JP2001288379A - Water-soluble trisazo compound, water-based ink composition and colored form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black printing liquid to be used for ink jet printing and in writing utensils, giving high printed image density when printed on sheets of regular paper or paper for ink jet exclusive use, excellent in light resistance, water resistance and color rendering tendency, and good in preservability as well. SOLUTION: This printing liquid contains a trisazo compound of general formula (1) (wherein, D is a 8-hydroxy-1-naphthyl group substituted with one or two sulfonic acid group(s) ; A is a 1,4-phenylene or 1,4-naphthylene group optionally substituted with amino, hydroxy carboxy, sulfonic acid or alkoxy group or the like; B is a naphthyl group optionally substituted with hydroxy, amino or sulfonic acid group or the like) or a salt thereof. A printing is conducted using the above printing liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel water-soluble trisazo compound and a colored product thereof.

[0002]

2. Description of the Related Art Among various color recording methods, a recording method using an ink jet printer, which is one of the representative methods, generates small droplets of ink, which is used for various recording materials (paper, film, cloth, etc.). ) For recording. This method is quiet because there is no sound because the recording head does not come into contact with the recording material, and it has been rapidly spreading in recent years because of its features of miniaturization, high speed, and easy colorization. Large growth is expected. Conventionally, aqueous inks obtained by dissolving a water-soluble dye in an aqueous medium have been used as inks for fountain pens, felt-tip pens, and ink jet recording inks. Generally, a water-soluble organic solvent is added to prevent clogging of the ink. In these conventional inks, it is necessary to provide an image having a sufficient density, not to cause clogging of a pen tip and a nozzle, to have good drying property on a recording material, to have little bleeding, and to have a high storage stability. It is required that the image is excellent and that the formed image has sufficient light resistance and water resistance. Also, various hue inks are prepared from various dyes, of which black ink is the most important ink used for both mono-color and full-color images. To date, a great number of patent applications (for example, Japanese Patent Application Laid-Open No.
No. 144067, JP-A-57-207660, JP-A-58-147470, JP-A-59-93766, JP-A-62-190269, JP-A-62-246975
JP-A-63-22867, JP-A-63-3348
4, JP-A-1-93389, JP-A-2-14027
0, JP-A-3-167270, JP-A-3-2008
No. 52, JP-A-4-359065, JP-A-6-172
668, JP-A-6-248212, JP-A-7-26
No. 160, Japanese Patent Application Laid-Open No. 7-268256, etc., but it has not yet been possible to provide a product that sufficiently satisfies the market requirements.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a high solubility, is stable even when stored for a long period of time, has a high density of a printed image, and is excellent in water resistance and light resistance. It is an object of the present invention to provide an ink composition which gives the following.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, the present invention provides (1) a trisazo compound represented by the following general formula (1) or a salt thereof,

[0005]

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Wherein D is an 8-hydroxy-1-naphthyl group substituted by one or two sulfo groups,
Is the general formula (2)

[0007]

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Or the general formula (3)

[0009]

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(Wherein R ¹ and R ² are each independently a hydrogen atom, an amino group, a hydroxyl group, a carboxyl group, a sulfo group, a phospho group, a (C1-C4) alkoxycarbonyl group, a hydroxyl group or a (C1-C4 A) a (C1-C4) alkyl group, a hydroxyl group or a (C1-C4) alkoxy group, a hydroxyl group or a (C1-C4) optionally substituted by a (C1-C4) alkoxy group which may be substituted by an alkoxy group; A) a (C2-C4) alkanoylamino group or a ureido group which may be substituted by an alkoxy group, wherein R ³ is a hydrogen atom, a (C1-C4) alkyl group or a (C1-C4)
An alkoxy group, R ⁴ represents a hydrogen atom, a sulfo group or a phospho group), and B is a group represented by the general formula (4)

[0011]

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(R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group,
(C1-C4) alkoxy group, (C1-C4) alkyl group, mono- or bis-carboxy- (C1-C3) alkylamino group, hydroxyl group or (C1-C4) alkoxy group may be substituted (C1 ~ C
4) an alkylamino group, a (C1-C4) alkanoylamino group, a carboxyl group or a phenylamino group optionally substituted with a sulfo group or an amino group, a sulfo group,
It means a halogen atom or a ureido group. Where R ⁵
At least one of to R ⁸ is an amino group substituted with an amino group or the substituent. And m is 0 or 1.], (2) D is 8-hydroxy-3,6-disulfo-1-naphthyl, 8-hydroxy-4,6-disulfo-1-naphthyl, 8-hydroxy -2,4-disulfo-1-naphthyl, 8-hydroxy-3,5-disulfo-1-naphthyl, 8-hydroxy-4,7-disulfo-
1-naphthyl, 8-hydroxy-5,7-disulfo-1
-Naphthyl, 8-hydroxy-4-sulfo-1-naphthyl, 8-hydroxy-5-sulfo-1-naphthyl, 8-
A trisazo compound or a salt thereof according to (1), which is any group of hydroxy-6-sulfo-1-naphthyl, and (3) D is 8-hydroxy-3,6-disulfo-1.
-Naphthyl, 8-hydroxy-4,6-disulfo-1-
A trisazo compound or a salt thereof according to (1) or (2), which is any of naphthyl, 8-hydroxy-2,4-disulfo-1-naphthyl, and 8-hydroxy-4-sulfo-1-naphthyl; (4) In A, R ¹ and R ²
Is independently a group of the general formula (2) meaning hydrogen, methyl, ethyl, methoxy, ethoxy, methoxyethoxy, amino, hydroxy, carboxy, sulfo, acetylamino, n-propionylamino or ureido, or R The trisazo compound or a salt thereof according to any one of (1) to (3), wherein ³ is hydrogen, methyl or methoxy and R ⁴ is hydrogen or sulfo, a group of the general formula (3), (5) In A, R ¹ is methyl, methoxy, ethoxy or methoxyethoxy and R ² is a group of the general formula (2) meaning hydrogen, methyl, methoxy, ethoxy, amino, hydroxy, acetylamino or ureido; Any one of (4)
(6) A in the formula (3), wherein R ³ is hydrogen or methoxy, and R ⁴ is a group of the general formula (3) meaning sulfo.
Or the salt thereof, or (7) B, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent hydrogen, methyl, methoxy, carboxy, sulfo,
Any one of (1) to (6), which is a group of the general formula (4) meaning hydroxy, amino, carboxymethylamino, carboxymethoxy, acetylamino, carboxyphenylamino, sulfophenylamino, phenylamino or ureido (8) The trisazo compound or a salt thereof according to any one of (1) to (7), wherein m is 0,
(9) An aqueous ink composition containing the trisazo compound or a salt thereof according to any one of (1) to (8), (10) any one of (1) to (8) (1) a colored body colored with the trisazo compound or a salt thereof or the aqueous ink composition of (9),
1) The present invention relates to the colored body (10), which is colored by a printer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Specific examples of the substituents defined above are as follows.
Examples of (C1-C4) alkyl groups are methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, s
ec-butyl or tert-butyl and the like, preferably methyl and ethyl. Hydroxyl group or (C
Examples of the (C1-C4) alkoxy group which may be substituted with a 1-C4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2- or 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxy Propoxy, isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy and the like, preferably methoxy, ethoxy, methoxyethoxy or ethoxyethoxy, and methoxy, ethoxy and methoxyethoxy are particularly preferred. Examples of the (C1-C4) alkanoylamino group optionally substituted by a hydroxyl group or a (C1-C4) alkoxy group include acetylamino, n-propionylamino, isopropionylamino, hydroxyacetylamino, 2- or 3
-Hydroxy-n-propionylamino, 2- or 3
-Methoxy-n-propionylamino or butyrylamino and the like. Of these, acetylamino is particularly preferred. Mono- or bis-carboxy- (C1-C3)
Examples of alkylamino groups are carboxymethylamino, carboxyethylamino, carboxypropylamino, bis-carboxymethylamino, bis-carboxyethylamino, bis-carboxypropylamino, preferably carboxymethylamino, bis-carboxymethylamino, Carboxyethylamino. Carboxy-
Examples of (C1-C3) alkoxy groups are carboxymethoxy, carboxyethoxy, carboxypropoxy, with carboxymethoxy being particularly preferred.

R ¹ and R ² are preferably each independently hydrogen, methyl, ethyl, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, amino, hydroxy, carboxy, sulfo, phospho, acetylamino, n-propionylamino or ureido. means. Hydrogen, methyl, methoxy, ethoxy, methoxyethoxy, amino,
Hydroxy, carboxy, acetylamino or ureido are particularly preferred.

The formula (2) is preferably derived from any of the following intermediate components: 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 1-amino -2-methoxy-5-acetylaminobenzene, 1-amino-2-methoxyethoxy-5
-Acetylaminobenzene, 1-amino-2-methoxybenzene, 1-amino-2-methylbenzene, 1-amino-2,5-dimethoxybenzene, 1-amino-2,5
-Diethoxybenzene, 1-amino-2-methyl-5
Acetylaminobenzene, 1-amino-2-methoxy-
5-ureidobenzene, 1-amino-2-methyl-5
Ureidobenzene, 1-amino-3-methoxybenzene, 1-amino-3-methylbenzene, 1-amino-2
-(2'-hydroxyethoxy) -5-methylbenzene, 3-aminobenzoic acid, 3-amino-4-methylbenzoic acid, 3-amino-4-methoxybenzoic acid, 2,4-diaminobenzoic acid, 2, 4-diaminobenzenesulfonic acid, 2-amino-4-acetylaminobenzenesulfonic acid, 3-aminobenzenephosphonic acid, 4-methoxy-3
-Aminophenol, 2,4-diaminoanisole

R ³ is preferably hydrogen, methyl, ethyl,
Methoxy or ethoxy. Particularly, hydrogen, methyl or methoxy is preferred. R ⁴ is preferably sulfo. The residue A in the general formula (3) is 1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, or 1-aminonaphthalene-7 as an intermediate component. -Sulfonic acid, 1-aminonaphthalene-8-sulfonic acid or 1-amino-2
Particularly preferred is a residue derived from -methoxynaphthalene-6-sulfonic acid.

In the general formula (1), the component from which a naphthalene residue is derived is 7-amino-1-hydroxynaphthalene-3-sulfonic acid (γ-acid) when m is 0, and m is 1
In the case of 7-amino-1-hydroxynaphthalene-3,
6-disulfonic acid (2R acid).

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (4)
Are each independently hydrogen, methyl, methoxy, chlorine, carboxyl, sulfo, hydroxy, amino, carboxymethylamino, carboxypropylamino, bis-carboxymethylamino, acetylamino, ureido, phenylamino, sulfophenylamino, carboxyphenylamino, etc. And preferably amino, methoxy, sulfo, phenylamino, sulfophenylamino, carboxyphenylamino and biscarboxymethylamino. Particularly, amino, hydroxy, sulfo and phenylamino are preferred. Residue B of the general formula (4) has 1 as an intermediate component.
-Amino-8-hydroxynaphthalene-3,6-disulfonic acid (H acid), 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K acid), 2-amino-8-
Hydroxynaphthalene-3,6-disulfonic acid (2R
Acid), 2-hydroxynaphthalene-3,6-disulfonic acid (R acid), 7-amino-1-hydroxynaphthalene-
3-sulfonic acid (γ-acid), 7- (N-3-sulfophenyl) amino-1-hydroxynaphthalene-3-sulfonic acid, 7- (N-4-carboxyphenyl) amino-1-
Hydroxynaphthalene-3-sulfonic acid, 6-amino-
1-hydroxynaphthalene-3-sulfonic acid (J acid),
6- (N-phenyl) amino-1-hydroxynaphthalene-3-sulfonic acid, 5-amino-1-hydroxynaphthalene-3-sulfonic acid (M acid), 8-aminonaphthalene-1-sulfonic acid, 8-amino Naphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-
Examples thereof include aminonaphthalene-2-sulfonic acid and 8- (N-phenylamino) naphthalene-1-sulfonic acid, preferably 8-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, and 5-aminonaphthalene-2-sulfonic acid. -Aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 8- (N-phenylamino) naphthalene-1-sulfonic acid, 7-amino-1-hydroxynaphthalene-3-sulfonic acid (γ-acid ), 6-amino-1-
Hydroxynaphthalene-3-sulfonic acids (J acids), but they can also be used in mixtures.

Salts are salts of inorganic or organic cations. Among them, specific examples of inorganic salts include alkali metal salts and alkaline earth metal salts, and preferred inorganic salts are
Lithium, sodium and potassium salts, and the compound represented by the following formula (5) include, but are not limited to, substituted or unsubstituted ammonium salts.

[0020]

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In the above general formula (5), R ⁹ to R ^9
12 are each independently a hydrogen atom, a (C1-C4) alkyl group, a hydroxy- (C1-C4) alkyl group or a hydroxyethoxy- (C1-C4) alkyl group.
Examples of the (C1-C4) alkyl group include a methyl group,
Examples include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a secondary butyl group, and a tertiary butyl group.

Examples of the hydroxy- (C1-C4) alkyl group include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, And a hydroxybutyl group. Examples of the hydroxyethoxy- (C1-C4) alkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, a 3-hydroxyethoxypropyl group,
Examples thereof include a hydroxyethoxypropyl group, a 4-hydroxyethoxybutyl group, a 3-hydroxyethoxybutyl group, and a 2-hydroxyethoxybutyl group.

A specific example of the general formula (5) is shown in (Table 1).

(Table 1) Table 1 General formula (5) Compound No. R9 R10 R11 R12 5-1 H-C2H4OH-C2H4OH-C2H4OH 5-2 CH3-C2H4OH-C2H4OH-C2H4OH 5-3H-CH2CH (OH) CH3 -CH2CH (OH) CH3 -CH2CH (OH) CH3 5-4 CH3 -CH2CH (OH) CH3 -CH2CH (OH) CH3 -CH2CH (OH) CH3 5-5 H -C2H4OH H -C2H4OH 5-6 CH3 -C2H4OH H -C2H4OH 5-7 H -CH2CH (OH) CH3 H -CH2CH (OH) CH3 5-8 CH3 -CH2CH (OH) CH3 H -CH2CH (OH) CH3 5-9 CH3 -C2H4OH CH3 -C2H4OH 5-10 CH3 -CH2CH (OH) CH3 CH3 -CH2CH (OH) CH3

Next, specific examples of preferred trisazo compounds represented by the general formula (1) are shown in the general formulas (1-1) (Table 2) to (1-5) and Table (11).

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by the general formula (1) can be synthesized, for example, by the following method. That is, the general formula (6)

[0043]

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(Wherein Y represents a hydrogen atom, a (C1-C4) alkyl group, and halogen, and A has the above-mentioned meaning).

[0045]

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(Wherein m is 0 or 1) to form a compound of the general formula (8)

[0047]

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(Where A, Y and m have the same meanings as above), and hydrolyzes the disazo compound represented by the general formula (9).

[0049]

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(Wherein A or m has the above-mentioned meaning) and then coupling with the compound of the general formula (4 ′)

[0051]

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(Wherein R ⁵ , R ⁶ , R ⁷ , and R ⁸ have the same meaning as described above) or diazotization again in the general formula (8) and coupling with the compound of the general formula (4 ′) After that, it can be synthesized by hydrolysis.

The compounds of the general formulas (6), (7) and (4 ') can be produced by known methods. The diazotization of the compound of the general formula (6) is carried out by a method known per se, for example, in an inorganic acid medium, for example, at -5 to 30 ° C.
It is preferably carried out at a temperature of 0 to 10 ° C. using a nitrite, for example an alkali metal nitrite such as sodium nitrite. The coupling between the diazotized compound of the general formula (6) and the compound of the general formula (7) is also carried out under conditions known per se. It is advantageous to use in aqueous or aqueous organic media, for example, temperatures of -5 to 30 ° C., preferably 0 to 10 ° C., and weakly acidic to alkaline pH values. It is preferably carried out at a neutral to alkaline pH value, for example pH 7-11. The adjustment of the pH value is carried out by adding a base. As the base, for example, an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide, an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, an acetate such as sodium acetate, or ammonia or an organic amine is used. it can. The compounds of the general formulas (6) and (7) are used in the process in almost stoichiometric amounts. The production of the general formula (9) by hydrolysis of the compound of the general formula (8) is also carried out by a method known per se. The method is preferably heating in an aqueous alkaline medium. For example, sodium hydroxide or potassium hydroxide is added to the reaction solution of the general formula (8) to adjust the pH to 9.5 or more.
It is carried out by heating to a temperature of 150C, preferably a temperature of 30-100C. At this time, p
The H value is preferably maintained between 9.5 and 11.5. The diazotization of the hydrolyzed compound of the general formula (9) is carried out under the same conditions as the diazotization of the general formula (6). And the diazotized compound of the general formula (6) and the general formula (4 ′)
Is also carried out under conditions known per se. In aqueous or aqueous organic media, for example 0-40
° C, preferably a temperature of 10 to 30 ° C and a pH of 4-1.
0, preferably 6-8.

After the coupling reaction, the trisazo compound represented by the general formula (1) according to the present invention can be prepared by a conventional method using a reverse osmosis membrane, or a dried product of the dye component of the present invention or a wet cake obtained by adding alcohol such as methanol and water. The inorganic salt in the reaction solution can be removed by a method such as stirring in a mixed solvent of, and filtration and drying. In addition, an acid dye having a low salt content can be obtained by filtering, washing and drying the dye precipitated acidic with a mineral acid or the like, and the acid dye is dissolved in an aqueous medium by a desired organic or inorganic base. By neutralizing, a solution of the corresponding salt can be obtained. Examples of the organic or inorganic base 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 sodium carbonate. Examples include, but are not limited to, alkali metal carbonates such as potassium carbonate.

The trisazo compound represented by the general formula (1) is remarkably suitable for dyeing natural products such as paper, cellulose, wool, and leather and blended products thereof with synthetic fiber materials. It is extremely suitable for the production of writing inks and recording liquids.

The reaction liquid containing the trisazo compound of the present invention represented by the general formula (1) can be used directly for producing a recording ink composition. But first dry these,
For example, they can be isolated by spray drying and then processed into ink compositions. The recording ink composition of the final product contains the trisazo compound of the present invention represented by the general formula (1) in an amount of, for example, 0.1 to 20% by weight, more preferably 1 to 10% by weight, and still more preferably 2 to 8% by weight. Content. The ink composition of the present invention further comprises, for example, 0 to 30% by weight of a water-soluble organic solvent and 0 to 30% by weight of an ink preparation agent.
It may be contained at 5% by weight.

The aqueous ink composition of the present invention is obtained by dissolving the trisazo compound represented by the general formula (1) in water or an aqueous solvent (a water-soluble organic solvent or water containing an organic solvent miscible with water). is there. The pH of the ink is preferably about 5 to 11. When this aqueous ink composition is used as an ink for an ink jet printer, it is preferable to use a trisazo compound having a low content of inorganic substances such as metal cation chlorides and sulfates. For example, it is about 1% by weight or less. In order to produce a trisazo compound containing less inorganic substances, for example, a method using a reverse osmosis membrane or a dried product or a wet cake of the trisazo compound or a salt thereof of the present invention is stirred in a mixed solvent of alcohol such as methanol and water, filtered, and dried. Desalting treatment may be carried out.

Examples of water-soluble organic solvents that can be used in the present invention include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,
C1-C4 alkanols such as secondary butanol and tertiary butanol, N, N-dimethylformamide or N, N-
Carboxylic acid amides such as dimethylacetamide, lactams such as ε-caprolactam, N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimidin-2-one; Cyclic ureas, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3-propylene Glycol, 1,2- or 1,
4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol,
(C2 such as dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc.)
-C6) Monomers, oligomers or polyalkylene glycols or thioglycols having alkylene units, glycerin, polyols (triols) such as hexane-1.2.6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether Or a polyhydric alcohol such as diethylene glycol monoethyl ether or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether (C
1-C4) alkyl ether, γ-butyrolactone, dimethyl sulfoxide and the like.

As the ink preparation agent, for example, an antiseptic / antifungal agent, a pH adjuster, a chelating agent, a rust inhibitor, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like can be used. . Examples of preservatives and fungicides include sodium acetate anhydrous, sodium sorbate, 2-pyridinethiol-
Examples thereof include sodium 1-oxide, sodium benzoate, and sodium pentachlorophenol. As the pH adjuster, any substance can be used as long as it can control the pH of the ink, for example, in the range of 5 to 11 without adversely affecting the ink to be prepared. Examples thereof include alkanolamines such as diethanolamine and triethanolamine, lithium hydroxide, alkali hydroxides such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, and lithium carbonate, sodium carbonate, and potassium carbonate. Examples thereof include carbonates of alkali metals. Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracildiacetate. Examples of the rust preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, polyimine and the like. Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole. Examples of the dye dissolving agent include ε-caprolactam and ethylene carbonate.
And urea. Examples of the surfactant include known surfactants such as an anionic surfactant, a cationic surfactant, and a nonionic surfactant. The ink composition may be filtered through a membrane filter or the like to remove impurities.

The colored product of the present invention is a product colored with the above-mentioned compound of the present invention or the aqueous ink composition containing the compound. Examples of materials that can be colored include paper, fiber and cloth (cellulose, nylon, wool, and the like), leather, base materials for color filters, and the like. Examples of the coloring method include a printing method such as a dip dyeing method, a printing method, screen printing, and a method using an ink jet printer, and a method using an ink jet printer is preferable.

The aqueous ink composition which may contain the compound represented by the general formula (1), a salt thereof, or at least one other compound is prepared by printing, copying, marking, writing,
Suitable for use in drafting, stamping or recording methods, especially ink jet printing. This gives a high quality black colored body with a remarkably high concentration and good resistance to water, sunlight and rubbing. General formula (1) of the present invention
The trisazo compound represented by or a salt thereof has higher light resistance especially in paper dedicated to inkjet.

The aqueous ink composition according to the present invention does not cause separation of a precipitate during storage, and furthermore does not cause clogging of the jet nozzle when the aqueous ink composition of the present invention is used in ink jet printing. When the aqueous ink composition of the present invention is used in an inkjet printing machine under constant recirculation for a relatively long period of time or intermittently with an intermediate shutdown of the inkjet printing machine, the aqueous ink composition of the present invention is physically No change in properties occurs.

[0063]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the text, “parts” and “%” are based on weight unless otherwise specified.

Example 1 A solution obtained by dissolving 62.1 parts of the compound of the formula (10) in 500 parts of water under a weak alkaline condition and adding 10.3 parts of sodium nitrite was dissolved in 400 parts of 4.5% hydrochloric acid. The solution is dropped at 10 ° C. for diazotization.

[0065]

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Next, the obtained diazo suspension of the formula (10) was dissolved in 500 parts of water with 22.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid dissolved in the presence of sodium hydroxide. The solution is dropped at a temperature of 0 to 5 ° C over about 30 minutes. During this dropping, the pH value of the coupling solution is maintained at 8.5 to 9.5 by addition of aqueous sodium carbonate solution. After completion of the dropwise addition, the mixture is further heated at 5 to 10 ° C. for 3 hours,
Stir at 0 ° C. for 3 hours, all at pH 8.5-9.0, to complete the coupling reaction. Then, after adjusting the pH value to 10 to 11 with a sodium hydroxide solution, the reaction mixture is stirred at a pH value of 10 to 11 and a temperature of 80 to 85 ° C. for about 2 hours. After cooling to room temperature, the resulting solution is neutralized with concentrated hydrochloric acid to pH 7-8. Thereafter, sodium chloride was added thereto, salted out, isolated by filtration and dried to obtain 62.4 parts of a compound of the formula (11).

[0067]

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Next, 7.2 parts of the compound of the formula (11) obtained above was dissolved in 150 parts of warm water, and an aqueous solution to which 0.83 part of sodium nitrite was added was added to a solution of 4.5% hydrochloric acid in 50 parts.
The mixture is added dropwise at 10 to 15 ° C. for diazotization. 2.3 parts of dissolved 8-aminonaphthalene-2-sulfonic acid were added to the obtained diazo suspension of the formula (11) at the same temperature in the presence of sodium hydroxide, and then the reaction suspension was treated with sodium carbonate. Neutralize to pH 6.5 with solution over about 1 hour. After neutralization, the mixture is further stirred at 10 to 15 ° C. for 3 hours and at 15 to 20 ° C. for 3 hours at pH 7 to 8 to complete the coupling reaction. Thereafter, the pH value was adjusted to 4.0 with concentrated hydrochloric acid, and sodium chloride was added to perform acid precipitation. The precipitated dye was isolated by filtration and dried to obtain a black trisazo compound of the formula (12) (Compound No. 0001). ) 8.2 parts were obtained. The absorption spectrum of this compound in water is λmax = 593 nm.
It is.

[0069]

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Example 2 8- (N-phenylamino) naphthalene dissolved in a suspension of a diazonium salt of the compound of the formula (11) obtained in the same manner as in Example 1 in the presence of sodium hydroxide. −
After adding 3.0 parts of 1-sulfonic acid, the reaction suspension is neutralized with sodium carbonate solution to pH 6.5 over about 1 hour. After neutralization, further 15 hours at 10 to 15 ° C for 3 hours
Stir at pH 7 to 8 for 3 hours to complete the coupling reaction. Thereafter, sodium chloride is added thereto for salting out, and the precipitated dye is isolated by filtration and dried to obtain a black trisazo compound of the formula (13) (Compound No. 0005)
7.9 parts were obtained. The absorption spectrum of this compound in water is λmax = 592 nm.

[0071]

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Example 3 The same conditions as in Example 2 were used except that 8- (N-phenylamino) -1-naphthalenesulfonic acid was changed to 2.3 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid. To obtain 8.2 parts of a black trisazo compound of the formula (14) (Compound No. 0006). The absorption spectrum of this compound in water is λmax = 604 nm.

[0073]

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Example 4 A solution obtained by dissolving 77.5 parts of the compound of the formula (15) in 800 parts of water under weak alkalinity and adding 8.3 parts of sodium nitrite was dissolved in 400 parts of 4.5% hydrochloric acid. The solution is dropped at 10 ° C. for diazotization.

[0075]

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Next, the obtained diazo suspension of the formula (15) was dissolved in 500 parts of water in the presence of sodium hydroxide by dissolving 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid in the presence of sodium hydroxide. The solution is dropped at a temperature of 0 to 5 ° C over about 30 minutes. During this dropping, the pH value of the coupling solution is maintained at 8.5 to 9.5 by addition of aqueous sodium carbonate solution. After dropping, further 5 hours to 10 ° C. for 3 hours, 15 to 20 ° C.
For 3 hours at pH 8.5 to 9.0 to complete the coupling reaction. Then the pH is adjusted to 11 with sodium hydroxide solution. The reaction mixture is brought to pH
Stir for about 2 hours at a value of 10-11 and a temperature of 80-85 ° C.
Thereafter, the mixture is cooled to room temperature, and the resulting solution is concentrated with concentrated hydrochloric acid.
Is neutralized to 8-9. Thereafter, sodium chloride was added thereto for salting out, followed by filtration, isolation and drying to obtain 73.8 parts of a compound of the formula (16).

[0077]

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The compound 8.7 of the formula (16) obtained above.
Was dissolved in 100 parts of warm water and a solution to which 0.83 part of sodium nitrite had been added was added in 50 parts of 4.5% hydrochloric acid in 1 part.
The solution is dropped at 5 to 20 ° C. for diazotization. Next, 2.3 parts of dissolved 8-amino-2-naphthalenesulfonic acid are added to the obtained diazo suspension of the formula (16) at the same temperature in the presence of sodium hydroxide, and the reaction suspension is added. Neutralize to pH 6.5 with sodium carbonate solution over about 1 hour. After neutralization, the mixture is further stirred at 10 to 15 ° C. for 3 hours and at 15 to 20 ° C. for 3 hours at pH 7 to 8 to complete the coupling reaction. Thereafter, the pH value of the reaction solution is made strongly acidic with concentrated hydrochloric acid, and the precipitated dye is filtered off and washed with water to remove the electrolyte. And the obtained dye wet cake is 500 ml of water
The dye paste is neutralized with 70 ml of a 5N lithium hydroxide solution, and then the resulting dye solution is spray-dried to obtain a black trisazo compound represented by the formula (17) (compound No. 0013). 8.7 parts of salt were obtained. The absorption spectrum of this compound in water is λmax = 602 nm.

[0079]

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Example 5 8-amino-2-naphthalenesulfonic acid was converted to 6-amino-
Coupling was carried out under the same conditions as in Example 4 except that 2.4 parts of 4-hydroxy-2-naphthalenesulfonic acid was used, and a black trisazo compound of the formula (18) (Compound No. 001)
6) 8.2 parts were obtained. The absorption spectrum of this compound in water is λmax = 608 nm.

[0081]

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Example 6 A solution obtained by dissolving 68.6 parts of the compound of the formula (19) in 500 parts of water under weak alkaline conditions, and adding 10.3 parts of sodium nitrite to 400 g of 4.5% hydrochloric acid was added. The solution is dropped at 10 ° C. for diazotization.

[0083]

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Next, 31.9 parts of 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid were dissolved in 500 parts of water in the presence of sodium hydroxide. About 3 at a temperature of 0-5 ° C
Add dropwise over 0 minutes. During this drop, the coupling p
The H value is maintained at 8.5-9.5 by addition of aqueous sodium carbonate solution. After the dropping, it is further carried out at 5 to 10 ° C. for 3 hours, 15 to 2
Stir at 0 ° C. for 3 hours, all at pH 8.5-9.0, to complete the coupling reaction. Then the pH is adjusted to 11 with sodium hydroxide solution and the reaction mixture is p
The mixture is stirred for about 4 hours at a temperature of 10 to 11, H value of 70 to 75C. After cooling to room temperature, the resulting solution is neutralized with concentrated hydrochloric acid to pH 6-7. Thereafter, sodium chloride is added, salted out, isolated by filtration and dried to obtain the compound of the formula (2)
72.5 parts of compound 0) were obtained.

[0085]

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The compound 9.1 of the formula (20) obtained above.
Was dissolved in 100 parts of warm water and a solution to which 0.83 part of sodium nitrite had been added was added in 50 parts of 4.5% hydrochloric acid in 1 part.
The solution is dropped at 0 to 15 ° C. for diazotization. Next, 2.3 parts of dissolved 8-amino-2-naphthalenesulfonic acid are added to the obtained diazo suspension of the formula (20) at the same temperature in the presence of sodium hydroxide, and the reaction suspension is added. Neutralize to pH 6.5 with sodium carbonate solution over about 1 hour. After neutralization, the mixture is further stirred at 10 to 15 ° C. for 3 hours and at 15 to 20 ° C. for 3 hours at pH 7 to 8 to complete the coupling reaction. Thereafter, the pH value was adjusted to 4.0 with concentrated hydrochloric acid, and sodium chloride was added for acid precipitation. The precipitated dye was isolated by filtration and dried to obtain a black trisazo compound of the formula (21) (Compound No. 0070). ) 10.1 parts were obtained. The absorption spectrum of this compound in water is λmax = 593n
m.

[0087]

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Example 7 6-amino-4-hydroxy-2 was dissolved in a suspension of a diazonium salt of the compound of the formula (20) obtained in the same manner as in Example 6 in the presence of sodium hydroxide. After addition of 2.3 parts of naphthalenesulfonic acid, the reaction suspension is neutralized with sodium carbonate solution to pH 6.5 over about 1 hour. After neutralization, further 15 hours at 10 to 15 ° C for 3 hours
Stir at pH 7 to 8 for 3 hours to complete the coupling reaction. Thereafter, sodium chloride is added thereto for salting out, and the precipitated dye is isolated by filtration and dried to obtain a black trisazo compound of the formula (22) (Compound No. 0071).
9.6 parts were obtained. The absorption spectrum of this compound in water is λmax = 605 m.

[0089]

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Example 8 A solution obtained by dissolving 57.2 parts of the compound of the formula (23) in 500 parts of water under weak alkalinity and adding 8.3 parts of sodium nitrite was dissolved in 400 parts of 4.5% hydrochloric acid. The solution is dropped at 10 ° C. for diazotization.

[0091]

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Next, the obtained diazo suspension of the formula (23) was dissolved in 500 parts of water in the presence of sodium hydroxide by dissolving 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid in the presence of sodium hydroxide. The solution is dropped at a temperature of 0 to 5 ° C over about 30 minutes. During this dropping, the pH value of the coupling solution is maintained at 8.5 to 9.5 by addition of aqueous sodium carbonate solution. After dropping, it is further 15-20 ° C. for 3 hours at 5-10 ° C.
For 3 hours at pH 8.5 to 9.0 to complete the coupling reaction. Thereafter, sodium chloride is added, salted out, isolated by filtration and dried to obtain formula (24).
69.8 parts of the compound were obtained.

[0093]

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Compound 8.2 of formula (24) obtained above
Was dissolved in 100 parts of warm water and a solution to which 0.83 part of sodium nitrite had been added was added in 50 parts of 4.5% hydrochloric acid in 1 part.
The solution is dropped at 0 to 15 ° C. for diazotization. Subsequently, 2.1 parts of dissolved 8-amino-2-naphthalenesulfonic acid are added to the obtained diazo suspension of the formula (24) at the same temperature in the presence of sodium hydroxide, and the reaction suspension is added. Neutralize to pH 6.5 with sodium carbonate solution over about 1 hour. After neutralization, the mixture is further stirred at 10 to 15 ° C. for 3 hours and at 15 to 20 ° C. for 3 hours at pH 7 to 8 to complete the coupling reaction. After that, add sodium chloride and salt out,
The precipitated dye is isolated by filtration and dried to obtain the compound of the formula (2)
5) Black trisazo compound (Compound No. 0057) 8.6
Got a part. The absorption spectrum of this compound in water is λm
ax = 591 nm.

[0095]

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Example 9 A solution obtained by dissolving 68.1 parts of the compound of the formula (26) in 500 parts of water under weak alkaline conditions and then adding 7.6 parts of sodium nitrite to 10% in 400 g of 4.5% hydrochloric acid. The solution is dropped at 15 ° C. for diazotization.

[0097]

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Next, the obtained diazo suspension of the formula (26) was dissolved in 500 parts of water with 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid dissolved in the presence of sodium hydroxide. About 30 at a temperature of 10-15 ° C
Add dropwise over a minute. During this drop, the pH of the coupling
The value is kept between 9 and 10 by addition of aqueous sodium carbonate solution. After dropping, further at 10 to 15 ° C for 3 hours, 15 to 20 ° C
For 3 hours at pH 9.0 to 9.5 to complete the coupling reaction. The pH was then adjusted to 11 with sodium hydroxide solution and the reaction mixture was adjusted to pH 10
11. Stir at a temperature of 70-75 ° C for about 4 hours. After cooling to room temperature, the resulting solution is neutralized to pH 9 with concentrated hydrochloric acid. After this, add sodium chloride and salt out,
The compound 6 of the formula (27) is isolated by filtration and dried.
3.9 parts were obtained.

[0099]

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The compound 9.5 of the formula (27) obtained above.
Part in 100 parts of warm water and add a solution of 0.83 part of sodium nitrite in 50 parts of 4.5% hydrochloric acid.
The solution is dropped at 0 to 25 ° C. for diazotization. Next, 2.2 parts of dissolved 8-amino-2-naphthalenesulfonic acid was added to the obtained diazo suspension of the formula (27) at the same temperature in the presence of sodium hydroxide, and the reaction suspension was added. Neutralize to pH 6.5 with sodium carbonate solution over about 1 hour. After neutralization, the mixture is further stirred at 20 to 25 ° C. and pH 7 to 8 for 5 hours to complete the coupling reaction. Then, add concentrated hydrochloric acid to pH
After adjusting the value to 4.0, sodium chloride was added to perform acid precipitation, and the precipitated dye was isolated by filtration and dried to obtain a black trisazo compound of the formula (28) (Compound No. 0026).
9.2 parts were obtained. The absorption spectrum of this compound in water is λmax = 599 nm.

[0101]

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Example 10 A solution obtained by dissolving 70.9 parts of the compound of the formula (29) in 500 parts of water under weak alkaline conditions and adding 7.6 parts of sodium nitrite to 10 parts of 400% of 4.5% hydrochloric acid was added. The solution is dropped at 15 ° C. for diazotization.

[0103]

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Next, an aqueous solution obtained by dissolving the obtained diazo suspension of the formula (29) in 500 parts of water and dissolving 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid in the presence of sodium hydroxide. About 30 at a temperature of 10-15 ° C
Add dropwise over a minute. During this dropping, the coupling liquid p
The H value is kept between 9 and 10 by addition of aqueous sodium carbonate solution. After dropping, further at 10 to 15 ° C for 3 hours, 15 to 20 ° C
For 3 hours at pH 9.0 to 9.5 to complete the coupling reaction. The pH is then adjusted to 11 with sodium hydroxide solution and the reaction mixture is stirred for about 4 hours at a temperature between 10 and 11 and a temperature between 70 and 75 ° C.
Thereafter, the mixture is cooled to room temperature, and the resulting solution is concentrated with concentrated hydrochloric acid.
Neutralize to 9. Thereafter, sodium chloride was added thereto, salted out, isolated by filtration and dried to obtain 66.1 parts of a compound of the formula (30).

[0105]

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Compound 8.3 of the formula (30) obtained above.
Parts were dissolved in 100 parts of warm water and 0.85 part of sodium nitrite was added to a solution of 2 parts in 50 parts of 4.5% hydrochloric acid.
The solution is dropped at 0 to 25 ° C. for diazotization. Subsequently, 2.2 parts of dissolved 8-amino-2-naphthalenesulfonic acid were added to the obtained diazo suspension of the formula (30) at the same temperature in the presence of sodium hydroxide, and the reaction suspension was added. Neutralize to pH 6.5 with sodium carbonate solution over about 1 hour. After neutralization, the mixture is further stirred at 20 to 25 ° C. and pH 7 to 8 for 5 hours to complete the coupling reaction. Then, add concentrated hydrochloric acid to pH
After adjusting the value to 4.0, sodium chloride was added to perform acid precipitation, and the precipitated dye was isolated by filtration and dried to obtain a black trisazo compound of the formula (31) (Compound No. 0029).
9.4 parts were obtained. The absorption spectrum of this compound in water is λmax = 605 nm.

[0107]

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Example 11 (A) Preparation of Ink A liquid having the following composition was prepared and filtered with a 0.45 μm membrane filter to obtain an aqueous ink composition for each ink jet. The aqueous ink composition of the present invention did not undergo sedimentation and separation during storage, and did not change in physical properties even after long-term storage.

Table 2 2.5 parts of the trisazo compound obtained in each of the examples (used after desalting) Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA (Isopropyl alcohol) 3.0 parts Butyl carbitol 2.0 parts Water 78.5 parts Total 100.0 parts

(B) Inkjet printing Inkjet printer (brand name: NEC Corporation, Picty)
100L) using plain paper (Canon Printer Paper A4 (TLB5A4S)) and special paper A (Colo
r BJ PaperLC101 (manufactured by Canon)) and special paper B (coated paper for color image jet STX7)
3A4 (manufactured by Sharp)) was subjected to inkjet recording. Table 3 shows the results of the hue, light resistance test, water resistance test, and color rendering of the recorded image of the aqueous ink composition of the invention (the aqueous ink composition containing the compound obtained in the example). As a comparative object, C.I. I. Food
Table 3 shows the results of hue, light resistance test, water resistance test, and color rendering of the recorded image of the ink composition prepared by adjusting Black 2 (Comparative Example) to have the same optical composition as the black ink of the present invention with the same ink composition. .

(C) Evaluation of Recorded Image Hue Evaluation The hue of the recorded image is GRETAG SPM50 (GRET
(Manufactured by AG), and L ^* , b ^* , and c ^* values were calculated. Light resistance test The recorded image was irradiated for 40 hours using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.). Judgment class is JIS
The color difference (ΔE) before and after the test was determined using the above-mentioned colorimetric system, while determining according to the blue scale rating specified in L-0841. Water resistance test Put the recording paper in a beaker filled with water, stir for 2 minutes, take out and air dry, judge the change before and after the test by JIS discoloration gray scale, and use the above colorimetric system to measure The color difference was measured. Color Rendering Based on the hue of the standard light source, the degree of discoloration when viewed under tungsten light was visually determined. ○ Small hue change. △ Hue change is slightly large. × Large hue change.

(Table 3) Table 3 Hue Light fastness Water fastness Color rendering properties Compound No. L * a * b * Judgment value (ΔE) Judgment value (ΔE) 0001 Plain paper 33.9 -1.6 -4.6 Grade 4 (3.8) Grade 2 (10.0) ○ Special paper A 23.5 -0.6 -5.6 Class 4 (2.3) Class 5 (0.8) ○ Special paper B 16.0 0.4 -4.1 Class 4 (3.3) Class 5 (1.3) ○ 0013 Plain paper 27.8 3.5 2.7 4-5 Grade (1.7) Grade 2 (12.6) ○ Special paper A 21.6 2.4 3.7 Class 4-5 (1.2) Class 3 (7.3) ○ Special paper B 16.8 1.1 -0.7 Class 4-5 (1.7) Class 3-4 (4.7) ○ 0026 Plain paper 34.9 -2.4 -3.5 Class 4 (2.6) Class 2 (14.1) ○ Special paper A 21.3 -0.3 -7.2 Class 4-5 (1.8) Class 5 (0.9) ○ Special paper B 15.8 0.1 -5.0 Class 4 (1.9) 5th grade (1.2) ○ 0029 Plain paper 32.7 -4.1 -5.0 4th grade (3.1) 2nd grade (10.0) ○ Exclusive paper A 22.7 -2.7 -6.9 4th grade (2.6) 5th grade (0.7) ○ Exclusive paper B 15.6 -1.8 -4.9 Grade 4 (2.0) Grade 5 (1.4) ○ Comparative example Plain paper 31.6 -2.0 -0.4 Grade 2 (12.4) Grade 1 (35.7) × Special paper A 24.5 -1.7 -1.8 Grade 2 (10.8) 5 Grade (1.6) × Special paper B 17.3 1.8 1.0 Grade 3-4 (4.1) Grade 2 (15.9) ×

From Table 3, it can be seen that the ink composition containing the trisazo compound of the present invention has water fastness equivalent to or higher than that of the conventional black dye (comparative example), and is more excellent in light fastness and color rendering. The light resistance of the inkjet paper is very good. Further, the ink composition of the present invention was found to be excellent in storage stability and ejection stability of the recording liquid because of high solubility in water.

Further, the four compounds (compound Nos. 0001, 0013, 0026, and
0029) was prepared as a 10% by weight aqueous solution at pH 10 and then left at 70 ° C. for 7 days, but no decomposition of the dye was observed.

[0115]

The recording ink liquid containing the trisazo compound of the present invention is used for ink jet recording and writing instruments, and has a high print density of a recorded image when recorded on plain paper and paper dedicated to ink jet. Light fastness,
It has excellent water resistance and color rendering properties, and also has good storage stability as a recording liquid.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 2C056 EA13 FC01 2H086 BA53 BA56 4J039 BA29 BA30 BC07 BC12 BC19 BC20 BC29 BC33 BC36 BC42 BC54 BC56 BC66 BC67 BC71 BC72 BC73 BC75 BC77 BC79 EA19 EA35 EA38 EA44

Claims (11)

[Claims] 1. A trisazo compound represented by the following general formula (1) or a salt thereof. Embedded image [Wherein, D is an 8-hydroxy-1-naphthyl group substituted by one or two sulfo groups, and A is a general formula (2) Or the general formula (3) (Wherein R ¹ and R ² are each independently a hydrogen atom, an amino group, a hydroxyl group, a carboxyl group, a sulfo group, a phospho group, a (C1-C4) alkoxycarbonyl group, a hydroxyl group or a (C1-C4) alkoxy group A (C1-C4) alkyl group, a hydroxyl group or a (C1-C4) alkoxy group which may be substituted by a (C1-C4) alkoxy group, a hydroxyl group or a (C1-C4) alkoxy group which may be substituted by A (C2-C4) alkanoylamino group or a ureido group which may be substituted by R ³ is a hydrogen atom, (C
1 to C4) an alkyl group or a (C1 to C4) alkoxy group, R ⁴ represents a hydrogen atom, a sulfo group or a phospho group), and B is a group represented by the general formula (4) (R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, (C 1 -C
4) optionally substituted by an alkoxy group, a (C1-C4) alkyl group, a mono- or bis-carboxy- (C1-C3) alkylamino group, a hydroxyl group or a (C1-C4) alkoxy group (C1-C4) It means an alkylamino group, a (C1-C4) alkanoylamino group, a carboxyl group or a phenylamino group, a sulfo group, a halogen atom or a ureido group optionally substituted with a sulfo group or an amino group. However, at least one of R ^{5 to} R ⁸ is an amino group or an amino group substituted with the above substituent. ), And m is 0 or 1.] (2) D is 8-hydroxy-3,6-disulfo-1-naphthyl, 8-hydroxy-4,6-disulfo-
1-naphthyl, 8-hydroxy-2,4-disulfo-1
-Naphthyl, 8-hydroxy-3,5-disulfo-1-
Naphthyl, 8-hydroxy-4,7-disulfo-1-naphthyl, 8-hydroxy-5,7-disulfo-1-naphthyl, 8-hydroxy-4-sulfo-1-naphthyl, 8
The trisazo compound or a salt thereof according to claim 1, which is any one of -hydroxy-5-sulfo-1-naphthyl and 8-hydroxy-6-sulfo-1-naphthyl. (3) D is 8-hydroxy-3,6-disulfo-1-naphthyl, 8-hydroxy-4,6-disulfo-
1-naphthyl, 8-hydroxy-2,4-disulfo-1
The trisazo compound according to claim 1 or 2, which is any one of -naphthyl and 8-hydroxy-4-sulfo-1-naphthyl, or a salt thereof. 4. In A, R ¹ and R ² each independently represent hydrogen, methyl, ethyl, methoxy, ethoxy, methoxyethoxy, amino, hydroxy, carboxy, sulfo, acetylamino, n-propionylamino or ureido. The compound according to any one of claims 1 to 3, wherein the group is a group of the general formula (2), or R ³ is hydrogen, methyl or methoxy and R ⁴ is a hydrogen or a sulfo. Or a salt thereof. 5. A compound of the general formula (2) wherein R ¹ is methyl, methoxy, ethoxy or methoxyethoxy and R ² is hydrogen, methyl, methoxy, ethoxy, amino, hydroxy, acetylamino or ureido. The trisazo compound according to any one of claims 1 to 4, or a salt thereof. 6. In A, R ³ is hydrogen or methoxy,
And a general formula (3) in which R ⁴ represents hydrogen or sulfo
The trisazo compound or a salt thereof according to any one of claims 1 to 4, which is a group represented by the formula: 7. In B, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, methyl, methoxy, carboxy, sulfo, hydroxy, amino, carboxymethylamino, carboxymethoxy, acetylamino, carboxyphenylamino And sulphophenylamino, phenylamino or ureido.
7. The trisazo compound or a salt thereof according to any one of items 6 to 6. 8. The trisazo compound or a salt thereof according to any one of claims 1 to 7, wherein m is 0. 9. An aqueous ink composition comprising the trisazo compound according to claim 1 or a salt thereof. 10. A colored body colored with the trisazo compound or a salt thereof according to any one of claims 1 to 8, or the aqueous ink composition according to claim 9. 11. The printer according to claim 1, wherein the coloring is performed by a printer.
0 colored body.