JP5724598B2 - Compound - Google Patents

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 excellent in light resistance and heat 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.

［式（Ｉ）中、Ｒ^１は、水素原子又は置換基を有していてもよい炭素数１〜３０の１価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
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のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^４〜Ｒ^８は、互いに独立に、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数２〜８のアルコキシアルキル基、ヒドロキシ基、シアノ基、ニトロ基、ハロゲン原子又は式（Ｉａ）で表される基を表し、Ｒ^４〜Ｒ^８のうち少なくとも１つは式（Ｉａ）で表される基を表す。］

［式（Ｉａ）中、Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。］ The present invention includes the inventions described in [1] to [7] below.
[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 which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is , -O- or -CO-.
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, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, 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 a nitro group. , A halogen atom or a group represented by formula (Ia), and at least one of R ^{4 to} R ⁸ represents a group represented by formula (Ia). ]

[In Formula (Ia), L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. ]

[2] The compound according to [1], wherein R ⁸ is a group represented by formula (Ia).
[3] The compound according to [1] or [2], wherein R ¹ is a group represented by -L ² -X ¹ -R ⁹ .
[Wherein L ² represents an alkanediyl group having 1 to 8 carbon atoms. X ¹ represents —CO—O—. R ⁹ represents 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. ]
[4] ^{R 1 is} a group represented by ^{-L 2 -X 1 -L 3 -X 2} -R 10 [1] A compound according any one of to [3].
[Wherein, L ² and L ³ each independently represent an alkanediyl group having 1 to 8 carbon atoms. X ¹ and X ² represent —CO—O—. R ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group. ]
[5] The compound according to [3] or [4], wherein X ¹ is * —O—CO—.
[In the formula, * represents a bond with L ² . ]
[6] The compound according to any one of [1] to [5], wherein at least one of R ^{4 to} R ⁸ is a nitro group.
[7] A dye comprising the compound according to any one of [1] to [6] as an active ingredient.

  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 which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is , -O- or -CO-.
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, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, 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 a nitro group. , A halogen atom or a group represented by formula (Ia), and at least one of R ^{4 to} R ⁸ represents a group represented by formula (Ia). ]

[In Formula (Ia), L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. ]

Examples of the monovalent hydrocarbon group represented by 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, for example, a hydroxy group, a carboxy group, a sulfanyl group, an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Of the alkoxy group.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the 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 alicyclic hydrocarbon group having a substituent include 4-methylcyclohexyl group, 4-hydroxymethylcyclohexyl group, 4-aminocyclohexyl group, 4- (N, N′-dimethylamino) cyclohexyl group, and 2-aminocyclohexyl group. Group, 2- (N, N′-dimethylamino) cyclohexyl group, 4-carboxycyclohexyl group, 4-methoxycyclohexyl group, 2-carboxycyclohexyl group and the like.
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.
The monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably has 2 to 16 carbon atoms.

R ¹ is preferably a group represented by -L ² -X ¹ -R ⁹ , more preferably a group represented by -L ² -X ¹ -L ³ -X ² -R ¹⁰ . When R ¹ is these groups, the solubility of the compound of the present invention in an organic solvent tends to be improved.
L ² and L ³ are each independently an alkanediyl group having 1 to 8 carbon atoms, such as methylene group, ethylene group, propane-1,3-diyl group, 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.
L ² is preferably an alkanediyl group having 1 to 5 carbon atoms, and more preferably an alkanediyl group having 2 to 4 carbon atoms.
L ³ is preferably an alkanediyl group having 1 to 4 carbon atoms, and more preferably an alkanediyl group having 1 to 2 carbon atoms.

X ¹ and X ² are —CO—O—. X ¹ is preferably * —O—CO— (* represents a bond to L ² ). When X ¹ is * —O—CO—, the compound of the present invention can be easily produced.
R ⁹ 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. As the aliphatic hydrocarbon group represented by R ⁹ , among the groups listed as the monovalent aliphatic hydrocarbon group represented by R ¹ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably Examples thereof include an alkyl group having 1 to 10 carbon atoms.
R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group.

Examples of the group represented by -L ² -X ¹ -R ⁹ include groups represented by formulas (f-1) to (f-25) (in each formula, ● represents a bond to a nitrogen atom). Represents a hand). Among ^them, preferred are ^{-L 2 -X 1 -L 3 -X 2} -R 10, for example, include groups represented by the formula (f-1) ~ formula (f-20), more preferably formula (f -1), formula (f-2), formula (f-5), formula (f-6), formula (f-9), formula (f-10), formula (f-13), formula (f- 14), groups represented by formula (f-17) or formula (f-18), and more preferably, formula (f-2), formula (f-6), formula (f-10), And groups represented by formula (f-14) or formula (f-18).

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 represented by 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. A hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. As a C1-C4 alkyl group by which the hydrogen atom is substituted by the halogen atom, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.
R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

R ^{4 to} R ⁸ are each independently a hydrogen atom, 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 a nitro group. , A halogen atom or a group represented by formula (Ia), and at least one of R ^{4 to} R ⁸ is a group represented by formula (Ia). When compound (I) has a group represented by formula (Ia), the solubility of compound (I) in an organic solvent tends to increase. Among these, R ⁸ is preferably a group represented by the formula (Ia).
Compound (I) preferably has, as R ^{4 to} R ⁸ , a hydrogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a bromine atom in addition to the group represented by formula (Ia). .

Ｌ^１は、炭素数１〜８のアルカンジイル基である。該アルカンジイル基としては、Ｌ^２及びＬ^３で表される炭素数１〜８のアルカンジイル基として挙げたものと同じ基が挙げられる。炭素数１〜４のアルカンジイル基が好ましく、メチレン基であることがより好ましい。

L ¹ is an alkanediyl group having 1 to 8 carbon atoms. Examples of the alkanediyl group include the same groups as those exemplified as the alkanediyl group having 1 to 8 carbon atoms represented by L ² and L ³ . An alkanediyl group having 1 to 4 carbon atoms is preferable, and a methylene group is more preferable.

Moreover, it is preferable that at least one of R ^{4 to} R ⁸ is a nitro group. When the compound (I) has a nitro group, the spectral density tends to increase. Of R ^{4 to} R ^8, the number of nitro groups is preferably 1 to 2, more preferably 1. Among them, it is preferable that R ⁵ or R ⁶ is a nitro group, further more preferably R ⁶ is a nitro group. If the nitro group is in these positions, the spectral density tends to be higher.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. A linear alkyl 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, 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-dimethylpentyl 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 Til-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- Examples thereof include branched alkyl groups such as methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, 1,1-diethylbutyl group, and 1,2-diethylbutyl group.

  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.

Examples of compound (I) include compounds (I-1) to (I-126) shown in Tables 1 to 4. In Tables 1 to 4, the R ¹ column indicates the number of the group formula exemplified above.

Among them, compound (I-1) to compound (I-22), compound (I-45), compound (I-46), compound (I-65), compound (I-66), compound (I-85) , Compound (I-86) and Compound (I-105) to Compound (I-126) are preferable, Compound (I-45), Compound (I-46), Compound (I-65), Compound (I-66) ), Compound (I-85), compound (I-21), compound (I-125) and compound (I-86) are more preferred.
If compound (I) is these compounds, it exists in the tendency for the solubility to an organic solvent to be higher.

The method for producing the compound of the present invention will be described.
In the compound (I), for example, when R ⁸ is a group represented by the formula (Ia), a carboxy group contained in the azo compound represented by the formula (a4) and a compound represented by the formula (a5) A compound represented by the formula (Iaa) (hereinafter sometimes referred to as “compound (Iaa)”) can be obtained by reacting (esterifying) with the hydroxy group it has. Even when any of R ^{4 to} R ⁷ is a group represented by the formula (Ia), it can be produced in the same manner as the method for producing the compound (Iaa).

[In Formula (a4) and Formula (a5), R ^{1 to} R ⁷ and L ¹ each have the same meaning as described above. ]

[In formula (Iaa), R ^{1 to} R ⁷ and L ¹ each have the same meaning as described above. ]

The azo compound represented by the formula (a4) is obtained by diazo cupping a diazonium salt represented by the formula (a2) and a pyridone compound represented by the formula (a3) according to the method described in JP-B-7-88633. It can be manufactured by ringing.
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.
The pyridone compound represented by the formula (a3) is obtained, for example, by reacting an amine represented by the formula (a4) with a compound represented by the formula (a5) and a compound represented by the formula (a6). be able to.

[In Formula (a1), Formula (a2), Formula (a3), Formula (a4), Formula (a5), and Formula (a6), R ^{1 to} R ⁷ each have 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 formula (a4) by diazo coupling a diazonium salt represented by formula (a2) and a pyridone compound represented by 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 water and N-methylpyrrolidone, and water is preferred.

Subsequently, a compound (Iaa) can be obtained by esterifying the azo compound represented by the formula (a4) and the compound represented by the formula (a5) in the presence of an organic solvent.
In the esterification reaction, a condensing agent (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and dicyclohexylcarbodiimide etc.) and / or an additive (N, N-dimethyl-4-aminopyridine, triethylamine, (±) -10-camphorsulfonic acid or the like) is preferably used. 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, and more preferably 1 hour to 5 hours.

0.5-10 mol is preferable with respect to 1 mol of azo compounds represented by Formula (a4), and, as for the usage-amount of the compound represented by Formula (a5), More preferably, it is 1-5 mol.
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; N-methyl An amide solvent such as pyrrolidone;

In the compounds of the present invention, Compound (I) wherein R ¹ is a group represented by -L ² -X ¹ -R ⁹ and X ¹ is * -O-CO- (* represents L ² ), That is, a compound represented by formula (Ib) (hereinafter sometimes referred to as “compound (Ib)”) will be described.

[In formula (Ib), R ^{2 to} R ⁷ , R ⁹ , L ¹ and L ² each 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) by the same method as described above. can do.

[In formula (b3) and formula (b4), R ^{2 to} R ⁷ and L ² each represent the same meaning as described above. ]

  Next, an azo compound represented by the formula (b6) is obtained by reacting the azo compound represented by the formula (b4) with the compound represented by the formula (b5) in the presence of an organic solvent. it can. 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.

[In formula (b5) and formula (b6), R ^{2 to} R ⁷ , R ⁹ and L ² each represent the same meaning as described above. Z ¹ represents a chlorine atom or a bromine atom. ]
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; N-methyl An amide solvent such as pyrrolidone;

  The amount of the compound represented by the formula (b5) to be used is 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less, with respect to 1 mol of the azo compound represented by the formula (b4).

  Next, the compound (Ib) can be obtained by esterifying the azo compound represented by the formula (b6) and the compound represented by the formula (a5) by the same method as described above.

In the compound of the present invention, R ¹ is a group represented by -L ² -X ¹ -R ⁹ and X ¹ is * -CO-O- (* is L ² The method for producing the compound represented by the formula (Ic) (hereinafter sometimes referred to as “compound (Ic)”) will be described.

[In formula (Ic), R ^{2 to} R ⁷ , R ⁹ , L ¹ and L ² each represent the same meaning as described above. ]

The azo compound represented by the formula (c4) is produced by diazo coupling the diazonium salt represented by the formula (a2) and the pyridone compound represented by the formula (c3) by the same method as described above. can do.

[In formula (c3) and formula (c4), R ^{2 to} R ⁷ and L ² each represent the same meaning as described above. ]

Subsequently, the azo compound represented by the formula (c6) is obtained by reacting the azo compound represented by the formula (c4) and the compound represented by the formula (c5) in the presence of an organic solvent. it can. 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 the compound represented by the formula (b5).

[In Formula (c5) and Formula (c6), R ^{2 to} R ⁷ , R ⁹ and L ² each represent the same meaning as described above. ]
The amount of the compound represented by the formula (c5) to be used is 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less, with respect to 1 mol of the azo compound represented by the formula (c4).

In order to smoothly advance the reaction between the azo compound represented by the formula (c4) and the compound represented by the formula (c5), it is more preferable to add an acidic catalyst. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01-4 mol with respect to 1 mol of compounds represented by Formula (c5), More preferably, it is 0.8-2 mol.

  Next, the compound (Ic) can be obtained by esterifying the azo compound represented by the formula (c6) and the compound represented by the formula (a3) by the same method as described above.

  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, 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 dye of the present invention contains compound (I). The dye of the present invention may be a dye composed only of the compound (I) or may contain a dye described later other than the compound (I). The dye of the present invention contains compound (I) in a proportion of preferably 70 to 100% by weight.

  Since compound (I) is excellent in solubility in an organic solvent, it is useful as a colorant for a colored photosensitive resin composition. Such a colored photosensitive resin composition includes a colorant containing the compound of the present invention (hereinafter sometimes referred to as “colorant (A)”), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator ( D) and solvent (E).

The colorant (A) may further contain a dye and / or pigment different from the compound (I) in addition to the compound (I).
As dyes other than Compound (I), Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, Reactive, Direct ( Examples thereof include compounds classified as Direct, Disperse, and 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 and 47 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 compound (I) in the colorant (A) is preferably 3 to 100% by mass.
Compound (I) and dyes and pigments different from compound (I) 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.
The acid value of the resin (B) is preferably 50 to 150, and more preferably 60 to 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 photopolymerizable compound having 3 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 photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The polymerizable compound (C) may be used alone or in combination of two or more. The molecular weight of the polymerizable compound (C) is usually 150 to 800, preferably 190 to 700.
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 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenone compounds such as benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone compounds such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone;
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-methyl) Furan-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-dimethoxypheny ) Ethenyl] -1,3,5-triazine compounds such as triazine;
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.

Examples of the acid generator include triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexa Examples thereof include onium salts such as fluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.
The photopolymerization initiator (D) may be used alone or in combination of two or more.

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

  Examples of the solvent (E) include ether, ketone, alcohol, ester, amide and the like.

  Examples of the ether 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 mono Ropirueteru, 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 and the like.

Examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, And cyclohexanone.
Examples of the alcohol include hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the ester include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, 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, ethyl 3-ethoxypropionate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- - methylpropionic acid ethyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, .gamma.-butyrolactone.

Examples of the amide 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.
Moreover, the above-mentioned colored photosensitive resin composition relates to various colored images such as a display device (for example, a liquid crystal display device, an organic EL device, etc.), a solid-state image sensor, etc., which includes a color filter as a part of its constituent parts. The device can be used in a known manner.

Next, the present invention will be described more specifically with reference to examples.
In Examples, Reference Examples and Comparative Examples, “%” and “part” representing the content or amount used 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.).

Example 1
After 80 parts of water was added to 18.2 parts of 5-nitroanthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Meanwhile, 26.0 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 ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 24.4 The parts were mixed and stirred 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 suction filtration residue and dried to obtain 20.4 parts of a compound represented by the formula (d1).

  Subsequently, 20.4 parts of the compound represented by the formula (d1) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 38.7 parts of a compound represented by the formula (d2).

25.7 parts of the compound represented by the formula (d3) were added to 30.1 parts of the compound represented by the formula (d2), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 37.0 parts of a compound represented by the formula (d4). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d4)>
¹ H-NMR: 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 30.2 parts of the compound represented by the formula (d4), 1.89 parts of (±) -10-camphorsulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.2 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. To this suspension, a solution prepared by dissolving 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. After the solvent of the filtrate was distilled off with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 29.0 parts of a compound represented by the formula (I-45). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-45)>
¹ H-NMR: 1.10 (3H, t), 2.49 (2H, t), 2.49 (2H, t), 2.56 (3H, s), 2.83 (2H, m), 3.45 (1H, m), 3.97 (2H , q), 4.11 (2H, t), 4.23 (2H, t), 4.45 (2H, m), 8.21 (1H, d), 8.51 (1H, dd), 8.74 (1H, d), 15.03 (1H) .

0.10 g of the compound represented by the formula (I-45) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 435 nm and a high molar extinction coefficient of 48000.

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.

[Evaluation of solubility]
Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), propylene glycol monomethyl ether (hereinafter abbreviated as PGM), ethyl lactate (hereinafter abbreviated as EL), N- of the compounds obtained in Example 1 and Comparative Example 1. The solubility in methylpyrrolidone (hereinafter abbreviated as NMP) was determined as follows.
In a 50 mL sample tube, the compound and the solvent were mixed at the following ratio, and then the sample tube was sealed and shaken at 30 ° C. for 3 minutes with an ultrasonic shaker. Then, after standing at room temperature for 30 minutes, the mixture was filtered, and the residue was visually observed. When insoluble matter could not be confirmed as a residue, it was judged that the solubility was good and marked in Table 5, and when insoluble matter could be confirmed, the solubility was judged to be poor and shown in Table 5. X was marked. The results are shown in Table 5.
0.5% Compound 0.01g, Solvent 2g
1% compound 0.01g, solvent 1g
3% 0.03 g of compound, 1 g of solvent

Reference example 1
[Preparation of colored photosensitive resin composition]
(I-45) Colorant: Compound synthesized in Example 1 20 parts (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 (registered trademark) 651; BASF Japan Ltd.) Manufactured) 15 parts (E-1) Solvent: 680 parts of N, N-dimethylformamide are mixed to obtain a colored photosensitive resin composition.

[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.

Example 2
After adding 80 parts of water to 18.0 parts of 4-nitroanthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.8 parts of 35% aqueous sodium nitrite solution was added, and then 26.1 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt. Next, 20.3 parts of the compound represented by the formula (d1) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 38.4 parts of a compound represented by the formula (d5).

<Identification of compound represented by formula (d5)>
¹ H-NMR: 2.38 (3H, s), 3.53 (2H, dd), 3.89 (2H, t), 5.23 (1H, bs), 7.83 (1H, dd), 8.04 (1H, d), 8.11 (1H , d), 16.56 (1H, s).

To 30.0 parts of the compound represented by the formula (d5), 25.6 parts of the compound represented by the formula (d3) was added, followed by stirring at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the mixture was charged in water to obtain 36.9 parts of a compound represented by the formula (d6). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d6)>
¹ H-NMR: 1.11 (3H, t), 2.48 (2H, t), 2.48 (2H, t), 2.55 (3H, s), 3.95 (2H, q), 4.09 (2H, t), 4.22 (2H , t), 7.83 (1H, dd), 8.04 (1H, d), 8.11 (1H, d), 14.52 (1H, bs), 15.54 (1H, s).

To 30.1 parts of the compound represented by the formula (d6), 1.89 parts of (±) -10-camphorsulfonic acid, 3.20 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.3 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. To this suspension, a solution prepared by dissolving 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 29.1 parts of a compound represented by the formula (I-46). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-46)>
¹ H-NMR: 1.10 (3H, t), 2.49 (2H, t), 2.49 (2H, t), 2.56 (3H, s), 2.83 (2H, m), 3.45 (1H, m), 3.97 (2H , q), 4.11 (2H, t), 4.23 (2H, t), 4.45 (2H, m), 7.83 (1H, dd), 8.04 (1H, d), 8.11 (1H, d), 15.10 (1H) .

0.10 g of the compound represented by the formula (I-46) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 425 nm, and the molar extinction coefficient was as high as 48000.

Example 3
25.4 parts of the compound represented by the formula (d7) was added to 30.2 parts of the compound represented by the formula (d5), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 37.3 parts of a compound represented by the formula (d8). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d8)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (2H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 14.50 (1H), 15.03 (1H).

To 30.0 parts of the compound represented by the formula (d8), 1.89 parts of (±) -10-camphorsulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.4 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. To this suspension, a solution prepared by dissolving 17.0 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 28.4 parts of a compound represented by the formula (I-86). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-86)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 2.83 (2H), 3.45 (1H), 4.11 (2H), 4.23 (2H), 4.45 (2H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 15.03 (1H).

0.10 g of the compound represented by the formula (I-86) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 425 nm, and the molar extinction coefficient was as high as 48000.

Example 4
To 30.0 parts of the compound represented by the formula (d2), 25.2 parts of the compound represented by the formula (d7) was added, followed by stirring at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 36.9 parts of a compound represented by the formula (d9). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d9)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (2H), 8.22 (1H), 8.50 (1H), 8.75 (1H), 14.50 (1H), 15.03 (1H).

To 30.1 parts of the compound represented by the formula (d9), 1.89 parts of (±) -10-camphorsulfonic acid, 3.27 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.5 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. A solution prepared by dissolving 17.1 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise to this suspension while keeping the temperature at 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator and then dried under reduced pressure at 60 ° C. to obtain 28.4 parts of a compound represented by the formula (I-85). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (I-85)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 2.83 (2H), 3.45 (1H), 4.11 (2H), 4.23 (2H), 4.45 (2H), 8.20 (1H), 8.53 (1H), 8.76 (1H), 15.05 (1H).

0.10 g of the compound represented by the formula (I-85) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 435 nm and a high molar extinction coefficient of 48000.

Example 5
After 80 parts of water was added to 18.2 parts of 5-nitroanthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  On the other hand, 26.0 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 30.0 The parts were mixed and stirred 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 filter and dried to obtain 21.9 parts of a compound represented by the formula (d10).

<Identification of compound represented by formula (d10)>
¹ H-NMR: 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)

  Subsequently, 21.9 parts of the compound represented by the formula (d10) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 42.3 parts of a compound represented by the formula (d11).

<Identification of compound represented by formula (d11)>
¹ H-NMR: 1.12 (3H), 2.38 (3H), 3.53 (2H), 3.89 (1H), 5.23 (1H), 8.21 (1H), 8.52 (1H), 8.75 (1H), 15.44 (1H).

25.7 parts of the compound represented by the formula (d3) was added to 32.9 parts of the compound represented by the formula (d11), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 38.0 parts of a compound represented by the formula (d12). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d12)>
¹ H-NMR: 1.10 (3H), 1.12 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 3.96 (2H), 4.10 (2H), 4.23 (1H), 8.16 (1H), 8.46 (1H), 8.70 (1H), 14.50 (1H), 15.56 (1H).

To 31.0 parts of the compound represented by the formula (d12), 1.89 parts of (±) -10-camphorsulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.2 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. To this suspension, a solution prepared by dissolving 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator, and then dried under reduced pressure at 60 ° C. to obtain 29.7 parts of a compound represented by the formula (I-65). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-65)>
¹ H-NMR: 1.10 (3H), 1.12 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 2.83 (2H), 3.45 (1H), 3.97 (2H), 4.11 (2H), 4.23 (1H), 4.45 (2H), 8.21 (1H), 8.51 (1H), 8.74 (1H), 15.50 (1H).

0.10 g of the compound represented by the formula (I-65) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (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 a high molar extinction coefficient of 48000.

Example 6
After adding 80 parts of water to 18.3 parts of 4-nitroanthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Subsequently, 21.9 parts of the compound represented by the formula (d10) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 42.5 parts of a compound represented by the formula (d13).

<Identification of compound represented by formula (d13)>
¹ H-NMR: 1.12 (3H), 2.38 (3H), 3.53 (2H), 3.89 (1H), 5.23 (1H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 15.95 (1H).

25.7 parts of the compound represented by the formula (d3) were added to 32.9 parts of the compound represented by the formula (d13), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 36.9 parts of a compound represented by the formula (d14). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d14)>
¹ H-NMR: 1.10 (3H), 1.12 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 3.96 (2H), 4.10 (2H), 4.23 (1H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 14.50 (1H), 15.56 (1H).

To 30.9 parts of the compound represented by the formula (d14), 1.89 parts of (±) -10-camphorsulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.2 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. To this suspension, a solution prepared by dissolving 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated with a rotary evaporator and then dried under reduced pressure at 60 ° C. to obtain 28.7 parts of a compound represented by the formula (I-66). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-66)>
¹ H-NMR: 1.10 (3H), 1.12 (3H), 2.49 (2H), 2.49 (2H), 2.56 (3H), 2.83 (2H), 3.45 (1H), 3.97 (2H), 4.11 (2H), 4.23 (1H), 4.45 (2H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 15.80 (1H).

0.10 g of the compound represented by the formula (I-66) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 424 nm and a high molar extinction coefficient of 48000.

Example 7
27.0 parts of the compound represented by the formula (d7) were added to 30.5 parts of the compound represented by the formula (d13), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 37.2 parts of a compound represented by the formula (d15). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d15)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.14 (3H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (1H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 14.48 (1H), 15.01 (1H).

To 30.8 parts of the compound represented by the formula (d15), 1.89 parts of (±) -10-camphorsulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.4 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. A solution prepared by dissolving 17 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise to this suspension while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. After the solvent was distilled off from the filtrate with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 28.3 parts of a compound represented by the formula (I-125). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (I-125)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.15 (3H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 2.83 (2H), 3.45 (1H), 4.11 (2H), 4.23 (1H), 4.45 (2H), 7.83 (1H), 8.04 (1H), 8.11 (1H), 15.03 (1H).

0.10 g of the compound represented by the formula (I-125) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound had a bright yellow color at λmax = 425 nm, and the molar extinction coefficient was as high as 48000.

Example 8
26.8 parts of the compound represented by the formula (d7) were added to 30.6 parts of the compound represented by the formula (d11), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 37.1 parts of a compound represented by the formula (d16). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (d16)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.14 (3H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 4.11 (2H), 4.23 (1H), 8.21 (1H), 8.51 (1H), 8.74 (1H), 14.48 (1H), 15.01 (1H).

To 30.6 parts of the compound represented by the formula (d16), 1.89 parts of (±) -10-camphorsulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 2,3-epoxy- 15.4 parts of 1-propanol and 450 parts of chloroform were added and stirred at 5 ° C. A solution prepared by dissolving 17 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was added dropwise to this suspension while maintaining a temperature of 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was taken out using a separatory funnel, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator and then dried under reduced pressure at 60 ° C. to obtain 28.6 parts of a compound represented by the formula (I-21). ^The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (I-21)>
¹ H-NMR: 0.75 (3H), 0.77 (3H), 1.08 (2H), 1.15 (3H), 1.18 (2H), 1.37 (2H), 1.42 (2H), 2.16 (1H), 2.55 (3H), 2.83 (2H), 3.45 (1H), 4.11 (2H), 4.23 (1H), 4.45 (2H), 8.23 (1H), 8.55 (1H), 8.78 (1H), 15.24 (1H).

0.10 g of the compound represented by the formula (I-21) 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 Absorption spectrum was measured using a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound exhibited a bright yellow color at λmax = 433 nm, and showed a high molar extinction coefficient of 48000.

  The compounds obtained in Examples 2 to 8 were evaluated for solubility in the same manner as in Example 1. The results are shown in Table 6.

  From the results of Tables 5 and 6, it can be seen that the compounds of the present invention exhibit high solubility in organic solvents.

Reference example 2
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-46) synthesized in Example 2. A photosensitive resin composition and a color filter are obtained.

Reference example 3
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-86) synthesized in Example 3. A photosensitive resin composition and a color filter are obtained.

Reference example 4
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-85) synthesized in Example 4. A photosensitive resin composition and a color filter are obtained.

Reference Example 5
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-65) synthesized in Example 5. A photosensitive resin composition and a color filter are obtained.

Reference Example 6
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-66) synthesized in Example 6. A photosensitive resin composition and a color filter are obtained.

Reference Example 7
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-125) synthesized in Example 7. A photosensitive resin composition and a color filter are obtained.

Reference Example 8
Coloring in the same manner as in Reference Example 1, except that the compound represented by formula (I-45) synthesized in Example 1 is replaced with the compound represented by formula (I-21) synthesized in Example 8. A photosensitive resin composition and a color filter are obtained.

  When the colored photosensitive resin composition containing the compound of the present invention is used, it is possible to produce a high-quality color filter with less generation of foreign matters.

  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 (7)

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 which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is , it may also be replaced by -O- or -CO- rather, substituents which may be possessed by the hydrocarbon group, a hydroxy group, a carboxy group, a sulfanyl group, a substituted alkyl group having 1 to 6 carbon atoms Represents an amino group and an alkoxy group having 1 to 4 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, and a hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
R ^{4 to} R ⁸ are each independently a hydrogen atom, 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 a nitro group. , A halogen atom or a group represented by formula (Ia), and at least one of R ^{4 to} R ⁸ represents a group represented by formula (Ia). ]

[In Formula (Ia), L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. ] The compound according to claim 1, wherein R ⁸ is a group represented by the formula (Ia). The compound according to claim 1 or 2, wherein R ¹ is a group represented by -L ² -X ¹ -R ⁹ .
[Wherein L ² represents an alkanediyl group having 1 to 8 carbon atoms. X ¹ represents * —CO—O— or * —O—CO— . R ⁹ represents 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. * Represents a bond to ^{L 2.} ] The compound according to any one of claims 1 to 3, wherein R ¹ is a group represented by -L ² -X ¹ -L ³ -X ² -R ¹⁰ .
[Wherein, L ² and L ³ each independently represent an alkanediyl group having 1 to 8 carbon atoms. X ¹ represents * —CO—O— or * —O—CO—, and * represents a bond to L ² .
X ² is * -CO-O-or * -O-CO- were table, * represents a bond to ^{L 3.} R ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group. ] The compound according to claim 3 or 4, wherein X ¹ is * -O-CO-.
[In the formula, * represents a bond with L ² . ] The compound according to claim 1, wherein at least one of R ^{4 to} R ⁸ is a nitro group.   The dye which uses the compound in any one of Claims 1-6 as an active ingredient.