JPH1129729A - Formation of color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent color images in an ink jet method with aq. magenta, yellow, and cyan inks by using those inks each of which contains at least one colorant selected from a specific group of colorants. SOLUTION: The magenta ink contains a colorant having a free acid form represented by formula I (wherein Y1 is a divalent linking group selected from among groups represented by formulas II to VIII). The yellow ink contains a colorant having a free acid form represented by formula IX (wherein J and J1 are each independently a linking group represented by formula X, XI, or XII; and X3 and X4 are each independently a linking group represented by formula XIII, XIV, or XV)(e.g. C.I. Acid Yellow 23 or Direct Yellow 86). The cyan ink contains a colorant having a free acid form represented by formula XVI (e.g. C.I. Direct blue 86 or 199).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for forming a color image, and more particularly to a method for forming a full-color image using a combination of magenta, yellow, and cyan aqueous inks by an ink jet method.

[0002]

2. Description of the Related Art In an ink jet system, small droplets of ink are ejected from an orifice by various methods and adhere to a recording material for recording. The ink used in the ink jet system requires the following performance. Is done. (1) Electrophotographic paper, fan hold paper, uncoated paper such as bond paper, pulp paper such as art paper or coated paper, polyester film, polyvinyl chloride film, etc., which are widely used as recording materials in offices That good recording can be performed even on an aqueous resin formed on a non-porous film or a film composed of an aqueous resin and organic or inorganic fine particles. (2) To give an image excellent in water resistance and light resistance. (3) The dissolution or storage stability with respect to the liquid medium component is high, and the ejection orifice is unlikely to be clogged. (4) To provide an image having a high optical density, a clear color tone, and good reproducibility.

In order to satisfy such strict requirements,
For example, JP-A-54-89811 and JP-A-55-543.
No. 67, JP-A-57-76071, JP-A-57-16
No. 4170, JP-A-57-195775, JP-A-57-195775
-197191, JP-A-58-12786, JP-A-58-101171, JP-A-59-75964, JP-A-59-106989, and JP-A-62-197466.
JP-A-62-199665 and JP-A-62-199
666, JP-A-62-199667, JP-A-63-1996
A number of patents have been filed, such as 28690,
The complete is not yet available.

[0004]

The present invention relates to the above (1)
An object of the present invention is to provide an ink jet recording method which provides excellent color images by using inks which fully satisfy all of the requirements of (4) to (4).

[0005]

The present inventors have determined that the characteristics (1) to (4) required for inks are greatly influenced by the characteristics of the water-soluble dye contained in the ink, Satisfies all the above-mentioned characteristics (1) to (4),
Further, they have found that an ink set suitable for a color image forming method in which the obtained color image is also excellent is provided, and the present invention has been achieved.

That is, the gist of the present invention is to provide a method for forming a color image by ejecting aqueous inks of magenta, yellow and cyan by an ink jet system, wherein the magenta ink has a free acid type represented by the following general formula (I) ) Containing at least one of the dyes represented by the following formulas, and having a color index (CI) of Acid Yellow 2
3, and direct yellow 86, 132, 142,
And the type of free acid contains one or more dyes selected from the group consisting of compounds represented by the following general formula (a). The cyan ink has a color index (CI) of Direct Blue 86, 199, Acid Blue 9, and a free acid type containing one or more dyes selected from the group consisting of compounds represented by the following general formula (b). General formula (I)

[0007]

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[Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent 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, sulfonic acid ester groups, and sulfonyl groups , A carboxyl group or a carboxylic ester group. m and n each independently represent a number of 0, 1, or 2. X ₁ and X ₂ each independently represent a group represented by —OR ₇ , wherein R ₇ is a hydrogen 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, of which groups other than a hydrogen atom may further have a substituent. . Y ₁ is the following general formula (II)
And a divalent linking group selected from the groups represented by the formulas (IV) and (A). General formula (II)

[0009]

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(Wherein R ₈ and R ₁₀ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ₉ represents a linear or branched alkylene group having 1 to 12 carbon atoms) Represents an alkylene group in the form of, or the following formula (a), and p represents a number of 0 to 20.

[0011]

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General formula (III)

[0013]

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(In the general formula (III), R ₁₁ and R ₁₂ represent a hydrogen atom or a methyl group.) The general formula (IV)

[0015]

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(In the general formula (IV), R ₁₃ and R ₁₄ represent a hydrogen atom, a methyl group or a methoxy group.) (Group A)

[0017]

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General formula (a)

[0019]

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In the formula, Ar and Ar ₁ each independently represent an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ has at least one substituent selected from a COOH group and a COSH group. , J and J ₁ are each independently a linking group represented by the following formula (i), (ii) or (iii).

[0021]

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[Wherein R ₁₉ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, a halogen atom, a CN group,
A ureido group and an NHCOR ₂₀ group, wherein R ₂₀ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, W ₁ is an alkyl group, and W ₂ is Hydrogen atom, CN
Group, CONR ₂₄ R ₂₅ group, pyridinium group and COOH group, Q is an alkylene chain having 2 to 8 carbon atoms, W ₃ is a hydrogen atom, an alkyl group or a COOH group, and R ₂₄ and R ₂₅ are Each is independently a hydrogen atom, an alkyl group or a substituted alkyl group. ]. R ₁₅ , R ₁₆ , R ₁₇ , R
₁₈ each independently represents a hydrogen atom, an alkyl group, or a substituted alkyl group; L is a divalent linking group; q is 0 or 1; X ₃ and X ₄ are each independently a carbonyl group or the following formula ( a connecting group represented by (iv), (v) or (vi).

[0023]

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Wherein Z ₁ is OR ₂₁ , SR ₂₁ or NR ₂₂
R ₂₃ , Y ₂ is a hydrogen atom, a chlorine atom or a CN group, Y ₃ is a chlorine atom or a CN group, R ₂₁ , R ₂₂ , R
₂₃ is each independently a hydrogen atom, an alkenyl group, a substituted alkenyl group, an alkyl group, a substituted alkyl group, an aryl group,
It may be a substituted aryl group, an aralkyl group or a substituted aralkyl group, or R ₂₂ and R ₂₃ together with the nitrogen atom to which they are attached may form a 5- or 6-membered ring. ].
If the case where the compound represented by the general formula (a) has no SO ₃ H group which has a group selected from at least two COOH groups and COSH group, with SO ₃ H group, COO
Group selected from H group and COSH group is at least SO ₃
It is the same as the number of H groups. ｝ General formula (b)

[0025]

Embedded image Pc (SO ₃ H) _j (SO ₂ —NR ₂₆ —L ₁ —NR ₂₇ —X ₄ —NR ₂₈ —G) _k (b)

Wherein Pc is a metal-containing phthalocyanine nucleus, and R ₂₆ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or A substituted aralkyl group, L ₁ is a divalent linking group, and X ₄ is each independently a carbonyl group or a linking group represented by the following formula (vii), (viii) or (ix).

[0027]

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[Wherein, Z_ThreeIs NR₂₉R₃₀, SR₃₁Or O
R₃₁And Y_FourIs a hydrogen atom, a chlorine atom, Z_Three, SR₃₂
Or OR₃₂And Y_FiveIs a chlorine atom or a CN group,
R₂₉, R₃₀, R₃₁, R₃₂Are each independently a hydrogen atom,
Alkyl group, substituted alkyl group, aryl group, substituted aryl
Group, aralkyl group or substituted aralkyl group, or R
₂₉And R₃₀Is 5 members together with the nitrogen atom to which they are attached
A ring or a 6-membered ring may be formed. ]. G is a COSH group
And one or two groups selected from COOH groups
A substituted colorless organic group, wherein (j + k) is 3 to 4
is there. At least one compound represented by the general formula (b)
SO_ThreeH group, COSH group and COOH group
A group selected from_ThreeIt has the same number or more as the H group. ｝

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail. As a pigment of an aqueous ink used in an ink jet system, various performances are required. It is important that the performances such as light fastness and water fastness of each of the magenta, yellow, and cyan dyes be balanced with each other, and that the mutual color rendering relationship be good. It has been extremely difficult to find a combination of three colorants having various characteristics. However, according to the present invention, it is possible to form a color image by the most excellent ink jet method using a group of specific dyes as described below. The method has been realized.

The dye used in the magenta ink of the present invention has a free acid type represented by the general formula (I). Specifically, in the general formula (I), R ₁ , R ₂ ,
The substituents represented by R ₃ , R ₄ , R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group) , N-butyl group, trifluoromethyl group, dimethylaminomethyl group, etc.), alkoxy group having 1 to 9 carbon atoms (for example, methoxy group, isopropoxy group, n
-Butoxy group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), hydrogen atom, hydroxyl group, substituted or unsubstituted carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, phenyl) Carbamoyl group, etc.), substituted or unsubstituted sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N, N- Dimethylsulfamoyl group, p-carboxyphenylsulfamoyl group, etc.), substituted or unsubstituted amino group (for example, N-methylamino group, carbamoylamino group, N,
N-diethylamino group, acetylamino group, N-methyl-N-acetylamino group, etc., nitro group, sulfonic ester group (eg, phenoxysulfonyl group, etc.), sulfonyl group (eg, hydroxyethylsulfonyl group, etc.) Or an unsubstituted alkylsulfonyl group having 1 to 9 carbon atoms, for example, a substituted or unsubstituted arylsulfonyl group having 6 to 15 carbon atoms such as a benzylsulfonyl group),
Examples include a carboxyl group (COOH group) and a group of a carboxylic ester (for example, a methoxycarbonyl group or the like).

M and n each represent 0, 1 or 2.
X ₁ and X ₂ each represent a group represented by —OR ₇ , and the substituents represented by R ₇ each independently represent:
A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, an n-butyl group,
-Octyl group, ethylhexyl group, isopropyl group, t
tert-butyl group, carboxylmethyl group, etc., substituted or unsubstituted alkenyl group having 2 or 3 carbon atoms (eg, vinyl group, allyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 4- Nitrophenyl group, 4-butylphenyl group, 4-carboxyphenyl group, etc., substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.), cyclohexyl group, nitrogen-containing heterocyclic group (eg, pyridyl group, etc.) ) And the like.

Y ₁ represents a group represented by any of the general formulas (II) to (IV) and a divalent linking group selected from the group A. In the general formula (II), R ₈ and R ₁₀ are carbon atoms. Number 1
8, preferably a linear or branched alkylene group having 2 to 4 (eg, an ethylene group, a propylene group, a trimethylene group, etc.), and R ₉ has a carbon number of 1 to 12, preferably 2 to 8; A linear or branched alkylene group (eg, an ethylene group, a propylene group, a butylene group, a hexylene group, etc.) or the following formula (a), and p is preferably 0
Represents a number from 10 to 10.

[0033]

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The dye used in the present invention may be used as it is in the form of the free acid represented by formula (I), or may be in the form of a salt. A part of the plurality of acid groups may be of a salt type, and a salt type dye and a free acid type dye may be mixed. Examples of such salt forms include salts of alkali metals such as Na, Li, and K, salts of ammonium which may be substituted with an alkyl group or hydroxyalkyl group, and salts of organic amines. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines,
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 these dyes include the following Nos. (1)-(24)
Dyes having the structure shown below.

[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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[0041]

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[0042]

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The dye represented by formula (I) can be produced according to a known method. For example, no. (1)
Can be produced by the following steps (A) and (B). (A) From 2-aminobenzoic acid and 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid) in a conventional manner [for example, Yutaka Hosoda, "Shin-Dye Chemistry" (December 21, 1973) Mono-azo compound is produced through a diazotization coupling step in accordance with the publication of Gihodo, 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, a weakly alkaline diethylene glycol bis (3-aminopropyl) ether is added to the monoazo compound in a molar ratio of 0.5 to carry out a condensation reaction.

Then, 25% aqueous sodium hydroxide solution was added to 5
After adding at 0 to 60 ° C. and performing a hydrolysis reaction, the mixture is cooled and salted out with sodium chloride to obtain a target dye. In the present invention, as a yellow ink, Acid Yellow 2 having a color index (CI) is used.
3, and direct yellow 86, 132, 142,
And an ink containing one or more yellow dyes whose free acid type is selected from the group consisting of the compounds represented by the general formula (a).

A specific example of the compound represented by the general formula (a) wherein the type of free acid used in the yellow ink is represented by the following formula:
The following are mentioned.

[0047]

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In the present invention, C.I. I. Direct Blue 86 and 199, Acid Blue 9 and at least one dye whose free acid type is selected from the compounds represented by the general formula (b) are used. One specific example of the compound represented by the general formula (b) is
The following are mentioned.

[0049]

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Each of the aqueous inks of these colors used in the present invention contains an aqueous solvent and a dye as main components,
It is prepared by a conventionally known method. That is, the content of the above-mentioned specific dye in each ink is preferably 0.1 to 8% by weight, particularly preferably about 0.5 to 5% by weight based on the total amount of the ink. In addition, with respect to the magenta ink used in the present invention, it is preferable to add a xanthene-based dye shown in the following group B as needed in order to improve the density and saturation of the printed matter. At that time, the compounding ratio of the dye represented by the general formula (I) and the xanthene dyes of the following group B is 1 / weight ratio.
It is 9 to 9/1, preferably 2/8 to 8/2.

(Group B) In each of the color indexes, Acid Red 50, 51, 52, 87, 91,
92, 93, 94, 95, 98, and 289, Basic Red 1, and Basic Violet 10 Solvents used for the ink used in the present invention include water and water-soluble organic solvents such as ethylene glycol, propylene glycol, and butylene. Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as glycol, diethylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol and hexylene glycol; polyethylene glycol (weight average molecular weight of about 190 To 400), polyalkylene glycols such as polypropylene glycol; glycerin;
Methyl-2-pyrrolidone, N-ethylpyrrolidone; 1,
3-dimethyl-2-imidazolidinone; thiodiethanol; dimethyl sulfoxide; ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene Lower alkyl ethers of polyhydric alcohols such as glycol monoethyl ether; 2
-Pyrrolidone; sulfolane; methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n
Alkyl alcohols having 1 to 4 carbon atoms such as -butanol, sec-butanol, tert-butanol and isobutanol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; tetrahydrofuran;
It preferably contains ethers such as dioxane. Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferred. These water-soluble organic solvents are generally used in the range of 1 to 50% by weight, preferably in the range of 5 to 45% by weight, based on the total amount of the ink. On the other hand, water is used in the range of 45 to 90% by weight based on the total amount of the ink.

In the present invention, 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the total amount of the ink.
A compound selected from urea, thiourea, biuret, and semicarbazide, and a surfactant of 0.001 to 5.0% by weight, and a viscosity modifier such as polyvinyl alcohol, cellulose, and a water-soluble resin. By adding a surface tension adjuster such as diethanolamine and triethanolamine, a pH adjuster with a buffer solution and the like, a fungicide and the like, the ink quality, quick drying after printing, print quality and the like can be further improved. .

In the method of the present invention, the storage stability of each color ink can be further improved by maintaining the pH of each color ink at preferably 5 to 11, more preferably 6 to 10. The present invention can form a good color image such as full-color printing by using a combination of the above specific magenta, yellow, and cyan inks as an ink for a printer of an ink jet recording system. . The printer of the ink jet recording system can be used in any of a system using electric energy, a system using heat energy, an on-demand system, and a continuous system, and is not particularly limited.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. In the following, parts and percentages are by weight unless otherwise specified. In addition, the dye No. No. of the exemplified dyes shown above. Corresponding to

Reference Example 1 (Preparation of Ink) Each component having the following composition was mixed,
Then, after filtration under pressure with a Teflon filter having an average pore diameter of 0.45 μm, deaeration treatment was performed with a vacuum pump and an ultrasonic cleaner to prepare aqueous inks of magenta, yellow and cyan colors.

Magenta ink (1) Yellow ink (1) Cyan ink (1)

Magenta ink (2) Yellow ink (2) Cyan ink (2)

Magenta ink (3) Yellow ink (3) Cyan ink (3)

Magenta ink (4) Yellow ink (4) Cyan ink (4)

Magenta ink (5) Yellow ink (5) Cyan ink (5)

REFERENCE EXAMPLE 2 (Preparation of Recording Material) A polyvinyl chloride film having a thickness of 150 μm was used as a substrate, and 50 parts by weight of a polyamide resin aqueous solution (solid content: 30%) and urea formalin resin 12 were used as an ink absorbing layer. A composition consisting of parts by weight was applied on a film using a bar coater to a dry film thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a recording material.

Example 1 One of the three colors of magenta ink (1), yellow ink (1) and cyan ink (1) obtained in Reference Example 1
One set consisting of three colors of set, magenta ink (3), yellow ink (3), and cyan ink (3), and three colors of magenta ink (4), yellow ink (4), and cyan ink (4) An ink jet printer (trade name: IO-735, Sharp Corp.) was used by using each of the three ink sets as a set including three colors of magenta ink (5), yellow ink (5), and cyan ink (5). Inkjet recording is performed on each of electrophotographic paper (Xerox Co., Ltd. product), pond paper, and stock form paper (Lion Business Machine Co., Ltd. product) using the following products (a) and (b).
The quick drying property and the print quality were evaluated by the method described above.

(A) Quick-drying After ink-jet recording, the printed portion was rubbed with a finger after standing for 60 seconds, and the presence or absence of image displacement was visually determined. In any case, no image displacement was observed. (B) Print Quality The printed dots were observed under a microscope, and the presence or absence of feathering (whisker-like bleeding) around the dots and the sharpness of the outline were visually evaluated. The results were all good.

Further, according to the following methods (c) to (f), evaluation regarding ink jet recording was performed. (C) Long-term storage properties of the ink Even after the ink was sealed in a glass container and stored at 0 ° C. and 60 ° C. for 6 months, no precipitation of insolubles was observed, and there was no change in the physical properties and color tone of the ink. . (D) Discharge stability Continuous discharge was performed for 24 hours in an atmosphere at room temperature, 5 ° C., and 40 ° C., and stable high-quality recording was performed at all temperatures. (E) Discharge responsiveness Clogging at the tip of the orifice was observed for intermittent discharge every 2 seconds and discharge after standing for 2 months, but none of them was recognized, and stable and uniform discharge was performed. (F) Quality of Recorded Image The recorded image was high in density and clear. The density reduction rate after exposure to room light for 3 months was 1% or less, and the bleeding of the image after immersion in water for 1 minute was very slight. The recorded full-color image also had a good color balance, and could be recorded close to the primary colors.

Example 2 Using the magenta ink (2), the yellow ink (2), and the cyan ink (2) of Reference Example 1 as one set, the same procedure as in Example 1 was performed on the recording material of Reference Example 2. As a result of performing (a) to (f), all were good.

[0066]

According to the present invention, magenta, yellow,
Each of the dyes used in the three-color aqueous inks of cyan and cyan has solubility stability in a liquid medium,
Storage stability, recording characteristics (signal responsiveness, droplet formation stability, ejection stability, long-time continuous recording, ejection stability after long-time recording pause), fixability to recording material, etc. Excellent in various physical properties and also suitable as a general inkjet water-based ink.Especially all inks are well-balanced and excellent in weather resistance, light resistance, water resistance, sharpness of color tone and color of recorded images. Since it has a density and mutual color rendering properties, it is possible to provide excellent color image quality.

Claims (2)

[Claims] 1. An ink-jet method for magenta,
Ejects yellow and cyan water-based inks to produce color images.
In the method of forming an image, each color ink is
One or more dyes selected from the group of (1) to (3)
A method for forming a color image, comprising: (1) Magenta ink; the form of the free acid is the following general formula (I)
The dye represented by General formula (I)[Wherein, R₁, R_Two, R_Three, R_Four, R_FiveAnd R₆Is
Each independently represents a substituted or unsubstituted C 1 -C 9
Alkyl group, substituted or unsubstituted alkoxy having 1 to 9 carbon atoms
Xyl group, halogen atom, hydrogen atom, hydroxyl group,
Substituted or unsubstituted carbamoyl group, substituted or unsubstituted
A substituted sulfamoyl group, a substituted or unsubstituted amino
Group, nitro group, sulfonate group, sulfonyl
Group, carboxyl group or carboxylate group
I forgot. m and n each independently represent a number of 0, 1, or 2
Express. X₁, X_TwoAre independently -OR₇Indicated by
R represents a group₇Is a hydrogen atom, an alkyl having 1 to 8 carbon atoms
Alkenyl group having 2 or 3 carbon atoms, aryl group,
Aralkyl, cyclohexyl, or nitrogen-containing heterocyclic group
Represents a group other than a hydrogen atom,
May be provided. Y₁Are the following general formulas (II) to (IV)
And a divalent linking group selected from the group of group A
Show. General formula (II)(Where R₈And R_TenEach independently has 1 to 8 carbon atoms
Represents a linear or branched alkylene group;₉
Is a linear or branched alkylene having 1 to 12 carbon atoms
Wherein p is a number from 0 to 20
Represents Embedded imageGeneral formula (III)(In the general formula (III), R₁₁, R₁₂Is a hydrogen atom or a methyl group
Represents ) General formula (IV)(In the general formula (IV), R₁₃, R₁₄Is a hydrogen atom, a methyl group or
Represents a methoxy group. (Group A)(2) Yellow ink; color index (C.I.
I. ) In Acid Yellow 23, Direct Yellow 8
6, 132 and 142, and the type of free acid is represented by the following general formula:
A dye represented by (a). General formula (a)Ａｒwhere Ar, Ar₁Is each independently an aryl group or
Ar, Ar represents a substituted aryl group₁At least one of
One is a substituent selected from a COOH group and a COSH group.
Have at least one, J, J₁Are independently
It is a linking group represented by (i), (ii) or (iii). Embedded image[Wherein, R₁₉Is hydrogen atom, alkyl group, substituted alkyl
Group, alkoxy group, halogen atom, CN group, ureide group
And NHCOR₂₀Selected from the group₂₀Is a hydrogen atom,
Alkyl group, substituted alkyl group, aryl group, substituted aryl
A aralkyl group or a substituted aralkyl group;₁Is
An alkyl group;_TwoIs a hydrogen atom, a CN group, CONR
_{twenty four}R_{twenty five}Group, pyridinium group and COOH group.
Q is an alkylene chain having 2 to 8 carbon atoms;_ThreeIs water
A hydrogen atom, an alkyl group or a COOH group;_{twenty four}, R_{twenty five}
Are each independently a hydrogen atom, an alkyl group or a substituted alkyl.
Group. ]. R_Fifteen, R₁₆, R₁₇, R₁₈Is German
Stands for a hydrogen atom, an alkyl group, a substituted alkyl group,
L is a divalent linking group, q is 0 or 1,
X_Three, X_FourAre each independently a carbonyl group or the following formula (i
It is a linking group represented by v), (v) or (vi). Embedded image[Wherein, Z₁Is OR_{twenty one}, SR_{twenty one}Or NR_{twenty two}R_{twenty three}And
Y_TwoIs a hydrogen atom, a chlorine atom or a CN group;_ThreeIs salt
A hydrogen atom or a CN group,_{twenty one}, R_{twenty two}, R_{twenty three}Are each
Independently a hydrogen atom, an alkenyl group, a substituted alkenyl group,
Alkyl group, substituted alkyl group, aryl group, substituted aryl
Group, aralkyl group or substituted aralkyl group, or R
_{twenty two}And R_{twenty three}Is 5 members together with the nitrogen atom to which they are attached
A ring or a 6-membered ring may be formed. ]. General formula (a)
Is represented by SO_ThreeLess if there is no H group
A group selected from at least two COOH groups and COSH groups
And SO_ThreeWhen having an H group, a COOH group and CO 2
The group selected from the SH groups is at least SO_ThreeSame as the number of H groups
Is a number. ｝ (3) Cyan ink; color index (CI)
Direct Blue 86 and 199, Acid Blue
9, and a color whose free acid type is represented by the following general formula (b)
Elementary. General formula (b): Pc (SO_ThreeH)_j(SO_Two-NR₂₆-L₁-NR₂₇-X_Four-NR₂₈-G)_k (B) wherein Pc is a metal-containing phthalocyanine nucleus.
R₂₆, R₂₇, R₂₈Are each independently a hydrogen atom,
Kill group, substituted alkyl group, alkenyl group, substituted alkenyl
A aralkyl group or a substituted aralkyl group;₁
Is a divalent linking group, and X_FourAre each independently carboni
Or a group represented by the following formula (vii), (viii) or (ix)
It is a group. Embedded image[Wherein, Z_ThreeIs NR₂₉R₃₀, SR₃₁Or OR₃₁And
Y_FourIs a hydrogen atom, a chlorine atom, Z_Three, SR₃₂Or OR₃₂so
Yes, Y_FiveIs a chlorine atom or a CN group;₂₉, R₃₀,
R₃₁, R₃₂Are each independently a hydrogen atom, an alkyl group,
Substituted alkyl, aryl, substituted aryl, aralkyl
Or a substituted aralkyl group, or R ₂₉And R₃₀Is
A 5- or 6-membered ring together with the nitrogen atom to which they are attached
May be formed. ]. G is COSH group and COOH group
Substituted with one or two groups selected from
It is a color organic group, and (j + k) is 3-4. General formula
The compound represented by (b) has at least one SO_ThreeH
Group selected from COSH and COOH groups
SO_ThreeIt has the same number or more as the H group. ｝ 2. A magenta ink comprising at least one dye whose free acid type is selected from the dyes represented by the general formula (I) and at least one dye selected from the xanthene dyes represented by the following group B: 2. The method for forming a color image according to claim 1, wherein the ink comprises: [Group B] Acid Red 50, 51, 52, 87, 91, 92, 9 in the color index (CI)
3, 94, 95, 98, and 289, Basic Red 1, Basic Violet 10