JPH0762282A - Recording liquid - Google Patents

Abstract

PURPOSE:To provide a recording liquid capable of obtaining black, red or yellow recorded materials when recorded on plain paper, excellent in print denseness, light resistance, water resistance and preservability, suitable for ink jet recording etc., containing an aqueous medium and specific coloring matter. CONSTITUTION:The objective recording liquid containing (A) pref. 45-95wt.% of an aqueous medium and (B) pref. 2-4wt.% of at least one kind of coloring matter of formula I [A and A' are each of formula II or III (R<1> and R<2> are each H, methyl, methoxy, ethoxy or acylamino; R<3> is H, CH2COOH or C2H4 COOH; R<4> is CH2COOH or C2H4COOH; R<5> is H or carboxyl); B and D are each (substituted) phenylene] for free acid form.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording liquid. Specifically, it relates to black, red, and yellow recording liquids suitable for ink jet 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 can be ejected stably for a long time, and is also 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 is required that the printed matter be fast-fixed to the recording paper, and that the print quality of the printed matter be good, that is, the print has no bleeding and the contour is clear, and the stability of the recording liquid during storage is also high. Since it is necessary to be excellent, the solvents that can be used in the recording liquid are 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. 59-226072 and 62-1902.
69, JP-A-62-190271, JP-A-62-1
90272, JP 62-250082, JP 6
2-246975, JP-A-62-264974, JP-A-62-288659, JP-A-63-8463,
JP-A-63-22867, JP-A-63-117079
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 2-16
171, JP-A-2-140270, JP-A-3-20
No. 0882, etc.) has been proposed, but a dye that satisfies market demands in terms of performance and is easy to manufacture has not yet 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 inventors of the present invention have confirmed that when a dye having a specific structure is used as a recording liquid component, the performance particularly satisfying the above objects can be obtained, and the present invention has been accomplished. Is. That is, the gist of the present invention resides in a recording liquid containing an aqueous medium and at least one dye represented by the general formula [I] in the free acid form.

The present invention will be described in detail below. The dye of the present invention is in the form of the free acid in the above-mentioned claim 1 in the general formula [I].
It is represented by. Specifically, in the general formula [I], B
The substituent of the phenylene group represented by
4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, sulfonic acid groups, halogen atoms such as chlorine atoms and bromine atoms, and the phenylene group represented by D has a carbon number of 1 To 4 alkyl groups, 1 to 4 carbon atoms
Alkoxy groups, halogen atoms such as chlorine atoms and bromine atoms, and the acylamino groups represented by R ¹ and R ² include alkylcarbonylamino groups such as acetylamino groups and arylcarbonylamino groups such as benzoylamino groups. Is mentioned. A and A ′ in the formula may be the same or different, but the same one is preferable in terms of production.

The dye used in the present invention may be used in the form of the free acid represented by the general formula [I] as it is, or when it is obtained in the salt form at the time of production, it may be used as it is, Further, it may be used by exchanging it with a desired salt form. In addition, a part of acid groups in one molecule of the dye may be a salt type, and a salt type dye and a free type dye may be used in combination. Examples of such salt type include salts of alkali metals such as Na and Li, ammonium salts which may be substituted with an alkyl group or a hydroxyalkyl group, and salts of organic amines. Examples of salts of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type of salt is not limited to one type, and a plurality of types may be mixed.

Specific examples of these dyes include, for example, Table 1 No. 1 below. 1-No. The azo dyes having the structure shown in 21 are mentioned, and these dyes may be used alone or in combination depending on the desired color tone.

[0009]

[Table 1]

[0010]

[Table 2]

[0011]

[Table 3]

[0012]

[Table 4]

[0013]

[Table 5]

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) No. 396-409.
Refer to page], and can be manufactured through a tetrazotization process and a coupling process. 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.

The solvent used in the present invention includes water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 4).
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.

[0017]

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 Co.) 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. 8 dyes 2
Water was added to parts by weight, the pH was adjusted to 9 with ammonia water 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. Using this recording liquid, printing was performed in the same manner as in Example 1 to obtain a red recorded product. Further, with respect to this recorded matter, (a) to (c) of Example 1
Various evaluations 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. Water was added to 2 parts by weight of the dye of 15 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. This composition was treated by the method described in Example 1 to prepare a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1 to obtain a yellow recorded material.
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 10] Table 1 No. 1 used in Example 1 1N in place of the dye of Table 1N
o. A recording liquid was prepared and printing was carried out by the method of Example 1 except that the dyes of 2, 4, 6, 10, 14, 18, and 20 were used, respectively. )-(C). As a result, as in Example 1, good results were obtained.

[0023]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording and writing instruments, and when recorded on plain paper, black, red, and yellow recorded matter can be obtained. In addition to excellent light resistance and water resistance,
Storage stability as a recording liquid is also good.

Claims (1)

[Claims] 1. A recording liquid comprising an aqueous medium and at least one dye represented by the following general formula [I] in the form of a free acid. A-N = N-D-CONH-B-N = NA '[I] (wherein A and A'are respectively And B and D each represent a phenylene group which may have a substituent. However, R ¹ and R ² each represent a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, an acylamino group, and R ³ is H, —CH ₂ COOH or —C ₂ H ₄ CO.
Represents OH, R ⁴ is —CH ₂ COOH or —C ₂ H ₄ COO.
H represents and R ⁵ represents a hydrogen atom or a carboxyl group. )