JPH09202043A - Formation of color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a color image of excellent quantity, in emitting aq. inks of magenta, yellow, cyan and black by an ink jet system to form a color image on a receiving material, by using a specific dye combination in each of the color inks. SOLUTION: One or more kinds of a dye represented by formula I is added to magenta ink and one or more kinds of a dye selected from the group consisting of acid yellow and direct yellow of a color index is added to yellow ink. Further, one or more kinds of a dye selected from the group consisting of direct blue and acid blue of a color index is added to cyan ink and one or more kinds of a dye selected from the group represented by formula II and/or III in a form of free acid is added to black ink. In the formulae, R1 -R3 are each an alkyl group or the like, R4 -R6 are each a hydrogen atom or the like, R7 is an alkoxy group, R8 is an alkyl group or the like, R9 is a hydrogen atom or the like and R10 is a hydrogen atom or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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, cyan and black water-based inks by an ink jet method.

[0002]

2. Description of the Related Art The ink jet system is one in which a small amount of ink is ejected from an orifice by various methods and adhered to a recording material to perform recording. Performance such as is required. (1) Electrophotographic paper, fan hold paper, non-coated paper such as bond paper, art paper, paper such as coated paper, polyester film, polyvinyl chloride film which are commonly used in the office as recording materials Good recording can be performed on a water-based resin formed on a non-porous film such as that described above, or a recording layer composed of the water-based resin and organic or inorganic fine particles.

(2) To give an image excellent in water resistance and light resistance. (3) The dye used has a high solubility stability in the liquid medium component of the ink, and a high storage stability as an ink.
The discharge orifice is unlikely to be clogged. (4) To provide an image with high optical density, clear color tone and good reproducibility.

In order to satisfy such various requirements, for example, JP-A-54-89811 and JP-A-55-5436.
7, JP-A-57-76071, JP-A-57-164
170, JP-A-57-195775, JP-A-57-
197191, JP-A-58-12786, JP-A-5
8-101171, JP-A-59-75964, JP-A-59-106989, JP-A-62-1974466.
JP-A-62-199665, JP-A-62-199.
666, JP-A-62-199667, JP-A-63-
A number of patents have been filed, such as 28690,
The perfect one has not been obtained yet.

[0005]

The present invention is based on the above (1).
The four color inks satisfy all of the requirements (4) to (4) in good balance, the performances of the respective color inks are well balanced, and the combination of color tones is also suitable. The present invention provides a method for forming a color image by inkjet recording that provides the above.

[0006]

SUMMARY OF THE INVENTION The inventors of the present invention have found that the properties (1) to (4) required for an ink are largely dependent on the properties of the dye contained in the ink, and therefore the properties of the specific dye It has been found that the combination is suitable for a color image forming method that satisfies all the characteristics (1) to (4) above,
The present invention has been reached.

That is, the present invention is a method for forming a color image on a recording material by ejecting magenta, yellow, cyan and black aqueous inks by an ink jet method, respectively. 1} or more of one of the dyes represented by 1}, and the yellow ink has acid yellow 2 according to the color index.
3, and Direct Yellow 86, 132 and 142
The cyan ink contains at least one dye selected from the group consisting of Direct Blue 86 and 199 of the color index, and Acid Blue 9, and The black ink is in a method of forming a color image, characterized in that the free acid form contains one or more dyes selected from the group of dyes represented by the following general formulas {2} and / or {3}. .

[0008]

[Chemical 6]

(Wherein R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a hydrogen atom, Hydroxyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted amino group, nitro group, sulfonate group, alkylsulfonyl group having 1 to 9 carbon atoms, 6 to 6 carbon atoms 15 arylsulfonyl group, carboxyl group,
Alternatively, it represents a group of carboxylic acid ester, and k is 0, 1
Or a number from 2, R _4, R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, Arisai It represents a click group or a heterocyclic group, and of these, other than hydrogen atom may have a substituent. )

[0010]

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(In the formula, R ₇ represents a substituted or unsubstituted alkoxy group having 2 to 9 carbon atoms, and R ₈ is an alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents a group, X represents —CO— or —SO ₂ —, R ₉ represents a hydrogen atom, a phenyl group optionally substituted with a sulfo group or a carboxyl group, or a C1 to C3 group substituted with a carboxyl group. Represents an alkyl group of
R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group, l, m and p each represent 0 or 1, and n represents 0, 1 or 2. )

[0012]

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(Wherein R ₁₁ and R ₁₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 9 carbon atoms, and R ₁₃ and R ₁₄ represents a hydrogen atom, a sulfo group, a phenyl group which may be substituted with a carboxyl group, or a C 2 or C 3 alkyl group substituted with a carboxyl group (provided that R ₁₃ and R ₁₄ are simultaneously a hydrogen atom). , Q, r, t each represent 0 or 1,
s represents 1 or 2. )

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail. As a dye for an aqueous ink used in an inkjet system, various performances are required. Magenta in addition to performance
It is important that the yellow, cyan, and black dyes have well-balanced performances such as light resistance and water resistance, and that they have a good color rendering relationship. Although it has been extremely difficult to find the combination of the dyes, the present invention has realized the most excellent color image formation by the inkjet method by the combination of the specific dyes as described below.

The dye used in the magenta ink of the present invention has a free acid form represented by the above general formula {1}. Specifically, in the general formula {1}, R ₁ , R ₂
The substituents represented by R ₃ and R ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, trialkyl group). Fluoromethyl group, dimethylaminomethyl group, etc.), C1-C9 alkoxy group (eg, 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, phenylcarbamoyl group, etc.), substituted or unsubstituted sulfamoyl group (eg, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenyl) Sulfamoyl group, N, N-dimethylsulfamoyl group, p-carboxyphenylsulfamoyl group and the like), substituted or unsubstituted amino group (for example, N-methylamino group, carbamoylamino group, N, N- Diethylamino group, acetylamino group, etc.), nitro group, sulfonate group (eg, phenoxysulfonyl group, etc.), alkylsulfonyl group having 1 to 9 carbon atoms (eg, hydroxyethylsulfonyl group, etc.), aryl having 6 to 15 carbon atoms Sulfonyl group (eg benzylsulfonyl group), carboxyl group (COOH And groups of the carboxylic acid ester (e.g. methoxy carbonyloxy group, etc.).

K represents 0, 1 or 2. R ₄ , R ₅
And the substituents represented by R ₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (for example, ethyl group, n-butyl group, n-octyl group, ethylhexyl group, Hydroxyethyl group, carboxypropyl group, carboxycyclohexylmethyl group, 1-carboxy-2-mercaptoethyl group, 1-carboxy-2-carbamoyl-ethyl group, 1-isopropyl-1-carboxymethyl group, 1,2-dicarboxyl An alkyl group having a carboxyl group such as a propyl group), a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, vinyl group, allyl group, etc.), aryl group (for example, , 3,4-dicarboxyphenyl group, 4-butylphenyl group, 4-carboxyphenyl group, etc.), Aralkyl group (e.g., benzyl group, 1-carboxy-2-phenyl - ethyl, 1-
Carboxy-2-hydroxyphenylethyl group, 4-carboxybenzyl group, etc.), alicyclic group (eg, cyclohexyl group, 4-carboxycyclohexyl group, etc.), heterocyclic group (eg, pyridyl group,
Thiadiazolyl group, benzothiazolyl group, 2,2,6
6-tetramethylpiperidinyl group) and particularly preferably at least one of R ₄ , R ₅ or R ₆ is 1 to 4
Examples thereof include an alkyl group, an alkenyl group, an aryl group, an alicyclic group, an aralkyl group, or a heterocyclic group, each of which is substituted with one carboxyl group.

More preferably, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a cyclohexyl group, in which at least one of R ₄ , R _{5 and} R ₆ is substituted with 1 to 4 carboxyl groups, is particularly preferable. In order to obtain a magenta recording liquid, R ₄ and R ₅ each independently represent a hydrogen atom or a group represented by the following general formula {4}.

[0018]

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(In the formula, A ¹ , A ² and A ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, It represents a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, or a carboxylic acid ester group.)

The dye used in the present invention has a total of 6 or less, preferably 5 or less, groups of sulfo group (SO ₃ H) and carboxyl group (COOH) or salts of these acids in the structure. Those having 4 or less are particularly preferable. The dye used in the present invention may be used in the free acid form represented by the general formula {1} as it is, but may be in the salt form. In addition, a part of a plurality of acid groups in the dye molecule may be a salt type, and a salt type dye and a free acid type dye may be mixed. Examples of such salt type are Na, Li,
Examples thereof include salts of alkali metals such as K, ammonium salts optionally substituted with an alkyl group or a hydroxyalkyl group, or organic amine salts. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of salt type dyes may be mixed, or a plurality of salt groups formed by a plurality of acid groups in the dye molecule are different from each other. It may be a seed. Specific examples of these dyes include the following Nos. I-
Examples thereof include dyes having the structures shown in (1) to I- (55).
Although these specific examples are shown in the salt form, it goes without saying that the dyes used in the present invention are not limited to these exemplified salt forms.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[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]

[Chemical 21]

[0033]

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[0034]

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The free acid form of the dye used in the black ink of the present invention is represented by the general formula {2} and / or {3} in claim 1. Specifically, examples of the substituent of the alkoxy group represented by R ₇ in the general formula {2} include an alkoxy group, a hydroxyl group, a hydroxyalkoxy group, a phenyl group, a carboxyl group, and an alkoxy group substituted with a carboxyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by R ₈ include an unsubstituted aryl group such as a phenyl group and a naphthyl group, a phenyl group having a substituent such as an alkyl group, and a substituted aryl group such as a naphthyl group (having a substituent group of The total number of carbon atoms and the number of carbon atoms of the aryl group is 6 to 12). R ₁₁ in the general formula {3}
Examples of the substituent of the alkyl group represented by R ₁₂ and R ₁₂ include a phenyl group, and examples of the substituent of the alkoxy group include an alkoxy group, a hydroxyl group, a phenyl group and a benzyloxy group.

The dye used in the present invention may be used as it is as a free acid type represented by the general formula {2} and / or {3}, but may be a salt type. Further, a salt type dye and a free acid type dye may be mixed. An example of such a salt type is N
Examples thereof include salts of alkali metals such as a, Li and K, ammonium salts optionally substituted with an alkyl group or hydroxyalkyl group, and salts of organic amines. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. Further, when a dye molecule contains a plurality of acid groups, a part of them may be a salt type dye, and in the case of a salt type, the type of salt is not limited to one type and a plurality of types are mixed. You may have.

Specific examples of the dye represented by the general formula {2} include the dyes shown below. Although the following specific examples are shown in the salt form, it goes without saying that the dyes used in the present invention are not limited to these exemplified salt type structures.

[0038]

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[0039]

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[0040]

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Specific examples of the dye represented by the general formula {3} include dyes shown in Table 1 below.
Although the following specific examples are shown in the salt form, it goes without saying that the dyes used in the present invention are not limited to these exemplified salt type structures.

[0042]

[Table 1]

The four-color water-based ink used in the present invention comprises one or more magenta dyes represented by the general formula {1} as described above, and acid yellow 23 and direct yellows 86, 132 and 142 as yellow dyes. One or more of the dyes selected from the group, one or more of the dyes selected from the group consisting of Direct Blue 86 and 199 as the cyan dye, and Acid Blue 9, and the free acid form of the above general formula {2} as the black dye. And / or magenta, yellow, cyan and black water-based inks each containing one or more pigments represented by {3}. It is good to follow.

Further, in the magenta ink, a xanthene dye shown in the following group A may be added, if necessary, in order to improve the density and saturation of the printed matter. In this case, the mixing ratio of the magenta dye represented by the general formula {1} to the xanthene dye of the following Group A is 1/9 to 9/1 by weight, preferably 3/7 to 7/3.

[Group A] C. I. AR-50, C.I. I. A
R-51, C.I. I. AR-52, C.I. I. AR-87,
C. I. AR-91, C.I. I. AR-92, C.I. I. A
R-93, C.I. I. AR-94, C.I. I. AR-95,
C. I. AR-98, C.I. I. AR-289, C.I. I.
BR-1, C.I. I. BV-10 (“C.I” indicates “color index” and “AR” indicates “acid red”)
"BR" indicates "Basic Red", and "B"
"V" indicates "basic violet". )

The dye content in each of the above inks is 0.1 to 8% by weight, preferably 0.5 to 5%, in the total weight of each ink. The solvent used in the ink of the present invention is water and a water-soluble organic solvent, such as methyl alcohol, ethyl alcohol, and n.
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, sec-butyl alcohol, ter
C1-C4 alkyl alcohols such as t-butyl alcohol and isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane:
Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol;
Propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol and other alkylene groups containing 2 to 6 carbon atoms; glycerin; ethylene glycol Lower alkyl ethers of polyhydric alcohols such as methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; N-methyl-
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferable.

The content of the water-soluble organic solvent in the ink is in the range of 10 to 70% by weight, preferably 10 to 50% by weight, based on the total weight of the ink. The ink of the present invention prepared from such components has recording characteristics (signal responsiveness, droplet formation stability, ejection stability,
Excellent long-term continuous recording performance, ejection stability after long-term recording suspension), storage stability, stability to recording material, light resistance of recorded images, weather resistance, water resistance, etc. It is a thing. In order to further improve such characteristics, various conventionally known additives may be further added and contained. For example, viscosity adjusting agents such as polyvinyl alcohol, celluloses, water-soluble resins, various surface active agents of cation, anion or nonionic type, surface tension adjusting agents such as diethanolamine and triethanolamine, pH adjusting agents with buffer solutions, antifungal agents. Examples thereof include agents.

[0048]

EFFECTS OF THE INVENTION According to the present invention, the dyes used in the four color water-based inks of magenta, yellow, cyan and black used in the present invention are equivalent in level to each other in the liquid medium. Dissolution stability in
Since it has excellent storage stability, it has suitability as a general inkjet type water-based ink, and in particular, it has excellent light resistance, water resistance, sharpness, mutual color rendering, etc., in which all dyes are well balanced. Therefore, a color image of excellent quality can be provided.

[0049]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Examples. The invention is not limited to these examples. In the text, parts and% are based on weight unless otherwise specified. Reference Example 1 (Preparation of Ink) The following components were mixed, and then pressure-filtered with a Teflon filter having an average pore size of 0.45 μm,
After degassing, magenta, yellow, cyan, and black aqueous inks used in Examples 1 and 2 were prepared. In the following, A is acid, D is direct, F is hood, Y is yellow, R is red, B is blue, and BK is black.

Magenta ink (1) No. Dye of I- (1) 2 parts Water 69 parts Diethylene glycol 18 parts Polyethylene glycol # 200 11 parts Yellow ink (1) AY-23 2 parts Water 69 parts Diethylene glycol 18 parts Polyethylene glycol # 200 11 parts

Cyan ink (1) DB-86 2 parts Water 69 parts Diethylene glycol 18 parts Polyethylene glycol # 200 11 parts Black ink (1) No. Dye of II- (1) 3 parts Water 68 parts Diethylene glycol 18 parts Polyethylene glycol # 200 11 parts

Magenta ink (2) No. Dye of I- (8) 3 parts Water 69 parts Triethylene glycol 15 parts Glycerin 13 parts Yellow ink (2) DY-86 3 parts Water 69 parts Triethylene glycol 15 parts Glycerin 13 parts

Cyan ink (2) DB-199 3 parts Water 69 parts Triethylene glycol 15 parts Glycerin 13 parts Black ink (2) No. III- (6) Dye 4 parts Water 68 parts Triethylene glycol 15 parts Glycerin 13 parts

Magenta ink (3) No. Dye of I- (39) 2 parts AR-52 1 part Water 77 parts Diethylene glycol monobutyl ether 3 parts Polyethylene glycol # 300 17 parts Yellow ink (3) DY-132 2 parts Water 78 parts Diethylene glycol monobutyl ether 3 parts Polyethylene glycol # 300 17 copies

Cyan ink (3) AB-9 3 parts Water 77 parts Diethylene glycol monobutyl ether 3 parts Polyethylene glycol # 300 17 parts Black ink (3) No. II- (5) Dye 2 parts No. III- (1) Dye 2 parts Water 76 parts Diethylene glycol monobutyl ether 3 parts Polyethylene glycol # 300 17 parts

Magenta ink (4) No. Dye of I- (55) 2 parts Water 74 parts Glycerin 8 parts Diethylene glycol 8 parts Urea 8 parts Cyan ink (4) DB-86 2 parts Water 74 parts Glycerin 8 parts Diethylene glycol 8 parts Urea 8 parts

Yellow ink (4) DY-142 2 parts Water 74 parts Glycerin 8 parts Diethylene glycol 8 parts Urea 8 parts Black ink (4) No. II- (10) Dye 2 parts No. III- (2) Dye 1 part Water 73 parts Glycerin 8 parts Diethylene glycol 8 parts Urea 8 parts

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 an aqueous solution of polyamide resin (solid content 30%) and 12 parts by weight of urea formalin resin were used as an ink absorbing layer. The composition consisting of was applied onto a film by a bar coater method so as to have a dry film thickness of 20 μm, and dried at 80 ° C. for 10 minutes to obtain a recording material.

Example 1 One set of four colors of magenta ink (1), yellow ink (1), cyan ink (1) and black ink (1) obtained in Reference Example 1, magenta ink (3), yellow ink (3), one set of four colors of cyan ink (3) and black ink (3) and magenta ink (4),
Inkjet recording of each set with an inkjet printer (trade name IO-735, a product of Sharp Corporation) using one set of recording liquid of four colors of yellow ink (4), cyan ink (4), and black ink (4). Do The quick-drying property and print quality were evaluated according to the methods (a) and (b) below.

(A) Quick-drying: Printing is performed on electrophotographic paper (product of Xerox Co., Ltd.), bond paper and stock form paper (product of Lion Office Equipment Co., Ltd.), and after 60 seconds, the printing part is rubbed with a finger to prevent misalignment of the image. The presence or absence was judged. All of them showed no deviation and showed excellent stability. (B) Print quality: Each dot printed on the recording paper was 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.

All had no feathering and had a sharp contour. In addition, according to the following methods (c) to (f), evaluations regarding inkjet recording were performed. (C) Long-term storability of recording liquid: After the recording liquid was sealed in a glass container and stored at 0 ° C. and 60 ° C. for 6 months, no precipitation of insoluble matter was observed, and the physical properties and color tone of the liquid did not change. There wasn't.

(D) Discharge stability: Continuous discharge was performed for 24 hours in each of the atmospheres at room temperature, 5 ° C. and 40 ° C.
Stable, high-quality recording was possible from beginning to end under all conditions. (E) Discharge responsiveness: Intermittent discharge every 2 seconds and discharge after being left for 2 months were examined, and in any case, stable and uniform recording was performed without clogging at the tip of the orifice. (F) Quality of recorded image: The recorded image was high in density and clear. After 3 months exposure to room light, the decrease in concentration is less than 1%, and when immersed in water for 1 minute,
Image bleeding was very slight.

Example 2 Magenta ink (2), yellow ink (2), cyan ink (2) and black ink (2) of Reference Example 1
Recording was performed on the recording material of Reference Example 2 in the same manner as in Example 1 using the inks of 4 colors 1 set, and evaluation results of (a) to (f) were all good results.

Claims (7)

[Claims] 1. A magenta ink jet system,
In the method of forming a color image on a recording material by ejecting each of yellow, cyan and black aqueous inks, the magenta ink comprises one or more dyes whose free acid form is represented by the following general formula {1}. The yellow ink contains Acid Yellow 2 of the color index.
3, and Direct Yellow 86, 132 and 142
The cyan ink contains at least one dye selected from the group consisting of Direct Blue 86 and 199 of the color index, and Acid Blue 9, and The method for forming a color image, wherein the black ink contains at least one dye selected from the group of dyes represented by the following general formulas {2} and / or {3} in the form of free acid. Embedded image (In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms and 1 carbon atom.
~ 9 alkoxy group, halogen atom, hydrogen atom, hydroxyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted amino group, nitro group, sulfonate group, carbon number 1-9 alkylsulfonyl group, C6-C15 arylsulfonyl group, a carboxyl group, or a carboxylic acid ester group, k represents a number of 0, 1 or 2, R ₄ , R ₅ and R ₆ independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, an alicyclic group, or a heterocyclic group, and among these, Other than a hydrogen atom, it may have a substituent. ) (In the formula, R ₇ represents a substituted or unsubstituted alkoxy group having 2 to 9 carbon atoms, and R ₈ represents an alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. , X represents —CO— or —SO ₂ —, R ₉ is a hydrogen atom, a phenyl group optionally substituted with a sulfo group or a carboxyl group, or an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group. R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms substituted with a carboxyl group, l, m and p each represent 0 or 1, and n represents 0, 1 or 2. ) [Chemical 3] (In the formula, R ₁₁ and R ₁₂ are each a hydrogen atom and a carbon number of 1 to
9-substituted or unsubstituted alkyl group or 1 to 9 carbon atoms
Represents a substituted or unsubstituted alkoxy group of R ₁₃ ,
R ₁₄ represents a hydrogen atom, a sulfo group, a phenyl group which may be substituted with a carboxyl group, or a C 2 or C 3 alkyl group substituted with a carboxyl group (provided that R ₁₃ and R ₁₄ are hydrogen atoms at the same time; Is not represented),
q, r, and t each represent 0 or 1, and s represents 1 or 2. ) 2. The magenta ink has the general formula {1}
Medium, R_Four, R_FiveOr R ₆At least one of 1 to 4
Alkenyl groups substituted with carboxyl groups, alkeni
Group, aryl group, aralkyl group or cyclohexyl group
At least one selected from dyes having a structure represented by a group
2. The color according to claim 1, which contains the pigment of
-How to form an image. 3. The magenta ink has the general formula {1}
Wherein either R ₄ or R ₅ represents a hydrogen atom,
Another one contains at least one dye selected from dyes having a structure represented by an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a cyclohexyl group substituted with 1 to 4 carboxyl groups. The method for forming a color image according to claim 1 or 2. 4. The magenta ink has the general formula {1}.
Wherein k is 0, at least one of R ₁ , R ₂ and R ₃ is a hydrogen atom, and at least one of R ₁ , R ₂ and R ₃ is a trifluoromethyl group in the ortho position with respect to the azo group, It comprises at least one dye selected from a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a sulfonic acid lower alkyl ester group, a carboxyl group or a carboxylic acid lower alkyl ester group. The method for forming a color image according to claim 1, wherein the color image is formed. 5. The magenta ink has the general formula {1}.
Wherein R ₄ and R ₅ each independently contain at least one dye selected from a dye having a structure represented by a hydrogen atom or a group represented by the following general formula {4}. 5. The method for forming a color image according to any one of 4 above. Embedded image (In the formula, A ¹ , A ² and A ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a substituted or non-substituted It represents a substituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, or a carboxylic acid ester group.) 6. The magenta ink has the general formula {1}.
Wherein either R ₄ or R ₅ represents a hydrogen atom,
The method for forming a color image according to any one of claims 1 to 5, characterized in that the remaining one contains at least one dye selected from dyes having a structure represented by a group represented by the following general formula {5}. . Embedded image (In the formula, B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear alkyl group having 4 to 15 carbon atoms, an amino group mono- or di-substituted with an alkyl group having 4 to 9 carbon atoms, Carbamoyl group or sulfamoyl group, or a carbon number of 4 to
9 represents an alkoxycarbonyl group, provided that B ¹ , B
² and B ³ do not represent hydrogen atoms at the same time. ) 7. A magenta ink comprising at least one dye selected from the dyes represented by the general formula {1} in the form of the free acid and at least one xanthene dye selected from the group A below. The method for forming a color image according to claim 1, further comprising a dye. [Group A] C.I. I. AR-50, C.I. I. AR-51,
C. I. AR-52, C.I. I. AR-87, C.I. I. A
R-91, C.I. I. AR-92, C.I. I. AR-93,
C. I. AR-94, C.I. I. AR-95, C.I. I. A
R-98, C.I. I. AR-289, C.I. I. BR-1,
C. I. BV-10 (“C.I” indicates “color index”, “AR” indicates “acid red”,
“BR” indicates “basic red” and “BV” indicates “basic violet”. )