JP2010222442A - Azo compound, ink composition, recording method, and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment compound for black ink, which has high solubility over a medium containing water as a main component, is stable even if high concentration aqueous solution and the ink are stored for a long period of time, has high printed image density, does not cause bronzing of the image even when printed using a high concentration solution, and gives a black printed image excellent in the fastness of the printed image; and to provide an ink composition using the pigment composition. <P>SOLUTION: The pigment compound is an azo compound represented by formula (1) or its salt, wherein n is 1, or the like, R<SP>1</SP>is an alkyl group, or the like, R<SP>2</SP>is a cyano group, or the like, R<SP>3</SP>and R<SP>4</SP>are each independently a hydrogen atom, a sulfo group or the like. R<SP>5</SP>to R<SP>7</SP>are each independently a hydrogen atom, an alkyl group, a sulfoalkoxy group, or the like, X, Y and Z are an NH group, or the like, R<SP>8</SP>is a sulfoalkyl group, or the like, a group A is a substituted phenyl group, or the like, and a group B is a substituted phenylene group, or the like. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product colored with them.

A recording method using an ink jet printer, which is one of representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is. In this method, since the recording head and the recording material are not in direct contact with each other, there is little generation of sound and it is quiet. In addition, it has been rapidly spreading in recent years due to the feature of being easy to downsize and speed up, and is expected to grow greatly in the future. Conventionally, as inks for fountain pens, felt-tip pens and the like and inks for ink jet recording, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used. In these inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. These inks have good color rendering and give a recorded image with sufficient density, do not cause clogging of the pen tip and nozzle, have good drying properties on the recording material, and have little bleeding. It is required to have excellent storage stability. Further, the water-soluble dye used is required to have particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

Among these, ozone gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action that exists in the air acts on the dye in the recording paper and discolors the printed image. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx and SOx. However, among these oxidizing gases, ozone gas is regarded as a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Many ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper use a material such as a porous white inorganic material in order to speed up drying of ink and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on such recording paper. Since the color fading phenomenon due to the oxidizing gas mainly composed of ozone gas is characteristic of ink jet images, the improvement of ozone gas resistance is one of the most important issues in the ink jet recording method.

In the future, in order to expand the field of use of the ink jet recording method, the ink composition used for ink jet recording and the colored body colored thereby have various fastness properties such as light resistance, ozone gas resistance, moisture resistance, and water resistance. There is a strong demand for further improvements.

Various hues of ink are prepared from various dyes, of which black ink is an important ink used for both monocolor and full color images. Many pigments for these black inks have been proposed to date. Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as poor color rendering, poor water resistance and moisture resistance, and insufficient light resistance and ozone gas resistance. In general, polyazo dyes having extended conjugated systems have problems such as low water solubility and easy occurrence of a bronzing phenomenon in which a recorded image has a partially metallic luster, and light resistance and ozone gas resistance are not yet sufficient. Similarly, many azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, so there are concerns about biological safety and environmental problems, and ozone gas resistance is extremely weak. There is a problem.

Examples of the black dye for ink jet recording improved with respect to ozone gas resistance, which has become the most important issue in recent years, include compounds described in Patent Documents 1 to 3. These compounds are not sufficient in terms of light resistance because ozone gas resistance does not sufficiently satisfy market requirements. Examples of the azo compound having a benzimidazolopyridone skeleton, which is one of the features of the azo compound of the present invention, include those disclosed in Patent Documents 4 to 7 and the like. Patent Documents 5 and 6 also disclose trisazo compounds, but these trisazo compounds are symmetrical in which two benzimidazolopyridone skeletons are further bonded with azo structures to both ends of a linking group containing an azo structure. Nothing similar to the asymmetric disazo compound of the present invention is disclosed. Moreover, there are few water-soluble compounds and there is no usage example as a black compound for inkjet inks. Examples of the trisazo compound for inkjet ink having excellent ozone gas resistance include compounds described in Patent Document 8.

JP 2003-183545 A JP 2003-201412 A Special table 2007-517082 International Publication No. 2004/050768 Pamphlet German Patent No. 2000004488 German Patent No. 2023295 JP 05-134435 A International Publication No. 2007/077931 Pamphlet

The present invention contains an azo compound or a salt thereof used as a pigment in a black ink particularly suitable for inkjet recording, and the compound as a pigment, and is excellent in ozone gas resistance and light resistance of a recorded image, and has a high print density, and An object is to provide an ink composition having excellent color rendering properties.

As a result of intensive studies to solve the problems as described above, the present inventors have found that a specific azo compound can solve the problems, and have completed the present invention. That is, the present invention
1)
An azo compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
n is an integer from 0 to 2,
R ¹ is a carboxy group; a C1-C4 alkyl group; a C1-C4 alkyl group substituted with a carboxy group; a phenyl group; or a phenyl group substituted with a sulfo group;
R ² is a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a sulfo group; a C1-C4 alkyl group; or a C1-C4 alkoxy group;
R ⁵ to R ⁷ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group; a mono- or di-C1-C4 alkylamino group; As a substituent, a mono- or di-C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a C1-C4 alkylcarbonylamino group; Substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group N′-C1-C4 alkylureido group; N ′ substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group as a substituent -C1-C4 alkylureido group; phenylamino group; as a substituent, at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group, wherein the benzene ring is Substituted phenylamino group; benzoylamino group; benzene ring substituted with at least one group selected from the group consisting of chlorine atom, C1-C4 alkyl group, nitro group, sulfo group and carboxy group Benzoylamino group; phenylsulfonylamino group; or as a substituent, chlorine atom, C1-C4 alkyl , A nitro group, at least one group selected from the group consisting of sulfo and carboxy groups, phenylsulfonylamino groups in which the benzene ring is substituted; represent, respectively,
X, Y, and Z each independently represent an oxygen atom, a sulfur atom, or a group represented by the following formula (22);

[In formula (22), R ⁹ represents a hydrogen atom or a C1-C4 alkyl group. ],

R ⁸ is hydrogen atom; phenyl group; substituted with at least one group selected from the group consisting of hydroxy group, C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group and carboxy group A phenyl group; a C1-C4 alkyl group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group as a substituent. Each represents a group;
The group A represents a phenyl group; or a substituted phenyl group;
The group B represents a phenylene group; or a substituted phenylene group. ],

2)
The azo compound or a salt thereof according to the above 1) represented by the following formula (2):

[In formula (2), n, X, Y, Z, group A, group B, R ¹ to R ⁸ represent the same meaning as in formula (1). ],

3)
The azo compound or salt thereof according to 1) or 2) represented by the following formula (3):

[In formula (3), n, X, Y, Z, group A, group B, and R ¹ to R ⁸ represent the same meaning as in formula (1). ],

4)
The azo compound or a salt thereof according to any one of 1) to 3) above, wherein the group A is a group represented by the following formula (4):

[In Formula (4),
R ¹⁰ to ¹² each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a nitro group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of -C4 alkoxy group, hydroxy group, sulfo group and carboxy group; C1-C4 alkylcarbonylamino group; A C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of carboxy groups; a C1-C4 alkylsulfonyl group; or a group consisting of a hydroxy group, a sulfo group and a carboxy group as a substituent C1-C4 alkyls substituted with at least one group selected from It represents a; Honiru group. ],

5)
The azo compound or a salt thereof according to any one of 1) to 4) above, wherein the group B is a group represented by the following formula (5):

[In Formula (5),
R ¹³ to ¹⁵ are each independently a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; as a substituent, at least one selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A C1-C4 alkoxy group substituted with a group; a C1-C4 alkylcarbonylamino group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent Represents a carbonylamino group; ],

6)
The azo compound or a salt thereof according to the above 1) represented by the following formula (101):

[In the formula (101), n, X, Y, Z, and R ¹ to R ⁸ represent the same meaning as in the formula (1),
R ¹⁰ to ¹² each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a nitro group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C4 alkoxy group, a hydroxy group, a sulfo group and a carboxy group; a C1-C4 alkylcarbonylamino group; a hydroxy group and a carboxy group A C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group; a C1-C4 alkylsulfonyl group; or a substituent selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with at least one group; And,
R ¹³ to ¹⁵ are each independently a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; as a substituent, at least one selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A C1-C4 alkoxy group substituted with a group; a C1-C4 alkylcarbonylamino group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent Represents a carbonylamino group; ],

7)
R ⁸ is a hydrogen atom; a phenyl group substituted with a sulfo group; a phenyl group substituted with a carboxy group; a C1-C4 alkyl group; or a substituent selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A C1-C4 alkyl group substituted with at least one group selected from 1) to 6) above or a salt thereof,
8)
The azo compound according to any one of 1) to 7) above, wherein R ¹ is a methyl group, R ² is a cyano group or carbamoyl group, one of R ³ and R ⁴ is a hydrogen atom, and the other is a sulfo group. Or its salt,
9)
R ⁵ and ⁷ each independently represent a hydrogen atom; a chlorine atom; a C1-C4 alkyl group; a C1-C4 alkoxy group substituted with a sulfo group; a C1-C4 alkylcarbonylamino group; or a benzoylamino group;
The azo compound or a salt thereof according to any one of 1) to 8) above, wherein R ⁶ is a hydrogen atom,
10)
The azo according to any one of 1) to 9) above, wherein R ⁵ is a sulfopropoxy group or a sulfobutoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom, a methyl group, an acetylamino group, or a benzoylamino group. A compound or a salt thereof,
11)
X, Y and Z are groups represented by the formula (22) wherein R ⁹ is a hydrogen atom,
The azo compound or a salt thereof according to any one of 1) to 10) above, wherein R ⁸ is a 2-sulfoethyl group,
12)
n is 1,
R ¹ is a C1-C4 alkyl group,
R ² is a cyano group,
Either one of R ³ or R ⁴ is a hydrogen atom, the other is a sulfo group,
R ⁵ is a C1-C4 alkoxy group substituted with a sulfo group,
R ⁶ is a hydrogen atom,
R ⁷ is a chlorine atom; a C1-C4 alkyl group; a C1-C4 alkylcarbonylamino group; or a benzoylamino group;
The substitution positions of R ⁵ , R ⁶ and R ⁷ are the 2-position, 6-position and 5-position, respectively, with the substitution position of the azo group bonded to the benzimidazolopyridone ring being 1-position,
X, Y and Z are groups represented by the formula (22) in which R ⁹ is a hydrogen atom,
R ⁸ is a C1-C4 alkyl group substituted with a sulfo group;
R ¹⁰ to R ¹² are each independently a hydrogen atom; a nitro group; a sulfo group; a carboxy group; or a C1-C4 alkoxy group;
R ¹³ is a sulfo group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a hydroxy group; or a C1-C4 alkoxy group substituted with a sulfo group;
R ¹⁴ is a hydrogen atom,
R ¹⁵ is a hydrogen atom; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a hydroxy group; or a C1-C4 alkoxy group substituted with a sulfo group;
The azo compound or a salt thereof according to 6) above,
13)
n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
One of R ³ and R ⁴ is a hydrogen atom, the other is a sulfo group,
R ⁵ is a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
The substitution positions of R ⁵ , R ⁶ and R ⁷ are the 2-position, 6-position and 5-position, respectively, with the substitution position of the azo group bonded to the benzimidazolopyridone ring being 1-position,
X, Y and Z are all groups represented by formula (22) wherein R ⁹ is a hydrogen atom,
R ⁸ is a 2-sulfoethyl group,
Two of R ^{10 to} R ¹² are sulfo groups and one is a hydrogen atom;
R ¹³ is sulfo propoxy group, R ¹⁴ is a hydrogen atom, R ¹⁵ is a methyl group, an azo compound or a salt thereof according to the above 6),
14)
An ink composition containing at least one azo compound or salt thereof according to any one of 1) to 13) as a pigment;
15)
An ink jet recording method for recording on a recording material by using the ink composition described in 14) as an ink, and discharging ink droplets of the ink according to a recording signal;
16)
The inkjet recording method according to 15) above, wherein the recording material is an information transmission sheet,
17)
The ink jet recording method according to 16) above, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
18)
An inkjet printer loaded with a container containing the ink composition described in 14) above,
19)
A colored body colored with the azo compound or salt thereof according to any one of 1) to 13) above;
About.

The azo compound of the present invention or a salt thereof has characteristics such as high solubility in a medium containing water as a main component, easy synthesis, and low cost.
Since the azo compound of the present invention is excellent in water solubility, the filterability by a membrane filter in the process of producing an ink composition is good, and the ink composition containing the compound or the ejection stability in an inkjet printer is also good. Are better.
Further, the ink composition containing the azo compound of the present invention is suitably used for various recordings, particularly for inkjet recording, and has a very high print density of an image recorded on an inkjet dedicated paper, excellent color rendering, Both light resistance and ozone gas resistance are excellent.
As described above, the azo compound of the present invention or a salt thereof and an ink composition containing the azo compound are extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail.
The azo compound or salt thereof of the present invention is a black pigment. Hereinafter, for the sake of convenience, the term “azo compound of the present invention” will be simply described, including both the “azo compound of the present invention or a salt thereof”.
The azo compound represented by the formula (1) has a tautomer, and examples of the tautomer include the following formulas (6) and (7) in addition to the compound represented by the formula (1). Conceivable. These tautomers are also included in the present invention. In the following formulas (6) and (7), the ring substituted by n, X, Y, Z, group A, group B, R ^{1 to} R ⁸ , and R ^{5 to} R ⁷ is represented by a broken line. Including the ring, it has the same meaning as in the above formula (1).

In the above formula (1), n in “— (SO ₃ H) n” on the benzothiazole ring represents the number of substitution of the sulfo group, and is usually an integer of 0 to 2, preferably an integer of 1. is there. The substitution position of the sulfo group is not particularly limited, but the position of the sulfur atom of the benzothiazole ring is the 1st position. When n is 2, the 4th and 7th positions are preferable, and when n is 1, the 4th position is preferable.

In the above formula (1), the C1-C4 alkyl group in R ^1, can be mentioned those of unsubstituted straight or branched chain, a straight chain is preferred. Specific examples of the C1-C4 alkyl group include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and t-butyl.

Examples of the C1-C4 alkyl group substituted with a carboxy group in R ¹ include those in which any hydrogen atom in the C1-C4 alkyl group is substituted with a carboxy group. Specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and the like.

Specific examples of the phenyl group substituted with a sulfo group in R ¹ include, for example, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like. And a phenyl group substituted with 1 to 4, preferably 1 to 3, more preferably 1 to 2 sulfo groups.

Among the above, R ¹ is preferably a C1-C4 alkyl group; or a phenyl group, and more preferably a C1-C4 alkyl group.
Specific examples of preferable R ¹ in the formula (1) are methyl, ethyl, n-propyl, t-butyl and phenyl, more preferably methyl, n-propyl and phenyl, and still more preferably methyl.

In the above formula (1), R ² represents a cyano group; a carbamoyl group; or a carboxy group. Cyano or carbamoyl is preferred, and cyano is more preferred.

In formula (1), the C1-C4 alkyl group in R ³ and R ⁴ has the same meaning as the C1-C4 alkyl group in R ¹ and preferred ones.

Examples of the C1-C4 alkoxy group for R ³ and R ⁴ include linear or branched ones, and linear ones are preferred. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, sec-butoxy and t-butoxy;

R ³ and R ⁴ are preferably a hydrogen atom; sulfo; a C1-C4 alkyl group; or a C1-C4 alkoxy group, more preferably a hydrogen atom or sulfo.

Preferred combinations of R ¹ to R ⁴ in the formula (1) is, R ¹ is C1-C4 alkyl group, preferably a methyl group, R ² is a cyano group or a carbamoyl group, either preferably a cyano group, R ³ and R ⁴ One of them is a hydrogen atom and the other is a combination of sulfo.

In the above formula (1), examples of the C1-C4 alkyl group in R ⁵ to R ⁷ include the same as the C1-C4 alkyl group in R ¹ including preferable ones.

The C1-C4 alkoxy group from R ⁵ in R ^7, the same thing can be mentioned including such preferred and C1-C4 alkoxy group in the above R ³ and R ^4.

As a substituent in R ⁵ to R ⁷ , C1-C4 substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group Examples of the C4 alkoxy group include hydroxy C1-C4 alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, C1-C4 alkoxy C1-C4 alkoxy groups such as methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy C1-C4 alkoxy C such as 2-hydroxyethoxyethoxy 1-C4 alkoxy group; sulfo C1-C4 alkoxy group such as 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy; carboxy C1-C4 alkoxy group such as carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy; Etc. One kind of these substituents in the substituted C1-C4 alkoxy group is preferable. The number of these substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.

Examples of the mono- or di-C1-C4 alkylamino group in R ⁵ to R ⁷ include unsubstituted linear or branched ones. Specific examples include linear amino acids such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; isopropyl Branched chain such as amino, sec-butylamino, t-butylamino, diisopropylamino; and the like.

Examples of the substituent in R ⁵ to R ⁷ include a mono- or di-C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group. Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as hydroxyethylamino, 2-hydroxypropylamino, 2,2′-dihydroxydiethylamino; 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3 Sulfo-substituted mono- or di-C1-C4 alkylamino groups such as 3,3′-disulfodipropylamino; carboxy such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino Substituted mono- or di-C1-C4 alkylamino groups; It is done. One type of these substituents in the substituted mono- or di-C1-C4 alkylamino group is preferred. The number of substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1 for one alkylamino group.

Examples of the C1-C4 alkylcarbonylamino group in R ⁵ to R ⁷ include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight chain such as methylcarbonylamino (acetylamino), ethylcarbonylamino (propionylamino), propylcarbonylamino (butyrylamino); branched chain such as isopropylcarbonylamino; and the like.

In the R ⁵ R ^7, specific examples of C1-C4 alkyl carbonyl amino group substituted with at least one group selected from the group consisting of hydroxy and carboxy groups as substituents such as hydroxy acetylamino, 2 -Hydroxy C1-C4 alkylcarbonylamino groups such as hydroxypropionylamino and 4-hydroxybutyrylamino; Carboxy C1-C4 alkylcarbonylamino groups such as 3-carboxypropionylamino; and the like. One kind of these substituents in the substituted C1-C4 alkylcarbonylamino group is preferable. The number of substituents is usually 1 or 2, preferably 1.

Examples of the N′-C1-C4 alkylureido group in R ⁵ to R ⁷ include straight-chain or branched-chain groups, and straight-chain groups are preferable. Specific examples thereof include linear ones such as N′-methylureido, N′-ethylureido, N′-propylureido; branched ones such as N′-isopropylureido;

Examples of the N′-C1-C4 alkylureido group substituted with a group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group in R ⁵ to R ⁷ include N′-2-hydroxyethylureido, N ′ N′-hydroxy C1-C4 alkylureido group such as -3-hydroxyethylureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N N'-carboxy C1-C4 alkylureido groups such as' -carboxymethylureido, N'-2-carboxyethylureido, N'-3-carboxypropylureido, N'-4-carboxybutylureido; and the like. As these substituents in the substituted N′-C1-C4 alkylureido group, one kind is preferable. The number of substituents is usually 1 or 2, preferably 1.
Moreover, as said N'-C1-C4 alkylureido group, what has a substituent is preferable rather than unsubstituted.

In R ⁵ to R ⁷ in the formula (1), as a C1-C4 alkyl group as a substituent in a phenylamino group, a benzoylamino group or a phenylsulfonylamino group each having a benzene ring substituted with a C1-C4 alkyl group, , Straight chain, branched chain or cyclic, and straight chain or branched chain are preferable. Specific examples include, for example, straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and t-butyl; cyclic one such as cyclopropyl; Etc.

As a substituent in R ⁵ to R ⁷ , phenylamino having a benzene ring substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group Examples of the group include chlorine-substituted phenylamino groups such as 2-chlorophenylamino, 4-chlorophenylamino and 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, 4-t-butylphenylamino and the like C1-C4 alkyl-substituted phenylamino group; 2-nitrophenylamino, nitro-substituted phenylamino groups such as 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, Sulfo-substituted phenylamino groups such as 3,5-disulfophenylamino Carboxy-substituted phenylamino groups such as 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, 3,5-dicarboxyphenylamino; and the like. As these substituents in the phenylamino group in which the benzene ring is substituted, one kind is preferable. The number of substituents is usually 1 or 2, preferably 1.

A benzoylamino group in which the benzene ring is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group as a substituent in R ⁵ to R ⁷ As, for example, chlorine atom-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino, etc. C1-C4 alkyl-substituted benzoylamino groups; nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino; sulfos such as 2-sulfobenzoylamino and 4-sulfobenzoylamino Substituted benzoylamino group; Carboxy-substituted benzoylamino groups such as ruboxybenzoylamino, 4-carboxybenzoylamino, 3,5-dicarboxybenzoylamino; and the like. As these substituents in the benzoylamino group substituted with a benzene ring, one kind is preferable. The number of substituents is usually 1 or 2, preferably 1.

As a substituent in R ⁵ to R ⁷ , phenylsulfonyl in which a benzene ring is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group Examples of the amino group include chlorine atom-substituted phenylsulfonylamino groups such as 2-chlorophenylsulfonylamino and 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-t-butylphenylsulfonylamino and the like. A C1-C4 alkyl-substituted phenylsulfonylamino group; a nitro-substituted phenylsulfonylamino group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino; A sulfo-substituted phenylsulfonylamino group such as mino and 4-sulfophenylsulfonylamino; a carboxy-substituted phenylsulfonylamino group such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino; and the like. As these substituents in the phenylsulfonylamino group substituted with a benzene ring, one kind is preferable. The number of substituents is usually 1 or 2, preferably 1.

R ⁵ to R ⁷ are each independently preferably a hydrogen atom, a chlorine atom, a C1-C4 alkyl group, a C1-C4 alkoxy group substituted with a sulfo group, a C1-C4 alkylcarbonylamino group, or a benzoylamino group. Among them, it is more preferable that at least one of R ⁵ to R ⁷ is a group other than a hydrogen atom, and the remainder is a hydrogen atom. More preferably, two of R ⁵ to R ⁷ are groups other than hydrogen atoms, and the rest are hydrogen atoms.

A preferred combination of R ⁵ to R ⁷ in formula (1) is a C1-C4 alkoxy group (preferably sulfopropoxy or sulfobutoxy, more preferably 3-sulfopropoxy or 4-sulfobutoxy) in which R ⁵ is substituted with a sulfo group. More preferably 3-sulfopropoxy); R ⁶ is a hydrogen atom; R ⁷ is a hydrogen atom, a C1-C4 alkyl group (preferably methyl or ethyl, more preferably methyl), a C1-C4 alkylcarbonylamino (preferably acetyl) Amino), or a combination of benzoylamino.
A more preferable combination includes a combination of C1-C4 alkoxy group in which R ⁵ is substituted with a sulfo group; R ⁶ is a hydrogen atom; and R ⁷ is a C1-C4 alkyl group.

X, Y, and Z in the above formula (1) each independently represent an oxygen atom, a sulfur atom, or a group represented by the above formula (22). X, Y, and Z are preferably a group represented by the above formula (22).
In formula (22), R ⁹ represents a hydrogen atom or a C1-C4 alkyl group.
Examples of the C1-C4 alkyl group for R ⁹ include the same as the C1-C4 alkyl group for R ¹ , including preferred ones.
Of the above, R ⁹ is preferably a hydrogen atom.

In the above formula (1), in R ⁸ , a phenyl group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group As hydroxy-substituted phenyl groups such as 2-hydroxyphenyl, 3-hydroxyphenyl and 4-hydroxyphenyl; C1-C4 alkoxy-substituted phenyl groups such as 2-methoxyphenyl; hydroxy-C1-C4 alkoxy such as 4-hydroxyethoxyphenyl A substituted phenyl group; a sulfo-substituted phenyl group such as 2,5-disulfophenyl; a carboxy-substituted phenyl group such as 3,5-dicarboxyphenyl; and the like. One kind of these substituents in the substituted phenyl group is preferable. The number of substituents is usually 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

Examples of the C1-C4 alkyl group for R ⁸ include the same C1-C4 alkyl groups as those described above for R ^1, including preferred ones.

As the substituent in R ⁸ , the C1-C4 alkyl group substituted with at least one group selected from the group consisting of a hydroxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group includes 2-hydroxy Hydroxy C1-C4 alkyl groups such as ethyl, 3-hydroxypropyl, 2-hydroxypropyl; hydroxy C1-C4 alkoxy C1-C4 alkyl groups such as 2-hydroxyethoxyethyl, 3-hydroxypropoxyethyl, 2-hydroxypropoxyethyl; And sulfo C1-C4 alkyl groups such as 2-sulfoethyl and 3-sulfopropyl; carboxy C1-C4 alkyl groups such as carboxymethyl and 2-carboxymethyl; and the like. One kind of these substituents in the substituted C1-C4 alkyl group is preferable. The number of substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.

R ⁸ is a hydrogen atom; a phenyl group substituted with a sulfo group; a phenyl group substituted with a carboxy group; a C1-C4 alkyl group; or, as a substituent, a group consisting of a hydroxy group, a sulfo group, and a carboxy group C1-C4 alkyl groups substituted with at least one selected group are preferred. More preferably, it is a phenyl group substituted with a sulfo group, a C1-C4 alkyl group, or a C1-C4 alkyl group substituted with a sulfo group, and more preferably a C1-C4 alkyl group substituted with a sulfo group. Among them, 2-sulfoethyl is particularly preferable.

The substituted phenyl group in the group A includes one having usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and further preferably 2 substituents. The substitution position of the substituent in the group A is not particularly limited.

The type of substituent in group A is not particularly limited, but is chlorine atom; hydroxy group; nitro group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; C1-C4 alkyl group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy group, a sulfo group and a carboxy group; a C1-C4 alkylcarbonylamino group; A C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group; a C1-C4 alkylsulfonyl group; or, as a substituent, a hydroxy group, a sulfo group, and a carboxy group C1 substituted with at least one group selected from the group consisting of C4 alkylsulfonyl group; and the like preferably.

Examples of the C1-C4 alkyl group in the substituent of the group A include the same as the C1-C4 alkyl group in the above R ^1, including preferable ones.

Examples of the C1-C4 alkoxy group in the substituent of the group A include the same as the C1-C4 alkoxy group in R ³ and R ⁴ , including preferable ones.

As the substituent in the substituent of the group A, a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy group, a sulfo group, and a carboxy group is preferable. in R ^7, including things like the R ⁵ in the formula (1) include those similar to the C1-C4 alkoxy group substituted respectively with the same groups. One kind of these substituents in the substituted C1-C4 alkoxy group is preferable. The number of these substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.

In the substituents of the group A, as the C1-C4 alkyl carbonyl amino group, a C1-C4 alkyl carbonyl amino group in R ⁷ from the R ^5, the same can be listed, including the preferred ones, and the like.

The C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent in the substituent of the group A includes the above R ⁵ to R ⁷ . Examples of the substituent include the same ones including a C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group, and preferred ones. One kind of these substituents in the substituted C1-C4 alkylcarbonylamino group is preferable. The number of substituents is usually 1 or 2, preferably 1.

Examples of the C1-C4 alkylsulfonyl group in the substituent of the group A include linear or branched ones. Specific examples include straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl; branched chains such as isopropylsulfonyl, sec-butylsulfonyl, and t-butylsulfonyl; .

As the substituent in the substituent of the group A, the C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is a linear or branched chain. And linear ones are preferred. Specific examples include, for example, hydroxy-substituted C1-C4 alkylsulfonyl groups such as 2-hydroxyethylsulfonyl and 3-hydroxypropylsulfonyl; sulfo-substituted C1 such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl and 4-sulfobutylsulfonyl. -C4 alkylsulfonyl group; carboxy-substituted C1-C4 alkylsulfonyl groups such as carboxymethylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl; and the like. One type of these substituents in the substituted C1-C4 alkylsulfonyl group is preferred. The number of substituents is usually 1 to 3, preferably 1 or 2, and more preferably 2.

The group A is preferably a substituted phenyl group rather than an unsubstituted phenyl group.
Of the above, the substituent of the group A is preferably a nitro group, a sulfo group, a carboxy group, or a C1-C4 alkoxy group, and particularly preferably a sulfo group.

When the substituent of the group A is one, the substitution position of the substituent in the group A is preferably the 4-position with the substitution position of the azo group bonded to the group A as the 1-position.

When the substituent of the group A is two, as a preferable combination of the substituents, one is a nitro group, a sulfo group, a carboxy group, or a C1-C4 alkoxy group (among them, preferably a sulfo group), and the other is a nitro group. , A sulfo group, a carboxy group, or a C1-C4 alkoxy group (among these, preferably a nitro group, a sulfo group, or a C1-C4 alkoxy group, more preferably a sulfo group).
When there are two substituents of the group A, the substitution position of the two substituents is that the substitution position of the azo group bonded to the group A is the first position, the former substituent in the above combination is the second position, and the latter substituent is Substitution at the 4-position is preferred.

In the above formula (1), examples of the substituted phenylene group in the group B include those in which the divalent unsubstituted aromatic ring group has a substituent. The number of substituents is usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 2. The position of the substituent in the group B is not particularly limited.

The kind of the substituent in the group B is not particularly limited, but is at least selected from the group consisting of a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a hydroxy group, a sulfo group, and a carboxy group. C1-C4 alkoxy group substituted with one group; C1-C4 alkylcarbonylamino group; or C1 substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent -C4 alkylcarbonylamino group; and the like.

Examples of the C1-C4 alkyl group in the substituent of the group B include the same as the C1-C4 alkyl group in R ¹ above, including preferable ones.

Examples of the C1-C4 alkoxy group in the substituent of the group B include the same as the C1-C4 alkoxy group in R ³ and R ⁴ including preferable ones.

As the substituent in the substituent of the group B, the C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group includes the above preferable ones and the like. in R ⁷ from R ⁵ in the formula (1) include those similar to the C1-C4 alkoxy group substituted respectively with the same groups.

In the substituents of group B, as the C1-C4 alkyl carbonyl amino group, a C1-C4 alkyl carbonyl amino group in R ⁷ from the R ^5, the same can be listed, including the preferred ones, and the like.

As the substituent in the substituent of the group B, the C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group is the above R ⁵ to R ⁷ , C1-C4 alkylcarbonylamino group substituted with the same group and the same thing including a preferable thing etc. are mentioned.

As the group B, a substituted phenylene group is preferable to an unsubstituted phenylene group.
Among the above, the substituent of the group B includes a sulfo group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group substituted with a hydroxy group, or a C1- substituted with a sulfo group. A C4 alkoxy group is preferred.
The substitution position of the substituent in group B is the 2-position when the substitution position of the bond binding to Y is position 1 and the substitution position of the bond with the azo group binding to group A is 4-position. Two are preferably substituted at the 2-position and 5-position, and three are substituted at the 2-position, 5-position and 6-position.

As a preferable combination of the substituents in the group B, there are two substituents, and one of them is a sulfo group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group substituted with a hydroxy group, or a sulfo group. A substituted C1-C4 alkoxy group (among them, preferably a C1-C4 alkoxy group substituted with a sulfo group, particularly preferably a 3-sulfopropoxy group), the other being a C1-C4 alkyl group, a C1-C4 alkoxy group , A C1-C4 alkoxy group substituted with a hydroxy group, or a C1-C4 alkoxy group substituted with a sulfo group (among them, preferably a C1-C4 alkyl group, particularly preferably a methyl group).

A preferable compound represented by the above formula (1) is a compound represented by the above formula (2), and a more preferable compound is a compound represented by the above formula (3). In formulas (2) and (3), n, X, Y, Z, group A, group B, and R ¹ to R ⁸ used as appropriate include those preferred in formula (1) above. The same combinations that represent the same meaning and that are preferred are the same combinations as in formula (1).

In the above formulas (1) to (3), a preferable group A is a group represented by the above formula (4).
In the formula (4), the C1-C4 alkyl group in R ¹² from R ^10, the same thing can be mentioned a C1-C4 alkyl group in the above R ^1, including preferred and the like.

Examples of the C1-C4 alkoxy group in R ¹⁰ to R ¹² include the same groups as those described above including preferable ones and the like for the C1-C4 alkoxy group in R ³ and R ⁴ .

As the substituent in R ¹⁰ to R ¹² , a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy group, a sulfo group, and a carboxy group is preferable. in R ^7, including things like the R ⁵ in the formula (1) include those similar to the C1-C4 alkoxy group substituted respectively with the same groups. One kind of these substituents in the substituted C1-C4 alkoxy group is preferable. The number of these substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.

From R ¹⁰ in R ^12, as the C1-C4 alkyl carbonyl amino group, a C1-C4 alkyl carbonyl amino group in R ⁷ from the R ^5, the same can be listed, including the preferred ones, and the like.

As the substituent in R ¹⁰ to R ¹² , the C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group includes the above R ⁵ to R ⁷ , C1-C4 alkylcarbonylamino group substituted with the same group and the same thing including a preferable thing etc. are mentioned. One kind of these substituents in the substituted C1-C4 alkylcarbonylamino group is preferable. The number of substituents is usually 1 or 2, preferably 1.

From R ¹⁰ in R ^12, as the C1-C4 alkylsulfonyl group, the substituent of the group A, and C1-C4 alkylsulfonyl group may be the same as those including the preferred ones, and the like.

As the substituent in R ¹⁰ to R ¹² , the C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group is the same as in the above group A. And the same as the C1-C4 alkylsulfonyl group substituted with a group, including preferable ones. One type of these substituents in the substituted C1-C4 alkylsulfonyl group is preferred. The number of substituents is usually 1 or 2, preferably 1.

Among the above, R ¹⁰ to R ¹² are each independently preferably a hydrogen atom, a nitro group, a sulfo group, a carboxy group, or a C1-C4 alkoxy group, and at least one is a group other than a hydrogen atom. More preferred. More preferably, one is a hydrogen atom and the other two are groups other than a hydrogen atom, or two are a hydrogen atom and the other one is a group other than a hydrogen atom, and the former is particularly preferable. The group other than the hydrogen atom is preferably a sulfo group.
The substitution position of R ¹⁰ to R ¹² is not particularly limited, but preferably the substitution position of the azo group is the 1st position, and when 2 are hydrogen atoms, the other is the 4th position; Are 2nd and 4th, 2nd and 5th, more preferably 2nd and 4th;

Examples of the combination of R ¹⁰ to R ¹² include the following combinations (i) and (ii). The latter combination is preferred.
In the following combination (i), the substitution position of R ¹² is preferably the 4-position with the substitution position of the azo group as the 1-position.
In the case of the combination (ii) below, similarly, the substitution positions of R ¹⁰ and R ¹² are preferably the 2-position and the 4-position, respectively.
(I)
A combination in which R ¹⁰ and R ¹¹ are a hydrogen atom, R ¹² is a nitro group, a sulfo group, a carboxy group, or a C1-C4 alkoxy group (preferably R ¹² is a sulfo group).
(Ii)
R ¹⁰ is a nitro group, a sulfo group, a carboxy group, or a C1-C4 alkoxy group (preferably R ¹⁰ is a sulfo group), R ¹¹ is a hydrogen atom, R ¹² is a nitro group, a sulfo group, a carboxy group, or C1- A combination in which a C4 alkoxy group (preferably R ¹² is a nitro group, a sulfo group, or a C1-C4 alkoxy group, more preferably a sulfo group).

In the above formulas (1) to (3), preferred as the group B is a group represented by the above formula (5). In the formula (5), the bond of the carbon atom adjacent to R ¹⁴ is bonded to Y, and the bond of the carbon atom adjacent to R ¹⁵ is bonded to the azo group bonded to the group A.

In the above formula (5), the C1-C4 alkyl group in R ¹⁵ from R ^13, and C1-C4 alkyl group in the above R ^1, the same thing can be mentioned including the preferred ones, and the like.

The C1-C4 alkoxy group in R ¹⁵ from R ^13, the same thing can be mentioned including such preferred and C1-C4 alkoxy group in the above R ³ and R ^4.

As the substituent in R ¹³ to R ¹⁵ , the C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group includes the above preferable ones. in R ⁷ from R ⁵ in the formula (1) include those similar to the C1-C4 alkoxy group substituted respectively with the same groups.

In R ¹⁵ from R ^13, as the C1-C4 alkyl carbonyl amino group, a C1-C4 alkyl carbonyl amino group in R ⁷ from the R ^5, the same can be listed, including the preferred ones, and the like.

As the substituent in R ¹³ to R ¹⁵ , the C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group includes the above R ⁵ to R ⁷ , C1-C4 alkylcarbonylamino group substituted with the same group and the same thing including a preferable thing etc. are mentioned.

Among the above, R ¹³ to R ¹⁵ are each independently a hydrogen atom, a sulfo group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group substituted with a hydroxy group or a sulfo group. Is preferred. More preferably, one is a hydrogen atom and the other two are groups other than a hydrogen atom, or two are hydrogen atoms and the other one is a group other than a hydrogen atom, and the former is more preferable.
The substitution position of R ¹³ is not particularly limited, but the substitution position of the bond binding to Y is position 1, the substitution position of the bond with the azo group binding to group A is position 4, and the substitution position of R ¹⁵ is 5 The substitution position of R ¹⁴ and the R ¹⁴ position is the 2nd or 3rd position, with the 2nd position being preferred.

As the combination of R ¹³ to R ¹⁵ , R ¹³ is a sulfo group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group substituted with a hydroxy group or a sulfo group; R ¹⁴ is a hydrogen atom; R ¹⁵ is hydrogen A combination of an atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group substituted with a hydroxy group, or a C1-C4 alkoxy group substituted with a sulfo group is preferable. More preferably, C1-C4 alkoxy groups R ¹³ is substituted by a sulfo group, R ¹⁴ is a hydrogen atom, R ¹⁵ can be mentioned a combination of C1-C4 alkyl group. Particularly preferred is a combination in which R ¹³ is 3-sulfopropoxy, R ¹⁴ is a hydrogen atom, and R ¹⁵ is methyl.

Of the compounds represented by the above formula (1), one of the preferred ones is a compound represented by the above formula (101). The compound represented by the formula (101) is a compound in which the group A is represented by the formula (4) and the group B is represented by the formula (5) in the above formula (1).
In the formula (101), n, X, Y, Z, and R ¹ to R ⁸ have the same meaning as in the above formula (1), and include the same ones including preferable ones. R ¹⁰ to R ¹² and R ¹³ to R ¹⁵ represent the same meanings as in the above formulas (4) and (5), respectively, and include the same ones including preferred ones.
In formula (101), the substitution positions of R ⁵ to R ⁷ are preferably the same as those in formula (2), and more preferably the same as those in formula (3).

With respect to the substituents and substitution positions in the above formulas (1) to (5) and formula (101), a compound in which preferable ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to combinations of preferable ones and more preferable ones. As described above, in the formulas (6) to (7), n, the group A, the group B, and the ring in which R ¹ to R ⁸ are substituted include the ring represented by the broken line. ) Has the same meaning as in The same applies to preferable ones and combinations of preferable ones.

The salt of the compound represented by the formula (1) is a salt with an inorganic or organic cation. Among them, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium salts and ammonium salts, and as organic cations. Examples thereof include, but are not limited to, quaternary ammonium represented by the following formula (8). The free acid, its tautomer, and various salts thereof may be a mixture. For example, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt and ammonium salt may be used. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate; if multiple salts are included, change the ratio; etc. A mixture having physical properties can also be obtained.

Z ^1, Z ^2, Z ^3, Z ⁴ in the formula (8) each independently represents a hydrogen atom, an alkyl group, hydroxyalkyl groups and hydroxyalkoxy alkyl group selected from the group consisting of groups, Z ¹ to Z ^At least one of ⁴ is a group other than a hydrogen atom.
In the formula (8), specific examples of the alkyl group in Z ¹ , Z ² , Z ³ and Z ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. Can be mentioned.
Specific examples of the hydroxyalkyl group include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl and 2-hydroxybutyl.
Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. A C1-C4 alkoxy C1-C4 alkyl group is mentioned.
Of these, hydroxyethoxy C1-C4 alkyl is preferred.
Particularly preferred are hydrogen atoms; hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, hydroxy And hydroxyethoxy C1-C4 alkyl groups such as ethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. .

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 in} the quaternary ammonium preferable as the above formula (8) are shown in Table 1 below.

The azo compound represented by the above formula (1) can be synthesized, for example, by the following method. In addition, the acidic functional group of the compound in each process shall be represented in the form of a free acid for convenience. In addition, n, X, Y, Z, group A, group B, and R ¹ to R ⁸ used as appropriate in the following formulas (9) to (12) have the same meaning as in the above formula (1). To express.
A compound represented by the following formula (9) is diazotized by a conventional method, and this and a compound represented by the following formula (10) are coupled by a conventional method to obtain a compound represented by the following formula (11).

The obtained compound represented by the formula (11) is diazotized by a conventional method, and then this and a compound represented by the following formula (12) are subjected to a coupling reaction by a conventional method, whereby the above formula (1) The azo compound of the present invention represented can be obtained.

The compound represented by the above formula (12) can be synthesized according to the method described in Patent Document 5. In addition, the compound represented by the above formula (9) is obtained by a conventional method using a monoazo compound represented by “A—N═NB—YH”, a 2,6-diaminobenzothiazole derivative, and “R ⁸ —. By synthesizing each of the three compounds represented by “ZH” and reacting these compounds with cyanuric halide such as cyanuric chloride by a conventional method, it can be easily obtained. The compound represented by “R ⁸ —ZH” can be synthesized or can be obtained as a commercial product.

Although it does not specifically limit as a suitable specific example of the azo compound of this invention represented by the said Formula (1), The compound etc. which were listed in following Table 2 to Table 5 are mentioned.
In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience.

The diazotization of the compound represented by the above formula (9) is carried out by a method known per se. For example, using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of -5 to 20 ° C, preferably 5 to 10 ° C. Coupling of the diazotized compound of the compound represented by formula (9) and the compound represented by formula (10) is also carried out under conditions known per se. It is carried out at a temperature of, for example, −5 to 30 ° C., preferably 10 to 30 ° C. in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent). The compound represented by formula (9) and the compound represented by formula (10) are used in approximately stoichiometric amounts.

The diazotization of the compound represented by the formula (11) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. The coupling of the diazotized compound of the compound represented by the formula (11) and the compound represented by the formula (12) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C., preferably 10 to 30 ° C. and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to 10, and the pH value is adjusted by adding a base. As the base, the same ones as described above can be used. The compounds represented by formulas (11) and (12) are used in approximately stoichiometric amounts.

In order to make the azo compound represented by the formula (1) of the present invention into a desired salt, it is possible to salt out by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction. Alternatively, it is isolated in the form of a free acid by adding a mineral acid such as hydrochloric acid, and this is washed with water, acidic water or an aqueous organic medium as necessary to remove inorganic salts, and then in an aqueous medium. By neutralizing with a desired inorganic or organic base, a corresponding salt solution can be obtained. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. Further, the aqueous organic medium refers to water-containing organic substances miscible with water and / or so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride; ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above-mentioned formula (8). The halogen salt of the organic amine represented by these, etc. are mentioned. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide (ammonia water), or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of organic bases include, but are not limited to, organic amines such as quaternary ammoniums represented by the above formula (8) such as diethanolamine and triethanolamine. It is not something.

The ink composition of the present invention will be described. The aqueous ink composition containing the azo compound represented by the formula (1) of the present invention can dye a material made of cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabrics and paper. On the other hand, a typical use of the compound of the present invention is an ink composition dissolved in a liquid medium, and is particularly suitable as an ink composition for inkjet recording.

The reaction liquid containing the azo compound of the present invention represented by the above formula (1), for example, the reaction liquid after completion of the final process in the compound synthesis process, can be directly used for the production of the ink composition. However, it is first isolated by drying, eg spray drying; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; minerals such as hydrochloric acid, sulfuric acid, nitric acid The acid precipitation is carried out by adding an acid; or the acid precipitation with a combination of the above-mentioned salting out and acid precipitation; the azo compound of the present invention is isolated and the ink composition is prepared using the azo compound. You can also.

The ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the azo compound represented by the above formula (1) of the present invention. The balance is a composition using water as a medium. The ink composition of the present invention may further contain a water-soluble organic solvent, for example, 0 to 30% by mass, and an ink preparation agent, for example, 0 to 15% by mass. Further, if desired, other dyes may be included for the purpose of toning and the like within a range not impairing the effects of the present invention. Even in this case, the total mass of the pigment contained in the total mass of the ink composition including the pigment for toning may be in the above range. The pH of the ink composition is preferably 5 to 11 and more preferably 7 to 10 in terms of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less. The pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent, a surfactant, or the like as described later.

In the ink composition of the present invention, the azo compound represented by the formula (1) is dissolved in water and, if necessary, a water-soluble organic solvent (an organic solvent miscible with water), and further, an ink preparation is prepared as necessary. The formulation is added. The water-soluble organic solvent may function as a dye solubilizer, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, and the like, and the ink composition of the present invention. Is preferably contained. For the purpose of preparing a neutral black ink composition having no color, other toning dyes and the like may be appropriately added to the azo compound of the present invention. When this ink composition is used as an ink for an ink jet printer, the azo compound of the present invention has a low content of inorganic impurities such as metal cation chlorides such as sodium chloride and sulfates such as sodium sulfate. Is preferably used. The standard of the inorganic impurity content is approximately 1% by mass or less with respect to the total mass of the dye, and the lower limit may be equal to or less than the detection limit of the detection instrument, that is, 0%. In order to produce the azo compound of the present invention with less inorganic impurities, for example, a conventional method using a reverse osmosis membrane; or a dried product or wet cake of the azo compound of the present invention in a mixed solvent of C1-C4 alcohol such as methanol and water And then desalting the precipitate by filtration and drying.

Specific examples of the water-soluble organic solvent that can be used in the preparation of the ink composition include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol; A carboxylic acid amide such as dimethylformamide or N, N-dimethylacetamide; a lactam such as 2-pyrrolidone or N-methyl-2-pyrrolidone; 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexa Cyclic ureas such as hydropyrimido-2-one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2-propylene glycol 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, Mono-, oligo- or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as thiodiglycol or dithiodiglycol; polyols (triols) such as glycerin or hexane-1,2,6-triol; ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Le (butyl carbitol) C1-C4 alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; .gamma.-butyrolactone or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

Examples of ink preparations that are appropriately used in the preparation of the ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and antioxidants. Agents and / or surfactants. These drugs are described below.

Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. . These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.

Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone , Benzyl bromacetate-based or inorganic salt-based compounds. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide, and isothiazoline compounds include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4 -Isothiazoline-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and the like.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water); Alternatively, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate;

Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate or sodium uracil diacetate.

Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate or dicyclohexylammonium nitrite.

Examples of water-soluble UV absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Specific examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea, and the like.
As examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines or heterocyclic rings. .

Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates Salt polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate , Diethylsulfosuccinate, diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, or Examples include imidazoline derivatives.
Specific examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and the like. Ether type; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. Ester series; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, - dimethyl-1-hexyne-3-acetylene alcohol such as ol; for example, as other specific examples, Nissin Chemical Industry Co., Ltd., trade name Surfynol 104,105,82,465, Olfine STG and the like.
These ink preparation agents are used alone or in combination.

The ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. Further, in order to adjust the black color as an ink composition, other dyes having various hues in addition to the azo compound represented by the formula (1) of the present invention are included in a range not inhibiting the effect of the present invention. You may mix. In that case, black having a different hue or yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc.), orange (for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc. ), Brown, scarlet (for example, CI Direct Red 89), red (for example, CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red) 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226, etc.), magenta (for example C.I. Direct Red 227, etc.), can be violet, blue, navy, cyan, green, be used as a mixture of other colors of dye.

The ink composition of the present invention can be used in various fields, but is suitable for a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. The ink jet recording method is preferably used.

Next, the ink jet recording method of the present invention will be described. The ink jet recording method of the present invention is a method for recording on a recording material by using the ink composition of the present invention as an ink and discharging ink droplets of the ink according to a recording signal. The ink jet recording method of the present invention performs recording on a recording material using the ink composition of the present invention. There are no particular restrictions on the ink nozzles used at that time, and they can be appropriately selected according to the purpose. it can.
A known method, for example, a charge control method that ejects ink using electrostatic attraction; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; an electric signal is converted into an acoustic beam and the ink is irradiated And adopting an acoustic ink jet method that discharges ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Can do.
In the ink jet recording method, a method called a photo ink, in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentration in the ink is different with substantially the same hue. A system that improves image quality using a plurality of inks; a system that uses colorless and transparent ink, and the like are also included.

The colored product of the present invention is colored by the compound of the present invention represented by the formula (1) or an ink composition containing the compound, and more preferably by an inkjet recording method using an inkjet printer. The recording material is colored with the ink composition.
The recording material that can be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters. A transmission sheet is preferred.
The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; or inorganic fine particles capable of absorbing pigments in ink such as porous silica, alumina sol, and special ceramics, such as polyvinyl alcohol and polyvinylpyrrolidone. A method of coating the surface of the substrate together with the hydrophilic polymer; Those provided with such an ink receiving layer are usually called ink jet exclusive paper, ink jet exclusive film, glossy paper, or glossy film.

Of the above information transmission sheets, a sheet coated with a porous white inorganic material on the surface is particularly suitable for recording (printing) photographic images because of its high surface gloss and excellent water resistance. However, it is known that the images recorded in these images are greatly discolored by ozone gas. However, since the ink composition of the present invention is excellent in ozone gas resistance, a great effect is exhibited even when ink jet recording is performed on such a recording material.
An example of a typical commercially available sheet coated with the above porous white inorganic material is Canon Inc. Product name: Professional Photo Paper, Super Photo Paper, and Matt Photo Paper; Seiko Epson Product Name: Photographic Paper Crispia (High Gloss), Photographic Paper (Glossy), Photomat Paper; Nihon Hewlett-Packard Co., Ltd. Product Name: Advanced Photo Paper (Glossy); Fuji Film Co., Ltd. Name: Painted Photo Finishing Pro;

In order to record on a recording material such as an information transmission sheet by the ink jet recording method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of an ink jet printer, and the recording material is processed by a normal method. Can be recorded.
The inkjet recording method of the present invention comprises the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color ink such as green, blue (or violet) and red (or orange). A composition can also be used in combination.
The ink composition of each color is poured into each container, and each container is set at a predetermined position of the ink jet printer in the same manner as the container containing the black ink composition of the present invention, and used for ink jet recording.

The azo compound or a salt thereof of the present invention has high solubility in a medium containing water as a main component, is stable even when a high concentration aqueous solution or ink of the compound is stored for a long period of time, and the density of a printed image is high. It is very high and has features such as easy synthesis and low cost.
Since the azo compound of the present invention is excellent in water solubility, the filterability by a membrane filter in the process of producing the ink composition is good, and the ink composition containing the compound or the ink prepared from the ink composition Excellent storage stability and discharge stability. That is, the ink composition of the present invention containing the azo compound of the present invention is free from solid precipitation, physical property change, color change and the like after long-term storage, and has good storage stability. Further, the ink composition containing the azo compound of the present invention is suitably used for inkjet recording and writing instruments, and when recorded on plain paper and inkjet dedicated paper, the print density of the recorded image is very high and high. Even when a concentrated solution is printed, the image does not cause bronzing, is excellent in color rendering, and is excellent in various fastness properties such as water resistance and moisture resistance, particularly light resistance and ozone gas resistance. By using the black ink composition of the present invention in combination with a magenta, cyan and yellow ink composition, full-color ink jet recording excellent in various fastness properties and excellent in storage stability is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples.
In the text, “parts” and “%” are based on mass unless otherwise specified.
In the following formulas, functional groups such as sulfo and carboxy are expressed in the form of free acids.
Moreover, both the pH value and reaction temperature described below show measured values in the reaction system.
Further, the maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value was described in the examples for the measured compound.
The synthesized azo compounds of the present invention all showed a solubility of 100 g / L or more in water.

Example 1
(1)
40 parts of 6-nitrobenzothiazole were slowly added into 240 parts of 30% fuming sulfuric acid. After stirring this reaction liquid at 100-110 degreeC for 2 hours, it was dripped in about 10 minutes in 400 parts ice water. The precipitated solid was separated by filtration and dried to obtain 45 parts of a compound represented by the following formula (13). The obtained compound is added to 440 parts of water, adjusted to pH 7-8 with 25% aqueous sodium hydroxide solution, 4.4 parts of activated carbon and 0.8 part of anhydrous ferric chloride are added, and 80% hydrazine is stirred. 30.6 parts of monohydrate was added dropwise at 70 to 80 ° C. over about 30 minutes. After dropping, the reaction solution was stirred at 85 to 95 ° C. for 3 hours and cooled to room temperature. Insoluble matter was removed by filtration, and 50% sulfuric acid was added for acid precipitation, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound represented by the following formula (14).

(2)
A 25% aqueous sodium hydroxide solution is added to an aqueous solution containing a compound represented by the following formula (15) obtained by the method described in Patent Document 8 to adjust the pH to 3 to 4, and the compound represented by the formula (15) is contained. An aqueous solution was prepared.
On the other hand, with stirring, 12.9 parts of cyanuric chloride was added to 300 parts of ice water and suspended, and an aqueous solution containing the compound represented by the formula (15) prepared previously at a reaction temperature of 0 to 5 ° C. was added. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 3.5 to 4.5, and after stirring for 1 hour at the same temperature, the liquid temperature was adjusted to 40 to 50 ° C., and the above formula (14 The wet cake containing the compound represented by) was added. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 6.0 to 7.0, and after stirring for 1 hour at the same temperature, the liquid temperature was adjusted to 70 to 80 ° C., and 2-aminoethane was added to this liquid. 35 parts of sulfonic acid was added. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.5 to 8.5, and the mixture was stirred at the same temperature for 1 hour and cooled to room temperature. 35% hydrochloric acid was added to the reaction solution for acid precipitation, and the precipitated solid was separated by filtration and dried to obtain a solid containing a compound represented by the following formula (16).

(3)
The solid containing the compound represented by the formula (16) obtained in Example 1 (2) is added to 300 parts of 85% phosphoric acid, and 25 parts of 40% nitrosylsulfuric acid is added dropwise at 5 to 10 ° C. over 10 minutes with stirring. Then, a diazo reaction liquid was obtained by reacting for 3 hours.
An aqueous solution was obtained by adding 6.1 parts of a compound represented by the following formula (17), 7.0 parts of sulfamic acid, and then sodium hydroxide to 200 parts of water to adjust the pH to 5.0 to 5.5.
The above diazo reaction solution was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 30 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, 500 parts of acetone was added, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound represented by the following formula (18). The compound represented by the following formula (17) was obtained by the method described in JP-A No. 2004-083492.

(4)
The wet cake containing the compound represented by the formula (18) obtained in Example 1 (3) was dissolved in 150 parts of water, 4.1 parts of 35% hydrochloric acid was added, and the reaction temperature was 20-25 ° C. and 40%. A sodium nitrite aqueous solution (1.8 parts) was added dropwise over about 5 minutes and reacted for 1 hour to obtain a diazo reaction liquid.
On the other hand, by adding 2.4 parts of a compound represented by the following formula (19) obtained by the method described in Patent Document 8 and sodium hydroxide to 55 parts of water to adjust the pH to 7.5 to 8.0. An aqueous solution was obtained. The diazo reaction liquid obtained as described above was dropped into this aqueous solution at a reaction temperature of 20 to 30 ° C. for 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 160 parts of water, 350 parts of acetone was added, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 110 parts of water, 280 parts of acetone was added, and the precipitated solid was separated by filtration and dried to obtain 4.3 parts of a compound represented by the following formula (20) of the present invention. Was obtained as the sodium salt.
λmax: 595 nm.

Example 2
(A) Preparation of ink After obtaining the black ink composition of the present invention by mixing the components described in Table 6 below, impurities were separated by filtration with a 0.45 μm membrane filter, and the test ink was obtained. Got. This ink preparation is referred to as Example 2.
During the ink preparation, ion exchange water was used as the water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion exchange water was added to make the total amount 100 parts.

Table 6
Compound obtained in Example 1 3.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0 .1 (Product name: Surfinol 104, manufactured by Nissin Chemical)
Water + sodium hydroxide 77.4 parts Total 100.0 parts

Comparative Example As a comparative black pigment, the same procedure as in Example 2 was conducted except that the pigment represented by the following formula (21) disclosed in Example 2-6 of Patent Document 8 was used instead of the compound of Example. Comparative inks were prepared.

(B) Inkjet recording Using each ink obtained above, Canon's inkjet printer, product name PIXUS iP4100, as an information recording sheet (inkjet dedicated paper), HP product, product name: Advanced Photo Paper (Glossy) Inkjet recording was performed. At the time of recording, an image pattern was made so that the reflection density was obtained with several gradations, and a black recorded matter was obtained. The following evaluation test was performed using the obtained recorded matter as a test piece.

(C) Evaluation of recorded image
Each test piece obtained using each ink of Example 2 and the comparative example was evaluated for the density change of the image before and after the test for each of light resistance and ozone gas resistance. In addition, each test piece used what was dried at room temperature for 24 hours or more after printing.
The density change of the test piece is a gradation part where the black reflection density Dk value of the print image before the test is in a range of 1.1 to 1.3 using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye Was measured by measuring the color. In the measurement of the black reflection density Dk, DIN was used as a density reference, and the viewing angle was 2 degrees.
The test results are shown in Table 7.
The specific test method is as follows.

1) Ozone gas resistance test, manufactured by Suga Test Instruments Co., Ltd., trade name: A test piece was placed in an ozone weatherometer, and left for 24 hours under conditions of ozone concentration of 40 ppm, humidity of 60% RH, and temperature of 24 ° C. CIE L *, a *, and b * were measured for each test piece before and after ozone exposure, and a color difference ΔE was calculated using the following equation. ΔL *, Δa *, and Δb * mean differences between L *, a *, and b * before and after the test, respectively.

ΔE = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2

The test results were evaluated according to the following criteria. The evaluation results are shown in Table 7.
◎: ΔE is less than 10 ○: ΔE is 10 or more and less than 20 Δ: ΔE is 20 or more and less than 30 ×: ΔE is 30 or more

2) Light resistance test Suga Test Instruments Co., Ltd., product name: Low temperature xenon weatherometer XL75, test pieces were placed on each test piece under conditions of 100,000 Lux illuminance, humidity 60% RH, temperature 24 ° C. Time irradiation was performed. For each test piece before and after exposure to xenon light, CIE L *, a *, and b * were measured, and a color difference ΔE was calculated using the following equation. ΔL *, Δa *, and Δb * mean differences between L *, a *, and b * before and after the test, respectively.

ΔE = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2

The test results were evaluated according to the following criteria. The evaluation results are shown in Table 7.
○: ΔE is less than 10 Δ: ΔE is 10 or more and less than 20 ×: ΔE is 20 or more

3) Evaluation of color developability Using the above colorimetric system, the reflection density Dk value of black was measured for the darkest recorded portion of each test piece. The measured values are shown in Table 8 below. A larger Dk value indicates that the higher the print density is, the higher the density is.
4) Evaluation of color rendering properties In order to confirm whether or not the hue as black changes depending on the observation light source, CIE L *, a *, and b * were measured with a D65 light source, an F10 light source, and an A light source, respectively. For L *, a *, and b * measured with these three light sources, the color difference ΔE1 between the D65 light source and the F10 light source and the color difference ΔE2 between the F10 light source and the A light source were calculated from the following equations. ΔL1 *, Δa1 *, and Δb1 * are differences between L *, a *, and b * in the D65 light source and the F10 light source, and ΔL2 *, Δa2 *, and Δb2 * are L in the F10 light source and the A light source. The difference between *, a * and b * is represented respectively. ΔE1 and ΔE2 indicate that the smaller the color rendering property, the better.

ΔE1 = [(ΔL1 *) ² + (Δa1 *) ² + (Δb1 *) ² ] ^1/2

ΔE2 = [(ΔL2 *) ² + (Δa2 *) ² + (Δb2 *) ² ] ^1/2

The obtained ΔE1 and ΔE2 values are shown in Table 8 below.

Table 7
Ozone gas resistance Light resistance Example 2 ◎ ○
Comparative example ○ ○

Table 8
Dk value Color rendering property ΔE1 Color rendering property ΔE2
Example 2 2.01 3.9 2.6
Comparative Example 1.84 6.2 19.1

As is clear from the results in Table 7, both Example 2 and Comparative Example showed high light resistance, but for ozone gas resistance, Example 2 clearly showed superior results over Comparative Example. Indicated.
Further, as is clear from the results in Table 8, it can be seen that Example 2 has a clearly higher print density than the comparative example, and is very good in color rendering.
From the above results, the recorded image obtained with the ink containing the azo compound of the present invention is superior in ozone gas resistance as compared with the conventional one, and in particular, the high print density and good required for black for inkjet recording. It can be seen that it has excellent color rendering properties. Therefore, the azo compound of the present invention and the ink composition containing the azo compound are extremely suitable for recording, particularly for inkjet recording.

The ink composition containing the azo compound of the present invention is suitably used as a black ink for ink jet recording and writing instruments.

Claims (19)

An azo compound represented by the following formula (1) or a salt thereof,

[In Formula (1),
n is an integer from 0 to 2,
R ¹ is a carboxy group; a C1-C4 alkyl group; a C1-C4 alkyl group substituted with a carboxy group; a phenyl group; or a phenyl group substituted with a sulfo group;
R ² is a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a chlorine atom; a sulfo group; a C1-C4 alkyl group; or a C1-C4 alkoxy group;
R ⁵ to R ⁷ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group; a mono- or di-C1-C4 alkylamino group; As a substituent, a mono- or di-C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a C1-C4 alkylcarbonylamino group; Substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group N′-C1-C4 alkylureido group; N ′ substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group as a substituent -C1-C4 alkylureido group; phenylamino group; as a substituent, at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group, wherein the benzene ring is Substituted phenylamino group; benzoylamino group; benzene ring substituted with at least one group selected from the group consisting of chlorine atom, C1-C4 alkyl group, nitro group, sulfo group and carboxy group Benzoylamino group; phenylsulfonylamino group; or as a substituent, chlorine atom, C1-C4 alkyl , A nitro group, at least one group selected from the group consisting of sulfo and carboxy groups, phenylsulfonylamino groups in which the benzene ring is substituted; represent, respectively,
X, Y, and Z each independently represent an oxygen atom, a sulfur atom, or a group represented by the following formula (22);

[In formula (22), R ⁹ represents a hydrogen atom or a C1-C4 alkyl group. ],
R ⁸ is hydrogen atom; phenyl group; substituted with at least one group selected from the group consisting of hydroxy group, C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group and carboxy group A phenyl group; a C1-C4 alkyl group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group as a substituent. Each represents a group;
The group A represents a phenyl group; or a substituted phenyl group;
The group B represents a phenylene group; or a substituted phenylene group. ]. The azo compound or a salt thereof according to claim 1 represented by the following formula (2):

[In formula (2), n, X, Y, Z, group A, group B, R ¹ to R ⁸ represent the same meaning as in formula (1). ]. The azo compound or a salt thereof according to claim 1 or 2, represented by the following formula (3):

[In formula (3), n, X, Y, Z, group A, group B, and R ¹ to R ⁸ represent the same meaning as in formula (1). ]. The azo compound or a salt thereof according to any one of claims 1 to 3, wherein the group A is a group represented by the following formula (4):

[In Formula (4),
R ¹⁰ to ¹² each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a nitro group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of -C4 alkoxy group, hydroxy group, sulfo group and carboxy group; C1-C4 alkylcarbonylamino group; A C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group consisting of carboxy groups; a C1-C4 alkylsulfonyl group; or a group consisting of a hydroxy group, a sulfo group and a carboxy group as a substituent C1-C4 alkyls substituted with at least one group selected from It represents a; Honiru group. ]. The azo compound or a salt thereof according to any one of claims 1 to 4, wherein the group B is a group represented by the following formula (5):

[In Formula (5),
R ¹³ to ¹⁵ are each independently a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; as a substituent, at least one selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A C1-C4 alkoxy group substituted with a group; a C1-C4 alkylcarbonylamino group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent Represents a carbonylamino group; ]. The azo compound or a salt thereof according to claim 1 represented by the following formula (101):

[In the formula (101), n, X, Y, Z, and R ¹ to R ⁸ represent the same meaning as in the formula (1),
R ¹⁰ to ¹² each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a nitro group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C4 alkoxy group, a hydroxy group, a sulfo group and a carboxy group; a C1-C4 alkylcarbonylamino group; a hydroxy group and a carboxy group A C1-C4 alkylcarbonylamino group substituted with at least one group selected from the group; a C1-C4 alkylsulfonyl group; or a substituent selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with at least one group; And,
R ¹³ to ¹⁵ are each independently a hydrogen atom; a sulfo group; a C1-C4 alkyl group; a C1-C4 alkoxy group; as a substituent, at least one selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A C1-C4 alkoxy group substituted with a group; a C1-C4 alkylcarbonylamino group; or a C1-C4 alkyl substituted with at least one group selected from the group consisting of a hydroxy group and a carboxy group as a substituent Represents a carbonylamino group; ]. R ⁸ is a hydrogen atom; a phenyl group substituted with a sulfo group; a phenyl group substituted with a carboxy group; a C1-C4 alkyl group; or a substituent selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group The azo compound or a salt thereof according to any one of claims 1 to 6, which is a C1-C4 alkyl group substituted with at least one kind of group. The azo compound according to any one of claims 1 to 7, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, one of R ³ and R ⁴ is a hydrogen atom, and the other is a sulfo group. Its salt. R ⁵ and ⁷ each independently represent a hydrogen atom; a chlorine atom; a C1-C4 alkyl group; a C1-C4 alkoxy group substituted with a sulfo group; a C1-C4 alkylcarbonylamino group; or a benzoylamino group;
The azo compound or a salt thereof according to any one of claims 1 to 8, wherein R ⁶ is a hydrogen atom. The azo compound according to any one of claims 1 to 9, wherein R ⁵ is a sulfopropoxy group or a sulfobutoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom, a methyl group, an acetylamino group, or a benzoylamino group. Or a salt thereof. X, Y and Z are groups represented by the formula (22) wherein R ⁹ is a hydrogen atom,
The azo compound or a salt thereof according to any one of claims 1 to 10, wherein R ⁸ is a 2-sulfoethyl group. n is 1,
R ¹ is a C1-C4 alkyl group,
R ² is a cyano group,
Either one of R ³ or R ⁴ is a hydrogen atom, the other is a sulfo group,
R ⁵ is a C1-C4 alkoxy group substituted with a sulfo group,
R ⁶ is a hydrogen atom,
R ⁷ is a chlorine atom; a C1-C4 alkyl group; a C1-C4 alkylcarbonylamino group; or a benzoylamino group;
The substitution positions of R ⁵ , R ⁶ and R ⁷ are the 2-position, 6-position and 5-position, respectively, with the substitution position of the azo group bonded to the benzimidazolopyridone ring being 1-position,
X, Y and Z are groups represented by the formula (22) in which R ⁹ is a hydrogen atom,
R ⁸ is a C1-C4 alkyl group substituted with a sulfo group;
R ¹⁰ to R ¹² are each independently a hydrogen atom; a nitro group; a sulfo group; a carboxy group; or a C1-C4 alkoxy group;
R ¹³ is a sulfo group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a hydroxy group; or a C1-C4 alkoxy group substituted with a sulfo group;
R ¹⁴ is a hydrogen atom,
R ¹⁵ is a hydrogen atom; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a hydroxy group; or a C1-C4 alkoxy group substituted with a sulfo group;
The azo compound or a salt thereof according to claim 6. n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
One of R ³ and R ⁴ is a hydrogen atom, the other is a sulfo group,
R ⁵ is a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
The substitution positions of R ⁵ , R ⁶ and R ⁷ are the 2-position, 6-position and 5-position, respectively, with the substitution position of the azo group bonded to the benzimidazolopyridone ring being 1-position,
X, Y and Z are all groups represented by formula (22) wherein R ⁹ is a hydrogen atom,
R ⁸ is a 2-sulfoethyl group,
Two of R ^{10 to} R ¹² are sulfo groups and one is a hydrogen atom;
The azo compound or a salt thereof according to claim 6, wherein R ¹³ is a sulfopropoxy group, R ¹⁴ is a hydrogen atom, and R ¹⁵ is a methyl group. An ink composition comprising at least one azo compound or salt thereof according to any one of claims 1 to 13 as a coloring matter. 15. An ink jet recording method in which recording is performed on a recording material by using the ink composition according to claim 14 as ink and ejecting ink droplets of the ink in accordance with a recording signal. The inkjet recording method according to claim 15, wherein the recording material is an information transmission sheet. The inkjet recording method according to claim 16, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. An ink jet printer loaded with a container containing the ink composition according to claim 14. A colored body colored with the azo compound or a salt thereof according to any one of claims 1 to 13.