JP2000178463A - Recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a magenta-colored recording liquid showing a good printed character quality for an ink jet recording in the case of recording on an ordinary paper and also a high concentration of the recorded image, and excellent in light fastness by making the recording liquid contain an aqueous medium and a specific coloring matter. SOLUTION: This recording liquid is obtained by being made to contain (A) an aqueous medium (e.g.; ethylene glycol), (B) (i) one kind or two or more kinds of coloring matters of which free acid forms are expressed by formula I ring A, B are each a (substituted) phenyl; R1, R2 are each H or an organic group; X1, X2 are each Cl, OR3 [R3 is H, a (substituted) 1-8C alkyl, a (substituted) 2-3C alkenyl, a (substituted)aryl or the like]; Y is a (substituted) 2-18C alkylene} and (ii) 0.5-8 wt.% another coloring matter. As the component (i), e.g. as the free acid form, a coloring matter, etc., expressed by formula II [R4 to R9 are each a (substituted) 1-9C alkyl, a (substituted) 1-9C alkoxy, a halogen, H or the like] are preferably used.

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 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 acid dye are jetted from a fine ejection orifice to perform recording. Regarding this recording liquid, the P
Fast fixing to recording paper used for general office work, such as PC (plain paper copier) paper and fan hold paper (continuous paper such as a computer), and good print quality of prints, that is, printing is blurred. It is required that the outline is clear and the recording liquid is excellent in stability during storage, and thus the solvent that can be used 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. In particular, for magenta dyes conventionally used in recording liquids,
Since the recording material is mainly paper and has good water resistance, commercially available dyes (direct dyes) having a high affinity for cellulose, that is, high directivity, were used, but the color tone was unclear. On the contrary, the bright acid dye of the color tone is
It has been desired to develop a magenta dye having poor water resistance and satisfying both color tone and water resistance.

[0004] In particular, with respect to a magenta recording liquid, discoloration and fading of an image due to light irradiation, that is, light resistance has become a problem, and a recording liquid that satisfies many of these requirements at the same time has been demanded. For this reason, various proposals (for example, JP-A-61-101574, JP-A-61-101576) have been proposed.
JP-A-61-195176, JP-A-61-625
No. 62, JP-A-61-247771, JP-A-62-1
56168, JP-A-63-63765, JP-A-63-63765
Japanese Unexamined Patent Publications Nos. 295658 / 1995-123866, 1-240584, 2-161171, 3-122171, 3-203970, 4-153272, etc.) In particular, JP-A No. 62-246974 and JP-A-7-9021
No. 2, JP-A-9-216873, JP-A-10-176
129, JP-A-4-279671, JP-A-8-21
No. 8021, WO94 / 16021, GB230837
7, discloses a dimer type magenta dye,
The market has not been fully satisfied.

[0005]

SUMMARY OF THE INVENTION The present invention provides good print quality even when recorded on plain paper for ink jet recording, writing implements, etc., as well as high density of recorded images, light fastness, and water fastness. It is an object of the present invention to provide a magenta recording liquid which has excellent properties and color tone of a recorded image and has good stability when stored for a long period of time.

[0006]

Means for Solving the Problems The present inventors have previously described a dye having a structure in which two molecules of a monoazo dye having a triazinyl group are linked via a divalent organic bonding group. A dye which overcomes the above-mentioned disadvantages by selecting a substituent of a triazinyl group and the like has been proposed (Japanese Patent Laid-Open Publication No.
-218021). The present inventors have proposed such a dye,
Furthermore, it was found that by selecting a substituent of a linking group, a substituent of a triazinyl group and a substituent of a phenyl group at both ends, a magenta dye capable of satisfying overall performances such as color tone, light fastness and water fastness can be obtained. The present invention has been achieved. That is, the gist of the present invention resides in a recording liquid characterized by comprising an aqueous medium and at least one dye whose free acid type is selected from dyes represented by the following general formula (I).

[0007]

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In the above formula, rings A and B each independently represent a phenyl group which may further have a substituent;
R ₁ and R ₂ each independently represent a hydrogen atom or an organic group, and X ₁ and X ₂ each represent a group represented by —OR ₃ or a chlorine atom (R ₃ is a hydrogen atom, a carbon atom having 1 to 8 carbon atoms). Represents an alkyl group, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group or a nitrogen-containing heterocyclic group, and a group other than a hydrogen atom may further have a substituent.) Y represents a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms. ｝

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dye used in the recording liquid of the present invention has a free acid type represented by the general formula (I). The dye of the general formula (I) is such that the linking group Y is an alkylene group which may have a substituent, and the triazinyl group has specific substituents represented by X ₁ and X ₂ , respectively. It is characterized in that the benzene rings A and B each have a carboxyl group at the ortho position to the diazo group. Rings A and B may further have a substituent other than those shown in formula (I).

In the general formula (I), R ₁ and R ₂ represent a hydrogen atom or an organic group. As the organic group, an alkyl group,
Examples thereof include an alkenyl group and an aryl group, and these groups may be further substituted. As the organic group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl, t-
Butyl, 2-ethylhexyl group, hydroxyethyl, carboxymethyl and the like.

R₁, R_TwoIs a hydrogen atom or carbon number
1-4 alkyl groups are preferred. X ₁And X_TwoEach
Re-OR_ThreeRepresents a group represented by or a chlorine atom. R_Three
As a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to
8 alkyl groups (for example, methyl group, ethyl group, n-butyl group)
Butyl, n-octyl, ethylhexyl, isopro
Pill group, tert-butyl group, methoxyethyl group, cal
Boxylmethyl group etc.), substituted or unsubstituted carbon number 2
Or 3 alkenyl groups (for example, vinyl group, allyl group
Etc.), aryl groups (for example, phenyl group, tolyl group, 4
-Nitrophenyl group, 4-butylphenyl group, 4-cal
Boxyphenyl group), aralkyl group (eg, benzyl
Group, phenethyl group, etc.), cyclohexyl group, nitrogen-containing compound
Ring groups (eg, pyridyl group, morpholino group, etc.);
It is. X₁, X_TwoIs preferably -OR_ThreeIndicated by
And especially R_ThreeIs hydrogen atom, alkyl having 1 to 4 carbon atoms
And a phenyl group. Most preferred
Is R_ThreeIs a hydrogen atom.

Y is a substituted or unsubstituted C 2 -C 18
And specifically includes ethylene, propylene, neopentylene, 2-methyl-2-butylpentylene, 2,2-dimethyl-4-methylhexylene, 2-ethylhexylene, n-octaethylene and the like. 2 to 1 carbon atoms
And 8 straight-chain or branched alkylene groups.

Y is preferably an alkylene group having 2 to 12 carbon atoms, more preferably a linear alkylene group having 2 to 8 carbon atoms. Further, it is preferable that the sulfo groups to be substituted on the two naphthalene rings are independently located at the substitution positions shown in the following (a) or (b).

[0014]

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The dye of the general formula (I) preferably has a structure represented by the following general formula (II).

[0016]

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In the formula, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted carbon group. Number 1
To 9 alkoxy groups, halogen atoms, hydrogen atoms, hydroxyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted amino groups, nitro groups, sulfo groups, and sulfonate groups , A substituted sulfonyl group, a carboxyl group or a carboxylic acid ester group, R ₁ and R ₂ each independently represent a hydrogen atom or an organic group, and X ₁ and X ₂ represent —O
Represents a group represented by R ₃ or a chlorine atom. (R ₃ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group or a nitrogen-containing heterocyclic group; The group may further have a substituent.)
Y represents a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms. ｝

In the general formula (II), R ₄ , R ₅ , R ₆
And the substituents represented by R ₇ , R ₈ and R ₉ are each independently a C 1-9 alkyl group which may have a halogen atom, an amino group, etc.
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, trifluoromethyl group, dimethylaminomethyl group, etc.); the number of carbon atoms which may have a halogen atom as a substituent 1 to 9 alkoxy groups (for example, methoxy group, isopropoxy group, n-
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.); a hydrogen atom; a hydroxy group; a carbamoyl group which may have an alkyl group, an aryl group, or the like as a substituent ( For example, a carbamoyl group, an N, N-dimethylcarbamoyl group, a phenylcarbamoyl group, etc.); a sulfamoyl group which may have an alkyl group, an aryl group, or the like as a substituent (eg, a sulfamoyl group, an N-methylsulfamoyl group) ,
An N-ethylsulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, an N, N-dimethylsulfamoyl group, a p-carboxyphenylsulfamoyl group, etc.); an alkyl group, a carbamoyl group as a substituent, Amino group which may have an acyl group or the like (for example, amino group, N-methylamino group, carbamoylamino group, N, N-diethylamino group, acetylamino group, N-methyl-N-acetylamino group, etc.) Nitro group; sulfo group; sulfonic ester group (eg, phenoxysulfonyl group, etc.); substituted sulfonyl group (eg, hydroxyethylsulfonyl group, methylsulfonyl group, benzylsulfonyl group, etc.);
Carboxyl group or carboxylic ester group (for example,
Methoxycarbonyl group).

R _{4 to} R ₉ are preferably a hydrogen atom, a halogen atom, a nitro group, a sulfo group, an optionally substituted alkyl group, an amino group or a sulfamoyl group. Further, at least one of R _{4 to} R ₆ and / or R _{7 to} R ₉ is preferably a hydrogen atom. R ₁ , R ₂ ,
X ₁ and X ₂ are the same as those in the general formula (I).

In formula (I) or (II), the number of carboxyl groups in one molecule is preferably 3 or less from the viewpoint of water resistance of the dye. Among the dyes represented by the general formula (I), a water-soluble dye having a free acid type represented by the following general formula (III) is a novel dye.

[0021]

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In the above formula, rings A and B each independently represent a phenyl group which may further have a substituent;
R ₁ ′ and R ₂ ′ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms;
₁ , X ₂ represents a group represented by —OR ₃ or a chlorine atom (R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group,
Represents a cyclohexyl group or a nitrogen-containing heterocyclic group, and a group other than a hydrogen atom may further have a substituent. ). Y represents a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms. ｝

Among the dyes of the general formula (III), a novel water-soluble dye represented by the following general formula (IV) is more preferable.

[0024]

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In the above formula, R ₄₁ , R ₅₁ , R ₆₁ , R ₇₁ , R
₈₁ and R ₉₁ each independently represent a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 9 carbon atoms, a halogen atom, a hydrogen atom, a hydroxy group, a substituted or unsubstituted It represents a substituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfo group, a sulfonate group, a substituted sulfonyl group, a carboxyl group or a carboxylate group. R ₁₁ and R ₂₁ each independently represent a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms.
X ₁₁ and X ₂₁ each represent a group represented by —OR ₃₁ or a chlorine atom (R ₃₁ is a hydrogen atom, and has 1 to 8 carbon atoms).
Represents an alkyl group, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group or a nitrogen-containing heterocyclic group, and a group other than a hydrogen atom may further have a substituent. ). Y ₁ is a substituted or unsubstituted carbon number 2
Represents 18 alkylene groups. However, the number of carboxyl groups in one molecule is three or less. ｝

In the general formula (III), R ₁₁ , R ₂₁ , Y ₁ ,
X ₁₁ and X ₂₁ respectively correspond to R ₁ , R ₂ , Y, X ₁ and X ₂ in the general formula (I) or (II);
R ₄₁ , R ₅₁ , R ₆₁ , R ₇₁ , R ₈₁ and R ₉₁ are represented by the general formula (II)
Corresponds to R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ .

Further, among the dyes represented by the above general formulas (I) to (IV), the type of the free acid is formed through a linking group Y represented by the following general formula (V) to form a left-right symmetric structure. Dyes are preferably used. This dye is preferred in terms of color tone, water resistance and practicality.

[0028]

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(Wherein R ₁₂ , R ₄₂ , R ₅₁ , R ₆₂ , X ₁₂ and Y ₁ are respectively R ₁ ,
R ₄ , R ₅ , R ₆ , X ₁ and Y have the same definition). The dyes represented by the general formulas (I) to (V) used in the present invention may be used as they are in a free acid form, or may be used in a salt form. Further, a part of the free acid group may be a dye having a salt type structure, or a salt type dye and a free acid type dye may be used in combination. Examples of such salt types include salts of alkali metals such as Na, Li, and K, salts of ammonium which may be substituted with a lower alkyl group and a hydroxyalkyl group, and salts of organic amines. Examples of the organic amine include methylamine, diethylamine, lower alkylamine such as tripropylamine, hydroxy-substituted lower alkylamine,
Examples thereof include 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.

Specific examples of the dye used in the present invention include, for example, Dyes having the structures shown in (1) to (28) are mentioned, but the dye of the present invention is not limited to these.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The dye represented by formula (I) can be produced according to a method known per se. For example, N
o. The dye represented by (1) can be produced by the following steps (A) and (B). (A) diazotization of 2-aminobenzoic acid according to a conventional method
Coupling with -amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid) produces a monoazo compound. [See, for example, Yushin Hosoda, "New Dye Chemistry" (published by Gihodo on December 21, 1973), pages 396 to 409).

(B) The obtained monoazo compound is added to the cyanuric chloride suspension while maintaining the pH at 4 to 6 and the temperature at 0 to 5 ° C., and the reaction is carried out for several hours. Then, at room temperature, ethylenediamine is added at a 0.5 molar ratio with respect to the monoazo compound under mildly alkaline conditions to carry out a condensation reaction. Next, a 25% aqueous sodium hydroxide solution is added at 50 to 60 ° C. to carry out a hydrolysis reaction, followed by cooling and salting out with sodium chloride to obtain a target dye.

In the recording liquid of the present invention, all dyes containing at least one dye selected from the dyes represented by the general formula (I) as a colorant are added in a total amount of 0.5 to the total weight of the recording liquid. It is preferably contained in an amount of -8% by weight, particularly 2-5% by weight. The aqueous medium used in the present invention includes water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol (weight average molecular weight of about 190
-400), glycerin, N-methylpyrrolidone, N-
Contains ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropanol, etc. Is preferred. 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 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 pH of the recording liquid of the present invention is preferably 5 to 11, more preferably 6 to 11.
The storage stability of the recording liquid can be further improved by maintaining the recording liquid at 10.

[0045]

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 thereof. The dye Nos. No. of the above-mentioned exemplified dyes Means

Production Example 1 An aqueous solution of 13.7 g of 2-aminobenzoic acid was cooled to 5 ° C., and 7.25 g of sodium nitrite was added thereto and reacted under stirring to obtain a diazonium salt solution. Next, an aqueous solution of 31.9 g of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid was gradually added to the diazonium salt solution at 5 ° C. for coupling. Sodium chloride was added to the reaction solution for salting out, and the monoazo compound was taken out by filtration.

The whole amount of the obtained monoazo compound was redissolved in water and cooled to 5 ° C. Cyanuric chloride (14.7 g) was dissolved in acetone (150 ml), and the solution was added to the above monoazo dye aqueous solution while maintaining the pH at 4 to 6 and the temperature at 0 to 5 ° C., and reacted for several hours. Next, 2.4 g of ethylenediamine was added, and a condensation reaction was performed at a temperature of 40 ° C and a pH of 6 to 7 for 7 to 8 hours. Further, the temperature was raised to 60 ° C. and 25%
An aqueous solution of sodium hydroxide was added to adjust the pH to 13 to 1-2.
The hydrolysis reaction was performed for a time. After cooling to room temperature, salting out was performed with sodium chloride. Thus, the above-mentioned No. A dye having the structure 1 was obtained. This dye had a maximum absorption wavelength (λmax) in water of 512 nm. Similarly, the following dyes were synthesized and λmax was measured. The results are shown in Table 1.

[0048]

Table 1 Table 1 λmax. (nm) ───────────────────────── 2 518 3 510 4 513 5 506

Example 1 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, Dye (1) (maximum absorption wavelength λma
(x = 512 nm), water was added to 3 parts by weight, and the pH was adjusted to 9 with 5% by weight aqueous ammonia to make the total amount 100 parts by weight. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon (registered trademark) 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 (Xerox product) and a special coated paper: HR-101 (Canon product) were printed using an ink jet printer (BJC-610JW, product of Canon Inc.). Ink jet recording was performed to obtain a magenta printed matter having a clear color tone (saturation). Also, (a), (b), (c),
The evaluation methods (d) and (e) and the results of various evaluations are shown.

(A) Light fastness of recorded image: Using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.), 10
Irradiation was performed for 0 hours, but the discoloration after irradiation was small. (B) Water resistance of recorded image (only performed on electrophotographic paper): (1) Test method After immersing the recorded image in tap water for 5 minutes, the image was visually inspected for bleeding. OD value of solid printing part before and after immersion (optical
density value) with a Macbeth densitometer (trade name: TR9)
27, a product of Macbeth).

(2) Test Results The above results showed that the image was slightly blurred. The change in the density of the solid printed portion before and after the above immersion was 90.4% as indicated by the following equation in terms of the OD residual ratio.

[0053]

(Equation 1)

(C) Storage stability of recording solution: The recording solution was sealed in a Teflon (registered trademark) container, and stored at 5 ° C. and 60 ° C. for 1 hour.
Examination of the change after storage for a period of 5 months revealed no precipitation of insolubles. (D) Reliability of recording liquid Clogging property (adhesion recovery property) A predetermined ink was filled in the printer, left for 1 month in an environment of 35 ° C., and then a recovery operation (a suction operation by pumping) was performed. Later, when printing was performed, the printing state returned to a normal state. Stability of intermittent ejection After filling the printer with the specified ink and printing alphanumeric characters continuously for one minute, stop printing, leave it for one minute without a cap, etc., and then print it again. Scratch, chipping, etc. were not recognized from the first character.

(E) Migrating property of recorded image (performed only on specially coated paper) The printed matter was left for 1 hour in a 40 ° C., 90% RH tank, and the degree of bleeding of the character of the printed matter was visually determined. As a result, no bleeding of the character of the printed matter was recognized at all.

Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol,
The above No. Water was added to 2.5 parts by weight of the dye of (2), the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to make the total amount 100 parts by weight, and the composition was treated by the method described in Example 1 and recorded. A liquid was prepared. Using this recording liquid, printing was performed in the same manner as in Example 1, and as a result, a magenta color recorded matter having a clear color tone (saturation) was obtained. Various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. as a result,
As in Example 1, good results were obtained in each case. Also O
The D residual ratio was 94.2%.

Examples 3 and 4 The above-described No. 1 used in Example 1 was used. Instead of 3 parts by weight of the dye of (1), each of the above Nos. (3) and No.
A recording liquid was prepared and printed by the method of Example 1 except that the dye of (4) was used, and various evaluations of (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained. Also O
The D residual rates were 88.6% and 90.8%, respectively.

Example 5 The above No. 1 used in Example 1 was used. In place of 3 parts by weight of the dye of (1), No. 1 was used. The dye of (1) and No. (20)
A recording liquid was prepared and printed by the method of Example 1, except that 1.5 parts by weight of each of the dyes was mixed and used, and printing was performed. ) Were evaluated. As a result, similar to Example 1, good results were obtained. The residual OD ratio was 93.4.
%Met.

Examples 6 to 24 The above Nos. Used in Example 1 were used. In place of the dye of (1), (5) -No. (19),
No. (21) -No. A recording liquid was prepared and printed by the method of Example 1 except that the dye of (24) was used, and various evaluations of (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained. No. When the dye of (5) was used (Example 6), the OD residual ratio was 94.0%.

Comparative Example 1 The above No. 1 used in Example 1 was used. A recording liquid was prepared and printed by the method of Example 1 except that a dye having the following structure (A) was used in place of the dye of (1), and printing was performed. Various evaluations according to a) to (e) were performed.

[0061]

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Comparative Example 2 The above No. 1 used in Example 1 was used. Instead of the dye of (1), Example of International Publication WO94 / 16021
A recording solution was prepared and printed by the method of Example 1 except that the dye having the following structure (B) used in Example 2 was used, and printing was performed. Various evaluations according to (e) were performed.

[0063]

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Comparative Example 3 The above-mentioned No. 1 used in Example 1 was used. Example 1 was repeated except that, instead of the dye of (1), a dye having the following structure (C) in which Z of the compound described in Example 5 of JP-A-4-279671 was an OH group was used. A recording liquid was prepared by the method, printing was performed, and various evaluations of the recorded matter were performed according to (a) to (e) of Example 1.

[0065]

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Comparative Example 4 The above No. 1 used in Example 1 was used. A recording liquid was prepared by the method of Example 1, except that the dye of the following (D) used in Examples of JP-A-8-218021 was used instead of the dye of (1). Printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter.

[0067]

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Comparative Example 5 The above-described No. 1 used in Example 1 was used. No. 1 of JP-A-62-246974 is used instead of the dye of (1). Except for using the dye No. 9 (dye having the following structure (E)), a recording liquid was prepared and printed by the method of Example 1, and the recorded matter was subjected to printing in Examples 1 (a) to ( Various evaluations according to e) were performed.

[0069]

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Comparative Example 6 The above No. 1 used in Example 1 was used. Example 1 except that the following dye (F) used in Example 11 of GB2308377 was used instead of the dye (1).
The recording liquid was prepared by the method described above, printing was performed, and various evaluations were performed on the recorded matter according to (a) to (e) of Example 1.

[0071]

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Comparative Example 7 The above-described No. 1 used in Example 1 was used. A recording liquid was prepared by the method of Example 1 except that the dye of (G) used in Example 1 of JP-A-10-176129 was used instead of the dye of (1), and printing was performed. Then, various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter.

[0073]

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Comparative Example 8 The above-described No. 1 used in Example 1 was used. A recording solution was prepared and printed by the method of Example 1 except that a dye having the following structure (H) was used instead of the dye of (1), and the recorded matter was subjected to the printing of ( Various evaluations according to a) to (e) were performed.

[0075]

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Example 25 The above-described No. 1 used in Example 1 was used. In place of the dye of (1), A recording solution was prepared and printed by the method of Example 1 except that the dye of (25) was used, and various evaluations of (a) to (e) of Example 1 were performed on the recorded material. . As a result, good results were obtained in all cases as in Example 1. The OD residual ratio was 90.6%.

Example 26 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol,
The above No. Water was added to 2.5 parts by weight of the dye of (26), and the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to adjust the total amount to 100.
The composition was treated by the method described in Example 1 to prepare a recording solution. Using this recording liquid, printing was performed in the same manner as in Example 1, and as a result, a magenta color recorded matter having a clear color tone (saturation) was obtained. Various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. As a result, good results were obtained in all cases as in Example 1. The OD residual ratio was 87.5%.

Examples 27 and 28 The above-mentioned No. 1 used in Example 1 was used. Instead of 3 parts by weight of the dye of (1), each of the above Nos. (27) and No.
A recording liquid was prepared and printed by the method of Example 1 except that the dye of (28) was used, and various evaluations of (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained. Also O
The D residual rates were 93.2% and 91.5%, respectively.
The results of Examples 1 to 6 and Comparative Examples 1 to 8 are shown in Table 2 below. The results of Examples 25 to 28 are shown in Table 3 below.

[0079]

[Table 2]

[0080]

[Table 3]

In the above Tables 1 and 2, the evaluation of the color tone was as follows.
It is represented by the color saturation of the image, and is described in detail in CIE1976 (L ^*
a ^* b ^* ) Color difference meter using color system (trade name: SZ- # 8)
0, product of Nippon Denshoku Industries Co., Ltd.) to measure the color tone of the recorded image to determine the values of L ^* , a ^* , b ^* , and calculate according to the following formula,

[0082]

(Equation 2)

Regarding the electrophotographic paper, the value was 60 when the value was 60 or more, Δ when the value was 55 or more and less than 60, and X when the value was 55 or less. In the special coated paper, the value was 70 when the value was 70 or more, Δ when the value was 65 or more and less than 70, and X when the value was less than 65. Regarding the light fastness, は indicates that the discoloration is hardly observed visually, Δ indicates that the discoloration is slightly observed visually, and X indicates that the discoloration is remarkable and not at a practical level. Regarding the water-resistant bleeding, the symbol “滲” indicates that the bleeding was slightly observed from the state where almost no bleeding was visually observed, but the outline of the image was slightly blurred, and the density of the image was hardly reduced. However, the range of the bleeding is small, the decrease in the density of the image is small, and X is remarkable bleeding, the range of the bleeding is large, and it is difficult to identify the original image portion.
Indicates a state that is not at a practical level.

Regarding the storage stability, the recording solution was taken in a test tube and observed. ○ indicates a state where no insoluble component was observed, Δ indicates a state where a small amount of insoluble component was observed, and X indicates a condition where the insoluble component was conspicuous. , Indicating a state that is not at a practical level. Among the reliability of the recording liquid, the clogging property (fixation recovery property)
Represents a state of returning to a normal printing state within two recovery operations, Δ represents a state of returning to a normal printing state three to four times of the recovery operation, and X represents non-discharge or printing disorder even after five or more recovery operations. Indicates the state that will occur.

In the stability of the intermittent discharge, は indicates a state in which the first character is blurred and no chipping, Δ indicates a state in which the first character is partially blurred or chipped, and X indicates that the first character is completely blurred. Indicates that printing is not possible. Regarding the migration property of the recorded image, ○ indicates a state in which the characters of the printed matter are not squeezed at all, Δ indicates a state in which the characters of the printed matter are slightly squeezed, and X indicates a state in which the characters of the printed matter are squeezed.

[0086]

The recording liquid of the present invention is used for ink-jet recording and for writing utensils. When recorded on plain paper or special paper, a clear magenta-colored recorded matter can be obtained, and its print density can be improved. In addition to being excellent in light resistance, water resistance, and migration property in special paper, the recording liquid has good reliability and storage stability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H056 JA06 JB02 JD21 4J039 BA29 BC05 BC07 BC08 BC09 BC10 BC11 BC12 BC13 BC19 BC20 BC32 BC33 BC36 BC41 BC50 BC51 BC52 BC54 BC55 BC66 BC73 BC77 BC79 BE01 BE02 CA03 CA06 EA15 EA35 EA38 EA42 GA24

Claims (8)

[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 In the above formula, rings A and B each independently represent a phenyl group which may further have a substituent, and R ₁ and R ₂
Each independently represents a hydrogen atom or an organic group,
X ₁ and X ₂ represent a group represented by —OR ₃ or a chlorine atom (R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group,
Represents a cyclohexyl group or a nitrogen-containing heterocyclic group, and a group other than a hydrogen atom may further have a substituent. ). Y represents a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms. ｝ 2. The dye is a free acid type represented by the following general formula (II):
2. A dye selected from the group consisting of:
The recording solution described in the above. Embedded image (Wherein R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R
₉ is independently a substituted or unsubstituted carbon atom of 1
To 9 alkyl groups, substituted or unsubstituted 1 to 9 carbon atoms
Alkoxy, halogen, hydrogen, hydroxy, substituted or unsubstituted carbamoyl, substituted or unsubstituted sulfamoyl, substituted or unsubstituted amino, nitro, sulfo, sulfonate, substituted Represents a sulfonyl group, a carboxyl group or a carboxylic acid ester group. R ₁ , R ₂ , X ₁ , X ₂ and Y
Has the same meaning as in formula (I). ) 3. A general formula (I) or (II), R ₁
3. The recording liquid according to claim 1, wherein R ₂ and R ₂ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 4. The recording liquid according to claim 1, wherein the number of carboxyl groups in the general formula (I) or (II) is 3 or less. 5. The recording liquid according to claim 1, wherein in the general formula (I) or (II), Y is an alkylene group having 2 to 12 carbon atoms. 6. In the general formula (I) or (II),
_{2. The method according} to claim ₁ , wherein X ₁ and X ₂ are —OH groups.
6. The recording liquid according to any one of items 1 to 5, 7. A water-soluble dye having a free acid type represented by the following general formula (III). Embedded image In the above formula, rings A and B each independently represent a phenyl group which may further have a substituent, and R ₁ ′ and R ₁ ′
₂ 'each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ represent-
Represents a group represented by OR ₃ or a chlorine atom (R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group; And a group other than a hydrogen atom may further have a substituent.) Y represents a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms. ｝ 8. A water-soluble dye having a free acid type represented by the following general formula (IV). Embedded image 中 wherein R ₄₁ , R ₅₁ , R ₆₁ , R ₇₁ , R ₈₁ and R
₉₁ is independently substituted or unsubstituted carbon atom 1
To 9 alkyl groups, substituted or unsubstituted 1 to 9 carbon atoms
Alkoxy, halogen, hydrogen, hydroxy, substituted or unsubstituted carbamoyl, substituted or unsubstituted sulfamoyl, substituted or unsubstituted amino, nitro, sulfo, sulfonate, substituted Represents a sulfonyl group, a carboxyl group or a carboxylate group. R ₁₁ and R ₂₁ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, X _11, X ₂₁ represents a group or a chlorine atom represented by -OR ₃₁ (R ₃₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group or a nitrogen-containing heterocyclic group, and a group other than a hydrogen atom further has a substituent. May be included.) Y ₁ is a substituted or unsubstituted 2-1 carbon atom
And 8 represents an alkylene group. However, the number of carboxyl groups in one molecule is three or less. ｝