JPH10204308A - Polyazo compound, water-base ink composition, and colored body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble polyazo compound (salt) that can give a black water-base recording fluid which, when it is used for printing on paper, can give prints having high printing density, and is excellent in light fastness, water resistance, color rendering properties and storage stability. SOLUTION: This compound (salt) is represented by formula I wherein Y is a group represented by formula II [wherein R<3> is H, a 1-4C alkyl, a halogen or -SO3 H; A is a 1-4C alkylcarbonyl, a 1-4C alkoxy-1-4C-alkylcarbonyl or -CONH2 ; p is 1-4 on the average; r is 0 or 1; and t is 4-(p+r)]; Y' is a group represented by formula III [wherein R<4> is R<3> ; B is A; q is p; s is r; and u is 4-(q+s)]; R<1> and R<2> are each H, a 1-4C alkyl, a halogen or -SO3 H}. 0.1-20wt.%, desirably 1-10wt.%, more desirably 2-8wt.% this compound is added to water or an aqueous solvent to obtain a recording ink. This ink does not undergo the separation of a precipitate during storage, and when used in ink jet printing, it is not problematic in nozzle plugging.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-soluble polyazo compound, its production method and use.

[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, has been developed with various ink ejection methods. This is applied to various recording materials (paper, film, cloth, etc.) to perform recording. This is quiet because there is no sound because the recording head does not come in 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. Growth is expected. In this,
In order to record an image or character information on a color display of a computer in color by an ink jet printer, it is generally expressed by subtractive color mixture using four inks of yellow, magenta, cyan and black. In order to reproduce an additive color image of R, G, B on a CRT display or the like as faithfully as possible with a subtractive color image, the hue of the pigment used and its sharpness are the most important items. In addition, the ink composition is required to be stable for long-term storage, to have a high density of a printed image, and to be excellent in fastness such as water fastness and light fastness. For this reason, Japanese Patent Application Laid-Open
-97629, JP-A-57-92055, JP-A-5-92055
7-115468, JP-A-58-215467, JP-A-58-215468, and JP-A-61-98769.
JP-A-63-278891, JP-A-1-1537
No. 75, JP-A-2-2333782, JP-A-4-202
No. 271, JP-A-8-170041, JP-A-8-29
Although many applications have been filed, such as No. 5807, they have not yet completely satisfied the market requirements.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a black recording liquid which has 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. The purpose is to provide.

[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 polyazo compound represented by the following general formula (1) or a salt thereof

[0005]

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(Where Y is a general formula (2)

[0007]

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(R ³ is a hydrogen atom, a (C1-C4) alkyl group, halogen or —SO ₃ H, and A is (C1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group, -CON
Representing the H _2. p is an average number of 1 to 4, r is 0 or 1, and t is 4- (p + r). And Y 'is a group represented by the general formula (3)

[0009]

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(R ⁴ is a hydrogen atom, a (C 1 -C ⁴ ) alkyl group, halogen or —SO ₃ H, and B is (C 1 -C 4)
C4) alkylcarbonyl group, (C1-C4) alkoxyalkyl- (C1-C4) carbonyl group, -CONH
Represents ₂ . q is an average number of 1 to 4, s is independently 0 or 1, and u is a number represented by 4- (q + s). ), Wherein R ¹ and R ² are each independently a hydrogen atom, a (C1-C4) alkyl group,
Halogen or —SO ₃ H. (2) the salt is a lithium salt, a sodium salt or the general formula (4)

[0011]

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(Wherein R ⁵ to R ⁸ are each independently a hydrogen atom, a (C1-C4) alkyl group, a hydroxy-
(C1-C4) alkyl group or hydroxyethoxy-
(1) The polyazo compound of (1), which is an ammonium salt represented by (C1 to C4) an alkyl group, or a salt thereof (3) R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms (1)
Or the polyazo compound or salt thereof according to (2), (4) any one of (1) to (3), wherein r and s are 0, and R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms. (5) r and s are 1, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, A and B are each independently an acetyl group,-
The polyazo compound according to any one of (1) to (3), which is CONH ₂ , or a salt thereof (6) R ¹ , R ² , R ³ , and R ⁴ are hydrogen atoms, and the salt is each independently The polyazo compound according to any one of (1) to (3) or a salt thereof, which is a lithium salt, a sodium salt or an ammonium salt represented by the general formula (4) described in (2) (7) (1) to In the method for producing a polyazo compound or a salt thereof according to any one of (6), the compound represented by the general formula (5):

[0013]

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Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a (C1-C4) alkyl group, halogen or —SO ₃ H, and A and B are each independently ( (C1-C4) alkylcarbonyl group, (C1-C4)
An alkoxy- (C1-C4) alkylcarbonyl group,-
Represents CONH ₂ , and r and s are each independently 0 or 1
Or a salt thereof with a compound represented by the general formula (6) X-CH ₂ COOH (6) (wherein X represents a halogen) or a salt thereof. (8) The method for producing a polyazo compound or a salt thereof according to any one of (1) to (6), wherein

[0015]

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(Wherein R ¹ and R ² are (1) to (6)
Or a salt thereof, and the product is represented by the general formula (8)

[0017]

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(R ³ is a hydrogen atom, a (C1-C4) -alkyl group, halogen or —SO ₃ H, and A is (C1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group, -CON
Representing the H _2. p is an average number of 1 to 4, r is 0 or 1, and t is 4- (p + r). And / or the general formula (9)

[0019]

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(R ⁴ is a hydrogen atom, a (C1-C4) -alkyl group, halogen or —SO ₃ H, and B is (C1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group, -CON
Representing the H _2. q is an average number of 1 to 4, s is represented by 0 or 1, and u is 4- (q + s). (1) characterized by being coupled with the compound represented by (1)
(9) A water-based ink composition comprising the polyazo compound or a salt thereof according to any one of (1) to (6). (6) A colored body colored with the polyazo compound or a salt thereof according to any one of (6) or the aqueous ink composition described in the above (9). (11) A colored body of (10) colored by a printer.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the above general formulas (1) to (3), R ¹ , R ² ,
R ^3, R ⁴ each independently represent a hydrogen atom, (C1 -C4) -
An alkyl group, a halogen or —SO ₃ H;
Each independently (C1 -C4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, a -CONH _2. p and q are numbers of 1 to 4 on average, r and S are each independently represented by 0 or 1, t is 4- (p + r), and u is 4-
It is a number indicated by (q + s).

Examples of the (C1-C4) alkyl group include a methyl group, 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. Is raised. Examples of the (C1 to C4) alkylcarbonyl group include an acetyl group, a propionyl group, and a butyroyl group. Examples of the (C1 to C4) alkoxyalkylcarbonyl group include a methoxypropionyl group and an ethoxypropionyl group. Examples of the halogen include fluorine, chlorine, bromine and iodine, and chlorine and bromine are preferred.

Salts are salts of inorganic or organic cations. Suitable inorganic salts are alkali metal and alkaline earth metal salts; preferred inorganic salts are the lithium and sodium salts. Suitable organic salts include, in particular, an annonium salt represented by the general formula (4).

In the above general formula (4), R ⁵ to R ^5
8 is 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 2-hydroxybutyl group. And the like. 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.

Specific examples of the compound represented by the general formula (4) are shown in (Table 1).

[0026]

TABLE 1 Formula (4) Compound ^{No. R 3 R 4 R 5 R} 6 4 over _{1 H -C 2 H 4 OH -C} 2 H 4 OH -C 2 H 4 OH 4-2 CH 3 - C ₂ H ₄ OH -C ₂ H ₄ OH -C ₂ H ₄ OH 4-3 H -CH ₂ CH (OH) CH ₃ -CH ₂ CH (OH) CH ₃ -CH ₂ CH (OH) CH ₃ 4- 4 CH ₃ -CH ₂ CH (OH) CH ₃ -CH ₂ CH (OH) CH ₃ -CH ₂ CH (OH) CH ₃ 4-5 H -C ₂ H ₄ OH H -C ₂ H ₄ OH 4-6 CH ₃ -C ₂ H ₄ OH H -C ₂ H ₄ OH 4-7 H -CH ₂ CH (OH) CH ₃ H -CH ₂ CH (OH) CH ₃ 4-8 CH ₃ -CH ₂ CH (OH) CH ₃ H -CH ₂ CH (OH) CH ₃ 4-9 CH ₃ -C ₂ H ₄ OH CH ₃ -C ₂ H ₄ OH 4-10 CH ₃ -CH ₂ CH (OH) CH ₃ CH ₃ -CH ₂ CH (OH) CH ₃

Preferred polyazo compounds represented by the general formula (1) are those wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms,
A compound in which r and s are 0.

Next, specific examples of the compound represented by the general formula (1) are shown in (Table 2).

[0029]

Table 2 YY 'Compound No. R ¹ R ³ A prt R ² R ⁴ B qsu 0001 HH-1.7 0 2.3 HH-1.7 0 2.3 0002 HH-2.5 0 1.5 HH-2.5 0 1.5 0003 HH COCH _{3 1.5 1 0.5 HH COCH 3 1.5 0} 0.5 0004 HH - 3 0 1 HH - 3 0 1 0005 H CH 3 - 3 0 1 H CH 3 - 3 0 1 0006 H CH 3 COCH 3 1 1 2 H CH 3 - 3 0 1 0007 H CH ₃ COCH ₃ 1 1 2 H CH ₃ COCH ₃ 1 1 2 0008 H Cl-2 0 2 H Cl-2 0 2 0009 H SO ₃ H-2 0 2 H SO ₃ H-2 0 2 0010 Cl _{CH 3 - 3 0 1 Cl CH} 3 - 3 0 1 0011 Cl CH 3 COCH 3 1 1 2 Cl CH 3 - 3 0 1 0012 Cl CH 3 COCH 3 1 1 2 Cl CH 3 COCH 3 1 1 2 0013 Cl Cl - 2 0 2 Cl Cl-2 0 2

The polyazo compound of the present invention represented by the general formula (1) is obtained, for example, by reacting the compound represented by the general formula (5) or a salt thereof with the compound represented by the general formula (6). This carboxyalkylation reaction is preferably carried out in an aqueous medium at 40 to 120 ° C., pH 4-1.
2, particularly preferably 60 to 100 ° C., pH 6 to
9. Suitable compounds represented by the general formula (6) are, for example, monochloroacetic acid, monobromoacetic acid and salts thereof, and monochloroacetic acid and sodium monochloroacetate are preferred.

Further, the compound represented by the general formula (7) is tetrazotized, and then the compound represented by the general formula (8) or (9)

[0032]

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[0033]

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Wherein R ³ , R ⁴ , A, B, p, q,
r, s, t and u have the above-mentioned meanings) or a mixture of the general formula (8) and the general formula (9).
This coupling reaction is preferably carried out at pH 3-10, particularly preferably at 5-8.

The compound represented by the general formula (7) is represented by the general formula (10)

[0036]

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Wherein D is R ¹ or R ² , and the product is treated with 8-amino-1-hydroxy-
By coupling with 3,6-disulfonic acid (trade name H acid), the compound represented by the general formula (11)

[0038]

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(Wherein R ¹ and R ² have the above-mentioned meanings)
After that, it can be produced by successively reducing the nitro group. In this coupling reaction, a diazonium salt is used in an amount twice as large as that of H acid, and the first mole is subjected to coupling under acidic conditions, and the remaining mole is subjected to coupling under alkaline conditions. In acidic coupling,
The reaction is preferably carried out at a pH of 4 or less, and the alkali coupling is preferably carried out at a pH of 7 to 10. Suitable compounds represented by the general formula (10) include, for example, 2-chloro-4-nitroaniline, 2-methyl-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-amino-5-nitroaniline Aniline and 4-nitroaniline, of which 4-nitroaniline is preferred.

It is preferred that the compound represented by the general formula (7) is not isolated, but is subjected to tetrazolation and coupling subsequent to its production. General formula (8) or (9)
The compound represented by the general formula (12)

[0041]

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(Wherein, C has the meaning of R ³ and R ⁴ ), and can be obtained by reacting the compound with the compound represented by the general formula (6). The reaction is preferably carried out in an aqueous medium at a pH of from 3 to 9, particularly preferably from 5 to 8, and a temperature of from 40 to 120 ° C., particularly preferably from 50 to 100 ° C. The resulting compound represented by the general formula (8) or (9) is preferably used as an aqueous solution for the reaction with the compound represented by the general formula (7) without isolation in the middle. The general formula (1
The compound represented by 2) is, for example, 4-chloro-1,3-
Phenylenediamine, 4-bromo-1,3-phenylenediamine, 4-ethyl-1,3-phenylenediamine,
4-methyl-1,3-phenylenediamine, 2,4-diaminobenzenesulfonic acid, 3-amino-4-methoxyacetanilide, 3-aminoacetanilide, 1,3-
Examples include phenylenediamine, and 1,3-phenylenediamine is preferred.

The compounds represented by formulas (6), (10) and (12) are known and can be easily obtained on the market. After the coupling reaction, the polyazo compound represented by the general formula (1) of the present invention can be isolated in the form of a free acid by adding a mineral acid, from which an inorganic salt is removed by washing with water or acidified water. It can be removed. next,
The acid dyes having a low salt content obtained in this way can be used in aqueous media in the form of hydroxides and / or carbonates, such as LiOH, Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ or K ₂ CO ₃ or By neutralizing with an amine, a solution of the corresponding salt can be obtained. Preferred amines include, for example, ammonia, ethanolamine, diethanolamine, triethanolamine, N-methyl-
N-ethanolamine, N-methyl-N, N-diethanolamine, 2- (2-hydroxyethoxy) -ethylamine, di-2- (2-hydroxyethoxy) -ethylamine and tri-2- (2-hydroxyethoxy)-
Ethylamine and the like can be mentioned.

The polyazo compound of the present invention represented by the general formula (1) is suitable for dyeing a natural or synthetic fiber material having a hydroxyl group or an amino group.
It is excellent in showing dark colors on leather. Furthermore, these compounds are extremely suitable for the production of writing inks and recording liquids.

The aqueous solution of the polyazo compound of the present invention represented by the general formula (1) can be used directly for producing a recording ink composition. However, it is also possible to first isolate them by drying, for example by spray drying, and then to process them into ink compositions. The recording ink composition of the final product contains 0.1 to 20% by weight, more preferably 1 to 1% by weight of the polyazo compound of the present invention represented by the general formula (1).
0% by weight, more preferably about 2 to 8% by weight.
The ink composition of the present invention further comprises a water-soluble organic solvent 0 to 0.
It may contain 30% by weight and 0 to 5% by weight of an ink preparation.

The aqueous ink composition of the present invention is obtained by dissolving the polyazo compound of the present invention represented by the general formula (1) in water or an aqueous solvent (water containing a water-soluble organic solvent). When this aqueous ink composition is used as an ink for an ink jet printer, it is preferable to use, as the polyazo compound of the present invention, a low content of inorganic substances such as chlorides and sulfates of metal cations. Is about 1% or less, for example. In order to produce the polyazo compound of the present invention having a small amount of inorganic substances, desalting may be carried out by an ordinary method such as a method using a reverse osmosis membrane.

Examples of the water-soluble organic solvent include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethylformamide or N, N-dimethyl. Carboxylic acid amides such as acetamide, lactams such as ε-caprolactam, N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimidin-2-one; Cyclic urea, acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentane-
Ketones or keto alcohols such as 4-one, cyclic ethers such as tetrahydrofuran and dioxane, ethylene glycol, 1,2- or 1,3-propylene glycol,
Monomers having C2-C6 alkylene units such as 1,2- or 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. Oligomers or polyalkylene glycols or thioglycols, glycerin, polyols (triols) such as hexane-1.2.6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or triethylene glycol C1-C of polyhydric alcohol such as monomethyl ether or triethylene glycol monoethyl ether Alkyl ether, gamma-butyrolactone or dimethyl sulfoxide and the like.

Preferred organic solvents miscible with water include:
N-methylpyrrolidin-2-one, mono-, di- or trialkylene glycols having C2-C6 alkylene units, especially mono-, di- or triethylene glycol, dipropylene glycol, dimethyl sulfoxide, etc., and especially N-methyl The use of pyrrolidin-2-one, diethylene glycol, dimethyl sulfoxide is preferred.

Examples of the ink preparation agent include 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. 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 in the range of 8.0 to 11.0 without adversely affecting the ink to be prepared. Examples thereof include, for example, alkanolamines such as diethanolamine and triethanolamine, lithium hydroxide,
Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uracildiacetate. Examples of the rust inhibitor 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.

The colored article of the present invention is colored with the above-mentioned compound of the present invention or an aqueous ink composition containing the same. There are no particular restrictions on what should be colored,
For example, paper, fiber or cloth (made of nylon, wool, etc.), leather, base material for color filters and the like can be mentioned. 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 recording liquid containing one or more compounds represented by the general formula (1) is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording, especially ink jet printing. . In this case, very high densities are obtained and high-quality black prints with good resistance to water, sunlight and rubbing are obtained. The polyazo compound represented by the general formula (1) of the present invention has higher water solubility and better water resistance especially on a weakly acidic paper, but the water resistance is further improved particularly by using a polyamine and a polyimine together. These dyes are also advantageous in terms of toxicity.

No separation of precipitate occurs during storage of the aqueous ink composition of the present invention, and further, no clogging of the ejector occurs 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 ink jet printing machine under constant recirculation for a relatively long period of time or intermittently with an intermediate shutdown, the physical properties of the aqueous ink composition of the present invention No change in properties occurs.

[0053]

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) Preparation of N-carboxymethyl-substituted m-phenylenediamine and its salt 10.8 parts of m-phenylenediamine (hereinafter referred to as MPDA) and a predetermined amount of sodium monochloroacetate were introduced into 100 ml of water. The mixture was heated to 60 ° C. under a nitrogen atmosphere. Then, the reaction was carried out at the same temperature for 4 hours to complete the carboxymethylation. During the reaction, the pH is maintained at 7 to 8 with a 10% aqueous sodium carbonate solution. The carboxymethylation ratio of MPDA in the obtained solution was measured by high performance liquid chromatography, and the results in Table 3 were obtained.

[0055]

Table 3 Table 3 Sodium monochloroacetate Carboxymethyl group substitution number (Molar ratio / MPDA) 0 12 or more 1 1.2 18 72 5 1.7 1.7 768 20 3 2.3 251 46 4 3.0 0 15 85

B) Preparation of Dye 13.8 parts of 4-nitroaniline was charged into 65 ml of water, stirred overnight, 7 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. This was mixed with 200 ml of water and 0.1 ml of sodium nitrite. 06
And a mixture of 31.3 parts of 35% hydrochloric acid at 10 ° C. After stirring at the same temperature for 10 to 20 minutes, the diazo liquid becomes almost transparent. After the mixture has been stirred for a further hour at 5 DEG to 10 DEG C., the excess nitrous acid is removed with sulfamic acid. On the other hand, a solution prepared by dissolving 15.9 parts of H acid in 300 ml of water is added to the diazo solution under vigorous stirring for 1 hour, and then acidic coupling is performed.
The reaction is completed in about 3 hours. Continue with 20%
Neutralize to pH 8 with aqueous sodium carbonate solution and perform alkaline coupling. During the reaction, the pH is maintained at 8-9.
Alkali coupling is completed in about 2 hours and the general formula (1)
1) A coupling liquid containing a dye (wherein R ¹ and R ² are hydrogen atoms) is obtained. Next, the coupling solution is warmed to 25 ° C., and a solution of 11.7 parts of sodium sulfide and 150 ml of water is added. The reduction is completed in about 1 hour, and the general formula (7) (where R ¹ and R ² are hydrogen atoms) Is obtained.
Then 52 parts of 35% hydrochloric acid and 60 g of ice are added to the suspension of disazo dye obtained above and the diazotization is carried out by adding 18.1 parts of a 40% aqueous sodium nitrite solution. The mixture is subsequently stirred at 0-5 ° C. for 2 hours, then the excess nitrous acid is removed with sulfamic acid. The resulting suspension of bisdiazonium salt was prepared according to (a) -2 in 1 hour, aqueous solution of sodium salt of N-carboxymethylated metaphenylenediamine, sodium carbonate 2
Add to a mixture of 7.4 g and 150 g of ice. After completing the coupling reaction and adding 90 g of 30% hydrochloric acid, the precipitated dye is filtered off and washed with water to remove the electrolyte. The obtained dye wet cake is washed with water 500m.
was suspended in l, the dye paste was neutralized with 5N lithium hydroxide solution 70 ml, by drying then the resulting dye solution, the general formula (1) ... wherein R ^1,
R ² , R ³ and R ⁴ are hydrogen atoms, r and s are 0,
p and q are 1.7 and n is 1 to obtain 95.0 parts of a black polyazo compound (Compound No. 0001) represented by. The absorption spectrum of this compound in water is λm
ax = 661 nm.

Example 2 Formula (5): wherein R ¹ , R ² , R ³ , and R ⁴ are hydrogen atoms, r and s are 0, and u and t are 4. After suspending 10.0 parts of the tetrakisazo dye in 100 ml of water, 8.8 parts of sodium chloroacetate was added. Next, the mixture was reacted at 60 to 65 ° C. for 4 hours with stirring, heated to 80 ° C., and reacted at the same temperature for 2 hours. During the reaction, the pH was maintained at 8 to 9 with a 10% aqueous sodium carbonate solution. After the reaction, 9.2 parts of 30% hydrochloric acid was added, and the precipitated dye was filtered off and washed with water to remove the electrolyte. The obtained dye wet cake was treated in the same manner as in Example 1 to obtain 6.3 g of a black polyazo compound (Compound No. 0002). λmax = 657 nm (in water).

Example 3 a) Preparation of N- (m-acetylaminophenyl) glycine and its salt 15 parts of m-aminoacetanilide and 17.5 parts of sodium monochloroacetate were introduced into 100 ml of water, and the mixture was mixed under a nitrogen atmosphere. Was heated to 60 ° C. Then at the same temperature 4
Carboxymethylation was completed by reacting for hours. During the reaction, the pH was adjusted to 7 with a 10% aqueous sodium carbonate solution.
Keep at ~ 8. The reaction product is used for the next dye synthesis without isolating the reaction solution. b) Preparation of the dye A sodium salt of N- (acetylaminophenyl) glycine prepared according to a) over a period of one hour by suspension of a bisdiazonium salt prepared under the same conditions as in b) of Example 1. Aqueous solution, 27.4 parts of sodium carbonate and ice 1
Add dropwise to 50 parts of the mixture. After completion of the coupling reaction, 90 parts of 30% hydrochloric acid are added, the precipitated dye is filtered off and washed with water to remove the electrolyte. The obtained dye wet cake is suspended in 500 ml of water, and the dye paste is neutralized with 70 ml of a 5N lithium hydroxide solution.
Thereafter, the obtained dye solution is dried to obtain a compound represented by the general formula (1), wherein R ¹ , R ² , R ³ , and R ⁴ are hydrogen atoms,
A and B are acetyl groups, n, r, and s are 1, p and q are 1.5, and m is 0. 126 g of a black polyazo compound (Compound No. 0003) is obtained. .
The absorption spectrum of this compound in water is λmax = 64
8 nm.

Example 4 (A) Preparation of Ink A liquid having the following composition was prepared and filtered through a 0.45 μm membrane filter to obtain three types of aqueous ink compositions for inkjet. Composition 3.0 parts of each compound obtained in Examples 1 to 3 (used after desalting) Water 67.0 parts Ethylene glycol 5.0 parts Glycerin 5.0 parts N-methylpyrrolidone 7.0 parts Urea 10.0 parts IPA 3.0 parts

(B) Inkjet printing Inkjet printer (trade name: ENCAD NO.
VAJET III), plain paper (Canon Printer Paper A4 (TLB5A4S)), special paper A (C
Ink jet recording was performed on three types of paper, ie, color BJ Paper LC101 (manufactured by Canon) and special paper B (coated paper for color image jet STX73A4 (manufactured by Sharp)). (C) Light fastness test of recorded image The recorded image was irradiated for 20 hours using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.). Judgment class is JIS
It was determined according to the blue scale rating specified in L-0841. (D) Waterfastness test of recorded image A test piece was placed in water placed in a beaker with gentle stirring.
After soaking for a minute and drying, the degree of the compound falling off before the test treatment is visually determined. ◎ Almost no drops. ○ About 10% drop. △ About 50% drop off. X: Drops 80% or more. (E) Color rendering properties The degree of discoloration when viewed under tungsten light is visually determined based on the hue of the standard light source. ○ Small hue change. △ Hue change is slightly large. × Large hue change.

COMPARATIVE EXAMPLES 1, 2, 3 Three types of dyes used or proposed as black in ink jet printing were picked and tested as comparative examples. (1) Comparative Example 1 I. Direct Black 19 was prepared by the method (A).
Ink was prepared according to (B) and printed on each paper. (2) Comparative Example 2 Canon Black Ink (BC1-21) (3) Comparative Example 3 EPSON Black Ink (MJ1C7C) The evaluation results are shown in Table 4.

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[Table 4] Table 4 Lightfastness and waterfastness Color rendering properties Plain paper Plain paper Dedicated paper A Dedicated paper B Example 1 Class 5 ◎ ◎ ◎ ○ Example 2 Class 5 ◎ ◎ ◎ ○ ○ Comparative Example 1 Class 5 ○ ○ ○ ○ Comparative Example 2 Class 4-5 ○ ◎ ○ × Comparative Example 3 Class 3-4 ○ ○ ○ ×

From Table 4, it can be seen that the ink compositions of Examples 1, 2, and 3 of the present invention exhibit light fastness equivalent to or higher than that of the conventional black dye (comparative example), and are more excellent in water resistance and color rendering. I have. In addition, the ink composition of the present invention was found to have excellent storage stability and ejection stability of the recording liquid because of its high solubility in water.

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The aqueous ink composition containing the 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 paper.
In addition, it has excellent light fastness, water fastness and color rendering properties, and also has good storage stability as a recording liquid.

Claims (11)

[Claims] 1. A polyazo compound represented by the following general formula (1) or a salt thereof. Embedded image (Wherein Y is a general formula (2) (Wherein R ³ is a hydrogen atom, a (C1-C4) -alkyl group, a halogen or —SO ₃ H, and A is (C1-C4
4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, -CONH ₂
Represents p is an average number of 1 to 4, r is 0 or 1, and t is 4- (p + r). And Y ′ is a group represented by the general formula (3): (Wherein R ⁴ is a hydrogen atom, a (C1-C4) -alkyl group, a halogen or —SO ₃ H, and B is (C1-C4
4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, -CONH ₂
Represents q is an average number of 1 to 4, s is represented by 0 or 1, and u is 4- (q + s). ), Wherein R ¹ and R ² are each independently a hydrogen atom, (C
1 to C4) an alkyl group, halogen or —SO ₃ H; ) 2. The salt is a lithium salt, a sodium salt or a compound of the general formula (4). (Wherein, R ⁵ to R ⁸ are each independently a hydrogen atom,
(C1-C4) alkyl group, hydroxy- (C1-C4)
4) alkyl group or hydroxyethoxy- (C1-C
4) The polyazo compound according to claim 1 or a salt thereof, which is an ammonium salt represented by the formula: 3. The polyazo compound according to claim ¹ , wherein R ¹ , R ² , R ³ , and R ⁴ are hydrogen atoms, or a salt thereof. 4. The method according to claim 1, wherein r and s are 0, and R ¹ , R ² , R ³ , R
^{4. The method according} to claim 1, wherein ⁴ is a hydrogen atom.
The polyazo compound or a salt thereof according to any one of the above. 5. The method according to claim 1, wherein r and s are 1, and R ¹ , R ² , R ³ , R
⁴ is a hydrogen atom, A, B are each independently acetyl group, any one of claims 1 is -CONH ₂ 3 1
Or the salt thereof. 6. R ¹ , R ² , R ³ , R ⁴ are hydrogen atoms, and each salt is independently a lithium salt, a sodium salt or an ammonium salt represented by the general formula (4) according to claim 2. The polyazo compound according to any one of claims 1 to 5, or a salt thereof. 7. The method for producing a polyazo compound or a salt thereof according to claim 1, wherein the compound has the general formula (5): (In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a (C1-C4) alkyl group, a halogen or —S
O ₃ H, A and B are each independently (C1 to C4)
Alkylcarbonyl group, (C1-C4) alkoxy-
(C1 -C4) alkylcarbonyl group, a -CONH _2, r, s compounds represented by each independently 0 or 1) or a salt thereof with the general formula _{(6) X-CH 2 COOH} (6) ( Wherein X represents a halogen) or a salt thereof. The method for producing a polyazo compound and a salt thereof according to claim 1, wherein 8. The method for producing a polyazo compound or a salt thereof according to claim 1, wherein the compound has the general formula (7): (Wherein R ¹ and R ² have the meanings described in any one of claims 1 to 6) or a salt thereof, and the product is converted to a compound represented by the general formula (8). (Wherein R ³ is a hydrogen atom, a (C1-C4) -alkyl group, a halogen or —SO ₃ H, and A is (C1-C4
4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, -CONH ₂
Represents p is an average number of 1 to 4, r is 0 or 1, and t is 4- (p + r). And / or a compound represented by the general formula (9): (Wherein R ⁴ is a hydrogen atom, a (C1-C4) -alkyl group, a halogen or —SO ₃ H, and B is (C1-C4
4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, -CONH ₂
Represents q is an average number of 1 to 4, s is represented by 0 or 1, and u is 4- (q + s). 2. The method for producing a polyazo compound or a salt thereof according to claim 1, wherein the compound is coupled with the compound represented by the formula (1). 9. An aqueous ink composition comprising the polyazo compound according to claim 1 or a salt thereof. 10. A colored body colored with the polyazo compound or a salt thereof according to any one of claims 1 to 6, or the aqueous ink composition according to claim 9. 11. The printer according to claim 1, wherein the coloring is performed by a printer.
1 colored body.