JPH09124965A - Disazo dye composition and water-base black ink composition containing the same - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a dye composition having high-quality images even on plain paper, rapid ink fixing properties, and the like. SOLUTION: In a dye composition containing at least a disazo dye represented by the following formula I and a disazo dye represented by the following formula II, when the dye composition is analyzed by liquid chromatography, the disazo dye represented by the formula I Of the disazo dye represented by the formula II and the area ratio Sp: Sc of 1: 0.4 to 1:
2. A disazo dye composition which is 2.4. Embedded image Embedded image (In the formula, X and Y represent an alkoxy group having 1 to 4 carbon atoms, and M represents a cation selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, piperidinium, etc.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a disazo dye composition, a black aqueous ink composition containing the same, and an ink jet recording method using the same.

[0002]

2. Description of the Related Art Ink used in an ink jet recording system is generally one in which various dyes are dissolved in water, an organic solvent, or a mixed solution thereof, but it has various characteristics such as a fountain pen and a ballpoint pen. More stringent conditions are required as compared with various writing inks.

More recent trends include high-quality images (high optical density and clear images without bleed), high-speed printing, and water resistance and light resistance of printed matter for output from an inkjet printer. Demand is high.

Therefore, in order to realize high-speed printing, quick fixing of the ink is required, and therefore, attempts have been made to improve the permeability of the ink into the recording medium. For example, JP-A-4-183761, JP-A-5,156,675, and US-A-5,183,50.
No. 2 and the like disclose addition of diethylene glycol monobutyl ether, addition of both glycol ethers and a nonionic acetylene glycol surfactant.

However, these penetrating inks are especially used for plain paper (office, school,
Copy paper, report paper, pound paper, used at home,
It is difficult to obtain a clear image because the ink penetrates into the paper, resulting in poor color development and high optical density. If the dye concentration is increased to solve this problem, reliability such as clogging occurs, and therefore the dye used in the penetrating ink is required to have extremely high solubility.

On the other hand, due to the demand for water resistance of printed matter, Japanese Patent Publication No. 5-30956 discloses a dye having a phosphoric acid group, JP-A-3-91577, and JP-A-5-26.
In 2998 and the like, there are many proposals for an ink having good water resistance, such as an aqueous ink containing a disazo dye having a carboxylic acid group.

However, although these inks are excellent in water resistance, when recorded on acidic paper having a pH of the paper surface in an acidic range, an image becomes brownish and the image density is low,
High-quality images cannot be obtained. In addition, since the solubility of the dye in the liquid medium is insufficient, there is a problem that clogging is likely to occur at a fine ejection port of an inkjet head, which is not suitable for a penetrating ink.

In addition, various proposals have been made for ink compositions having excellent water resistance using existing dyes and novel structural dyes, but none have been satisfied with sufficient water resistance and high quality images. I can't see it.

[0009]

The present invention provides a high-quality image (a high optical density and a clear image without bleeding), quick ink fixing, and water resistance and light resistance of printed matter even on plain paper. An object is to provide a dye composition and an ink composition.

[0010]

Means for Solving the Problems Accordingly, the present inventors have:
Of the known black disazo dyes, two types of water-soluble dyes having a similar structure and having excellent properties are selected, and these dyes are blended at a fixed ratio or directly synthesized as a dye composition. It has been found that by using as a recording material for ink, both the high quality image and the water resistance can be achieved.

That is, the present invention provides a dye composition containing at least a disazo dye represented by the following formula I and a disazo dye represented by the following formula II, when the dye composition is analyzed by liquid chromatography. Area ratio of the peak area (Sp) of the disazo dye represented by the formula to the peak area of the disazo dye represented by the formula II (Sc) Sp: Sc
Is 1: 0.4 to 1: 2.4, preferably 1: 0.6 to 1:
A disazo dye composition characterized by being 1.5 and an ink composition using the same.

[0012]

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[0013]

Embedded image (In the formula, X and Y represent an alkoxy group having 1 to 4 carbon atoms, and M represents a cation selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, piperidinium, etc.)

Formula I and Formula II used in the present invention
Examples of the alkoxy group having 1 to 4 carbon atoms represented by X and Y in the dye represented by are methoxy group, ethoxy group, propoxy group and butoxy group. The alkoxy groups X and Y may be the same or different.

M is selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, piperidinium and the like.

Specific examples include the following. Formula I above includes, but is not limited to, the following dyes of formula I, which may be of any type:

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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Formula II above includes, but is not limited to, the dyes of Formula II of any type.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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When M is hydrogen, the water-soluble acid group is a free acid in the form of a phosphoric acid group (PO ₃ H ₂ ), a carboxylic acid group (COOH),
A sulfonic acid group (SO ₃ H) is shown. M is an alkali metal, N
Alkali metal salts of H ₄ , alkyl-substituted ammonium, alkanolammonium, or cations of nitrogen-containing cyclic compounds such as morpholinium and piperidinium,
An ammonium salt, an alkyl-substituted ammonium salt, an alkanolamine salt, a morpholinium salt, a piperidinium salt, etc. are formed and dissolved in water. In general, this type of acid dye is soluble in an aqueous medium mainly composed of water having a basic pH. At this time, M may be one kind or different.

Further, the present inventors have found that the water resistance on paper is M
Have been found to be particularly excellent when they form NH ₄ , alkyl-substituted ammonium, alkanolammonium, or volatile alkali salts such as morpholinium and piperidinium. Examples of amines used to form such salts include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine,
Alkyl-substituted amines such as isobutylamine, sec-butylamine, tert-butylamine, dibutylamine, allylamine, alkanolamines such as ethanolamine, diethanolamine, triethanolamine, propanolamine, diethylethanolamine, morpholine, piperidine. Included are nitrogen cyclic compounds and mixtures thereof. However, the dye of the present invention does not need to be completely an ammonium salt, an alkyl-substituted ammonium salt, an alkanolamine salt, a morpholinium salt, or a piperidinium salt, and may be a mixture with an alkali metal salt. In that case, the ratio of the alkali metal salt to the entire dye is preferably 50% or less.

The disazo dye represented by the above formula I is a disazo dye having a phosphoric acid group which is included in the dye group disclosed in JP-B-5-80956. In the synthesis of this dye, m-aminobenzenephosphonic acid is diazotized by a conventional method and coupled with a 2,5-dialkoxy-substituted aniline having 1 to 4 carbon atoms to produce a monoazo compound having an amino group. This is isolated or subsequently subjected to diazotization by a conventional method and coupled with γ-acid (2-amino-8-naphthol-6-sulfonic acid) to easily obtain it in high yield and high purity.

Further, since the dye represented by the formula I has a phosphoric acid group in the dye structure, it has good dyeability to cellulose fibers such as paper and excellent water resistance. Moreover, since it has a water-soluble acid group such as a sulfonic acid group at the same time, it has excellent solubility in an aqueous liquid medium. Solubility in water depends on the pH of the water solvent, but it is pH 7.5 to 11, preferably pH.
It shows good solubility at H 8.5 to 10 and becomes poorly soluble at acidic pH.

However, using only this disazo dye,
When the ink for inkjet recording is prepared, the optical density of the image is insufficient, and in order to increase the optical density,
There is also a problem with respect to the dissolution stability of the dye, such that increasing the dye concentration causes a problem in reliability such as clogging.

The disazo dye represented by the formula II is disclosed in JP-A-5-262998 or JP-A-5-1253.
No. 18, which is a disazo dye having a carboxylic acid group. In the synthesis of this dye, m-aminobenzenecarboxylic acid is diazotized by a conventional method and coupled with a 2,5-dialkoxy-substituted aniline having 1 to 4 carbon atoms to produce a monoazo compound having an amino group. It can be easily obtained in high yield and high purity by isolating it, or subsequently diazotizing it by a conventional method and coupling it with γ-acid (2-amino-8-naphthol-6-sulfonic acid).

Further, the dye represented by the formula II has good water resistance since it has a carboxylic acid group in the dye structure. At the same time, since it has a water-soluble acid group such as a sulfonic acid group, it dissolves in an aqueous liquid medium in the form of an alkali metal salt or ammonium salt. Since it becomes insoluble at a pH of 6 or less, the pH is preferably 8.0 to 10.

However, using only this disazo dye,
When the ink for inkjet recording is adjusted, the optical density of the image is insufficient, and in order to increase the optical density,
There is also a problem with respect to the dissolution stability of the dye, such that increasing the dye concentration causes a problem in reliability such as clogging.

However, the disazo dye of the formula I and the formula II
It was found that the solubility of these dye mixtures in water was remarkably improved by blending the disazo dye of (1) with a certain ratio. With this discovery, it is possible to provide high-quality images (clear images with high optical density and no bleed) and high reliability even on plain paper, as well as the water resistance and light resistance characteristics of these dyes themselves. , Came to solve the problem.

The dye composition of the present invention comprises a disazo dye represented by the above formula I and a disazo dye represented by the above formula II.
Of the disazo dye represented by the formula I and the peak area (Sc) of the disazo dye represented by the formula II when the dye composition is analyzed by liquid chromatography. Area ratio Sp: Sc is 1: 0.4-
It is characterized in that it is 1: 2.4, preferably 1: 0.6 to 1: 1.5.

In particular, when the ink for ink jet recording is manufactured, the dye concentration is set to 1 in consideration of workability of ink manufacturing.
In many cases, a concentrated solution of 0% by weight or more is used, but when the area ratio of Sc to Sp is 0.4 times or less, the dye represented by the formula I precipitates and a problem occurs in dissolution storage stability. . Further, when the area ratio of Sc to Sp is 2.4 times or more, the dye represented by the formula II is precipitated and a problem arises in dissolution storage stability.

The range of the area ratio Sp: Sc at which the dye composition of the present invention shows the best storage stability in a basic aqueous liquid medium is Sp: Sc = 1: 0.6 to 1: 1.5. I found out.

Here, the peak area ratio Sp: Sc of the present invention means the area Sp of the peak showing the disazo dye represented by the formula I and the formula II in the (high speed) liquid chromatography analysis under the following analysis conditions. It is the ratio with the area Sc of the peak showing the disazo dye represented. Analysis conditions column filler: ODS (L-Column) Size: 4.6 × 250 mm eluent A: 10% CH ₃ CN aqueous solution containing KH ₂ PO ₄ of 0.02N B: 70% CH ₃ CN aqueous Measurement conditions flow rate: 1.2 ml / Min Pressure: Approx. 120 kgf / cm ² Temperature: 45 ° C Detection wavelength: 313 nm Gradient conditions (see Figure 12) Eluent B initial concentration: 10% Eluent B final concentration: 70% Gradient time: 20 minutes (Eluted at the same concentration for 5 minutes)

In addition, the dye composition of the present invention has a peak area (Sp + Sc) of the disazo dye represented by the above formula I and the disazo dye represented by the above formula II in the liquid chromatography analysis when the detection wavelength is 313 nm. Is 90% or more, and particularly preferably 95% or more. If it is 90% or less, the object of the present invention may not be achieved.

The method for producing the dye composition of the present invention satisfying the above-mentioned dye dissolution characteristics (dissolution storage stability) comprises synthesizing the above-mentioned disazo dye represented by the formula I and the disazo dye represented by the formula II individually. , Can also be blended. However, in order to simplify the synthesis process of the dye, it is preferable to use the following diazotization reaction of the mixed amine of m-aminobenzenephosphonic acid and m-aminobenzenecarboxylic acid and the 2,5-diamine used as the first coupler. The coupling reaction with the alkoxy-substituted aniline can be performed by a usual method. The reaction conditions are diazotization at a temperature of 0 to 5 ° C, a temperature of 0 to 5 ° C, and a pH of
Coupling at 0.5 to 3.5 is preferable. The diazotization of the monoazo compound and the coupling reaction with the γ-acid (2-amino-8-naphthol-6-sulfonic acid) used as the second coupler are not particularly limited and can be performed by a usual method. The reaction conditions are preferably such that diazotization is carried out at a temperature of 25 to 35 ° C, and coupling is carried out at a temperature of 5 to 15 ° C and a pH of 9 to 10.

[0049]

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The composition of the dye concentrate of the present invention has a blending weight ratio of the disazo dye composition or the disazo dye represented by the formula I to the disazo dye represented by the formula II in the range of 1: 0.4 to 1: 2. .4, preferably 1: 0.6-1: 1.
A concentrated dye solution containing a compounded dye of No. 5 and an aqueous medium containing water as a main component and having a dye concentration of 10% by weight or more.

The ink composition of the present invention has at least the formula I
Containing a disazo dye represented by the formula and a disazo dye represented by the formula II, the mixing ratio of which is an area ratio Sp of a peak area in liquid chromatography analysis (where the peak area of the formula I is Sp and the peak area of the formula II is Sc). : Sc: 1: 0.4
~ 1: 2.4, preferably 1: 0.6 ~ 1: 1.5, so that the dissolution stability is very high, so the image with high optical density and the reliability such as clogging are high. It has been discovered that it is possible to achieve both.

Further, the dyes of the formula I and formula II according to the present invention are excellent in water resistance and color development by combining them with a nitrogen-containing cyclic compound both in these dyes and in the dye composition formulated in the ratio of the present invention. It was discovered that improvement in dissolution storage stability can be obtained.

These nitrogen-containing cyclic compounds include 1,
3-Dimethyl-2-imidazolidinone, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam and the like can be mentioned, and they can be used alone or in combination of two or more kinds. These solvents are essential solvents for the ink composition of the present invention because they enhance the dissolution stability of the dye and the printing stability and also have the function of a color-forming auxiliary agent and a water-resistant auxiliary agent. The amount added is 1 to 30% by weight, preferably 3 to 20
% By weight. If the addition amount is less than 1% by weight, the above-mentioned function cannot be exhibited, and if it exceeds 30% by weight, image bleeding occurs and image quality is deteriorated, which is not preferable.

However, since these nitrogen-containing cyclic compounds are poor in moisturizing ability, that is, wettability, clogging is likely to occur only with these nitrogen-containing cyclic compounds, and once,
When the clogging occurs, there is a problem that it is difficult to recover it. Therefore, an anti-clogging agent became indispensable, and as a result of examining various solvents, it was found that polyhydric alcohols are the most effective anti-clogging agents. However, a phenomenon occurred in which the polyhydric alcohols alone did not exhibit sufficient water resistance, and the color development of the dye was slightly inferior. Therefore, it is essential for the ink composition of the present invention to combine the dye of the general formula (I), the polyhydric alcohol and the nitrogen-containing cyclic compound.

Examples of these polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,2,6-hexanetriol, Glycerin and the like can be used, and they can be used alone or in combination of two or more. The amount added is 1 to 30% by weight, preferably 3 to 20
% By weight. If the addition amount is less than 1% by weight, clogging that is difficult to recover is caused, and if it exceeds 30% by weight, the drying property of the image is deteriorated and the image quality is deteriorated, which is not preferable.

However, it cannot be denied that there is a large difference in the dissolution storage stability of the dyes when the dyes of the formulas I and II are used alone and when they are compounded, and the use of the dyes of the formulas I and II alone Was difficult to ensure reliability.

In the ink composition of the present invention, a nonionic acetylene glycol-based surface active agent is used as an additive effective for maintaining quick fixing (permeability) of the ink and maintaining the roundness of one dot. It is characterized by containing an agent.

Specific examples of the nonionic acetylene glycol-based surfactant used in the present invention include Surfynol 465, Surfynol 104, Olfine STG (trade name, manufactured by Nisshin Chemical Co., Ltd.) and the like. However, Olfine STG is particularly effective. The amount added is 0.05 to 3% by weight, preferably 0.5 to 2% by weight. If the addition amount is less than 0.05% by weight, sufficient penetrability cannot be obtained, and if it exceeds 30% by weight, image bleeding occurs and image quality is deteriorated, which is not preferable.

Further, by adding glycol ethers in addition to the nonionic acetylene glycol-based surfactant, the permeability is further increased, and the bleeding at the boundary between the adjacent color inks when color printing is performed. It has been found that a reduced and very sharp image can be obtained.

The glycol ethers of the present invention include
Examples thereof include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and triethylene glycol monobutyl ether. The amount added is 3 to 30% by weight, preferably 5 to 15% by weight. If the addition amount is less than 3% by weight, the effect of preventing bleeding cannot be obtained. Further, if the amount exceeds 30% by weight, not only image bleeding occurs but also oily separation occurs, so that a dissolution aid for these glycol ethers is required, and the viscosity of the ink increases accordingly, and the ink jet head discharges. Becomes difficult.

Further, the ink composition of the present invention may optionally contain a lower alcohol, a pH adjusting agent such as triethanolamine or a hydroxide of an alkali metal, a water-soluble polymer such as sodium alginate, a water-soluble resin, Fluorine-based surfactants, fungicides, rust preventives and the like may be added.

The ink using the above-mentioned ink composition can be produced by a conventional method. For example, there is a method in which the components are sufficiently mixed and dissolved, filtered under pressure with a membrane filter having a pore size of 0.8 μm, and then deaerated using a vacuum pump to prepare an ink.

Next, the recording method of the present invention using the above ink will be described. In the recording method of the present invention, an ink jet recording method in which ink is ejected as droplets from fine holes for recording can be particularly preferably used, but it can also be used for general writing instruments, recorders, pen plotters and the like. I'm sorry.

As the ink jet recording method, any conventionally known method can be used, and particularly excellent image recording is performed in the method of ejecting liquid droplets by utilizing the vibration of the piezoelectric element or the method of utilizing thermal energy. Is possible.

[0065]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. First, the method for producing the dye composition of the present invention will be described in Examples 1-5 and Comparative Examples 1-2.

[0066]

Example 1 17.5 g of m-aminobenzenephosphonic acid
(0.1 mol) and m-aminobenzenecarboxylic acid 13.85 g
(0.1 mol) of the mixed amine was suspended in 400 ml of water while stirring, and 30.4 g (0.29 mol) of 35% hydrochloric acid was added thereto.
Cooled to 0 ° C. To this solution was gradually added 40.0 g (0.2%) of 36% sodium nitrite aqueous solution so that the temperature did not exceed 5 ° C.
1 mol) was added dropwise and the mixture was stirred for 50 minutes to diazotize the mixed amine, and then thiourea was added to the obtained aqueous solution to remove excess nitrous acid to obtain a diazo component-containing liquid. On the other hand, 3,5-diethoxyaniline 36.3 g (0.2
2 mol) was dispersed in 500 ml of water, and 21.3 g (0.1%) of 35% hydrochloric acid was added.
21 mol) was added and dissolved to obtain a coupling component-containing liquid. Here, the coupling component-containing liquid was cooled to 0 ° C., and the above diazo component-containing liquid was added dropwise thereto so that the temperature did not exceed 5 ° C. Then, the mixture was stirred at 3 to 5 ° C for 20 hours to obtain a monoazo compound (mixture); m- (2,5-diethoxy-
4-amino-phenylazo) benzenephosphonic acid and m-
(2,5-Diethoxy-4-phenylazo) benzenecarboxylic acid was obtained.

The obtained monoazo compound mixture was mixed with water 900
Dispersed in 4 ml of 45% aqueous sodium hydroxide solution 43.0 g
(0.48 mol) was added and dissolved. To this solution was added 36% aqueous sodium nitrite solution (38.5 g, 0.20 mol) and the temperature was 25 ° C.
The mixture was cooled to 130 ° C., and 130 g (0.71 mol) of 20% hydrochloric acid was added to 30
The mixture of monoazo compounds was diazotized by gradually adding the mixture so that the temperature did not exceed ℃, and then stirring at 25 to 30 ℃ or less for 3 hours. Then, sulfamic acid was added to the obtained aqueous solution to remove excess nitrous acid to obtain a diazo component liquid.

On the other hand, 51.6 g (0.21 mol) of gamma acid was added to 60 parts of water.
In addition to 0 ml, 37.0 g of 45% sodium hydroxide aqueous solution
(0.42 mol) and the mixture was cooled to 5 ° C. to prepare a coupler solution. The diazo component-containing liquid of the monoazo compound prepared in advance was added so that the reaction temperature did not exceed 8 ° C.
The reaction pH was adjusted to 8. by adding 0% aqueous sodium hydroxide solution.
After dropping while maintaining at 5 or more, the mixture was stirred at 8 ° C. for 3 hours. About 75 g of Dye Composition 1 mainly containing the two disazo dyes shown in the above (A) and (J) was obtained by salting / acidifying operation.
Obtained.

The dye composition 1 thus obtained was analyzed by high performance liquid chromatography (HPLC).
The area ratio Sp: Sc of the disazo dyes of (A) and (J) is 50.
It was 4: 49.6 (1: 0.98). This chromatogram is shown in FIG. The peak area sum (Sp + Sc) of the obtained disazo dye was about 99% of the total area sum at the detection wavelength of 313 nm.

The liquid chromatography analysis was carried out under the above-mentioned analysis conditions using the measuring device shown below. Measuring device (manufactured by Shimadzu Corporation) Controller: SCL-6A Detector: SPD-6AV Pump unit: LC-6A (x2) Column oven: CTO-6A Plotter: C-R6A Disazo dye represented by Formula I and Formula II Peak area ratio S
p / Sc was calculated based on the area of the peak analyzed by the plotter. The analysis parameters of the plotter are shown below. Plotter analysis parameters WIDTH: 5 SLOPE: 330 DIRFT: 0 MIN. AREA: 4000 T.I. DBL: 5 STOP TIME: 25 ATTEN: 6 SPEED: 2 Samples were prepared by dissolving 3 mg of the dye composition (ammonium salt) in 50 ml of carrier liquid. The visible absorption spectrum of Dye Composition 1 is shown in FIG.

[0071]

Example 2 The mixed amine used in Example 1 was changed to a mixed amine of 21.00 g (0.12 mol) of m-aminobenzenephosphonic acid and 11.08 g (0.08 mol) of m-aminobenzenecarboxylic acid. In exactly the same way as in Example 1, the above formula (A)
About 76 g of Dye Composition 2 containing mainly two disazo dyes represented by (J) was obtained.

When the obtained dye composition 2 was analyzed by high performance liquid chromatography, the area ratio Sp: Sc of the disazo dyes of the formulas (A) and (J) was 56.0: 44.0.
(1: 0.79). This chromatogram is shown in FIG. Also, the sum of peak areas of the obtained disazo dyes (Sp
+ Sc) is about 99 of the total area when the detection wavelength is 313 nm.
%Met.

[0073]

Example 3 The mixed amine used in Example 1 was changed to a mixed amine of 14.00 g (0.08 mol) of m-aminobenzenephosphonic acid and 16.62 g (0.12 mol) of m-aminobenzenecarboxylic acid. In exactly the same way as in Example 1, the above formula (A)
About 73 g of Dye Composition 3 mainly containing two disazo dyes represented by (J) was obtained.

The obtained dye composition 3 was analyzed by high performance liquid chromatography to find that the area ratio Sp: Sc of the disazo dyes of the formulas (A) and (J) was 33.8: 66.2.
(1: 1.96). This chromatogram is shown in FIG. Also, the sum of peak areas of the obtained disazo dyes (Sp
+ Sc) is about 99 of the total area when the detection wavelength is 313 nm.
%Met.

[0075]

Example 4 The mixed amine used in Example 1 was changed to a mixed amine of 24.50 g (0.14 mol) of m-aminobenzenephosphonic acid and 8.31 g (0.06 mol) of m-aminobenzenecarboxylic acid. In exactly the same manner as in Example 1, the above formulas (A) and (J)
A dye composition 4 mainly containing two disazo dyes represented by
About 77 g was obtained.

The obtained dye composition 4 was analyzed by high performance liquid chromatography to find that the area ratio Sp: Sc of the disazo dyes of the formulas (A) and (J) was 64.4: 35.6.
(1: 0.55). This chromatogram is shown in FIG. Also, the sum of peak areas of the obtained disazo dyes (Sp
+ Sc) is about 99 of the total area when the detection wavelength is 313 nm.
%Met.

[0077]

Example 5 The mixed amine used in Example 1 was changed to a mixed amine of 10.50 g (0.06 mol) of m-aminobenzenephosphonic acid and 19.39 g (0.14 mol) of m-aminobenzenecarboxylic acid. In exactly the same way as in Example 1, the above formula (A)
About 72 g of Dye Composition 5 containing mainly two disazo dyes represented by (J) were obtained.

When the obtained dye composition 5 was analyzed by high performance liquid chromatography, the area ratio Sp: Sc of the disazo dyes of the formulas (A) and (J) was 24.0: 76.0.
(1: 3.17). This chromatogram is shown in FIG. Also, the sum of peak areas of the obtained disazo dyes (Sp
+ Sc) is about 99 of the total area when the detection wavelength is 313 nm.
%Met.

The above examples are summarized in Table 1.

[0080]

[Table 1]

Next, a single synthesis of the disazo dye represented by the above formulas I and II contained in the dye composition of the present invention or used as a compounding dye will be described as a comparative example.

[0082]

COMPARATIVE EXAMPLE 1 Instead of the mixed amine used in Example 1, m
About 80 g of the disazo dye represented by the above formula (A) was obtained in exactly the same manner as in Example 1 except that 34.62 g (0.20 mol) of aminobenzenephosphonic acid was used.

The obtained dye composition was analyzed by high performance liquid chromatography. This chromatogram is shown in FIG. 7. The visible absorption spectrum of this disazo dye is shown in FIG.

[0084]

Comparative Example 2 Instead of the mixed amine used in Example 1, m
About 70 g of the disazo dye represented by the above formula (J) was obtained in exactly the same manner as in Example 1 except that 27.40 g (0.20 mol) of aminobenzenecarboxylic acid was used.

The obtained dye composition was analyzed by high performance liquid chromatography. This chromatogram is shown in FIG. The visible absorption spectrum of this disazo dye is shown in FIG.

Next, Examples 6 to 10 will explain concentrated solutions containing the dye composition of the present invention and having a dye concentration of 10% by weight or more.

[0087]

Example 6 The wet cake (dye content: about 25% by weight) obtained by the method of Example 1 was redispersed in ion-exchanged water and a reverse osmosis membrane (NTR-7410 manufactured by Nitto Denko Corporation) was used. After purification and concentration, 15% by weight dye concentrate A or the like in the form of ammonium salt or sodium salt was obtained using aqueous ammonia or aqueous sodium hydroxide.

The dye concentrate A and the like thus obtained were subjected to the following two-month dissolution and storage safety test. Table 2 shows the results.

<Test method for dissolution storage stability of concentrated dye solution>
100 ml of the obtained concentrated dye solution was placed in a heat-resistant glass bottle and tightly stoppered, and the mixture was left standing for 2 months in an incubator set at 60 ° C. Then, the presence or absence of dye deposition was observed by spotting on filter paper and evaluated as follows. ⊚: No dye deposition is observed ◯: Dye deposition is slightly observed x: Dye deposition is observed

[0090]

Examples 7 to 10 The wet cakes obtained by the methods of Examples 2 to 5 before drying were subjected to the same operations as in Example 6 to obtain the dye concentrates having the counter ion and the dye concentration shown in Table 2. Obtained.

Regarding the obtained dye concentrates B to E, etc., 2
A dissolution storage stability test for a month was performed. Table 2 shows the results.

[0092]

[Comparative Examples 3 to 4] The wet cakes obtained by the methods of Comparative Examples 1 and 2 before drying were subjected to the same operations as in Example 6 to prepare the dye concentrates having the counter ion and the dye concentration shown in Table 2. Obtained.

The obtained dye concentrates a and b were subjected to a two-month dissolution and storage stability test. Table 2 shows the results.

Further, the dye examples obtained in Comparative Example 1 above
(A) and the dye example (J) obtained in Comparative Example 2 above,
Ammonia water was used to prepare the following concentrated dye concentrates having a dye concentration of 15% by weight in the form of ammonium salts.

[0095]

Example 11 Compounded dye concentrate F; (A): (J) = 5: 5 Compounded dye concentrate G; (A): (J) = 6: 4 Compounded dye concentrate H; (A): ( J) = 4: 6 Blended dye concentrate I; (A): (J) = 7: 3 Blended dye concentrate J; (A): (J) = 3: 7 Obtained dye concentrates F to J and Each of the concentrated dye concentrates shown in Table 2 was subjected to a dissolution storage stability test for 2 months. Table 2 shows the results.

[0096]

[Table 2]

Next, the ink composition will be specifically described. The ink compositions of Examples 12 to 20 and Comparative Examples 5 to 7 were manufactured by the above-described ink manufacturing method with the compounding ratios shown in Table 3. In addition, each component of the ink shown in the table indicates the weight% of each component with respect to the total amount of the ink, and the remaining amount is water.

[0098]

[Table 3]

[0099]

[Table 4]

In the evaluation test, an inkjet printer MJ-700V2 / C (manufactured by Seiko-Epson Corporation) was used. The black ink cartridge for MJ-700V2 / C was used in Examples 12 to 20 and Comparative Examples 5 to 5.
7 inks were filled and the following tests 1 to 5 were evaluated.

<Test 1: Water resistance> (1) EPP paper (Epson Sales Co., Ltd .; acid paper), (2) Xerox P (Fuji Xerox Co., Ltd .; neutral paper) were printed in alphabet letters. Water droplets were dropped on the printed sample, and the state of the sample after natural drying was visually observed and evaluated as follows. ◎: No change from the initial state ○: Slightly melted dye, but characters can be clearly read △: Bleeding, but characters can be read ×: Characters cannot be read

<Test 2: Image quality><2-1> Alphabet printing and graphic printing were performed on the following test papers, and the visual density and the optical density (OD value) of the solid part were measured and evaluated as follows. . (1) EPP paper (Epson Sales Co., Ltd.) (2) Xerox P (Fuji Xerox Co., Ltd.) (3) Xerox 4024 (Xerox Co., Ltd.) (4) Ricopy 6200 (Ricoh Co., Ltd.)

For the OD value measurement, Macbeth TR-927 manufactured by Macbeth was used to measure the reflection density. ⊚: No bleeding and OD value of 1.30 or more. ◯: Some bleeding is seen, but it does not affect the image, OD value is 1.25 or more Δ: Little bleeding, but OD value is less than 1.25 x: OD value is less than 1.20

<2-2> Color printing was performed on the following test papers, and bleeding with adjacent color inks was visually evaluated as follows. (1) EPP paper (Epson Sales Co., Ltd.) (2) Xerox P (Fuji Xerox Co., Ltd.) (3) Xerox 4024 (Xerox Co., Ltd.) (4) Ricopy 6200 (Ricoh Co., Ltd.) ◎: No bleed, Sharp. ◯: There is some bleeding, but it is clear. Δ: Bleed is slightly conspicuous. X: Bleed is severe.

<Test 3: Recovery from clogging> MJ-700
After filling the V2 / C recording head with ink, the recording head was left at 40 ° C. for one month in a state of being displaced from the cap position. After that, the number of cleanings until normal printing was possible was evaluated as follows. ◎: 0 to 2 times ○: 3 to 5 times △: 5 to 10 times ×: Performed up to 10 times without recovery

<Test 4: Printing stability> MJ-700V2
Continuous printing was performed using the self-check pattern mounted on / C, and the time for stable printing was evaluated as follows. ◎: 24 hours or more ○: 10 hours or more and less than 24 hours ×: less than 10 hours

<Test 5: Storage stability> MJ-700V2
/ C ink cartridge is filled with ink, -30 ℃
After being left at 70 ° C. for 2 weeks, the physical properties of the ink, the change in color tone, the presence or absence of foreign matters and precipitates were observed before and after the evaluation, and evaluated as follows. ◯: No change in physical property / color tone, no generation of foreign matter / precipitate ×: Change in physical property / color tone, or generation of foreign matter / precipitate The above evaluation results of Tests 1 to 5 are shown in Table 4 Shown in.

[0108]

[Table 5]

[0109]

In the dye composition of the present invention, two disazo dye components having a similar structure are well-balanced and mixed or formed, so that the disazo dye alone has insufficient properties (solubility and color density). Etc.) are mutually promoted, and good dissolution storage stability can be obtained.

Further, according to the ink composition of the present invention, high image quality can be obtained especially on so-called plain paper such as copy paper, report paper, bond paper, notepaper, postcard, slip paper used in offices, schools and homes. It has become possible to provide an ink composition capable of recording and excellent in water resistance of a recorded image.

[Brief description of the drawings]

FIG. 1 is a chromatogram of Dye composition 1 obtained in Example 1.

FIG. 2 is a visible light spectrum of Dye Composition 1 obtained in Example 1.

3 is a chromatogram of Dye composition 2 obtained in Example 2. FIG.

4 is a chromatogram of Dye Composition 3 obtained in Example 3. FIG.

5 is a chromatogram of Dye composition 4 obtained in Example 4. FIG.

6 is a chromatogram of Dye composition 5 obtained in Example 5. FIG.

7 is a chromatogram of the dye composition obtained in Comparative Example 1. FIG.

8 is a visible light spectrum of the dye composition obtained in Comparative Example 1. FIG.

9 is a chromatogram of the dye composition obtained in Comparative Example 2. FIG.

10 is a visible light spectrum of the dye composition obtained in Comparative Example 2. FIG.

11 is a chromatogram of a compounded dye concentrate F obtained in Example 11. FIG.

FIG. 12 is a graph schematically showing the gradient condition of liquid chromatography.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Saruwatari No. 8-1, Sanrahigashi-cho, Neyagawa-shi, Osaka Prefecture Orient Chemical Industry Co., Ltd. (72) Inventor Masaki Sasaki No. 8 Sanrahigashi-cho, Neyagawa-shi, Osaka No. 1 Orient Chemical Industry Co., Ltd. (72) Inventor Miharu Kanaya 3-5 Yamato, Suwa, Nagano Prefecture 3-5 Seiko Epson Co., Ltd. (72) Hiroko Hayashi 3-35 Yamato, Suwa City, Nagano Prefecture No. Seiko Epson Co., Ltd. (72) Inventor Akio Owado 3-3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Co., Ltd. (72) Inventor Yasuhiro Koki 3-3-5 Yamato, Suwa City, Nagano Seiko Epson Within the corporation

Claims (12)

[Claims] 1. A dye composition containing at least a disazo dye represented by the following formula I and a disazo dye represented by the following formula II, wherein when the dye composition is analyzed by liquid chromatography, the disazo dye represented by the formula I The area ratio Sp: Sc of the peak area (Sp) of the dye and the peak area (Sc) of the disazo dye represented by the formula II is 1: 0.4 to 1:
2. A disazo dye composition which is 2.4. Embedded image Embedded image (In the formula, X and Y represent an alkoxy group having 1 to 4 carbon atoms, and M represents a cation selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, and piperidinium.) 2. The area ratio Sp: Sc is 1: 0.6 to 1: 1.5.
The disazo dye composition according to claim 1. 3. A mixing ratio of m-aminobenzenephosphonic acid and m-aminobenzenecarboxylic acid in molar ratio:
= 1: 0.4-1: 2.5 mixed amine is simultaneously diazotized and coupled with 2,5-dialkoxy-substituted aniline to obtain a monoazo compound, and the obtained monoazo compound is diazotized, The method for producing a disazo dye composition according to claim 1, which comprises a step of coupling with an acid. Embedded image 4. The disazo dye composition according to claim 1
A concentrated dye solution characterized by containing 0% by weight or more. 5. A black ink composition containing at least a disazo dye represented by the following formula I and a disazo dye represented by the following formula II, wherein the disazo dye represented by the formula I and the disazo dye represented by the formula II are liquids. When analyzed by chromatography, the area ratio Sp: Sc of the peak area (Sp) of the disazo dye represented by the formula I and the peak area (Sc) of the disazo dye represented by the formula II is 1: 0.4 to.
1: 2.4 The black aqueous ink composition characterized by being 1: 2.4. Embedded image Embedded image (In the formula, X and Y represent an alkoxy group having 1 to 4 carbon atoms, and M represents a cation selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, and piperidinium.) 6. The area ratio Sp: Sc is 1: 0.6 to 1: 1.5.
6. The black aqueous ink composition according to claim 5. 7. The black aqueous ink composition according to claim 5, further comprising a polyhydric alcohol and a nitrogen-containing cyclic compound. 8. The black aqueous ink composition according to claim 5, further comprising a nonionic acetylene glycol-based surfactant. 9. The black aqueous ink composition according to claim 8, which further comprises glycol ethers. 10. In an ink jet recording system for recording on a recording medium by ejecting ink as droplets from fine holes, the ink is at least a disazo dye represented by the following formula I and a disazo dye represented by the following formula II. And the area ratio S of the peak area (Sp) of the disazo dye represented by the formula I and the peak area (Sc) of the disazo dye represented by the formula II when analyzed by liquid chromatography.
The inkjet recording method is characterized in that p: Sc is 1: 0.4 to 1: 2.4. [Chemical 6] Embedded image (In the formula, X and Y represent an alkoxy group having 1 to 4 carbon atoms, and M represents a cation selected from hydrogen, alkali metal, NH ₄ , alkyl-substituted ammonium, alkanol ammonium, morpholinium, and piperidinium.) 11. The area ratio Sp: Sc is 1: 0.6 to 1: 1.
The ink jet recording method according to claim 10, wherein the ink jet recording method is 5. 12. The ink, in addition to the disazo dye represented by the formulas I and II, a polyhydric alcohol, a nitrogen-containing cyclic compound, a nonionic acetylene glycol-based surfactant,
The ink jet recording method according to claim 10, further comprising a glycol ether.