JP2012041461A - Compound - Google Patents

Abstract

［式（Ｉ）中、Ｒ^１は、水素原子、又は炭素数１〜３０の１価の炭化水素基を表す。Ｒ²は、水素原子、シアノ基、又はカルバモイル基を表す。Ｒ^３は、炭素数１〜４のアルキル基又はトリフルオロメチル基を表す。Ａは、置換基を有していてもよいフェニレン基を表す。Ｍは、水素原子又はアルカリ金属原子を表す。Ｙ^１及びＹ^２は、−Ｏ−、−ＮＲ^６−又は−Ｓ−を表す。Ｚは、炭素数１〜２４の（ｍ＋ｎ）価の脂肪族炭化水素基を表す。ｍは、０〜５の整数を表す。ｎは、１〜６の整数を表す。ただし、ｍ＋ｎは２〜６の整数を表す。］
【選択図】なしDisclosed is a compound having excellent solubility in an organic solvent and useful as a dye for use in a color filter of a display device such as a liquid crystal display device.
A compound represented by formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ² represents a hydrogen atom, a cyano group, or a carbamoyl group. R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group. A represents a phenylene group which may have a substituent. M represents a hydrogen atom or an alkali metal atom. Y ¹ and Y ² represent —O—, —NR ⁶ — or —S—. Z represents an (m + n) -valent aliphatic hydrocarbon group having 1 to 24 carbon atoms. m represents an integer of 0 to 5. n represents an integer of 1 to 6. However, m + n represents an integer of 2-6. ]
[Selection figure] None

Description

  The present invention relates to a compound useful as a dye for use in a color filter of a display device.

Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like.
For example, in Example 1 of Patent Document 1, a compound represented by the following formula is described.

JP 2004-2630 A

    The above compounds are known as water-based inks having excellent light resistance. The compound has low solubility in an organic solvent, and it has not been easy to use as a dye used for a color filter of a display device such as a liquid crystal display device.

The present invention provides the following [1] to [3].
[1] A compound represented by the formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group contained in the hydrocarbon group includes —O—, —CO—, — It may be replaced by NR ^6- , -SO ₂ -or -S-.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
A represents a phenylene group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
Y ¹ and Y ² represent —O—, —NR ⁶ — or —S—.
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z represents a (m + n) valent aliphatic hydrocarbon group having 1 to 24 carbon atoms, a methylene group contained in the aliphatic hydrocarbon group, -O -, - CO -, - NR 7 -, - SO ₂ - or -S- in may be replaced, methine group contained in the aliphatic hydrocarbon group may be replaced by a nitrogen atom, a hydrogen atom contained in the aliphatic hydrocarbon group is -SO ₃ M may be replaced.
R ⁷ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
m represents an integer of 0 to 5. When m is an integer greater than or equal to ² , several Y2 may mutually be same or different.
n represents an integer of 1 to 6. If n is an integer of 2 or more, plural ^{R 1, R 2, R 3} , A and ^{Y 1} may being the same or different.
However, m + n represents an integer of 2-6. ]

[2] The compound according to [1], wherein A is a phenylene group having at least one selected from the group consisting of a nitro group and —SO ₃ M.
[3] The compound according to [1] or [2], wherein the phenylene group is an o-phenylene group.
[4] A dye comprising the compound according to any one of [1] to [3] as an active ingredient.
[5] A dye containing two or more compounds according to any one of [1] to [3].

  The compound of the present invention is excellent in solubility in an organic solvent, and is excellent as a dye used for a color filter of a display device such as a liquid crystal display device.

  The present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group contained in the hydrocarbon group includes —O—, —CO—, — It may be replaced by NR ^6- , -SO ₂ -or -S-.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
A represents a phenylene group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
Y ¹ and Y ² represent —O—, —NR ⁶ — or —S—.
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z represents a (m + n) valent aliphatic hydrocarbon group having 1 to 24 carbon atoms, a methylene group contained in the aliphatic hydrocarbon group, -O -, - CO -, - NR 7 -, - SO ₂ - or -S- in may be replaced, methine group contained in the aliphatic hydrocarbon group may be replaced by a nitrogen atom, a hydrogen atom contained in the aliphatic hydrocarbon group is -SO ₃ M may be replaced.
R ⁷ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
m represents an integer of 0 to 5. When m is an integer greater than or equal to ² , several Y2 may mutually be same or different.
n represents an integer of 1 to 6. If n is an integer of 2 or more, plural ^{R 1, R 2, R 3} , A and ^{Y 1} may being the same or different.
However, m + n represents an integer of 2-6. ]

Examples of the monovalent hydrocarbon group representing R ¹ include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a group obtained by combining these. The carbon number is 1-30. Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxy group, and an alkoxy group having 1 to 4 carbon atoms.

Examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. A linear alkyl group such as nonyl group and decyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, Examples thereof include branched alkyl groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group.

Examples of the monovalent aliphatic hydrocarbon group having a substituent include a 2-hydroxyethyl group, a 2-aminoethyl group, and a 2-sulfanylethyl group.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the aromatic hydrocarbon group having a substituent include a 4-hydroxyphenyl group, a 4-methoxyphenyl group, a 2-carboxyphenyl group, and a 4-carboxyphenyl group.

Examples of R ¹ include groups represented by formulas (e-1) to (e-5).

R ¹ is preferably -L ¹ -X ¹ -R ⁴ , more preferably -L ¹ -X ¹ -L ² -X ² -R ⁵ . When R ¹ is these groups, the solubility of the compound of the present invention in an organic solvent tends to be improved.
L ¹ and L ² are each independently an alkanediyl group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, butane. -1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7- A diyl group, an octane-1,8-diyl group, etc. are mentioned.

X ¹ and X ² are —CO—O—. X ¹ is preferably * —O—CO— (* represents a bond to L ¹ ). When X ¹ is * —O—CO—, the compound of the present invention can be easily produced.
R ⁴ is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the aliphatic hydrocarbon group is replaced by —O— or —CO—. Also good. Examples of the aliphatic hydrocarbon group representing R ⁴ include those having 1 to 20 carbon atoms among the groups listed as the monovalent aliphatic hydrocarbon group representing R ¹ .
R ⁵ is a hydrogen atom, a methyl group or an ethyl group.

Examples of -L ¹ -X ¹ -R ⁴ include groups represented by formula (f-1) to formula (f-30). Among ^them, the ^{-L 1 -X 1 -L 2 -X 2} -R 5, for example, a group represented by the formula (f-1) ~ formula (f-22) Ageraru. Among them, Formula (f-1), Formula (f-2), Formula (f-5), Formula (f-6), Formula (f-9), Formula (f-10), Formula (f-13) , Groups represented by formula (f-14), formula (f-17) and formula (f-18) are preferred, and formula (f-2), formula (f-6), formula (f-10), The groups represented by formula (f-14) and formula (f-18) are more preferable.

R ² is a hydrogen atom, a cyano group, or a carbamoyl group. Of these, a cyano group is preferable in terms of easy availability of raw materials.

Examples of the alkyl group having 1 to 4 carbon atoms representing R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

  A is a phenylene group which may have a substituent. Examples of the substituent that the phenylene group in A may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a cyano group, or And halogeno groups.

Among them, as A, a phenylene group having at least one selected from the group consisting of a nitro group and —SO ₃ M is preferable, and a phenylene group having at least one nitro group is more preferable. It is preferable that the compound (I) has a nitro group because the spectral density tends to increase. Further, compound (I) to have a -SO 3 _M, excellent in heat resistance, and can suppress the sublimation of compound (I).
M is a hydrogen atom or an alkali metal atom. Examples of the alkali metal include lithium, sodium, and potassium. As M, a hydrogen atom and a sodium atom are preferable, and a hydrogen atom is more preferable.

  The phenylene group in A is preferably an o-phenylene group. When it is an o-phenylene group, it has excellent heat resistance and can suppress sublimation of the compound (I).

Examples of the alkyl group having 1 to 8 carbon atoms include groups having 1 to 8 carbon atoms among the linear alkyl groups and branched chain alkyl groups mentioned as the monovalent aliphatic hydrocarbon group representing R ^1. Can be mentioned.
Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and the like. .

  Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1-ethoxy- 1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1-methyl Examples include an ethyl group, 2- (1-methylethoxy) -1-methylethyl group, and 3-ethoxypropyl group.

Y ¹ and Y ² are —O—, —NR ⁶ — or —S—. Among these, -O- and -S- are preferable. R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the (m + n) valent (i.e., 2 to 6 valent) aliphatic hydrocarbon group having 1 to 24 carbon atoms representing Z include groups in which (m + n) hydrogen atoms have been removed from an alkane having 1 to 24 carbon atoms. Can be mentioned.
Examples of the alkane having 1 to 24 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, Henicosane, docosane, tricosane, tetracosane, 3,3,4-trimethyldecane, 2-methyl-4-propylheptane, 6-pentyl-6-ethylundecane, 2,2-diethylbutane, 3,3-diethylpentane, 3 -Methyl-4-methylhexane, 2-methyl-9-methyldecane, 6,6-dipentylethylundecane, 7,7-dihexyltridecane, 2-methyl-12-methyl-7,7-di (5-methylhexyl) ) Tridecane, 3,4,5-trime Ruheputan, 2,12- dimethyl tridecane, 3,4,5,6-tetramethyl octane, 3,3,7,7- tetraethyl nonane, 3,3,9,9- tetraethyl undecane, and the like.

The methylene group contained in the aliphatic hydrocarbon group may be replaced by —O—, —CO—, —NR ⁷ —, —SO ₂ — or —S—, and is contained in the aliphatic hydrocarbon group. The methine group may be replaced by a nitrogen atom.
The hydrogen atom contained in the aliphatic hydrocarbon group may be replaced with —SO ₃ M. Examples of M include the same as described above.

  Examples of the divalent aliphatic hydrocarbon group include groups represented by formula (z-1) to formula (z-32).

  Examples of the trivalent aliphatic hydrocarbon group include groups represented by formula (z-33) to formula (z-38).

Examples of the tetravalent aliphatic hydrocarbon group include groups represented by formula (z-39) to formula (z-46).

Examples of the pentavalent aliphatic hydrocarbon group include groups represented by formula (z-47) to formula (z-48).

Examples of the hexavalent aliphatic hydrocarbon group include groups represented by formula (z-49) to formula (z-51).

Examples of compound (I) include compound (I-1) to compound (I-456). In the table, the R ¹ and Z columns represent the numbers of the formulas of the groups exemplified above. For example, compound (I-1) is a compound represented by the following formula (I-1).

In the following tables, (p-1) to (p-13) represent groups represented by the following formulae. * Represents a bond.

  For example, compound (I-350) represents a compound represented by the following formula (I-350).

  The compound of the present invention can be produced by subjecting an azo compound represented by the formula (s1) and a compound represented by the formula (t1) to a condensation reaction in an organic solvent.

[In formula (s1) and formula (t1), R ^{1 to} R ³ , A, Y ¹ , Y ² , Z, m, and n represent the same meaning as described above. ]

  In the condensation reaction, the reaction temperature is preferably 0 ° C to 180 ° C, more preferably 20 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Moreover, it is preferable to use an acid catalyst and / or a condensing agent in terms of shortening the reaction time and improving the yield.

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform, nitro hydrocarbon solvents such as nitrobenzene, ketone solvents such as methyl isobutyl ketone, and 1-methyl-2. Examples include amide solvents such as pyrrolidone and N, N-dimethylacetamide, ether solvents such as tetrahydrofuran and 1,4-dioxane, and nitrile solvents such as acetonitrile.

  Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid. The amount of the acid catalyst to be used is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, per 1 mol of the azo compound represented by the formula (s1).

Examples of the condensing agent include carbodiimides such as 1,3-dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC), and 1,3-diisopropylcarbodiimide (DIC). Is mentioned.
The amount of the condensing agent to be used is preferably 1 to 4 mol, more preferably 1 to 2 mol, per 1 mol of the azo compound represented by the formula (s1).

  In the condensation reaction, it is preferable to add an additive such as 4-dimethylaminopyridine (DMAP), (±) -10-camphorsulfonic acid, 1-hydroxybenzotriazole, N-hydroxysuccinimide. By adding these additives, dehydration condensation can be promoted and side reactions can be suppressed. The amount of the additive to be used is preferably 0.01 to 4 mol, more preferably 0.05 to 0.5 mol, per 1 mol of the azo compound represented by the formula (s1).

Further, azocarboxylic acid ester compounds (for example, diethyl azocarboxylate and diisopropyl azocarboxylate) or azodicarboxamide compounds (for example, N, N, N ′, N′-tetraisopropyl azodicarboxamide, N, N, N ′, N '-Tetramethylazodicarboxamide, 1,1'-(azodicarbonyl) dipiperidine, etc.) and a phosphine compound (eg, triphenylphosphine, tributylphosphine, etc.) or a phosphorylide compound (eg, (cyano (Methylene) trimethylphosphorane, (cyanomethylene) tributylphosphorane, etc.) is added to react the azo compound represented by formula (s1) with the compound represented by formula (t1) by Mitsunobu reaction. May be.
The amount of the condensing agent used in the Mitsunobu reaction is preferably 1 to 4 mol, more preferably 1 to 2 mol, per 1 mol of the azo compound represented by the formula (s1).

In addition, the condensation reaction is performed by condensing the carboxylic acid in the azo compound represented by the formula (s1) with a compound represented by the formula (t1) after converting the carboxylic acid halide to an carboxylic acid halide using an electrophilic halogenating agent. You may react.
Electrophilic halogenating agents include electrophilic chlorinating agents such as thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, and electrophilic bromating agents such as phosphorus tribromide. Is mentioned.
The amount of these electrophilic halogenating agents to be used is preferably 1 to 4 mol, more preferably 1 to 2.5 mol, per 1 mol of the azo compound represented by the formula (s1).

  In the condensation reaction between the carboxylic acid halide and the compound represented by the formula (t1), it is preferable that a basic compound such as pyridine or triethylamine is present in view of shortening the reaction time or improving the yield.

The azo compound represented by the formula (s1) is a diazo coupling of the method described in JP-B-7-88633, a diazonium salt represented by the formula (a2) and a pyridone compound represented by the formula (a3). It can be manufactured by a method or the like.
The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In Formula (a1), Formula (a2) and Formula (a3), R ^{1 to} R ³ and A represent the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]

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

  Producing an azo compound represented by the formula (s1) by diazo coupling a diazonium salt represented by the formula (a2) and a pyridone compound represented by the formula (a3) in an aqueous solvent. Can do. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

In the azo compound represented by the formula (s1), a compound (Ib) in which R ¹ is —L ¹ —X ¹ —R ⁴ and X ¹ is * —O—CO— (* represents L ¹ represents a bond with ¹ ), that is, a compound represented by the formula (Ib) (hereinafter sometimes referred to as “compound (Ib)”) will be described.

[In formula (Ib), R ² , R ³ , R ⁴ , A and L ¹ represent the same meaning as described above. ]

  The azo compound represented by the formula (b4) is produced by diazo coupling the diazonium salt represented by the formula (a2) and the pyridone compound represented by the formula (b3) in the same manner as described above. can do.

[In Formula (b3) and Formula (b4), R ² , R ³ , A and L ¹ represent the same meaning as described above. ]

Next, the azo compound represented by the formula (b4) and R ⁴ —CO—Z ¹ (where R ⁴ represents the same meaning as described above, and Z ¹ represents a chlorine atom or a bromine atom) are combined with an organic solvent. Compound (Ib) can be obtained by reacting in the presence of. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform, nitro hydrocarbon solvents such as nitrobenzene, ketone solvents such as methyl isobutyl ketone, -Amide type solvents such as methyl-2-pyrrolidone.

The amount of R ^{4 -CO-Z 1,} relative to the azo compound to 1 mole of the formula (b4), is 1 mol or more 8 mole or less, preferably 4 mol or less 1 mole or more.

In the azo compound represented by the formula (s1), R ¹ is -L ¹ -X ¹ -R ⁴ and X ¹ is * -CO-O- (* is L ¹ ), that is, a method for producing a compound represented by formula (Ic) (hereinafter sometimes referred to as “compound (Ic)”).

[In formula (Ic), R ² , R ³ , R ⁴ , A and L ¹ represent the same meaning as described above. ]

By reacting the pyridone compound represented by the formula (c3) and R ⁴ —OH (where R ⁴ represents the same meaning as described above) in the presence of an organic solvent, the pyridone compound is represented by the formula (c4). The pyridone compound is obtained. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the organic solvent used here include the same solvents as those used in the reaction of the azo compound represented by the formula (b4) and R ⁴ —CO—Z ¹ .

[In formula (c3) and formula (c4), R ² , R ³ , R ⁴ and L ¹ represent the same meaning as described above. ]

The amount of R 4 ^-OH, relative pyridone 1 mole of the compound represented by the formula (c3), is 1 mol or more 8 mole or less, preferably 4 mol or less 1 mole or more.
In the reaction, it is more preferable to add an acid catalyst (for example, sulfuric acid, hydrochloric acid, etc.) in terms of shortening the reaction time and improving the yield. The amount of the acid catalyst to be used is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, per 1 mol of R ⁴ —OH.

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

The compounds of the present invention are useful as dyes.
The dye of the present invention is a dye containing the compound of the present invention as an active ingredient. The dye of the present invention is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device because of its high solubility in an organic solvent.

  The colored photosensitive resin composition of the present invention comprises a colorant containing the dye of the present invention (hereinafter sometimes referred to as “colorant (A)”), a resin (B), a polymerizable compound (C), a polymerization initiator ( D) and solvent (E).

The colorant (A) may further contain a dye and / or pigment different from the dye of the present invention in addition to the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned.
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, pigments having the following color index (CI) numbers can be mentioned, but the invention is not limited to these.

C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored photosensitive resin composition. Here, solid content means the sum total of the component except a solvent in a coloring photosensitive resin composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
The dye of the present invention, the dye different from the dye of the present invention, and the pigment may be used alone or in combination of two or more.

  The resin (B) is not particularly limited, and any resin may be used. The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
40-150 are preferable and, as for the acid value of resin (B), More preferably, it is 60-135.
Content of resin (B) is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can initiate polymerization by an active radical, an acid, or the like generated from the polymerization initiator (D) by the action of light or heat. For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a polymerizable compound having three or more polymerizable groups. Here, the polymerizable group means a group that undergoes a polymerization reaction with the active radical, acid, or the like. Examples of the polymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Can be mentioned. The polymerizable compound (C) may be used alone or in combination of two or more.
The content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 10 to 60% by mass, based on the solid content of the colored photosensitive resin composition.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. An active radical generator generates an active radical by the action of light or heat. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

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

  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- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the resin (B) and the polymerizable compound (C). is there. When the content of the polymerization initiator is within the above range, the sensitivity is increased and the exposure time is shortened, which is preferable because productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol model Examples include propyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. .

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropion Methyl, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

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

  Content of the solvent (E) in a colored photosensitive resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-90 mass%.

  The colored photosensitive resin composition of the present invention includes, as necessary, surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like. Various additives may be included.

The compounds of the present invention are useful as dyes. Since it is highly soluble in organic solvents, it is particularly useful as a dye for use in color filters of display devices such as liquid crystal display devices.
In addition, the colored photosensitive resin composition of the present invention has various colored images such as a display device (for example, a known liquid crystal display device or an organic EL device) having a color filter as a part of its constituent parts, a solid-state imaging device, or the like. It can be used in a known manner for equipment related to the above.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.

In the following Examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) and high performance liquid chromatograph-mass spectrometry (Agilent HP 1200 LC / MSD type; manufactured by Agilent Technologies). did.
The mixing ratio of each compound contained in the obtained dye was determined by a surface percentage ratio (observation wavelength: 254 nm) of a high performance liquid chromatograph (Prominence LC-20A type; manufactured by Shimadzu Corporation).

The solubility of the obtained dye in an organic solvent was determined as follows.
In a 50 mL sample tube, the compound and the organic solvent were mixed in the following ratio, and then the sample tube was sealed and shaken with an ultrasonic shaker at 30 ° C. for 3 minutes. Then, after standing at room temperature for 30 minutes, the mixture was filtered, and when the residue was visually observed and insoluble matter could not be confirmed, it was judged that the dye was dissolved.
Solubility: 1% 0.01 g of compound, 0.99 g of solvent
0.02 g of 2% compound, 0.98 g of solvent
3% compound 0.03g, solvent 0.97g
20% compound 0.20 g, solvent 0.80 g

Example 1
To 26 parts of 2-amino-5-nitrobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 182 parts of water, 6.3 parts of sodium hydroxide and 182 parts of ethanol were added and stirred to obtain a suspension. Under ice cooling, 29.6 parts of sodium nitrite was added and stirred for 30 minutes. Subsequently, 89.2 parts of 35% hydrochloric acid was added little by little, followed by stirring for 3 hours. An aqueous solution in which 27.7 parts of amidosulfuric acid was dissolved in 277 parts of water was further added and stirred to obtain a suspension containing a diazonium salt.

  Meanwhile, 26 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) Mix and stir at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtrate and dried to obtain 20.4 parts of a compound represented by the formula (d1).

  Under ice cooling, 213 parts of water and 6.3 parts of sodium hydroxide were added to 10.5 parts of the compound represented by the formula (d1) and stirred.

  To a solution obtained by adding 213 parts of water and 6.3 parts of sodium hydroxide to 10.5 parts of the compound represented by the formula (d1), a 30% aqueous sodium hydroxide solution was further added to adjust the pH of the solution to 7. While adjusting to 0.5 to 9, the suspension containing the diazonium salt was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 51.0 parts (yield 92%) of the compound represented by the formula (d2).

To 50 parts of the compound represented by the formula (d2), 450 parts of dehydrated N, N′-dimethylacetamide was added and stirred, and 25.2 parts of succinic acid monoethyl chloride was added dropwise at 60 ° C. Stir for hours. Furthermore, 25.2 parts of succinic acid monoethyl chloride and 420 parts of N, N′-dimethylacetamide were added and stirred at 60 ° C. for 0.5 hour, then heated to 80 ° C. and further stirred for 1.5 hours. A reaction solution was obtained. The reaction solution was cooled to room temperature and poured into 2502 parts of ice water. The precipitate was separated by filtration, washed with repulp with water, and dried at 60 ° C. under reduced pressure to obtain 63.4 parts (yield 95%) of the compound represented by the formula (d4). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d4)>
¹ H-NMR (500 MHz, (δ value (ppm, TMS standard), CDCl ₃ ): 1.10 (3H, t), 2.49 (2H, t), 2.49 (2H, t), 2.56 (3H, s), 3.96 (2H, q), 4.10 (2H, t), 4.23 (2H, t), 8.16 (1H, d), 8.46 (1H, dd), 8.70 (1H, d), 14.50 (1H, bs), 15.56 ( 1H, s)

  To 4.0 parts of the compound represented by the formula (d4), 48 parts of dehydrated chloroform, 0.19 part of 4-dimethylaminopyridine, 0.23 part of (±) -10-camphorsulfonic acid, 4.66 triethylene glycol. Part was added and stirred at 60 ° C. for 0.5 hour. A solution prepared by dissolving 2.16 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 32 parts of dehydrated chloroform was added dropwise thereto and stirred at 60 ° C. for 2 hours to obtain a reaction solution. The reaction solution was cooled to room temperature, and then separated and washed twice with 80 parts of a 2N aqueous hydrochloric acid solution, and further separated and washed twice with 80 parts of water. The washed reaction solution was dehydrated with sodium sulfate. Subsequently, chloroform was distilled off under reduced pressure, 20 parts of methanol was added, and the precipitate was separated by filtration. The obtained residue was washed with methanol and dried at 60 ° C. under reduced pressure to obtain a mixture of Compound (I-2) and Compound (I-172) (mixing ratio 85: 3) (Dye 1) 3.7. Got a part.

<Identification of Compound (I-2)>
Mass spectrometry: ionization mode = ESI +: m / z = 648.2 [M + H] ⁺
Exact Mass: 647.2
<Identification of Compound (I-172)>
Mass spectrometry: ionization mode = ESI +: m / z = 1145.3 [M + H] ⁺
Exact Mass: 1144.3

0.35 g of the obtained dye 1 was dissolved in dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), and UV-visible spectroscopy The absorption spectrum was measured using a photometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 431 nm, and the molar extinction coefficient was as high as 54000.

  About the obtained dye 1, the solubility to the organic solvent was evaluated. Insoluble matters were not observed in any of 2% ethyl lactate solution, 1% propylene glycol monomethyl ether acetate solution and 20% N, N-dimethylformamide solution.

(Example 2)
To 4.0 parts of the compound represented by the formula (d4), 48 parts of dehydrated chloroform, 0.19 part of 4-dimethylaminopyridine, 0.23 part of (±) -10-camphorsulfonic acid, 0.58 of triethylene glycol Part was added and stirred at 60 ° C. for 0.5 hour. A solution prepared by dissolving 2.16 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 32 parts of dehydrated chloroform was added dropwise thereto and stirred at 60 ° C. for 4 hours. Furthermore, 1.16 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred at 60 ° C. for 3 hours to obtain a reaction solution. The reaction solution was cooled to room temperature, and then separated and washed twice with 80 parts of a 2N aqueous hydrochloric acid solution, and further separated and washed twice with 80 parts of water. The washed reaction solution was dehydrated with sodium sulfate. Subsequently, chloroform was distilled off under reduced pressure, 20 parts of methanol was added, and the precipitate was separated by filtration. The obtained residue was washed with methanol and dried at 60 ° C. under reduced pressure to obtain a mixture (mixing ratio 20:35) of compound (I-2) and compound (I-172) (dye 2) 3.2. Got a part.

<Identification of Compound (I-2)>
Mass spectrometry: ionization mode = ESI +: m / z = 648.2 [M + H] ⁺
Exact Mass: 647.2
<Identification of Compound (I-172)>
Mass spectrometry: ionization mode = ESI +: m / z = 1145.3 [M + H] ⁺
Exact Mass: 1144.3

0.35 g of the obtained dye 2 was dissolved in dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), and UV-visible spectroscopy The absorption spectrum was measured using a photometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 434 nm, and had a molar extinction coefficient as high as 51000.

  About the obtained dye 2, the solubility to the organic solvent was evaluated. Insoluble matter was not observed in either the 2% ethyl lactate solution or the 20% N, N-dimethylformamide solution.

(Example 3)
To 10.0 parts of the compound represented by the formula (d4), 120 parts of dehydrated chloroform, 0.47 parts of 4-dimethylaminopyridine, 0.59 parts of (±) -10-camphorsulfonic acid, and 4.66 parts of ethylenediamine are added. In addition, the mixture was stirred at 60 ° C for 0.5 hour. A solution prepared by dissolving 5.39 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 80 parts of dehydrated chloroform was added dropwise thereto and stirred at 60 ° C. for 2 hours to obtain a reaction solution. After the reaction solution was cooled to room temperature, the precipitate was filtered off to obtain a residue and a filtrate. The residue was repulped with 100 parts of 2N aqueous hydrochloric acid and then repulped with 100 parts of water. The filtrate was separated and washed twice with 200 parts of a 2N aqueous hydrochloric acid solution, further separated and washed twice with 200 parts of water, and dehydrated with sodium sulfate. Subsequently, chloroform was depressurizingly distilled and the solid substance was obtained. 50 parts of methanol was added to the combined solid and the residue after washing, and the precipitate was separated by filtration. The obtained residue was washed with methanol and dried at 60 ° C. under reduced pressure to obtain a mixture of Compound (I-18) and Compound (I-185) (mixing ratio 32:31) (Dye 3) 5.5. Got a part.

<Identification of Compound (I-18)>
Mass spectrometry: ionization mode = ESI +: m / z = 558.2 [M + H] ⁺
Exact Mass: 557.2
<Identification of Compound (I-185)>
Mass spectrometry: ionization mode = ESI +: m / z = 1055.3 [M + H] ⁺
Exact Mass: 1054.3

0.35 g of the obtained dye 3 was dissolved in dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), and UV-visible spectroscopy The absorption spectrum was measured using a photometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 440 nm and a high molar extinction coefficient of 48000.

  About the obtained dye 2, the solubility to the organic solvent was evaluated. Insoluble matter was not observed in the 3% N, N-dimethylformamide solution.

Example 4
To 4.0 parts of the compound represented by the formula (d4), 80 parts of dehydrated chloroform, 0.09 part of 4-dimethylaminopyridine, 0.23 part of (±) -10-camphorsulfonic acid, 6.03 of tetraethylene glycol Part was added and stirred at room temperature for 0.5 hour. Here, 1.96 parts of N, N′-diisopropylcarbodiimide was added dropwise and stirred at room temperature for 2.5 hours to obtain a reaction solution. To the residue obtained by distilling chloroform from the reaction solution under reduced pressure, 40 parts of methanol was added and filtered to obtain a residue. The residue was repulped twice with 40 parts of methanol, once with a mixed solution of 40 parts of methanol and 40 parts of water and once with 40 parts of methanol, and then dried at 60 ° C. under reduced pressure to give compound (I- 4) and a compound (I-173) (mixing ratio 39:25) (dye 4) 0.85 part was obtained.

<Identification of Compound (I-4)>
Mass spectrometry: ionization mode = ESI +: m / z = 692.2 [M + H] ⁺
Exact Mass: 691.2
<Identification of Compound (I-173)>
Mass spectrometry: ionization mode = ESI +: m / z = 1189.4 [M + H] ⁺
Exact Mass: 1188.4

(Example 5)
To 5.0 parts of the compound represented by the formula (d4), 100 parts of dehydrated chloroform, 0.12 part of 4-dimethylaminopyridine, 0.29 part of (±) -10-camphorsulfonic acid, pentaerythritol tetrakis (mercaptoacetate). (Tart) 2.10 parts was added and stirred at 30 ° C. for 0.5 hour. To this, 1.96 parts of N, N′-diisopropylcarbodiimide was added dropwise and stirred at 30 ° C. for 4 hours to obtain a reaction solution. Chloroform reduced pressure from the reaction solution? 100 parts of methanol was added to the distilled product and filtered to obtain a residue. The residue was repulped twice with 50 parts of methanol, once with a mixed solution of 50 parts of methanol and 50 parts of water and once with 50 parts of methanol, and then dried at 60 ° C. under reduced pressure to give compound (I- 405), a compound (I-406) and a compound (I-407) (mixing ratio 2: 3: 4) (dye 5) 5.35 parts.

<Identification of Compound (I-405)>
Mass spectrometry: ionization mode = ESI +: m / z = 930.1 [M + H] ⁺
Exact Mass: 929.1
<Identification of Compound (I-406)>
Mass spectrometry: ionization mode = ESI +: m / z = 14.27.2 [M + H] ⁺
Exact Mass: 1426.2
<Identification of Compound (I-407)>
Mass spectrometry: ionization mode = ESI +: m / z = 1924.4 [M + H] ⁺
Exact Mass: 1923.4

Comparative Example 1
Example 1 Example 1 except that 2-aminoterephthalic acid is used instead of 5-nitroanthranilic acid, and the compound represented by formula (e1) is used instead of the compound represented by formula (d1). In the same manner as described above, a compound represented by the formula (i) was obtained.

0.35 g of the compound represented by the formula (i) thus obtained was dissolved in dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g). / L), an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound had a λmax = 440 nm and a molar extinction coefficient of only 42000.

  About the compound represented by the obtained formula (i), the solubility to an organic solvent was evaluated. Insoluble matters were observed in 1% ethyl lactate solution, 1% propylene glycol monomethyl ether acetate solution, and 3% N, N-dimethylformamide solution.

Example 6
[Preparation of colored photosensitive resin composition]
(A) Colorant: 20 parts of dye 1 (B-1) Resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, acid value 70 mg KOH / g) 70 parts (C-1 ) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) Photopolymerization initiator: benzyl dimethyl ketal (Irgacure 651; manufactured by BASF Japan) 15 parts (E-1) Solvent: 680 parts of N, N-dimethylformamide is mixed to obtain a colored photosensitive resin composition.

Examples 7-10
A colored photosensitive resin composition is obtained in the same manner as in Example 6 except that the dye 1 is replaced with the dyes 2 to 5, respectively.

[Production of color filters]
On the glass, the colored photosensitive resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and heating in an oven yields a color filter.

  From the above results, it can be seen that the compounds of Examples exhibit high solubility in organic solvents. The colored photosensitive resin composition containing the compound generates little foreign matter and can produce a high-quality color filter.

  The compound of the present invention is excellent in solubility in an organic solvent, and is excellent as a dye used for a color filter of a display device such as a liquid crystal display device.

Claims (5)

A compound represented by formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group contained in the hydrocarbon group includes —O—, —CO—, — It may be replaced by NR ^6- , -SO ₂ -or -S-.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
A represents a phenylene group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
Y ¹ and Y ² represent —O—, —NR ⁶ — or —S—.
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z represents a (m + n) valent aliphatic hydrocarbon group having 1 to 24 carbon atoms, a methylene group contained in the aliphatic hydrocarbon group, -O -, - CO -, - NR 7 -, - SO ₂ - or -S- in may be replaced, methine group contained in the aliphatic hydrocarbon group may be replaced by a nitrogen atom, a hydrogen atom contained in the aliphatic hydrocarbon group is -SO ₃ M may be replaced.
R ⁷ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
m represents an integer of 0 to 5. When m is an integer greater than or equal to ² , several Y2 may mutually be same or different.
n represents an integer of 1 to 6. If n is an integer of 2 or more, plural ^{R 1, R 2, R 3} , A and ^{Y 1} may being the same or different.
However, m + n represents an integer of 2-6. ] A A compound according to claim 1, wherein the phenylene group having at least one selected from the group consisting of nitro and -SO 3 _M.   The compound according to claim 1 or 2, wherein the phenylene group is an o-phenylene group.   The dye which uses the compound in any one of Claims 1-3 as an active ingredient.   The dye which contains 2 or more types of compounds in any one of Claims 1-3.