JP2009132794A - Azo compound, ink composition, method for recording, and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye compound for black ink and an ink composition thereof, having high solubility in a medium comprising water as a main component, stable even when preserving its aqueous solution at a high concentration and its ink over a long period of time, having a very high density of printed images, not causing bronzing in the images even when printing its solution at a high concentration and excellent in fastness of the printed images, particularly both excellent in light fastness and ozone gas resistance. <P>SOLUTION: An azo compound in the form of a free acid is represented by formula (1) (wherein, R<SP>1</SP>represents an unsubstituted or a substituted 1-4C alkyl group or the like; R<SP>2</SP>represents a cyano group or the like; R<SP>3</SP>and R<SP>4</SP>represent each independently a hydrogen atom or the like; R<SP>5</SP>to R<SP>7</SP>represent each independently a hydrogen atom or the like; and a ring in which R<SP>5</SP>to R<SP>7</SP>are substituted represents a benzene ring). <P>COPYRIGHT: (C)2009,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 thereby.

A recording method using an inkjet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact, so there is little noise and quietness, and it is easy to reduce the size and speed. Expected. Conventionally, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as fountain pens, felt-tip pens, and inks for inkjet printing. In these water-based inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. The water-soluble dye used is required to have a particularly high solubility in water and a 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, gas resistance and moisture resistance.

Among these, the gas resistance is resistance to a phenomenon in which ozone gas having an oxidizing action existing 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 considered as a main causative substance that further promotes the discoloration and fading phenomenon of inkjet print images, and in particular, ozone gas resistance is regarded as important. 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 or the like is remarkably observed on such recording paper. Since this discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, improvement of gas resistance is one of the most important issues in the ink jet printing method.

In the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet printing and the colored bodies colored thereby will be further improved in light resistance, gas resistance, moisture resistance and water resistance. There is a strong demand for improvement.

Various hue inks 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, but they have not yet provided a pigment that sufficiently satisfies the market demand. 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 water resistance and moisture resistance, insufficient light resistance and gas resistance, and poor metamerism. A polyazo dye having an extended conjugated system generally has problems such as low water solubility, a bronzing phenomenon in which a recorded image partially has a metallic luster, and insufficient light resistance and gas resistance. Similarly, many azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which is undesirable for biological safety and environmental problems, and extremely resistant to gas. There are problems such as weakness.

Examples of black compounds (black pigments) for ink-jet inks that have been improved with respect to gas resistance, which have become the most important issues in recent years, include the compounds described in Patent Documents 1 and 2, for example. These compounds do not sufficiently satisfy the market demand for gas resistance and are not sufficient for light resistance. Moreover, as an azo compound having a benzimidazolopyridone skeleton which is one of the characteristics of the black pigment of the present invention, there are descriptions in Patent Documents 3 to 6 and the like. Patent Documents 4 and 5 also disclose trisazo compounds, but these trisazo compounds have a symmetric structure in which two benzimidazolopyridone skeletons are further bonded by azo structures to both ends of a linking group containing an azo structure. Nothing similar to the asymmetric azo compound of the present invention is disclosed, and no tetrakisazo compound 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 black trisazo compound for inkjet ink having excellent ozone gas resistance include compounds described in Patent Document 7.

JP 2003-183545 A JP 2003-201412 A WO2004 / 050768 International Publication Pamphlet German Patent No. 2000004488 German Patent No. 2023295 JP 05-134435 A International Publication Pamphlet of WO2005 / 054374

An object of the present invention is to provide an azo compound or a salt thereof used for a black ink particularly suitable for inkjet printing, and an ink composition containing the compound. Hereinafter, the azo compound of the present invention or a salt thereof is simply referred to as “azo compound of the present invention”. The azo compound of the present invention is a black pigment, has high solubility in a medium containing water as a main component, is stable even when a high-concentration aqueous solution and ink are stored for a long period of time, and the density of a printed image is very high. Even when a high-concentration solution is printed on photographic image-quality inkjet paper, bronzing does not occur in the image, and a printed black image with excellent fastness, particularly light resistance and ozone gas resistance is obtained. In addition, it has features such as easy synthesis and low cost.

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),
R ¹ represents an unsubstituted or carboxy-substituted C1-C4 alkyl group; an unsubstituted or sulfo-substituted phenyl group; or a carboxy group,
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; a methyl group; a chlorine atom; or a sulfo group;
R ⁵ to R ⁷ are each independently a hydrogen atom; carboxyl group; sulfo group; hydroxy group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group C1-C4 alkoxy group substituted with a group, a sulfo group or a carboxy group; unsubstituted or a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group or a carboxy group; C1 substituted with an unsubstituted or carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; a ureido group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 N ′-(C1-C8) substituted with an alkoxy group, a sulfo group or a carboxy group Ruylureido group; N′-phenyl in which the benzene ring is unsubstituted or substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group Represents a ureido group,
The ring in which R ⁵ to R ⁷ are substituted represents a benzene ring when no ring represented by a broken line is present; or a naphthalene ring when a ring represented by a broken line is present;
n represents 0 or 1,
The substitution position of the (SO ₃ H) n group is c or d,
The substitution position of the azo group to which the benzimidazolopyridone ring substituted by R ¹ to R ⁴ is bonded is a, b, c or d, but they are not substituted at the same position,
The group A represents a substituted phenyl group or a substituted naphthyl group, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group, or a chlorine atom; a fluorine atom; Atom; bromine atom; cyano group; nitro group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group C1-C4 alkoxy group substituted; C1-C4 alkylthio group unsubstituted or substituted with a hydroxy group, sulfo group or carboxy group; C1-C4 unsubstituted or substituted with a hydroxy group, sulfo group or carboxy group Alkylsulfonyl group; unsubstituted or substituted with a carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; a benzene ring is unsubstituted, or a methyl group, a nitro group or a chlorine atom A benzenesulfonylamino group substituted with a ureido group; an N '-(C1-C8) alkylureido group substituted with an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group; a benzene ring And N′-phenylureido group substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group; A group represented by the following formula (2); a group selected from the group consisting of:

{In Formula (2),
The group B represents a substituted phenyl group or a substituted naphthyl group, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a fluorine atom; Atom; bromine atom; cyano group; nitro group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group A substituted C1-C4 alkoxy group; an unsubstituted or C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; Benzene ring is unsubstituted, sulfo group, carboxy group, unsubstituted A benzoylamino group substituted with a 1-C4 alkyl group; and a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; a ureido group; an unsubstituted group, or a hydroxy group, A substituted C1-C4 alkoxy group, a N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group; and the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted group A N′-phenylureido group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a sulfo group and a carboxy group; a group selected from the group consisting of: }. ],
2)
In equation (1),
The azo compound or salt thereof according to 1) above, wherein the group A is a group represented by the following formula (3):

[In Formula (3),
R ⁸ to R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a chlorine atom; A nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-C4 substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group An alkoxy group, unsubstituted or a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or a C1-C8 alkylcarbonylamino group substituted with a carboxy group; an unsubstituted benzene ring; Or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group. Benzoylamino group; benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, nitro group or chlorine atom; ureido group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group or carboxy N ′-(C1-C8) alkylureido group substituted with a group; or the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group and a carboxy group An N′-phenylureido group substituted with a group selected from the group consisting of
R ¹¹ is a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group Unsubstituted C1-C4 alkyl group; unsubstituted or C1-C4 alkoxy group substituted with a hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group; unsubstituted, or A C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring is unsubstituted, or a sulfo group, a carboxy group; A benzoylamino group substituted with an unsubstituted C1-C4 alkyl group; A benzenesulfonylamino group in which the zen ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; unsubstituted or N ′ substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group -(C1-C8) alkylureido group; a group in which the benzene ring is unsubstituted or selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group; A group selected from the group consisting of a substituted N′-phenylureido group; and a group represented by formula (2) in claim 1; ],
3)
In equation (1),
(SO ₃ H) The substitution position of the n group is d, and the substitution position of the azo group to which the benzimidazolopyridone ring substituted by R ¹ to R ⁴ is c is 1) or 2) An azo compound or a salt thereof,
4)
The azo compound or a salt thereof according to the above 1) represented by the following formula (4):

[In formula (4), R ¹ to R ⁷ , n and group A have the same meaning as in formula (1). ],
5)
In equation (4),
R ⁵ is a sulfo group; unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ⁶ is a hydrogen atom,
R ⁷ is an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring is unsubstituted, or a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; A substituted benzoylamino group; a ureido group; an N ′-(C1-C8) alkylureido group substituted by an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group; 4 above which is a substituted or substituted N′-phenylureido group with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group and a carboxy group; ) Or an azo compound thereof,
6)
In equation (1),
The azo compound or a salt thereof according to any one of 1) to 5) above, wherein the group A is a group represented by the following formula (5):

[In Formula (5),
R ¹² is a hydrogen atom; a sulfo group; a carboxy group; a nitro group; an unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ¹³ represents a hydrogen atom; a sulfo group; an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group. A C4 alkoxy group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; A ureido group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group,
R ¹⁴ is a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1- C1-C4 alkoxy group substituted with C4 alkoxy group, sulfo group or carboxy group; unsubstituted or C1-C4 alkylsulfonyl group substituted with hydroxy group, sulfo group or carboxy group; unsubstituted or substituted with carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; an unsubstituted or hydroxy group or an unsubstituted C1-C4 N ′-(C1-C8) substituted with an alkoxy group, a sulfo group or a carboxy group Alkylureido group; N′— in which the benzene ring is unsubstituted or substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group A phenylureido group; a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; and a group represented by formula (2) in claim 1; Each represents a substituent. ],
7)
In equation (5),
R ¹³ is a hydrogen atom or a sulfo group,
R ¹⁴ is a sulfo group; a nitro group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group A benzoylamino group; an azo compound or a salt thereof according to 6) above, wherein the benzene ring is unsubstituted, or is a benzenesulfonylamino group substituted with a methyl group, a nitro group or a chlorine atom;
8)
In equation (5),
R ¹² is a sulfo group; a carboxy group; an unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ¹³ is an unsubstituted C1-C4 alkyl group; unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; Or a benzoylamino group substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; a ureido group; an unsubstituted group; Or an N ′-(C1-C8) alkylureido group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group,
The azo compound or the salt thereof according to 6) above, wherein R ¹⁴ is a group represented by formula (2) in claim 1;
9)
The azo compound or a salt thereof according to 6) above, wherein the group B in the group represented by the formula (2) described in 1) is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom; a sulfo group; an unsubstituted C1-C4 alkyl group; a hydroxy group; a benzenesulfonyloxy in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group, or a chlorine atom A nitro group; a sulfamoyl group; an unsubstituted or C1-C4 alkoxy group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring Is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; unsubstituted or substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group, or a carboxy group N ′-(C1-C8) alkylureido group; benzene ring is unsubstituted or hydroxy group An N′-phenylureido group substituted with a group selected from the group consisting of an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group and a carboxy group; or the benzene ring is unsubstituted, or It represents a benzenesulfonylamino group which may be substituted with a methyl group, a nitro group or a chlorine atom. ],
10)
The azo compound or a salt thereof according to 6) above, wherein the group B in the group represented by the formula (2) described in 1) is a group represented by the following formula (7):

[In Formula (7),
R ¹⁹ to R ²¹ are each independently a hydrogen atom; a carboxy group; a sulfo group; a fluorine atom; a chlorine atom; a bromine atom; a cyano group; a nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; Hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, C1-C4 alkoxy group substituted with sulfo group or carboxy group; unsubstituted or C1 substituted with hydroxy group, sulfo group or carboxy group -C4 alkylsulfonyl group; C1-C8 alkylcarbonylamino group unsubstituted or substituted with a carboxy group; benzoylamino where the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group Group: unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group Or a N ′-(C1-C8) alkylureido group substituted with a carboxy group; the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group An N′-phenylureido group substituted with a group selected from the group consisting of a group; and a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom. ],
11)
The azo compound or a salt thereof according to any one of 1) to 10) above, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group,
12)
In equation (4),
n is 1,
R ⁵ is a sulfo C3-C4 alkoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
Group A is a group represented by the following formula (5),

[In Formula (5),
R ¹² is a sulfo group or a sulfo C3-C4 alkoxy group,
R ¹³ is a methyl group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group; a ureido group; an unsubstituted or substituted N ′-(C1- C8) an alkylureido group,
R ¹⁴ represents a group represented by the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to 4) above, wherein the group B in the formula (2) according to claim 1 is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom; a sulfo group; a benzene ring unsubstituted or substituted with a methyl group, nitro group or chlorine atom; a benzenesulfonyloxy group; a nitro group; unsubstituted or sulfo Each represents a C1-C4 alkoxy group substituted by a group or a carboxy group. ],
13)
In Formula (4), n is 1,
R ⁵ is a sulfo group or a sulfo C3-C4 alkoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group; a ureido group; an unsubstituted, or a N ′-(C1- C8) an alkylureido group,
Group A is a group represented by the following formula (5),

[In Formula (5),
R ¹² is a sulfo group or a sulfo C3-C4 alkoxy group, and R ¹³ is a methyl group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzoylamino group; a ureido group; An N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group,
R ¹⁴ represents the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to the above 4), wherein the group B in the formula (2) described in the above 1) is represented by the following formula (7):

[In Formula (7),
R ¹⁹ to R ²¹ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a sulfamoyl group; an unsubstituted or a C1-C4 alkylsulfonyl substituted with a hydroxy group, a sulfo group or a carboxy group A C1-C8 alkylcarbonylamino group that is unsubstituted or substituted with a carboxy group; a benzene ring that is unsubstituted or a benzoylamino group that is substituted with a sulfo group or a carboxy group; or a benzene ring that is unsubstituted or methyl Benzenesulfonylamino group substituted by a group, a nitro group or a chlorine atom, respectively. ],
14)
In Formula (4), n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
R ³ is a hydrogen atom,
R ⁴ is a sulfo group,
R ⁵ is a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
A group represented by the following formula (5):

[In Formula (5),
R ¹² is a sulfo group or a sulfopropoxy group,
R ¹³ is a methyl group; an acetylamino group; a carboxyethylcarbonylamino group; a benzoylamino group; an N′-sulfoethylureido group;
R ¹⁴ represents the formula (2) according to claim 1. ],
The azo compound or the salt thereof according to 4) above, wherein the group B in the formula (2) described in 1) is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ , R ¹⁷ and R ¹⁸ are a hydrogen atom or a sulfo group, and at least two of R ¹⁵ , R ¹⁷ and R ¹⁸ are a sulfo group,
R ¹⁶ represents a hydrogen atom. ],
15)
In Formula (4), n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
R ³ is a hydrogen atom,
R ⁴ is a sulfo group,
R ⁵ is a sulfo group or a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group or an N′-sulfoethylureido group,
A group represented by the following formula (5):

[In the formula (5), R ¹² is a sulfo group or a sulfopropoxy group,
R ¹³ is a methyl group; an acetylamino group; a carboxyethylcarbonylamino group; a benzoylamino group; or an N′-sulfoethylureido group,
R ¹⁴ represents a group represented by the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to the above 4), wherein the group B in the formula (2) described in the above 1) is represented by the following formula (7):

[In formula (7), R ¹⁹ represents a hydrogen atom or a sulfo group;
R ²⁰ is a sulfo group; a chlorine atom; or a nitro group,
R ²¹ is a hydrogen atom or a sulfo group,
At least one of R ¹⁹ to R ²¹ represents a sulfo group. ],
16)
An ink composition comprising at least one azo compound or salt thereof according to any one of 1) to 15) as a pigment;
17)
An ink-jet printing method comprising recording on a recording material by ink-jet printing using the ink composition described in 16) above;
18)
The inkjet printing method according to 17) above, wherein the recording material in the inkjet printing method is an information transmission sheet,
19)
The inkjet printing method according to 18) above, wherein the information transmission sheet contains a porous white inorganic substance,
20)
An ink jet printer loaded with a container containing the ink composition according to 16),
21)
A colored product colored with the azo compound or salt thereof according to any one of 1) to 15) above;
About.

Since the azo compound of the present invention is excellent in water solubility, it has good filterability with a membrane filter in the production process of the ink composition, and is excellent in stability during storage and ejection stability of the recording liquid. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. The ink composition of the present invention is characterized by containing at least one azo compound of the present invention. The ink composition is suitably used for ink jet printing and writing instruments. When recording on plain paper and ink jet dedicated paper, the recording density of the recorded image is very high, and the image is printed even when a high concentration solution is printed. In addition, it does not cause bronzing and has excellent fastness, especially light resistance and ozone gas resistance. When used in combination with ink compositions containing magenta, cyan and yellow dyes, full-color inkjet printing with excellent fastness and storage stability is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet printing.

Hereinafter, the present invention will be described in detail.
The azo compound represented by the formula (1) has a tautomer, and as the tautomer, in addition to the compound of the formula (1), the following formulas (8), (9), (10), ( 11) and (12) can be considered. These compounds are also included in the present invention. In formulas (8) to (12), n, R ^{1 to} R ⁷ , a, b, c, d and group A have the same meaning as in formula (1) above.

When R ¹ in Formula (1) is an unsubstituted or carboxy-substituted C1-C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples thereof include unsubstituted straight chain such as methyl, ethyl, n-propyl and n-butyl; unsubstituted branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl; carboxymethyl, Carboxy-substituted ones such as 2-carboxyethyl;

When R ¹ in the above formula (1) is an unsubstituted or sulfo-substituted phenyl group, specific examples thereof include phenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5 -Disulfophenyl etc. are mentioned.

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); When each group of R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in Formula (7) is an unsubstituted C1-C4 alkyl group, the alkyl group may be linear or branched. A straight chain is more preferable. Specific examples thereof include linear ones such as methyl, ethyl, n-propyl and n-butyl; branched ones such as isopropyl, isobutyl, sec-butyl and tert-butyl;

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); Each group of R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in (7) is unsubstituted or a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group In the case of a C1-C4 alkoxy group substituted with a group, the alkoxy moiety may be either linear or branched, but is more preferably linear. Specific examples thereof include unsubstituted straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; unsubstituted branched chain such as isopropoxy, sec-butoxy and tert-butoxy; 2-hydroxyethoxy Hydroxy substituted ones such as 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxy Alkoxy substituted such as butoxy and n-propoxybutoxy; hydroxy C1-C4 alkoxy substituted such as 2-hydroxyethoxyethoxy; carboxyl such as carboxymethoxy, 2-carboxyethoxy and 3-carboxypropoxy Those Bokishi substituted; 3-sulfopropoxy, those sulfo-substituted and 4-sulfobutoxy; and the like.

When the substituent of the group A in formula (1) and R ^{5 to} R ⁷ are unsubstituted or a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group or a carboxy group, the alkyl moiety is linear or Either a branched chain may be used, but a straight chain is more preferable. Specific examples thereof include, for example, unsubstituted straight chain such as methylthio, ethylthio, n-propylthio, n-butylthio; unsubstituted branched chain such as isopropylthio, isobutylthio, sec-butylthio, t-butylthio; 2 -Hydroxy-substituted ones such as hydroxyethylthio, 2-hydroxypropylthio, 3-hydroxypropylthio; sulfo-substituted ones such as 2-sulfoethylthio, 3-sulfopropylthio; 2-carboxyethylthio, 3-carboxy Carboxy-substituted ones such as propylthio and 4-carboxybutylthio;

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); When each group of R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in (7) is an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group, the alkyl moiety is Either a chain or a branched chain may be used, but a straight chain is more preferable. Specific examples thereof include unsubstituted straight chain such as acetylamino, propionylamino, butyrylamino, valerylamino, hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino; isobutyrylamino, pivaloylamino, isovale Unsubstituted branched chain such as arylamino and 2-ethylhexanoylamino; carboxy-substituted one such as 3-carboxypropionylamino and 4-carboxybutyrylamino; and the like.

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in (7) are benzoyl groups in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group. When it is an amino group, specific examples thereof include, for example, benzoylamino; sulfo-substituted ones such as 2-sulfobenzoylamino; carboxy-substituted ones such as 2-carboxybenzoylamino and 2,5-dicarboxybenzoylamino; 3 -Alkyl-substituted ones such as methylbenzoylamino, 4-methylbenzoylamino, 4-ethylbenzoylamino, 4-propylbenzoylamino; and the like.

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); N) wherein each group of R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in (7) is unsubstituted or substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group When it is a '-(C1-C8) alkylureido group, the alkyl moiety may be either a straight chain or a branched chain, and both are preferred. Either mono- or di-substituted ureido may be used, and both are preferred. Specific examples of the mono-substitution include, for example, N'-ethylureido, N '-(n-propyl) ureido, N'-(n-butyl) ureido, N '-(n-pentyl) ureido, N'-( n-hexyl) ureido, N ′-(n-heptyl) ureido, N ′-(n-octyl) ureido, etc., non-substituted straight chain; N′-isopropylureido, N′-isobutylureido, N ′ Unsubstituted branched chain such as-(t-butyl) ureido and N '-(2-ethylhexyl) ureido; N'-(2-hydroxyethyl) ureido, N '-(4-hydroxybutyl) ureido and the like Hydroxy-substituted ones; alkoxy-substituted ones such as N ′-(2-methoxyethyl) ureido, N ′-(2-ethoxyethyl) ureido, N′N ′-(2-methoxyethyl) methylureido; N ′ -(2-sulfoethyl) Sulfo-substituted compounds such as raid; N ′-(2-carboxymethyl) ureido, N ′-(2-carboxyethyl) ureido, N ′-(3-carboxypropyl) ureido, N ′-(4-carboxybutyl) Carboxyl-substituted ones such as ureido and N ′-(6-carboxyhexyl) ureido; Specific examples of disubstitution include unsubstituted straight chain such as N′N′-diethylureido and N′N′-di (n-butyl) ureido; and N′N′-di (isopropyl) ureido and the like. Substituted branched chain; hydroxy-substituted one such as N′N′-di (2-hydroxyethyl) ureido, N′N′-di (2-hydroxyisopropyl) ureido; N′N′-di (carboxymethyl) Carboxy-substituted ones such as ureido;

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹³ or R ¹⁴ in formula (5); Each of R ^{15 to} R ¹⁸ in 6) and R ^{19 to} R ²¹ in (7) is unsubstituted, a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group Or an N′-phenylureido group substituted with a carboxy group, and when the group has a substituent, the number of the substituent is usually 1 to 5, preferably 1 to 3, more preferably 1 or 2. Specific examples thereof include, for example, N′-phenylureido; hydroxy-substituted ones such as N ′-(4-hydroxyphenyl) ureido; alkyl-substituted ones such as N ′-(4-methylphenyl) ureido; N′- Alkoxy-substituted ones such as (4-methoxyphenyl) ureido and N ′-(4-ethoxyphenyl) ureido; Two alkoxy-substituted ones such as N ′-(2,5-diethoxyphenyl) ureido; N ′ Sulfo-substituted ones such as-(3-sulfophenyl) ureido and N '-(2,5-disulfophenyl) ureido; N'-(3-carboxyphenyl) ureido and N '-(3,5-dicarboxy Substituted by carboxy such as phenyl) ureido; substituted by alkoxy and alkyl such as N ′-(2-methoxy-5-methylphenyl) ureido; N ′-(2-me Carboxymethyl-5-sulfophenyl) those alkoxy and sulfo ureido or the like is substituted; N '- (2-carboxy-5-sulfophenyl) as the carboxy and sulfo ureido or the like is substituted; and the like.

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹⁴ in formula (5); in formula (6) R ^{15 to} R ¹⁸ ; and R ^{19 to} R ²¹ in (7), when each group is unsubstituted or a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group, the alkyl moiety May be either linear or branched, but is preferably linear. Specific examples thereof include, for example, unsubstituted ones such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl; hydroxy-substituted ones such as hydroxyethylsulfonyl, 2-hydroxypropylsulfonyl; 2-sulfoethylsulfonyl, 3-sulfo Sulfo-substituted ones such as propylsulfonyl; carboxy-substituted ones such as 2-carboxyethylsulfonyl and 3-carboxypropylsulfonyl; and the like.

Group A and R ^{5 to} R ⁷ in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ¹⁴ in formula (5); in formula (6) In the case where each group of R ^{15 to} R ¹⁸ ; and R ^{19 to} R ²¹ in (7) is a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom, Examples include benzenesulfonylamino; alkyl-substituted ones such as 4-toluenesulfonylamino; nitro-substituted ones such as 4-nitrobenzenesulfonylamino; those substituted with a chlorine atom such as 4-chlorobenzenesulfonylamino; Be

Group A in formula (1) or (4); group B in formula (2); R ^{8 to} R ¹¹ in formula (3); R ^{15 to} R ¹⁸ in formula (6); and R ¹⁹ in formula (7) When each group of R ²¹ is a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group and a chlorine atom, specific examples thereof include, for example, benzenesulfonyloxy; 4-toluenesulfonyloxy And the like; methyl-substituted ones such as 4-nitrobenzenesulfonyloxy; those substituted with a chlorine atom such as 4-chlorobenzenesulfonyloxy; and the like.

Preferred R ¹ in the formula (1) is a linear C1-C4 alkyl group such as methyl, ethyl, n-propyl, n-butyl; a branched C1-C4 alkyl group such as t-butyl; a carboxy substitution such as carboxymethyl A C1-C4 alkyl group; an unsubstituted or sulfo-substituted phenyl group such as phenyl, 4-sulfophenyl; or a carboxy group, more preferably methyl, n-propyl, carboxymethyl, 4-sulfophenyl, and still more preferably. Is methyl, n-propyl.

A preferred combination of R ¹ and R ² in formula (1) is R ¹ is methyl and R ² is cyano, or R ¹ is methyl and R ² is carbamoyl.

Preferred R ³ and R ⁴ than in equation (1) is a hydrogen atom, a methyl or sulfo, preferably R ³ and the combination of R ⁴ is R ³ is R ⁴ is sulfo a hydrogen atom or R ³ is sulfo, R ⁴ is a hydrogen atom.

More preferable R ⁵ to R ⁷ in the formula (1) are a hydrogen atom, carboxyl, sulfo, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxy. Methoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, N ′-(2-sulfoethyl) ureido, N ′-(2-carboxyethyl) Ureido, N ′-(3-sulfophenyl) ureido, N ′-(3,5-dicarboxyphenyl) ureido and the like, more preferably hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2- Sulfoethoxy, 3-sulfopropoxy, 4-sulfobut Si, carboxymethoxy, N ′-(2-sulfoethyl) ureido, N ′-(2-carboxyethyl) ureido, more preferably hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy, N ′-( 2-sulfoethyl) ureido.

Preferred substituents of the group A in the formula (1) include cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxy Ethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, 4 -Toluenesulfonyloxy, 4-toluenesulfonylamino, N '-(2-sulfoethyl) ureido, N'-(2-carboxyethyl) ureido, N '-(3-sulfophenyl) ureido, N'-(3,5 - Ruboxyphenyl) ureido, a group represented by the formula (2), and the like, more preferably carboxyl, methyl, sulfo, sulfamoyl, methylsulfonyl, hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, 3-sulfopropoxy , Acetylamino, 3-carboxypropionylamino, benzoylamino, N ′-(2-sulfoethyl) ureido, a group represented by formula (2), more preferably carboxyl, nitro, methyl, sulfo, 3-sulfo Propoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, N ′-(2-sulfoethyl) ureido, a group represented by the formula (2). The group A has 1 to 4, preferably 1 to 3 of these substituents.

Preferred substituents of the group B in the formula (2) include cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, chlorine atom, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoyl Amino, 4-toluenesulfonyloxy, 4-toluenesulfonylamino, N ′-(2-sulfoethyl) ureido, N ′-(2-carboxyethyl) ureido, N ′-(3-sulfophenyl) ureido, N ′-( , 5-dicarboxyphenyl) ureido and the like, more preferably carboxy, methyl, sulfo, sulfamoyl, 3-sulfopropylsulfonyl, chlorine atom, nitro, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfo Benzoylamino and 2-carboxybenzoylamino, and more preferably carboxy, sulfo, chlorine atom, nitro, and acetylamino. The group B has 1 to 4, preferably 1 to 3 of these substituents.

A preferred group A in formula (1) is represented by formula (3).
Preferred R ⁸ to R ¹⁰ in the formula (3) are a hydrogen atom, carboxyl, sulfo, sulfamoyl, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy , Carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, 4-toluenesulfonyloxy, 4-toluenesulfonylamino, N ′-(2 -Sulfoethyl) ureido, N '-(2-carboxyethyl) ureido, N'-(3-sulfophenyl) ureido, N '-(3,5-dicarboxyphenyl) ureido and the like, more preferably a hydrogen atom , Carboxyl, methyl, sulfo 3-sulfopropoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, N ′-(2-sulfoethyl) ureido, more preferably methyl, sulfo, 3-sulfopropoxy, N ′-(2-sulfoethyl) Ureid.

Preferable R ¹¹ in the formula (3) is a hydrogen atom, cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxy Ethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, 4 -Toluenesulfonyloxy, 4-toluenesulfonylamino, N '-(2-sulfoethyl) ureido, N'-(2-carboxyethyl) ureido, N '-(3-sulfophenyl) ureido, N'-(3,5 -Zical Boxyphenyl) ureido, formula (2), etc., more preferably carboxy, sulfo, sulfamoyl, 3-sulfopropylsulfonyl, nitro, 3-sulfopropoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, formula (2) More preferred are carboxyl, nitro, sulfo, acetylamino, 3-carboxypropionylamino, and a group represented by formula (2).

A preferred compound in formula (1) is represented by formula (4).
As a preferable combination of R ⁵ to R ⁷ in the formula (4), R ⁵ is sulfo, R ⁶ is a hydrogen atom, R ⁷ is N ′-(2-sulfoethyl) ureido, or R ⁵ is 3-sulfopropoxy, R ⁶ is a hydrogen atom and R ⁷ is methyl.

A preferable group A in the formula (1) is represented by the formula (5). As the group A, the formula (5) is more preferable than the formula (3).
Preferred R ¹² in the formula (5) is carboxy, sulfo, nitro, sulfamoyl, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy. More preferably carboxy, sulfo, 3-sulfopropoxy, and still more preferably carboxy, sulfo.
Preferred examples of R ¹³ include a hydrogen atom, carboxyl, sulfo, sulfamoyl, methyl, methoxy, ethyl, ethoxy, 3-sulfopropoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2- Carboxybenzoylamino, 4-toluenesulfonylamino, N ′-(2-sulfoethyl) ureido, N ′-(2-carboxyethyl) ureido, N ′-(3-sulfophenyl) ureido, N ′-(3,5- Dicarboxyphenyl) ureido and the like, more preferably hydrogen atom, methyl, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, N ′-(2-sulfoethyl) Ureido, N '-(3-s Hofeniru) ureido, more preferably a hydrogen atom, methyl, acetylamino, 3-carboxy-propionylamino, benzoylamino, N '- (2-sulfoethyl) ureido.
Preferred examples of R ¹⁴ include a hydrogen atom, a chlorine atom, cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, methyl, methoxy, 3-sulfopropoxy, acetylamino , 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, 4-toluenesulfonylamino, a group represented by formula (2), and the like, more preferably carboxy, sulfo, sulfamoyl 3-sulfopropylsulfonyl, nitro, acetylamino, 3-carboxypropionylamino, benzoylamino, a group represented by the formula (2), more preferably carboxyl, nitro, sulfo, acetylamino, 3-carboxy Boki Cipro propionylamino, a group represented by the formula (2).

As a preferable combination of R ¹² to R ¹⁴ in the formula (5), R ¹² is sulfo, R ¹³ is a hydrogen atom, acetylamino, 3-carboxypropionylamino, benzoylamino or N ′-(2-sulfoethyl) ureido; R ¹⁴ is a group represented by the formula (2), or R ¹² is 3-sulfopropoxy, R ¹³ is methyl, R ¹⁴ is a group represented by the formula (2), or R ¹² is sulfo, R ¹³ Is a hydrogen atom and R ¹⁴ is nitro or sulfo.

More preferable R ¹⁵ to R ¹⁸ in the formula (6) are a hydrogen atom, sulfo, sulfamoyl, nitro, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, Benzoylamino, 2-sulfobenzoylamino, 2-carboxybenzoylamino, 4-toluenesulfonyloxy, 4-toluenesulfonylamino, N ′-(2-sulfoethyl) ureido, N ′-(2-carboxyethyl) ureido, N ′ -(3-sulfophenyl) ureido, N '-(3,5-dicarboxyphenyl) ureido, etc., more preferably sulfo, nitro, 3-sulfopropoxy, acetylamino, benzoylamino, 4-toluenesulfonyloxy And more preferably A hydrogen atom and sulfo. It is preferred that at least two of ¹⁵ to R ¹⁸ are sulfo, and in a preferred combination, at least two of R ¹⁵ , R ¹⁷ and R ¹⁸ are sulfo, and R ¹⁶ is a hydrogen atom.

More preferable R ¹⁹ to R ²¹ in the formula (7) are a hydrogen atom, cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, chlorine atom, nitro, methyl, methoxy, ethyl , Ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 2 -Carboxybenzoylamino, 4-toluenesulfonyloxy, 4-toluenesulfonylamino, N '-(2-sulfoethyl) ureido, N'-(2-carboxyethyl) ureido, N '-(3-sulfophenyl) ureido, N '− (3,5-dicarboxyphenyl) ureido and the like, more preferably hydrogen atom, carboxy, methyl, sulfo, sulfamoyl, 3-sulfopropylsulfonyl, chlorine atom, nitro, acetylamino, 3-carboxypropionylamino, benzoyl Amino, 2-sulfobenzoylamino, and 2-carboxybenzoylamino, and more preferably carboxy, sulfo, chlorine atom, nitro, and acetylamino.
As a preferred combination, R ¹⁹ is sulfo or carboxy, R ²⁰ is chlorine atom, nitro or acetylamino, and R ²¹ is hydrogen atom or sulfo.

In the above formula (1), the substitution position of the (SO ₃ H) n group is c or d,
The substitution position of the azo group to which the benzimidazolopyridone ring substituted by R ¹ to R ⁴ is bonded is a, b, c or d, but they are not substituted at the same position.
When the latter substitution position is a or b, it is preferable that n is 1 and the former substitution position is c or d, or n is 0.
When the latter substitution position is c, it is preferable that n is 1 and the former substitution position is d or n is 0.
When the latter substitution position is d, n may be 1 and the former substitution position may be c, but it is preferable that n is 0.
Of the above, more preferred substitution positions are b and n are 1 and the former is c or d; the latter is c and n is 1 and the former is d;
Further preferred substitution positions are c for the latter, 1 for n and d for the former.

The compound which combined the preferable groups described about the various substituents of the said Formula (1) to (7) is more preferable, and what combined the more preferable groups is further more preferable. The same applies to a combination of more preferable groups. Moreover, what described the preferable combination is the same also about the compound which combined the preferable combination. Moreover, what described the substitution position is the same for the combination of the preferred substitution position and each of the above preferred substituents.

The salt of the azo compound represented by the formula (1) is an inorganic or organic cation salt. Of these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts, and organic cation salts. Examples of the salt include, but are not limited to, quaternary ammonium ions represented by the following formula (11). Moreover, the free acid of the azo compound of the present invention, 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, the type of salt is selected as appropriate, or when multiple salts are included, the ratio can be changed to change the ratio to suit the purpose. It is also possible to obtain a mixture having.

In the formula (13), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.
Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (11) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Specific examples of the hydroxyalkyl group include hydroxy- (C1-C4) alkyl 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- Hydroxyethoxy Chill such as hydroxyethyl (C1-C4) alkoxy - include (C1-C4) alkyl group, among these hydroxyethoxy - (C1-C4) alkyl. Particularly preferred are hydrogen atoms; hydroxy- (C1-C4) alkyl such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc. Group, hydroxyethoxy- (C1-C4) such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. ) Alkyl group.

Table 1 shows specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 which} are preferable compounds as the formula (13).

The azo compound represented by the formula (1) can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each step shall be expressed in the form of a free acid. In the following formulas (14) to (19), R ¹ to R ²¹ , n, a, b, c, d, group A and The groups B each have the same meaning as above.
A compound represented by the following formula (14) is diazotized by a conventional method, and this and a compound represented by the following formula (15) are coupled by a conventional method to obtain a compound represented by the following formula (16).

The obtained compound of the formula (16) is diazotized by a conventional method, and then this and a compound represented by the following formula (17) are coupled by a conventional method to obtain a compound represented by the following formula (18). .

The present invention represented by the formula (1) is obtained by diazotizing the obtained compound of the formula (18) by a conventional method and then coupling it with a compound represented by the following formula (19) by a conventional method. The azo compound can be obtained.

In addition, the compound represented by Formula (19) can be synthesized according to the method described in Patent Document 4.

As a synthesis method when the group A has a group represented by the above formula (2) as a substituent, a compound represented by the following formula (51) is diazotized by a conventional method, and this is combined with the above formula (14). The compound of the following formula (52) is obtained by a coupling reaction by a conventional method.

The obtained compound of formula (52) is diazotized by a conventional method, and then this and the compound represented by the above formula (15) are coupled by a conventional method to obtain a compound represented by the following formula (53). .

By using the obtained compound of the formula (53) instead of the compound of the above formula (16), a compound corresponding to the case where the group A has the compound represented by the above formula (2) as a substituent is synthesized. I can do it. The compound of the above formula (52) can also be synthesized. For example, C.I. I. Some, such as Acid Yellow 9, can be obtained as commercial products. Any of these can be used for the synthesis of the azo compound of the present invention.

Although it does not specifically limit as a suitable specific example of the compound of this invention shown in Formula (1), The compound shown by the structural formula shown to following Table 2-8 is mentioned.
In each table, functional groups such as sulfo groups and carboxy groups are described in the form of free acids for convenience.

The diazotization of the compound of the above formula (14) is carried out by a method known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. Coupling of the diazotized compound of the compound of formula (14) with the compound of formula (15) 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 30 ° C, preferably 5 to 25 ° C, and at an acidic to neutral pH value, for example pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound of formula (14) and the compound of formula (15) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (16) is carried out by a method known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of, for example, -5 to 40 ° C, preferably 5 to 30 ° C. Coupling of the diazotized compound of the compound of formula (16) with the compound of formula (17) 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 40 ° C, preferably 10 to 30 ° C and a neutral to weakly alkaline pH value, for example pH 6-10. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. As the base, the same ones as described above can be used. The compound of formula (16) and the compound of formula (17) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (18) is also carried out by a method known per se. For example, it is carried out using a nitrite, for example an alkali metal nitrite such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C. Coupling of the diazotized compound of the compound of formula (18) and the compound of formula (19) 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 of formulas (18) and (19) are used in approximately stoichiometric amounts.

The diazotization of the compound of the above formula (51) is carried out by a method known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. Coupling of the diazotized compound of the compound of formula (51) with the compound of formula (14) 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 30 ° C, preferably 5 to 25 ° C, and at an acidic to neutral pH value, for example pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound of formula (51) and the compound of formula (14) are used in approximately stoichiometric amounts.

Diazotization of the compound of formula (52) is carried out in a manner known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of, for example, -5 to 40 ° C, preferably 5 to 30 ° C. Coupling of the diazotized compound of the compound of formula (52) with the compound of formula (15) 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 40 ° C., preferably 5 to 30 ° C., and at an acidic to neutral pH value, for example pH 1-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound of formula (52) and the compound of formula (15) 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, salting out is performed 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 desired in an aqueous medium. By neutralizing with an 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. The aqueous organic medium refers to water-miscible organic substances miscible with water and so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Organic substances that are not classified can be used as needed as long as they are miscible with water. Examples of organic substances not normally classified as solvents include urea and saccharides. Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above-described formula (13). The halogen salt of the organic amine represented by these is mentioned. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates 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 (13) such as diethanolamine and triethanolamine. .

The ink composition of the present invention will be described. The aqueous 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.

The reaction liquid containing the azo compound of the present invention represented by the formula (1), for example, the reaction liquid in Example 1 (4) described later, can be used directly in the production of the ink composition. However, it is first isolated by drying, eg spray drying, or salted out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, or minerals such as hydrochloric acid, sulfuric acid, nitric acid. It is also possible to take out the azo compound of the present invention by acid precipitation by printing with addition of acid, or by acid precipitation which combines the salting-out and acid precipitation described above, and then use this to prepare an ink composition. it can.

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, using the azo compound represented by the formula (1) of the present invention as a pigment. The balance is a composition containing water as a main medium. In the ink composition of the present invention, in order to adjust the viscosity of the ink, to adjust the drying property of the ink, to adjust the permeability to a recording medium after printing (including those provided with an ink receiving layer). For the purpose, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 10% by mass of an ink preparation agent may be further contained. The pH of the ink composition is preferably pH 5 to 11 and more preferably pH 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 and a surfactant as described later.

In the ink composition of the present invention, water or a water-soluble organic solvent (an organic solvent miscible with water) is mixed with the azo compound represented by the above formula (1), if necessary, with other coloring materials such as toning. And an ink preparation agent is added if necessary. For the purpose of adjusting 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. Even in this case, the total amount of the coloring matter contained in the ink composition may be in the above range. When this ink composition is used as an ink for an ink jet printer, it is preferable to use an azo compound of the present invention having a low content of inorganic substances such as metal cation chlorides and sulfates. The standard of the inorganic content is approximately 1% by mass or less with respect to the total weight of the pigment. In order to produce the azo compound of the present invention with a small amount of inorganic substances, for example, a usual method using a reverse osmosis membrane or a dried product or wet cake of the azo compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water, and precipitated. What is necessary is just to desalinate by the method of filtering and separating a thing and drying.

Specific examples of water-soluble organic solvents 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; N Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide; lactams such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone or N-methylpyrrolidin-2-one; 1 Cyclic ureas such as 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one; ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one Or keto alcohol; tetrahydrofura Cyclic ethers such as 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 Mono-, oligo- or poly-alkylene glycols or thioglycols having (C2-C6) alkylene units such as glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol; trimethylol Polyols (triols) such as propane, glycerin or hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, (C1-C4) alkyl ethers of polyhydric alcohols such as diethylene glycol monobutyl ether (butyl carbitol) triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; γ-butyrolactone or dimethyl Examples thereof include sulfoxide. These organic solvents may be used alone or in combination of two or more.
The water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent for the sake of convenience.

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-dissolving agents, 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 And compounds such as benzyl bromacetate and inorganic salts. 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 potassium acetate; inorganic bases such as sodium silicate and disodium phosphate, and the like.

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 ultraviolet 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 dissolving agent 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 or dioctylsulfosuccinate.
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, and polyoxyethylene alkyl ether. Ether type, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, poly Esters such as oxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4 Acetylene glycol (alcohol) systems such as octyne-3,6-diol and 3,5-dimethyl-1-hexyn-3-ol (for example, trade name Surfinol 104, 105, 82, 465, manufactured by Nissin Chemical Co., Ltd.) Orphine STG), polyglycol ether type (eg, Tergitol 15-S-7 manufactured by SIGMA-ALDRICH) 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. Moreover, in order to adjust the black color as an ink composition, in addition to the azo compound represented by the formula (1) of the present invention, other dyes having various hues may be mixed. In this case, black having a different hue, yellow (for example, CI direct yellow 34, CI direct yellow 86, CI direct yellow 132, etc.), orange (for example, CI direct orange) 26, CI Direct Orange 29, CI Direct Orange 49, etc.), Brown, Scarlet, Red (for example, CI Direct Red 62, CI Direct Red 75, CI Direct Red 79) CI Direct Red 80, CI Direct Red 84, etc.), magenta, violet, blue, navy, cyan, green, and other color pigments can be mixed and used.

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. It is suitably used in the inkjet printing method.

Next, the ink jet printing method of the present invention will be described. The ink jet printing method of the present invention is characterized in that recording is performed using the ink composition of the present invention. The ink jet printing method of the present invention performs recording on an image receiving material using an ink jet ink containing the ink composition, but there is no particular limitation on the ink nozzles used at that time, and it is appropriately selected according to the purpose. can do.
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 using an acoustic ink jet method that discharges ink using the radiation pressure; a thermal ink jet (bubble jet (registered trademark)) method that uses ink to form bubbles by heating the ink; Can do.
In the inkjet printing 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 concentrations in the ink differ substantially in 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 azo compound of the present invention represented by the formula (1) or an ink composition containing the same, and more preferably by an inkjet printing method using an inkjet printer. The ink composition is colored.
Although there is no restriction | limiting in particular as what can be colored, For example, sheets for information transmission, such as paper and a film, fiber, cloth (cellulose, nylon, wool, etc.), leather, a base material for color filters, etc. are mentioned.
Among them, the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer; or by using a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol or special ceramics, polyvinyl alcohol or polyvinyl Coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone;
The information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Specific examples include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photographic Paper (Glossy), PM Matt Paper, Crispia; Japan Hewlett-Packard Co., Ltd. Commercially available products such as a company-made product name, Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper; Of course, plain paper can also be used.

  Among the information transmission sheets described above, it is known that an image recorded on a sheet coated with a porous white inorganic material on the surface is particularly prone to discoloration by ozone gas. However, since the ink composition of the present invention has excellent gas resistance, it is particularly effective when inkjet printing is performed on such a recording material.

In order to record on a recording material such as an information transmission sheet by the ink jet printing 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 printing method of the present invention includes 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 printing.

The azo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this dye does not cause crystal precipitation, change in physical properties, change in hue, etc. even when stored for a long period of time. Good stability.
The ink composition containing the coloring matter of the present invention can be used for ink jet printing and writing instruments.
Further, when printing on an information recording sheet, particularly ink jet dedicated paper, the print density of the print image is high, and in addition, the durability of the print image, particularly ozone gas resistance and light resistance is excellent.

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.
Further, the pH value and reaction temperature described below are 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.

Example 1
(1)
Under stirring, 6.0 parts of sodium 4-nitroaniline-2-sulfonate is dissolved in 60 parts of warm water, 7.3 parts of 35% hydrochloric acid is added, cooled to 0-5 ° C. in an ice bath, and then at the same temperature. The diazo reaction liquid was obtained by adding 4.6 parts of 40% sodium nitrite aqueous solution.
On the other hand, 6.0 parts of the compound of the following formula (20) and then sodium hydroxide were added to 70 parts of warm water, and the pH was adjusted to 5.0 to 5.5 with stirring to obtain an aqueous solution.
0.2 parts of sulfamic acid is added to the above diazo reaction liquid and stirred for about 5 minutes, and then the aqueous solution containing the compound of the following formula (20) obtained previously is reacted at a reaction temperature of 5 to 15 ° C. for about 20 minutes. Dropped in minutes.
After completion of the dropwise addition, sodium carbonate was added and the reaction solution was stirred at pH 2.0 to 3.0 for 2 hours. The precipitate was collected by filtration to obtain a wet cake containing the monoazo compound of the following formula (21). Obtained.
The compound of the following formula (20) was obtained by the method described in JP-A-2004-083492.

(2)
Under stirring, 7.0 parts of 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid and sodium hydroxide were added to 50 parts of water to obtain an aqueous solution having a pH of 7.0 to 7.5.
On the other hand, an aqueous solution having a pH of 7.0 to 7.5 was obtained by adding a wet cake containing the compound of the formula (21) obtained in Example 1 (1) and sodium hydroxide to 130 parts of water under stirring. . To this, 4.2 parts of 40% aqueous sodium nitrite solution was added, and the resulting solution was dropped into a mixed solution of 130 parts of water and 9.2 parts of 35% hydrochloric acid at a reaction temperature of 15 to 25 ° C. for 30 minutes. A diazo reaction solution was obtained.
To the obtained diazo reaction liquid, 0.4 part of sulfamic acid was added and stirred for about 10 minutes, and this liquid was added to the previously obtained aqueous solution containing 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid. The reaction temperature was dropped at 15 to 30 ° C. for about 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 7.5.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, salted out by addition of sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (22).

(3)
2- (Cyanomethyl) benzimidazole and ethyl acetoacetate were reacted by heating in ethanol in the presence of sodium methoxide, and acidified by addition of dilute hydrochloric acid to obtain a compound of the following formula (23). 8.9 parts of the obtained compound was slowly added to 64 parts of 6% fuming sulfuric acid at 15 to 25 ° C. After the addition, the mixture was stirred at the same temperature for 2 hours and then dropped into 190 parts of ice water in about 10 minutes. The precipitated crystals were collected by filtration, washed with dilute hydrochloric acid on the funnel and dried to obtain 10.7 parts of a compound of the formula (24).

(4)
Under stirring, 2.7 parts of the compound of the formula (24) obtained in Example 1 (3) and sodium hydroxide were added to 50 parts of water to obtain an aqueous solution having a pH of 7.0 to 8.0.
On the other hand, with stirring, 1/2 amount of the wet cake containing the compound of formula (22) obtained in Example 1 (2) was dissolved in 100 parts of water, and 2.0 parts of 40% sodium nitrite aqueous solution was added. did. The obtained solution was added dropwise to a mixed solution of 30 parts of water and 4.7 parts of 35% hydrochloric acid with stirring at a reaction temperature of 15 to 30 ° C. for 30 minutes to obtain a diazo reaction liquid.
The obtained diazo reaction liquid was dripped at reaction temperature 15-30 degreeC for 30 minutes to the aqueous solution containing the compound of the formula (24) obtained previously. 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 dropping, the mixture was stirred at the same temperature for 3 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 120 parts of water, 180 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 100 parts of water, 250 parts of methanol was added to crystallize, and the precipitated solid was collected by filtration and dried to obtain a compound of the following formula (25) (Table 9.0 parts of No. 1 compound in No. 2 was obtained as a sodium salt.
λmax: 578 nm.

Example 2
In Example 1 (1), the same procedure as in Example 1 was repeated except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate was changed to 6.4 parts of aniline-2,4-disulfonic acid. 8.2 parts of the compound of the following formula (26) (No. 4 compound in Table 2) was obtained as a sodium salt.
λmax: 581 nm.

Example 3
Example 1 in Example 1 (1) except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate is changed to 11.8 parts of 4-amino-5-tosyloxynaphthalene-2,7-disulfonic acid. In the same manner as in Example 1, 10.9 parts of the compound of the following formula (27) (No. 19 compound in Table 4) of the present invention was obtained as a sodium salt.
In addition, 4-amino-5-tosyloxynaphthalene-2,7-disulfonic acid is prepared by converting 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid and 4-toluenesulfonyl chloride into water and alkaline according to a conventional method. It can be easily obtained by reacting.

Example 4
10.9 parts of the compound of the formula (27) obtained in Example 3 was dissolved in 120 parts of water with stirring, and then heated to 70 ° C. The pH value was adjusted to 10.0 to 11.0 by adding sodium hydroxide, and the mixture was stirred at 70 to 75 ° C for 1.5 hours. During the reaction, the pH value was maintained at 10.0 to 11.0 by adding sodium hydroxide. After the reaction, the mixture was cooled to room temperature, and the pH value was adjusted to 7.0 to 7.5 by adding 35% hydrochloric acid. Sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 120 parts of water, 120 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 100 parts of water, 150 parts of methanol was added to cause crystallization, and the precipitated solid was collected by filtration and dried to obtain a compound of the following formula (28) (Table Compound No. 21 in No. 4) was obtained as a sodium salt.
λmax: 603 nm.

Example 5
Example 1 Example 1 except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate was changed to 8.9 parts of the compound of formula (29) (CI Acid Yellow 9) below. In the same manner as above, 9.6 parts of the compound of the following formula (30) of the present invention (No. 22 compound in Table 5) was obtained as a sodium salt.
λmax: 584 nm.

Example 6
(1)
Under stirring, 7.0 parts of 2,4-disulfoaniline is dissolved in 30 parts of water, 4.3 parts of 35% hydrochloric acid is added, cooled to 0 to 5 ° C. in an ice bath, and then 40% sublimated at the same temperature. A diazo reaction liquid was obtained by adding 5.0 parts of an aqueous sodium nitrate solution.
On the other hand, an aqueous solution was obtained by adding 6.7 parts of the compound of the above formula (20) and then sodium hydroxide to 70 parts of warm water and adjusting the pH to 5.0 to 5.5 with stirring.
0.2 parts of sulfamic acid is added to the above diazo reaction liquid and stirred for about 5 minutes, and then the aqueous solution containing the compound of the following formula (20) obtained previously is reacted at a reaction temperature of 5 to 15 ° C. for about 20 minutes. Dropped in minutes.
After completion of the dropping, sodium carbonate was added and the reaction solution was stirred at pH 1.0 to 2.0 for 2 hours to obtain a reaction solution containing a monoazo compound of the following formula (31).

(2)
Example 1 Example (1) except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate was used as the reaction solution containing the compound of formula (31) obtained in Example 6 (1) above. In the same manner as in Example 1, 9.6 parts of the compound of the following formula (32) of the present invention (No. 23 compound in Table 5) was obtained as a sodium salt.
λmax: 592 nm.

Example 7
(1)
Under stirring, 7.7 parts of 1,4-phenylenediamine-2,5-disulfonic acid and sodium hydroxide were added to 100 parts of water and dissolved to a pH of 7.0 to 7.5. The acetic anhydride 3.0 part was dripped here over 15 minutes at 15-25 degreeC, and it stirred at the same temperature after that for 1 hour. After adding 7.2 parts of 35% hydrochloric acid, the mixture was cooled to 0 to 5 ° C. in an ice bath, and then 5.0 parts of 40% aqueous sodium nitrite solution was added at the same temperature to obtain a diazo reaction liquid.
On the other hand, an aqueous solution was obtained by adding 6.7 parts of the compound of the above formula (20) and then sodium hydroxide to 70 parts of warm water and adjusting the pH to 5.0 to 5.5 with stirring.
0.2 parts of sulfamic acid is added to the above diazo reaction liquid and stirred for about 5 minutes, and then the aqueous solution containing the compound of the following formula (20) obtained previously is reacted at a reaction temperature of 5 to 15 ° C. for about 20 minutes. Dropped in minutes.
After completion of dropping, sodium carbonate was added and the reaction solution was stirred at pH 2.5 to 3.5 for 2 hours to obtain a reaction solution containing a monoazo compound of the following formula (33).

(2)
Example 1 Example (1) except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate was used as the reaction solution containing the compound of formula (33) obtained in Example 7 (1) above. In the same manner as in Example 1, 9.2 parts of the compound of the following formula (34) (No. 24 compound in Table 5) of the present invention was obtained as a sodium salt.
λmax: 603 nm.

Example 8
(1)
Under stirring, 5.3 parts of 4-chloroaniline-3-sulfonic acid and sodium hydroxide were added to 40 parts of water and dissolved to a pH of 4.0 to 5.0. After adding 8.0 parts of 35% hydrochloric acid, the mixture was cooled to 0 to 5 ° C. in an ice bath, and then 5.0 parts of 40% sodium nitrite aqueous solution was added at the same temperature to obtain a diazo reaction liquid.
On the other hand, 6.1 parts of 5-acetylaminoaniline-2-sulfonic acid and then sodium hydroxide were added to 40 parts of water, and the pH was adjusted to 4.5 to 5.5 with stirring to obtain an aqueous solution.
0.2 parts of sulfamic acid was added to the above diazo reaction liquid and stirred for about 5 minutes, and then the aqueous solution containing 5-acetylaminoaniline-2-sulfonic acid obtained above was reacted at a reaction temperature of 10 to 15 ° C. For about 20 minutes.
After completion of dropping, sodium carbonate was added and the reaction solution was stirred at pH 2.0 to 3.0 for 2 hours to obtain a reaction solution containing a monoazo compound of the following formula (35).

(2)
Example 1 except that 6.0 parts of sodium 4-nitroaniline-2-sulfonate in Example 1 (1) is used as the reaction solution containing the compound of formula (35) obtained in Example 8 (1) above. In the same manner, 9.0 parts of the compound of the following formula (36) of the present invention (the compound of No. 33 in Table 6) was obtained as a sodium salt.
λmax: 586 nm.

Example 9
Similar to Example 8 except that 8.3 parts of 7-aminonaphthalene-1,3-disulfonic acid are used instead of 5.3 parts of 4-chloroaniline-3-sulfonic acid in Example 8 (1). Then, 9.3 parts of the compound of the following formula (37) of the present invention (No. 38 compound in Table 7) was obtained as a sodium salt.
λmax: 588 nm.

Example 10
Example except that 10.5 parts of 7-aminonaphthalene-1,3,5-trisulfonic acid was used instead of 5.3 parts of 4-chloroaniline-3-sulfonic acid in Example 8 (1). In the same manner as in Example 8, 10.3 parts of the compound of the following formula (38) of the present invention (the compound of No. 39 in Table 7) was obtained as a sodium salt.
λmax: 597 nm.

Example 11
(1)
Under stirring, 30 parts of 2,4-diaminobenzenesulfonic acid and sodium hydroxide were added to 200 parts of water and dissolved to a pH of 6.5 to 7.5. To this, 16.8 parts of succinic anhydride was added at 10 to 20 ° C. for about 10 minutes. After the addition, the mixture was stirred at the same temperature for 2 hours and at 15 to 30 ° C. for 2 hours. Salting out was performed by adding sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (39).

(2)
Instead of using 5.3 parts of 4-chloroaniline-3-sulfonic acid in Example 8 (1), 8.3 parts of 7-aminonaphthalene-1,3-disulfonic acid was used and 5-acetylaminoaniline- Instead of using 6.1 parts of 2-sulfonic acid, the procedure was as in Example 8, except that 2/11 of the wet cake containing the compound of formula (39) obtained in Example 11 (1) above was used. Then, 10.3 parts of a compound of the following formula (40) of the present invention (No. 40 compound in Table 7) was obtained as a sodium salt.
λmax: 591 nm.

Example 12
Instead of using 8.3 parts of 7-aminonaphthalene-1,3-disulfonic acid in Example 11 (2), 10.5 parts of 7-aminonaphthalene-1,3,5-trisulfonic acid was used. In the same manner as in Example 11, 10.9 parts of the compound of the following formula (41) of the present invention (No. 42 compound in Table 7) was obtained as a sodium salt.
λmax: 598 nm.

Example 13
(1)
Under stirring, 20.7 parts of 2,4-diaminobenzenesulfonic acid and sodium hydroxide were added to 120 parts of water to dissolve at pH 6.5 to 7.5. To this, 18.1 parts of phenyl chloroformate was added at 10 to 20 ° C. for about 15 minutes. After the addition, the mixture was stirred at the same temperature for 4 hours while maintaining the pH value at 4.0 to 5.0 by adding sodium carbonate. The precipitated crystals were collected by filtration and suspended in 140 parts of water with stirring. After adding 15.8 parts of 2-aminoethanesulfonic acid, the pH value was adjusted to 7.0 to 7.5 by adding sodium carbonate. The temperature was raised to 50 to 55 ° C., and the aqueous solution containing the compound of the following formula (42) was obtained by stirring at the same temperature for 4 hours while maintaining the pH value at 7.0 to 7.5 by adding sodium carbonate. . This compound was used as it was after cooling to room temperature in subsequent reactions.

(2)
In Example 7 (1), instead of using 6.7 parts of the compound of the formula (20), 1/4 of the aqueous solution containing the compound of the formula (42) obtained in the above Example 13 (1) is used. 8.6 parts of the following formula (43) of the present invention (No. 34 compound in Table 6) was obtained as a sodium salt in the same manner as in Example 7.
λmax: 601 nm.

Example 14
Instead of using 5.3 parts of 4-chloroaniline-3-sulfonic acid in Example 8 (1), 10.5 parts of 7-aminonaphthalene-1,3,5-trisulfonic acid was used and 5-acetyl Similar to Example 8 except that instead of using 6.1 parts of aminoaniline-2-sulfonic acid, 1/4 of the aqueous solution containing the compound of formula (42) obtained in Example 13 (1) above is used. Then, 9.6 parts of the compound of the following formula (44) of the present invention (No. 41 compound in Table 7) was obtained as a sodium salt.
λmax: 599 nm.

Example 15
(1)
Under stirring, 6.6 parts of sodium 4-nitroaniline-2-sulfonate is dissolved in 60 parts of warm water, 8.0 parts of 35% hydrochloric acid is added, cooled to 0-5 ° C. in an ice bath, and then at the same temperature. A diazo reaction liquid was obtained by adding 5.0 parts of 40% sodium nitrite aqueous solution.
To the diazo reaction liquid, 0.2 part of sulfamic acid was added and stirred for about 5 minutes, and then 1/4 of the aqueous solution containing the compound of the formula (42) obtained in Example 13 (1) was reacted at a reaction temperature of 5 It was added dropwise at ˜15 ° C. for about 20 minutes.
After completion of the dropwise addition, the mixture was stirred for 2 hours to obtain an aqueous solution containing a monoazo compound of the following formula (45).

(2)
After adding 2.6 parts of 35% hydrochloric acid to the aqueous solution containing the monoazo compound of formula (45) obtained in Example 15 (1) above, 4.3 parts of 40% aqueous sodium nitrite solution is added at 15 to 25 ° C. As a result, a diazo reaction solution was obtained. To this, 0.2 part of sulfamic acid was added and stirred for about 5 minutes, and then 1/5 of the aqueous solution containing the compound of formula (42) obtained in Example 13 (1) was reacted at a reaction temperature of 15-30. The solution was added dropwise at about 10 minutes.
After dropping, the mixture was stirred at a reaction temperature of 15 to 30 ° C. for 2 hours while maintaining the pH value at 1.5 to 2.0 by adding sodium carbonate. Salting out was performed by adding sodium chloride, and the precipitate was collected by filtration to obtain a wet cake containing a disazo compound of the following formula (46).

(3)
In Example 1 (2), instead of using a wet cake containing the compound of formula (21) obtained in Example 1 (1), the compound of formula (46) obtained in Example 15 (2) above 9.3 parts of the compound of the following formula (47) of the present invention (No. 32 compound in Table 6) was obtained as a sodium salt in the same manner as in Example 1 except that a wet cake containing was used.
λmax: 570 nm.

Example 16
(1)
Under stirring, 16.9 parts of 2,4-diaminobenzenesulfonic acid and sodium hydroxide were added to 220 parts of water and dissolved to a pH of 6.5 to 7.5. 13.8 parts of benzoyl chloride was added thereto at 10 to 20 ° C. for about 10 minutes. The mixture was stirred at a reaction temperature of 10 to 20 ° C. for 2 hours while maintaining the pH value at 5.5 to 6.5 by adding sodium carbonate. Further, 3.0 parts of benzoyl chloride was added at 10 to 20 ° C. for about 5 minutes, and the mixture was stirred at a reaction temperature of 10 to 20 ° C. for 2 hours while maintaining the pH value at 5.5 to 6.5 by adding sodium carbonate. . The precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (48).

(2)
Instead of using 5.3 parts of 4-chloroaniline-3-sulfonic acid in Example 8 (1), 10.5 parts of 7-aminonaphthalene-1,3,5-trisulfonic acid was used and 5-acetyl Example 8 with the exception of using 1/3 of the wet cake containing the compound of formula (48) obtained in Example 16 (1) above instead of using 6.1 parts of aminoaniline-2-sulfonic acid. Similarly, 10.6 parts of the compound of the following formula (49) of the present invention (the compound of No. 43 in Table 8) was obtained as a sodium salt.
λmax: 597 nm.

Examples 17-23
(A) Preparation of ink After mixing the following components, a black ink composition of the present invention was obtained, and then impurities were separated by a 0.45 μm membrane filter. For convenience, the obtained ink composition is hereinafter referred to as “ink”.
The water used was ion exchange 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 a total amount of 100 parts.

Table 6
Each compound obtained in Examples 2 to 7, 9, and 11 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 parts (Brand name Surfinol 104, manufactured by Nissin Chemical)
Water + sodium hydroxide 77.4 parts Total 100.0 parts

In Table 6, the following various tests performed using the ink containing each compound obtained in Examples 1, 2, 4, 7, 8, 13, and 14 are referred to as Examples 17 to 23, respectively. The aqueous black ink of the present invention did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

Comparative Example 1
As a black pigment for comparison, the same composition as in Table 6 was used except that the pigment of the following formula (50) disclosed in Example 1-2 of Patent Document 7 was used instead of the compound of each Example. Ink was prepared. The following various tests conducted using this ink are referred to as Comparative Example 1.

(B) Inkjet printing Using the ink obtained above, Canon paper, product name PIXUS iP4100, glossy paper 1 (Canon, product name Professional Photo Paper PR-101), glossy paper 2 (EPSON) Inkjet printing was carried out on three types of information recording sheets (inkjet paper), manufactured by the company, trade name: photographic paper Krispia (high gloss), and glossy paper 3 (manufactured by HP, trade name: Advanced Photo Paper (gloss)).
At the time of printing, an image pattern was prepared so that the reflection density was obtained with several gradations, and a black printed matter was obtained.

(C) Evaluation of Printed Images Each print image obtained using the inks of Examples 17 to 23 and Comparative Example 1 was evaluated for change in image density before and after the test with respect to light resistance and ozone gas resistance. Went.
The change in density of the printed image is measured by measuring the gradation portion where the reflection density D value of the printed image before the test is closest to 1.0 using a colorimeter manufactured by GRETAG-MACBETH and the product name SpectroEye. did.
The test was performed for each of glossy papers 1, 2, and 3, and the test results are shown in Table 7.
The specific test method is as follows.
1) Light Resistance Test Using a low-temperature xenon weatherometer XL75, manufactured by Suga Test Instruments Co., Ltd., 96 for each of the above print images under the conditions of 100,000 Lux illuminance, humidity 60% RH, temperature 24 ° C. After the time irradiation, the colorimetry was performed using the above colorimeter, and the residual ratio of the dye of each image was obtained by (reflected density after test / reflected density before test) × 100 (%). The test results were evaluated according to the following criteria.
○: Residual rate of 85% or more △: Residual rate of 75% or more and less than 85% ×: Residual rate of less than 75% 2) Ozone gas resistance test Suga Test Instruments Co., Ltd., product name Ozone concentration is 40 ppm using an ozone weatherometer Each print image was allowed to stand for 4 hours under the conditions of humidity 60% RH and temperature 24 ° C. After completion of the test, the colorimetry was performed using the above colorimeter, and the residual ratio of the dye in each print image was determined by (reflection density after test / reflection density before test) × 100 (%). The test results were evaluated according to the following criteria.
○: Residual rate of 80% or more Δ: Residual rate of 65% or more and less than 80% ×: Residual rate of less than 65% Note that the formula numbers described in Table 7 are the compounds contained as dyes in the ink used in the test Represents the formula number.

Table 7
Ozone gas resistance Light resistance Example 17 (Formula (25))
Glossy paper 1 △ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ △
Example 18 (Formula (26))
Glossy paper 1 △ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ △
Example 19 (Formula (28))
Glossy paper 1 △ ○
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 20 (Formula (34))
Glossy paper 1 △ ○
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 21 (Formula (36))
Glossy paper 1 △ ○
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 22 (Formula (43))
Glossy paper 1 △ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 23 (Formula (44))
Glossy paper 1 △ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ △
Comparative Example 1 (Formula (50))
Glossy paper 1 × ×
Glossy paper 2 △ ×
Glossy paper 3 △ ×

As is clear from the results of Table 7, the printed images of Examples 17 to 23 and the image of Comparative Example 1 are each better when the results of the ozone gas test are compared for each glossy paper. The result was better than Comparative Example 1. That is, in Comparative Example 1, when the glossy paper 1 is used, the dye residual ratio is less than 65%, and when the glossy paper 2 or 3 is used, the dye residual ratio is 65% or more and less than 80%. In Examples 17 to 23 of the present invention, when glossy paper 1 was used, the dye residual ratio was 65% or more and less than 80%, and when glossy paper 2 or 3 was used, the dye residual ratio was 80% or more. Indicated.
Moreover, the difference was similarly recognized also in light resistance, and the results of each Example were better than Comparative Example 1. That is, in Examples 19 to 21, the residual dye ratio was 85% or more when any glossy paper was used, and in Example 22, the residual dye ratio was 75% or more and less than 85% when glossy paper 1 was used. Thus, when glossy papers 2 and 3 are used, the residual dye ratio is 85% or more. In Examples 17, 18 and 23, when glossy papers 1 and 3 are used, the residual dye ratio is 75% or more and 85%. When the glossy paper 2 is used, the residual dye rate is 85% or more, whereas in the comparative example 1, the residual pigment rate is less than 75% when any glossy paper is used. In Examples 17 to 23, good results were obtained with respect to Comparative Example 1.
From the above results, the fastness of the printed image obtained with the ink containing the azo compound of the present invention is extremely superior to the image of the conventional trisazo compound used in Comparative Example 1, and particularly for the inkjet printed image. It can be seen that the required ozone gas resistance and light resistance are excellent.

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

Claims (21)

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

[In Formula (1),
R ¹ represents an unsubstituted or carboxy-substituted C1-C4 alkyl group; an unsubstituted or sulfo-substituted phenyl group; or a carboxy group,
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; a methyl group; a chlorine atom; or a sulfo group;
R ⁵ to R ⁷ are each independently a hydrogen atom; carboxyl group; sulfo group; hydroxy group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group C1-C4 alkoxy group substituted with a group, a sulfo group or a carboxy group; unsubstituted or a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group or a carboxy group; C1 substituted with an unsubstituted or carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; a ureido group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 N ′-(C1-C8) substituted with an alkoxy group, a sulfo group or a carboxy group Ruylureido group; N′-phenyl in which the benzene ring is unsubstituted or substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group Represents a ureido group,
The ring in which R ⁵ to R ⁷ are substituted represents a benzene ring when no ring represented by a broken line is present; or a naphthalene ring when a ring represented by a broken line is present;
n represents 0 or 1,
The substitution position of the (SO ₃ H) n group is c or d,
The substitution position of the azo group to which the benzimidazolopyridone ring substituted by R ¹ to R ⁴ is bonded is a, b, c or d, but they are not substituted at the same position,
The group A represents a substituted phenyl group or a substituted naphthyl group, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group, or a chlorine atom; a fluorine atom; Atom; bromine atom; cyano group; nitro group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group C1-C4 alkoxy group substituted; C1-C4 alkylthio group unsubstituted or substituted with a hydroxy group, sulfo group or carboxy group; C1-C4 unsubstituted or substituted with a hydroxy group, sulfo group or carboxy group Alkylsulfonyl group; unsubstituted or substituted with a carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; a benzene ring is unsubstituted, or a methyl group, a nitro group or a chlorine atom A benzenesulfonylamino group substituted with a ureido group; an N '-(C1-C8) alkylureido group substituted with an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group; a benzene ring And N′-phenylureido group substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group; A group represented by the following formula (2); a group selected from the group consisting of:

{In Formula (2),
The group B represents a substituted phenyl group or a substituted naphthyl group, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a fluorine atom; Atom; bromine atom; cyano group; nitro group; sulfamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group A substituted C1-C4 alkoxy group; an unsubstituted or C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; Benzene ring is unsubstituted, sulfo group, carboxy group, unsubstituted A benzoylamino group substituted with a 1-C4 alkyl group; and a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; a ureido group; an unsubstituted group, or a hydroxy group, A substituted C1-C4 alkoxy group, a N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group; and the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted group A N′-phenylureido group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a sulfo group and a carboxy group; a group selected from the group consisting of: }. ]. In equation (1),
The azo compound or a salt thereof according to claim 1, wherein the group A is a group represented by the following formula (3):

[In Formula (3),
R ⁸ to R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a chlorine atom; A nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-C4 substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group An alkoxy group, unsubstituted or a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or a C1-C8 alkylcarbonylamino group substituted with a carboxy group; an unsubstituted benzene ring; Or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group. Benzoylamino group; benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, nitro group or chlorine atom; ureido group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group or carboxy N ′-(C1-C8) alkylureido group substituted with a group; or the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group and a carboxy group An N′-phenylureido group substituted with a group selected from the group consisting of
R ¹¹ is a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group in which the benzene ring is unsubstituted or substituted by a methyl group, a nitro group or a chlorine atom; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group Unsubstituted C1-C4 alkyl group; unsubstituted or C1-C4 alkoxy group substituted with a hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group or carboxy group; unsubstituted, or A C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring is unsubstituted, or a sulfo group, a carboxy group; A benzoylamino group substituted with an unsubstituted C1-C4 alkyl group; A benzenesulfonylamino group in which the zen ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; unsubstituted or N ′ substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group -(C1-C8) alkylureido group; a group in which the benzene ring is unsubstituted or selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group; A group selected from the group consisting of a substituted N′-phenylureido group; and a group represented by formula (2) in claim 1; ]. In equation (1),
The substitution position of the (SO ₃ H) n group is d, and the substitution position of the azo group to which the benzimidazolopyridone ring substituted by R ¹ to R ⁴ is bonded is c. The azo compound or its salt as described. The azo compound or a salt thereof according to claim 1 represented by the following formula (4):

[In formula (4), R ¹ to R ⁷ , n and group A have the same meaning as in formula (1). ]. In equation (4),
R ⁵ is a sulfo group; unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ⁶ is a hydrogen atom,
R ⁷ is an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring is unsubstituted, or a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; A substituted benzoylamino group; a ureido group; an N ′-(C1-C8) alkylureido group substituted by an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group; An N′-phenylureido group substituted or substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group; 4. The azo compound or a salt thereof according to 4. In equation (1),
The azo compound or a salt thereof according to any one of claims 1 to 5, wherein the group A is a group represented by the following formula (5):

[In Formula (5),
R ¹² is a hydrogen atom; a sulfo group; a carboxy group; a nitro group; an unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ¹³ represents a hydrogen atom; a sulfo group; an unsubstituted C1-C4 alkyl group; an unsubstituted or C1-substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group. A C4 alkoxy group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; A ureido group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group,
R ¹⁴ is a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted or hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1- C1-C4 alkoxy group substituted with C4 alkoxy group, sulfo group or carboxy group; unsubstituted or C1-C4 alkylsulfonyl group substituted with hydroxy group, sulfo group or carboxy group; unsubstituted or substituted with carboxy group A benzoylamino group in which the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group; an unsubstituted or hydroxy group or an unsubstituted C1-C4 N ′-(C1-C8) substituted with an alkoxy group, a sulfo group or a carboxy group Alkylureido group; N′— in which the benzene ring is unsubstituted or substituted with a group selected from the group consisting of a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group A phenylureido group; a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom; and a group represented by formula (2) in claim 1; Each represents a substituent. ]. In equation (5),
R ¹³ is a hydrogen atom or a sulfo group,
R ¹⁴ is a sulfo group; a nitro group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group The azo compound or a salt thereof according to claim 6, wherein the benzoylamino group is a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom. In equation (5),
R ¹² is a sulfo group; a carboxy group; an unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group;
R ¹³ is an unsubstituted C1-C4 alkyl group; unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; Or a benzoylamino group substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; a ureido group; an unsubstituted group; Or an N ′-(C1-C8) alkylureido group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group or a carboxy group,
The azo compound or a salt thereof according to claim 6, wherein R ¹⁴ is a group represented by the formula (2) in claim 1. The azo compound or a salt thereof according to claim 6, wherein the group B in the group represented by the formula (2) according to claim 1 is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom; a sulfo group; an unsubstituted C1-C4 alkyl group; a hydroxy group; a benzenesulfonyloxy in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group, or a chlorine atom A nitro group; a sulfamoyl group; an unsubstituted or C1-C4 alkoxy group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzene ring Is unsubstituted or substituted with a sulfo group, a carboxy group, or an unsubstituted C1-C4 alkyl group; unsubstituted or substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group, or a carboxy group N ′-(C1-C8) alkylureido group; benzene ring is unsubstituted or hydroxy group An N′-phenylureido group substituted with a group selected from the group consisting of an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group and a carboxy group; or the benzene ring is unsubstituted, or It represents a benzenesulfonylamino group which may be substituted with a methyl group, a nitro group or a chlorine atom. ]. The azo compound or a salt thereof according to claim 6, wherein the group B in the group represented by the formula (2) according to claim 1 is a group represented by the following formula (7):

[In Formula (7),
R ¹⁹ to R ²¹ are each independently a hydrogen atom; a carboxy group; a sulfo group; a fluorine atom; a chlorine atom; a bromine atom; a cyano group; a nitro group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; Hydroxy group, unsubstituted C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, C1-C4 alkoxy group substituted with sulfo group or carboxy group; unsubstituted or C1 substituted with hydroxy group, sulfo group or carboxy group -C4 alkylsulfonyl group; C1-C8 alkylcarbonylamino group unsubstituted or substituted with a carboxy group; benzoylamino where the benzene ring is unsubstituted or substituted with a sulfo group, a carboxy group or an unsubstituted C1-C4 alkyl group Group: unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group Or a N ′-(C1-C8) alkylureido group substituted with a carboxy group; the benzene ring is unsubstituted, or a hydroxy group, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a sulfo group, and a carboxy group An N′-phenylureido group substituted with a group selected from the group consisting of a group; and a benzenesulfonylamino group in which the benzene ring is unsubstituted or substituted with a methyl group, a nitro group or a chlorine atom. ]. The azo compound or a salt thereof according to any one of claims 1 to 10, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group. In equation (4),
n is 1,
R ⁵ is a sulfo C3-C4 alkoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
Group A is a group represented by the following formula (5),

[In Formula (5),
R ¹² is a sulfo group or a sulfo C3-C4 alkoxy group,
R ¹³ is a methyl group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group; a ureido group; an unsubstituted or substituted N ′-(C1- C8) an alkylureido group,
R ¹⁴ represents a group represented by the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to claim 4, wherein the group B in the formula (2) according to claim 1 is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ to R ¹⁸ are each independently a hydrogen atom; a sulfo group; a benzene ring unsubstituted or substituted with a methyl group, nitro group or chlorine atom; a benzenesulfonyloxy group; a nitro group; unsubstituted or sulfo Each represents a C1-C4 alkoxy group substituted by a group or a carboxy group. ]. In Formula (4), n is 1,
R ⁵ is a sulfo group or a sulfo C3-C4 alkoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group; an unsubstituted or substituted C1-C8 alkylcarbonylamino group with a carboxy group; a benzoylamino group; a ureido group; an unsubstituted, or a N ′-(C1- C8) an alkylureido group,
Group A is a group represented by the following formula (5),

[In Formula (5),
R ¹² is a sulfo group or a sulfo C3-C4 alkoxy group, and R ¹³ is a methyl group; an unsubstituted or C1-C8 alkylcarbonylamino group substituted with a carboxy group; a benzoylamino group; a ureido group; An N ′-(C1-C8) alkylureido group substituted with a sulfo group or a carboxy group,
R ¹⁴ represents the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to claim 4, wherein the group B in the formula (2) according to claim 1 is represented by the following formula (7):

[In Formula (7),
R ¹⁹ to R ²¹ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a sulfamoyl group; an unsubstituted or a C1-C4 alkylsulfonyl substituted with a hydroxy group, a sulfo group or a carboxy group A C1-C8 alkylcarbonylamino group that is unsubstituted or substituted with a carboxy group; a benzene ring that is unsubstituted or a benzoylamino group that is substituted with a sulfo group or a carboxy group; or a benzene ring that is unsubstituted or methyl Benzenesulfonylamino group substituted by a group, a nitro group or a chlorine atom, respectively. ]. In Formula (4), n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
R ³ is a hydrogen atom,
R ⁴ is a sulfo group,
R ⁵ is a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group,
A group represented by the following formula (5):

[In Formula (5),
R ¹² is a sulfo group or a sulfopropoxy group,
R ¹³ is a methyl group; an acetylamino group; a carboxyethylcarbonylamino group; a benzoylamino group; an N′-sulfoethylureido group;
R ¹⁴ represents the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to claim 4, wherein the group B in the formula (2) according to claim 1 is a group represented by the following formula (6):

[In Formula (6),
R ¹⁵ , R ¹⁷ and R ¹⁸ are a hydrogen atom or a sulfo group, and at least two of R ¹⁵ , R ¹⁷ and R ¹⁸ are a sulfo group,
R ¹⁶ represents a hydrogen atom. ]. In Formula (4), n is 1,
R ¹ is a methyl group,
R ² is a cyano group,
R ³ is a hydrogen atom,
R ⁴ is a sulfo group,
R ⁵ is a sulfo group or a sulfopropoxy group,
R ⁶ is a hydrogen atom,
R ⁷ is a methyl group or an N′-sulfoethylureido group,
A group represented by the following formula (5):

[In the formula (5), R ¹² is a sulfo group or a sulfopropoxy group,
R ¹³ is a methyl group; an acetylamino group; a carboxyethylcarbonylamino group; a benzoylamino group; or an N′-sulfoethylureido group,
R ¹⁴ represents a group represented by the formula (2) according to claim 1. ],
The azo compound or a salt thereof according to claim 4, wherein the group B in the formula (2) according to claim 1 is represented by the following formula (7):

[In formula (7), R ¹⁹ represents a hydrogen atom or a sulfo group;
R ²⁰ is a sulfo group; a chlorine atom; or a nitro group,
R ²¹ is a hydrogen atom or a sulfo group,
At least one of R ¹⁹ to R ²¹ represents a sulfo group. ]. An ink composition comprising at least one azo compound or salt thereof according to any one of claims 1 to 15 as a dye. An ink jet printing method comprising recording on a recording material by ink jet printing using the ink composition according to claim 16. The inkjet printing method according to claim 17, wherein the recording material in the inkjet printing method is an information transmission sheet. 19. The ink jet printing method according to claim 18, wherein the information transmission sheet contains a porous white inorganic substance. An ink jet printer loaded with a container containing the ink composition according to claim 16. A colored product colored with the azo compound according to any one of claims 1 to 15 or a salt thereof.