare a solution (s1). Methanol (1080 parts) was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t1). Thereafter, solution (s1) and solution (t1) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 占 폚, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 占 폚 to obtain 263 parts (yield: 65%) of a compound represented by the formula (1-1) .

The structure of the compound represented by the formula (1-1) was determined by elemental analysis. The analytical instrument is an ICP emission analyzer [ICPS-8100; (Manufactured by Shimadzu Corporation) was used.

C 55.6 H 4.7 N 12.0 Cr 3.57

[Synthesis Example 2]

≪ Synthesis of Compound (1-2) >

, 40 parts of anhydrous chloroform (manufactured by KANTO CHEMICAL Co., Ltd.), 0.3 part of camphorsulfonic acid (manufactured by Aldrich), 4.0 parts of 4- (N, N-dimethylamino ) 0.3 part of pyridine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 3.9 parts of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred for about 30 minutes. Thereafter, 10 parts of anhydrous chloroform was added to 2.9 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and the previously dissolved solution was slowly added thereto. Lt; / RTI > for about 2 hours. The separating operation was carried out twice with a 1N aqueous hydrochloric acid solution (100 parts), and then the organic layer was washed twice with 100 parts of 10% saline. Subsequently, 12 parts of anhydrous magnesium sulfate was added, stirred for about 30 minutes, and then the drying agent was filtered to remove the solvent by evaporation to obtain 5.0 parts (yield: 85%) of a compound represented by the formula (g-2).

Identification of the compound represented by the formula (g-2)

(Mass Spec.) Ionization mode = ESI +: m / z = 531.3 [M-Cl -] +

Exact Mass: 566.3

100 parts of N-methylpyrrolidone was added to 10 parts of the compound represented by the formula (z-1) to prepare a solution (s2). Further, 50 parts of N-methylpyrrolidone was added to 5.6 parts of the compound represented by the formula (g-2) to prepare a solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature, stirred for about 1 hour, and then injected into 500 parts of water. The resulting red solid was filtered and dried under reduced pressure at 60 캜 to obtain 15 parts (yield 95%) of a compound represented by the formula (1-2) (dye A2).

The structure of the compound represented by the formula (1-2) was determined by elemental analysis. The analytical instrument is an ICP emission analyzer [ICPS-8100; (Manufactured by Shimadzu Corporation) was used.

C 56.0 H 4.9 N 12.2 Cr 3.47

[Synthesis Example 3]

≪ Synthesis of Compound (1-3) >

A compound represented by the formula (g-1) was obtained from the compound represented by the formula (rh-1) by the same method as in Synthesis Example 1. [ Further, a compound represented by the formula (1-3) (dye A3) was obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 4]

<Synthesis of Resin Solution B1>

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping rod to make a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate [compound represented by the following formula (I-1) and compound represented by the formula (II- : 50 parts by mass] and 140 parts by mass of ethyl lactate was prepared, and the resulting solution was added dropwise into a flask maintained at 70 占 폚 for 4 hours using a dropping rod. On the other hand, a solution obtained by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was added dropwise in a flask over 4 hours using a separate dropping rod. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a solution having a weight average molecular weight (Mw) of 1.3 占⁰⁴ , a solid content of 33% g (solution) of resin solution B1.

[Synthesis Example 5]

&Lt; Synthesis of Resin Solution B2 >

300 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, and then a mixture composed of 176.2 parts of benzyl methacrylate, 30.2 parts of methacrylic acid, 3.6 parts of azobisisobutyronitrile, and 197 parts of propylene glycol monomethyl ether acetate Was added dropwise to the flask over a period of 2 hours using a dropping rod. After completion of the dropwise addition, stirring was continued at 100 占 폚 for 2.5 hours to obtain a copolymer having a weight average molecular weight (Mw) of 9.8 占⁰³ , a solid content of 34% To obtain a resin solution B2 of -KOH / g (in terms of solid content).

[Synthesis Example 6]

&Lt; Synthesis of Resin Solution B3 >

333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction pipe, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, and then 18.7 g of N-benzylmaleimide, 70.5 g of benzyl methacrylate, 51.7 g of methacrylic acid, 90.0 g of methyl methacrylate, 5.2 g of azobisisobutyronitrile And 182 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over a period of 2 hours using a dropping rod, and stirring was continued at 100 DEG C for 5 hours after completion of the dropwise addition.

After the completion of the stirring, air was introduced into the flask through the gas inlet tube, and the atmosphere in the flask was replaced with air. Then, 28.5 g of glycidyl methacrylate, 1.3 g of trisdimethylaminomethyl phenol and 0.165 g of hydroquinone were placed in a flask The reaction was continued at 110 캜 for 6 hours to obtain a resin solution B3 having a weight average molecular weight (Mw) of 16 × 10 ³ , a solid content of 31% and an acid value of 80 mg-KOH / g (in terms of solid content).

The polystyrene reduced weight average molecular weight of the above resin was measured using the GPC method under the following conditions.

Substitution; HLC-8120GPC (manufactured by Tosoh Corporation)

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01%

Dose; 50 μl

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

F-40, F-4, F-1, A-2500, A-500

[Manufactured by Tosoh Corporation]

[Example 1]

[Preparation of colored photosensitive resin composition 1]

(A) Pigment: C.I. Pigment Red 242 Part 22

Acrylic pigment dispersant 6.7 parts

(B) Resin: Resin Solvent B2 27 parts

Propylene glycol monomethyl ether acetate 131 parts

And the pigment is sufficiently dispersed by using a beads mill, and then,

(A) Compound (1): 7.1 parts of pigment A1

(B) Resin: Resin solution B1 37 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

32

(D) Photopolymerization initiator: oxime ester compound [N-1919; (Manufactured by ADEKA)

9.5 parts

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.6 parts

(E) Solvent: propylene glycol monomethyl ether 172 parts

(E) Solvent: propylene glycol monomethyl ether acetate 33 parts

(E) Solvent: Ethyl 3-ethoxypropionate 22 parts

(F) Surfactant: Megapack F554 (manufactured by DIC Corporation) 0.1 part

To obtain a colored photosensitive resin composition 1.

[Formation of pattern]

The colored photosensitive resin composition 1 was applied on a glass substrate (Igloo 2000; Corning) having a 2-inch square by a spin coat method, and then pre-baked at 100 ° C for 3 minutes. After cooling, the space between the substrate coated with the colored photosensitive resin composition 1 and the quartz glass photomask was set to 100 μm, and exposed using an exposure machine (TME-150RSK; (Manufactured by TOPCON CO., LTD.) At an exposure dose of 80 mJ / cm ² (365 nm standard) in an air atmosphere. As the photomask, a 100 占 퐉 line and space pattern was formed. After the light irradiation, the substrate was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds to be developed, washed with water and then post-baked at 230 DEG C for 30 minutes in an oven. bake) was performed. After cooling, the film thickness of the obtained color pattern was measured with a film thickness measuring device [DEKTAK3; (Manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.0 탆.

[Evaluation of solvent resistance]

In the above-mentioned pattern formation, a colored coating film was formed by carrying out the same operation except that the photomask was not used. The resultant coating film was immersed in N-methyl-2-pyrrolidone at 23 占 폚 for 30 minutes, and a colorimeter [OSP-SP-200; Olympus Co. No.] to color matching functions of the measured spectral and C light source is immersed before and after the xy chromaticity coordinates (R _x, R _y) in the XYZ coloring system of the CIE using i.e., chromaticity] and brightness RY And the coloration? Eab * before and after immersion was calculated. When? Eab * is 2 or more, it can be judged that the solvent resistance is good. The results are shown in Table 1.

[Example 2]

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

[Example 3]

A colored photosensitive resin composition 3 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A3. Evaluation of the colored photosensitive resin composition 3 was carried out in the same manner as in Example 1, and a good solvent resistance result was obtained.

[Example 4]

(A) Pigment: C.I. Pigment Red 242 23

Acrylic pigment dispersant 6.8 parts

(B) Resin: Resin Solvent B2 27 parts

Propylene glycol monomethyl ether acetate 132 parts

And the pigment was thoroughly dispersed using a beads mill to obtain a dispersion a.

(A) Pigment: C.I. Pigment Red 177 5.1

Acrylic pigment dispersant 2.0 parts

(B) Resin: Resin solution B2 5.3 parts

Propylene glycol monomethyl ether acetate 24 parts

, The pigment is thoroughly dispersed using a beads mill and then mixed with the dispersion a,

(A) Compound (1): Dye A3 6.4 parts

(B) Resin: Resin solution B1 25 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

Part 29

(D) Photopolymerization initiator: oxime ester compound [N-1919; (Manufactured by ADEKA)

8.6 part

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.0 part

(E) Solvent: propylene glycol monomethyl ether 180 parts

(E) Solvent: propylene glycol monomethyl ether acetate 20 parts

(E) Solvent: Ethyl 3-ethoxypropionate 6 parts

(F) Surfactant: Megapack F554 (manufactured by DIC Corporation) 0.1 part

To obtain a colored photosensitive resin composition 4. The evaluation of the colored photosensitive resin composition 4 was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]

(A) Pigment: C.I. Pigment Red 242 Part 22

Acrylic pigment dispersant 6.7 parts

(B) Resin: Resin Solvent B2 27 parts

Propylene glycol monomethyl ether acetate 131 parts

And the pigment is sufficiently dispersed by using a beads mill, and then,

(A) Compound (1): 7.1 parts of pigment A1

(B) Resin: Resin solution B1 37 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

32

(D) Photopolymerization initiator: oxime ester compound [N-1919; (Manufactured by ADEKA)

6.3 parts

(D) a photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine [compound represented by the following formula (Dt)] [TAZ-PP; Manufactured by Nippon-shi Beegan Co., Ltd.] 3.2 parts

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.6 parts

(E) Solvent: propylene glycol monomethyl ether 172 parts

(E) Solvent: propylene glycol monomethyl ether acetate 33 parts

(E) Solvent: Ethyl 3-ethoxypropionate 22 parts

(F) Surfactant: Megapack F554 (manufactured by DIC Corporation) 0.1 part

To obtain a colored photosensitive resin composition 5. The color photosensitive resin composition 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]

(A) Pigment: C.I. Pigment Red 254 Part 12

Acrylic pigment dispersant 6.9 parts

(A) Compound (1): Pigment A2 8.1 parts

Propylene glycol monomethyl ether acetate 81 parts

And the pigment was fully dispersed using a beads mill to obtain a dispersion b.

(A) Pigment: C.I. Pigment Red 242 Part 11

Acrylic pigment dispersant 3.3 parts

(B) Resin: Resin Solvent B2 13 parts

Propylene glycol monomethyl ether acetate 65 parts

, The pigment is thoroughly dispersed using a beads mill, and then the mixture is mixed with the dispersion body b,

(A) Compound (1): 7.0 parts of dye A3

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

30 copies

(B) Resin: Resin solution B1 39 parts

(D) Photopolymerization initiator: oxime ester compound [N-1919; (Manufactured by ADEKA)

8.9 part

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.0 part

(E) Solvent: Propylene glycol monomethyl ether 160 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 48 parts

(E) Solvent: Ethyl 3-ethoxypropionate 6 parts

(F) Surfactant: Megapack F554 (manufactured by DIC Corporation) 0.1 part

To obtain a colored photosensitive resin composition 6. The evaluation of the colored photosensitive resin composition 6 was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]

(A) Colorant: Orasol Red G (manufactured by Chiba Japan K.K.) 47.5 parts

(B) Resin: Resin solution B3 16 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

23.9 parts

(D) Photopolymerization initiator: 3.6 parts of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure 907: manufactured by Chiba Japan K.K.

(D) Photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine [TAZ-PP; (Manufactured by Nippon-shi Beechner Co., Ltd.) 2.8 parts

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.2 part

(E) Solvent: Propylene glycol monomethyl ether 267 parts

(E) Solvent: propylene glycol monomethyl ether acetate 138 parts

(F) Surfactant: 0.1 part of Megafac F475 (manufactured by DIC)

To obtain a colored photosensitive resin composition 7. The color photosensitive resin composition 7 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]

(A) Colorant: Orasol Red G (manufactured by Chiba Japan K.K.) 47.5 parts

(B) Resin: Resin solution B3 13 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Kayaku Co., Ltd.]

Part 19

(D) Photopolymerization initiator: 2.9 parts of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure 907: manufactured by Chiba Japan K.K.

(D) Photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine [TAZ-PP; Manufactured by Nippon-shi Beechner Co., Ltd.] 2.2 parts

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EABF; Manufactured by Hodogaya Chemical Co., Ltd.] 1.0 part

(E) Solvent: Propylene glycol monomethyl ether 203 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 203 parts

(F) Surfactant: 0.1 part of Megafac F475 (manufactured by DIC)

Epoxy compound: Sumiepoxy ESCN-195XL-80 [manufactured by Sumitomo Chemical Co., Ltd.] 9.6 parts

Were mixed to obtain a colored photosensitive resin composition 8. The colored photosensitive resin composition 8 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

*) During the immersion in N-methyl-2-pyrrolidone, the colored coating film peeled off from the glass substrate, and the color difference? Eab * could not be measured.

[Synthesis Example 7]

&Lt; Synthesis of Compound (1-23) >

To 65 parts of water was added 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No.101861-04-5), and 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of 35% aqueous solution of sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by dissolving 19.4 parts of 35% hydrochloric acid in small portions and stirring for 2 hours to obtain a suspension containing the diazonium salt. Subsequently, an aqueous solution prepared by dissolving 5.6 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added thereto, and excess sodium nitrite was quenched.

Subsequently, 5.6 parts of 3-methyl-1-phenol-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water and the pH was adjusted to 8.0 using sodium hydroxide. Then, the suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of dropwise addition, stirring was continued for 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 11.7 parts (yield: 87%) of a compound represented by the formula (p-2).

10 parts of the compound represented by the formula (p-2) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and then 0.1 part of ammonium chromate (III) sulfate (manufactured by Wako Pure Chemical Industries, And 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and refluxed for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the red-orange solid obtained after filtration was dried at 60 캜 to obtain 13.6 parts (yield: 63%) of a compound represented by the formula (z-2).

Identification of the compound represented by the formula (z-2)

(Mass spectrometry) Ionization mode = ESI-: m / z = 882.1 [M-Na ⁺ ] ^-

Exact Mass: 905.1

To 253 parts of the compound represented by the formula (z-2), 4030 parts of methanol was added to prepare a solution (s3). Methanol (1080 parts) was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried at 60 占 폚 under reduced pressure, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 占 폚 to obtain 263 parts (yield: 65%) of a compound represented by the formula (1-23) .

The structure of the compound represented by the formula (1-23) was determined by elemental analysis. The analytical instrument is an ICP emission analyzer [ICPS-8100; (Manufactured by Shimadzu Corporation) was used.

C 55.6 H 5.1 N 11.9 Cr 3.71

[Example 7]

A colored photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A3. The color photosensitive resin composition 7 was evaluated in the same manner as in item 1. As a result, the xy chromaticity coordinates (R x, Ry) [chromaticity] of the obtained colored coating film were (0.641, 0.326) and the lightness RY was 20.3. Further, regarding the solvent resistance test, the color difference? Eab * before and after immersion was good at 0.7.

The colored coating films formed using the colored photosensitive resin compositions of Examples 1, 2, and 4 to 7 were found to have good solvent resistance. In this respect, it has been found that it is possible to obtain a coloring pattern and a high-quality color filter exhibiting good solvent resistance.

The colored photosensitive resin composition of the present invention can provide a colored coating film having excellent solvent resistance, a coloring pattern, and a color filter of high quality.

Claims (9)

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

[In the formula (1), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .
R ²⁹ represents -OH or -NHR ³⁰ .
R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.
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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.
R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.
R ²⁷ represents an ethylene group, a propane-1,3-diyl group or a propane-1,2-diyl group.
And R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R &lt; ²⁷ &gt; s may be the same or different.] The method according to claim 1,
Wherein the colorant is also a colorant containing a pigment. 3. The method of claim 2,
Wherein the pigment is at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242 and CI Pigment Red 254 By weight. 3. The method according to claim 1 or 2,
Wherein the resin comprises a structural unit derived from a monomer having a cyclic ether and an ethylenically unsaturated double bond having 2 to 4 carbon atoms and a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, Wherein the resin is a resin containing a copolymer having a hydroxyl group. A colored pattern formed using the colored photosensitive resin composition according to any one of claims 1 to 3. A color filter comprising the coloring pattern according to claim 5. A compound represented by formula (2).

[In the formula (2), R ¹ to R ¹⁸ independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO ₂ R ²⁹ or -SO ₂ R ³² .
R ²⁹ represents -OH or -NHR ³⁰ .
R ³⁰ represents 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 -OR ³² , -R ³¹ -CO-OR ³² , -R ^31- O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.
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 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.
M ¹ represents Cr or Co.
R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group are hydrocarbons -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.
R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. 8. The method of claim 7,
Wherein M &lt; ^{1 &gt;} is Cr. 9. The method according to claim 7 or 8,
Wherein at least one of R &lt; ¹ &gt; to R &lt; ¹⁸ &gt; is a nitro group.