JP3264051B2 - Recording liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid. More specifically, the present invention relates to a black, red, and yellow recording liquid suitable for ink jet recording.

[0002]

2. Description of the Related Art A so-called ink jet recording method has been put to practical use, in which droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acidic dye are ejected from a fine discharge orifice to perform recording. This recording liquid is used for general office work such as PPC (plain paper copier) paper such as electrophotographic paper and fan hold paper (continuous paper such as a computer), in addition to being capable of stable ejection for a long time. It is required that the fixation to the recording paper is fast and the print quality of the printed matter is good, that is, the print has no blur and the outline is clear, and the stability at the time of storage as a recording liquid is also required. The need for excellence greatly limits the solvents that can be used in the recording liquid.

On the other hand, dyes for recording liquids have sufficient solubility in the above-mentioned limited solvents and are stable even when stored as recording liquids for a long time.
Further, it is required that the density of the printed image is high, and that it is excellent in water resistance and light resistance. However, it has been difficult to satisfy many of these requirements at the same time. For this reason, various methods (for example, JP-A-55-140467, JP-A-55-152747, JP-A-57-207660)
No., JP-A-59-226072, JP-A-62-1902.
No. 69, JP-A-62-190271, JP-A-62-1
90272, JP-A-62-250082, JP-A-62-250082
JP-A-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
No. 079, JP-A-64-31877, JP-A-1-93
No. 389, JP-A-1-210644, JP-A-2-16
No. 171, JP-A-2-140270, JP-A-3-20
No. 0882, etc.) have been proposed, but dyes which sufficiently satisfy market demands in terms of performance and which are easy to produce have not yet been developed.

[0004]

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

[0005]

Means for Solving the Problems The present inventors have confirmed that, when a dye having a specific structure is used as a recording liquid component, the performance particularly satisfying the above object can be obtained, and the present invention has been achieved. It is. That is, the gist of the present invention resides in a recording liquid in which the form of an aqueous medium and a free acid contains at least one kind of the dye represented by the general formula [I] in the above-mentioned claim 1.

Hereinafter, the present invention will be described in detail. The dye of the present invention may be in the form of the free acid according to the above-mentioned general formula [I]
It is represented by Specifically, in general formula [I], B
As a substituent of the phenylene group represented by
And an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a sulfonic acid group, a halogen atom such as a chlorine atom and a bromine atom, and the substituent of the phenylene group represented by D is 1 carbon atom. To 4 alkyl groups, 1 to 4 carbon 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 are preferably the same in production.

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

[0008] Specific examples of these dyes include, for example, Table 1 No. 1 to No. An azo dye having the structure shown in No. 21 may be used, and these dyes may be used alone or in combination depending on a 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 prepared by a method known per se [for example, Yutaka Hosoda, "New Dye Chemistry" (published by Gihodo on December 21, 1973, Gihodo), 396-409.
Page]], and can be produced through a tetrazotization and coupling step. The content of the dye of the general formula [I] in the recording liquid is preferably 0.5 to 5% by weight, particularly preferably about 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) and 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 and the like. These water-soluble organic solvents are usually 1 to 10 parts with respect 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 based on the total amount of the recording liquid.

In the recording liquid of the present invention, 0.1% of the total amount of the recording liquid is used.
1 to 10% by weight, preferably 0.5 to 5% by weight of urea,
By adding a compound selected from thiourea, biuret and semicarbazide, or by adding 0.001 to 5.0% by weight of a surfactant, it is possible to further improve the quick drying property after printing and the print quality. it can.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. Example 1 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, Water was added to 3 parts by weight of dye No. 1 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. This composition was thoroughly mixed and dissolved, filtered under pressure through a Teflon filter having a pore size of 1 μm, and then deaerated by a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.

Using the obtained recording liquid, ink jet recording was performed on electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an ink jet printer (trade name: HG-3000, manufactured by Epson Corporation) to obtain a high density black print. Obtained. The results of various evaluations by the methods (a), (b) and (c) are shown below. (A) Light fastness 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 after irradiation was small.

(B) Water resistance of recorded image: The bleeding of the image after immersing the recording paper in water for 5 seconds was examined. The bleeding of the image was slight and the decrease in density was small. (C) Storage stability of the recording solution: When the recording solution was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for one month, no change of the insoluble matter was observed.

Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, Dye 8
Water was added to parts by weight, and the pH was adjusted to 9 with ammonia water to make the total amount 100 parts by weight. The 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 matter. In addition, this recorded matter was compared with (a) to (c) of Example 1.
Various evaluations were performed. As a result, good results were obtained in all cases as in 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, Water was added to 2 parts by weight of the dye No. 15 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. The 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 matter.
Various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, good results were obtained in all cases as in Example 1.

[Embodiments 4 to 10] As shown in Table 1 No. In place of the dye No. 1,
o. Except that the dyes 2, 4, 6, 10, 14, 18, and 20 were respectively used, the recording liquid was adjusted and printed by the method of Example 1, and (a) of Example 1 was applied to the recorded matter. ) To (c). As a result, similar to Example 1, good results were obtained.

[0023]

The recording liquid of the present invention is used for ink-jet recording and for writing utensils. When recorded on plain paper, black, red and yellow recordings can be obtained. And light resistance, water resistance is excellent,
The storage stability as a recording liquid is also good.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-63-120776 (JP, A) JP-A-5-125318 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 C09B 35/28-35/32 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A dye for a recording liquid , wherein the form of the free acid is represented by the following general formula [1] . Embedded image AN = ND-CONH-BN = NA ′ [1] (where A and A ′ are both at least in the following p-positions:
Represents a phenyl group having a substituted amino group, or
A hydroxyl group at the 1-position below, a sulfonic acid group at the 3-position and a 7-position
Represents a 2-naphthyl group having a substituted phenylamino group , and B and D each independently represent a phenylene group which may have a substituent. Embedded image However, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, or an acylamino group, R ₃ represents H, a -CH ₂ COOH or -C ₂ H ₄ COOH, R ₄ represents -CH ₂ COOH or -C ₂ H ₄ COOH, R ₅ is table but a hydrogen atom or a carboxyl group, and a
A ′ may have different substituents and different positions.
No. ) 2. The free acid form is represented by the following general formula [2].
The dye for a recording liquid according to claim 1, wherein Embedded image (Wherein R ₁ and R ₂ are each independently a hydrogen atom,
Methyl group, methoxy group, ethoxy group or acylamino group
R ₃ represents H, —CH ₂ COOH or —C ₂ H ₄ COO
It represents H, R ₄ is -CH ₂ COOH or -C ₂ H ₄ COOH
Wherein B and D each independently have a substituent
Represents a phenylene group which may be substituted. However, the p-substituted
In the aminophenyl group, R ₁ to R ₄ are different from each other
May be. ) 3. The form of the free acid is represented by the following general formula [3].
The dye for a recording liquid according to claim 1, wherein Embedded image (Wherein, R ₅ represents a hydrogen atom or a carboxyl group;
And D each independently represent a substituent which may have a substituent.
Represents a phenylene group. However, carboxy-substituted phenyl at both terminals
The ruamino groups may be different from one another. ) 4. An aqueous medium and any one of claims 1 to 3
Contains at least one of the dyes for recording liquid described in (1).
A recording solution characterized by the above-mentioned.