JPH10195321A - Polyazo compound, water-base ink composition and colored material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a black recording fluid high in the state of being dissolved, stable even after long-term storage, high in the density of a printed image and excellent in water resistance and light fastness by using a phenylazo- containing polyazo compound or it lithium or sodium salt or its salt with an ammonium compound. SOLUTION: This invention provides a compound of formula I or its salt (wherein m is 0 or 1). In the formula, Y is formula II, Y' is phenylazo of formula III. R1 and R2 are each H, a 1-4C alkyl, SO3 H or a halogen; a and b are each a 1-4C alkylcarbonyl, a (1-4C) alkoxy-(1-4C)alkylcarbonyl or CONH2 ; n=1 or 2; p and q are each 1-4 on the average; r and s are each 0 or 1; t=4-(p+r); and u=4-(q+s). This polyazo dye can show further improved water resistance when used in combination with a polyamine or a polyimide. A water-base ink composition containing this dye is suitable for especially ink jet printing and does not plug the jetting unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble polyazo dye, a process for producing the same, and a colored product.

[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 is because the recording head does not come into contact with the recording material, so there is no sound and the recording is quiet.
Due to the feature of easy colorization, it has been rapidly spreading in recent years, and great growth is expected in the future. Of these, when an image or character information on a color display of a computer is recorded in color by an ink jet printer, it is generally expressed by subtractive color mixture using four inks of yellow, magenta, cyan and black. C
The hue and sharpness used are the most important items in order to faithfully reproduce an additive color image by R, G, B such as an RT display as much as a subtractive color image. 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,
No. 7070, JP-B-61-18947, JP-A-55-947.
JP-A-151071, JP-A-57-36693, JP-A-57-36693
Many applications have been filed, such as JP-A-2-156177, JP-A-1-197580, and JP-A-8-245894, but they have not yet completely satisfied the requirements of the market.

[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]

Embedded image

(Where Y is a general formula (2)

[0007]

Embedded image

(R ¹ is a hydrogen atom, a (C ¹ -C 4) alkyl group, —SO ₃ H or halogen, and A is (C 1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group or -C
ONH ₂ , and n is 1 or 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]

Embedded image

(R ² is a hydrogen atom, a (C 1 -C 4) alkyl group, —SO ₃ H or halogen, and B is (C 1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group or -C
ONH ₂ , and n is 1 or 2. q is an average number of 1 to 4, s is 0 or 1, and u is 4-
It is a number represented by (q + s). And m is 0 or 1.) (2) The salt is a lithium salt, a sodium salt or the general formula (4)

[0011]

Embedded image

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

[0013]

Embedded image

(Wherein R ¹ and R ² are each independently a hydrogen atom, a (C1-C4) alkyl group, —SO ₃ H or halogen, and A and B are each independently a (C1-C4)
Alkylcarbonyl group, (C1-C4) alkoxy-
(C1 -C4) alkylcarbonyl group, a -CONH _2, m, r, s are each independently 0 or 1)
And a compound thereof or a salt thereof and a compound represented by the general formula (6) X-C _n H _2n COOH (6) (wherein X is a halogen and n is 1 or 2) 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 the method is a method for producing the polyazo compound or a salt thereof according to (1). (7)

[0015]

Embedded image

(Wherein m has the meaning described in any one of (1) to (6)) or a salt thereof, and the product is converted to a compound of the general formula (8)

[0017]

Embedded image

(R ¹ is a hydrogen atom, a (C ¹ -C 4) alkyl group, —SO ₃ H or halogen, and A is (C 1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group or -C
ONH ₂ , and n is 1 or 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]

Embedded image

(R ² is a hydrogen atom, a (C1-C4) alkyl group, —SO ₃ H or halogen, and B is (C1
-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1-C4) alkylcarbonyl group or -C
ONH ₂ , and n is 1 or 2. q is an average number of 1 to 4, s is 0 or 1, and u is 4-
It is a number represented by (q + s). (9) The method for producing a polyazo compound or a salt thereof according to (1), wherein the polyazo compound or a salt thereof according to any one of (1) to (6) is used. Aqueous ink composition characterized by containing (10) a colored body colored with a polyazo compound or a salt thereof according to any one of (1) to (6). (11) Coloring was performed by a printer. )).

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the general formulas (1) to (3), R ¹ and R ² are a hydrogen atom, a (C1 to C4) -alkyl group, —SO ₃ H or a halogen, and A and B are each independently (C1 to C4). C
4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1 -C4) alkylcarbonyl group, -CONH ₂
And n is 1, 2. p and q are each a number of 1 to 4 on average, m, r, and s are each independently represented by 0 or 1, t is 4- (p + r), and u is 4- (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, in particular, alkali metal salts and alkaline earth metal salts. Preferred inorganic salts are lithium or sodium salts, and suitable organic salts include ammonium salts represented by the above general formula (4). In the general formula (4), examples of the (C1-C4) alkyl group for R ³ to R ⁶ include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, and a
-Butyl group, i-butyl group, secondary butyl group, tertiary butyl group and the like. 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, a 2-hydroxyethoxypropyl group, a 4-hydroxyethoxybutyl group and a 3-hydroxy An ethoxybutyl group, a 2-hydroxyethoxybutyl group and the like can be mentioned.

Next, typical specific examples of the ammonium salt represented by the general formula (4) are shown in Table 1 below.

[0025]

TABLE 1 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 _Three

In the general formula (1), the substitution position of Y or Y 'is preferably the 1, 2 or 3 position of the naphthalene skeleton, particularly preferably the 2 position. - (SO ₃ H) _m is preferably substituted in the 3 and 4 positions of the naphthalene skeleton. Then - (SO ₃ H) _m can be used in the form of a salt, lithium salt independently is preferred salt, sodium salt or the general formula (4) R ³ to the ammonium salt of from hydrogen irrespective R ⁶ to each other Atom, hydroxy- (C1-C4) alkyl group or hydroxy- (C
1 to C4) Ammonium salts which are alkyl groups.

In a preferred polyazo compound represented by the general formula (1), m is 0, R ¹ and R ² are hydrogen atoms, and A and B are each independently an acetyl group, -CONH ₂
It is.

Next, specific examples of the compound represented by the general formula (1) are shown separately in general formulas (1-1) (Table 2) to general formulas (1-4) (Table 5).

[0029]

Embedded image

[0030]

Table 2 Table 2 General formula (1-1) Y Y ′ Compound No. R ¹ Anprt R ² B nqsu 01 H-11.1 0 2.9 H-11.10 2.902 H-1 202 O 2 H-1 _{2 0 2 03 H COCH 3 1} 1.2 1 0.8 H COCH 3 1 1.2 1 0.8 04 H - 1 3 0 1 H - 1 3 0 1 05 H - 2 2 0 2 H - 2 2 0 2 06 CH 3 - 1 3 _{0 1 CH 3 - 1 3 0} 1 07 CH 3 COCH 3 1 1 1 2 CH 3 - 1 3 0 1 08 CH 3 COCH 3 1 1 1 2 CH 3 COCH 3 1 1 1 2 09 CH 3 - 2 2 0 2 _{CH 3 - 2 2 0 2 10} Cl - 1 2 0 2 Cl - 1 2 0 2 11 H CONH 2 1 1.5 1 0.5 H CONH 2 1 1.5 1 0.5

[0031]

Embedded image

[0032]

[Table 3] Table 3 General formula (1-2) Y Y 'Compound No. R ¹ A nprt R ² B nqsu 12 H-13 01 H-13 01 13 H-220 2 H-2 _{2 0 2 14 CH 3 - 1} 3 0 1 CH 3 - 1 3 0 1 15 CH 3 COCH 3 1 1 1 2 CH 3 - 1 3 0 1 16 CH 3 COCH 3 1 1 1 2 CH 3 COCH 3 1 1 1 _{2 17 CH 3 - 2 2 0} 2 CH 3 - 2 2 0 2 18 Cl - 1 2 0 2 Cl - 1 2 0 2 19 H CONH 2 1 1.5 1 0.5 H CONH 2 1 1.5 1 0.5

[0033]

Embedded image

[0034]

Table 4 Table 4 General formula (1-3) Y Y 'Compound No. R ¹ Anprt R ² B nqsu 20 H-1 310 1 H-1 330 121 H-2202 H-2 _{2 0 2 22 CH 3 - 1} 3 0 1 CH 3 - 1 3 0 1 23 CH 3 COCH 3 1 1 1 2 CH 3 - 1 3 0 1 24 CH 3 COCH 3 1 1 1 2 CH 3 COCH 3 1 1 1 _{2 25 CH 3 - 2 2 0} 2 CH 3 - 2 2 0 2 26 Cl - 1 2 0 2 Cl - 1 2 0 2 27 H CONH 2 1 1.5 1 0.5 H CONH 2 1 1.5 1 0.5

[0035]

Embedded image

[0036]

Table 5 Table 5 General formula (1-4) Y Y 'Compound No. R ¹ A nprt R ² B nqsu 28 H-1 310 1 H-1 330 1 29 H-2 202 H-2 _{2 0 2 30 CH 31 3 0} 1 CH 31 3 0 1 31 CH 3 COCH 3 1 1 1 2 CH 31 3 0 1 32 CH 3 COCH 3 1 1 1 2 CH 3 COCH 3 1 1 1 _{2 33 CH 3 - 2 2 0} 2 CH 3 - 2 2 0 2 34 Cl - 1 2 0 2 Cl - 1 2 0 2 35 H CONH 2 1 1.5 1 0.5 H CONH 2 1 1.5 1 0.5

The polyazo compound of the present invention represented by the general formula (1) can be produced by a method known per se. For example, it can be obtained by reacting the compound represented by the general formula (5) or a salt thereof with the compound represented by the general formula (6). The carboxyalkylation reaction is preferably carried out in an aqueous medium at 40 to 120 ° C, pH 4 to 12, particularly preferably at 60 to 100 ° C, pH 6 to 9. Examples of the compound represented by the general formula (6) include monochloroacetic acid, monobromoacetic acid, 3-chloropropionic acid, 3-bromopropionic acid and salts thereof, and monochloroacetic acid and sodium monochloroacetate are preferred.

Further, the compound represented by the general formula (7) is tetrazotized in an aqueous medium, and then the compound represented by the general formula (8) or (9) or the compound represented by the general formula (8) and the general formula (9) Can also be produced by coupling with a mixture of This coupling reaction is preferably
H4-10, particularly preferably 6-8.

The compound represented by the general formula (7) is 4,
4'-Diaminodiphenylamine-2-sulfonic acid is tetrazotized to give a product represented by the general formula (10)

[0040]

Embedded image

(Wherein m has the same meaning as described above). This coupling reaction is preferably carried out at a pH of from 7 to 12, particularly preferably from 7.5 to 9.5. It is preferred that the compound represented by the general formula (7) is not isolated, but is directly subjected to the above-mentioned another tetrazolation and coupling directly after its production. Examples of the compound represented by the general formula (10) include 2-amino-8-hydroxynaphthalene-6-sulfonic acid and 2-amino-8-hydroxynaphthalene-3,6
-Disulfonic acid, 3-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and the like Of which 2-amino-8-hydroxynaphthalene-
6-sulfonic acid is particularly preferred.

The compound represented by the general formula (8) or (9) is represented by the general formula (11)

[0043]

Embedded image

(Wherein R represents the above R ¹ and R ² and Z
Having the meanings of A and B) can be obtained by reacting the compound represented by the above general formula (6). The reaction is preferably carried out in an aqueous medium for 3 hours.
-9, particularly preferably a pH value of 5-8 and 40-12
It is carried out at a temperature of 0 ° C, particularly preferably 50-100 ° C. The resulting compound of the general formula (8) or (9) is preferably used as an aqueous medium solution for the reaction with the compound of the general formula (7) without isolation in the middle. Examples of the compound represented by the general formula (11) include 4-ethyl-1,3-phenylenediamine,
4-methyl-1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 2,4-diaminobenzenesulfonic acid, 1,3-phenylenediamine and the like, and 1,3-phenylenediamine is particularly preferred. preferable.

The compounds represented by formulas (6), (10) and (11) are known and can be easily obtained on the market. After the coupling reaction, the general formula (1) according to the present invention
Can be isolated in the form of a free acid by addition of a mineral acid, from which inorganic salts can be removed by washing with water or acidified water. The acid dye with low salt content obtained in this way is then converted to hydroxides and / or carbonates such as LiOH, Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ or K ₂ CO _{3 in} an aqueous medium. By neutralizing with ₃ or 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 represented by the general formula (1) is remarkably suitable for dyeing a blended product with natural and synthetic fiber materials, and is particularly excellent in that a deep color appears on leather. Furthermore, these dyes are very suitable for producing writing inks and recording liquids.

The reaction 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, or to crystallize the polyazo compounds and remove them from the reaction liquid, and then to process them further into ink compositions. The recording ink composition of the final product contains the polyazo compound of the present invention represented by the general formula (1) in an amount of 0.1 to 20% by weight, more preferably 1 to 20% by weight.
The content is about 10% by weight, more preferably about 2 to 8% by weight. The ink composition of the present invention may further contain 0 to 30% by weight of a water-soluble organic solvent 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 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, one having a low content of inorganic substances such as chlorides and sulfates of metal cations. For example, 1%
Below. In order to produce a polyazo compound 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, tert-butanol, N, N-dimethylformamide and 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-dimethylhexahydropyrimid-2-one; Cyclic ureas, acetone,
Ketones such as methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or keto alcohols, cyclic ethers such as tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1 , 4-butylene glycol,
Monomers, oligomers or polyalkylene glycols or thioglycols having (C2-C6) alkylene units, such as 1,6-hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. , Polyol such as 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 triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, etc. (C1-C4) alkyl ethers of polyhydric alcohols, γ-butyrolact Emissions 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 and the like, 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. As chelating reagents,
Examples include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracildiacetate, and the like. 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 product of the present invention is colored by the above-mentioned compound of the present invention. To be colored,
There is no particular limitation, and examples thereof 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 recording liquid containing one or more dyes represented by the general formula (1) is used for printing, copying, marking, writing,
Significantly suitable for use in drafting, stamping or recording methods, especially ink jet printing. This gives high quality black prints with remarkably high concentrations and good resistance to water, sunlight and rubbing. Compared with comparable dyes, the polyazo dyes of the general formula (1) according to the invention have a higher water solubility and a better water resistance, especially on weakly acidic papers, but especially in combination with polyamines and polyimines. Thereby, the water resistance is further improved. These dyes are also advantageous in terms of safety.

No separation of the precipitates occurs during storage of the inks according to the invention, and furthermore no clogging of the injectors occurs when the inks according to the invention are used in ink jet printing. When the ink according to the invention is used in an ink-jet printing machine under constant recirculation for a relatively long period of time or intermittently under intermediate interruptions, no change in the physical properties of the ink according to the invention takes place. .

[0055]

The present invention will be described in more detail 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 a salt thereof 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 resulting solution was measured by high performance liquid chromatography, and the results in Table 6 were obtained.

[0057]

Table 6 Table 6 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 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid and 50 parts of 30% hydrochloric acid were charged into 200 ml of water, and ice was added to adjust the temperature to 5 ° C. or less, and then 40%. 35.2 parts of an aqueous solution of sodium nitrite are charged at 0 to 5 ° C. and tetrazotized. After addition of the 40% aqueous sodium nitrite solution, the mixture is stirred for 1 hour at 0-5 ° C., then the excess nitrous acid is removed with sulfamic acid. Next, the resulting solution of the bisdiazonium salt was mixed with 47.8 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 300 ml of water, 48
% Sodium hydroxide, sodium carbonate 46.
It is added to a mixed solution of 8 parts and 150 parts of ice and coupled. The mixture is then heated at 10-15 ° C, pH 9-9.5 for 2 hours to complete the coupling reaction.
Stir for hours. To this reaction solution, 120 parts of 30% hydrochloric acid and 150 parts of ice are added, and then 35.2 parts of a 40% aqueous sodium nitrite solution is added to carry out diazotization. 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 the bisdiazonium salt was dissolved in an aqueous solution of the sodium salt of N-carboxymethylated metaphenylenediamine ((a) -2 above), 27.4 parts of sodium carbonate and ice for 15 minutes.
Add to 0 parts of the mixture. After completion of the coupling reaction and addition of 90 parts of 30% hydrochloric acid, the precipitated dye is filtered off and washed with water to remove the electrolyte.

The obtained dye wet cake was washed with 500 m of water.
and the resulting dye paste is neutralized with 70 ml of a 5N lithium hydroxide solution, and the resulting dye solution is dried to obtain a compound of the general formula (1) (wherein R ¹ , R
² is a hydrogen atom, r, s, and m are 0;
1 and n is 1) to obtain 123 parts of a lithium salt of a black polyazo dye (Compound No. 01). The absorption spectrum of this dye in water is λmax = 60
2 nm.

Example 2 Formula (5) (R ¹ and R ² are hydrogen atoms, and r, s,
m is 0, u and t are 4 and n is 1) 10.2 parts of a tetrazo dye represented by the following formula:
After the suspension, 7.0 parts of sodium chloroacetate was added.
Then, after stirring at 60-65 ° C for 4 hours under stirring, 80 ° C
And reacted at the same temperature for 2 hours. 10 during the reaction
The pH was maintained at 8 to 9 with a 20% aqueous sodium carbonate solution.
After the reaction, 9.7 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 11.4 parts of a lithium salt of a black polyazo dye (Compound No. 02). λmax = 478 nm.

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 Dye A suspension of bisdiazonium salt prepared under the same conditions as in b) of Example 1 was prepared in the same manner as in a) of Example 1 over 1 hour. Add dropwise to a mixture of an aqueous solution of the sodium salt of acetylaminophenyl) glycine, 27.4 parts of sodium carbonate and 150 parts of ice. 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 washed with a 5N lithium hydroxide solution 70 m.
Then, the resulting dye solution is spray-dried to obtain a compound represented by the general formula (1) (wherein R ¹ and R ² are hydrogen atoms, A and B are acetyl groups, n, r, and s are 1). And p and q were 1.2, and m was 0), thereby obtaining 126 parts of a lithium salt of a black polyazo dye (Compound No. 03). The absorption spectrum of this dye in water is λmax = 568 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 an aqueous ink composition for inkjet. Composition 3.0 parts of the compound obtained in Example 1 (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)). Next, a light fastness test of the recorded image, a water fastness test of the recorded image, and a color rendering test were performed.

(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 detachment of the dye 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 A change in hue due to the presence of color rendering is visually determined. ○ No change due to color rendering. △ Some color rendering properties. × Color rendering properties.

Comparative Examples 1, 2, and 3 Three types of dyes used or proposed as black in ink jet printing were picked up and tested as comparative examples. (1) Comparative Example 1 I. Direct Black 22 (A)
Ink was prepared and printed according to (B). (2) Comparative Example 2 Canon BJ Black Ink (3) Comparative Example 3 EPSON HJ Black Ink The evaluation results are shown in Table 7.

[0067]

Table 7 Table 7 Solubility Light fastness Water fastness Color rendering (g / l) Plain paper Plain paper Dedicated paper A Dedicated paper B Example 1 40 or higher 4-5 class ◎ ◎ ◎ ○ Example 2 40 or higher 4- Grade 5 ◎ ◎ ◎ ○ Example 3 40 or higher 4-5 Class ◎ ◎ ◎ ○ Comparative Example 1 20 or lower 4-5 Class ○ ◎ ○ ○ Comparative Example 2 Class 4-5 ○ ◎ ○ × Comparative Example 3 Class 3 × ○ × ×

From Table 7, it can be seen that the ink compositions of Examples 1, 2 and 3 of the product of the present invention exhibit light fastness equivalent to or higher than that of the conventional black dye (comparative example) and also have excellent water resistance and color rendering properties. ing. In addition, it was found that the storage stability and the ejection stability of the recording liquid were excellent because of the high solubility in water.

[0069]

The recording liquid containing the polyazo 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 has light resistance and water resistance. In addition to being excellent in color rendering properties, storage stability as a recording liquid is also good.

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) (R ¹ is a hydrogen atom, a (C1-C4) alkyl group, -S
O ₃ H or halogen, and A represents a (C1-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1
-C4) alkylcarbonyl group or -CONH _2, n is 1 or 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): (R ² is a hydrogen atom, a (C1-C4) alkyl group, -S
O ₃ H or halogen, B is a (C1-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1
-C4) alkylcarbonyl group or -CONH _2, n is 1 or 2. q is an average number of 1 to 4, s is 0 or 1, and u is a number represented by 4- (q + s). ), And m is 0 or 1.) (2) the salt is a lithium salt, a sodium salt or a compound of the general formula (4): (Wherein, R ^{3 to} R ⁶ are each independently a hydrogen atom, (C
The polyazo compound or a salt thereof according to claim 1, which is an ammonium salt represented by the following formula: 1 to C4) an alkyl group, a hydroxy- (C1 to C4) alkyl group or a hydroxyethoxy- (C1 to C4) alkyl group. 3. The polyazo compound according to claim ¹ , wherein m is 0, and R ¹ and R ² are hydrogen atoms. 4. The polyazo compound or a salt thereof according to claim ¹ , wherein m, r, and s are 0, and R ¹ and R ² are hydrogen atoms. 5. The method according to claim 1, wherein r and s are 1, m is 0, R ¹ ,
R ² is a hydrogen atom, and A and B are each independently an acetyl group or a propionyl group.
4. The polyazo compound or a salt thereof according to any one of items 1 to 3. 6. A compound according to claim ² , wherein R ¹ and R ² are hydrogen atoms, m is 0, n is 1 and the salts are each independently a lithium salt, a sodium salt or a salt of the general formula (4). The polyazo compound or a salt thereof according to any one of claims 1 to 5, which is an ammonium salt represented by the following formula: 7. The method for producing a polyazo compound or a salt thereof according to claim 1, wherein the compound has the general formula (5): (Wherein R ¹ and R ² are each independently a hydrogen atom, (C1
-C4) alkyl group, a -SO ₃ H or halogen, A, B respectively independently (C1 -C4) alkylcarbonyl group, (C1 -C4) alkoxy - (C1~C
4) alkylcarbonyl group, a -CONH _2, m,
wherein r and s are each independently 0 or 1, or a salt thereof and a general formula (6) X—C _n H _2n COOH (6) (wherein X is a halogen and n is 1 or 2. The method for producing a polyazo compound or a salt thereof according to claim 1, wherein the compound is reacted with the compound or a salt thereof. 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 m has the meaning described in any one of claims 1 to 6) or a salt thereof, and the product is converted to a general formula (8). (R ¹ is a hydrogen atom, a (C1-C4) alkyl group, -S
O ₃ H or halogen, and A represents a (C1-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1
-C4) alkylcarbonyl group or -CONH _2, n is 1 or 2. 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): (R ² is a hydrogen atom, a (C1-C4) alkyl group, -S
O ₃ H or halogen, B is a (C1-C4) alkylcarbonyl group, (C1-C4) alkoxy- (C1
-C4) alkylcarbonyl group or -CONH _2, n is 1 or 2. q is an average number of 1 to 4, s is 0 or 1, and u is a number represented by 4- (q + s). 2. The method for producing a polyazo compound or a salt thereof according to claim 1, which 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 according to claim 1 or a salt thereof. 11. The printer according to claim 1, wherein the coloring is performed by a printer.
0 colored body.