JPH07173422A - Recording fluid - Google Patents

Abstract

PURPOSE:To obtain a recording fluid which gives a black-printed record excellent in deepness of color of print and in resistances to light and water when used for recording on plain paper and which has a good storage stability. CONSTITUTION:A recording fluid contains an aq. medium and at least one member selected from coloring matters of which the free acid forms are represented by the formula (wherein A and D are each optionally substd. phneyl or naphthyl; B, C, E, and F are each optionally substd. phenylene or naphthylene; R1 and R2 are each independently H, a 1-18C optionally substd. alkyl or alkenyl group, or an optionally substd. aryl, cycloalkyl, aralkyl, or heterocyclic group; and l, m, and n are each 0 or 1).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording liquid. Specifically, it relates to a recording liquid suitable for inkjet recording.

[0002]

2. Description of the Related Art A so-called ink jet recording method has been put into 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 minute ejection orifice to perform recording. Regarding this recording liquid, P of electrophotographic paper is used.
Fast fixing to general-purpose office paper such as PC (plain paper copier) paper and fan-hold paper (continuous paper for computers etc.) and good print quality, that is, print bleeding It is required to have a clear outline and to have excellent stability during storage as a recording liquid.
Therefore, the solvent that can be used is extremely 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 period of time.
Further, although it is required that the printed image has a high density and is excellent in water resistance and light resistance, it has been difficult to satisfy many of these requirements at the same time. Therefore, various methods (for example, JP-A-61-101574, JP-A-61-101576, JP-A-61-195176) are used.
No. 61-62562, JP-A 61-2477.
71, JP-A-62-156168, JP-A-63-6.
3765, JP-A-63-295685, JP-A-1-
123866, JP-A-2-16171, JP-A-3-
122171, JP-A-3-203970, JP-A-4
No. 15327, JP-A No. 4-279671, etc.) have been proposed, but they have not yet fully satisfied the market demands.

[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, light resistance and especially It is an object of the present invention to provide a black recording liquid which is excellent in water resistance and color tone of a recorded image and has good stability when stored for a long period of time.

[0005]

The present inventors have accomplished the present invention by confirming that the above objects can be achieved when a specific dye is used as a recording liquid component. That is, the gist of the present invention is to provide an aqueous medium and at least one of the dyes whose free acid form is represented by the general formula {1} in claim 1.
It exists in the recording liquid containing the seed.

The present invention will be described in detail below. Used in the present invention
The dye used is in the form of the free acid as defined in claim 1.
It is represented by the general formula {1}. Specifically, the general formula
In {1}, represented by A, B, C, D, E and F
Phenyl group, naphthyl group, phenylene group, naphthylene group
As a substituent of ₃H group, -COOH group, ami
Group, an acylamino group (for example, an acetylamino group,
Alkylamino groups such as butanoylamino groups or benzoyl
An aryloylamino group such as a ruamino group), a carbon number of 1 to
9 substituted or unsubstituted alkyl groups (eg, methyl
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, t-butyl group, n-heptyl group, n-nonyl
Group, etc., trifluoromethyl group, dimethylaminomethyl group
Etc.), a substituted or unsubstituted alkoxy group having 1 to 9 carbon atoms
(For example, methoxy group, isopropoxy group, n-butoxy group
Aralkyloxy groups such as Si group and benzyloxy group, hydr
Hydroxyalkoxy group such as Roxyethoxy group
Alkoxyalkoxy groups such as cyethoxy groups, benzyl
An aralkyloxyalkoxy group such as an oxyethoxy group,
Carboxyalkoxy group such as carboxymethoxy group
Etc.), hydroxyl group, halogen atom (eg, fluorine atom, salt
Element atom, bromine atom, etc.)
You may have several. R₁And R₂Substituent represented by
Are independently substituted or non-substituted having 1 to 9 carbon atoms.
Substituted alkyl group (eg, methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, steari
Group, carbamoylmethyl group, hydroxyethyl group,
Ruboxyethyl group, carboxypropyl group, carboxy
Carboxyalkyl group such as pentyl group, 1-carboxy
-2-hydroxyethyl group, carboxycyclohexyl
Methyl group, carboxycyclohexylmethyl group, 1-carb
Rubox-2-mercaptoethyl group, 1-carboxy-
2-carbamoylethyl group, 1-isopropyl-1-carbo
Ruboxymethyl group, 1,2-dicarboxyethyl group,
Carboxyl groups such as 1,2-dicarboxypropyl group
Alkyl group having, etc.), substituted or non-substituted with 1 to 18 carbon atoms
A substituted alkenyl group (eg, 2-methyl-1-propene)
Nyl group, vinyl group, allyl group, etc.), substituted or unsubstituted
Aryl groups (eg 3,4-dicarboxyphenyl
Group, 4-butylphenyl group, 4-carboxyphenyl group
Etc.), a substituted or unsubstituted aralkyl group (eg benzene
Zyl group, 1-carboxy-2-phenyl-ethyl group, 1
-Carboxy-2-hydroxyphenylethyl group, 4-
Carboxybenzyl group), substituted or unsubstituted cyclo
Alkyl groups (eg cyclohexyl group, 4-carboxyl group
Cyclohexyl group, etc.), substituted or unsubstituted heterocyclic group
(For example, pyridyl group, thiazolyl group, thiadiazolyl group
Group, benzothiazolyl group, 2,2,6,6-tetramethyi group
(E.g., rupiperidinyl group), and particularly preferably R₁or
Is R₂At least one of them is substituted with 1 to 4 COOH groups
Alkyl group, alkenyl group, aryl group,
Examples include chloroalkyl group, aralkyl group or heterocyclic group.
You can

The dye used in the present invention has the general formula {1}
Although it may be used as it is as a free acid form, it may be used as it is when it is obtained in a salt form at the time of production, or may be converted into a desired salt form. A part of the acid group may be a salt type, and a salt type dye and a free acid type dye may be mixed. Examples of such salt type are Na, Li, K
Alkali metal salts such as, ammonium salts optionally substituted with an alkyl group or a hydroxyalkyl group,
Alternatively, salts of organic amines can be used. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

In the structure of the dye used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and different from each other. Good. Specific examples of these dyes include, for example, Nos. Examples thereof include dyes having a structure shown in 1-30.

[0009]

[Chemical 2]

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11] The azo dye represented by the general formula {1} can be produced according to a method known per se. For example, No. (1)
The dye represented by can be produced by the following steps (A) to (E).

(A) A conventional method from 3-aminobenzoic acid and 2,5-diethoxyaniline [for example, Yutaka Hosoda, "New Dye Chemistry" (published by Gihodo on December 21, 1973) No. 396).
, Page 409], a monoazo compound is produced through a diazotization step and a coupling step.

(B) The obtained monoazo compound and 7-amino-1-hydroxy-naphthalene-3-sulfonic acid (γ
Acid) and a disazo compound through a coupling step according to a conventional method to produce a disazo compound. (C) A trisazo compound is produced from the obtained disazo compound and 2,5-diethoxyaniline by a conventional method through a diazotization and a coupling step. (D) The obtained trisazo compound is added to a cyanuric chloride suspension, and a condensation reaction is carried out at room temperature for several hours so as not to become alkaline. Then, the glycine solution is added at 50 to 60 ° C. to complete the condensation reaction for several hours to complete the reaction. (E) After cooling, salting out with 20% saline was performed to obtain the desired dye No. (1) is obtained.

The content of the dye of the general formula {1} in the recording liquid is preferably 0.5 to 5% by weight, more preferably 2 to 4% by weight, based on the total amount of the recording liquid. Examples of the solvent used in the present invention 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, and N. -Methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether,
It preferably contains ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane, 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 45 to 95% by weight with respect to the total amount of the recording liquid.
Used in the range of.

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.

[0023]

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, 1
Water was added to 3 parts by weight of the above dye, and the pH was adjusted to 9 with aqueous ammonia to adjust the total amount to 100 parts by weight. The composition was thoroughly mixed and dissolved, pressure-filtered 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, inkjet recording was performed on an electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an inkjet printer (trade name: HG-3000, manufactured by Epson Corp.) to obtain a high density black printed matter. The results of various evaluations by the methods (a), (b) and (c) are shown below.

(A) Light resistance of recorded image: A xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) was used to measure 100 on recording paper.
After irradiation for a long time, the discoloration after irradiation was small.

(B) Water resistance of recorded image: Water resistance test (1) Test method After the recorded image was immersed in tap water for 5 minutes, the bleeding of the image was visually examined. The OD value of the solid printed portion before and after the immersion was measured with a Macbeth densitometer (TR927).

(2) Test Results The above-mentioned result image had little bleeding. The change in the density of the solid printed portion before and after the immersion was represented by the OD residual rate by the following formula, and was 99.8%.

[Formula 1] OD residual rate = (OD value after immersion / OD value before immersion)
× 100 (%)

(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 1 month, the change was examined and no precipitation of insoluble matter was observed. .

Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, the above-mentioned No. Water was added to 25 parts by weight of the dye of No. 8 and the pH was adjusted to 9 with ammonia water so that the total amount was 100 parts by weight. This composition was treated by the method described in Example 1 to prepare a recording liquid. Printing was carried out in the same manner as in Example 1 using this recording liquid, and as a result, a high density black recorded material was obtained. Further, various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, good results were obtained as in the case of Example 1. The OD residual rate was 93.3%.

Example 3 10 parts by weight of diethylene glycol, 5 parts by weight of N-methylpyrrolidone, 3 parts by weight of isopropyl alcohol, the above-mentioned No. Water was added to 3 parts by weight of 16 dyes and the pH was adjusted to 9 with aqueous ammonia to adjust the total amount to 10
The recording liquid was prepared by treating the composition in an amount of 0 part by weight with the method described in Example 1. Printing was carried out in the same manner as in Example 1 using this recording liquid, and as a result, a high density black recorded material was obtained. Further, for this recorded matter, (a) to
Various evaluations according to (c) were performed. As a result, good results were obtained as in the case of Example 1. OD residual rate is 9
It was 8.4%.

[Examples 4 to 30] In Example 1, the above No. Instead of the dye of No. 1, 2-7, No.
9-15, No. A recording liquid was prepared and printing was carried out by the method of Example 1 except that the dyes of 17 to 30 were respectively used, and various evaluations according to (a) to (c) of Example 1 were performed on this recorded matter. It was As a result, as in Example 1, good results were obtained. In addition, dye No. The residual OD of the recording liquid using No. 2 was 92.8%, and the dye No. It was 98.7% in the recording liquid using No. 3.

[0032]

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.

Claims (1)

[Claims] 1. A recording liquid containing an aqueous medium and at least one dye selected from the dyes represented by the following general formula {1} in the form of a free acid. [Chemical 1] (In the formula, A and D each represent an optionally substituted phenyl group or naphthyl group, B, C, E and F each represent an optionally substituted phenylene group or naphthylene group, and R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted Represents a cycloalkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted heterocyclic group, and l and m each represent a number of 0 or 1.)