JP3389761B2 - Recording liquid - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a recording liquid and to it
It relates to the dye used . Specifically, it relates to a black recording liquid suitable for inkjet recording and a dye used therefor .

[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. It is necessary to have

Therefore, as a dye for a recording liquid, it has sufficient solubility in a solvent of the recording liquid, is stable even when stored as a recording liquid for a long time, and has a density of a printed image. Although it is required to be high and have excellent water resistance and light resistance, it is difficult to satisfy many of these requirements at the same time. Therefore, various methods (for example, JP-A-55-144067 and JP-A-55-152) are used.
747, JP-A-57-207660, JP-A-58-
147470, JP-A-62-190269, JP-A-62-190271, JP-A-62-190272,
JP-A-62-250082, JP-A-62-24697
5, JP-A-62-257971, JP-A-62-28
8659, JP-A-63-8463, JP-A-63-2
2867, JP-A-63-22874, JP-A-63-
30567, JP-A-63-33484, JP-A-63.
-63764, JP-A-63-105079, JP-A-64-31877, JP-A-1-93389, JP-A1-2104464, JP-A-2-140270, JP-A-3-167270, JP-A-3-167270. No. 3-200882, etc.) has been proposed, but a dye that satisfies the market requirements 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 recording liquid according to the present invention comprises:
It is characterized in that the free acid form contains a dye represented by the general formula (1) in an aqueous medium.

[0006]

[Chemical 3]

(In the formula, A is an amino group, an acylamino group,
Hydroxyl group, a carboxylic acid group (-COOH), and represents a sulfonic acid group (-SO ₃ H) may have a substituent group selected from the group consisting of phenyl or naphthyl group, X is a hydrogen atom, a carbon Represents an alkyl group having 1 to 4 or an alkoxy group having 1 to 4 carbon atoms, and Y is

[0008]

[Chemical 4] And Z represents a hydrogen atom or a phenyl group which may have a substituent. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. The recording liquid according to the present invention is characterized by containing the dye represented by the general formula (1) in an aqueous medium. . This dye will be described in more detail. Examples of the acylamino group which may be substituted on the phenyl group or naphthyl group represented by A in the general formula (1) include an acetylamino group, a propionylamino group, and other alkyl group carbons. Examples thereof include an alkylcarbonylamino group having a number of 1 to 4 or a benzoylamino group. Also, Z
Examples of the substituent of the phenyl group represented in, a carboxylic acid group (-COOH), sulfonic group (-SO ₃ H), an alkyl group having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms .

As the counter ion of the acidic group of the dye used in the present invention, an alkali metal such as lithium or sodium, ammonia, or a carbon atom which may have a hydroxyl group is 1
1 to 4 alkyl groups bonded to 1 to 4 nitrogen atoms 1
˜Tertiary amines, quaternary ammonium, and the like.
Incidentally, some different counter ions may coexist in the recording liquid. Some of the dyes used in the present invention are shown in Table 1.

[0011]

[Table 1]

[0012]

[Table 2]

The dye represented by the general formula (1) used in the present invention 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 represented by the general formula (1) in the recording liquid is
The amount is preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total amount of recording liquid. The dyes may be used alone or in combination.

The aqueous medium which constitutes the recording liquid of the present invention is preferably one containing water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include 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 is preferable to use isopropanol or the like. These water-soluble organic solvents are usually used in an amount of 5 to 30 with respect to the total amount of the recording liquid.
Used in the weight% range. On the other hand, water is used in the range of 60 to 90% 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.

[0016]

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 Dye 3 of 1
Water was added to parts by weight 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, 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, ink jet recording was carried out on an electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an ink jet printer (BJ-10V, trade name, manufactured by Canon Inc.) to obtain a high-concentration bluish black color. A printed matter was obtained. In addition, the results of evaluation by the following methods (a), (b) and (c) are shown. (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. 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 tap water for 5 seconds, but almost no bleeding of the image was recognized. (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 one month, the change was examined and no precipitation of insoluble matter was observed.

[Examples 2 to 4] No. 1 in Table 1 used in Example 1 Instead of the dye of No. 1, No. 1 in Table 1 was used.
2, No. 3 and No. A recording liquid was prepared in the same manner as in Example 1 except that each of the dyes of 4 was used, and printing was performed using the recording liquid to obtain a black recorded product. Further, when various evaluations according to (a) to (c) of Example 1 were performed on this recorded material, good results were obtained in the same manner as in Example 1.

[Comparative Examples 1 and 2] No. 1 in Example 1
Instead of the dye of 1, dyes of the following structural formulas R-1 and R-2 described in JP-A-7-34020 are used,
A recording liquid was prepared in the same manner as in Example 1 and printing was performed on electrophotographic papers A to C to obtain a recorded matter. Table 2 shows the results of various evaluations of the recorded matter according to Examples 1 (a) to (c).

[0021]

[Chemical 5]

[0022]

[Table 3]

[0023] Electrophotographic paper A: p measured according to JIS P8133
H is 5.35 Electrophotographic paper B: p measured according to JIS P8133
H is 6.29 Electrophotographic paper C: p measured according to JIS P8133
H is 9.23

[Examples 5 to 10] No. 1 in Table 1 used in Example 1 Instead of the dye of No. 1, No. 1 in Table 1 was used.
5 to No. A recording liquid was prepared and printed by the same method as in Example 1 except that the dye of 10 was used, and various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, as in Example 1, good results were obtained.

[0025]

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. In particular, good water resistance can be obtained regardless of the pH of the paper.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A 64-66272 (JP, A) JP-A 5-125318 (JP, A) JP-A 7-34020 (JP, A) JP-A 7- 268256 (JP, A) JP-A-8-92512 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A free acid type compound represented by the general formula (1) in an aqueous medium:
A recording liquid containing a dye represented by: [Chemical 1] (In the formula, A is a phenyl group which may have a substituent selected from the group consisting of an amino group, an acylamino group, a hydroxyl group, a carboxylic acid group (—COOH), and a sulfonic acid group (—SO ₃ H). Or a naphthyl group, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and Y represents And Z represents a hydrogen atom or a phenyl group which may have a substituent. ) 2. The free acid form is represented by the general formula (1).
And a dye for inkjet recording. [Chemical 3] (In the formula, A is an amino group, an acylamino group, a hydroxyl group
Group, carboxylic acid group (-COOH), and sulfonic acid group
Having a substituent selected from the group consisting of (--SO ₃ H)
Represents an optional phenyl group or naphthyl group, and X represents water
Elementary atom, C1-4 alkyl group or C1-4
Represents an alkoxy group, and Y is And Z may have a hydrogen atom or a substituent.
Represents a phenyl group. )