JP3306945B2 - 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. Specifically, the present invention 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 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 during storage as a recording liquid is also excellent. Therefore, the solvent that can be used for the recording liquid is significantly limited.

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-58-147470, 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-62-257971, 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
No. 079, JP-A-64-31877, JP-A-1-93
No. 389, Japanese Patent Application Laid-Open No. 1-210464, Japanese Patent Application Laid-Open No. 2-14
0270, JP-A-3-167270, JP-A-3-2
No. 00882, etc.), but a dye that satisfies the market requirements in terms of performance and is easy to produce has 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 black dye having a specific structure is used as a recording liquid component, a performance satisfying the above object can be obtained, and the present invention has been achieved. Things. 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.

Hereinafter, the present invention will be described in detail. 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 a benzyloxy group. Groups and the like,
Examples of the substituent of the phenyl group represented by Z include a lower alkyl group, a COOM group, an SO ₃ M group, a halogen atom, and the like. 1-4 alkyl groups and / or 1-4 carbon atoms
And mono-, di-, and tri-substituted amines.

In the structure of the dye used in the present invention, when one molecule contains a plurality of Ms, the plurality of Ms may be different from each other. Specific examples of these dyes include, for example, Table 1 No. 1 to N
o. An azo dye having the structure shown in No. 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 prepared by a method known per se [for example, Yutaka Hosoda, "New Dye Chemistry" (published by Gihodo on December 21, 1973), 396-409.
Page]], diazotization and coupling steps. 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.

[0019]

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 the 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 (product 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 the 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, Water was added to 2.5 parts by weight of the dye No. 2 and the pH was adjusted to 9 with aqueous ammonia to adjust the total amount to 1.
The composition was treated in the same manner as in Example 1 to prepare a recording liquid. Using this recording liquid,
As a result of performing printing in the same manner as in Example 1, a high-density black recorded matter was obtained. In addition, this recorded matter was compared with those of the first embodiment (a) to (a).
Various evaluations according to (c) 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, Add water to 3 parts by weight of dye 3
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, and as a result, a high-density black recorded matter was obtained.
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. [Examples 4 to 12] Table 1 used in Example 1
No. In place of the dye No. 1, 4-N
o. A recording liquid was prepared and printed by the method of Example 1 except that each of the 12 dyes was used, and various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, similar to Example 1, good results were obtained.

[0022]

The recording liquid of the present invention is used for ink-jet recording and writing instruments, and when recorded on plain paper, a black-based recording can be obtained, and its print density, light resistance, and water resistance can be obtained. And the storage stability as a recording liquid is also good.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yukichi Murata 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Research Institute (56) References JP-A-2-187474 (JP, A) JP-A Sho JP-A-61-261379 (JP, A) JP-A-4-366179 (JP, A) JP-A-4-304274 (JP, A) JP-A-2-276873 (JP, A) A) JP-A-55-151072 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00 C09D 11/02 C09B 31/072

Claims (20)

(57) [Claims] 1. A recording liquid comprising an aqueous medium and at least one dye represented by the following general formula [1]. Embedded image (In the formula, A an amino group, an acylamino group, a hydroxyl group, COOM group, and SO ₃ 1 kind selected from the group consisting of M group or may have one or more two or more substituents phenyl X or Y represents 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. Is 3 or more, and Z is H,
A phenyl group which may have a substituent, CH ₂ COOM
Represents a group or a C ₂ H ₄ COOM group, n is 0 or 1, M is H, alkali metal, NH _4, and organic Amin
Or represents one or more counterions selected from Ranaru group. ) 2. In the general formula [1], A is hydroxy
Having at least one substituent selected from the group consisting of
A phenyl group or a naphthyl group
3. The recording liquid according to claim 1. 3. In the general formula [1], A is a COOM group
And at least one amino group, an acylamino
Groups, hydroxyl groups and SO _Three Selected from the group consisting of M groups
Optionally substituted phenyl or naphthyl
The recording liquid according to claim 1, wherein the recording liquid is a base. 4. In the general formula [1], A is a COOM group
Is a phenyl or naphthyl group having one or two
2. The recording liquid according to claim 1, wherein: 5. In the general formula [1], carbons of X and Y
4. The method according to claim 1, wherein the sum of the numbers is 4 or more.
5. The recording liquid according to any one of 4. 6. In the general formula [1], a small amount of X and Y
At least one is an alkoxy group which may have a substituent.
6. The method according to claim 1, wherein Not a note
Recording liquid. 7. In the general formula [1], a small amount of X and Y
At least one is an alkyl group which may have a substituent.
The method according to any one of claims 1 to 5, wherein
Recording liquid. 8. In the general formula [1], X and Y are
Being an alkoxy group which may have a substituent
The recording according to any one of claims 1 to 5, characterized in that:
liquid. 9. In the general formula [1], X and Y are
Each of them is an alkoxy group having a hydroxyl group
6. A record according to claim 1, characterized in that
liquid. 10. In the general formula [1], Z is COOM.
Group: SO _Three From M group, halogen atom and lower alkyl group
Phenyl optionally having a substituent selected from the group consisting of
10. A group according to claim 1, wherein
The recording liquid according to 1. 11. An aqueous medium represented by the following general formula [2]:
Characterized in that it contains at least one kind of dye
Recording liquid. Embedded image (Wherein A ′ has at least one COOM group,
Amino group, acylamino group, hydroxyl group, and SO
May have a substituent selected from the group consisting of ₃ M groups
X 'and Y' represent phenyl or naphthyl groups.
H, substituted or unsubstituted alkyl having 1 to 7 carbon atoms,
Or a substituted or unsubstituted alkoxy having 1 to 9 carbon atoms
Represents at least one of X ′ and Y ′,
Is an unsubstituted alkoxy group, and X 'and Y' are
The sum of the prime numbers is 3 or more, Z is H, and has a substituent.
Phenyl group, CH ₂ COOM group or C ₂ H ₄ CO
Represents an OM group, n represents 0 or 1, M represents H, alkali
1 selected from the group consisting of metal, NH ₄ and organic amine
Represents a species or two or more counterions. ) 12. In the general formula [2], A ′ is COO
A phenyl or naphthyl group having one or two M groups
The recording liquid according to claim 11, wherein: 13. In the general formula [2], X ′ and Y ′
Is an alkoxy group which may have a substituent.
The recording liquid according to claim 11, wherein the recording liquid is used. 14. In the general formula [2], X ′ and Y ′
Is an alkoxy group each having a hydroxyl group
13. The recording liquid according to claim 11, wherein: 15. In the general formula [2], Z is COOM.
Group, SO _Three From M group, halogen atom and lower alkyl group
Phenyl optionally having a substituent selected from the group consisting of
15. The method according to claim 11, wherein
A recording liquid according to any of the above. 16. An aqueous medium represented by the following general formula [3]:
Characterized in that it contains at least one kind of dye
Recording liquid. Embedded image (In the formula, A ″ is a phenyl having one or two COOM groups.
And X ″ and Y ″ are charcoal, respectively.
A substituted or unsubstituted alkyl group having 1 to 7 carbon atoms or carbon
A substituted or unsubstituted alkoxy group of the formulas 1 to 9,
The total number of carbon atoms of X ″ and Y ″ is 3 or more, and Z is H,
Optionally substituted phenyl group, CH ₂ COOM group
Or a C ₂ H ₄ COOM group, wherein M is H, an alkali metal,
One or more selected from the group consisting of NH ₄ and organic amines
Represents two or more counterions. ) 17. In the general formula [3], X ″ and Y ″
Is a substituent An alkoxy group which may have
17. The recording liquid according to claim 16, wherein the recording liquid is used. 18. In the general formula [3], X ″ and Y ″
Are all alkoxy groups having a hydroxyl group
17. The recording liquid according to claim 16, wherein: 19. In the general formula [3], Z is H.
The method according to any one of claims 16 to 18, wherein
Recording liquid. 20. An aqueous medium represented by the following general formula [4]:
A recording liquid comprising a dye. Embedded image