JPH06145573A - Recording fluid - Google Patents

Abstract

PURPOSE:To obtain a black recording fluid which givevs a high-quality printing even on a plain paper, forms a high-density recorded image, and is excellent in water resistance, light resistance, and stability in long storage by compounding a specific pigment into an aq. medium. CONSTITUTION:A recording fluid contains an aq. medium and at least one pigment represented by the formula wherein A is an optionally substd. phenyl or naphthyl group; B is an optionally substd. phneylene or naphthylene group; M is Li, ammonium, or an org. amine salt; and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording liquid. Specifically, it relates to a 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 dye such as a direct dye or an acid dye is ejected from a minute ejection orifice to perform recording. Regarding this recording, in addition to being capable of stable ejection for a long time, it is commonly 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). Fast fixing to recording paper and good print quality of printed matter, that is, print without blurring and clear contour, are required, and stability during storage as recording liquid is also excellent. Therefore, the solvent that can be used for the recording liquid is extremely limited.

On the other hand, the dye for the recording liquid has a sufficient solubility in the limited solvent as described above, which enables stable ejection for a long time as the recording liquid.
Stable even after long-term storage, high density of printed images, excellent water resistance and light resistance, easy to manufacture, no safety issues However, it has been difficult to satisfy many of these requirements at the same time.

Therefore, various methods (for example, JP-A-55-55)
144067, JP-A-55-152747, JP-A-57-207660, JP-A-58-147470,
JP-A-62-190269, JP-A-62-19027
1, JP-A-62-190272, JP-A-62-25
0082, JP-A-62-246975, 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-63-33484. No. 63-63764,
JP-A-63-105079, JP-A-64-31877
JP-A-1-93389, JP-A-1-210464
JP-A-2-140270 and JP-A-3-16727.
No. 0 and Japanese Patent Laid-Open No. 3-200882) have been proposed, but in addition to satisfying the market requirements in terms of performance,
It has not been possible to develop a dye that is easy to manufacture.

[0005]

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 black recording liquid which is excellent in stability and has good stability when stored for a long period of time.

[0006]

The present inventor has accomplished the present invention by confirming that the above object is achieved when a specific black dye is used as a recording liquid component. 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 used in the present invention is represented by the general formula (I) in claim 1. In the general formula (I), a phenyl group, a naphthyl group represented by A and B, as the substituent of the phenylene group or naphthylene group, -SO ₃ M group, M being a -COOM group (M is the formula (I) Has the same meaning as), an amino group,
Acylamino group (for example, lower alkylcarbonylamino group such as acetylamino group and propionylamino group, arylcarbonylamino group such as benzoylamino group, etc.), linear or branched alkoxy group having 1 to 4 carbon atoms, hydroxyl group , Halogen atom such as chlorine atom, bromine atom and fluorine atom, straight or branched chain carbon number 1 to
And the like, and may have a plurality of these substituents. M in the formula represents the salt form of the dye.

Specific examples of these dyes include dyes (lithium salt type) having the structures shown in Table 1 below, their ammonium salts and organic amine salts. Examples of the organic amine salt are mono-, di-, and tri-organic group-substituted amino salts, and specifically, lower alkylamine salt, hydroxy-substituted lower alkylamine salt, carboxy-substituted lower alkylamine salt and carbon number. Examples thereof include salts of polyamines having 2 to 10 2 to 4 alkyleneimine units.

[0009]

[Table 1]

[0010]

[Table 2]

[0011]

[Table 3]

[0012]

[Table 4]

[0013]

[Table 5]

The azo dye represented by the above formula (I) can be produced by a method known per se [see, for example, Yutaka Hosoda, "New Dye Chemistry" (published by Gihodo on December 21, 1973, pages 396 to 409)]. It can be manufactured through a diazotization, coupling step. The content of the dye of formula (I) in the recording liquid is preferably 0.5 to 8% by weight, more preferably 2 to 5% by weight, based on the total amount of the recording liquid. When the dye of the present invention is used in the recording liquid, it may be used alone.
It is also possible to use a mixture of two or more species.

As the solvent used in the recording liquid of the present invention, water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol (# 200, # 400), glycerin, α-pyrrolidone, N-methylpyrrolidone, N-
Ethylpyrrolidone, 1,3-dimethylimidazolidinone, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, bis (β-hydroxyethyl) thioether, dimethylformamide, diethanolamine, trieta Ruamin, isopropanol,
It preferably contains ethanol, methanol and the like. These water-soluble organic solvents are usually used in the range of 1 to 50% by weight based on the total amount of the recording liquid. 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, burette, and semicarbazide, or by adding 0.001 to 5% by weight of a surfactant, the quick-drying property after printing and the printing quality can be further improved. .

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples unless it exceeds the gist. Example 1 Composition of recording liquid

[0018]

[Table 6] recording liquid component amount (wt%) the No. 1 dye 3 Diethylene glycol 15 N-methyl pyrrolidone 5 Triethanolamine 3 isopropanol 3 Water balance Total 100

The above components were sufficiently mixed and dissolved, filtered under pressure 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, an inkjet printer (HG-3000, manufactured by Epson Corporation) was used to perform inkjet recording on electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) to obtain a black recorded matter with high color density. . In addition, the results of various evaluations by the following methods (a), (b) and (c) are shown.

(A) Lightfastness of recorded image The recorded matter was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours, but discoloration and fading after irradiation were small. (B) Water resistance of recorded image The bleeding of the image was examined after the recorded matter was immersed in water for 5 minutes. The bleeding of the image was slight and the decrease in density was small. Further, when the recorded matter was sprinkled with 10 ml of water and allowed to stand, there was no bleeding and no white field contamination was observed. (C) Storage stability of recording liquid The recording liquid was sealed in a Teflon container and kept at 5 ° C and 60 ° C for 1 hour.
The change in the recording liquid after the storage for a month was examined, but there was no change in the recording liquid. Example 2 Composition of recording liquid

[0021]

Table 7 recording liquid component amount (wt%) the No. 1 dye 3 Glycerin 10 Ethylene glycol 10 Water balance Total 100

The above components were treated by the method described in Example 1 to prepare a recording liquid.
Various evaluations of (c) were performed. As a result, good results were obtained as in the case of Example 1. Example 3 Composition of recording liquid

[0023]

TABLE 8 recording liquid component amount (wt%) dye 3 of the No. 1 Diethylene glycol monobutyl ether 5 Glycerin 15 Water balance Total 100

The above components were treated by the method described in Example 1 to prepare a recording liquid.
Various evaluations of (c) were performed. As a result, good results were obtained as in the case of Example 1.

Examples 4 to 18 In place of the dye (No. 1) used in Example 1, No. 2, No. 3, No. 10, No. 18, No. 1 were used.
9, No. 20, No. 21, No. 22, No. 23, No. 2
4, No. 25, No. 26, No. 27, No. 28, No. 2
A recording liquid was prepared by the method of Example 1 except that each of the dyes of 9 was used, and (a) to (c) similar to Example 1 were used.
Various evaluations were performed. As a result, good results were obtained as in the case of Example 1.

Examples 19 to 34 Instead of the dye (lithium salt type) of the above (No. 1) used in Example 2, the above No. 1, No. 2, No. 3, No.
10, No. 18, No. 19, No. 20, No. 21, No.
22, No. 23, No. 24, No. 25, No. 26, No.
A recording liquid was prepared by the method of Example 2 except that the ammonium salt type dyes of No. 27, No. 28 and No. 29 were used, respectively, and various evaluations (a) to (c) similar to Example 2 were performed. I went. As a result, good results were obtained as in the case of Example 2.

[0027]

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 recorded matter of high color density with excellent print quality is obtained, and the light resistance and water resistance of a recorded image are obtained. In addition to being excellent, the storage stability of the recording liquid is also good.

Claims (1)

[Claims] 1. A recording liquid containing an aqueous medium and at least one dye represented by the following general formula (I). [Chemical 1] (In the formula, A represents a phenyl group or a naphthyl group, which may have a substituent, B represents a phenylene group or a naphthylene group, which may have a substituent, and M represents Li. , An ammonium group or an organic amine salt, and n is 0 or 1.)