KR20110126537A - Compounds - Google Patents

Abstract

PURPOSE: A compound as a dye is provided to ensure excellent solubility in an organic solvent and to be used in a color filter. CONSTITUTION: A compound as a dye is denoted by chemical formula I. In chemical formula I, R1 is a monovalent hydrocarbon group of 1-30 carbon atoms containing hydrogen atom or substituent; R2 is hydrogen atom, cyano group, or carbamoyl group; and R3 is an alkyl group of 1-4 carbon atoms. A dye contains the compound of chemical formula I as an active ingredient.

Description

Compound {COMPOUNDS}

The present invention relates to compounds and the like useful as dyes.

Dyestuffs are used for color display using reflected light or transmitted light, for example in the field of a textile material, a liquid crystal display device, and an inkjet.

For example, Example 1 of Unexamined-Japanese-Patent No. 2004-2630 has described the compound represented by the following formula.

The above compound is a dye excellent in light resistance and heat resistance, and is known as an aqueous ink. On the other hand, the compound has low solubility in organic solvents and was not easy to use as a dye used in color filters of display devices such as liquid crystal displays.

This invention is the following invention.

[1] The compound represented by formula (I).

In the formula (Ⅰ), R ¹ is -CH ₂ groups contained represents a monovalent hydrocarbon group of 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, the art hydrocarbon-substituted by the -O- or -CO- do.

R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.

R <^3> represents a C1-C4 alkyl group and the hydrogen atom contained in the said alkyl group may be substituted by the 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 hydroxyl group, a cyano group, a nitro group, a halogen atom or a formula ( Group represented by (Ia), and at least one represents group represented by Formula (Ia).]

[In formula (Ia), L <^1> represents a C1-C8 alkanediyl group.]

[2] The compound as described in [1], wherein R ⁸ is a group represented by formula (Ia).

[3] The compound as described in [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 -included in the aliphatic hydrocarbon group may be substituted with -O- or -CO-.]

[4] The compound according to any one of [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 X ¹ represent the same meaning as described above. L ³ represents an alkanediyl group having 1 to 8 carbon atoms. X ² represents -CO-O-. R ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group.]

[5] The compound as described in [3] or [4], wherein X ¹ is * -O-CO-.

Where * represents a bonding position 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 organic solvents and excellent as a dye used in color filters of display devices such as liquid crystal display devices.

This invention is a compound represented by Formula (I) [Hereinafter, it is called compound (I).].

In the formula (Ⅰ), R ¹ is -CH ₂ groups contained represents a monovalent hydrocarbon group of 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, the art hydrocarbon-substituted by the -O- or -CO- do.

R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.

R <^3> represents a C1-C4 alkyl group and the hydrogen atom contained in the said alkyl group may be substituted by the 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 hydroxyl group, a cyano group, a nitro group, a halogen atom or a formula ( Group represented by (Ia), and at least one represents group represented by Formula (Ia).]

[In formula (Ia), L <^1> represents a C1-C8 alkanediyl group.]

Examples of the monovalent hydrocarbon group which may have a substituent represented by R ¹ include a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a substituent, a monovalent alicyclic hydrocarbon group, a monovalent alicyclic hydrocarbon group having a substituent, and a monovalent aromatic hydrocarbon. The monovalent aromatic hydrocarbon group which has a group, a substituent, and group which combined these are mentioned. Carbon number of the said monovalent hydrocarbon group is 1-30.

Examples of the substituent which may have the hydrocarbon group include an hydroxy group, a carboxy group, a sulfanyl group, an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. As an aliphatic hydrocarbon group which has a substituent, 2-hydroxyethyl group, 2-aminoethyl group, 2-sulfanylethyl group, etc. are mentioned.

Cyclopentyl group, cyclohexyl group, etc. are mentioned as said alicyclic hydrocarbon 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-aminocyclo Hexyl group, 2- (N, N'-dimethylamino) cyclohexyl group, 4-carboxycyclohexyl group, 4-methoxycyclohexyl group, 2-carboxycyclohexyl group, etc. are mentioned.

A phenyl group, a naphthyl group, etc. are mentioned as said aromatic hydrocarbon group. As an aromatic hydrocarbon group which has a substituent, 4-hydroxyphenyl group, 4-methoxyphenyl group, 2-carboxyphenyl group, 4-carboxyphenyl group, etc. are mentioned.

C1-C20 is preferable and, as for said monovalent hydrocarbon group, C2-C16 is more preferable.

-CH ₂ -contained in the hydrocarbon group described above may be substituted with -O- or -CO-. In the above hydrocarbon group, it is preferable that _{2 to} 4 -CH ₂ -are substituted with -O- or -CO-, and that two adjacent -CH ₂ -are substituted with -CO- or -O-. More preferred.

R ¹ is preferably a group represented by -L ² -X ¹ -R ⁹ , and more preferably a group represented by -L ² -X ¹ -L ³ -X ² -R ¹⁰ . R <^1> is these groups, and there exists a tendency which the solubility with respect to the organic solvent of the compound of this invention improves.

L ² and L ³ are each independently an alkanediyl group having 1 to 8 carbon atoms, for example, 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-diyl group, Octane-1, 8- diyl group etc. are mentioned.

L ² is preferably an alkanediyl group having 1 to 5 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms.

L ³ is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 2 carbon atoms.

X ¹ and X ² are -CO-O-. As X <^1> , it is preferable that it is * -O-CO- (* represents a coupling | bonding position with L <^2> ). When X <^1> is * -O-CO-, manufacture of the compound of this invention is easy.

R ⁹ is a divalent aliphatic hydrocarbon group of 1 a hydrogen atom or a carbon number of 1~20, -CH ₂ that is art aliphatic hydrocarbon groups include - may be substituted with -O- or -CO-. As an aliphatic hydrocarbon group which shows R <^9> , a C1-C20 aliphatic hydrocarbon group, More preferably, a C1-C10 alkyl group is mentioned among the group contained as a monovalent aliphatic hydrocarbon group which shows R <^1> .

R ¹⁰ is a hydrogen atom, a methyl group or an ethyl group, and an ethyl group is preferable.

Examples of -L ² -X ¹ -R ^9, examples thereof include a group represented by the formula (f- 1) ~ expression (f- 25). Among these, -L ² -X ¹ -L ³ -X ² -R ¹⁰ is preferable, and examples thereof include groups represented by formulas (VII-1) to (VII-20), and more preferably formulas. (ｆ-1), formula (ｆ-2), formula (ｆ-5), formula (ｆ-6), formula (ｆ-9), formula (ｆ-10), formula (ｆ- 13), formula ( Groups represented by Formula (VII-14), Formula (VII-17), and Formula (VII-18) are more preferable, Formula (VII-2), Formula (VII-6), Formula (VII-10), The group represented by a formula (VII-14) and a formula (VII-18) is mentioned.

R ² is a hydrogen atom, a cyano group, or a carbamoyl group. Among these, a cyano group is preferable at the point which is easy to acquire a dye.

As a C1-C4 alkyl group which shows R <^3> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, etc. are mentioned. The hydrogen atom contained in the said alkyl group may be substituted by the halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. As a C1-C4 alkyl group in which a hydrogen atom is substituted by the halogen atom, a trifluoromethyl group, pentafluoroethyl group, etc. are mentioned, for example.

As R ^{3, a} methyl group and a trifluoromethyl group are preferable, and a methyl group is more preferable.

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 hydroxyl group, a cyano group, a nitro group, a halogen atom or a formula ( It is group represented by (Ia), At least 1 is group represented by Formula (Ia).

Since compound (I) has group represented by Formula (Ia) in at least 1 of R <^4> -R <^8> , there exists a tendency for the solubility to the organic solvent of compound (I) to become high.

It is preferable that compound (I) is added to group represented by Formula (Ia) as R <^4> -R <^8> , and has a hydrogen atom, a nitro group, a C1-C6 alkyl group, a chloro group, or a bromo group.

It is preferable that one of R <^4> -R <^8> is group represented by Formula (Ia). Especially, it is preferable that R <^8> is group represented by Formula (Ia).

L ¹ is an alkanediyl group having 1 to 8 carbon atoms. Examples of the alkanediyl group include the same groups as those contained as the alkenediyl group having 1 to 8 carbon atoms in L ² and L ³ . As L <^1> , a C1-C4 alkanediyl group is preferable and it is more preferable that it is a methylene group.

Moreover, it is preferable that at least 1 of R <^4> -R <^8> is a nitro group. When compound (I) has a nitro group, there exists a tendency for spectral density to become high. Among the R ⁴ to R ⁸ , the nitro group is preferably 1 to 2, more preferably 1. Among these, it is preferable that R <^5> or R <^6> is a nitro group, and it is more preferable that R <^6> is a nitro group. If the nitro group is in these positions, the spectral concentration tends to be higher.

Of R ⁴ ~R ^8, R ⁸ is a group represented by the formula (Ⅰa) preferably R ⁵ or R ⁶ is a nitro group, R ⁸ is represented by the equation group (Ⅰa) and R ⁵ is a hydrogen atom or a methyl group R ⁶ is more preferably a nitro group. R ⁴ and R ⁷ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group.

As a C1-C8 alkyl group represented by R <^4> -R <^8> , for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Linear alkyl groups such as octyl groups;

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-ethyl Butyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 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, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 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-dimethyl Butyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethyl Pentyl 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-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-me Butyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, 1,1-diethylbutyl group, 1,2-diethylbutyl group Branched chain alkyl groups, such as these, are 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. Can be.

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-methyl Methoxy) -1-methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group, etc. are mentioned.

As compound (I), a compound (I-1)-a compound (I-126) etc. are mentioned, for example. In Table 1, the column of R ¹ records the number of the formula of the group illustrated above.

Among them, compound (I-1) to compound (I-22), compound (I-45), compound (I-46), compound (I-65), compound (I-66) and compound (I-85). ), Compound (I-86) and Compound (I-105) to Compound (I-126) are preferable, and Compound (I-45), Compound (I-46), Compound (I-65) and Compound (I) 66), compound (I-85), compound (I-21), compound (I-125) and compound (I-86) are more preferable.

If compound (I) is these compounds, there exists a tendency for the solubility to an organic solvent to become high.

The method for producing the compound of the present invention will be described.

In compound (I), when R <^8> is group represented by Formula (Ia), for example, it reacts with the hydroxyl group which has the carboxyl group which has an azo compound represented by Formula (a4), and the compound represented by Formula (a5) (esterification) ), A compound represented by the formula (Iaa) (hereinafter may be referred to as "compound (Iaa)") can be obtained. Even when any of R <^4> -R <^7> is group represented by Formula (Ia), it can manufacture similarly to the method of manufacturing compound (Iaa).

[In formula (a4) and formula (a5), R <^1> -R <^7> and L <^1> show the same meaning as the above.]

[In formula (Iaa), R <^1> -R <^7> and L <^1> represent the same meaning as the above.]

The azo compound represented by Formula (a4) can be manufactured by diazo-coupling the diazonium salt represented by Formula (a2) and the pyridone compound represented by Formula (a3) according to description of Unexamined-Japanese-Patent No. 7-88633.

The diazonium salt represented by Formula (a2) can be obtained by diazotizing the amine represented by Formula (a1) with nitrous acid, nitrite, or nitrite ester, for example.

The pyridone compound represented by formula (a3) can be obtained by, for example, reacting the amine represented by formula (a4) with the compound represented by formula (a5) and the compound represented by formula (a6).

[In Formula (a1), Formula (a2), Formula (a3), Formula (a4), Formula (a5) and Formula (a6), R ¹ to R ⁷ represent the same meaning as described above. A ¹ represents an inorganic anion or an organic anion.]

As said inorganic anion, fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, etc. are mentioned, for example.

Examples of the organic ion Ana, for example CH ₃ COO ^-, and the like ^-, PhCOO.

Preferably, chloride ion, bromide ion, CH ₃ COO ^-, and the like.

The azo compound represented by Formula (a4) can be manufactured by diazo-coupling the diazonium salt represented by Formula (a2) and the pyridone compound represented by Formula (a3) with an aqueous solvent. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. 1 hour-12 hours are preferable, and, as for reaction time, 1 hour-4 hours are more preferable. Water, N-methylpyrrolidone, etc. are mentioned as said aqueous solvent, Water is preferable.

Compound (Iaa) can be obtained by esterifying the azo compound represented by Formula (a4) and the compound represented by Formula (a5) in presence of an organic solvent. The esterification reaction includes a condensing agent [1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and dicyclohexylcarbodiimide and the like] and / or an additive [N, N-dimethyl-4-aminopyridine, Triethylamine, (±) -10-campasulfonic acid, and the like]. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. 1 hour-12 hours are preferable, and, as for reaction time, 1 hour-5 hours are more preferable.

As for the usage-amount of the compound represented by Formula (a5), 0.5-10 mol is preferable with respect to 1 mol of azo compounds represented by Formula (a4), 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-methylpyrrolidone, Amide solvents such as 1-methyl-2-pyrrolidone.

In the compound of the present invention, R ¹ is -L ² -X ¹ -R ⁹ , and X ¹ is * -O-CO-, wherein [* represents a bonding position with L ² ]. That is, the manufacturing method in the case of a compound represented by Formula (I ') (henceforth "compound (I')") is demonstrated.

[In formula (I '), R <^2> -R <^7> , R <^9> , L <^1> and L <^2> represent the same meaning as the above.]

The azo compound represented by Formula (X4) can be manufactured by diazo coupling the diazonium salt represented by Formula (a2) and the pyridone compound represented by Formula (X3) by a method similar to the above.

[In Formula (X3) and Formula (X4), R <^2> -R <^7> and L <^2> represent the same meaning as the above.]

Next, the azo compound represented by Formula (X6) can be obtained by reacting the azo compound represented by Formula (X4) and the compound represented by Formula (X5) in the presence of an organic solvent. 30 to 180 degreeC is preferable and 50 to 120 degreeC of reaction temperature is more preferable. 1 hour-12 hours are preferable, and, as for reaction time, 1 hour-4 hours are more preferable.

[In Formula (X5) and Formula (X6), R <^2> -R <^7> , R <^9> and L <^2> represent the same meaning as the 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, and 1-methyl-. Amide system solvents, such as 2-pyrrolidone, are mentioned.

The usage-amount of the compound represented by Formula (X5) is 1 mol or more and 8 mol or less with respect to 1 mol of azo compounds represented by Formula (X4), Preferably they are 1 mol or more and 4 mol or less.

Subsequently, compound (I ') can be obtained by esterifying the azo compound represented by Formula (X6) and the compound represented by Formula (X5) by the method similar to the above.

In the compound of the present invention, Compound (I) wherein R ¹ is -L ² -X ¹ -R ⁹ and X ¹ is * -CO-O- [* represents a bonding position with L ² ], ie The manufacturing method of the compound represented by Formula (Ic) (henceforth a "compound (Ic)") is demonstrated.

[In formula (Ic), R <^2> -R <^7> , R <^9> , L <^1> and L <^2> represent the same meaning as the above.]

The azo compound represented by Formula (c4) can be manufactured by diazo coupling the diazonium salt represented by Formula (a2) and the pyridone compound represented by Formula (c3) by a method similar to the above.

[In formula (c3) and formula (c4), R <^2> -R <^7> and L <^2> represent the same meaning as the above.]

Next, the azo compound represented by Formula (c6) can be obtained by making the azo compound represented by Formula (c4) and the compound represented by Formula (c5) react in presence of an organic solvent. 30 to 180 degreeC is preferable and 50 to 120 degreeC of reaction temperature is more preferable. 1 hour-12 hours are preferable, and, as for reaction time, 1 hour-4 hours are more preferable.

As an organic solvent used here, the same solvent used for reaction of the azo compound represented by Formula (X4) and the compound represented by Formula (X5) is mentioned.

[In formula (c5) and formula (c6), R <^2> -R <^7> , R <^9> and L <^2> represent the same meaning as the above.]

The usage-amount of the compound represented by Formula (c5) is 1 mol or more and 8 mol or less with respect to 1 mol of azo compounds represented by Formula (c4), Preferably they are 1 mol or more and 4 mol or less.

In the reaction between the azo compound represented by the formula (c4) and the compound represented by the formula (c5), it is even more preferable to add an acidic catalyst in order to smoothly proceed the reaction. As an acidic catalyst, inorganic acids, such as a sulfuric acid and hydrochloric acid, etc. are mentioned.

Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01-4 mol, More preferably, it is 0.8-2 mol with respect to 1 mol of compounds represented by Formula (c5).

Subsequently, the compound (Ic) can be obtained by esterifying the azo compound represented by Formula (c6) and the compound represented by Formula (c3) in the same manner as above.

The method of obtaining the compound of this invention which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, it is preferable to mix the reaction mixture with an acid (for example acetic acid) and water, and to filter out the precipitated crystals. It is preferable that the said acid prepares the aqueous solution of an acid previously, and adds a reaction mixture to the said aqueous solution. The temperature at the time of adding a reaction mixture is 10 degreeC or more and 50 degrees C or less, Preferably they are 20 degreeC or more and 50 degrees C or less, More preferably, they are 20 degreeC or more and 30 degrees C or less. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to stir at the same temperature for 0.5 to 2 hours. The crystals obtained by filtration are 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 this invention has compound (I) as an active ingredient. The dye of this invention may be a dye which consists only of compound (I). The dye of the present invention preferably contains the compound of the present invention in a proportion of 70 to 100% by weight.

Since compound (I) is excellent in the solubility with respect to the organic solvent, it is used as a coloring agent of a coloring photosensitive resin composition.

As a coloring photosensitive resin composition containing a compound (I), the coloring agent (henceforth a "coloring agent (A)") containing the compound of this invention, resin (i), a photopolymerizable compound (C), and a photoinitiator The coloring photosensitive resin composition containing (D) and a solvent (E) is mentioned.

The coloring agent (A) may contain dye and / or pigment different from compound (I) in addition to compound (I).

Dyes other than Compound (I) include Solvent, Acid, Basic, Reactive, Direct, Color Index (Colour Index), published by The Society of Dyers and Colourists. The compound classified into disperse or bat is mentioned. More specifically, the dye of the color index (C.I.) number as follows, but is not limited to these.

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. Dispulse 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.

As a pigment, the organic pigment or inorganic pigment normally used for a pigment dispersion resist is mentioned. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Can be mentioned.

In addition, examples of the organic and inorganic pigments include compounds classified as pigments in the Color Index (Published by The Society of Dyers and Colourists). More specifically, the pigment of the color index (C.I.) number as follows, but 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.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass parts with respect to 100 mass parts of solid content in a coloring photosensitive resin composition. Here, as solid content, the sum total of the component except the solvent in a coloring photosensitive resin composition is said.

Content of compound (I) in a coloring agent (A) becomes like this. Preferably it is 3-100 mass%.

Dye and pigment different from compound (I) and compound (I) may be used individually or in combination of 2 or more types, respectively.

Although it does not specifically limit as resin (B), What kind of resin may be used. It is preferable that resin (i) is alkali-soluble resin, and it is more preferable that it is resin containing the structural unit guide | induced from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specific examples of the resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylate. Acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, etc. are mentioned.

As for the polystyrene conversion weight average molecular weight of resin, 5,000-35,000 are preferable, More preferably, it is 6,000-30,000.

50-150 are preferable and, as for the acid value of resin, 60-135 are more preferable.

Content of resin is 7-65 mass parts normally with respect to 100 mass parts of solid content of a coloring photosensitive resin composition, Preferably it is 13-60 mass parts.

The polymerizable compound (C) is not particularly limited as long as it is a compound which initiates polymerization by an active radical, an acid or the like generated from the polymerization initiator (D) by the action of light or heat.

Examples of the polymerizable compound (C) include compounds having a polymerizable carbon-carbon unsaturated bond.

As said polymeric compound (C), it is preferable that it is a photopolymerizable compound which has 3 or more of polymeric groups. Here, as a polymerizable group, it is the group which superposes | polymerizes by said active radical, an acid, etc .. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexaacrylate. And dipentaerythritol hexamethacrylate. Said polymeric compound (C) may be used individually or in combination of 2 or more types. The molecular weight of a polymeric compound (C) is 150-800 normally, Preferably it is 190-700.

It is preferable that content of a polymeric compound (C) is 5-65 mass parts with respect to 100 mass parts of solid content of a coloring photosensitive resin composition, More preferably, it is 10-60 mass parts.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of light or heat.

As said active radical generator, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-hydroxy-2-methyl-1-phenyl propane, for example Aceto, such as -1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, and 1-hydroxycyclohexylphenyl ketone Phenone compounds;

Thioxanes such as 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxycyxanthone Tone compounds;

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 (trichloro Methyl) -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, Triazine compounds such as 3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-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-phenan srenquinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like.

Examples of the acid generator include triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and diphenyliodonium p. Onium salts such as toluenesulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzointosylates and the like.

Said photoinitiator (D) may be used individually or in combination of 2 or more types.

Content of a photoinitiator (D) becomes like this. Preferably it is 0.1-30 mass% with respect to content of resin and a photopolymerizable compound (C), More preferably, it is 1-20 mass%. When content of a photoinitiator exists in the said range, since it becomes high sensitivity and an exposure time is shortened and productivity improves, it is preferable.

Examples of the solvent (E) include ethers, ketones, alcohols, esters, amides, and the like.

As said ether, for example, 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 methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl 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. are mentioned.

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 cyclo Pentanone, cyclohexanone, etc. are mentioned.

Hexanol, cyclohexanol, ethylene glycol, glycerin, etc. are mentioned as said alcohol.

As said ester, 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, metha Methyl oxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid Ethyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

You may use these solvents individually or in combination of 2 or more types.

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

The coloring photosensitive resin composition of this invention may contain various types of additives, such as surfactant, a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

The compounds of the present invention are useful as dyes. Since solubility in an organic solvent becomes high, it is especially useful as a dye used for the color filter of display apparatuses, such as a liquid crystal display device.

In addition, the above-mentioned colored photosensitive resin composition can be applied to various kinds of colored images such as a display device (for example, a known liquid crystal display device, an organic EL device, etc.), a solid-state image sensor, etc., which include a color filter as part of its component parts. It can be used in a form known to related equipment.

[Example]

Next, an Example etc. are given and this invention is demonstrated further more concretely.

In an Example, a reference example, and a comparative example,% and part which show content-usage-amount are based on mass unless there is particular notice.

In the following examples, the structure of the compound is NMR [JMM-ECA-500; It was confirmed by Nippon Electronics Co., Ltd. product.

Example 1

80 parts of water were added to 18.2 parts of 5-nitroanthranylic acid (manufactured by Tokyo Kasei Industry Co., Ltd.), and 0.4 parts of sodium hydroxide were added to dissolve it. Under ice-cooling, 19.7 parts of 35% sodium nitrite aqueous solution was added, then 26.2 parts of 35% hydrochloric acid was added little by little, dissolved, 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 Kasei Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.), and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and 95 It stirred at 24 degreeC. After cooling the said reaction liquid to room temperature, it added to the liquid mixture 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 filtration, and then dried to obtain 20.4 parts of the compound represented by the formula (d1).

Next, 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. Here, the suspension containing the diazonium salt was dripped at the pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 38.7 parts of compounds which are represented by a formula (d2) were obtained.

25.7 parts of compounds represented by Formula (d3) were added to 30.1 parts of compounds represented by Formula (d2), and it stirred at 70 degreeC for 3 hours in the solvent of N-methylpyrrolidone. After the reaction was completed, 37.0 parts of the compound represented by the formula (d4) was obtained by charging with water. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (d4)>

To 30.2 parts of the compound represented by the formula (d4), 1.89 parts of (±) -10-campasulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 15.2 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which melt | dissolved 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by addition of magnesium sulfate and filtered. The solvent was evaporated and removed by a rotary evaporator, and it dried under reduced pressure at 60 degreeC, and obtained 29.0 parts of compounds represented by a formula (I-45). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-45)>

0.10 g of the compound represented by the formula (I-45) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.0080 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 435 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Comparative Example 1

In Example 1, it carried out similarly to Example 1 except having used 2-amino terephthalic acid instead of 5-nitro anthranilic acid, and using the compound represented by Formula (e1) instead of the compound represented by Formula (d1), The compound represented by (i) was obtained.

0.35 g of the compound represented by the obtained formula (i) was dissolved in dimethylformamide to a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.028 g / L). Visible light photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 440 nm, and the molar extinction coefficient remained at 42000.

[Evaluation of Solubility]

Propylene glycol monomethyl ether acetate (hereinafter abbreviated to PGMEA), propylene glycol monomethyl ester (hereinafter abbreviated to PGME) and ethyl lactate (hereinafter abbreviated to EL) of the compounds obtained in Example 1 and Comparative Example 1. , Solubility in N-methylpyrrolidone (hereinafter abbreviated as NMP) was determined as follows.

In a 50 mL sample tube, after mixing the compound and the solvent in the following ratio, the sample tube was sealed and vibrated with an ultrasonic vibrator for 30 minutes at 30 deg. It was then left to stand at room temperature for 30 minutes and then filtered, and the residue thereof was visually observed. When no insolubles were identified as residues, the solubility was judged to be good, and the results are indicated by ○ in Table 2, and when the insolubles were confirmed, the solubility was determined to be poor and listed as × in Table 2. The results are shown in Table 2.

0.01 g of 0.5% compound, 2 g of solvent

0.01 g of 1% compound, 1 g of solvent

0.03 g of 3% compound, 1 g of solvent

Reference Example 1

[Preparation of Colored Photosensitive Resin Composition]

(I-45) Colorant: 20 parts of the compound synthesized in Example 1

(Iii-1) Resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70, weight average molecular weight; 10700, acid value; 70 mgKOH / g) 70 parts

(C-1) Polymerizable compound: 30 parts of dipentaerythritol hexaacrylate (manufactured by Nihon Kayaku Co., Ltd.)

(D-1) Photoinitiator: Benzyl dimethyl ketal (monocure 651; product made by Chiba Japan)

Part 15

(E-1) Solvent: 680 parts of N, N-dimethylformamide

It mixed and obtained the coloring photosensitive resin composition.

[Production of color filter]

The colored photosensitive resin composition obtained above on the glass was apply | coated by the spin coat method, and volatile matter was volatilized. After cooling, light was irradiated using a photomask and an exposure machine made of quartz glass having a pattern. After irradiating with light, the solution was developed with an aqueous potassium hydroxide solution and heated in an oven to obtain a color filter.

Example 2

After 80 parts of water was added to 18 parts of 4-nitroanthranilic acid (manufactured by Tokyo Kasei Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.8 parts of 35% sodium nitrite aqueous 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. Subsequently, 20.3 parts of the compound represented by a formula (d1) were suspended in 100 parts of water, and pH was adjusted to 9.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was dripped at the pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 38.4 parts of compounds represented by a formula (d5) were obtained.

<Identification of Compound Represented by Formula (d5)>

25.6 parts of the compound represented by a formula (d3) were added to 30 parts of compounds represented by a formula (d5), and it stirred at 70 degreeC in the solvent of N-methylpyrrolidone for 3 hours. After the reaction was completed, 36.9 parts of the compound represented by the formula (d6) was charged in water. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (d6)>

To 10.1 parts of the compound represented by the formula (d6), 1.89 parts of (±) -10-campasulfonic acid, 3.20 parts of N, N-dimethyl-4-aminopyridine, 15.3 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The solvent was evaporated and removed by a rotary evaporator, and it dried under reduced pressure at 60 degreeC, and obtained 29.1 parts of compounds represented by Formula (I-46). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-46)>

0.1 g of the compound represented by Formula (I-46) was dissolved in dimethylformamide to make the volume 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.0080 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 425 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 3

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

<Identification of Compound Represented by Formula (d8)>

To 30 parts of the compound represented by the formula (d8), 1.89 parts of (±) -10-campasulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 15.4 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 17 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The filtrate was evaporated and removed by a rotary evaporator, and dried under reduced pressure at 60 ° C to obtain 28.4 parts of the compound represented by the formula (I-86). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-86)>

0.10 g of the compound represented by the formula (I-86) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 425 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 4

25.2 parts of compounds represented by formula (d7) were added to 30.0 parts of compounds represented by formula (d2), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After the reaction was completed, 36.9 parts of the compound represented by the formula (d9) was charged in water. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (d9)>

To 30.1 parts of the compound represented by the formula (d9), 1.89 parts of (±) -10-campasulfonic acid, 3.27 parts of N, N-dimethyl-4-aminopyridine, 15.5 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 17.1 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The filtrate was removed by evaporation of the solvent by a rotary evaporator, and dried under reduced pressure at 60 ° C to obtain 28.4 parts of the compound represented by the formula (I-85). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-85)>

0.10 g of the compound represented by the formula (I-85) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 435 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 5

80 parts of water were added to 18.2 parts of 5-nitroanthranylic acid (manufactured by Tokyo Kasei Industry Co., Ltd.), and 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% sodium nitrite aqueous 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 Kasei Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.), and 30.0 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. It stirred at 24 degreeC. After cooling the said reaction liquid to room temperature, it added to the liquid mixture 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 filtration and dried to obtain 21.9 parts of the compound represented by the formula (d10).

<Identification of Compound Represented by Formula (d10)>

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

<Identification of Compound Represented by Formula (d11)>

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

<Identification of Compound Represented by Formula (d12)>

To 11.0 parts of compounds represented by the formula (d12), 1.89 parts of (±) -10-campasulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 15.2 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The filtrate was evaporated and removed by a rotary evaporator, and then dried under reduced pressure at 60 ° C to obtain 29.7 parts of the compound represented by the formula (I-65). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-65)>

0.10 g of the compound represented by the formula (I-65) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 434 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 6

80 parts of water were added to 18.3 parts of 4-nitroanthranilic acid (manufactured by Tokyo Kasei Industry Co., Ltd.), and 0.4 part of sodium hydroxide was added to dissolve it. Under ice-cooling, 19.7 parts of 35% sodium nitrite aqueous 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.

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

<Identification of Compound Represented by Formula (d13)>

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

<Identification of Compound Represented by Formula (d14)>

To 30.9 parts of the compound represented by the formula (d14), 1.89 parts of (±) -10-campasulfonic acid, 3.25 parts of N, N-dimethyl-4-aminopyridine, 15.2 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 16.4 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The solvent was evaporated and removed by a rotary evaporator, and it dried under reduced pressure at 60 degreeC, and obtained 28.7 parts of compounds represented by Formula (I-66). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-66)>

0.10 g of the compound represented by the formula (I-66) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical path part; 1 cm). This compound is λ _MAX = 424 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 7

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

<Identification of Compound Represented by Formula (d15)>

To 30.8 parts of the compound represented by the formula (d15), 1.89 parts of (±) -10-campasulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 15.4 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 17 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The filtrate was removed by evaporation of the solvent by a rotary evaporator, and dried under reduced pressure at 60 ° C to obtain 28.3 parts of the compound represented by formula (I-125). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I- 125)>

0.10 g of the compound represented by the formula (I-125) was dissolved in dimethylformamide to a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make a volume of 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical furnace part; 1 cm). This compound is λ _MAX = 425 nm, vivid yellow color, and a molar extinction coefficient of 48000.

Example 8

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

<Identification of Compound Represented by Formula (d16)>

To 10.6 parts of the compound represented by the formula (d16), 1.89 parts of (±) -10-campasulfonic acid, 3.26 parts of N, N-dimethyl-4-aminopyridine, 15.4 parts of 2,3-epoxy-1-propanol and 450 parts of chloroform were added. And it stirred at 5 degreeC. The solution which suspended 17 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 197 parts of chloroform was dripped at this suspension, maintaining the temperature of 5 degreeC. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the mixture was washed with 1N hydrochloric acid and saturated brine. The organic layer was extracted using a preparative rod, dried by adding magnesium sulfate and filtered. The filtrate was removed by evaporation of the solvent by a rotary evaporator, and dried under reduced pressure at 60 ° C to obtain 28.6 parts of the compound represented by the formula (I-21). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-21)>

0.10 g of the compound represented by the formula (I-21) was dissolved in dimethylformamide to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ethyl lactate to make the volume 100 cm 3 (concentration: 0.008 g / L). Ultraviolet visible photometer [V-650DS; The absorption spectrum was measured using Nihon Bunco Co., Ltd. (quartz cell, optical furnace part; 1 cm). This compound is λ _MAX = 433 nm, vivid yellow color, and high molar extinction coefficient of 48000.

Solubility evaluation was performed about the compound obtained in Examples 2-8 by the method similar to Example 1. The results are shown in Table 3.

From the results in Tables 2 and 3, it was found that the compounds of the examples showed high solubility in organic solvents.

Reference Example 2

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 2.

Reference Example 3

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 3.

Reference Example 4

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 4.

Reference Example 5

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 5.

Reference Example 6

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 6.

Reference Example 7

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 7.

Reference Example 8

A colored photosensitive resin composition and a color filter were obtained in the same manner as Reference Example 1 except that the compound synthesized in Example 1 was replaced with the compound synthesized in Example 8.

The colored photosensitive resin composition containing the said compound has little generation | occurrence | production of a foreign material, and can manufacture a high quality color filter.

The compound of the present invention is excellent in solubility in organic solvents and excellent as a dye used in color filters of display devices such as liquid crystal display devices.

Claims (7)

The compound represented by Formula (I).

In the formula (Ⅰ), R ¹ is -CH ₂ groups contained represents a monovalent hydrocarbon group of 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, the art hydrocarbon-substituted by the -O- or -CO- do.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R <^3> represents a C1-C4 alkyl group and the hydrogen atom contained in the said alkyl group may be substituted by the 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 hydroxyl group, a cyano group, a nitro group, a halogen atom or a formula ( The group represented by (Ia) is shown and at least 1 represents group represented by Formula (Ia).

(In formula (Ia), L <^1> shows the C1-C8 alkanediyl group.)] The method of claim 1,
The compound in which said R <^8> is group represented by Formula (Ia). The method of claim 1,
The compound in which R <^1> is 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 -included in the aliphatic hydrocarbon group may be substituted with -O- or -CO-.] The method of claim 1,
R ¹ is a group represented by -L ² -X ¹ -L ³ -X ² -R ¹⁰ .
[Wherein L ² and X ¹ represent the same meaning as described above. L ³ represents an alkanediyl group having 1 to 8 carbon atoms. X ² represents -CO-O-. R ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group.] The method according to claim 3 or 4,
X ¹ is * -O-CO-.
Where * represents a bonding position with L ² . The method of claim 1,
At least one of said R <^4> -R <^8> is a nitro group. The dye which uses the compound of Claim 1 as an active ingredient.