KR101834575B1 - Colored photosensitive resin composition - Google Patents

Abstract

(B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) is a colorant containing a salt represented by the formula According to the colored photosensitive resin composition, it is possible to obtain a coating film, a pattern and a color filter of high quality with good heat resistance and light resistance.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

JP-A-2010-168531 discloses a colored photosensitive resin composition containing a cyanine dye, a resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.

The colored photosensitive resin composition is used as a material such as a coating film or a pattern of a color filter. That is, the coated film, pattern, etc. of the color filter are colored cured products obtained by curing the colored photosensitive resin composition.

An object of the present invention is to provide a colored photosensitive resin composition which is superior in heat resistance and light resistance and a colored filter containing the colored cured product.

The present invention provides the following [1] to [5].

(1) a colorant (A) containing a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent By weight based on the total weight of the colored photosensitive resin composition.

[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 -OH, -NHR ³⁰ or -R ³² .

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.

Ring Z ¹ and the ring Z ² may each independently represent an aromatic ring which may have a substituent, R ²¹ and R ²² are each independently represents an import aliphatic hydrocarbon group or a hydrogen atom is also 1 to 12 carbon atoms which is a substituent, R ²³ and R ²⁴ An aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent independently of each other, or R ²³ and R ²⁴ may be combined to form an alkanediyl group, and R ²⁵ and R ²⁶ may be independently R ²⁵ and R ²⁶ may be taken together to form an alkanediyl group, and R ²⁷ and R ²⁸ independently of one another may have a substituent. The substituent may be a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, An aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, or R ²⁷ and R ²⁸ may be combined to form an alkanediyl group. X ¹ represents a hydrogen atom or a chlorine atom]

[2] The photopolymerization initiator according to [1], wherein the photopolymerization initiator is at least one photopolymerization initiator selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and imidazole compounds. Sensitive composition.

[3] The colored photosensitive composition according to [1] or [2], wherein M ¹ is Cr.

[4] The colored photosensitive composition according to [1], wherein the salt represented by the formula (1) is a salt represented by the formula (1-A).

[In the formula (1-A), R ^{21 -A} and R ^{22 -A} independently represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

R ^x and R ^y independently represent a hydrogen atom, a methyl group or a trifluoromethyl group,

[5] A color filter formed by the colored photosensitive resin composition according to any one of [1] to [4].

[6] A display device comprising the color filter according to [5].

According to the colored photosensitive resin composition of the present invention, a colored cured product (for example, a coating film, a pattern) excellent in light resistance and heat resistance can be formed, and a high quality color filter containing the colored cured product can be obtained.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) (Hereinafter sometimes referred to as " anion (A1) ") represented by the following formula (A1) (Hereinafter sometimes referred to as "salt (1)").

The anion A1 can be selected in accordance with the color of the target color filter. It is preferable that the salt containing anion (A1) is sufficiently dissolved in a solvent. It is also preferable that the salt containing anion (A1) is dissolved in a developer to be used for pattern formation to be described later to such an extent that the pattern can be formed.

Further, since the anion (A1) takes a resonance structure, the temperature at which the charge of anion described in formula (A1) is transferred is included in the present invention.

Examples of the monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms in anion (A1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- N-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, Dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in anion (A1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in anion (A1) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, Diyl group, a butane-1,3-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, .

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

Examples of -R ³¹ -OR ³² in anion (A1) include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, Propoxy group, propoxypropyl group, 2-oxo-4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group and 3- (2-ethylhexyloxy) propyl group.

Examples of -R ³¹ -CO-OR ³² in anion (A1) include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxy Carbonylethyl group, butoxycarbonylmethyl group, and butoxycarbonylethyl group.

Examples of -R ³¹ -O-CO-R ³² in anion (A1) include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxy An ethyl group, a butylcarbonyloxymethyl group, and a butylcarbonyloxyethyl group.

In an anion (A1), -SO ₂ R ²⁹ includes a sulfo group; Sulfamoyl group;

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

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ) -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;

(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) A pamoyl group, and a sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

Examples of -SO ₂ R ³² in the anion (A1) include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, Pentylsulfonyl group, hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, 1-methylbutylsulfonyl group, 1,1,3,3-tetramethylbutylsulfonyl group, 1,5-dimethylhexylsulfonyl group, Dimethylheptylsulfonyl group, 2-ethylhexylsulfonyl group, and 1,1,5,5-tetramethylhexylsulfonyl group. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

It is preferable that at least one of R ¹ to R ¹⁸ is a nitro group in view of the tendency to form a pattern or the like with better heat resistance.

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

-SO ₂ R ²⁹ is -SO ₂ H, -SO ₂ NHR ³⁰ or -SO ₂ R ³² , preferably -SO ₂ R ³² . Among them, preferably -SO ₂ CH _3.

If the compounds of the invention having a -SO ₂ R ^32, it is preferable that at least one of R ¹¹ ~ R ¹⁴ and at least one of R ¹⁵ ~ R ¹⁸ is -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.

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

Further, since the cation (A2) takes a resonance structure, the cationic temperature at which the charge of the cation represented by the formula (A2) is transferred is included in the present invention.

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

As the substituent of the benzene ring and the naphthalene ring, for example,

Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,

Aromatic hydrocarbon groups such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy;

An aryloxy group such as a phenoxy group;

An aralkyloxy group such as a benzyloxy group;

An acyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group;

Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propyl sulfamoyl group, di-n-propyl sulfamoyl group, isopropyl sulfamoyl group, diisopropyl sulfamoyl group, an alkylsulfamoyl group such as an n-butylsulfamoyl group and a di-n-butylsulfamoyl group;

Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

A nitro group, and a cyano group.

When such a substituent has a hydrogen atom, the hydrogen atom may be, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy; An aryloxy group such as a phenoxy group or a benzyloxy group; Aromatic hydrocarbon groups such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m- A carboxyl group; Cyano; A nitro group; Or the like.

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

In the cation (A2), it is preferable that X ¹ is a hydrogen atom.

In the cation (A2), R ²¹ and R ²² independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms More preferably an alkyl group having 1 to 4 carbon atoms which has no substituent, and particularly preferably a methyl group. R ²¹ and R ²² are preferably the same group.

In the cation (A2), R ²¹ and R ²² Is an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, Butyl group, a tert-butyl group, a 2-butenyl group, a 1,3-butadienyl group, a pentyl group, an isopentyl group, a neopentyl group, Pentyl-4-onyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group can be given.

As the substituent in the aliphatic hydrocarbon group, for example,

Aromatic hydrocarbon groups such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy.

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Further, a carboxyl group, a nitro group and a cyano group can be mentioned.

In the cation (A2), R ²³ ~ R, if ²⁸ aliphatic hydrocarbon group of 1 to 12 carbon atoms is which may have a substituent, wherein the aliphatic hydrocarbon group include, for example, a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group Propyl group, a 2-propynyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-butenyl group, a 1,3- Pentyl group, isopentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, Methylhexyl group, heptyl group, and octyl group.

As the substituent in the aliphatic hydrocarbon group, for example,

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy.

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Further, a carboxyl group, a nitro group and a cyano group can be mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- A dihexyl group, and a hexane-1, 6-diyl group.

When R ²³ to R ²⁸ in the cation (A2) independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent, it is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms An alkyl group, more preferably a methyl group which may have a substituent, and particularly preferably a methyl group which does not have a substituent.

R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , and R ²⁷ and R ²⁸ are preferably the same group.

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

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

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

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

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

Preferable examples of the pyrazole azo compound serving as a ligand of anion (A1) in the salt (1) include compounds represented by the formulas (1-a1) to (1-a64).

Preferable examples of anion (A1) in the salt (1) include anions represented by the formulas (1-b1) to (1-b60).

Preferred examples of the cation (A2) in the salt (1) include cation represented by the formulas (1-c1) to (1-c36).

Next, a method for producing a salt containing anion (A1) will be described. Anion (A1) can be produced by reacting a compound represented by (1d) (hereinafter sometimes referred to as "compound (1d)") with a chromium compound or a cobalt compound in an organic solvent.

[Wherein R ¹ to R ⁵ , R ¹¹ to R ¹⁴ and R ¹⁹ in the formula (1d) have the same meanings as defined above]

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 salt (1) can be produced by a method of diazotizing a diazonium salt and a pyrazole compound. For example, a compound represented by the formula (1b) obtained by diazotizing an amine represented by the formula (1a) (hereinafter sometimes referred to as "amine (1a)") with nitrous acid, nitrite or nitrite, It can be used as a zonium salt.

[Wherein R ¹¹ to R ¹⁴ in the formulas (1a) and (1b) have the same meanings as defined above. A ^1- represents an inorganic or organic anion.

Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a hypochlorite ion, and the like. Examples of the organic anion include CH ₃ COO ^- , C ₆ H ₅ COO ^- and the like. Preferable examples thereof include chloride ion, bromide ion, CH ₃ COO ^- and the like.

A compound represented by the formula (1d) (hereinafter sometimes 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) 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.

[Wherein R ¹ to R ⁵ and R ¹⁹ in the formula (1c) have the same meanings as defined above]

When compound (1d) has -SO ₂ R ²⁹ and -SO ₂ R ²⁹ is -SO ₂ NHR ³⁰ , it can be prepared by using amine (1a) having -SO ₂ NHR ³⁰ , It is preferable that the coupling reaction is carried out using the amine (1a), and then the sulfonic group is sulfonated. 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) can be prepared by sulfonating a sulfo group by reacting a sulfonyl halide compound with an amine (R ³⁰ NH ₂ ) to obtain a sulfonyl halide compound in the presence of a base (-SO ₂ X; X is a halogen atom) .

Specific examples of the compound (1s) include the compounds represented by the formula (1-a1), the formula (1-a2) and the formula (1-a5) -a5), (1-a6), (1-a15) and (1-a16). Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide, and the like, and preferred examples thereof include thionyl chloride and thionyl bromide. Particularly preferably, O'Neill. The thionyl halide is preferably used in an amount of 1 to 10 moles per 1 mole of the compound (1s). Further, when water is mixed in the reaction system, it is preferable to use a thionyl halide compound in excess.

The sulfonyl halide is carried out in a solvent. The solvent includes, 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. 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 the sulfonyl halide formation, it is preferable to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide) in combination. When N, N-dialkylformamide is used, its amount to be used is, for example, 0.05 to 1 mole relative to 1 mole of thionyl halide compound. After the compound (1s) and N, N-dialkylformamide are mixed in a solvent in advance, addition of a thionyl halide compound can suppress heat generation.

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 they may be isolated and then an amine (R ³⁰ NH ₂₎ and hold and be reacted, without isolation of the reaction mixture the amine (R ³⁰ NH ₂₎ and reaction. When isolation is carried out, for example, the reaction mixture and water may be mixed, and the precipitated crystals may be collected by filtration. The crystals of the obtained sulfonyl halide compound 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 (such as 1,5-dimethylhexylamine), tetramethylbutylamine Ethylhexylamine and the like), aminophenylbutane (3-amino-1-phenylbutane and the like), isopropoxypropylamine, and the like. The amount of the amine (R ³⁰ NH ₂ ) to be used is 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. The reaction of 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.

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 amines 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 timing of addition of the basic catalyst is not particularly limited and may be either before or after the addition of the amine (R ³⁰ NH ₂ ) amine may be added at the same timing, and (R ³⁰ NH _2). 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.

Examples of the method for obtaining compound (1d) as a target compound from the reaction mixture include a method of mixing the reaction mixture with an acid (for example, acetic acid etc.) and water and collecting the precipitated crystals by filtration have. It is preferable that the acid is prepared by preparing an aqueous solution of an acid in advance and then adding the reaction mixture to the aqueous solution. The temperature at the time of adding the reaction mixture is preferably 10 ° C to 50 ° C, more preferably 20 ° C to 50 ° C, and further preferably 20 ° C to 30 ° C. Further, after the reaction mixture is added to the aqueous solution of the acid, it is preferable to stir at the above temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like, and then dried. If necessary, it may be further purified by recrystallization or the like.

The anion (A1) in which M ¹ in the formula (A1) is Cr can be produced by reacting the compound (1d) and a chromium compound in an aqueous solvent at 70 to 100 ° C. It is preferable to react the compound (1d) with a chromium compound in a molar ratio of 2: 1 to 4: 1.

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

Next, a method for producing a salt capable of producing the cation (A2) of the salt (1) will be described. Examples of the salt containing the cation (A2) include those having the following structures.

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

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

Salts containing cations (A2) can be prepared by known synthetic methods.

For example, J. Mater. (B-0) by reacting an indole with an alkyl halide as described in Chem., 1999, 6 (4), 559-565, and reacting the halide To obtain cyanine (b-1) having the ion as a counter ion. (b-1) can be induced to a desired counter ion by a salt exchange reaction with NaClO ₄ , NaPF ₆ , and NaBF ₄ .

Next, a method for producing the salt (1) will be described.

The salt (1) can be prepared by subjecting a salt containing anion (A1) and a salt containing a cation (A2) to a salt exchange reaction in a solvent. It is preferable to react the anion (A1) with the cation (A2) in a molar ratio of 1: 1 to 1: 4.

(1d) and a cobalt compound in an aqueous solvent at 70 to 100 占 폚 in the case where anion (A1) is a cobalt complex anion (M ¹ in the formula (1) is Co). It is preferable to react the compound (1d) and the cobalt compound in a molar ratio of 2: 1 to 4: 1.

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

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

An embodiment of the salt (1) is, for example, a salt represented by the formula (1-A).

[In the formula (1-A), R ^{21 -A} and R ^{22 -A} independently represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

R ^x and R ^y independently represent a hydrogen atom, a methyl group or a trifluoromethyl group,

The content of the salt (1) may be, for example, 1% by mass or more and 100% by mass or less, or 3% by mass or more and 100% by mass or less in the colorant (A), and 1% by mass or more and 99% 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.

The colorant (A) may contain a dye different from the salt (1) together with the salt (1). The dyes include oil dyes, acid dyes, dyes such as amine salts of acid dyes and sulfonamide derivatives of acid dyes. For example, dyes are classified in the color index (The Society of Dyers and Colourists) , And known dyes described in Dyeing Note (Shika Sensha).

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

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

C.I. Solvent Orange 2, 7, 11, 15, 26, 56; C.I. Solvent dyes,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6B, 7, 9, 17, 19; C.I. Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

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

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

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

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

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

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

The colorant (A) may further contain a pigment together with the salt (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 containing the 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 surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, graft treatment on the surface of the pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that the organic pigment has a uniform particle size. 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 dispersing agent include surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersing agent include trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Fluren (manufactured by Kyowa Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA) (Manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by Big Chemical).

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, a pigment dispersion in a uniformly dispersed state tends to be obtained.

When the pigment is contained in the colorant (A), 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 salt (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, optimization of the transmission spectrum is facilitated, and high contrast and high brightness can be obtained. Further, heat resistance and chemical resistance are improved.

In particular, salts (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 from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the solid content in the colored photosensitive resin composition. Here, the solid content refers to the total of the components from which the solvent in the colored photosensitive resin composition has been removed. When the content of the colorant (A) is within the above range, the color density when formed into a color filter is sufficient and a required amount of the binder polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

The colored photosensitive resin composition of the present invention contains the resin (B). The resin (B) 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 also referred to as "(a)"), an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (B) (hereinafter may be referred to as " (b) ").

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

[K3] The copolymer of (b) and (c)

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

When the resin (B) contains a structural unit derived from (a), the reliability of heat resistance, chemical resistance and the like of the resulting colored pattern can be further improved.

(a) can be obtained, for example, by reacting a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring) and an ethylenically unsaturated bond ≪ / RTI > (a) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

(a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(a1)"), a monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(a2)"), a monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a3)") and the like.

(a1) having a structure obtained by epoxidizing a chain olefin (hereinafter sometimes referred to as " (a1-1) "), and a structure obtained by epoxidizing a cyclic olefin (Hereinafter sometimes referred to as " (a1-2) ").

(meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl (meth) acrylate, Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(a1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexyl (Meth) acrylate (for example, Cychroma A400, manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (I), and compounds 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 is 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 ³ represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O]

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

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

As R ¹ and R ² , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

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- And a 1,6-diyl group.

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

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

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

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. In addition, they can be mixed at an arbitrary ratio. The mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and particularly preferably from 20:90 to 90:10 in terms of the molar ratio, preferably in the formula (I): formula (II) 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.

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

(b) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- Cyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-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 (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and 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 and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, which is referred to in the art as dicyclopentanyl (meth) acrylate, in the art, which is referred to as dicyclopentanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl ) Acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, Such as methacrylate (meth) acrylic acid esters;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [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] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- hydroxyethyl) bicyclo [2.2.1] 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cycarbonylbicyclo [ 2,1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) Cyclo [2.2.1] hept-2-ene and the like;

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 and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the proportion 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% by mole (more preferably 65 to 95% by mole)

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

Resin [K1] can be synthesized by, for example, the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) Can be prepared by reference to the literature.

Specifically, there is exemplified a method in which a prescribed amount of (a) and (b), a polymerization initiator and a solvent are put into a reaction vessel and oxygen is replaced by nitrogen, thereby stirring, heating and maintaining the oxygen in the deoxygenation. The polymerization initiator and solvent used herein are not particularly limited, and any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide Etc.). The solvent may be any one which dissolves the respective monomers, and a solvent described later or the like may be used as the solvent of the photosensitive resin composition.

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

In the resin [K2], the ratio of the structural units derived from each 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% by mole (more preferably 1 to 60% by mole)

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 improved.

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

Specifically, there can be mentioned a method in which predetermined amounts 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, heating and keeping the temperature under deoxygenation . 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 it may be taken out as a solid (powder) by a method such as re-precipitation.

In the resin [K3], the ratio of the respective 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 described for the method of 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 in (a) is reacted with a part of the carboxyl group and / or carboxylic acid anhydride contained in the structural unit derived from (c) in the copolymer.

(b) and (c), the atmosphere in the flask is replaced with nitrogen in air, and a reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (dimethylaminomethyl) phenol ) In an amount of 0.001 to 5% by mass based on the total amount of (a) to (c), and 0.001 to 5% by mass with respect to the total amount of the polymerization inhibitor (such as hydroquinone) The resin [K4] can be obtained by placing it in a flask, for example, at 60 to 130 ° C for 1 to 10 hours. The reaction conditions such as the injection method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization. In addition, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization, as in the case of the polymerization conditions.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / A resin [K1] such as an acrylic acid copolymer; (Meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [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 in which glycidyl (meth) acrylate is added 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, still more preferably from 5,000 to 35,000, even more preferably from 6,000 to 30,000, It is 7,000 ~ 28,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion 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 an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

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

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which can be polymerized by an active radical and an acid generated in the photopolymerization initiator (D) upon irradiation with light, for example, a compound having a polymerizable ethylenically unsaturated bond , And preferably a (meth) acrylic acid ester compound.

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

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

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

The photo polymerization 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 to initiate 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 initiation assistant (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 at least a compound selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and non- A photopolymerization initiator containing one species is more preferable, and a photopolymerization initiator containing an oxime compound is more preferable.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl Phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, -1- (4-methylsulfanylphenyl) propan-1-one, and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Irgacure 369, 907 (manufactured by Chiba Japan) can be used.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

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

Examples of the oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy-1- [9 -Ethyl] -6-f2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} . Commercially available products such as Irgacure OXE-01, OXE-02 (manufactured by Chiba Japan) and N-1919 (manufactured by ADEKA) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373 and the like), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, Imidazole compounds in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913). Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the polymerization 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 photo-polymerization initiator (D1) (particularly amines) described below.

Examples of the acid generator which generates an acid by light include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl Dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl Onium salts such as iodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylates and the like.

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

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

Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4 , 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

The content of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 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, high sensitivity is obtained and the exposure time is shortened and the productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiator (D1). The photopolymerization initiation assistant (D1) is usually 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 photo-polymerization 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-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- City Oak Mountain, and the like.

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

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

When these photo-polymerization initiators (D1) are used, the amount thereof is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 50 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) 40 parts by mass. The amount 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 the above range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

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

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

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , 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 glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, A brush, 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, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, 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, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

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

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

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

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

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

Among these solvents, an organic solvent having a boiling point of 120 ° C or more and 180 ° C or less at 1 atm is preferable from the viewpoint of coatability and dryness. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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 these solvents are contained, 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, 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 characteristics are not insufficient when the color filter is formed, so that display characteristics tend to be good.

The colored photosensitive resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Concretely, it is preferable to use a silicone resin such as Tororensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether-denatured silicone oil SH8400 (trade name: Toor Dow Corning Co., , 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 Materials Japan Joint- And the like.

 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, a fluorine-containing resin (trade name) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapak (trade name) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30, (Trade name) S381, S382, SC101, and SC101 (trade names) manufactured by Mitsubishi Materials Corporation, 718-K (trade name, manufactured by DIC), EF301, EF303, EF351 and EF352 SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Chemical Laboratory Co., Ltd.).

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

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

The content of the surface active agent (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. When the content of the surfactant (F) is in the above range, the flatness of the coated 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) , It is possible to obtain a colored pattern excellent in coating property and excellent in solvent resistance and spectroscopy.

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 for forming a colored pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention may be applied to a substrate or another resin layer (for example, another colored photosensitive resin A method in which a colored layer is formed by removing / drying a volatile component such as a solvent, and the colored layer is exposed and developed through a photomask, a method using an inkjet device which does not require a photolithography method And the like.

In this case, the film thickness of the coating film can be appropriately adjusted depending on the material to be used, the use and the like, and is, for example, from 0.1 to 30 μm, preferably from 1 to 20 μm, more preferably from 1 to 6 μm.

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. It may also 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 flow 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 in the range of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The coated film after drying is exposed through a photomask for forming a desired pattern. The pattern shape on the photomask at this time is a pattern shape according to the intended use.

As a light source used for exposure, a light source that generates wavelength light 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 can be selectively cut out by using a filter that cuts a specific wavelength region or by using a band- .

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 to precisely 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 developing solution 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. It is preferable to rinse after development.

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

According to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film, a pattern and a high-quality color filter having good heat resistance and light resistance. It is also possible to use these color filters or patterns as a part of the constituent parts thereof in a known manner, for example, all devices related to various colored images, such as known liquid crystal display devices, organic EL devices, and solid-state image pickup devices .

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 part by mass unless otherwise specified.

Synthesis Example 1

To 63 parts of 2,3,3-trimethyl- 3H -indole (manufactured by Wako Pure Chemical Industries, Ltd.), 65 parts of methyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and refluxed at 140 ° C for 6 hours. After cooling, 120 parts of diethyl ether was added. The resulting precipitate was collected by filtration, washed with cold acetone and then dried under reduced pressure to obtain 102 parts of 1-methyl-2,3,3-trimethyl- 3H -indolium iodide (86 %). Subsequently, 470 parts of pyridine and 64 parts of triethylamine were added to 100 parts of 1-methyl-2,3,3-trimethyl- 3H -indole iodide and 64 parts of ethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) Lt; / RTI > After cooling, 800 parts of diethyl ether is slowly added to obtain a precipitate, which is obtained by filtration. This solid was recrystallized using ethanol and dried under reduced pressure at 60 DEG C for 24 hours to obtain 145 parts of cyanine compound (d-1) (90%).

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

(Mass analysis) Ionization mode = ESI +: m / z = 357.3 [MI ^- ] ⁺

Exact Mass: 484.1

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. And 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) were added. 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 consume excess sodium nitrite.

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 the pH was adjusted to 8.0 with sodium hydroxide. Then, the suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of the dropwise addition, stirring was further carried out for 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 캜 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 KASEI KOGYO CO., LTD.) And dissolved. 3.1 parts of ammonium sulfate chromium (Ⅲ) 12 water (manufactured by Wako Pure Chemical Industries, 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and refluxed for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline. After filtration, the resulting 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 ⁺ ] ^-

            ExactMass: 905.1

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

Synthesis Example 2

<Synthesis of Resin Solution B1>

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 305 parts of ethyl lactate was added and heated to 70 deg. Subsequently, 60 parts 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) and 140 parts of ethyl lactate to prepare a solution. The solution was dropped into a flask maintained at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts 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 占 폚 for 4 hours and then cooled to room temperature. The solution had a weight average molecular weight Mw of 1.3 占⁰⁴ , a solid content of 33 mass%, a solution acid value of 34 mg-KOH / g To obtain a resin B1 solution. Calculated from the solid content and the solution acid value, the solid content of the resin B1 is 100 mg-KOH / g.

Synthesis Example 3

&Lt; Synthesis of Resin Solution B2 &gt;

333 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction pipe, 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 parts of N-benzylmaleimide, 70.5 parts of benzylmethacrylate, 51.7 parts of methacrylic acid, 90.0 parts of methyl methacrylate, 5.2 parts of azobisisobutyronitrile And 182 parts 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 ° C 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 parts of trisdimethylaminomethylphenol and 0.165 part of hydroquinone were charged into 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 measurement of the polystyrene reduced weight average molecular weight of the resin was carried out by the GPC method under the following conditions.

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 ml / min

Solid concentration of the test solution; 0.001 to 0.01%

Dose; 50 μl

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500 and A-500 (manufactured by Tosoh Corporation)

Example 1

[Preparation of colored photosensitive resin composition]

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

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

(C) Photopolymerizable compound: 60 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: 12 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01; BASF Japan)

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

(D2) Photopolymerization initiator: 2 parts of 4,4'-bis (diethylamino) benzophenone (EAB-F manufactured by Hodogaya Chemical Co., Ltd.)

(E) Solvent: Propylene glycol monomethyl ether acetate 528 parts

(E) Solvent: propylene glycol monomethyl ether 69 parts

(F) Surfactant: 0.09 part of a polyether-modified silicone oil (Toorel silicone SH8400, 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) having a size of 2 inches by 2 inches by spin coating, and then prebaked at 100 占 폚 for 3 minutes. After cooling, the space between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask was set to 100 mu m and an exposure time of 100 mJ / cm &lt; 2 &gt; was attained by using an exposure machine (TME-150RSK; And irradiated with light at an exposure amount (based on 365 nm). 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 캜 for 80 seconds to perform development. After washing with water, post-baking was performed in an oven at 230 캜 for 30 minutes . After cooling, the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.0 占 퐉.

[Heat resistance evaluation]

In the above pattern formation, the same operation was performed except that the photomask was not used, thereby forming a coating film. The obtained coating film was stored in an oven at 230 캜 for 2 hours and then spectroscopically measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation). Using the color matching function of the C light source, Xy chromaticity coordinates (Rx, Ry) (i.e., chromaticity) and lightness RY before and after the heat resistance test in the heat resistance test were measured to calculate the color difference? Eab * before and after the heat resistance test. The smaller the color difference? Eab *, the better the heat resistance. Table 1 shows the results of the color difference DELTA Eab *.

[Evaluation of light resistance]

In the above pattern formation, the same operation was performed except that the photomask was not used, thereby forming a coating film. The obtained coating film was stored for 48 hours under irradiation with a xenon lamp (manufactured by Toyo Seiki Kogyo K.K., acid test CPS +), and spectroscopy was measured using a colorimeter (OSP-SP-200; Olympus Co., Ltd.) (Chromaticity) and brightness RY of the XY chromaticity coordinates before and after the heat resistance test in the CIE XYZ color coordinate system were measured to calculate the color difference DELTA Eab * before and after the heat resistance test. The smaller the color difference? Eab *, the better the heat resistance. Table 1 shows the results of the color difference DELTA Eab *.

Comparative Example 1

(A) Colorant: 10.2 parts of a compound represented by the formula (d-1)

(B) Resin: Resin solution B1 (in terms of solid content) 40 parts

(C) Photopolymerizable compound: 60 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: 12 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE 01; BASF Japan)

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

(D2) Photopolymerization initiator: 2 parts of 4,4'-bis (diethylamino) benzophenone (EAB-F manufactured by Hodogaya Chemical Co., Ltd.)

(E) Solvent: N, N-dimethylformamide 445 parts

(E) Solvent: Propylene glycol monomethyl ether 60 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 8 parts

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

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 1 Comparative Example 1 Heat resistance Color difference? Eab * 6.0 61.2 Light resistance Color difference? Eab * 7.3 58.8

The coating film formed using the colored photosensitive resin composition of the present invention was confirmed to have good heat resistance and light resistance. From this, it can be seen that a pattern showing good heat resistance and light resistance and a high-quality color filter can be obtained.

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

Claims (6)

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

[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 -OH, -NHR ³⁰ or -R ³² .
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.
The ring Z ¹ and the ring Z ² independently represent an aromatic ring which may have a substituent, R ²¹ and R ²² independently represent an aliphatic hydrocarbon group or a hydrogen atom of 1 to 12 carbon atoms which may have a substituent, R ²³ and R ²⁴ May be independently an aliphatic hydrocarbon group or a hydrogen atom of 1 to 12 carbon atoms which may have a substituent, or R ²³ and R ²⁴ may be taken together to form an alkanediyl group, and R ²⁵ and R ²⁶ may form a An aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent independently, or R ²⁵ and R ²⁶ may be taken together to form an alkanediyl group, and R ²⁷ and R ²⁸ independently of one another are a substituent An aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may be substituted, or R ²⁷ and R ²⁸ may be combined to form an alkanediyl group. X ¹ represents a hydrogen atom or a chlorine atom] The method according to claim 1,
Wherein the photopolymerization initiator (D) is a photopolymerization initiator containing at least one member selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a nonimidazole compound. The method according to claim 1,
And M &^lt; ^{1 &gt;} is Cr. The method according to claim 1,
A colored photosensitive composition wherein the salt represented by the formula (1) is a salt represented by the formula (1-A).

[In the formula (1-A), R ^{21 -A} and R ^{22 -A} independently represent an aliphatic hydrocarbon group having 1 to 4 carbon atoms,
R ^x and R ^y independently represent a hydrogen atom, a methyl group or a trifluoromethyl group, A color filter formed by the colored photosensitive resin composition according to claim 1. A display device comprising the color filter according to claim 5.