JPH0912910A - Tetrakisazo compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve e.g. discharge stability, discharge responsiveness or dissolving storage stability as a recording liquid for ink jet and obtain a recording image excellent in brightness and heat resistance, etc., by using a specific tetrakisazo compound. SOLUTION: This tetrakisazo compound is expressed by formula I [Q1 is phenylene or naphthylene; R is carboxyl or sulfo; Q2 is phenyl or naphthyl; either one of A and B is hydroxy an the other is amino; (k) is 1 or 2; (m) is 0 or 1; (n) is 1 or 2]. For example, a compound of formula II (R3 to R5 are each independently H, hydroxy, sulfo, a halogen, etc.) among the compounds of formula I is obtained by diazotizing an amine compound of formula III and carrying out coupling of the resultant compound with an aminonaphthod of formula IV. Furthermore, the compound is used as a recording liquid for ink jet printers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel tetrakisazo compound and its use, for example, a recording liquid for ink jet printers containing the tetrakisazo compound.

[0002]

2. Description of the Related Art For example, an aqueous ink composition useful for ink jet recording is basically composed of a dye, an organic solvent and water, but it is used for good ink jet recording. Various conditions are required for the ink composition. First, as the physical properties of the ink composition according to the droplet generation method and the droplet flight direction control method, for example, the viscosity, surface tension, specific electric conductivity, density, pH, etc. of the ink composition must be included in an appropriate range. Is.

It is necessary that these properties be maintained stably for a long period of time. That is, a deposit should not be generated due to a chemical change or the like during long-term storage, long-term use or recording suspension of the ink composition. In particular, the discharge nozzle of the recording device generally has a diameter of about 10 to 60 μm, and if the nozzle is clogged with deposits, it will not be possible to discharge droplets, and even if the nozzle is not completely clogged, solids and sticky substances will adhere to the vicinity of the nozzle. As a result, recording properties, ejection stability, and ejection responsiveness deteriorate.

Further, in recent ink jet systems utilizing heat energy, excellent heat resistance is required. In addition, it is naturally required that the recorded image has sufficiently high contrast, is clear, and has excellent water resistance and light resistance. In addition, printing performance such as stain resistance to a marker pen is also required. Conventionally, as a dye for improving such various properties, for example, JP-A-
The trisazo compounds described in JP-A-63-105079, the tetrakisazo compounds described in JP-A-55-144069, JP-A-1-141966 and JP-B-61-18590 are proposed. However, there has not yet been found one that simultaneously satisfies these various characteristics. Especially in the recording liquid for ink jet, these various properties largely influence the properties peculiar to the dye, and it is extremely important to find a dye satisfying such conditions.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies by the present inventors, the use of a specific tetrakisazo compound has led to various characteristics as a recording liquid for ink jet, such as ejection stability, ejection responsiveness or dissolution storage stability. The inventors have found that the recorded images are improved in sharpness, heat resistance, water resistance and light resistance as well as improved properties, and have completed the present invention.

[0006]

The present invention provides the following formula (1) as a free acid.

[0007]

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(Wherein Q ₁ represents a phenylene or naphthylene group which may have a substituent, R represents a carboxy or sulfo group, and Q ₂ represents a phenyl or naphthyl which may have a substituent. Represents a group, one of A and B represents hydroxy and the other represents an amino group, k represents 1 or 2, and m
Represents 0 or 1, and n represents 1 or 2. ) The tetrakisazo compound shown by these is provided. Among the compounds represented by the formula (1), as a free acid, the following formula (2)

[0009]

[Chemical 6]

(In the formula, Q ₁ represents a phenylene or naphthylene group which may have a substituent, and R ₃ , R ₄ and R
₅ each independently represents a hydrogen atom, a hydroxy group, a sulfo group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, m represents 0 or 1 and n represents 1 or 2. . The tetrakisazo compound represented by 4) is preferably used. Among the compounds represented by the formula (2), as the free acid, the following formula (3)

[0011]

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(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, a carboxy group, a hydroxyethylsulfonyl group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, The tetrakisazo compound represented by R ₃ , R ₄ , R ₅ , m and n has the above-mentioned meanings) is a preferable compound. Among these, as a free acid, the following formula (4)

[0013]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Has the above-mentioned meaning. The tetrakisazo compound represented by the formula (4) is preferably used as a recording liquid for the purpose of the present invention, particularly as a recording liquid for ink jet.

In the above formula (1), Q ₁ is a phenylene or naphthylene group, and Q ₂ is a phenyl or naphthyl group, each of which may be unsubstituted or substituted. Here, as the group capable of substituting the phenylene or naphthylene group and the phenyl or naphthyl group, for example, a carboxyl group, a halogen atom such as chlorine, fluorine and bromine, a hydroxy group, a hydroxyethylsulfonyl group, a sulfo group or even if substituted A good amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, wherein the amino group may be unsubstituted,
Further, it may be mono- or di-substituted, and specific examples of the substituted amino group include, for example, mono- or di-C ₁ -C ₄ alkylamino groups, acetylamino groups, propionylamino groups, benzoylamino groups, and other acylamino groups, and ureido. Base, C
₁ -C ₄ alkylsulfonylamino group and the like.
Further, as the substituted alkyl group, for example, C ₁ substituted with hydroxy, a halogen atom or a cyano group is used.
To C ₄ alkyl group, benzyl group and the like, and the substituted alkoxy group is, for example, hydroxy or a C _{1 to} C ₄ alkoxy group substituted with a C _{1 to} C ₄ alkoxy group and the like. The carbamoyl group is, for example, a C ₁ -C ₄ alkylcarbamoyl group, and the substituted sulfamoyl group is, for example, C ₁ -C ₄
Examples thereof include an alkylsulfamoyl group. In addition, Q ₁
And the phenylene or naphthylene group and the phenyl or naphthyl group represented by Q ₂ may have one or a plurality of substituents as described above within a range that does not impair the performance, but usually within a range of 2 or less. Those having a substituent are used.

In the above formula (1), R ₃ , R ₄
And R ₅ are each independently a hydrogen atom, a hydroxy group,
It represents a sulfonic acid group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, and specific examples of the substituent include phenylene or naphthylene groups represented by Q ₁ and Q ₂ and It is the same as that described as a specific example of the substituent of the phenyl or naphthyl group.

In the above formulas (3) to (4), R ₁ and R ₂ are each independently a hydrogen atom, a carboxy group, a hydroxyethylsulfonyl group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, It represents a carbamoyl or sulfamoyl group, and specific examples of the substituent are the same as those described as specific examples of the substituent of the phenylene or naphthylene group and the phenyl or naphthyl group represented by Q ₁ and Q ₂ .

The tetrakisazo compounds of the present invention are generally isolated in the free acid or salt form. Here, as the salt, alkali metal salts such as sodium, lithium and potassium, ammonium salts, quaternary ammonium salts such as tetramethylammonium salt and tetraethylammonium salt,
Examples thereof include organic amine salts such as ethanolamine, propanolamine, diethanolamine and triethanolamine.

Among these, the tetrakisazo compound in the form of an ammonium salt of the tetrakisazo compound or a mixed salt of the tetrakisazo compound and a sodium salt thereof is preferably used as a recording liquid for the purpose of the present invention, particularly as a recording liquid for ink jet.

In the production of the tetrakisazo compound represented by the general formula (1) of the present invention, each element (raw material compound) is prepared according to JP-A-63-105079, JP-A-55-144069 or German patent specification. It is easily carried out according to the method described in Book No. 943662, etc., but selecting the coupling order so that the desired tetrakisazo compound can be produced.

A specific method for producing the tetrakisazo compound represented by the general formula (1) will be described below by taking the tetrakisazo compound represented by the general formula (2) as an example. That is, in the form of free acid, the following formula (6)

[0022]

Embedded image A diazotized amine compound represented by the formula

[0023]

Embedded image And an aminonaphthol compound represented by
The following formula (8) in the form of free acid is obtained by coupling under acidic conditions.

[0024]

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A monoazo compound represented by is obtained. Then, the nitro group of the monoazo compound of the formula (8) is reduced by a general reduction method to give a free acid in the form of the following formula (9)

[0026]

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A monoazo compound represented by is obtained. on the other hand,
The following formula (10) in the form of free acid

[0028]

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The carboxylic acid represented by the formula (wherein m and n have the above-mentioned meanings) is diazotized by a conventional method, and then this and the following formula (11)

[0030]

Embedded image H—Q ₁ —NH ₂ (11)

By coupling the aromatic amine compound represented by the formula (wherein Q ₁ has the above meaning) in a weakly acidic aqueous medium, the following formula (12)

[0032]

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A monoazo compound represented by the formula (wherein Q ₁ , m and n have the above-mentioned meanings) is obtained.

Then, the monoazo compound represented by the formula (12) is diazotized by a conventional method, and the diazo compound and the monoazo compound represented by the formula (9) are coupled in a weakly acidic to weakly alkaline aqueous medium. Then, in the form of free acid, the following formula (13)

[0035]

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A trisazo compound represented by the formula (wherein Q ₁ , m and n have the above-mentioned meanings) is obtained.

Next, this trisazo compound (13) is diazotized by a conventional method to give the diazo compound and the following formula (14).

[0038]

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By coupling the compound represented by the formula (wherein R ₃ , R ₄ and R ₅ have the above-mentioned meanings) in a weakly acidic to weakly alkaline aqueous medium, a free acid form is obtained. A tetrakisazo compound represented by the general formula (2) is obtained.

Here, examples of the amine compound represented by the formula (6) include 1-amino-2-carboxy-4-nitrobenzene and 1-amino-3-carboxy-4-nitrobenzene.

Examples of the aminonaphthol compound represented by the formula (7) include 1-amino-8-naphthol-3,6-disulfonic acid and 1-amino-8-naphthol-4,6-disulfonic acid. To be

Examples of the carboxylic acids represented by the formula (10) include 3-aminophthalic acid, 4-aminophthalic acid, 2-aminoisophthalic acid, 4-aminoisophthalic acid, 5-aminoisophthalic acid and 3-aminobenzoic acid. Acid, 4
-Aminobenzoic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid and the like can be mentioned. Among them, 5-aminoisophthalic acid or 5-aminosalicylic acid is preferably used.

Next, as the aromatic amine compound represented by the formula (11), for example, 1-amino-3-β-hydroxyethylsulfo-6-methoxybenzene and 1-amino-
2-carboxybenzene, 1-amino-3-carboxybenzene, 1-amino-2,5-dimethoxybenzene,
1-amino-2,5-diethoxybenzene, 1-amino-2-methoxybenzene, 1-amino-2-ethoxybenzene, 1-amino-5-methyl-2-methoxybenzene, 1-amino-2-chlorobenzene , 1-amino-
2,5-dichlorobenzene, 1-amino-2-carbamoylbenzene, 1-amino-2-sulfamoylbenzene, 1-amino-3-carbamoylbenzene, 1-amino-3-sulfamoylbenzene, 1-amino -3-β
-Hydroxyethylsulfonylbenzene, 1-amino-
2-acetylaminobenzene, 1-amino-5-acetylamino-2-methoxybenzene, 1-amino-5-carboxy-2-methoxybenzene, 1-amino-5-carbamoyl-2-methoxybenzene, 1-amino- 5-
Carbamoyl-2-chlorobenzene, 1-amino-2-
Methoxy-5-sulfamoylbenzene, 1-aminonaphthalene, 1-aminonaphthalene-6-sulfonic acid, 1
Examples thereof include aniline derivatives and aminonaphthalene derivatives such as -aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid amide and 1-aminonaphthalene-7-sulfonic acid amide. Among them, 1-amino-
2,5-dimethoxybenzene or 1-amino-5-methyl-2-methoxybenzene is preferably used.

Further, examples of the compound represented by the formula (14) include 1-hydroxybenzene and 1-hydroxy-
2-, 3- or 4-methylbenzene, 1,3-dihydroxybenzene, 1-hydroxy-3-methoxybenzene, 1-hydroxy-3-aminobenzene, 3-di (β
-Hydroxyethyl) amino-1-hydroxybenzene, 1-di (β-hydroxyethyl) aminobenzene,
1,3-diamino-4-methylbenzene, 2-hydroxybenzoic acid, 1,3-diaminobenzene-6-sulfonic acid, 1-acetylamino-4-methoxy-3-di (β-
Benzoic acid derivatives such as (hydroxyethyl) aminobenzene, 3-diethylamino-1-hydroxybenzene, 1,3-diaminobenzene-4-sulfonic acid, and 3-aminobenzoic acid, aniline derivatives, phenol derivatives, aminophenol derivatives and the like. To be Among them, 1-hydroxy-3-aminobenzene is preferably used.

The tetrakisazo compound represented by the general formula (1) of the present invention is various fiber materials, for example, fiber materials having a hydroxy group and / or an amino group, particularly cellulosic fiber materials such as rayon and cotton, paper, It can be used for dyeing or printing leather, silk, synthetic polyamide and the like. In particular, the tetrakisazo compound of the present invention has an excellent solubility and, at the same time, retains a high dyeing property, so that the above material can be colored in dark black.

The tetrakisazo compound of the present invention exhibits excellent performance especially when used as a recording liquid for ink jet. The recording liquid for ink jet of the present invention comprises the tetrakisazo compound represented by the above formula (1), an organic solvent and water, and the composition thereof is 0.5 to 20 parts by weight of the tetrakisazo compound with respect to 100 parts by weight of the recording liquid. Parts by weight, preferably 1 to 15 parts by weight, organic solvent 1 to 80 parts by weight, preferably 2 to 60 parts by weight, and water 0 to.
98.5 parts by weight, preferably 20 to 90 parts by weight. In the recording liquid of the present invention, a known dye for water-based ink that has been conventionally used can be used in combination within a range that does not impair the characteristics of the tetrakisazo compound.

Specific examples of the organic solvent used in the recording liquid of the present invention include methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tert-butanol, isobutanol, and the like. Alcohols such as benzyl alcohol, amides such as dimethylformamide and diethylformamide,
Ketones such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, ethylene glycol, propylene glycol, butylene glycol, pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, thiodiglycol, hexylene glycol, 2- Methyl-2,
Polyhydric alcohols such as 4-pentanediol, glycerin, 1,2,6-hexanetriol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether,
Lower alkyl ethers of polyhydric alcohols such as dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, acetylene glycol derivatives (trade name: Surfynol: manufactured by Nisshin Chemical Co., Ltd.), monoethanolamine, Alkanolamines such as diethanolamine and triethanolamine, nitrogen-containing heterocyclic ketones such as 1,3-dimethyl-2-imidazolidine, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , N-vinyl-pyrrolidone, N-octyl-2
-Pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-
Dodecyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N-
(T-Butyl) -2-pyrrolidone, N-hexyl-2-
Pyrrolidone, N- (3-hydroxypropyl) -2-pyrrolidone, N- (2-methoxyethyl) -2-pyrrolidone, N- (3-methoxypropyl) -2-pyrrolidone,
Examples thereof include pyrrolidones such as N-benzyl-2-pyrrolidone and polyvinylpyrrolidone.

These organic solvents can be used alone or as a mixture of two or more as long as they do not affect each other. Particularly, it is preferable to use pyrrolidones, that is, 2-pyrrolidone or a derivative thereof as at least a part of the organic solvent.

Further, in the recording liquid for ink jet of the present invention, various additives which have been conventionally used in order to provide better properties are used in combination as required. Specifically, for example, preservatives, sodium dehydroacetate as a fungicide, 4-chloro-3-methylphenol, and the like, other UV absorbers, viscosity modifiers, surface tension modifiers such as surfactants, Examples thereof include pH adjusters, specific resistance value adjusters, infrared absorbers and penetrants.

The recording liquid of the present invention dissolves, for example, the above-mentioned tetrakisazo compound together with an organic solvent, if necessary, the above-mentioned various additives, and water, preferably at an elevated temperature, and when dissolved as it is or when it is cold. It can be easily prepared by passing it through a microporous filter membrane to separate the lysate. The recording liquid of the present invention has particularly excellent properties as a recording liquid for ink jet, but can also be used as a recording liquid for other writing instruments such as fountain pens, felt pens, and ballpoint pens.

[0051]

INDUSTRIAL APPLICABILITY The tetrakisazo compound represented by the general formula (1) of the present invention is various fiber materials, for example, fiber materials having hydroxy groups and / or amino groups, particularly cellulosic fiber materials such as rayon and cotton, It can be used for dyeing or printing paper, leather, silk, synthetic polyamide and the like.
In particular, the tetrakisazo compound of the present invention has an excellent solubility and, at the same time, retains a high dyeing property, so that the above material can be colored in dark black.

The recording liquid of the present invention is particularly useful for ink jet recording, and is excellent in sharpness of recorded images, stability during storage or use, heat resistance, water resistance and light resistance, and in particular clogging of ejection orifices. The recording liquid of the present invention has various performances required for an ink jet recording liquid, such as no problems, etc., and the recording liquid of the present invention is excellent in water resistance while having various performances as described above. It can be said that it has excellent characteristics not seen.

[0053]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In the example,
Parts and% mean parts by weight and% by weight, respectively.

(Synthesis of Tetrakisazo Compound) Example 1 1-Amino-2-carboxy-4-nitrobenzene 1
8.2 parts of the compound is diazotized by a conventional method, and the diazonium compound is subjected to a coupling reaction with 11.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid under acidic conditions at 0 to 5 ° C. Next, add 10% soda ash aqueous solution to adjust the pH.
After adjusting to 6.5 to 7.0, 11.7 parts of sodium sulfide is added and stirred at room temperature for 1 hour to reduce the nitro group. Next, 35% hydrochloric acid was added to adjust the pH to 1.5 to 2.0, and after stirring for 1 hour as it was, the reaction mass was filtered to obtain the following formula (A).

[0055]

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Wet cake 1 of monoazo compound represented by
61 parts were obtained. Then, 5-aminoisophthalic acid 18.1
Parts are diazotized by a conventional method, and this diazonium compound is subjected to a coupling reaction with 15.3 parts of 2,5-dimethoxyaniline at 0 to 5 ° C. under mildly acidic conditions. Next, the reaction mass is filtered to obtain the following formula (B).

[0057]

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Wet cake 1 of monoazo compound represented by
12 parts were obtained. This monoazo compound (B) was completely dissolved in a 10% aqueous soda ash solution, and then an aqueous solution containing 9.8 parts of a 36% sodium nitrite solution was added to the aqueous hydrochloric acid solution to diazotize.

Next, after completely removing sulfur from the wet cake of the monoazo compound (A), p was added with a 10% soda ash aqueous solution.
H is adjusted to 10.5-11.0 and completely dissolved.
Then, the diazotization liquid of the monoazo compound (B) was injected into this, and the pH was adjusted to 7.5 to 8.0.
The coupling reaction was carried out by stirring at 3 ° C for 3 hours. 50 parts of sodium chloride was added to the obtained Trisazo reaction mass for salting out, and the precipitated crystals were filtered to obtain a compound represented by the following formula (C).

[0060]

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280 parts of a wet cake of the trisazo compound represented by was obtained. Next, the wet cake of the trisazo compound (C) was completely dissolved in a 10% aqueous soda ash solution, and then 3
An aqueous solution prepared by adding 9.8 parts of a 6% sodium nitrite solution,
It was injected into a hydrochloric acid aqueous solution to be diazotized. To this diazotized mass was added 10.9 parts of m-aminophenol,
Stir for 3 hours at 15 ° C under weak alkaline conditions (pH 8-8.5) to carry out a coupling reaction.

Salt was added to the obtained tetrakisazo reaction mass.
0 parts was added and salting out was performed, and the precipitated crystals were filtered, and 10
It was washed with 200 parts of a saline solution to obtain 316 parts of a wet cake. Next, this wet cake was dispersed in 200 parts of isopropyl alcohol / water (1/1 mixed solution), filtered, and sufficiently desalted, and then the obtained wet cake was dried to obtain the following formula (D )

[0063]

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The tetrakisazo compound represented by 67.
I got 7 copies. The λmax of this tetrakisazo compound in an aqueous medium was 686 nm.

Example 2 The following formula (E) was carried out in the same manner as in Example 1 except that 13.7 parts of 3-aminobenzoic acid was used instead of 5-aminoisophthalic acid.

[0066]

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A tetrakisazo compound represented by 63.8
Got a part. The λmax of this tetrakisazo compound in an aqueous medium was 683 nm.

Example 3 Instead of 2,5-dimethoxyaniline, 1-amino-
The following formula (F) was obtained in the same manner as in Example 1 except that an equimolar amount of 2-methoxy-5-acetylaminobenzene was used.

[0069]

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A tetrakisazo compound 72.2 represented by
Got a part. The λmax of this tetrakisazo compound in an aqueous medium was 668 nm.

Example 4 10 parts of the tetrakisazo compound (D) obtained in Example 1 was placed in 100 parts of a 15% aqueous ammonium bicarbonate solution,
After stirring for 2 hours, the mixture was filtered, desalted sufficiently, and the obtained wet cake was dried to obtain the following formula (5).

[0072]

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9.0 parts of an ammonium salt of the tetrakisazo compound represented by

Example 5 (Use) Using the tetrakisazo compounds prepared in Examples 1 to 4, the following composition was obtained: tetrakisazo compound 2 parts glycerin 4 parts 2-pyrrolidone 10 parts ethanol 4 parts 4-chloro-3 -Methylphenol 8.0 x 10 ^-3 parts Ion-exchanged water A residual recording liquid was prepared and filtered with a 0.2 µm membrane filter to prepare a recording liquid for ink jet.

This recording liquid was filled in an ink cartridge for a Desk Jet 505 ink jet printer manufactured by Hewlett-Packard Company, and continuous recording was carried out for 500 hours with the printer, but no clogging of nozzles or abnormal ejection direction was observed. Further, even after these recording liquids were stored at 40 ° C. for 3 months and then continuously recorded by the printer for a long time, neither clogging nor abnormal jetting direction was observed.

Example 6 The recording liquid of the present invention prepared in Example 5 was used as a known dye for comparison with C.I. I. Direct Black 154 and C.I. I. Using a recording liquid prepared in the same manner as the direct black 168, a plain sample paper for copying (paper number 4024) manufactured by Xerox Co., Ltd. was applied to fill a range of 3 cm in length × 10 cm in width to prepare a test sample. Table 1 shows the results of the light and light resistance tests. In addition,
The hue of the printed matter was a good black tone.

Water resistance test Each of the above test samples was air-dried for 2 days, and then the print density was measured with a reflection densitometer (Macbeth RD915). Next, each sample was immersed in ion-exchanged water at 25 ° C. for 1 hour, sufficiently removed of water, air-dried for 1 day, and then the print density was measured again and evaluated according to the following criteria.

Water Resistance Evaluation Criteria ◎ The print density after immersion is 80% or more of the print density before immersion. ○ 〃 70% or more and less than 80%. △ 〃 50% or more and less than 70%. × It is less than 50%.

Light resistance test Each of the above test samples was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours, and each print density after irradiation was measured and evaluated according to the following criteria. Lightfastness Evaluation Criteria ◎ The print density after immersion is 90% or more of the print density before immersion. ○ 〃 80% or more and less than 90%. △ 〃 70% or more and less than 80%. × 〃 less than 70%.

[0080]

[Table-1]

Example 7 The tetrakisazo compounds shown in the following (G) to (P) are obtained as free acids in the same manner as in Example 1 except that the raw material compounds are replaced. The hue when a recording liquid was prepared and printed using this compound in the same manner as in Examples 5 and 6 is shown at the end of the structural formula.

[0082]

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[0083]

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[0084]

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[0085]

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Performance of Ink When Changing Organic Solvent A recording liquid having the composition of the following Examples 8 to 15 was prepared using the tetrakisazo compound or the alternative salt thereof obtained in Examples 1 to 4, and a membrane was prepared. The ink was adjusted by filtering with a filter. Each of these inks has a pH of 6 to 1.
0, viscosity 1.2-3.0 (cps), surface tension 35-
It was in the range of 60 (dyne / cm), and each was subjected to the performance tests 1) to 9) described below. As a result, the inks of this example all showed excellent performance.

Example 8 Potassium salt of tetrakisazo compound (D) of Example 1 3.0% Polyethylene glycol # 200 8.0% Diethylene glycol 3.0% Sodium dehydroacetate 0.1% Ion-exchanged water 85.9%

Example 9 Tetrakisazo compound (D) of Example 1 3.0% N-ethyl-2-pyrrolidone 5.0% Glycerin 5.0% Sodium dehydroacetate 0.1% Ion-exchanged water 86.9%

Example 10 Tetrakisazo compound (E) of Example 2 3.0% N-isopropyl-2-pyrrolidone 7.0% Propylene glycol monomethyl ether 3.0% 4-Chloro-3-methylphenol 0.08% Ion-exchanged water 86.92%

Example 11 Potassium salt of tetrakisazo compound (E) of Example 3.0 3.0% N-ethyl-2-pyrrolidone 10.0% 4-chloro-3-methylphenol 0.08% Ion-exchanged water 86.92%

Example 12 Tetrakisazo compound (F) of Example 3 3.0% N-ethyl-2-pyrrolidone 10.0% Monoethanolamine 0.2% 4-chloro-3-methylphenol 0.08% Ion-exchanged water 86.72%

Example 13 Tetrakisazo compound (5) of Example 4 3.0% N-ethyl-2-pyrrolidone 5.0% Nn-butyl-2-pyrrolidone 5.0% N-isopropyl-2-pyrrolidone 5.0% 4-chloro -3-Methylphenol 0.08% Ion-exchanged water 81.92%

Example 14 Tetrakisazo compound (5) of Example 4 3.0% N-methyl-2-pyrrolidone 10.0% 4-chloro-3-methylphenol 0.08% Isopropyl alcohol 3.0% Ion-exchanged water 83.92%

Example 15 Tetrakisazo compound (D) of Example 1 3.0% N-Ethyl-2-pyrrolidone 5.0% Glycerin 4.0% Polyvinylpyrrolidone 1.0% Sodium dehydroacetate 0.1% Ion-exchanged water 86.9%

1) Image sharpness: HG513 manufactured by Epson
It was recorded on plain paper using an ink jet printer manufactured by No. 0 company and judged by the following criteria by visual judgment. As a result, all of the inks of this example were clear black images without bleeding.

2) Storability: The ink was sealed in a glass container and stored at 20 ° C. for 6 months and at 70 ° C. for 2 weeks, respectively. As a result, the ink of this example has no precipitates and any abnormality is recognized. There wasn't.

3) Jet stability: The jet recording of 1) above was continuously performed for 500 hours, and the nozzle clogging and the change in jetting direction were observed. As a result, none of the inks of this example showed any abnormality. .

4) Jet response: After performing jet recording according to 1) above, at room temperature and normal humidity for 1 month and at 40 ° C.-30%.
They were left at RH for 1 week each, and then jet recording of 1) was performed again. As a result, a clear black image without bleeding was obtained with each of the inks of this example.

5) Lightfastness Tested by the method described in Example 6, all the inks of the present invention showed excellent performance.

6) Discoloration resistance The paper after jet recording according to the above 1) was left in the room for one month to determine the change in hue. All images recorded using the ink of this example were evaluated. There was no change in hue and it showed excellent resistance to discoloration.

7) Water resistance When tested by the method described in Example 6, it showed excellent performance.

8) Penetration After jet recording was performed according to the above 1), the time until the ink penetrated the paper was measured. As a result, all the inks of this example exhibited excellent performance with a penetration time of 30 seconds or less.

9) Marker Pen Stain Resistance After performing jet recording according to the above 1), the printed portion was marked with a marker pen and the presence or absence of dirt was observed. As a result, all the inks of this example had almost no stain and showed excellent performance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiko Kojima 4-2-11 Nishimikuni, Yodogawa-ku, Osaka City Taoka Chemical Industry Co., Ltd. (72) Hideo Kawashita 4-2-11, Nishimikuni, Yodogawa-ku, Osaka Taoka Chemical Industry Co., Ltd. (72) Inventor Kazuya Ogino 3-1, 98 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. (72) Inventor, Yuriko Tamura 3-chome, Kasugade, Konohana-ku, Osaka No. 98 Sumitomo Chemical Co., Ltd.

Claims (8)

[Claims] 1. A free acid represented by the following formula (1): (In the formula, Q ₁ represents a phenylene or naphthylene group which may have a substituent, R represents a carboxy or sulfo group, and Q ₂ represents a phenyl or naphthyl group which may have a substituent. , A and B each represent hydroxy and the other represents an amino group, k represents 1 or 2, m represents 0 or 1.
And n represents 1 or 2. The tetrakisazo compound shown by these. 2. The following formula (2) as the free acid: (In the formula, Q ₁ represents a phenylene or naphthylene group which may have a substituent, and R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a hydroxy group, a sulfo group, a halogen atom or a substituent. Optionally represents an amino, alkyl, alkoxy, carbamoyl or sulfamoyl group,
m represents 0 or 1, and n represents 1 or 2. The tetrakisazo compound shown by these. 3. A free acid represented by the following formula (3): (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, a carboxy group, a hydroxyethylsulfonyl group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a hydroxy group, a sulfo group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, m represents 0 or 1, and n represents A tetrakisazo compound represented by 1 or 2.). 4. A free acid represented by the following formula (4): (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, a carboxy group, a hydroxyethylsulfonyl group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a hydroxy group, a sulfo group, a halogen atom or an optionally substituted amino, alkyl, alkoxy, carbamoyl or sulfamoyl group. 5. A recording liquid containing the tetrakisazo compound according to any one of claims 1 to 4. 6. A recording liquid containing the tetrakisazo compound according to any one of claims 1 to 4, water and an organic solvent. 7. The recording liquid according to claim 6, wherein the organic solvent contains pyrrolidone or a derivative thereof. 8. The recording liquid according to claim 5, which is for an ink jet printer.