JP2008069331A - Aqueous black ink composition, inkjet recording method using the same and colored product formed using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous black ink composition which is used in inkjet recording and writing implements, has a neutral hue and is black high in printing density, further excels in ozone resistance, light resistance, and water resistance, and has good storage stability as a recording fluid. <P>SOLUTION: The aqueous black ink composition is a black ink composition comprising a water-soluble monoazo compound represented by formula (1) or its salt. The compound of formula (1) is also used as a color matching dye. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to an aqueous black ink composition, an ink jet recording method using the same, and a colored body thereof.

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, as inks for fountain pens, felt-tip pens, and inks for ink jet recording, water-based inks in which water-soluble dyes are dissolved in water-based media have been used. In these water-based inks, ink pens and ink discharge nozzles are used. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. 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 particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink. Further, the formed image is required to have image fastness such as light resistance, ozone gas resistance, water resistance and moisture resistance.

Among these, ozone gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action present 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, SOx, etc. Among these oxidizing gases, ozone gas is a main causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recording images. It is said that. Ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper often use materials such as porous white inorganic materials to accelerate ink drying and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on a fresh recording paper. Since this discoloration phenomenon due to the oxidizing gas is characteristic of an ink jet image, improvement of ozone gas resistance is one of the important problems in the ink jet recording method.

In the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet recording and the colored bodies colored thereby will be further improved in light resistance, ozone gas resistance, water resistance and moisture 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. However, there are many technical difficulties in developing pigments that have neutral hues, high color densities, and excellent fastness in both dark and light gamuts. Few have good performance. Therefore, generally, a black ink is prepared by mixing a plurality of various pigments. However, when an ink is prepared by mixing a plurality of dyes, the hue varies depending on the medium (recording material), and the discoloration is particularly large due to the decomposition of the dye by light or ozone gas, as compared with the case of preparing the ink with a single dye. Such problems are likely to occur.

Many of the pigments proposed as dyes for black ink are azo pigments. I. Disazo dyes such as Food Black 2 have problems such as low image optical density, poor water resistance and moisture resistance, and insufficient light resistance and gas resistance. In general, polyazo dyes having extended conjugated systems have problems such as low water solubility and easy occurrence of a bronzing phenomenon in which recorded images have a partial metallic luster, and insufficient light resistance and gas resistance. Similarly, some azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which is undesirable for safety and the environment for living organisms, and extremely low ozone gas resistance. There are problems such as. Many of these have been proposed, but have not yet been able to provide products that fully satisfy market demands.

As black inks in which yellow to orange dyes are further blended with black dyes, for example, those of Patent Documents 1 to 3 have been proposed, but they have not yet provided products that sufficiently satisfy market demands.

Although the dyes used in the present invention are described in Patent Documents 4 and 5, Patent Document 4 does not describe ink jet recording, and Patent Document 5 only describes use as an orange ink (composition). It is not used for toning black ink.

Japanese Examined Patent Publication No. 7-122044 Japanese Patent No. 3178200 JP-A-9-255906 JP-A-61-113885 JP-A-2005-272746

The present invention is stable even when stored in the form of a solution for a long time, exhibits neutral gray to black without color, and is excellent in fastness, light resistance, ozone gas resistance, and water resistance of printed images. An object of the present invention is to provide a black ink composition that gives a black recorded image.

As a result of intensive studies to solve the above-described problems, the present inventors have found that the hue can be improved by using a specific coloring matter, more specifically, a compound of the following formula (1) as a toning component of black ink. The present inventors have found that a black ink composition having improved and various fastness properties and particularly improved water resistance can be obtained, and the present invention has been achieved.
That is, the present invention
(1)
A water-based black ink composition comprising a water-soluble monoazo compound represented by the following formula (1) or a salt thereof:

(2)
The aqueous black ink composition according to (1), wherein at least one of the black dye components in the black ink composition is a black dye represented by the following formula (2) or a salt thereof,

(In the formula (2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfonyl group, or an N-phenylaminosulfonyl group. , May be substituted with a hydroxyl group (C1-C4) may be substituted with an alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) alkoxy group (C1-C4) ) Alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group (C1-C4) alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group in a good be substituted phenylsulfonylamino group, R ³ and R ⁴ Waso Each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a hydroxyl group or a (C1-C4) alkoxy group (C1-C4) alkyl group, hydroxyl group or ( C1-C4) phenylsulfonyl which may be substituted with alkoxy group, sulfo group or carboxyl group (C1-C4) which may be substituted with alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group An amino group, n is 0 or 1, and Q represents a substituted phenyl group or a substituted naphthyl group.
(3)
The aqueous black ink composition according to (2), wherein Q of the black dye represented by the formula (2) is the following formula (101) or the following formula (102):

(In formula (101), * represents a carbon atom bonded to an azo nitrogen atom, and R ⁵ to R ⁷ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) which may be substituted with hydroxyl group ) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with alkoxy group (C1-C4) alkoxy group, acylamino group, A phenyl group optionally substituted with an alkylsulfonylamino group, a halogen atom, an alkyl group or a nitro group. Represents a nylsulfonylamino group.)

(In the formula (102), * represents a carbon atom bonded to an azo nitrogen atom, and R ^{5 ′} to R ^{8 ′} are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group. Group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1) -C4) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with an alkoxy group (C1-C4) alkoxy group, acylamino Group, alkylsulfonylamino group, halogen atom or alkyl group or nitro group It represents a sulfonyl sulfonylamino group.)
(4)
The aqueous black ink composition according to (2), wherein R ^{1 of the} black dye represented by formula (2) is a carboxyl group or a sulfo group, R ² is a hydrogen atom, and n is 1.
(5)
When R ^{1 of the} black dye represented by formula (2) is a sulfo group and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group, and R 1 The aqueous black ink composition according to (2), wherein when the substitution position of ¹ is para to the azo group, the substitution position of the nitro group is ortho to the azo group,
(6)
The aqueous black ink composition according to any one of (3) to (5), wherein Q of the black dye represented by formula (2) is formula (101), and R ⁶ is a carboxyl group or a sulfo group,
(7)
The aqueous black ink composition according to any one of (3) to (5), wherein Q of the black dye represented by formula (2) is formula (102), and R ^{6 ′} and R ^{7 ′} are sulfo groups,
(8)
In the formula (2), Q of the black dye represented by formula (2) is formula (102), R ^{5 ′} is a hydrogen atom, R ^{6 ′} and R ^{7 ′} are sulfo groups, and R ^{8 ′} is a hydroxy group. The aqueous black ink composition according to the description,
(9)
Q of the black dye represented by formula (2) is formula (102), R ^{5 ′} is a hydrogen atom, R ^{6 ′} and R ^{7 ′} are sulfo groups, R ^{8 ′} is a hydroxy group, R ^{8 ′} The water-based black ink composition according to (8), wherein the substitution position is the 8-position when the carbon atom bonded to the azo group is the 1-position, and n is 1.
(10)
In the black dye represented by the formula (2), R ¹ and R ² are each independently a hydrogen atom, a carboxyl group, a sulfo group, or a (C1-C4) alkoxy group, and R ³ and R ⁴ are each independently a hydrogen atom. , A sulfo group, a (C1-C4) alkyl group, a hydroxyl group, a sulfo group, or a carboxyl group, a (C1-C4) alkoxy group, or a (C2-C5) aliphatic acylamino group, and n is 1 And when Q is the formula (101), R ^{5 to} R ⁷ are each independently a (C1-C4) alkylsulfonyl group which may be substituted with a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or a hydroxyl group. , A nitro group, a (C1-C4) alkoxy group or a (C1-C4) alkylphenylsulfonylamino group which may be substituted with a sulfo group, and Q is a group represented by the formula In the case of 2), the aqueous black ink composition according to (3), wherein R ^{5 ′ to} R ^{8 ′} are each independently a hydrogen atom, a hydroxyl group, a sulfo group, or a (C1-C4) alkylphenylsulfonylamino group,
(11)
When the substitution position of the nitro group of the black dye represented by formula (2) is para to the azo group, R ¹ is a carboxyl group, sulfo group, or methoxy group substituted in the ortho position with respect to the azo group. R ² is a sulfo group or hydrogen atom substituted at the meta position with respect to the azo group, n is 1, and R ³ is a sulfo group substituted at the meta position with respect to the azo group to which Q is bonded, carboxymethoxy Or a sulfopropoxy group, R ⁴ is a sulfo group, a methyl group or a hydrogen atom substituted in the ortho position with respect to the azo group to which Q is bonded, Q is the formula (101), and R ⁵ is an azo group Is a sulfo group, a carboxyl group, a methyl group or a hydrogen atom substituted in the ortho position relative to the carboxyl group substituted in the meta position with respect to the azo group, and R ⁶ is a hydroxyl group bonded in the para position to the azo group Group, sulfo group, Rufamoiru group, hydroxyethyl sulfonyl group, a nitro group, an acetylamino group, a methyl phenylsulfonylamino group or a hydrogen atom, R ⁷ is a carboxyl group, a sulfo group, a sulfopropoxy group or a hydrogen atom (3) an aqueous described Black ink composition,
(12)
When the substitution position of the nitro group of the black dye represented by formula (2) is para to the azo group, R ¹ is a carboxyl group or sulfo group substituted in the ortho position with respect to the azo group, and R ² Is a hydrogen atom, R ³ is a sulfo group, hydroxyethoxy group, carboxymethoxy group or sulfopropoxy group substituted at the meta position with respect to the azo group to which Q is bonded, and R ⁴ is an azo group to which Q is bonded. R is when the sulfo group, methyl group, hydroxyethoxy group, acetylamino group or hydrogen atom substituted in the ortho position, Q is the formula (102), and the carbon atom bonded to the azo group is the 1-position. ^{5 ′} is a sulfo group, methylphenylsulfonylamino group or hydrogen atom substituted at the 2-position, R ^{6 ′} is a sulfo group or hydrogen atom substituted at the 3-position or 4-position, and R ^{7 ′} is the 6-position or 7-position Replace with And a sulfo group or a hydrogen atom, a hydroxyl group R 8 ^'is substituted in 8-position, an aqueous black ink composition according to a sulfo group or a hydrogen atom (3),
(13)
The aqueous black ink composition according to (2) or (3), wherein the black dye represented by the formula (2) is a compound represented by the following formula (3) or the following formula (4) or a salt thereof:

(In the formulas (3) and (4), when R ¹ is a sulfo group and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group; ^When the substitution position of ¹ is para to the azo group, the substitution position of the nitro group is ortho to the azo group.)
(14)
(1) to an inkjet recording method using the aqueous black ink composition according to any one of (13),
(15)
The inkjet recording method according to (14), wherein the recording material in the inkjet recording method is an information transmission sheet,
(16)
The inkjet recording method according to (15), wherein the information transmission sheet contains a porous white inorganic substance,
(17)
An inkjet printer loaded with a container containing the ink composition according to any one of (1) to (13),
(18)
A colored body colored with the water-based black ink composition according to any one of (1) to (13),
About.

The ink composition of the present invention has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition of the present invention is used for ink jet recording, writing instruments, and the like, and when recording on plain paper and ink jet dedicated paper, the hue of the recorded image is neutral, and an ink having a low pigment concentration is prepared. However, a printed matter with a black hue can be obtained. Further, the printing density is high, and furthermore, ozone gas resistance, light resistance, moisture resistance, and particularly water resistance are excellent.
Further, by using it together with magenta, cyan and yellow dyes, full color ink jet recording excellent in ozone gas resistance, light resistance and moisture resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail.

  The salt of the compound represented by the following formula (1) independently means an inorganic or organic cation salt. Among these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of the organic cation salt include, but are not limited to, salts of the compound represented by the general formula (5).

The alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (5) is preferably a (C1 to C4) alkyl group, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples include isobutyl, sec-butyl, tert-butyl and the like.
Examples of hydroxyalkyl groups include hydroxy- (C1-C4) alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. It is done.
Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. A hydroxy (C1-C4) alkoxy- (C1-C4) alkyl group is mentioned, Among these, a hydroxyethoxy- (C1-C4) alkyl group is preferable. Particularly preferred is a hydrogen atom; methyl; hydroxy- (C1-C4) alkyl such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc. Groups: hydroxyethoxy- (C1-C4) such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. ) Alkyl group.

Specific examples of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (5) are shown in Table 1 below.

Preferable organic cation salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts, and triisopropanolamine salts.
Of the above inorganic and organic cation salts, lithium and sodium salts are particularly preferred.

  The compound represented by the formula (1) of the present invention is C.I. I. It is a compound known as Direct Orange 17 and can be produced, for example, as follows. That is, by a conventional method, an amine represented by the following formula (103) is diazotized, and a coupling reaction with a compound represented by the following formula (104) is performed at room temperature (20 to 25 ° C.) with weak alkalinity (pH 8 to 9). Can be obtained.

The aqueous black ink composition of the present invention is a black ink composition and contains the compound of the above formula (1).

Furthermore, it is preferable to contain a black dye component in the black ink composition.

Although there is no limitation in particular in the above black dye components, it is good to contain at least 1 type of black dye shown by following formula (2) as a black dye component.

(In the formula (2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfonyl group, or an N-phenylaminosulfonyl group. , May be substituted with a hydroxyl group (C1-C4) may be substituted with an alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) alkoxy group (C1-C4) ) Alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group (C1-C4) alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group in a good be substituted phenylsulfonylamino group, R ³ and R ⁴ Waso Each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a hydroxyl group or a (C1-C4) alkoxy group (C1-C4) alkyl group, hydroxyl group or ( C1-C4) phenylsulfonyl which may be substituted with alkoxy group, sulfo group or carboxyl group (C1-C4) which may be substituted with alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group An amino group, n is 0 or 1, and Q represents a substituted phenyl group or a substituted naphthyl group.

Q in the formula (2) is preferably a substituted phenyl group or a substituted naphthyl group represented by the following formula (101) or the following formula (102).

In the above formula (101), * represents a carbon atom bonded to an azo nitrogen atom, and R ⁵ to R ⁷ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) which may be substituted with hydroxyl group ) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with alkoxy group (C1-C4) alkoxy group, acylamino group, An alkylsulfonylamino group, a halogen atom, an alkyl group or a nitro group may be substituted with a nitro group. Represents an sulfonylsulfonylamino group;

In the above formula (102), * represents a carbon atom bonded to an azo nitrogen atom, and R ^{5 ′} to R ^{8 ′} are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group. Group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1) -C4) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with an alkoxy group (C1-C4) alkoxy group, acylamino Group, alkylsulfonylamino group, halogen atom or alkyl group or nitro group may be substituted. It represents the E sulfonyl sulfonylamino group.

R ¹ , R ² , R ³ and R ^{4 in} the above formula (2), R ⁵ , R ⁶ and R ^{7 in} the above formula (101), and R ^{5 ′} and R ^{6 ′} in the above formula (102) are described below. , R ^{7 ′} and R ^{8 ′} are described, but for the sake of convenience, R ^{5 to} R ⁷ and R ^{5 ′ to} R ^{8 ′} are expressed as “substituent of Q” unless otherwise specified.

Examples of the N-alkylaminosulfonyl group in R ^1, R ² and Q substituents in the above formula (2) include N-methylaminosulfonyl, N-ethylaminosulfonyl, N- (n-butyl) N- (C1-C4) alkylsulfonyl groups such as aminosulfonyl, N, N-dimethylaminosulfonyl, N, N-di (n-propyl) aminosulfonyl, or N-di (C1-C4) alkylsulfonyl groups. It is done.

Examples of the (C1-C4) alkylsulfonyl group which may be substituted with a hydroxyl group in the substituents of R ¹ and R ² and Q in the above formula (2) include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, Examples include butylsulfonyl, hydroxyethylsulfonyl, 2-hydroxypropylsulfonyl and the like.

Examples of the acyl group in the substituents of R ¹ and R ² and Q in the above formula (2) include (C2-C5) aliphatic acyl groups such as acetyl, propionyl, butyryl, isobutyryl, benzoyl, naphthoyl, etc. (C7-C11) aromatic acyl groups are preferred.

In the substituents of R ^{1 to} R ⁴ and Q in the formula (2), examples of the (C1 to C4) alkyl group which may be substituted with a hydroxyl group or a (C1 to C4) alkoxy group include, for example, methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl, 2-ethoxyethyl, n-propoxyethyl, Examples include isopropoxyethyl, n-butoxyethyl, methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, n-propoxybutyl and the like.

Examples of (C1 to C4) alkoxy groups which may be substituted with a hydroxyl group, (C1 to C4) alkoxy group, sulfo group or carboxyl group in the substituents of R ^{1 to} R ⁴ and Q in the above formula (2) As methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxy Ethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy, carboxymethoxy, 2-carboxyethoxy, 3 Carboxy propoxy, 3-sulfopropoxy, 4-sulfobutoxy and the like, sulfo (C1 -C4) alkoxy group and a carboxy (C1 -C4) alkoxy groups are particularly preferred.

In the substituents of R ^{1 to} R ⁴ and Q in the above formula (2), examples of the acylamino group include (C2-C5) aliphatic acylamino groups such as acetylamino, propionylamino, butyrylamino, isobutyrylamino and the like. And (C7-C11) aromatic acylamino groups such as benzoylamino and naphthoylamino are preferred.

In the substituents of R ^{1 to} R ⁴ and Q in the above formula (2), examples of the alkylsulfonylamino group include (C1 to C4) such as methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, butylsulfonylamino and the like. ) An alkylsulfonylamino group is preferred.

Examples of the phenylsulfonylamino group which may be substituted with a halogen atom, an alkyl group or a nitro group in the substituents of R ^{1 to} R ⁴ and Q in the above formula (2) include, for example, benzenesulfonylamino, toluenesulfonylamino , Chlorobenzenesulfonylamino, nitrobenzenesulfonylamino and the like.

Preferred R ¹ and R ² in the above formula (2) are hydrogen atom, chlorine atom, bromine atom, cyano, carboxyl, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl, Phosphoric acid, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy 2-carboxyethoxy, acetylamino, benzoylamino and the like, more preferably a hydrogen atom, a chlorine atom, cyano, sulfamoyl, acetyl, nitro, carboxyl and sulfo, particularly preferably a hydrogen atom, Boxyl and sulfo.

Preferred R ³ and R ⁴ in the above formula (2) are a hydrogen atom, cyano, carboxyl, sulfo, nitro, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxy. Ethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy and acetylamino, more preferably hydrogen atom, carboxyl, sulfo, methyl, methoxy, carboxymethoxy, 2-hydroxyethoxy and 3-hydroxy Sulfopropoxy, particularly preferably a hydrogen atom, methyl, 3-sulfopropoxy and sulfo.

Preferred R ⁵ to R ⁷ when Q is the above formula (101) are hydrogen atom, chlorine atom, bromine atom, cyano, carboxyl, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylaminosulfonyl, methylsulfonyl Hydroxyethylsulfonyl, phosphoric acid, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4- Sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino and benzoylamino, p-toluenesulfonylamino, etc., more preferably hydrogen atom, chlorine atom, cyano, sulfamoyl, acetyl, nitro, p-toluene Sulfonylamino, 3-sulfopropoxy, carboxyl and sulfo are particularly preferred, and are hydrogen atom, carboxyl and sulfo.

Preferred R ^{5 ′} to R ^{8 ′} when Q is the above formula (102) are hydrogen atom, chlorine atom, bromine atom, hydroxy, cyano, carboxyl, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylamino Sulfonyl, methylsulfonyl, hydroxyethylsulfonyl, phospho, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino, benzoylamino, p-toluenesulfonylamino, etc., more preferably hydrogen atom, hydroxy, carboxyl, sulfo, sulfamoyl, hydride Carboxyethyl sulfonyl, nitro, methyl, methoxy, ethyl, ethoxy, p- toluenesulfonyl amino, more preferably a hydrogen atom, hydroxy, carboxy, sulfo, sulfamoyl.

A specific combination of preferable substituents in the above formula (2) will be described.
Preferable specific examples of phenyl substituted with a nitro group, that is, a combination of R ¹ , R ² and a nitro group include 2-sulfo-4-nitrophenyl, 2- Carboxy-4-nitrophenyl, 2-methoxy-4-nitro-5-sulfophenyl, 2-carboxy-5-nitrophenyl and 2-nitro-4-sulfophenyl.
Preferable specific examples of phenyl substituted by R ³ and R ⁴ include 3-sulfophenyl, 3- (3- (sulfophenyl), and 3- (3- (sulfophenyl), when the bonding position of the azo group substituted by Q is 1-position and the substitution position of the other azo group is 4-position. 3-sulfopropoxy) phenyl, 3,6-disulfophenyl, 3- (3-sulfopropoxy) -6-methylphenyl, 3- (carboxymethoxy) phenyl, 3- (carboxymethoxy) -6-methylphenyl, 3 -Sulfo-6-acetylaminophenyl and 3,6-di-hydroxyethoxyphenyl.
When Q is the above formula (101), preferred specific examples of R ^{5 to} R ⁷ are 4-sulfophenyl, 2,5-disulfophenyl, 4 when the azo group-bonded carbon atom is in the 1-position. -Carboxyphenyl, 3,5-dicarboxyphenyl, 2-carboxy-5-sulfophenyl, 2,5-dicarboxyphenyl, 4- (2-hydroxyethylsulfonyl) phenyl, 3-carboxy-4-sulfophenyl, 2 -Carboxy-4-sulfamoylphenyl, 2-sulfo-4-nitrophenyl, 2-methyl-4- (p-toluenesulfonyl) amino-5- (3-sulfopropoxy) phenyl, 2-methyl-4-acetyl Amino-5- (3-sulfopropoxy) phenyl, 4-hydroxyphenyl and 2-carboxy-4-sulfophenyl.
When Q is the above formula (102), preferred specific examples of R ^{5 ′ to} R ^{8 ′} are 3,6,8-trisulfonaphthyl, 3, when the carbon atom to which the azo group is bonded is the first position, 6-disulfo-8-hydroxynaphthyl, 4,6-disulfo-8-hydroxynaphthyl, 4,8-disulfonaphthyl, 2- (p-toluenesulfonyl) amino-3,6-disulfo-8-hydroxynaphthyl, 4 , 7-disulfonaphthyl and 2,4-disulfo-8-hydroxynaphthyl.
n is preferably 0 or 1, particularly preferably 1.
Compounds that further combine these preferred specific examples are particularly preferred.

The black dye represented by the above formula (2) can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each step is expressed in the form of a free acid.
R ^{1 to} R ⁷ , R ^{5 ′ to} R ^{8 ′} and n used as appropriate in each formula have the same meaning as described above.
A compound of the following formula (7) obtained by reacting a compound of the following formula (6) with p-toluenesulfonyl chloride in the presence of an alkali is diazotized by a conventional method to obtain a diazo compound.

Next, the obtained diazo compound and 4-amino-5-naphthol-1,7-disulfonic acid are subjected to a coupling reaction under acidic conditions to obtain a compound of the following formula (8).

On the other hand, the compound of the following formula (9) is diazotized by a conventional method, and the compound of the following formula (10) is obtained by coupling reaction of this diazo compound and the compound of the above formula (8).

The obtained compound of the formula (10) is hydrolyzed under alkaline conditions to obtain a compound of the following formula (11).

On the other hand, the monoazo compound of the following formula (12) is diazotized by a conventional method, and the diazo compound and the compound of the above formula (11) are coupled, whereby the above formula (2) in which Q is the above formula (101). The black dye represented by these, or its salt can be obtained.

The monoazo compound of the above formula (12) can be synthesized by a conventional method. For example, the compound of the following formula (13) is diazotized by a conventional method to obtain a diazo compound.

A compound of the above formula (12) can be obtained by a coupling reaction between the obtained diazo compound and a compound of the following formula (14).

As another method for synthesizing the compound of the above formula (12), there is the following method. That is, a compound of the following formula (15) is diazotized by a conventional method, and then coupled with a compound of the following formula (16) to obtain a compound of the following formula (17).

The compound of the above formula (12) can also be obtained by hydrolyzing N-acetyl with the obtained compound of the above formula (17) acidic or alkaline.

In the above synthesis examples, the synthesis of the black dye represented by the above formula (2) in which Q is the above formula (101) has been described. However, when synthesizing the compound represented by the above formula (102), The following method may be used. That is, first, a compound of the following formula (19) is obtained by conducting a similar reaction using a compound of the following formula (18) instead of the compound of the above formula (13). Next, the obtained compound of the following formula (19) is used in the same manner by using the compound of the following formula (12) instead of the compound of the above formula (12). A black dye can be synthesized.

Although the preferable example of the black dye represented by the said Formula (2) is given to following Tables 2-6, this invention is not specifically limited to the ink composition using these dyes.

The esterification reaction of the compound of formula (6) with p-toluenesulfonyl chloride is carried out by a method known per se, and is carried out in neutral to alkaline water or an aqueous organic solvent, for example, 20 to 100 ° C., preferably 30 to 80 It is advantageous to carry out at a temperature of ° C. The inside of the reaction system is preferably adjusted from neutral to weakly alkaline, for example, pH 7 to 10. The pH is adjusted by the addition of a base. The base used is an inorganic base such as an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide, an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, and acetic acid. Acetates such as sodium, ammonia or organic amines can be used. The compound of formula (6) and p-toluenesulfonyl chloride are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (7) is carried out in a manner known per se, for example nitrites such as sodium nitrite in aqueous inorganic acids, for example at temperatures of -5 to 30 ° C., preferably 5 to 15 ° C. This is done using an alkali metal nitrite salt. Coupling of the diazotized compound of formula (7) with 4-amino-5-naphthol-1,7-disulfonic acid is also carried out under reaction conditions known per se. That is, it is advantageous to carry out the reaction in acidic to neutral water or an aqueous organic solvent, for example at a temperature of -5 to 30 ° C, preferably 5 to 25 ° C. Usually, the pH in the reaction system is acidified as the coupling reaction proceeds. Therefore, it is preferable to keep the reaction system from acidic to weakly acidic, for example, pH 1 to 4, by adding a base. The base that can be used is the same as described above. The compound of formula (7) and 4-amino-5-naphthol-1,7-disulfonic acid are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (9) is also carried out by a method known per se, for example, an alkali metal nitrite as described above in an inorganic acid aqueous solution, for example, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. Is implemented using. Coupling of the diazotized compound of formula (9) with the compound of formula (8) is also carried out under reaction conditions known per se. That is, it is advantageous to carry out the reaction in weakly acidic to alkaline water or an aqueous organic solvent, for example, at a temperature of -5 to 30 ° C, preferably 10 to 25 ° C. Preferably, the reaction is carried out at a weak acidity to a weak alkalinity, for example, pH 5 to 10, and the pH is adjusted by adding a base. The base that can be used is the same as described above. The compounds of formulas (8) and (9) are used in approximately stoichiometric amounts.

Production of the compound of the general formula (11) by hydrolysis of the compound of the formula (10) is also carried out by a method known per se. It is preferable to heat in an alkaline aqueous solution or an alkaline aqueous organic solvent. For example, after adding sodium hydroxide or potassium hydroxide to a solution containing the compound of the general formula (10) to adjust the pH to 9.5 or higher, for example, 20 It is preferable to heat to a temperature of ˜150 ° C., preferably 30 to 100 ° C. At this time, the pH of the reaction solution is preferably maintained at 9.5 to 11.5 while appropriately adding a base, and the above-mentioned inorganic bases can be used.

The diazotization of the compound of the formula (13) is also carried out by a method known per se, for example, an alkali metal nitrite in the same manner as described above in an aqueous inorganic acid solution at a temperature of, for example, -5 to 30 ° C, preferably 0 to 15 ° C. Is implemented using. Coupling of the diazotized compound of formula (13) with the compound of formula (14) is also carried out under reaction conditions known per se. That is, it is advantageous to carry out the reaction in acidic to neutral water or an aqueous organic solvent, for example at a temperature of -5 to 30 ° C, preferably 5 to 25 ° C. Usually, the pH in the reaction system is acidified as the coupling reaction proceeds. Therefore, it is preferable to keep the reaction system from acidic to weakly acidic, for example, pH 1 to 6, by adding a base. The base that can be used is the same as described above. The compounds of formulas (13) and (14) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (12) is also carried out by a method known per se, such as an alkali metal nitrite in the same manner as described above in an aqueous inorganic acid solution, for example at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. Is implemented using. Coupling of the diazotized compound of the compound of formula (12) with the compound of formula (11) is also carried out under reaction conditions known per se. That is, it is advantageous to carry out the reaction in weakly acidic to alkaline water or an aqueous organic solvent, for example, at a temperature of -5 to 30 ° C, preferably 10 to 25 ° C. It is preferably carried out at a weak acidity to a weak alkalinity, for example, pH 5 to 10, and the pH is adjusted by adding a base. The base that can be used is the same as described above. The compounds of formulas (11) and (12) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (18) is also carried out by a method known per se, for example, an alkali metal nitrite in the same manner as described above in an aqueous inorganic acid solution at a temperature of, for example, -5 to 30 ° C, preferably 0 to 15 ° C. Is implemented using. Coupling of the diazotized compound of the compound of formula (18) and the compound of formula (14) is also carried out under conditions known per se. It is advantageous to carry out the reaction in acidic to neutral water or an aqueous organic solvent, for example at a temperature of -5 to 30 ° C, preferably 5 to 25 ° C. For example, it is carried out at pH 1 to 7, and the pH is adjusted by adding a base in the same manner as described above. The base that can be used is the same as described above. The compounds of formulas (18) and (14) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (19) is also carried out by a method known per se, for example, an alkali metal nitrite as described above at a temperature of, for example, -5 to 30 ° C, preferably 5 to 25 ° C in an inorganic acid aqueous solution. Is implemented using. Coupling of the diazotized compound of formula (19) with the compound of formula (11) is also carried out under conditions known per se. It is advantageous to carry out the reaction in weakly acidic to alkaline water or an aqueous organic solvent, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C. It is preferably carried out at a weak acidity to a weak alkalinity, for example, pH 6 to 10, and the pH is adjusted by adding a base in the same manner as described above. The base that can be used is the same as described above. The compounds of formulas (11) and (19) are used in approximately stoichiometric amounts.

The compound represented by the above formula (2) or a salt thereof (hereinafter, unless otherwise specified, the compound or a salt thereof is simply referred to as a compound) is in the form of a free acid by adding a mineral acid such as hydrochloric acid after the coupling reaction. Can be isolated as a solid. By washing the obtained solid with water or acidic water, inorganic salts such as sodium chloride contained as impurities in the compound can be removed.
The acid type dye having a low salt content as an impurity thus obtained can be neutralized with a desired inorganic or organic base in an aqueous solvent to form a corresponding salt solution. 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 the organic base include, but are not limited to, organic amines such as alkanolamines such as diethanolamine and triethanolamine.

The salt of the compound represented by the formula (2) 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. Preferred examples of the salt include those of the compound represented by the above formula (5), for example, those preferable as the salt of the above formula (1), but are not limited thereto.

For example, when it is desired to prepare a sodium salt of the compounds of the above formulas (1) and (2), a reaction solution containing the compound or a cake or a dried product is dissolved in water, and salted out by adding salt to this, precipitation The sodium salt of the target compound can be obtained as a wet cake by filtering the solid.
Moreover, the wet cake is dissolved again in water, and a mineral acid such as hydrochloric acid is added to adjust the pH of the aqueous solution to a strong acidity such as 1 or less, so that the free acid of the compound is obtained again as a wet cake. Can do. Furthermore, if the precipitated solid is collected by adjusting the pH of the aqueous solution to an acidity of about 1 to 4, a mixture of the free acid and sodium salt of the compound can be obtained. The pH in this case is only a guideline, and it is preferable to adjust the pH appropriately depending on the substituents of the compound to obtain the target compound salt, free acid or a mixture thereof.
While stirring the above free acid wet cake with water, for example, by adding a base such as potassium hydroxide, lithium hydroxide, aqueous ammonia and a compound of formula (5) to make it alkaline, each corresponding potassium salt By obtaining a lithium salt, an ammonium salt, or an organic salt, the salt of the target compound can be arbitrarily exchanged. It is also possible to adjust a mixed salt of a compound such as a sodium salt and a lithium salt, or a sodium salt and an ammonium salt by appropriately adjusting the amount of a base to be added.

The compound of the above formula (1) and the black dye represented by the above formula (2) are usually 1%: 99% -60%: 40%, more preferably 10%: 90% -40%: It is recommended to mix at 60% and prepare and use it as an ink. In addition, the ratio of these dye compounds is a ratio when using the pigment | dye powder after desalting the inorganic metal salt contained as an impurity.
In addition, in order to finely adjust the black hue, the aqueous black ink composition of the present invention is further mixed with another pigment having a hue different from that of the compound represented by the above formula (1) and the above formula (2). May be.

  For example, when the compound of the above formula (1) or the formula (2) is obtained by a synthetic reaction by the above method, it contains the black dye of the above formula (1) or the above formula (2) obtained in the final step of the synthetic reaction. The reaction liquid for the synthesis reaction can be used directly for the production of the ink composition. However, the wet cake containing the compound of the formula (1) or the formula (2) obtained by isolation from the reaction solution using a method such as salting out is dried by, for example, spray drying, and this is again performed. It can also be processed into an ink composition by dissolving in an aqueous organic solvent or the like.

The water-based black ink composition of the present invention contains the dye compound in a total amount of usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass with respect to the entire ink composition. To do. The aqueous black ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 5% by mass of an ink preparation agent, for example. The remainder other than the above is water. The pH of the aqueous black ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 in terms of improving storage stability. The surface tension of the aqueous black ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the aqueous black ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

When the aqueous black ink composition of the present invention is used as an ink for an ink jet printer, it is preferable to prepare an ink composition containing a small amount of inorganic salt as an impurity such as a metal cation chloride or sulfate. For this purpose, it is preferable to reduce the content of the inorganic salt in the dye compound used, and the content is preferably about 0.1% by mass or less based on the total amount of the dye compound. In order to produce a compound with a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a method of suspending or crystallizing a dried product or wet cake of a dye compound in a mixed solvent of alcohol such as methanol and water. What is necessary is just to desalinate.

The water-soluble organic solvent that can be used in the aqueous black ink composition of the present invention is not particularly limited as long as it is an organic solvent miscible with water. In addition, for the sake of convenience, in the present specification, an organic compound that is not normally recognized as a solvent itself, such as urea, is classified as a water-soluble organic solvent for the sake of convenience. There is a case. Therefore, even such an organic compound can be used as an aqueous organic solvent as long as it is miscible with water. However, urea is generally classified as a dye solubilizer.
Specific examples of the water-soluble organic solvent include, for example, C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, N, N-dimethylformamide or N , Carboxylic acid amides such as N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Cyclic ureas such as ON, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as ketoalcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3 -Propylene glycol, 1,2- or 1,4- Monomers, oligomers or poly- having (C2-C6) alkylene units such as tylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. Polyols such as alkylene glycol or thioglycol, glycerin, hexane-1,2,6-triol (triol), ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or diethylene glycol monobutyl ether (butyl carbyl) Tall) or triethylene glycol monomethyl ether or Polyhydric alcohol (C1 -C4) alkyl ethers such as ethylene glycol monoethyl ether, .gamma.-butyrolactone or dimethyl sulfoxide. These water-soluble organic solvents are used alone or in combination. Among these, preferred are 2-pyrrolidone, N-methyl-2-pyrrolidone, mono-, di- or triethylene glycol, dipropylene glycol, glycerin, isopropyl alcohol, and butyl carbitol, more preferably 2-pyrrolidone, N -Methyl-2-pyrrolidone, diethylene glycol, glycerin, isopropyl alcohol and butyl carbitol.

  Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and surfactants. Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide, and examples of the isothiazoline compound include 1,2-benzisothiazoline-3-one. 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-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 can be mentioned. Other antiseptic / antifungal agents include sodium sorbate and sodium benzoate.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink in a range of usually 7.0 to 11.0 without adversely affecting the prepared ink composition. Examples of pH adjusters that can be used include, for example, alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, and lithium carbonate. And alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples of chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like. Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone or sulfonated benzotriazole. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. Urea is preferred.

Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.

Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, rosin acid soap, castor oil sulfate Examples thereof include salts, lauryl alcohol sulfates, alkylphenol phosphates, alkyl phosphates, alkylallylsulfone hydrochloride, diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. Etc.

Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ether type such as polyoxyalkylene alkyl ether such as alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioxide Esters such as oleate, polyoxyethylene monooleate, polyoxyethylene stearate, 2, 4, Acetylene glycols such as 3,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol ( Alcohol) type (for example, trade name Surfinol 104, 104PG50, 82, 465, Olphine STG, etc., manufactured by Nissin Chemical Co., Ltd.) and the like.
The ink preparation agents as described above may be used alone or in combination.

The water-based black ink composition of the present invention can be obtained by mixing the above components in an arbitrary order and making a solution by stirring or the like. The obtained ink composition may be filtered with a membrane filter or the like in order to remove impurities.

The water-based black ink composition of the present invention can be used in various fields, and is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and an ink-jet ink containing the ink composition. It is particularly preferable to use as Therefore, the inkjet ink of the present invention is preferably used in the inkjet recording method of the present invention described later.

Next, the ink jet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using the aqueous black ink composition of the present invention. That is, the ink jet recording method of the present invention performs recording on an image receiving material using the water-based black ink composition of the present invention, but there are no particular restrictions on the ink nozzles used at that time, and they are appropriately selected according to the purpose. be able to. Various known methods, 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, and an ink that converts an electrical signal into an acoustic beam An acoustic ink jet system that irradiates the ink and discharges ink using the radiation pressure, a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating the ink, and the like are employed. be able to. The ink jet recording method includes a method of ejecting many low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and a colorless and transparent type. A method using ink is included.

The colored body of the present invention is colored with the aqueous black ink composition of the present invention, and more preferably is colored with an ink jet printer using the aqueous black ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Among these, 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 base material with a cationic polymer, and a porous white inorganic substance capable of absorbing the pigment in the ink such as porous silica, alumina sol or special ceramics. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone. An information transmission sheet provided with such an ink receiving layer is usually called ink jet paper (film), glossy paper (film), etc., for example, trade names: professional photo paper, super photo paper, mat photo paper (any Product name: photographic paper (glossy), PM matte paper, crispia (all manufactured by Seiko Epson Corporation), product name: advanced photo paper, premium plus photo paper, premium glossy film, photo Paper (all manufactured by Nippon Hewlett-Packard Co., Ltd.) and trade name: Photolike QP (manufactured by Konica Corporation) are available as commercial products. Of course, plain paper can also be used.

  Among these, it is known that an image recorded on an information transmission sheet coated with a porous white inorganic substance on the surface is particularly prone to discoloration by ozone gas, but the aqueous black ink composition of the present invention is particularly resistant to water. Although it is excellent in the properties, it is also excellent in ozone gas resistance, so that it is effective when recording on such a recording material.

  In order to record on a recording material such as an information transmission sheet in the ink jet recording method of the present invention, for example, a container containing the above aqueous black ink composition is set at a predetermined position of an ink jet printer, What is necessary is just to record on a recording material. In the inkjet recording method of the present invention, the water-based black ink composition of the present invention is a known magenta ink composition, cyan ink composition, yellow ink composition, and, if necessary, a green ink composition, blue (or violet). It can be used in combination with an ink composition and a red (or orange) ink composition. The ink composition of each color is poured into each container, and the container is used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous black ink composition for ink jet recording of the present invention.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples. In the text, “parts” and “%” are based on mass unless otherwise specified. Further, acidic functional groups such as sulfo groups are expressed in the form of free acids. In this example, the target compound was synthesized as a sodium salt and used in various tests.

Synthesis example 1
Synthesis of Compound of Formula (1) 32.0 parts of dehydrothio-p-toluidinesulfonic acid was diazotized at room temperature (20 to 25 ° C.) with sodium nitrite in hydrochloric acid.
After dissolving 28.4 parts of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid in aqueous sodium hydroxide while maintaining pH 8-9, diazonium of dehydrothio-p-toluidinesulfonic acid obtained above The coupling reaction was carried out by mixing the salt with 20 to 25 ° C. and pH 8 to 9 to obtain 52.0 parts of a sodium salt of the compound represented by the above formula (1). The maximum absorption wavelength (λmax) of this compound in an aqueous solution of pH 9 was 453 nm, and the solubility was 100 g / l or more.

Synthesis example 2
(1) After reacting 20.1 parts of 2-amino-5-naphthol-1,7-disulfonic acid and 12.6 parts of p-toluenesulfonyl chloride at pH 8.0 to 8.5 at 70 ° C. for 1 hour. Salted out with acidity. 28.4 parts of the compound of the following formula (20) obtained by filtering the precipitated solid was dissolved in 300 parts of water while adjusting the pH to 6.0 to 8.0 with sodium carbonate. After adding 18.7 parts of 35% hydrochloric acid to this solution, the mixture was cooled to 0 to 5 ° C., and 10.7 parts of 40% aqueous sodium nitrite solution was added for diazotization.

After suspending 19.1 parts of 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid in 200 parts of water and adding this to a diazo suspension of the compound of the above formula (20), carbonic acid was added. The reaction solution was stirred at 10 to 20 ° C. for 12 hours while maintaining the pH of the reaction solution at 2.4 to 2.8 with sodium. The pH in the reaction system was adjusted to 7.0 to 8.5 with sodium carbonate, and the precipitated solid was dissolved to obtain a solution containing a monoazo compound of the following formula (21).

(2) 14.4 parts of sodium 4-nitroaniline-2-sulfonate are dissolved in 150 parts of water, and 18.8 parts of 35% hydrochloric acid and 10.6 parts of 40% aqueous sodium nitrite solution are added thereto at 0-5 ° C. Was added to diazotize. The obtained diazo suspension was added dropwise to a solution containing the monoazo compound of the formula (21) obtained in Synthesis Example 2 (1). During this time, the reaction temperature was maintained at 10 to 20 ° C., and the pH of the reaction solution was maintained at 8.0 to 9.0 with sodium carbonate. After completion of the dropwise addition, the mixture was further stirred for 2 hours at a reaction temperature of 15 to 30 ° C and a pH of the reaction solution of 8.0 to 9.0. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was collected by filtration to obtain a wet cake containing the compound of formula (22).

The wet cake obtained above was dissolved in 400 parts of water, heated to 70 ° C., and stirred for 1 hour while maintaining the pH value at 10.5 to 11.0 with sodium hydroxide. After cooling to room temperature, the pH was adjusted to 7.0 to 8.0 with 35% hydrochloric acid, and sodium chloride was added for salting out. The precipitated solid was collected by filtration to obtain a wet cake containing the compound of formula (23).

(3) 17.0 parts of the compound of formula (24) was added to 170 parts of water, and sodium hydroxide was added thereto to adjust the pH to 7.0 to 8.0 to obtain a solution. To the resulting solution, 17.4 parts of 35% hydrochloric acid and 8.7 parts of a 40% aqueous sodium nitrite solution were added at 0 to 5 ° C. for diazotization.

A wet cake containing the compound of the formula (23) is dissolved in 400 parts of water, and obtained as described above at an internal temperature of 10 to 25 ° C. while maintaining the pH at 8.0 to 9.0 with sodium hydroxide. The resulting diazo suspension of formula (24) was added dropwise. After completion of the dropwise addition, the mixture was further stirred for 2 hours while maintaining the internal temperature of 15 to 30 ° C. and the pH of 8.0 to 9.0. Sodium chloride was added for salting out, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved in 400 parts of water, 1000 parts of 2-propanol was added and crystallized, and the precipitated solid was collected by filtration. Further, the obtained wet cake was dissolved in 300 parts of water, 900 parts of 2-propanol was added for crystallization, and the precipitated solid was collected by filtration and dried to obtain a black water-soluble dye represented by the following formula (25). (No. 1 compound in Table 2) 49.0 parts were obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution at pH 9 was 590 nm, and the solubility was 100 g / l or more.

Synthesis example 3
Except that 14.4 parts of sodium 4-nitroaniline-2-sulfonate in Synthesis Example 2 (2) was changed to 14.4 parts of sodium 2-nitroaniline-4-sulfonate, the following formula ( 26) 47.0 parts of a black water-soluble dye represented by No. 26 (No. 3 compound in Table 2) was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution at pH 9 was 592 nm, and the solubility was 100 g / l or more.

Synthesis example 4
(1) 11.5 parts of sodium 4-nitroaniline-2-sulfonate are dissolved in 100 parts of water, and 14.1 parts of 35% hydrochloric acid and 8.6 parts of 40% aqueous sodium nitrite solution are added thereto at 0-5 ° C. Was added to diazotize to obtain a diazo suspension.
To 100 parts of water, 12.3 parts of a compound of the following formula (27) was added, and sodium hydroxide was added thereto to adjust the pH to 5.0 to 6.0 to obtain a solution. This solution was added dropwise to the diazo suspension obtained above while maintaining an internal temperature of 10 to 15 ° C. After completion of the dropwise addition, sodium carbonate was gradually added to adjust the pH to 6.0 to 7.0 over 1 hour, followed by stirring for 2 hours while maintaining the internal temperature of 15 to 20 ° C. and pH 6.0 to 7.0. Sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake containing the compound of formula (18).

(2) Synthesis except that the wet cake containing the compound of the formula (28) obtained in Synthesis Example 4 (1) is used instead of 17.0 parts of the compound of the formula (24) in Synthesis Example 2 (3). In the same manner as in Example 2, 50.1 parts of a black water-soluble dye of the following formula (29) (No. 13 compound in Table 3) was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution of pH 9 was 615 nm, and the solubility was 100 g / l or more.

Synthesis example 5
(1) The same as Example 3 (1) except that 10.4 parts of 5-sulfoanthranilic acid was used instead of 11.5 parts of sodium 4-nitroaniline-2-sulfonate in Synthesis Example 4 (1). Thus, a wet cake containing a compound of the following formula (30) was obtained.

(2) In the same manner as in Synthesis Example 2 except that a wet cake containing the compound of the formula (30) obtained by the above reaction was used instead of 17.0 parts of the compound of the formula (24) in Synthesis Example 2 (3). Then, 44.1 parts of a black water-soluble dye (No. 18 compound in Table 4) of the following formula (31) of the present invention was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution at pH 9 was 608 nm, and the solubility was 100 g / l or more.

Synthesis Example 6
(1) By reacting 6.4 parts of 2-amino-5-naphthol-1,7-disulfonic acid as a starting material in the same manner as in Synthesis Examples 1 (1) and (2), A wet cake containing the compound was obtained.

(2) 10.9 parts of the compound of the following formula (32) obtained by the method described in JP-A-2005-068416 (the reaction solution was acidified to a pH of 0.5 or less with 35% hydrochloric acid, and precipitated solid Was filtered and dried) in 100 parts of water, and this was dissolved in sodium hydroxide to a pH of 6.0 to 7.0. To this solution, 5.9 parts of 35% hydrochloric acid and 2.9 parts of 40% aqueous sodium nitrite were added at an internal temperature of 0 to 5 ° C. to diazotize to obtain a diazo suspension.
The wet cake containing the compound of formula (23) obtained in Synthesis Example 6 (1) was dissolved in 140 parts of water, and the diazo suspension obtained as described above was dissolved in this solution at an internal temperature of 15 It was added dropwise while maintaining the pH at 8.0 to 9.0 with sodium carbonate at -30 ° C. After completion of the dropping, the mixture was stirred for 2 hours at an internal temperature of 15 to 30 ° C. and a pH of 8.0 to 9.0. After heating to an internal temperature of 70 ° C., the mixture was further stirred for 1.5 hours while adjusting the pH to 10.5 to 11.0 with sodium hydroxide.
After cooling the reaction solution to room temperature, 35% hydrochloric acid was added to adjust the pH to 7.0 to 8.0, and sodium chloride was further added to salt out.
The wet cake obtained by filtering the precipitated solid was dissolved in 200 parts of water, and 300 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration. Next, the obtained wet cake was dissolved in 150 parts of water, 200 parts of 2-propanol was added for crystallization, and the precipitated solid was collected by filtration and dried to give a black water-soluble dye of the following formula (33) (Table 5). No. 21 compound) in 16.0 parts was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution having a pH of 7 to 8 was 626 nm, and the solubility was 100 g / L or more.

(A) Preparation of ink In the following, all the dye components were desalted. The impurity inorganic salt content after desalting was 0.1% by mass or less based on the total mass of each dye compound.

Example 1
The components in Table 7 below were mixed, and then filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention from which impurities were removed.

Table 7
Compound (Na salt) obtained in Synthesis Example 1 0.8 part Compound (Na salt) obtained in Synthesis Example 2 3.2 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4 0.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (trade name Surfinol 104, manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous sodium hydroxide solution 76.9 parts, total 100.0 parts

Example 2
The components shown in Table 8 below were mixed and then filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention from which impurities were removed.

Table 8
Compound (Na salt) obtained in Synthesis Example 1 0.8 part Compound (Na salt) obtained in Synthesis Example 6 3.2 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4 0.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (trade name Surfinol 104, manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous sodium hydroxide solution 76.9 parts, total 100.0 parts

(B) Inkjet printing Using each of the aqueous black ink compositions of the present invention obtained above, an Epson exclusive glossy paper (trade name: photographic paper crispia) is printed by an inkjet printer (trade name: PIXUS iP4100, Canon). (High gloss)). At the time of printing, an image pattern was prepared so that gradations with several levels of reflection density were obtained, and a half-tone black print was obtained. Among the test methods described below, in the hue evaluation measurement, which is an item to be evaluated using a colorimeter, when the a ^* value and b ^* value of the printed material are measured, the reflection density D value of the printed material is The highest part was used. Similarly, in the light resistance test and the ozone gas resistance test using the colorimeter, the measurement was performed using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0. In the water resistance test, a halftone pattern image was printed using an inkjet printer to prepare a printed matter for evaluation.

(C) Evaluation of recorded image
The recorded image by the water-based ink composition of the present invention was evaluated for hue, printing density, hue change after light resistance test, hue change after ozone gas resistance test, and water resistance test. The results are shown in Table 10. The test method is shown below.
(1) Hue evaluation The hue evaluation (numerical data) of the recorded image was evaluated by a colorimeter. The colorimeter measured the a ^* value and b ^* value using Gretag Macbeth SpectroEye (manufactured by GRETAG), and calculated the C ^* value. The formula for calculating the C ^* value is C ^* = {(a ^* ) ² + (b ^* ) ² } ^1/2 . The better black with no color, the smaller C ^* . Judgment criteria are shown below.
A C ^* <15.
B 15 ≦ C ^* ≦ 20.
C 20 <C ^* .

(2) Water resistance test 100 μl of ion-exchanged water was dropped onto a halftone print prepared for the water resistance test, and bleeding of the printed matter after natural drying was visually evaluated. Evaluation was performed according to the following criteria.
A Bleeding is hardly seen B Slight bleeding is seen C Severe bleeding is seen

(3) Light resistance test Using a xenon weatherometer (Ci4000, manufactured by ATLAS), a 2 mm thick glass plate is installed so that an air layer is formed between the printed sample and 0.36 W / square meter illuminance, humidity Irradiation was performed for 50 hours under conditions of 60% RH and temperature of 24 ° C. After the test was completed, color measurement was performed using the above colorimeter. The dye residual ratio was determined by (reflected density after test / reflected density before test) × 100 (%) and evaluated according to the following criteria.
A Residual rate: 95% or more B Residual rate: Less than 95% and 85% or more C Residual rate: Less than 85%

(4) Ozone resistance test Using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.), the print sample was allowed to stand for 4 hours at an ozone gas concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After the test, the color was measured in the same manner as described above, and the residual ratio of the dye concentration before and after the test was determined. The determination was made according to the following criteria.
A Residual rate: 90% or more B Residual rate: Less than 90% and 80% or more C Residual rate: Less than 80%

Comparative Examples 1 and 2
As an object for comparison, an ink composition having the composition shown in Table 9 below was prepared by using only the compounds obtained in Synthesis Example 2 and Synthesis Example 6 without using the compound of Formula (1) obtained in Synthesis Example 1. These were designated as Comparative Examples 1 and 2, respectively. The obtained ink composition was used for the same evaluation as described above, and the evaluation results are shown in Table 10.

Table 9
Compound obtained in Synthesis Example 2 or 6 4.0 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 Surface activity 0.1 parts (Surfinol 104 manufactured by Nissin Chemical)
Water + aqueous sodium hydroxide solution 76.9 parts, total 100.0 parts

Table 10
Hue Water resistance Light resistance Ozone gas resistance
Example 1 A A A A
Comparative Example 1 C B A A

Example 2 A B A A
Comparative Example 2 C C A A

As is clear from Table 10, it can be seen that Examples 1 and 2 have improved hue and water resistance compared to Comparative Examples 1 and 2, respectively. Moreover, the outstanding performance is maintained regarding light resistance and ozone resistance.
For water resistance, the evaluations of Comparative Examples 1 and 2 are B and C, respectively, whereas Examples 1 and 2 of the present invention using the compound of the above formula (1) are A and B in the same manner. It turns out that water resistance improves by adding the compound of the said Formula (1) compared with the case where the black dye represented by the said Formula (2) is used independently.
Patent Document 5 describes that the compound of the above formula (1) has a C ^* value higher than that of a commercially available orange ink and has a very high hue. However, as is clear from the results of hue evaluation in Table 10, the C ^* values of Examples 1 and 2 of the present invention containing the compound of the above formula (1) having a high C ^* value are both C ^* <15. In addition, it was found that Comparative Examples 1 and 2, which do not contain the compound of the above formula (1), both show a lower value as compared to 20 <C ^* , and show a better black color.
That is, when the compound of the above formula (1) is used alone, the C ^* value is high and the hue is very high, but when it is contained as a toning dye, it is contained. The effect of the present invention was clearly demonstrated by suppressing the C ^* value to be lower than that in the case of not giving it, and giving a good black print without color.
Therefore, the ink composition of the present invention is extremely useful as a black ink composition.

Claims (18)

An aqueous black ink composition comprising a water-soluble monoazo compound represented by the following formula (1) or a salt thereof, which is a black ink composition

2. The aqueous black ink composition according to claim 1, wherein at least one of the black dye components in the black ink composition is a black dye represented by the following formula (2) or a salt thereof.

(In the formula (2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfonyl group, or an N-phenylaminosulfonyl group. , May be substituted with a hydroxyl group (C1-C4) may be substituted with an alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) alkoxy group (C1-C4) ) Alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group (C1-C4) alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group in a good be substituted phenylsulfonylamino group, R ³ and R ⁴ Waso Each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, a nitro group, a hydroxyl group or a (C1-C4) alkoxy group (C1-C4) alkyl group, hydroxyl group or ( C1-C4) phenylsulfonyl which may be substituted with alkoxy group, sulfo group or carboxyl group (C1-C4) which may be substituted with alkoxy group, acylamino group, alkylsulfonylamino group, halogen atom, alkyl group or nitro group An amino group, n is 0 or 1, and Q represents a substituted phenyl group or a substituted naphthyl group. The aqueous black ink composition according to claim 2, wherein Q of the black dye represented by formula (2) is the following formula (101) or the following formula (102).

(In formula (101), * represents a carbon atom bonded to an azo nitrogen atom, and R ⁵ to R ⁷ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1-C4) which may be substituted with hydroxyl group ) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with alkoxy group (C1-C4) alkoxy group, acylamino group, A phenyl group optionally substituted with an alkylsulfonylamino group, a halogen atom, an alkyl group or a nitro group. Represents a nylsulfonylamino group.)

(In the formula (102), * represents a carbon atom bonded to an azo nitrogen atom, and R ^{5 ′} to R ^{8 ′} are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group. Group, N-alkylaminosulfonyl group, N-phenylaminosulfonyl group, (C1-C4) alkylsulfonyl group, phospho group, nitro group, acyl group, ureido group, hydroxyl group or (C1) -C4) (C1-C4) alkyl group, hydroxyl group or (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with an alkoxy group (C1-C4) alkoxy group, acylamino Group, alkylsulfonylamino group, halogen atom or alkyl group or nitro group It represents a sulfonyl sulfonylamino group.) The aqueous black ink composition according to claim 2, wherein R ^{1 of the} black dye represented by formula (2) is a carboxyl group or a sulfo group, R ² is a hydrogen atom, and n is 1. When R ^{1 of the} black dye represented by formula (2) is a sulfo group and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group, and R 1 The aqueous black ink composition according to claim 2, wherein when the substitution position of ¹ is para to the azo group, the substitution position of the nitro group is ortho to the azo group. ^6. The aqueous black ink composition according to claim 3, wherein Q of the black dye represented by formula (2) is formula (101), and R ⁶ is a carboxyl group or a sulfo group. ^6. The aqueous black ink composition according to claim 3, wherein Q of the black dye represented by formula (2) is formula (102), and R ^{6 ′} and R ^{7 ′} are sulfo groups. The black dye represented by formula (2) is represented by formula (102), R ^{5 ′} is a hydrogen atom, R ^{6 ′} and R ^{7 ′} are sulfo groups, and R ^{8 ′} is a hydroxy group. Aqueous black ink composition described Q of the black dye represented by formula (2) is formula (102), R ^{5 ′} is a hydrogen atom, R ^{6 ′} and R ^{7 ′} are sulfo groups, R ^{8 ′} is a hydroxy group, R ^{8 ′} The water-based black ink composition according to claim 8, wherein the substitution position is the 8-position when the carbon atom bonded to the azo group is the 1-position, and n is 1. In the black dye represented by the formula (2), R ¹ and R ² are each independently a hydrogen atom, a carboxyl group, a sulfo group, or a (C1-C4) alkoxy group, and R ³ and R ⁴ are each independently a hydrogen atom. , A sulfo group, a (C1-C4) alkyl group, a hydroxyl group, a sulfo group, or a carboxyl group, a (C1-C4) alkoxy group, or a (C2-C5) aliphatic acylamino group, and n is 1 And when Q is the formula (101), R ^{5 to} R ⁷ are each independently a (C1-C4) alkylsulfonyl group which may be substituted with a hydroxyl group, a carboxyl group, a sulfo group, a sulfamoyl group, or a hydroxyl group. , A nitro group, a (C1-C4) alkoxy group or a (C1-C4) alkylphenylsulfonylamino group which may be substituted with a sulfo group, and Q is a group represented by the formula (10 In the case of 2), R ^{5 ′ to} R ^{8 ′} are each independently a hydrogen atom, a hydroxyl group, a sulfo group or a (C1-C4) alkylphenylsulfonylamino group. When the substitution position of the nitro group of the black dye represented by formula (2) is para to the azo group, R ¹ is a carboxyl group, sulfo group, or methoxy group substituted in the ortho position with respect to the azo group. R ² is a sulfo group or hydrogen atom substituted at the meta position with respect to the azo group, n is 1, and R ³ is a sulfo group substituted at the meta position with respect to the azo group to which Q is bonded, carboxymethoxy Or a sulfopropoxy group, R ⁴ is a sulfo group, a methyl group or a hydrogen atom substituted in the ortho position with respect to the azo group to which Q is bonded, Q is the formula (101), and R ⁵ is an azo group Is a sulfo group, a carboxyl group, a methyl group or a hydrogen atom substituted in the ortho position relative to the carboxyl group substituted in the meta position with respect to the azo group, and R ⁶ is a hydroxyl group bonded in the para position to the azo group Group, sulfo group, Rufamoiru group, hydroxyethyl sulfonyl group, a nitro group, an acetylamino group, a methyl phenylsulfonylamino group or a hydrogen atom, aqueous claim 3 R ⁷ is a carboxyl group, a sulfo group, a sulfo propoxy group or a hydrogen atom Black ink composition When the substitution position of the nitro group of the black dye represented by formula (2) is para to the azo group, R ¹ is a carboxyl group or sulfo group substituted in the ortho position with respect to the azo group, and R ² Is a hydrogen atom, R ³ is a sulfo group, hydroxyethoxy group, carboxymethoxy group or sulfopropoxy group substituted at the meta position with respect to the azo group to which Q is bonded, and R ⁴ is an azo group to which Q is bonded. R is when the sulfo group, methyl group, hydroxyethoxy group, acetylamino group or hydrogen atom substituted in the ortho position, Q is the formula (102), and the carbon atom bonded to the azo group is the 1-position. ^{5 ′} is a sulfo group, methylphenylsulfonylamino group or hydrogen atom substituted at the 2-position, R ^{6 ′} is a sulfo group or hydrogen atom substituted at the 3-position or 4-position, and R ^{7 ′} is the 6-position or 7-position Replace with And a sulfo group or a hydrogen atom, a hydroxyl group R 8 ^'is substituted in 8-position, an aqueous black ink composition according to claim 3 is a sulfo group or a hydrogen atom The aqueous black ink composition according to claim 2 or 3, wherein the black dye represented by the formula (2) is a compound represented by the following formula (3) or the following formula (4) or a salt thereof.

(In the formulas (3) and (4), when R ¹ is a sulfo group and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group; ^When the substitution position of ¹ is para to the azo group, the substitution position of the nitro group is ortho to the azo group.) An inkjet recording method using the water-based black ink composition according to any one of claims 1 to 13. The inkjet recording method according to claim 14, wherein the recording material in the inkjet recording method is an information transmission sheet. The ink jet recording method according to claim 15, 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 1. A colored body colored with the aqueous black ink composition according to any one of claims 1 to 13.