JPH1135858A - Recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject recording liquid good in print quality, even when printed on plain paper, and giving recorded images high in concentration and good in water resistance, light resistance and long period storage stability by using a pigment produced by introducing a specific substituent to a disazo compound. SOLUTION: This recording liquid contains an aqueous medium and at least one kind of pigment selected from pigments whose free forms are represented by the formula [A is amino, an acylamino, hydroxyl or the like; X is H, an alkyl, an alkoxy or the like; Y is amino, an acylamino or a (substituted) alkyl; Z is H, a (substituted) alkyl or phenyl]. The pigment is obtained e.g. by diazotizing and coupling 3-aminobenzolic acid with 2-ethoxy-5- cyclohexylcarbamoylaniline, diazotizing the obtained compound, and subsequently coupling the product with 7-(p-carboxyphenyl)amino-1-hydroxy-3-naphthalene sulfonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid used for ink jet recording, writing implements, and the like. Specifically, the present invention relates to a black recording liquid suitable for ink jet recording.

[0002]

2. Description of the Related Art An 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.
In addition, 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 proposals (for example, Japanese Patent Application Laid-Open
No. 144067, JP-A-55-152747, JP-A-57-207660, JP-A-58-147470, JP-A-62-190269, JP-A-62-190271
JP-A-62-190272, JP-A-62-250
No. 082, JP-A-62-246975, JP-A-62-246975
No. 257971, JP-A-62-288659, JP-A-63-8463, JP-A-63-22867, JP-A-63-22874, JP-A-63-30567, and JP-A-63-33484 JP-A-63-63764, JP-A-63-105079, JP-A-64-31877
JP-A-1-93389, JP-A-1-210644
JP-A-2-140270, JP-A-3-16727
No. 0, Japanese Unexamined Patent Publication No. 3-200882, etc.), but have not yet sufficiently satisfied the market requirements.

The present inventors have previously proposed a recording solution using a specific disazo dye (JP-A-5-125318,
JP-A-7-34020, JP-A-9-137093
issue). All of these are superior to conventional ones in required physical properties such as density, light resistance, storage stability, and water resistance of printed matter, but are required to have more excellent performance.

[0006]

DISCLOSURE OF THE INVENTION The present invention has a good print quality even when recorded on plain paper for ink jet recording and writing instruments, 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 is excellent in stability when stored for a long time.

[0007]

Means for Solving the Problems The present inventors have studied and obtained a recording liquid having further excellent physical properties by using a dye having a specific substituent introduced into the previously proposed disazo compound. succeeded in. The recording liquid according to the present invention,
The aqueous medium and the form of the free acid are characterized by containing at least one dye selected from the dyes represented by the following general formula (I).

[0008]

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(Wherein A represents a phenyl group or a naphthyl group which may have an amino group, an acylamino group, a hydroxyl group, a carboxyl group, or a sulfo group as a substituent. X represents a hydrogen atom, an alkyl group, an alkoxy group, Y represents carbon which may have an amino group, an acylamino group, a substituted or unsubstituted alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, a carboxyl group or a sulfo group as a substituent; A cycloalkyl group of the number 3 to 12 or

[0010]

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Represents a heterocyclic group selected from Z represents a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group. )

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The dye used in the present invention has a free acid type represented by the general formula (I). In the general formula (1), examples of the acylamino group which may be substituted with the phenyl group or the naphthyl group represented by A include, for example, an alkyl group having 1 to 4 carbon atoms such as an acetylamino group and a propionylamino group. Examples include an alkylcarbonylamino group or an arylcarbonylamino group such as a benzoylamino group. When X is an alkyl group, specifically, a methyl group, an ethyl group, n
Carbon atoms such as -propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, etc.
And X is a linear or branched alkyl group, and when X is an alkoxy group or an alkoxyalkoxy group,
An alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 6 carbon atoms corresponding to the above alkyl group is exemplified. Specific examples of the substituted or unsubstituted alkyl group which is a substituent of the cycloalkyl group or the heterocyclic group represented by Y, and specific examples of the hydroxyalkyl group include the alkyl groups exemplified in the case of X, and the alkoxy group. In such a case, the alkoxy group exemplified for X can be mentioned, and the acylamino group can be A
And the acylamino groups exemplified above.

In the general formula (I), A is preferably a phenyl group or a naphthyl group having at least one substituent selected from an amino group, an acylamino group, a hydroxyl group, a carboxyl group and a sulfo group; More preferably, it is a phenyl group having at least one carboxyl group or sulfo group. X is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. is there. Y is preferably a cycloalkyl group or a heterocyclic group which may have a carboxyl group, an acylamino group or a hydroxyl group as a substituent.
Z is preferably a hydrogen atom or a phenyl group which may have a carboxyl group or an alkoxy group as a substituent, and more preferably a hydrogen atom or a phenyl group having at least one carboxyl group. The dye of the formula (I) is used as a salt form by neutralizing a free acidic group with a base, if necessary.

Examples of the counter ion of the acidic group of the dye include an alkali metal ion such as lithium, sodium and potassium, an ammonium group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group as a substituent, and Number 1
Mono-, di-, hydroxyalkoxy groups
Organic amine bases such as tri-substituted amino groups are included. Specific examples of the dye represented by the general formula (I) include, for example, 1 to No. An azo dye having a structure represented by 20 is exemplified, but the dye of the present invention is not limited thereto.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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The dye represented by the general formula (I) used in the present invention can be prepared by a method known per se [for example, Yutaka Hosoda, “Shin-Dye Chemistry”, published on December 21, 1973, Gihodo, 396- 409], and can be produced through a diazotization and coupling step. For example, no. 1
Is produced from 3-aminobenzoic acid and 2-ethoxy-5-cyclohexylcarbamoylaniline by a conventional method through a diazotization and coupling step to produce a monoazoamino compound. And obtained by coupling with 7- (p-carboxyphenyl) amino-1-hydroxy-3-naphthalenesulfonic acid.

The content of the dye represented by the general formula (I) in the recording liquid of the present invention is preferably 0.5 to 10% by weight, more preferably about 2 to 4% by weight based on the total amount of the recording liquid. The dye represented by the general formula (I) may be used singly, or two or more kinds may be mixed and used. Moreover, you may use together with another black (black) pigment | dye. Examples of the pigment used in combination include Food Black 2, Direct Black 17, 19, 154, 163, 168, 171, 19
5, Acid Black 2, Reactive Black 31
(Above, color index names), Pontamine Black SP Liquid (trade name, manufactured by Bayer AG), Bath Acid Black X-34 (trade name, manufactured by BASF) and the like. Further, although the dye used in the present invention is black,
To obtain a desired color tone, such as bluish black, reddish black, or yellowish black, if necessary, a dye of another color tone, for example, one kind of a red, yellow, or blue dye, Or more may be used together.

The aqueous medium constituting the recording liquid of the present invention is preferably composed of 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), 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 is preferable to use one or more selected from isopropanol, triethanolamine and the like. These water-soluble organic solvents are usually used in the range of 5 to 30% by weight based on the total amount of the recording liquid. On the other hand, water is 6% of the total volume of the recording liquid.
It is used in the range of 0 to 90% by weight.

The recording liquid of the present invention is used in an amount of 0.1% based on the total amount.
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. Further, the recording liquid of the present invention is a black recording liquid, and can be used not only for producing monochrome prints or monochrome printed matter, but also as a full-color printer or as one color for producing full-color printed matter. Is also good. In particular, in the case of full color printing, recording liquids of magenta, cyan and yellow are used together. In that case, the recording liquid of each color
An aqueous recording liquid of each color tone, for example, containing a water-soluble dye of each color tone, an aqueous medium, and if necessary, an additive. The aqueous medium and the additive may be the same as those usually used in the above-described recording liquid of the present invention. As the water-soluble dye having the color tone, in magenta, for example, Acid Red 35, 52, or 289, Direct Red 227 and hydrolyzate of Reactive Red 180 can be used. For cyan, for example, Direct Blue 86 or 199, Acid Blue 9 and the like can be used.
Alternatively, 142, Acid Yellow 23 and the like can be used. (All are color index names)

The present invention is particularly suitable for use as a recording liquid for ink jet. The type of the ink jet printer is not particularly limited, and for example, the means for discharging the droplets can be preferably used for any of those using electric energy, those using thermal energy, and the like.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist. The dye No. No. of the above-mentioned exemplified dyes Corresponding to

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 to a pore size of 1 μm.
After filtration under pressure with a Teflon filter, a recording solution was prepared by degassing with a vacuum pump and an ultrasonic cleaner. Using the obtained recording liquid, inkjet recording was performed on electrophotographic paper (manufactured by Fuji Xerox) using an inkjet printer (manufactured by BJ-10V Canon Inc.).
A high density black print was obtained. The following (a),
Table 1 shows the results of various evaluations by the methods (b), (c) and (d).

(A) Density of recorded image: The OD value of the recorded image on which solid printing has been performed is measured using a Macbeth densitometer (trade name: TR-9).
27). (B) Light fastness of recorded image: Using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.), irradiate recording paper for 100 hours, and apply it to a spectral color difference meter (trade name: SZ-80, manufactured by Nippon Denshoku Industries Co., Ltd.) The color difference (ΔE) of the recorded matter before and after the test was measured by using the following criteria.

[0028]

表: Discoloration and discoloration are ΔE and less than 10 Δ: Discoloration and discoloration are ΔE and 10 or more and less than 20 ×: Discoloration and discoloration are ΔE and 20 or more

(C) Water resistance of the recorded image: The bleeding of the image after immersing the recording paper in tap water for 5 minutes was visually judged according to the following criteria.

[0030]

[Table 2] A: No bleeding of image. Δ: Image bleeding is small. X: The image blur is large.

(D) Storage stability of the recording solution: The recording solution was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for one month, and the change was examined and judged according to the following criteria.

[0032]

[Table 3] ○: No change ×: Change

Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol,
No. Water was added to 2.5 parts by weight of the dye No. 10 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. . 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. Various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter. The results are shown in Table 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 3 parts by weight of the dye No. 13 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.
Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high-density reddish black recorded matter was obtained. Various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter. The results are shown in Table 1.

Comparative Example 1 In place of the dye 1,
No. 34020 described in Japanese Patent Publication No. A recording liquid was prepared in the same manner as in Example 1 using the dye (1) (the following structural formula R-1). Using this recording liquid, recording and printing were performed in the same manner as in Example 1 to obtain a black recorded matter. Various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter.
The results are shown in Table 1.

[0036]

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[0037]

[Table 4]

The recording liquid of the present invention is used for ink-jet recording and writing instruments, and when recorded on plain paper,
Black recordings can be obtained, and it is excellent not only for monochrome printed matter but also for full color printed matter, and has excellent printing density and light resistance and water resistance of the printed matter, as well as a recording liquid. Good storage stability.

Claims (6)

[Claims] 1. A recording liquid comprising an aqueous medium and at least one dye whose free acid type is selected from the dyes represented by the following general formula (I). Embedded image (Wherein A is an amino group, an acylamino group,
It represents a phenyl group or a naphthyl group which may have a hydroxyl group, a carboxyl group or a sulfo group. X represents a hydrogen atom, an alkyl group, an alkoxy group or an alkoxyalkoxy group. Y is an amino group, an acylamino group, a substituted or unsubstituted alkyl group, an alkoxy group,
A cycloalkyl group having 3 to 12 carbon atoms which may have a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfo group, or Represents a heterocyclic group selected from Z represents a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group. ) 2. In the general formula (I), A is an amino group,
The recording liquid according to claim 1, wherein the recording liquid is a phenyl group or a naphthyl group having at least one substituent selected from an acylamino group, a hydroxyl group, a carboxyl group, and a sulfo group. 3. The recording liquid according to claim 2, wherein A in the general formula (I) is a phenyl group having at least one carboxyl group or sulfo group. 4. X in the general formula (I) is a hydrogen atom,
The recording liquid according to any one of claims 1 to 3, wherein the recording liquid is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 5. The method according to claim 1, wherein Y in the general formula (I) is a cycloalkyl group or a heterocyclic group which may have a carboxyl group, an acylamino group or a hydroxyl group as a substituent. 5. The recording liquid according to any one of items 1 to 4. 6. Z in the general formula (I) is a hydrogen atom,
2. A phenyl group which may have a carboxyl group or an alkoxy group as a substituent.
6. The recording liquid according to any one of items 1 to 5,