JPH06220377A - Recording liquid - Google Patents

Abstract

PURPOSE:To obtain a recording liquid, comprising an aqueous medium and at least one of specific azo dyes, used for ink jet recording and writing utensils and capable of providing black records at a high color density and excellent in printing quality when recorded on plain paper. CONSTITUTION:This recording liquid is obtained by mixing (A) an aqueous medium composed of diethylene glycol, isopropyl alcohol and water with (B) at least one azo dye expressed by the formula [A is phenyl or naphthyl which may have one or more substituent groups such as amino, acylamino, hydroxyl, COOM (M is H, alkali metal NH4 or organic amine salt), SO3M, etc.; X and Y are H, 1-7C (substituted)alkyl or 1-9C (substituted)alkoxy; the sum total of carbon atoms in X and Y is >=3; Z is H, (substituted)phenyl, the formula CH2 COOM, etc.; (n) is 0 or 1], regulating the pH to 9 with aqueous ammonia, then filtering the regulated solution through a filter having 1mum pore diameter under pressure and subjecting the filtrate to deaeration treatment with a vacuum pump, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording liquid. Specifically, it relates to a black recording liquid suitable for inkjet recording.

[0002]

2. Description of the Related Art A so-called ink jet recording method has been put into practical use, in which a recording liquid droplet containing a water-soluble coloring matter such as a direct dye or an acid dye is ejected from a minute ejection orifice to perform recording. This recording liquid is capable of stable ejection for a long time, and is also widely used for general office work such as PPC (plain paper copier) paper such as electrophotographic paper and fan hold paper (continuous paper such as computers). It requires fast fixing to recording paper and good print quality, that is, the print has no bleeding and has a clear contour, and also has excellent stability when stored as a recording liquid. Therefore, the solvent that can be used for the recording liquid is extremely limited.

On the other hand, dyes for recording liquids have sufficient solubility in the above limited solvents and are stable even when stored as recording liquids for a long time.
Further, although it is required that the printed image has a high density and is excellent in water resistance and light resistance, it has been difficult to satisfy many of these requirements at the same time. Therefore, various methods (for example, JP-A-55-144067, JP-A-55-152747, and JP-A-57-207660) are used.
No. 58-147470, and 62-1902.
69, JP-A-62-190271, JP-A-62-1
90272, JP 62-250082, JP 6
2-246975, JP-A-62-257971, JP-A-62-288659, JP-A-63-8463,
JP-A-63-22867, JP-A-63-22874
JP-A-63-30567, JP-A-63-3348
4, JP-A-63-63764, JP-A-63-105.
079, JP-A-64-31877, JP-A-1-93.
389, JP-A 1-210464, JP-A 2-14
No. 0270, JP-A-3-167270, JP-A-3-2
No. 08882, etc.) has been proposed, but a dye that satisfies the market requirements in terms of performance and is easy to manufacture has not been developed.

[0004]

DISCLOSURE OF THE INVENTION The present invention has good print quality even when recorded on plain paper for ink jet recording, writing instruments, etc., and has a high density of recorded images, which is excellent in water resistance and light resistance. It is an object of the present invention to provide a recording liquid which is excellent in stability and has good stability when stored for a long time.

[0005]

The present inventors have achieved the present invention by confirming that the performance particularly satisfying the above-mentioned objects can be obtained when a black dye having a specific structure is used as a recording liquid component. It is a thing. That is, the gist of the present invention resides in a recording liquid containing an aqueous medium and at least one of the dyes represented by the general formula [I] in claim 1.

The present invention will be described in detail below. The dye of the present invention is represented by the general formula [I] in claim 1.
Specifically, in the general formula [I], examples of the substituent of the alkyl group represented by X and Y include a phenyl group, and examples of the substituent of the alkoxy group include an alkoxy group, a hydroxyl group, a phenyl group, and benzyloxy. Groups, etc.,
Examples of the substituent of the phenyl group represented by Z include a lower alkyl group, COOM group, SO ₃ M group, and halogen atom. Examples of the organic amine salt represented by M include a substituent having a carbon number. An alkyl group having 1 to 4 and / or 1 to 4 carbon atoms
And mono-, di-, and tree-substituted amines, which are hydroxyalkyl groups.

In the structure of the dye used in the present invention, when a plurality of M's are contained in one molecule, the plurality of M's may be different from each other. Specific examples of these dyes include, for example, Table 1 No. 1 below. 1 to N
o. An azo dye having a structure shown in 32 is exemplified.

[0008]

[Table 1]

[0009]

[Table 2]

[0010]

[Table 3]

[0011]

[Table 4]

[0012]

[Table 5]

[0013]

[Table 6]

[0014]

[Table 7]

[0015]

[Table 8]

The azo dye represented by the general formula [I] can be obtained by a method known per se [for example, Yutaka Hosoda, "New Dye Chemistry" (published by Gihodo, December 21, 1973) Nos. 396-409.
Refer to page], and can be manufactured through a diazotization and a coupling step. The content of the dye of the general formula [I] in the recording liquid is preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total amount of the recording liquid.

As the solvent used in the present invention, water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 4) are used.
00), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane, Ethyl alcohol,
It preferably contains isopropanol or the like. These water-soluble organic solvents are usually used in an amount of 1 to the total amount of the recording liquid.
Used in the range of 50% by weight. On the other hand, water is used in the range of 45 to 95% by weight with respect to the total amount of the recording liquid.

The recording liquid of the present invention contains 0.
1-10 wt% urea, preferably 0.5-5 wt% urea,
By adding a compound selected from thiourea, biuret, and semicarbazide, or by adding 0.001 to 5.0% by weight of a surfactant, the quick-drying property after printing and the printing quality can be further improved. it can.

[0019]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. [Example 1] 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, No. 1 in Table 1 above. Water was added to 3 parts by weight of dye 1 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. The composition was thoroughly mixed and dissolved, pressure-filtered with a Teflon filter having a pore size of 1 μm, and then deaerated with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.

Using the obtained recording liquid, ink jet recording was carried out on an electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an ink jet printer (trade name HG-3000, manufactured by Epson Corp.) to obtain a high density black printed matter. Obtained. The results of various evaluations by the methods (a), (b) and (c) are shown below. (A) Light resistance of recorded image: The recording paper was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours, but the discoloration and fading after irradiation was small.

(B) Water resistance of recorded image: The bleeding of the image was examined after immersing the recording paper in water for 5 seconds. The bleeding of the image was slight and the decrease in density was small. (C) Storage stability of recording liquid: When the recording liquid was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for 1 month, the change was examined. No precipitation of insoluble matter was observed. [Example 2] 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, No. 1 in Table 1 above. Water was added to 2.5 parts by weight of the dye of 2, and the pH was adjusted to 9 with aqueous ammonia to make the total amount 1
The recording liquid was prepared by treating the composition in an amount of 100 parts by weight by the method described in Example 1. With this recording liquid,
As a result of printing in the same manner as in Example 1, a high density black recorded material was obtained. Further, for this recorded matter, (a) to
Various evaluations according to (c) were performed. As a result, good results were obtained as in the case of Example 1. Example 3 10 parts by weight of diethylene glycol, 5 parts by weight of N-methylpyrrolidone, 3 parts by weight of isopropyl alcohol, No. 1 in Table 1 above. Add water to 3 parts by weight of the dye of 3,
The pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight, and this composition was treated by the method described in Example 1 to prepare a recording liquid. Printing was carried out in the same manner as in Example 1 using this recording liquid, and as a result, a high density black recorded material was obtained.
Further, various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, good results were obtained as in the case of Example 1. [Examples 4 to 12] Table 1 used in Example 1
No. 1 in place of the dye of Table 1 above. 4-N
o. A recording liquid was prepared and printing was carried out by the method of Example 1 except that each of the 12 dyes was used. As a result, as in Example 1, good results were obtained.

[0022]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording and writing instruments, and when recorded on plain paper, a black recorded matter can be obtained, and its printing density, light resistance, and water resistance. In addition to being excellent in storage stability as a recording liquid.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukichi Murata 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (1)

[Claims] 1. A recording liquid containing an aqueous medium and at least one kind of dye represented by the following general formula [I]. [Chemical 1] (In the formula, A is a phenyl group optionally having one or more substituents selected from the group consisting of an amino group, an acylamino group, a hydroxyl group, a COOM group, and a SO ₃ M group. Or a naphthyl group, X and Y each represent H, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 9 carbon atoms, and The sum is 3 or more, but when one is H, it is 2 or more, Z is H, a phenyl group which may have a substituent, CH ₂ COOM or C ₂ H ₄ COOM, and n is 0. Or 1, M is H, an alkali metal,
It represents one or more groups selected from the group consisting of NH ₄ and organic amine salts. )