JP2000239550A - Disazo coloring matter and recording liquid containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having a free acid form represented by a specific formula, capable of providing good print quality even in the case of a record recorded on a sheet of ordinary paper, cable of providing a recorded image in high density, excellent in water resistance and light resistance, good in stability when being preserved for a long time, and useful for inkjet recording or the like. SOLUTION: This new compound is the one having a free acid form of formula I (R1 and R2 are each H, an acylamino, OH or the like; X is an acylamino or a 1-7C alkyl; Y is a 1-7C alkoxy; Z is H, a carboxyalkyl or an aryl; n is 0 or 1), e.g. a compound of formula II. The compound is obtained by diazotizing a nitroaniline having R1 and R2 groups, coupling an aniline having X and Y groups therewith, diazotizing the product, and coupling the diazotized product with a naphthol derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel disazo dye suitable for a recording liquid and a black recording liquid suitable for ink jet recording using the same.

[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 acid dye are ejected from a fine ejection orifice to perform recording. The 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 is free from bleeding and the outline is clear, and the storage stability 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 dyes and recording methods (for example, JP-A-55-14406)
7, JP-A-55-152747, JP-A-57-20
No. 7660, JP-A-58-147470, JP-A-62
-190269, JP-A-62-190271, JP-A-62-190272, JP-A-62-250082
JP-A-62-246975, JP-A-62-257
971, JP-A-62-288659, JP-A-63-8859
No. 8463, JP-A-63-22867, JP-A-63-22867.
22874, JP-A-63-30567, JP-A-63
JP-A-33484, JP-A-63-63764, JP-A-63-63764
JP-A-3-105079, JP-A-64-31877, JP-A-1-93389, JP-A-1-210464, JP-A-2-140270, JP-A-3-167270, JP-A-3-200882, etc. Reference) has been proposed, but in terms of performance, a dye which sufficiently satisfies the market requirements and is easy to produce has not yet been developed.

[0004]

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

[0005]

Means for Solving the Problems The present inventors have confirmed a black dye having a specific structure capable of obtaining performance particularly satisfying the above-mentioned object when used as a recording liquid component, and have achieved the present invention. It is. That is, the gist of the present invention resides in a disazo dye whose free acid form is represented by the following general formula (1) and a recording liquid containing such a dye and an aqueous medium.

[0006]

Embedded image

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an acylamino group, a hydroxyl group, a carboxyl group or a sulfo group, X represents an acylamino group, and having 1 carbon atom.
Represents an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, Y represents an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, and Z represents a hydrogen atom, a carboxyalkyl group, or an aryl group. And n represents 0 or 1. These groups may be further substituted. )

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dye of the present invention is represented by the general formula (1). When R ¹ , R ² , and X in the general formula (1) represent an acylamino group, specific examples include an acetylamino group and a benzoylamino group. When X and Y represent an alkyl group or an alkoxy group having 1 to 7 carbon atoms, specifically, methyl, ethyl, n-propyl, i-propyl, n-
Examples thereof include a linear or branched alkyl group having 1 to 7 carbon atoms such as a butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, and an n-heptyl group, or an alkoxy group corresponding to these alkyl groups. . When Z represents a carboxyalkyl group, specifically, a carboxymethyl group, a carboxyethyl group and the like can be mentioned, and when Z is an aryl group, a phenyl group can be mentioned. These groups may be further substituted. Specifically, for example, when X and Y are an alkyl group or an alkoxy group, a hydroxy group,
It may have a lower alkoxy group, a phenyl group, a benzyloxy group, an alkoxyalkyl group and the like. When Z is a phenyl group, it may be substituted with a carboxyl group, a sulfo group, a halogen atom, a lower alkyl group or the like.

In the dye of the present invention, the nitro group on the benzene ring A is preferably substituted at the 4-position to the azo group. One of R ¹ and R ² is preferably a carboxyl group, and the carboxyl group and the nitro group are preferably substituted by carbon atoms adjacent to each other. One of R ¹ and R ² is preferably a hydrogen atom. X and Y are the same or different and have 1 to 1 carbon atoms.
It is preferably an alkyl group or an alkoxy group having 4 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Z is preferably a hydrogen atom, a carboxymethyl group, a sulfophenyl group or a carboxyphenyl group, and particularly when n is 1, a hydrogen atom is preferred. On the other hand, n
Is 0, Z is preferably a hydrogen atom, a sulfophenyl group or a carboxyphenyl group, and among them, a sulfophenyl group and a carboxyphenyl group are particularly preferred.

The dye of the present invention is suitable as a dye for a black recording liquid. In applying the dye of the present invention to a recording liquid, the free acid type represented by the general formula (1) may be used as it is, but a part or all of the acid group may be converted to a desired salt type. Is also good. The counter ion forming a salt is selected from the group consisting of alkali metal ions such as lithium, sodium and potassium, ammonium ions and substituted amines.
A species or two or more ions are used. Specific examples of the substituted amines include mono-, di-, and tri-substituted amines in which the substituent is an alkyl group having 1 to 4 carbon atoms and / or a hydroxyalkyl group having 1 to 4 carbon atoms. Further, different types of counter ions may be used in combination. Table 1 shows specific examples of these dyes and their maximum absorption wavelengths.
As shown in No. 1, the dye of the present invention is not limited to these.

[0011]

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3]

The azo dye represented by the general formula (1) 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]], and can be produced through a diazotization and coupling step. For example, it can be obtained by diazotizing nitroaniline having R ¹ and R ² groups and coupling with aniline having X and Y groups, then diazotizing the product and coupling with a naphthol derivative.

The recording liquid of the present invention contains an aqueous medium and a dye represented by the general formula (1) or a salt thereof. The content of the dye of the general formula (1) in the recording liquid is preferably 0.1 to 10% by weight, particularly preferably about 2 to 8% by weight, based on the total amount of the recording liquid. Examples of the solvent used for the recording liquid include water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 400), 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,
It preferably contains ethyl alcohol, isopropanol 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 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, and 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. The recording liquid of the present invention is used for writing implements or ink jet recording, and is particularly suitable as a recording liquid for ink jet. When recorded on plain paper, a black recording can be obtained, and its print density, water resistance, and light resistance are excellent. In particular, the density of the recorded image is high, and the storage stability as a recording liquid is also good. .

[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. The dye N in the examples
o. Is the dye No. in Table 1. Corresponding to “Parts” means “parts by weight” unless otherwise specified.

Production Example 1 46 parts of 2-nitro-5-aminobenzoic acid were suspended in 600 parts of water, the pH was adjusted to 9 by adding a 25% aqueous sodium hydroxide solution, and 18 parts of sodium nitrite was added and dissolved. . 91
The above-mentioned solution was added to 600 parts of water to which 35% hydrochloric acid had been previously added at 0 to 5 ° C. to diazotize 2-nitro-5-aminobenzoic acid. Thereafter, 2 parts of sulfamic acid was added to obtain a diazo solution of 2-nitro-5-aminobenzoic acid.

Separately, 38 parts of 2,5-dimethoxyaniline were suspended in 2700 parts of water, 26 parts of 35% hydrochloric acid was added, and the temperature was raised to 60 ° C. to obtain a uniform solution. The solution was cooled, the above-mentioned diazo solution of 2-nitro-5-aminobenzoic acid was added, and the resulting solid was collected by filtration. Add this to water 2
Suspended in 400 parts, the pH was adjusted to 12 with a 25% aqueous sodium hydroxide solution to obtain a uniform monoazo compound solution. To this monoazo compound solution, 33 parts of sodium nitrite was added and dissolved. After diazotizing the monoazo compound by dropping this solution to 1500 parts of water containing 35 parts of hydrochloric acid at 0 to 5 ° C., 13 parts of sulfamic acid was further added to form a diazo solution of the monoazo compound. Obtained.

Separately, 65 parts of N- (carboxymethyl)
Gamma acid is suspended in 1500 parts of water and p
H was adjusted to 9 to obtain a uniform solution. The diazo solution of the above-mentioned monoazo compound was dropped into this solution and coupled. During the dropping, the pH of the coupling bath was adjusted to 9 to 10 using a 25% aqueous sodium hydroxide solution. 200 parts of sodium chloride was added to the obtained coupling solution, and the solid content was collected by filtration. The obtained wet cake was dissolved in 3500 parts of water, a 35% aqueous hydrochloric acid solution was added to adjust the pH to 1, and acid precipitation was carried out. The resulting solid was collected by filtration. The obtained dye was dried and N-
o. 98 parts of one dye were obtained in the form of the free acid. The maximum absorption wavelength of the obtained dye was 580 nm (the solvent was water and the counter ion was lithium ion). Similarly, in the case of No. 1 in Table 1,
2-No. Twelve dyes were obtained.

Example 1 10 parts of diethylene glycol, 3 parts of isopropyl alcohol, Water is added to 3 parts of the dye (free acid form, the same applies hereinafter) of 1 and the pH is adjusted to 9 with an aqueous solution of lithium hydroxide.
The total amount was adjusted to 100 parts. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon filter having a pore size of 1 μm, and then degassed with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid. Using the obtained recording liquid, an electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an ink jet printer (trade name: HG-3000, manufactured by Epson)
Ink jet recording was performed to obtain a high-density black print. The print density (OD value) was 1.4. Various evaluations were made by the following methods (a), (b) and (c), and good results were obtained in each case.

(A) Light fastness of recorded image: 100% on recording paper using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.)
Irradiation was carried out for 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 of glycerin, 10 parts of ethylene glycol,
1No. Water was added to 2.5 parts of the dye No. 2 and the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to make the total amount 100 parts. This composition was treated by the method described in Example 1 to prepare a recording liquid. . Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high-density black recorded matter was obtained. The print density was 1.4. 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.

Example 3 10 parts of diethylene glycol, N-methylpyrrolidone 5
Part, 3 parts of isopropyl alcohol, and 3
Water was added to 3 parts of the dye, and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts. This composition was treated by the method described in Example 1 to prepare a recording liquid. Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high-density black recorded matter was obtained. The print density was 1.4. 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 No. 1 used in Example 1 was used. No. 1 in place of the dye No. 1 in Table 1. 4-No. A recording liquid was prepared and printed by the method of Example 1 except that the dye No. 12 and the neutralizing agent giving a counter ion described in the same table were used, and printing was performed. a) to (c)
Various evaluations were performed. As a result, similar to Example 1, good results were obtained.

[0026]

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 Continued on front page F term (reference) 2C056 FC01 2H086 BA53 BA55 4J039 BC06 BC19 BC32 BC41 BC65 BC73 BC75 BC77 BC79 BE02 CA03 EA19 EA35 EA38 EA42 EA44 EA46 GA24

Claims (10)

[Claims] 1. A disazo dye having a free acid form represented by the following general formula (1). Embedded image (Wherein R ¹ and R ² are each independently a hydrogen atom,
X represents an acylamino group, a hydroxyl group, a carboxyl group or a sulfo group, X represents an acylamino group, an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 7 carbon atoms, and Y represents an alkyl group having 1 to 7 carbon atoms or carbon atom. Represents an alkoxy group represented by Formulas 1 to 7, Z represents a hydrogen atom, a carboxyalkyl group, or an aryl group, and n represents 0 or 1. These groups may be further substituted. ) 2. In the general formula (1), R ¹ and R
^2. The disazo dye according to claim 1, wherein one of the ^two is a carboxyl group. 3. The disazo dye according to claim 1, wherein in the general formula (1), the nitro group of the benzene ring A is substituted at the 4-position with respect to the azo group. 4. In the general formula (1), R ¹ and R
4. The disazo dye according to claim 2, wherein one of the ^two is a carboxyl group, and the carboxyl group and the nitro group are substituted on carbons adjacent to each other. 5. In the general formula (1), X and Y
Are the same or different alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms, wherein the disazo dye according to any one of claims 1 to 4, wherein 6. In the general formula (1), X and Y
Is the same or different and is an alkoxy group having 1 to 4 carbon atoms, the disazo dye according to claim 5, wherein 7. The disazo dye according to claim 1, wherein n is 0 in the general formula (1). 8. In the general formula (1), R ¹ and R
7. The disazo dye according to claim 1, wherein one of the ^two is a hydrogen atom. 9. A recording liquid comprising an aqueous medium and the disazo dye according to claim 1. Description: 10. An ink-jet recording method using the recording liquid according to claim 9.