KR101766745B1 - Colored photosensitive resin composition and compound - 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 comprises a compound represented by the following formula (1). However, R ¹ to R ¹⁸ represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a nitro group. M ¹ represents Cr or Co. R ²¹ to R ²⁴ 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. R ²⁵ and R ²⁶ 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. n represents an integer of 0 to 3;

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COMPOUND [0002]

The present invention relates to a colored photosensitive resin composition and a compound.

A color filter used for a liquid crystal display element or a solid-state image pickup element has a red pixel, and the colored photosensitive resin composition forming the red pixel uses a dye as a coloring agent. For example, Patent Document 1 describes a colored photosensitive resin composition containing Orasol Red G as a red dye.

[Patent Document 1] JP-A-2009-163226

The above-mentioned colored photosensitive resin composition, which has been conventionally known, is not always sufficient from the viewpoint of the solvent resistance.

The present invention provides the following [1] to [10].

[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 or -SO ₂ R ²⁹ .

R ²⁹ represents -R ³² , -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 1 to 4 alkyl groups, -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.

n represents an integer of 0 to 3; and when n is an integer of 2 or more, the plurality of R < ²⁷ > are the same or different from each other]

[2] The compound according to [1], wherein R ²⁹ is -R ³² ,

R ³² is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,

R ¹⁹ and R ²⁰ independently of one another are a methyl group,

R ²¹ to R ²⁴ independently represent a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,

and n is 0. [2] The colored photosensitive resin composition according to [1], wherein n is 0.

[3] The colored photosensitive resin composition according to [2], wherein at least one of R ¹ to R ¹⁸ is a hydrogen atom, at least one of them is a nitro group, and at least one of them is -SO ₂ R ²⁹ .

[4] The colored photosensitive resin composition according to [3], wherein R ¹ to R ¹⁰ are each independently a hydrogen atom.

Wherein at least one of R ¹¹ to R ¹⁸ is a hydrogen atom,

At least one of R ¹¹ to R ¹⁸ is a nitro group,

The colored photosensitive resin composition according to [4], wherein at least one of R ¹¹ to R ¹⁸ is -SO ₂ R ²⁹ .

[6] The photosensitive resin composition according to [1], wherein the photopolymerization initiator is at least one photopolymerization initiator selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a biimidazole compound Composition.

[7] The colored photosensitive resin composition according to [1], wherein M ¹ is Cr.

[8] A color filter formed by the colored photosensitive resin composition according to any one of [1] to [7].

[9] A display device including the color filter according to [8].

[10] 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 or -SO ₂ R ²⁹ .

R ²⁹ represents -R ³² , -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.

n represents an integer of 0 to 3; and when n is an integer of 2 or more, the plurality of R < ²⁷ >

According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film, a pattern) having high solvent resistance can be formed.

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

The compound (1) is a salt of a chromium complex anion or a cobalt complex anion and a cation derived from a xanthene compound.

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

R ²⁹ represents -R ³² , -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.

n represents an integer of 0 to 3; and when n is an integer of 2 or more, the plurality of R < ²⁷ >

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Butyl group, 1, 3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethyl Hexyl 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 methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane- 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 group 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 which may be substituted with 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 , 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group and 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, A 4-methoxybutyl group, an octyloxypropyl group, a 3-ethoxypropyl group, and a 3- (2-ethylhexyloxy) propyl group.

-R ³¹ -CO-OR ³² is preferably a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, a propoxycarbonylethyl group, a butoxycarbonylmethyl group , And a butoxycarbonylethyl group.

Examples of -R ³¹ -O-CO-R ³² include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, And a carbonyloxyethyl group.

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, N-cyclopentylsulfamoyl group, 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 .;

(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- ) -S (-O-lower alkyl) sulfamoyl group such as N- (2-ethylhexyloxypropyl) sulfamoyl group, N- ^{31 a} sulfamoyl group substituted with -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 group such as a sulfamoyl group;

(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.

-SO ₂ R ²⁹ is -SO ₂ R ³² , -SO ₂ H or -SO ₂ NHR ³⁰ . Of these, -SO ₂ R ³² and -SO ₂ NHR ³⁰ are preferred.

R ^{30 in} -SO ₂ NHR ³⁰ is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a 2-ethylhexyl group.

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

R ³² in the -SO ₂ R ³² is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms of 1, preferably a group having 1 to 4 carbon atoms a monovalent aliphatic hydrocarbon. Examples of -SO ₂ R ³² include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert- A methylsulfonyl group, an isopropylsulfonyl group, an isopropylsulfonyl group, an isobutylsulfonyl group, an isobutylsulfonyl group, a sulfonyl group, an octylsulfonyl group, a 1-methylbutylsulfonyl group, a 1,1,3,3-tetramethylbutylsulfonyl group, Sulfonyl 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.

R ¹ to R ¹⁸ are preferably independently of each other a hydrogen atom, a nitro group or -SO ₂ R ²⁹ .

It is preferable that at least one of R ¹ to R ¹⁸ is a hydrogen atom. It is more preferable that R ¹ to R ¹⁰ are each independently a hydrogen atom, and at least one of R ¹⁰ to R ¹⁸ is a hydrogen atom. It is more preferable that at least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ is a hydrogen atom.

It tends higher heat resistance, R ¹ ~R ¹⁸ is one or more of the one or more of it, and R ¹¹ ~R ¹⁸ preferably nitro group is a nitro group is more preferable. It is more preferable that at least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ is a nitro group.

In addition, R ¹ ~R ¹⁸ and one or more of preferably from -SO ₂ R ^29, R ¹¹ is one or more of the ~R ¹⁸ is -SO ₂ R ²⁹ is still more preferable. It is more preferable that at least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ is -SO ₂ R ²⁹ . -SO case having a plurality of R ²⁹ _2, plural R ²⁹ are the same or different to each other.

In addition, the R ¹ ~R ¹⁰ are each independently a hydrogen atom, R ¹¹ ~R ¹⁴ is in one or more of the one or more ~R ¹⁵ and R ¹⁸ is a hydrogen atom, R ¹¹ and R ^14, one or more of the ~R ¹⁵ ~R ¹⁸ is a nitro group, and at least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ is -SO ₂ R ²⁹ .

R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a methyl group, an ethyl group or an amino group, and are preferably a methyl group or an ethyl group.

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 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms And more preferably a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms such as an ethyl group.

R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group, and are preferably independently a hydrogen atom.

As R ^{27, an} ethylene group and a propane-1,3-diyl group are preferable, and an ethylene group is more preferable.

n is an integer of 0 to 3, preferably 0 to 2, and more preferably 0. If n is such a value, it is easy to obtain the raw material of the compound (1).

In addition, the R ¹ ~R ¹⁰ are each independently a hydrogen atom, R ¹¹ ~R ¹⁴ is in one or more of the one or more ~R ¹⁵ and R ¹⁸ is a hydrogen atom, R ¹¹ and R ^14, one or more of the ~R ¹⁵ ~R ^At least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ is -SO ₂ R ²⁹ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a methyl group, and R ^{R 21} to R ²⁴ are each independently a monovalent aliphatic hydrocarbon having 1 to 4 carbon atoms, R ²⁵ and R ²⁶ are each independently a hydrogen atom, n is 0, R ²⁹ is -R ³² , R ³² is a To four monovalent aliphatic hydrocarbon groups.

In the compound (1), preferred examples of the pyrazole compound to be the ligand of the complex anion include compounds represented by the formulas (1-a1) to (1-a64).

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

In the compound (1), preferred examples of the cation derived from the xanthene compound include anions represented by the formulas (1-c1) to (1-c36).

The compound (1) can be obtained by forming a chromium complex salt using a compound represented by the formula (1d) (hereinafter referred to as " compound (1d) ") and a chromium compound, Or by using a 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 defined above]

[In the formula (b), R ²¹ to R ²⁷ and n have the same meanings as defined above. A ^- represents a monovalent anion]

Examples of the monovalent anion include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^-, or BF ₄ ^- .

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 ²⁷ , n and A ^- have the same meanings as defined above]

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. From the standpoint 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) phosphinic acid chloride; Di-2-pyridyl carbonate, and the like. Among them, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent because of easy post treatment and purification.

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

The compound (1d) which is a ligand of the complex anion 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. For example, a compound represented by the formula (1b) obtained by diazotizing an amine represented by the formula (1a) (hereinafter referred to as "amine (1a)") with a nitrite, a nitrite or a nitrite ester is used as the diazonium salt Can be used.

[In formulas (1a) and (1b), R ¹¹ to R ¹⁴ have the same meanings as defined above. A ^- 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 ^- , C ₆ H ₅ COO ^- and the like. Preferable examples include chloride ion, bromide ion, CH ₃ COO ^- and the like.

A compound represented by the formula (1d) (hereinafter referred to as "compound (1d)") can be prepared by diazotizing a compound represented by the formula (1b) and a compound represented by the formula (1c) in an aqueous solution have. 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 defined above]

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 , It is preferable to carry out a coupling reaction using the amine (1a) and then sulfonate the sulfo group. For example, an azo compound having a sulfo group in the compound (1d) (hereinafter referred to as "compound (1s)") is synthesized and a sulfo group (-SO ₃ H) (1d) is reacted with a sulfonyl halide compound and an amine (R ³⁰ NH ₂ ) by sulfonylation of the sulfo group by halidation (-SO ₂ X; X is a halogen atom) to obtain a sulfonyl halide compound, Can be manufactured.

Specific examples of the compound (1s) include the compounds represented by the formula (1-a1), the formula (1-a2) and the formula (1-a5) to the formula (1-a20) ), Formula (1-a6), Formula (1-a15) and Formula (1-a16). Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide and the like, and preferred examples thereof include 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 introduced into the reaction system, it is preferable to use a thionyl halide compound in excess.

The sulfonyl halidation 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, perchlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane can be used have. The amount of the solvent to be used is, for example, 3 parts by mass or more (preferably 5 parts by mass or more) and 10 parts by mass or less (preferably 8 parts by mass or less) based on 1 part by mass of the compound (1s).

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

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

The sulfonyl halide compound is prepared as described above is also possible to amine (R ³⁰ NH ₂₎ and a and be reacted, are not isolated reaction mixture as the amine (R ³⁰ NH ₂₎ and the reaction was isolated. Further, in the case of isolation, for example, the reaction mixture and water may be mixed and the precipitated crystals may be filtered. The obtained sulfonyl halide compound crystals may be washed with water and dried 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 amine (R ³⁰ NH ₂ ) to be used is 2 mol or more and 10 mol or less, preferably 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, the same solvent as that for preparing the sulfonyl halide compound can be used.

Also, the reaction of the sulfonyl halide compound with the amine (R ³⁰ NH ₂ ) is preferably carried out in the presence of a basic catalyst. Examples of the basic catalyst 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 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 addition time of the basic catalyst is not particularly limited, but may be either before or after the addition of the amine (R ³⁰ NH ₂ ) May be added at the same time as the amine (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, for example, 0 ° C or more and 50 ° C or less, preferably 0 ° C or more and 30 ° C or less. The reaction time is 1 to 5 hours.

A method for obtaining the desired compound (1d) from the reaction mixture is not particularly limited, but various known means can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (e.g., acetic acid etc.) and water, and the precipitated crystals are obtained by filtration. It is preferable that the acid is prepared in advance of the aqueous solution of the acid, and then the reaction mixture is added to the aqueous solution. The temperature at the time of adding the reaction mixture is preferably from 10 캜 to 50 캜, more preferably from 20 캜 to 50 캜, and still more preferably from 20 캜 to 30 캜. Further, after the reaction mixture is added to the aqueous solution of the acid, it is preferable to further stir at the above temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. Further, if necessary, it may be further purified by a known technique such as recrystallization.

(1d) and a chromium compound in an aqueous solvent at 70 to 100 캜 when the anion moiety of the compound (1) is a chromium anion [wherein M ¹ in the formula (1) is Cr). 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, and chromium fluoride, and preferably chromium formate, chromium acetate, ammonium chromium (III) sulfate, and the like.

Compound (1) can be prepared by subjecting a complex salt of chromium and a 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.

Can be prepared by reacting the compound (1d) and a cobalt compound in an aqueous solvent at 70 to 100 캜 when the anion portion of the compound (1) is a cobalt heterocycle and M ¹ in [Formula 1] is Co] . 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 sulphate, tris (2,4-pentanedionate) cobalt (III) and the like, preferably tris (2,4-pentanedionate) 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. The cobalt complex salt and the xanthene compound (b) are preferably reacted at a molar ratio of 1: 1 to 1: 4.

Specific examples of the compound (1) include compounds represented by the formulas (1-1) to (1-27).

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

The colorant (A) may contain a dye different from the compound (1) together with the compound (1). Examples of the base include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, the dyes in the color index (The Society of Dyers and Colourists) Or a known dye described in a dyeing note (dyeing yarn).

Specifically, C.I. 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Solvent Yellow 4 (hereinafter abbreviated as C.I.Solvent Yellow)

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, 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 the 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 further contain a pigment together with the compound (1).

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, based on the total weight of the composition. By including the above pigment, the transmission spectrum can be easily optimized and the chemical resistance can be improved.

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

The organic pigment may be subjected to a surface treatment using a rosin treatment, an acid group or a pigment derivative into which 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 or the like, A cleaning treatment with a solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

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

Examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, and acrylic surfactants. These pigment dispersing agents may be used singly or in combination of two or more kinds. Examples of the pigment dispersant include trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyowa Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), azerspheres (Manufactured by TECH CORPORATION), and Disperbyk (manufactured by BYKEMASE).

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.

When the pigment in the colorant (A) is contained, the content of the pigment 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. By setting the ratio to such a value, the transmission spectrum can be optimized easily, 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 amount of components excluding the solvent in the colored photosensitive resin composition. When the content of the colorant (A) is within the above range, the color density when the color filter is formed is sufficient, a required amount of the binder polymer can be contained in the composition, and a pattern having sufficient mechanical strength can be formed.

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.

Examples of the resin (B) include the following resins [K1] to [K4].

[K1] a monomer (a) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond [hereinafter referred to as "(a)") and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (B) (hereinafter, referred to as " (b) ").

(C) (hereinafter referred to as "(c)") which is copolymerizable with [K2] (a), (b) and (a).

[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 the obtained color pattern in heat resistance, chemical resistance and the like can be further enhanced.

(a) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring (oxolane ring)] and Refers to a polymerizable compound having an ethylenically unsaturated bond. (a) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Further, in the present specification, "(meth) acrylic acid" means at least one 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) (hereinafter referred to as "(a1)") having an oxiranyl group and an ethylenic unsaturated bond, a monomer (a2) having an oxetanyl group and an ethylenic unsaturated bond [hereinafter referred to as " (A2) "), a monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as" (a3) "), and the like.

(a1) (hereinafter referred to as " (a1-1) ") having a structure in which a chain olefin is epoxidized, a monomer having a structure in which a cyclic olefin is epoxidized a1-2) (hereinafter referred to as " (a1-2) ").

(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 and 2,4,6-tris (glycidyloxymethyl) styrene .

(a1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Selenoxide 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 hand in combination with O]

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

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 preferred is 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 formula (II) include compounds represented by formulas (II-1) to (II-15). (II-1), II-3, II-5, II-7, II-9, II- ). (II-1), (II-7), (II-9) and (II-15) are more preferable.

The compound represented by formula (I) and the compound represented by formula (II) can be used singly. They may be mixed at an arbitrary ratio. In case of mixing, the mixing ratio thereof is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10 in the formula (I): formula (II) 20:80 to 80:20.

As the monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (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.

As the monomer (a3) having a tetrahydrofuryl group and an ethylenic unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

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

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

(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-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

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

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [(meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] 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 from the viewpoint of copolymerization reactivity or 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 (Meth) acrylate, which is commonly known in the art as dicyclopentanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl Naphthyl (meth) acrylate , Benzyl (meth) (meth) acrylic acid esters such as acrylate;

Hydroxy-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;

2,1-hept-2-ene, 5-methylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-bihydroxybicyclo [2.2.1 ] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy- -Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxybenzyloxycarbonylbicyclo [2.2.1] Carbonyl) bicyclo [2.2.1] hept-2-ene, and 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 N-succinimidyl-3-maleimidepropionate 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, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each of the resins [K1] is preferably within the following range among the total structural units constituting the resin [K1].

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

(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 resistance of the storage stability, developability and curing pattern tends to be good.

Resin [K1] can be synthesized by the method described in, for example, "Experimental Method of Polymer Synthesis" (published by the Chemical Society of Japan, 1st Ed., 1st Ed., March 1, 1972, Can be prepared by reference to the literature.

Concretely, there is exemplified a method in which a prescribed 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 in deoxygenation. Furthermore, the polymerization initiator and solvent to be used herein are not particularly limited, and any of those conventionally used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) . Any solvent may be used as long as it dissolves the respective monomers. As the solvent of the photosensitive resin composition, a solvent described later or the like may be used.

The resulting copolymer may be used as it is, or may be a concentrated or diluted solution, or it may be a solid (powder) extracted by re-precipitation or the like. In particular, by using a solvent (D) described later as a solvent in the polymerization thereof, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

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

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

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

(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 is a method in which a predetermined amount of (a), (b) and (c), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by nitrogen, followed by stirring, 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 a solid (powder) extracted by a method such as re-precipitation may be used.

In the resin [K3], the ratio of the structural units derived from each of the resins [K3] is preferably within the following range among 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 a carboxyl group of (c) to a cyclic ether having 2 to 4 carbon atoms in (a).

First, the 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 the structural units constituting the copolymer of (b) and (c) is preferably within the following range.

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

Subsequently to the production of the copolymer of (b) and (c), the atmosphere in the flask is replaced with air in nitrogen, and a reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (dimethylaminomethyl) Phenol and the like) in an amount of 0.001 to 5 mass% based on the total amount of the components (a) to (c) and 0.001 to 5 mass% of the polymerization inhibitor (hydroquinone, etc.) relative to the total amount of components (a) % Is placed in a flask and reacted at, for example, 60 to 130 캜 for 1 to 10 hours to obtain resin [K4]. The reaction conditions such as the compounding 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 the same manner as the polymerization conditions, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization.

In this case, the amount of (a) to be used is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol% with respect to (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.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Resin [K1] such as a copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2] .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; (Meth) acrylate / styrene / (meth) acrylic acid copolymer obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) (K4) such as 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, and particularly 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 developer is good, and the resolution tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 150, more preferably 60 to 135, still 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 potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the resin (B) is within 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 a compound which can be polymerized by an active radical and an acid generated from the photopolymerization initiator (D) by irradiation with light, and includes, for example, a compound having a polymerizable ethylenically unsaturated bond, The (meth) acrylic acid ester compound is preferably used.

Among them, the photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenic unsaturated bonds. Examples of such photopolymerizable compounds include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, and the like. The photopolymerizable compound (C) may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, still more preferably from 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 takes place sufficiently, the ratio of the residual film before and after the development is improved, the undercut is less likely to enter the pattern, and the adhesion tends to be good Therefore, it is preferable.

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

The above-mentioned photopolymerization initiator (D) is not particularly limited as long as it is a compound which generates an active radical, an acid or the like by the action of light and initiates polymerization, and a known polymerization initiator can be used. 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 the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

As the photopolymerization initiator (D), a compound which generates an active radical by the action of light is preferable, and a compound having at least a group selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and biimidazole compounds Is more preferable, and a photopolymerization initiator comprising an oxime compound is even more preferable.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2-hydroxy-2-methyl-isobutyramide < / RTI > 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 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.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trichloromethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product 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 IGACURE-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'-tetraphenylbimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2,2'-bis (2-chlorophenyl) 4,4 ', 5,5'-tetra (alkoxyphenyl) bimidazole, 2, 2'-bis (2-chlorophenyl) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) bimidazole, 2,2'-bis 5,5'-tetra (trialkoxyphenyl) bimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-Open No. 62-174204), 4,4 ', 5,5'- Imidazole compounds in which the phenyl group is substituted by a carboalkoxy 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'-tetraphenylbimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbimidazole.

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. These are preferably used in combination with the photopolymerization initiator D1 (particularly amines) described later.

Examples of the acid generator which generates an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetoxyphenyl.methylbenzylsulfonium 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 a compound which simultaneously generates an active radical and an acid by light, such as a triazine compound.

Examples of the photopolymerization initiator (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-dimethylaminoethylbenzoate, (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzophenone, and N, N-dimethyl paratoluidine '-Bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. EAB-F [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

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

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

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

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylamino benzoic acid 2 (Ethylhexyl), N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Bis (ethylmethylamino) benzophenone, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. EAB-F [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

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

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

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

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

When the photopolymerization initiator (D1) is used, the amount thereof is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 50 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) 40 parts by mass. It is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (D). When the amount of the polymerization initiator (D1) is within this range, the pattern can be formed with higher sensitivity and the productivity of the pattern tends to be improved.

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

The solvent (E) is not particularly limited, and a solvent 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-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

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, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methyl anisole 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 , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono T-butyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, Pentanone, cyclohexanone, isopolone, 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.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. 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, N-methylpyrrolidone and the like are preferable, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, 3-ethoxypropionic acid Ethyl and the like are more preferable. When such a solvent is included, the flatness at the time of coating is excellent.

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 tends not to be insufficient when the color filter is formed.

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.

Examples of the silicone surfactant include surfactants having a siloxane bond. Specific examples of the silicone oil include Torenia DC3PA, Toresilicon SH7PA, Toresilicon DC11PA, Toresilicon SH21PA, Toresilicon SH28PA, Toresilicon SH29PA, Toresilicon SH30PA, and Polyether-denatured silicone oil SH8400 (trade name: Toray Dow Corning) , 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 Mater Real Japan Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, there are mentioned Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Co.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, (Trade name) EF301, EF TOP EF303, EF TOP EF351, and EF TOP EF352 [manufactured by Mitsubishi Materials Electronics Co., Ltd.], and the like, (Trade name) manufactured by Daikin Fine Chemical Research Co., Ltd.], and the like can be mentioned.

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, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.01 mass% or more and 0.05 mass% or less, relative to the colored photosensitive resin composition % Or less. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

If the colored photosensitive resin composition of the present invention is a composition comprising 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, solvent resistance and spectroscopy can be obtained.

In the colored photosensitive resin composition of the present invention, the content of the colorant (A) is 0.5 to 10 mass%, the content of the resin (B) is 1 to 20 mass%, the content of the photopolymerizable compound (C) By mass, the content of the photopolymerization initiator (D) is 0.5 to 10% by mass, and the content of the solvent (E) is 45 to 97% by mass. The content of the colorant (A) is 1 to 7 mass%, the content of the resin (B) is 3 to 10 mass%, the content of the photopolymerizable compound (C) is 3 to 12 mass% ) Is 1 to 5% by mass, and the content of the solvent (E) is 66 to 92% by mass. The content of the colorant (A) is 2 to 5 mass%, the content of the resin (B) is 4 to 8 mass%, the content of the photopolymerizable compound (C) is 5 to 10 mass% ) Is 2 to 4% by mass, and the content of the solvent (E) is 73 to 87% by mass.

When the photopolymerization initiator (D1) is used in the colored photosensitive resin composition of the present invention, the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass based on 100 parts by weight of the solid content in the colored photosensitive resin composition, More preferably from 1 to 5 parts by mass, still more preferably from 1 to 3 parts by mass.

When the surfactant (F) is used in the colored photosensitive resin composition of the present invention, the content of the surfactant (F) is preferably 0.001 to 1 part by mass, more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the solid content in the colored photosensitive resin composition, More preferably 0.5 to 1 part by mass, still more preferably 0.05 to 1 part by mass.

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

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

The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used and the purpose of use. For example, it is 0.1 to 30 탆, preferably 1 to 20 탆, more preferably 1 to 6 Mu m.

Examples of the application method of the colored photosensitive resin composition include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating and die coating. Alternatively, it may be coated with a coater such as a dip coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (die coater, curtain float coater, or spinless coater).

The removal / drying of the solvent includes, for example, natural drying, air drying, vacuum drying, and heat 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 of 50 to 150 Pa and at a temperature of 20 to 25 캜.

The dried coating film is exposed through a photomask for forming a desired pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape according to the intended use is 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, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like can be used. The light is selectively extracted using a band-pass filter that cuts a specific wavelength region using a filter or extracts a specific wavelength region, You can.

It is preferable to use an apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or accurately align the mask and the substrate.

After exposure, a pattern can be obtained by contacting a predetermined portion, for example, an unexposed portion with a developing solution, and developing the resultant. Examples of the developer include aqueous solutions of alkaline compounds (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.). The developer may contain a surfactant.

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

If necessary, post-baking may be performed. The post bake is preferably in the range of, for example, 150 to 230 캜 for 10 to 240 minutes.

The colored photosensitive resin composition of the present invention can obtain a coating film or pattern having good color density, brightness, contrast, sensitivity, resolution, heat resistance, etc., and they are useful as color filters. It is also possible to provide a display device having such a color filter as a part of its constituent parts, for example, a known liquid crystal display device, an organic EL device, a solid-state image pickup device, , Can be used.

Example

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

[Synthesis Example 1]

30 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 288 parts of chloroform, and 2.3 parts of N, N-dimethyl-4-aminopyridine, 1.75 parts of 10-camphorsulfonic acid and 16.24 parts of glycidol were added, Lt; / RTI > for 1 hour. While stirring, 17.41 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 72 parts of chloroform was added dropwise. After completion of the reaction, a 1N hydrochloric acid aqueous solution was added to the reaction solution, and the solution was separated to obtain an organic layer. This operation was repeated twice for the organic layer. Next, 10% saline was added to the organic layer and liquid separation was performed to obtain an organic layer. This operation was repeated twice for the organic layer. Magnesium sulfate was added to the obtained organic layer, followed by dehydration, followed by filtration to obtain a filtrate. The solvent was removed from the filtrate with an evaporator, and the obtained red solid was dried under reduced pressure at 60 占 폚 to obtain 30 parts (yield: 89.5%) of a compound represented by the formula (d-1).

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

(Mass Spec.) Ionization mode = ESI +: m / z = 499.3 [M-Cl -] +

Exact Mass: 534.2

[Example 1]

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS N0.101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of 35% aqueous solution of sodiumacetate (produced by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve and stirred 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 to quench excess sodium nitrate.

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

10 parts of the compound of the formula (p-2) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry 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 and refluxed 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 obtained red orange solid 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

5 parts of the compound represented by the formula (z-2) was dissolved in 75 parts of N-methyl-2-pyrrolidone. To this solution was added a solution prepared by dissolving 2.63 parts of the compound represented by the formula (d-1) in 35 parts of N-methyl-2-pyrrolidone, and the mixture was stirred for 2 hours. After completion of the reaction, this was added dropwise to 300 parts of water, and the precipitated red solid was filtered and dried under reduced pressure at 60 캜 to obtain 6.4 parts (yield: 86.8%) of a compound represented by the formula (1-27).

Identification of the compound represented by the formula (1-27)

(Mass Spec.) Ionization mode = ESI +: m / z = 1382.4 [M-Cl -] +

Exact Mass: 1381.3

[Synthesis Example 2]

≪ Synthesis of resin B1 solution >

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel 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 [the compound represented by the following formula (I-1) and the compound represented by the formula (II-1) , 50:50)] and 140 parts by mass of ethyl lactate to prepare a solution. The solution was dropped into a flask maintained at 70 ° C over 4 hours using a dropping funnel . On the other hand, a solution prepared 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 to the flask over 4 hours using another dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 1.3 × 10 ⁴ , the solid content was 33% by mass, the solution acid value was 34 mg-KOH / g To obtain a resin B1 solution. Calculated from the solid content and the solution acid value, the solids content of the resin B1 is 100 mg-KOH / g.

[Synthesis Example 3]

≪ Synthesis of resin B2 solution >

333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas inlet tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 占 폚 and then 18.7 g of N-benzylmaleimide, 70.5 g of benzylmethacrylate, 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 funnel, and stirring was further continued at 100 캜 for 5 hours after completion of dropwise addition.

After the completion of the stirring, air was introduced into the flask through the gas introduction pipe, 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 And the reaction was continued at 110 캜 for 6 hours to obtain a resin B2 solution having a weight average molecular weight Mw of 16 × 10 ³ , a solid content of 31% and an acid value of 80 mg-KOH / g (in terms of solid content).

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

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

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; 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-288, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

[Example 2]

(Preparation of colored photosensitive resin composition)

(A) Compound (1): 30 parts of a compound represented by the formula (1-27)

(B) Resin: Resin B1 (in solid content) 40 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; 60 parts < tb >

(D) Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure OXE 01; Manufactured by BASF Japan Ltd.] Part 12

(D) Photopolymerization initiator: 6 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; BASF Japan)

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EAB-F; Manufactured by Hodogaya Chemical Co., Ltd.] Part 2

(E) Solvent: propylene glycol monomethyl ether 597 parts

(E) Solvent: ethyl lactate 43 parts

(F) Surfactant: polyether-modified silicone oil [Torensilicon SH8400; 0.09 part (manufactured by Toray Dow Corning Co., Ltd.)

To obtain a colored photosensitive resin composition.

[Formation of pattern]

The colored photosensitive resin composition was applied on a glass substrate (Eagle 2000; Corning) of 2 inch square by a spin coating method, and then pre-baked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask was set at 100 mu m, and exposure equipment (TME-150RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 100 mJ / cm < 2 > (based on 365 nm) in an air atmosphere. As the photomask, a 100 μm 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 perform development. After the water was cleaned, post-baking was performed in an oven at 230 DEG C for 30 minutes . After cooling, the film thickness of the obtained pattern was measured with a film thickness measuring device [DEKTAK3; Quot; manufactured by Nippon Vacuum Technology Co., Ltd.], it was 2.0 탆.

[Color performance evaluation]

With respect to the obtained pattern, a colorimeter [OSP-SP-200; (X, y) (i.e., chromaticity) and brightness Y before and after immersion in an XYZ colorimetric system of CIE were measured using an isochromatic function of a C light source (manufactured by Olympus Corporation) . The results are shown in Table 1.

[Evaluation of solvent resistance]

In the above-mentioned pattern formation, the same operation was performed except that the photomask was not used, thereby forming a coating film. The obtained coating film was immersed in N-methyl-2-pyrrolidone at 23 占 폚 for 30 minutes, and a colorimeter [OSP-SP-200; (Chromaticity) and brightness RY before and after immersion in the XYZ colorimetric system of CIE were measured by using an isochromatic function of C light source , And the color difference DELTA Eab * before and after immersion. The smaller the color difference? Eab *, the better the solvent resistance. Table 1 shows the results of the color difference DELTA Eab *.

The coated film after immersion was cut at intervals of 1 mm using a cutter and a shooter cutter guide (manufactured by Daini Materials Co., Ltd.) to prepare 100 squares of 1 mm x 1 mm. Cellotape (registered trademark) 24 mm wide (manufactured by Nichiban Co., Ltd.) was attached to the grid, rubbed with an eraser on a cellotape (registered trademark), cellotape (registered trademark) was attached to the cured coating film, and after 2 minutes The ends of Cellotape (registered trademark) were held and peeled off at a time while being held at right angles to the coated film surface. Thereafter, the coating film was not peeled off, and the number of grits remaining on the substrate was counted with the naked eye. The number of these grids is shown in Table 1 as the adhesion.

[Comparative Example 1]

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

(B) Resin: Resin B2 Solution 16 parts

(C) Photopolymerizable compound: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [KAYARAD DPHA; Manufactured by Nippon Gakkai Co., Ltd.] 23.9 parts

(D) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one [Irgacure 907; Manufactured by BASF Japan Co., Ltd.] 3.6 parts

(D) Photopolymerization initiator: 2.8 parts of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (TAZ-PP;

(D1) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone [EAB-F; 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. The colored photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 2 Comparative Example 1 Chromaticity

x 0.550 - y 0.250 - Y 15.2 - Solvent resistance Color difference? Eab * 0.1 *) Adhesiveness 100 *)

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

The coating film formed using the colored photosensitive resin composition of the present invention was confirmed to have good solvent resistance. From this, it can be understood that the colored photosensitive resin composition of the present invention can obtain a coating film, pattern and high quality color filter excellent in solvent resistance.

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

Claims (10)

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 the following 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 or -SO ₂ R ²⁹ .
R ²⁹ represents -R ³² , -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.
n represents an integer of 0 to 3; and when n is an integer of 2 or more, the plurality of R < ²⁷ > The method according to claim 1,
R ¹ to R ¹⁸ independently from each other are a hydrogen atom, a nitro group, or -SO ₂ R ²⁹ ;
R ²⁹ is -R ³² ;
R ³² is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms;
R ¹⁹ and R ²⁰ are, independently from each other, a methyl group;
R ²¹ to R ²⁴ independently represent a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms;
R ²⁵ and R ²⁶ are each independently a hydrogen atom;
wherein n is 0. 3. The method of claim 2,
At least one of R ¹ to R ¹⁸ is a hydrogen atom, at least one of them is a nitro group, and at least one of them is -SO ₂ R ²⁹ . The method of claim 3,
And R ¹ to R ¹⁰ are each independently a hydrogen atom. 5. The method of claim 4,
^At least one of R ¹¹ to R ¹⁸ is a hydrogen atom,
At least one of R ¹¹ to R ¹⁸ is a nitro group, and
And at least one of R ¹¹ to R ¹⁸ is -SO ₂ R ²⁹ . The method according to claim 1,
Wherein the photopolymerization initiator is at least one photopolymerization initiator selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a biimidazole compound. The method according to claim 1,
And M &^lt; ^{1 >} is Cr. A color filter formed from the colored photosensitive resin composition according to any one of claims 1 to 7. A display device comprising the color filter according to claim 8. A compound represented by the following 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 or -SO ₂ R ²⁹ .
R ²⁹ represents -R ³² , -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 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.
n represents an integer of 0 to 3; and when n is an integer of 2 or more, the plurality of R < ²⁷ >