WO2000050515A1

WO2000050515A1 - Disazo dye, recording fluid containing the same, ink-jet recording fluid, and ink-jet recording method

Info

Publication number: WO2000050515A1
Application number: PCT/JP2000/001129
Authority: WO
Inventors: Wataru Shimizu; Masahiro Yamada
Original assignee: Mitsubishi Chemical Corporation
Priority date: 1999-02-25
Filing date: 2000-02-25
Publication date: 2000-08-31
Also published as: JP2000309721A; JP4004199B2

Abstract

A dye which, when used especially in ink-jet recording, can give high-quality prints in black excellent in printed-image density, light resistance, and water resistance. The dye has a free acid form represented by general formula (1). (In the formula, X represents carboxyl, sulfo, or hydrogen; l and m each is 0 or 1, provided that l+m is 1; q is 0 or 1; and Z represents hydrogen or phenyl optionally substituted by carboxyl or sulfo, provided that when q is 0, Z represents phenyl optionally substituted by carboxyl or sulfo.)

Description

Description Disazo dye, recording liquid using the same, recording liquid for ink jet, and ink jet recording method

TECHNICAL FIELD The present invention relates to a disazo dye and a recording liquid containing the same. Specifically, the present invention relates to a black dye suitable for ink jet recording.

Background art

A so-called ink jet recording method has been put to practical use, in which droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acidic dye are ejected from a minute ejection orifice to perform recording. Regarding the recording liquid used for this purpose, in addition to the fact that stable ejection is possible for a long time, PPC (plain paper copy) paper such as electrophotographic paper, fan-hold paper (continuous paper such as a computer, etc.) It is required that the fixation to the general-purpose record i) be fast and the print quality of the printed matter be good, that is, that the print be free from bleeding and have an outline. Since the stability during storage as a liquid must be excellent, the solvents that can be used for the recording liquid are significantly limited.

On the other hand, dyes for recording liquids have sufficient solubility in the above limited solvents and are stable even when stored as recording liquids for a long time. It is required that the density of the image be high, and that the image be excellent in water resistance and luminosity, but it has been difficult to simultaneously satisfy many of these requirements. Furthermore, recent ink jet recording liquids are required to have a drastically improved suitability for high-speed printing as compared with conventional ink jet recording liquids. In order to enable high-speed printing, the surface tension of the recording liquid is adjusted to a low level by adding an organic solvent, especially a surfactant, to the recording liquid to increase the penetration rate of the recording liquid into the paper. Some measures have been taken to reduce the blurring of printed images due to friction between recording papers. This type of recording liquid is called a high-penetration ink or a quick-drying ink.

However, in the case of a quick-drying ink, the dye in the recording liquid quickly permeates during printing, and quickly moves into the recording paper together with the recording liquid, so that a sufficient amount of the dye cannot be present near the surface of the paper. However, there is a drawback that is reduced. This phenomenon is remarkable on so-called plain paper such as copy paper, PPC paper, and fan paper that are widely used for general office work. That is, a black image printed on ordinary paper is required to have a print density (OD value) of 1.3 to 1.4 or more, whereas a commercially available quick-drying ink has a print density of 1.1. There is a problem that only ~ 2 can be obtained.

On the other hand, recent ink jet recording is also required to have a significantly improved suitability for photographic image printing as compared to the conventional ink jet recording. For this reason, special coated paper and special glossy paper, which embody high-definition and clear images, are used. However, on such recording media, which is generally referred to as photo glossy paper for ink jet printing, etc., silicon oxide, aluminum oxide, or polyamide is added to form high-definition and clear images. The action of water-proofing agents typified by water-soluble agents tends to accelerate the decomposition of dyes by light, and as a result, when a photographic image printed matter by an ink jet is displayed indoors or outdoors, the image can be easily displayed. Discoloration is a problem.

The light fastness of an image is measured by measuring the degree of image discoloration before and after the light degradation acceleration test, for example, when illuminated with xenon arc light, using a color difference meter to calculate the discoloration value (ΔΕ value). And discussed. In order to impart sufficient light resistance to photographic images formed on specialty paper by ink jet printing, for example, a Δ 数値 value before or after irradiation with xenon arc light for 80 hours, a value around 10 or less is given A black image is required. However, commercially available quick-drying inks generally give a discoloration of about 20 times, which is about twice the target.

In general, a disazo dye is a compound in which three aromatic ring components are combined and linked by two azo groups, and each of the aromatic ring components constituting the dye of the present invention is also a disazo dye. , Japanese Patent Application Laid-Open No. Hei 4-304024, Japanese Patent Application Laid-Open No. Hei 366/179, Japanese Patent Laid-Open No. Hei 5-292698, or Japanese Patent Laid-open No. Hei 6-220 / 377 It is known as a component of the compound described in each gazette. For example, JP-A-6-220377 discloses a dye in which two aromatic ring components corresponding to the benzene ring A and the naphthalene ring of the present application are the same. It does not disclose that it contains a methoxy group as a substituent on ring B. On the other hand, Japanese Unexamined Patent Publication No. 5-262988 discloses two aromatic rings in that the benzene ring B has two methoxy groups in agreement with the benzene ring A component of the present application. A dye having a component identical to that of the present application is disclosed, but is different from the dye of the general formula (1) because the substituent of the naphthalene ring component is an amino group. As described above, among the three aromatic components constituting the pigment of the general formula (1) of the present invention, an example in which two aromatic ring components are combined is disclosed. The dye of the present invention combined as a specific aromatic ring component was not known.

In these known documents, dyes that can satisfy the requirements of the market, which is complicated and sophisticated as described above, and that can be easily manufactured, have not been realized.

INDUSTRIAL APPLICABILITY The present invention has a high density of recorded images when recorded on plain paper for ink-jet recording and writing implements, and has good print quality and robustness. Provides a recording solution and a dye suitable for recording that has good light-fastness and that can record with sufficient light resistance even when recorded on glossy paper, and has good stability when stored for a long time. It is intended to do so.

Disclosure of the invention

The present inventors have repeatedly studied and found a black dye having a specific structure having a performance satisfying the above object as a recording liquid component, and have achieved the present invention. That is, the gist of the present invention is to provide a disazo dye whose free acid form is represented by the following general formula (1), a recording solution containing such a dye and an aqueous medium, a recording solution for an ink jet using the same, and It is in the ink jet recording method.

(1)

(In the formula, X represents a carboxyl group, a sulfo group or a hydrogen atom, 1 and m each represent 0 or 1, and l + m == l. Q represents 0 or 1, and Z represents a hydrogen atom Or a phenyl group which may be substituted with a carboxyl group or a sulfo group, provided that when q is 0, Z is a phenyl group which may be substituted with a carboxyl group or a sulfo group. Represents a group.)

As described above, among the three aromatic components constituting the dye of the general formula (1) of the present invention, an example in which up to two aromatic ring components are combined is disclosed. Until now, the dye of the present invention combined as a specific aromatic ring component has not been known. The present inventors have limited the three aromatic ring components to specific groups among these known aromatic ring components, and furthermore, optimized the combination of these three aromatic ring components. The specific disazo dye obtained gives a recorded image of sufficient density even on plain paper, even if it is applied in the form of a highly permeable ink (quick drying ink). In response to the market demand for ink jet recording described above, which is compatible with providing a recorded image having sufficient light fastness even if the recording liquid has been improved, the recording liquid and the The best mode for carrying out the invention, which led to the discovery that the dye used could be obtained, and led to the present invention

Hereinafter, the present invention will be described in detail. The dye of the present invention is a dye represented by the above general formula (1), which is different from similar dyes in that two methoxy groups are substituted on the benzene ring B.

In the general formula (1), it is preferable that X is a hydrogen atom, and that m is 1. Z is more preferably a hydrogen atom or a phenyl group having a carboxyl group or a sulfo group as a substituent, and the number of the substituents is preferably 1 or 2, particularly preferably 1.

When q is 0, it is preferable that Z is a fuunyl group substituted with a hydroxyl group as a substituent. When q is 1, Z is preferably a hydrogen atom.

The dye of the general formula (1) has one hydroxyl group or more preferably one amino group on the benzene ring A, and the substitution position is preferably the p-position with respect to the azo group. New The carboxyl group to be substituted on the benzene ring A is preferably substituted at the m-position with respect to the azo group.

The dye of the present invention is suitable as a dye for a black recording liquid. Further, the dye of the present invention is particularly suitable as a recording solution for ink jet, and is particularly suitable for ink jet recording. By applying this method to recording methods, recording with high print density and excellent print quality becomes possible.

When the dye of the present invention is applied to a recording liquid, it may be used as it is in the form of a free acid represented by a single-part formula (1), but some or all of the acid groups are converted to a desired salt form. You may use it. One or more selected from the group consisting of alkali metal ions such as lithium, sodium, and potassium, ammonium ion, and substituted amines may be used as the ion forming a salt. Is used. Specific examples of substituted amines include mono-, di-, and tri-substituted alkyl groups in which the substituent is an alkyl group having 1 to 4 carbon atoms and a hydroxyalkyl group having 1 to 4 carbon atoms. Min. Further, different kinds of counter ions may be used in combination.

The mechanism by which such a high function can be exhibited in the present invention is not clear, but two sulfone groups are introduced into the naphthyl group in the general formula (1), or an anion is formed on the amino group on the naphthyl group. By introducing a phenyl group which can be substituted with a functional group, the hydroxyl group or amino group introduced into the fuunyl group represented by A in the general formula (1) and the sulfonic group on the naphthalene ring of the same formula It is believed that the interaction becomes stronger, and that the dye molecules interact with each other while suppressing dye migration into the paper and improving print density. Further, by substituting the phenyl group represented by B in the general formula (1) with two methoxy groups, the light absorption wavelength of the dye is adjusted to a range suitable for a black dye, and the blackness of the image is improved. It has been improved favorably, and the appropriate bulkiness of the two methoxy groups has resulted in an appropriate adjustment of the state of aggregation of the dye after being applied on specialty paper, resulting in excellent light fastness. it is conceivable that.

Specific examples of the dye of the present invention and the maximum absorption wavelength thereof are shown in Table 1 below. The dye of the present invention is not limited to these. Table

Table 1 1 (continued)

(Continued)

The disazo dye represented by the general formula (1) can be prepared by a method known per se [for example, Yutaka Hosoda, “Shinsenka Kagaku” (published by Gihodo on February 21st, Showa 48) [See page 9]], followed by a diazotization and coupling step. For example, a dye with m force of 1 and 1 of 0 diazotizes nitroalanine having a substituent X and a sulfoxyl group, and after coupling with 2,5-dimethoxyaniline, the product is diazotized. It is obtained by coupling with a naphthol derivative and further reducing the nitro group of the obtained disazo compound.

The recording liquid of the present invention contains an aqueous medium and at least one 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 calculated based on the total amount of the recording liquid. 0.5 to 10% by weight, especially 1 to 3% by weight. / ₀ is preferred.

Solvents used for the recording liquid include water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol (# 200), polyethylene glycol (# 400), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiojetanol, dimethylsulfoxide, ethylene It preferably contains glycol monoaryl ether, ethylene glycol monomethyl ether, methylen glycol monomethyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropanol, and the like. These water-soluble organic solvents are usually used in an amount 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.

Recording liquid of the present invention, the 0.1 to 1 0% by weight based on the total amount of urea favored properly 2-8 weight ^_0/0, Chio urea, Biu Re' bets, adding a compound selected from semi Karubaji de In addition, by adding a surfactant in an amount of 0.001 to 5.0 weight by 96, the quick drying property after printing and the printing quality can be further improved.

As the surfactant, a nonionic surfactant is preferred, but a polymer-based or a nonionic surfactant can also be used.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan. Fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, poly Oxyethylene alkylamines and the like.

Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, and alkyl diphenyl tersulfonates. Acid salts, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, alkanesulfonates, formalin naphthalene sulfonate, poly Oxyethylene alkyl phosphates, α-amino sulfonic acid salts and the like.

Polymer surfactants include polyacrylic acid, styrene-noacrylic acid copolymer, styrene / polyacrylic acid-noacrylate ester copolymer. Styrene / maleic acid copolymer, styrene-maleic acid / α Ester copolymer of acrylate, styrene / methacrylic acid copolymer, styrene / methacrylic acid / noacrylate ester copolymer, styrene / maleic acid half ester copolymer, styrene / styrene sulfo Acid copolymer, vinyl naphthalene maleic acid copolymer, vinyl naphthalene diacrylic acid copolymer or salts thereof.

The recording liquid of the present invention is used for writing utensils or ink jet recording, and is particularly suitable as a recording liquid for ink jet. When recorded on plain paper, black-colored recordings can be obtained, and the print density and robustness are excellent, and the light resistance on glossy paper or glossy film used for photographs, etc. is also excellent. The storage stability as a recording liquid is also good.

Among ink jet recording liquids, a sufficient recording density can be achieved when used as a highly permeable ink (quick drying ink), but such a highly permeable ink is generally a surfactant. Is added to the ink to increase the penetration rate into the paper. The surface tension is as low as 4 OmN / m or less. According to the present invention, the surface tension is 40 mN / m or less. It is preferably used as a recording liquid for an ink jet, and the surface tension is preferably 30 mN / m or less. Hereinafter force ⁵ will be described in more detail the present invention embodiment ', the present invention is not limited to the embodiments thereof and the like as long as not exceeding the gist thereof.

The dye No. in the examples corresponds to the dye No. in Table 11 above. “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, and the pH was adjusted to 9 by adding a 25% aqueous sodium hydroxide solution. Sodium nitrite was added and dissolved. The above-mentioned solution was added to 600 parts of water to which 1 part of 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 were added to obtain a diazo solution of 2-nitro-5-aminobenzoic acid.

Separately, 38 parts of 2,5-dimethoxyaniline were suspended in 270 parts of water, 26 parts of 35% hydrochloric acid was added, and the temperature was raised to 60 to obtain a uniform solution. The solution was cooled, and the above-mentioned diazo solution of 2-2-tro-5-aminobenzoic acid was added, and the resulting solid was collected by filtration. This was suspended in 240 parts of water, and the pH was adjusted to 12 with a 25% aqueous solution of sodium hydroxide to obtain a uniform monoazo compound solution.

33 parts of sodium nitrite was added to and dissolved in this monoazo compound solution, and the resulting mixture was added dropwise to 150 parts of water containing 35 parts of hydrochloric acid at 0 to 5 ° C. to give the monoazo compound. Was diazotized. Further, 13 parts of sulfamic acid was added to obtain a diazo solution of a monoazo compound.

69 parts of RR acid were suspended in 150 parts of water, and the pH was adjusted to 9 with caustic soda to obtain a uniform solution. The solution is cooled and the above-mentioned 00/01129

13 A diazo solution of a noazo compound was added dropwise to allow coupling. During the dropping, the pH of the coupling bath was adjusted to 9 to 10 using a 25% aqueous solution of soda. To the obtained disazo compound solution was added 22 parts of sodium hydrogen sulfide, and the temperature was raised to 50 to 55 ° C to reduce the nitro group. After cooling the solution to 25, the solution was cooled to 25. 0 parts of sodium chloride was added, and the solid content was collected by filtration. The obtained wet cake was dissolved in 3500 parts of water, a 35% hydrochloric acid aqueous solution was added, and acid precipitation was performed at pH Hl. The resulting solid was filtered. The obtained dye was dried to obtain 100 parts of No. 1 dye in Table 1 in the form of free acid.

The maximum absorption wavelength of the obtained dye was 607 nm. (Solvent is water, ion is lithium ion).

Similarly, dyes of No. 2 to No. 13 shown in Table 11 were obtained. Example 1

Diethylene glycol monobutyl ether 10 parts, glycerin 10 parts, 2-pyrrolidone 5 parts, Olfine STG (nonionic surfactant, manufactured by Nissin Chemical Co., Ltd.) 0.5 part, the above table Water was added to 3 parts of the No. 1 dye (free acid form, the same applies hereinafter) of —1, and the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to make the total amount 100 parts. This composition was sufficiently mixed and dissolved, filtered under pressure through a teflon filter having a pore size of 1 m, and then degassed with a vacuum pump and an ultrasonic washing machine to prepare a recording solution. The obtained recording liquid has a surface tension of 28 mN / ra

Using the obtained recording liquid, an inkjet printer (trade name: MJ-8110C, manufactured by Seiko Epson Corporation) was used to form electrophotographic paper (plain paper, manufactured by Fuji Xerox Co., Ltd.). Ink jet recording was performed on photo glossy paper for ink jet (MJA 4SP3 paper, manufactured by Seiko Epson Corporation) to obtain a high density black print. When the print density on plain paper was measured with a Gretag Macbeth RD 918 (manufactured by Macbeth), a good value of 1.35 was obtained with a 0D value.

Further, various evaluations were made by the following methods (a), (b) and (c).

(a) Lightfastness of recorded images: A Xenon Fed meter (Atlas Co., Ltd.) prints recorded images on photo glossy paper for ink jet (MJA 4 SP3 paper, manufactured by Seiko Epson Corporation). ) For 80 hours, and the degree of discoloration before and after that was measured with a color difference meter Sigma 80 manufactured by Nippon Denshoku Co., Ltd., and quantified in the form of ΔΕ value. Here, the ΔΕ value is a numerical value indicating the degree of discoloration and fading. A larger value indicates a larger degree of discoloration and fading, that is, the light fastness of the image is low.

As a result of the test, the lightfastness of this dye on photo glossy paper for ink jets was as good as 10.2, and the degree of light discoloration and fading was about half that of the conventional dye. Could be suppressed. (See Table 1)

(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 surface image was slight, and the decrease in density was small.

(c) Storage stability of recording solution: When the recording solution was sealed in a Teflon container and stored at 5 and 60 for 1 month, no precipitation of insoluble matter was observed. Example 2

Example 1 was repeated except that the dye of Table 1 No. 1 used in Example 1 was replaced with ammonia water as the dye of Table 1 No. 0.2 and the neutralizing agent, respectively. A recording liquid was prepared by the method, printing was performed, and various evaluations of the above (a) to (c) were performed on the recorded matter in the same manner as in Example 1. The surface tension of the obtained recording liquid was 28 mN / m.

As a result, good results were obtained in all cases as in Example 1. (See Table 1) Example 3

The method of Example 1 except that the dye of Table 1 IN 0.3 used in Example 1 was replaced by the dye of Table 1 N0.3 and ammonium hydroxide as a neutralizing agent, respectively. A recording liquid was prepared by the method described above, and printing was performed. Various evaluations of the above (a) to (c) were performed on the recorded matter in the same manner as in Example 1. The surface tension of the obtained recording liquid was 28 mN / m.

As a result, good results were obtained in all cases as in Example 1. (See Table 1) Comparative Example 1

In place of the dye of Table 1 No. 1 used in Example 1, a dye denoted by a in Table 2 (a dye included in the claims of JP-A-6-220377) A recording liquid was prepared and printed by the method of Example 1, except that ammonia water was used as the neutralizing agent, and the neutralizing agent was used. a) to (c) were evaluated. The surface tension of the obtained recording liquid was 28ιηΝ / πι.

Although the print density of the obtained printed matter was almost good on plain paper, the light fastness on photo glossy paper was insufficient. (See Table 1 2) Comparative Example 2

Example 1 was repeated except that, in place of the dyes in Table 1 used in Example 1 and Table 1-1, 0.1, the dye indicated by b in Table 1 and ammonia water as a neutralizing agent were used. A recording solution was prepared by the method. Printing was performed using this, and various evaluations of the above (a) to (c) were performed on this recorded material in the same manner as in Example 1. The surface tension of the obtained recording liquid was 28 mN / m.

However, the print density on plain paper was remarkably low, and the light fastness was insufficient. (See Table 2) Comparative Example 3

A recording solution was prepared in the same manner as in Example 1 except that the dye indicated by c in Table 1 was used instead of the dye of Table 1 No. 1 used in Example 1. Printing was performed using this, and various evaluations of the above (a) to (c) were performed on this recorded material as in Example 1. The surface tension of the obtained recording liquid was 28 mN / m.

However, both print density on plain paper and light fastness on photo glossy paper were insufficient. (See Table 2) Comparative Example 4

Dye denoted by d in Table 2 in place of the dye of Table 1 N 0.1 used in Example 1 (dye of Example 12 in JP-A-6-220377) A recording liquid was prepared and printed according to the method of Example 1, except that was used, and the recorded materials were subjected to the above evaluations (a) to (c) in the same manner as in Example 1. Was. The surface tension of the obtained recording liquid was 28 mN / ra. As a result, the light fastness on the photo glossy paper was very good, but the print density on plain paper was insufficient. (See Table 1) Comparative Example 5

Instead of the dye of Table 1 1N 0.1 used in Example 1, the dye denoted by e in Table 1 (the dye of Example A of JP-A-4-304274) was used. A recording solution was prepared and printed by the method of Example 1 except that the recording material was used, and various evaluations of the above (a) to (c) were performed on the recorded matter as in Example 1. The surface tension of the obtained recording liquid was 28 mN / ra. As a result, the light fastness on the photo glossy paper was almost good, but the print density on plain paper was insufficient. (See Table 2) PT / JP00 / 01129

17 As is evident from the results described in Table 12, according to the present invention, particularly when the ink is highly permeable, the recording density on plain paper is as high as 1.3 or more. In addition, the light fastness and the ΔΕ value are as excellent as about 10, enabling extremely high-quality black recording. Example 4

10 parts of diethylene glycol, 3 parts of isopropyl alcohol, 1 part of surfanol (low molecular weight non-ionic surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) Water was added to 3 parts of the dye (free acid form, the same applies hereinafter) of 4, and the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to make the total amount 100 parts, thereby preparing a recording solution. The surface tension of the obtained recording liquid was 3 OmN / m. This recording liquid was treated in the same manner as in Example 1. Ink jet recording and evaluation were performed in the same manner as in Example 1 to obtain a high-density black recorded matter. Further, various evaluations were made by the methods (a), (b) and (c). The results were all good,

Table 1 2 (continued)

Example 5

Water was added to 5 parts of glycerin, 10 parts of ethylene glycol, and 2.5 parts of the dye of 1N0.5 in Table 1 above, and the pH was adjusted to 9 with ammonia water to make the total amount 100 parts. This composition was treated by the method described in Example 1 to prepare a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1, and as a result, a high-concentration black recorded matter was obtained. Also, for this recorded matter, (a) to

Various evaluations according to (c) were performed. As a result, as in Example 1, good results were obtained in all cases. Example 6

Water was added to 10 parts of diethylene glycol, 5 parts of N-methylpyrrolidone, 3 parts of isopropyl alcohol, and 3 parts of the dye of 10.3 in Table 1 above. The pH was adjusted to 9 with Ny water to make the total amount 100 parts, and this 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 high-density black recorded matter was obtained. Various evaluations according to (a) to (c) of Example 1 were performed on this recorded matter. As a result, as in Example 1, good results were obtained in all cases. Examples 7 to 13

Instead of the dye of Table 1 1N 0.1 used in Example 1, the dye of Table 1 No. 7 to No. 13 and a neutralizing agent which gives a counter ion shown in the same table A recording solution was prepared and printed by the method of Example 1 except that each was used, and 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.

Industrial applicability

The recording liquid of the present invention is used for ink jet recording and for writing implements. When recorded on plain paper, a black recording can be obtained, and its print density, light resistance, and water resistance can be obtained. In addition to excellent storage stability, the storage stability as a recording liquid is also good.

Claims

21 Claims A disazo dye, wherein the form of the free acid is represented by the following general formula (1).

(In the formula, X represents a carboxyl group, a sulfo group or a hydrogen atom, 1 and m each represent 0 or 1, and 1 + m = 1. Q represents 0 or 1, and Z represents Represents a hydrogen atom or a phenyl group which may be substituted with a carbonyl group or a sulfo group, provided that when q is 0, Z is substituted with a carbonyl group or a sulfo group; The disazo dye according to claim 1, wherein m is 1 in the formula (1). 3. The disazo color according to claim 1, wherein in the general formula (1), Z is a phenyl group substituted with a carboxyl group.

14. The disazo dye according to claim 13, wherein in the general formula (1), q is 0. 3. The disazo dye according to claim 1, wherein in the general formula (1), q is 1 and Z is a hydrogen atom. A recording liquid comprising an aqueous medium and the disazo dye according to claim 1. A recording liquid for an injection, comprising the recording liquid according to claim 6. The recording liquid for ink jet according to claim 7, wherein the surface tension of the recording liquid for ink jet is 4 OraN / m or less. An ink jet recording method comprising using the ink jet recording liquid according to claim 7.