JP2002371213A - Pigment set, ink set and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment set which can obtain images having an excellent printing quality level, a high density with a clear hue, good light resistance, good resistance to indoor discoloration and fading and, in addition, a good balance between fastness and color fading even after long-term storage, an ink set, and an inkjet recording method using this ink set. SOLUTION: The pigment set comprises, as the pigment units, a magenta pigment of a water-soluble azo metal chelate compound formed of an azo based compound to be represented by formula (1) (wherein X1 is a plurality of atoms for forming at least one 5- to 7-membered heterocycle other than a pyridine ring, and the heterocyle containing X1 may has a substituent on the heterocycle, and furthermore the substituent on the heterocycle may be condensed to form a fused ring; and Ar1 is a naphthyl group having a substituent) and a metallic element, a yellow pigment, and a cyan pigment. The ink set has this pigment set, and the recording method uses this ink set.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a dye set, an ink set, and an ink jet recording method using the same. More specifically, a dye set including at least three color dye units including a magenta dye containing a water-soluble azo metal chelate compound suitable for ink jet recording as a dye unit, an ink set including an ink of each dye, and an ink jet using the same It relates to a recording method.

[0002]

2. Description of the Related Art A so-called ink jet recording method has been put to practical use, in which droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye are jetted from a fine ejection orifice to perform recording. Regarding this recording liquid, the P
Fast fixing to recording papers used for general office work, such as PC (plain paper copier) paper and fan hold paper (continuous paper such as a computer), and the print quality of printed matter is good. It is required that the contour is clear without bleeding, and that the stability during storage as a recording liquid is also excellent, so that the solvent that can be used is significantly limited.

[0003] Dyes for recording liquids have sufficient solubility in the limited solvents described above, are stable even when stored as recording liquids for a long period of time, and have a high quality. It is required that the color saturation and density be high, and that it be excellent in water resistance, light resistance, indoor discoloration and the like. Direct dyes that have been used in the past have a poor color tone, whereas acid dyes with a clear color tone tend to have poor light fastness.Moreover, conventionally, metal-containing azo dyes have good light fastness. However, the color tone was dull, unclear and poor in color tone. Therefore, development of a dye for ink jet recording, which satisfies both color tone and light resistance, has been desired as a dye for a recording liquid.

On the other hand, in the ink jet recording method,
In order to form a full-color image, three primary colors of yellow (Y), magenta (M), and cyan (C), or four colors of black (Bk) are used, and the ejection amount of each ink is used. Is controlled, the colors are mixed on the recording material to form an image. Further, when forming a full-color image, it is necessary to express not only the difference in color but also the shading of the color, but the shading portion is usually formed using two or more types of inks having different dye densities. However, with regard to the conventional set of ink jet recording dyes, the problem is that the image is discolored by light irradiation, that is, the light resistance is poor, and in particular, the light resistance of the light-colored portion using an ink having a low dye concentration is low. Was a problem. Further, regarding the fading of a full-color image, it is required that the primary colors constituting the colors have the same fading balance. However, conventional dyes, especially magenta dyes,
It is liable to undergo catalytic fade due to cyan dyes, particularly phthalocyanine dyes, and the OD (print density) of magenta in the mixed color portion tends to be significantly fading from the degree of fading expected from the fastness of the magenta dye alone. Was. In order to compensate for this drawback, ink sets using various magenta dyes have been proposed, but satisfactory performance having both saturation, hue and fastness has not been obtained. In this specification, the following 3
Each dye of the primary color dye and the black dye is a dye unit,
A combination of two or more dyes is referred to as a dye set, and a combination of two or more inks containing each dye and a combination of two or more inks having different dye concentrations are referred to as an ink set.

[0005] For example, Japanese Patent Application Laid-Open No. 2000-256587 shows an example in which the light fastness of a mixed color print of magenta and cyan is improved, and it is apparent that the light fastness has been somewhat improved as compared with the prior art. However, according to the light fastness test result of the image, magenta had a large color difference of about three times that of cyan, that is, only a large degree of discoloration, and there was still room for improvement.

On the other hand, US Pat. No. 6,053,969 describes examples of a dye set and an ink set in which the types of yellow, cyan, and magenta dyes are specified. However, the above-mentioned problem of the fastness of the mixed color image of the magenta dye is not recognized at all, and there is no suggestion of using a specific magenta dye as in the present invention.

[0007]

According to the present invention, when full-color recording is performed by an ink jet recording method, the print quality is good, the color tone of the recorded image is clear, the density is high, and the light resistance is excellent. It is an object of the present invention to provide a dye set, an ink set, and an ink jet recording method using the same, which are capable of obtaining an image having little discoloration and fading and having good balance between fastness and fading even when stored for a long period of time. .

[0008]

Means for Solving the Problems The present inventors have achieved the above object by using a dye set containing, as a magenta dye, a water-soluble dye which is an azo chelate compound of a specific azo compound and a metal element. That is, the gist of the present invention is:
At least one magenta dye, at least one yellow dye, and at least one dye that are water-soluble azo metal chelate compounds formed from an azo compound represented by the following general formula (1) and a metal element as a dye unit: In a dye set characterized by containing a cyan dye.

Embedded image

(The general formula (1) is an azo compound having at least one hydrophilic group in the molecule, and X ₁ is required to form at least one 5- to 7-membered heterocyclic ring. Represents a plurality of atoms, but the heterocycle containing X ₁ is a heterocycle other than a pyridine ring, and the heterocycle containing X ₁ may have a substituent on the heterocycle, .Ar ₁ fused heterocyclic ring may be substituted including good .X ₁ combine to form a condensed ring group are more condensed in the following general formula (2)
And represents a naphthyl group selected from (4). Y ₁ represents a chelating group; Z ₁ represents an optional substituent which may be different from each other; and a represents an integer of 0 to 6. )

[0010]

Embedded image

Another gist of the present invention is characterized in that each of the dye units in the above-mentioned dye set is composed of an ink containing a yellow dye, a magenta dye, a cyan dye, and optionally a black dye. An ink set and an ink jet recording method using the ink set.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The dye set of the present invention is constituted by a dye unit composed of three primary color dyes of magenta, yellow and cyan and a black dye. The metal chelate dye of the magenta dye in the present invention is an azo compound represented by the general formula (1) and a water-soluble azo metal chelate compound formed from a metal element. The molecular weight is usually preferably 4000 or less, and particularly preferably 300 or more and 2000 or less in consideration of solubility, storage stability, print density and the like. In the general formula (1), X ₁ represents a plurality of atoms necessary to form at least one 5- to 7-membered heterocyclic ring, and the heterocyclic ring containing X ₁ is other than a pyridine ring. It is a heterocycle. The heterocyclic ring containing X ₁ is preferably an imidazole ring, a pyrazole ring, an isoxazole ring, a thiazole ring, a thiadiazole ring, a pyridazine ring,
A pyrimidine ring, a pyrazine ring, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring, or the like. Among them, the heterocyclic ring containing X ₁ is preferably an imidazole ring, a pyrazole ring, a thiazole ring, or a thiadiazole ring.

The heterocycle containing X ₁ may have one or more substituents on the heterocycle, and the substituents on the heterocycle may be further condensed to form a condensed ring. In this case, the substituents on the heterocyclic ring are each independently an optionally substituted alkyl group (for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, a carboxymethyl group, a carboxyethyl group, Methyl group), an optionally substituted aryl group (preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group), and an optionally substituted aralkyl group (a benzyl group and the like, preferably Carbon number 7-1
0), an optionally substituted allyl group (eg, vinyl group, 2-propenyl group, etc.), an optionally substituted alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms, eg, a methoxy group, An ethoxy group, etc.), an optionally substituted aryloxy group (eg, a phenoxy group, etc.), an optionally substituted acyloxy group (preferably an alkanoyloxy group having 2 to 7 carbon atoms such as an acetyloxy group, benzoyloxy Group), an optionally substituted alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 7 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group and the like), and an optionally substituted aryloxycarbonyl group (eg, a phenoxy group) Carbonyl group, naphthyloxycarbonyl group, etc.), carbamoyl which may be substituted An optionally substituted acyl group (eg, an acyl group having 2 to 10 carbon atoms such as an acetyl group), a carboxyl group, a hydroxyl group, a cyano group, and an optionally substituted acylamino group (eg, a carbon atom such as an acetylamino group). Alkanoylamino group, benzoylamino group of formulas 2 to 7, nitro group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), phosphono group, sulfo group, mercapto group, alkylthio group which may be substituted (For example, having 1 to 1 carbon atoms such as a methylthio group and an ethylthio group)
6 alkylthio groups), an optionally substituted alkylsulfoxy group (for example, an alkylsulfoxy group having 1 to 6 carbon atoms such as a methylsulfoxy group and an ethylsulfoxy group), and an optionally substituted alkylsulfonyl It is preferably selected from a group (for example, an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group and an ethylsulfonyl group) or a thiocyanato group.

Among them, in the general formula (1), the heterocyclic ring containing X ₁ is preferably a metal chelate dye represented by the following general formulas (5) to (8).

[0015]

Embedded image

(In the formula, R ₁ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted An alkoxy group, an optionally substituted aryloxy group, an optionally substituted acyloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, a carboxyl group, Carbamoyl group, hydroxyl group, an optionally substituted acyl group, a cyano group, an optionally substituted acylamino group, a nitro group,
It is a group selected from a halogen atom, a sulfo group, a mercapto group, an optionally substituted alkylthio group, and a thiocyanato group, and R ₁ may further form a condensed ring together with an imidazole ring. c represents an integer of 0 to 2.
R ₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted allyl group. In particular, R ₁ is preferably an optionally substituted alkoxycarbonyl group, a carboxyl group, or a cyano group, and R ₂ is preferably a hydrogen atom or an optionally substituted alkyl group. Most preferably, c is 2, R ₂ is both a cyano group, and R ₂ is a hydrogen atom or an optionally substituted alkyl group.

[0017]

Embedded image

(In the formula, R ₁ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, and an optionally substituted Represents an alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, a carboxyl group, an optionally substituted carbamoyl group, a hydroxyl group, a cyano group, or a sulfo group, and d represents an integer of 0 to 2. R ₄ Represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.)

[0019]

Embedded image

(Wherein R ₅ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted An alkoxy group, an optionally substituted aryloxy group, an optionally substituted acyloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, a carboxyl group, a hydroxyl group, Represents an optionally substituted acyl group, a cyano group, an optionally substituted acylamino group, a nitro group, a halogen atom, a sulfo group, an optionally substituted alkylthio group, or an optionally substituted arylthio group, ₅ may further form a condensed ring together with the thiazole ring .e represents an integer of 0 to 2.) preferably R ₅ If it is an optionally substituted alkyl group, if there is no R ₅ in e = 0, or R
Desirably, ₅ forms a condensed ring with a thiazole ring.

[0021]

Embedded image

Wherein R ₆ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group,
Represents an aralkyl group which may be substituted, a mercapto group, an alkylthio group which may be substituted, an alkylsulfoxy group which may be substituted, or an alkylsulfonyl group which may be substituted. ) R ₆ is preferably a hydrogen atom or an optionally substituted alkyl group.

Among the heterocycles represented by the general formulas (5) to (8), an imidazole ring represented by the general formula (5) is preferable. In particular, the one in which the general formula (5) is the following general formula (5 ′) is preferable.

Embedded image (Wherein, R ₂ ′ represents a hydrogen atom or an optionally substituted alkyl group)

Ar ₁ in the general formula (1) is a naphthyl group represented by the general formulas (2) to (4);
Y ₁ represents a chelating group. Y ₁ is preferably a hydroxyl group, a carboxyl group, an optionally substituted amino group (for example, an amino group, a methylamino group, a bis (2-hydroxyethyl) amino group and the like), a sulfo group, a carbamoyl group, a substituted or unsubstituted group. A good alkoxy group (for example, methoxy group, carbonyl group, 2-hydroxyethoxy group, etc.),
An optionally substituted alkylthio group (eg, a methylthio group, a 2-hydroxyethylthio group, etc.), an optionally substituted alkylsulfonylamino group (eg, a methylsulfonylamino group, etc.), or an optionally substituted arylsulfonyl An amino group (eg, a benzenesulfonylamino group); More preferably, Y ₁ is a hydroxyl group.

In the general formulas (2) to (4), Z ₁ is each independently an optionally substituted alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group); An optionally substituted aryloxy group (for example, a phenoxy group, etc.), an optionally substituted acyloxy group (for example, an alkanoyloxy group having 2 to 7 carbon atoms such as an acetyloxy group, a benzoyloxy group, etc.), Alkoxycarbonyl groups (for example, having 2 to 2 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group)
7), an optionally substituted aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), a carboxyl group, an optionally substituted carbamoyl group (eg, carbamoyl group, substituted A carboxyanilide group (e.g., 3-sulfocarboxyanilide group), a hydroxyl group, an amino group which may be substituted (for example, an amino group,
A C1-6 alkylamino group such as a methylamino group, etc.), a ureido group, an optionally substituted acylamino group (eg, a C2-7 alkanoylamino group such as an acetylamino group, a benzoylamino group) An optionally substituted alkylsulfonylamino group (for example, an alkylsulfonylamino group having 1 to 6 carbon atoms such as a methylsulfonylamino group), an optionally substituted arylsulfonylamino group (for example, a phenylsulfonylamino group,
4-methylphenylsulfonylamino group), phosphono group, sulfo group, and optionally substituted sulfamoyl group (eg, sulfamoyl group, N, N-bis (carboxymethyl) sulfamoyl group). Is preferred. a represents an integer of 0 to 6.

Z ₁ is preferably a carboxyl group, an optionally substituted carbamoyl group, a sulfo group or an optionally substituted sulfamoyl group. Further, among the naphthyl groups represented by the general formulas (2) to (4), the general formula (2) or (4) is preferable. In particular, those in which Ar ₁ is represented by the following general formula (5 ″) are preferably used.

Embedded image (Wherein R ₂ ″ represents a sulfo group and a sulfamoyl group which may be substituted) The azo compound represented by the general formula (1) has at least one hydrophilic group in the molecule. Compound. Examples of such a hydrophilic group include a sulfo group, a carboxyl group, a hydroxyl group, an amino group, a phosphono group and the like, and among these, a sulfo group or a carboxyl group is preferable.

In the present invention, the metal forming the chelate compound with the azo compound represented by (1) includes, for example, silver (I), aluminum (III), gold (III), cerium (III, IV), cobalt (II, III), chromium (III), copper (I, II), europium (III), iron (II, III), gallium (III), germanium (IV), indium (III),
Lanthanum (III), manganese (II), nickel (II), palladium (II), platinum (II, IV), rhodium (II, II
I), ruthenium (II, III, IV), scandium (II
I), silicon (IV), samarium (III), titanium (IV),
Uranium (IV), zinc (II), zirconium (IV) and the like. Preferably nickel (II), cobalt (II,
III) and copper (II). The anions of the metal salts used for the production of the metal complex include Cl ⁻ , Br ⁻ , and CH ₃ CO.
Monovalent or divalent anions such as O ⁻ and SO ₄ ²⁻ are exemplified.

The dye used in the present invention may be used as it is in the form of a free acid, but it may be used as it is when it is obtained in the form of a salt, or may be converted to the desired salt form. Good. A part of the 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 alkyl amines,
Examples include 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 types may be mixed.

In the structure of the dye used in the present invention, when one molecule contains a plurality of acid groups, the plurality of acid groups may be of a salt type or an acid type and different from each other. Good. Specific examples of these dyes include, for example, dyes having the structures shown in Tables 1 to 6 below, but the present invention is not limited thereto.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

[0037]

[Table 8]

[0038]

[Table 9]

[0039]

[Table 10]

[0040]

[Table 11]

[0041]

[Table 12]

[0042]

[Table 13]

[0043]

[Table 14]

[0044]

[Table 15]

[0045]

[Table 16]

[0046]

[Table 17]

[0047]

[Table 18]

[0048]

[Table 19]

[0049]

[Table 20]

[0050]

[Table 21]

[0051]

[Table 22]

[0052]

[Table 23]

[0053]

[Table 24]

[0054]

[Table 25]

[0055]

[Table 26]

The yellow dye as the dye unit in the present invention is not particularly limited. For example, dyes represented by the following formulas (9), (10), (11) and (12) are preferred. Used. Those having a molecular weight of 4000 or less are preferable, and those having a molecular weight of 300 or more and 2000 or less are preferable in consideration of solubility, storage stability, print density, and the like.

Embedded image (In the formula, R ^Y1 represents a hydrogen atom, a halogen atom, or an arbitrary substituent, a plurality of R ^{Y1 s} may be different or the same, and n represents 1 or 2.)

[0057]

Embedded image(Where R^Y2Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^Y2Are the same even if they are different
And n represents 1 or 2. )

[0058]

Embedded image (In the formula, R ^Y3 represents a hydrogen atom, a halogen atom, or an arbitrary substituent, and a plurality of R ^Y3 may be different or the same.)

[0059]

Embedded image (In the formula, R ^Y4 represents a hydrogen atom, a halogen atom, or an arbitrary substituent, and a plurality of R ^Y4 may be different or the same.)

In each of the general formulas (9) to (12),
R ^{Y1 to} R ^Y4 are, for example, a halogen atom, a carboxyl group,
A sulfo group, a phosphono group, a sulfamoyl group, an optionally substituted sulfonyl group, an optionally substituted carbonyl group, an optionally substituted triazinyl group, an optionally substituted C ₁ -C ₄ alkyl group, It is selected from an optionally substituted C ₁ -C ₄ alkoxy group, an optionally substituted phenyl group, an optionally substituted amino group, and the like. Among them, a sulfo group, a carboxyl group, or the like is used as a suitable substituent for the aromatic ring described on the left side of the azo group described in general formulas (9) to (12).
On the other hand, the aromatic ring described on the right side of the azo group described in the general formulas (9) to (12) is substituted with an alkyl group, an alkoxy group, a carboxyl group, a sulfo group, a halogen atom, or the like. An optionally substituted phenyl group or the like is used as a suitable substituent. Preferable examples of the substituent bonded to the amino group described in the general formulas (9) and (10) include a carbonyl group and a triazinyl group. And may be linked to another azo dye skeleton via an amino group or a thienyl group substituted with a substituted alkyl group.

Specific examples of these dyes include, for example, C.I. I. Acid Yellow 17: 1, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 49, C.I.
I. Acid Yellow 65, C.I. I. Acid Yellow 104, C.I. I. Acid Yellow 155, C.I. I. Acid Yellow 183, C.I. I. Acid Yellow 19
4, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 106, C.I. I. Direct Yellow 13
2, C.I. I. Direct Yellow 142, C.I. I. Direct Yellow 173, C.I. I. Direct Yellow 1
94.

Further, the dyes corresponding to the general formulas (9) and (10) are represented by [(AN = NB ¹ -NH-) n-R] (where n is 1 or 2). Equations (11) and (1)
When the dye corresponding to 2) is represented by [AN = NB ² ], the structures of the free acids represented by A, B ¹ and B ² are shown in Tables 7 and 8. The dye of the present invention can be appropriately selected from these, but is not limited thereto.

[0063]

[Table 27]

[0064]

[Table 28]

[0065]

[Table 29]

[0066]

[Table 30]

[0067]

[Table 31]

The cyan dye as the dye unit of the present invention is not particularly limited. For example, the following general formula (1)
The dyes represented by 3) and (14) are preferably used. Usually, those having a molecular weight of 5,000 or less are preferable, and those having a molecular weight of 300 or more and 3000 or less are preferable in consideration of solubility, storage stability, print density, and the like.
In particular, the phthalocyanine dye represented by the general formula (13) is preferable because of its good light fastness, but the general formula (14)
The triphenylmethane-based dye represented by is also excellent in hue and saturation, and is used for cyan ink.

[0069]

Embedded image (In the formula, R ^C1 represents a hydrogen atom, a halogen atom, or an arbitrary substituent, a plurality of R ^C1 may be different or the same, and M represents a metal atom.)

[0070]

Embedded image(Where R^C2Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^C2Are the same even if they are different
Is also good. )

In the general formulas (13) and (14), R ^C1 and R ^C2 are, for example, a halogen atom, a carboxyl group, a sulfo group, a phosphono group, a sulfamoyl group, an optionally substituted sulfonyl group, which may be a carbonyl group, an optionally substituted triazinyl group, optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy groups, optionally substituted It is selected from a good phenyl group, an optionally substituted amino group and the like. Among them, R ^C1 described in the general formula (13) includes an alkyl group, a halogen atom, a sulfo group, a sulfamoyl group, a sulfonyl group substituted by an alkyldiamino group bonded to a substituted triazinyl group, a substituted phenyl group, or the like. Substituents selected from are preferably used. on the other hand,
As R ^C2 described in the general formula (14), for example, a carboxyl group, a sulfo group, a sulfamoyl group, an amino group substituted with a substituted alkyl group, and the like are suitably used.

Specific examples of these dyes include C.I. I. Acid Blue 9, C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Reactive Blue 5, 7, 11, 14, 15:01, 1
8, 21, 23, 25, 35, 38, 41, 48, 6
3, 71, 72, 77, 80, 85, 92, 95, 10
5, 107, 118: 1, 123, 124, 136, 1
38, 140, 143, 148, 152, 153, 15
9, 174, 197, 207, 215, 227, 22
9, 23, or a hydrolyzate thereof, or a dye having a free acid structure shown in Tables 9 to 10, but the present invention is not limited thereto.

[0073]

[Table 32]

[0074]

[Table 33]

The black dye as the dye unit of the present invention is not particularly limited, and a pigment dye represented by carbon black or a dye dye is preferably used. In the dye-based pigment, for example, the general formula (15) or the general formula (1)
The dye represented by 6) is particularly preferably used, and its molecular weight is preferably 4,000 or less, and among them, 300 or more and 200 or more.
A value of about 0 or less is preferable in consideration of solubility, storage stability, print density, and the like.

[0076]

Embedded image(Where the general formula (15) has at least one or more
Wherein B, C and D are each a compound having a hydrophilic group
Each independently represents an aromatic ring, further having an optional substituent,
Is also good. m is 0-1, n is 0-3, p is 0-2, q is 0
Represents an integer of 1 to 4. When there are a plurality of B, each B is
They may be the same or different. R ^B1And R^B2Is each
Each independently represents a hydrogen atom or an optional substituent. )

[0077]

Embedded image (Here, the general formula (16) is a compound having at least one or more hydrophilic groups in the molecule, and B ′, C ′, and D ′
Each independently represents an aromatic ring, and may further have an arbitrary substituent. m 'is 0-1, n' is 0-3, p 'is 0
-2 and q 'represent an integer of 0-4. When there are a plurality of B's, each B may be the same or different.
R ^B1 and R ^B2 each independently represent a hydrogen atom or an optional substituent. M may also be in a tridentate or higher coordination, in which case M can be any ligand to metal, from any substituent or binding moiety in general formula (16), or by any ligand. May be coordinated. In the case where a plurality of B's are present, B's adjacent to each other across an azo group, or B '
And C ′, a metal ion may be further coordinated in the form of —OMO—. )

In each of the formulas (15) to (16), R ^B1 and R ^B2 are, for example, a hydrogen atom, an optionally substituted sulfonyl group, an optionally substituted carbonyl group, or an optionally substituted carbonyl group. which may triazinyl group, optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy group, a phenyl group which may be substituted is preferably used.

In the general formula (15), m is 1.
Are particularly preferable, and n is 1 or 2.
Is particularly preferable, and p is particularly preferably 1.^B1Passing
And R ^B2Is independently a hydrogen atom, an optionally substituted phenyl
Group, optionally substituted C₁~ C_FourIs an alkyl group
Are particularly preferred. q is more preferably 0 to 2
When q is 0 or 1, particularly when q is 0
In some cases, the aromatic ring represented by D is an aromatic ring-substituted azo group.
Substituted ones are also preferably used. When q is 1,
The aromatic ring represented by B is a sulfo group, a carboxyl group,
A phenyl or naphthyl group substituted with a hono group
The aromatic ring represented by C is preferably a sulfo group,
Ruboxyl group, optionally substituted C₁~ C_FourAlkyl
Group, C which may be substituted₁~ C_FourAlkoxy group, ace
Substituted with a toamino group, substituted alkylsulfonyl group, etc.
Those that are phenylene or naphthylene are more
It is preferably used. When q is 2 or more, the general formula (1)
Among the multiple Bs in 5), the B at the left end
Fe-, carboxyl-, or phosphono-substituted
Preferably, it is a nyl group or a naphthyl group.
Other than B and C are a sulfo group, a carboxyl group,
C that may be₁~ C_FourAlkyl group, substituted
Good C₁~ C_FourAlkoxy group, acetamino group, substituted
A phenylene group substituted with an alkylsulfonyl group, etc.
Is more preferably a naphthylene group,
You.

In the general formula (16), m ′ is particularly preferably 0, n ′ is particularly preferably 1 or 2, and p ′ is particularly preferably 1.
R ^B1 and R ^B2 independently represents a hydrogen atom, an optionally substituted phenyl group, it is particularly preferable an optionally substituted C ₁ -C ₄ alkyl group. q ′ is more preferably 0 to 2, and when q ′ is 0 or 1, particularly when q ′ is 0, the aromatic ring represented by D ′ is further an aromatic ring-substituted azo group. Substituted ones are also preferably used.
When q ′ is 1, the aromatic ring represented by B ′ is preferably a phenyl group or a naphthyl group substituted by a sulfo group, a carboxyl group, or a phosphono group, and the aromatic ring represented by C ′ is a sulfo group. , carboxyl group, optionally substituted C ₁ -C ₄ alkyl group, an C ₁ ~ substituted
A phenylene group or a naphthylene group substituted with a C ₄ alkoxy group, an acetamino group, a substituted alkylsulfonyl group or the like is more preferably used. When q ′ is 2 or more, B ′ at the left end among a plurality of B ′ present in general formula (16) may be a phenyl group or a naphthyl group substituted with a sulfo group, a carboxyl group, a phosphono group. Preferable, other B 'and C'
Is a sulfo group, a carboxyl group, an optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy group, acetamino group, is substituted by an substituted alkylsulfonyl group a phenylene group Alternatively, a naphthylene group is more preferably used.

Specific examples of these dyes include, for example,
C. I. Food black 2, C.I. I. Direct Black 19, C.I. I. Direct Black 154, C.I. I.
Direct Black 195, C.I. I. The structures of Direct Black 200, Reactive Black 31, or a hydrolyzate thereof, or a free acid are shown in Tables 11 to 12.
However, the present invention is not limited to these. In Tables 11 and 12, the following formulas (15 ′) and (1) were used to explain the structures of the black dyes represented by the general formulas (15) and (16).
6 ').

[0082]

Embedded image The black dye used in the present invention is represented by the formula (15 ′)
Is preferably 1 to 2, and when n is 2, B
May be the same or different. In the formula (16 ′), preferably, m is 0 to 1, and n is 0 to 2. When n is 2, B may be the same or different.

[0083]

[Table 34]

[0084]

[Table 35]

[0085]

[Table 36]

[0086]

[Table 37]

[0087]

[Table 38]

[0088]

[Table 39]

Table 13 specifically shows yellow and black dyes particularly preferably used in the dye set of the present invention. Further, Table 14 shows examples of particularly preferred combinations of these dyes and the magenta dye in the present invention.

[0090]

[Table 40]

[0091]

[Table 41]

[0092]

[Table 42] In Table 14, magenta compound No. In Tables 1 to 6
Compound No. With the yellow and black compounds N
o. Is the compound No. in Table 13. Respectively.

The magenta dye of the present invention can be prepared by diazotizing the starting cyclic amino compound and coupling it with naphthols, or by condensing the hydrazino compound with, for example, a 1,2-naphthoquinone derivative. None, it can be obtained according to a known method such as a method of reacting a metal compound such as nickel chloride or copper sulfate with an azo dye. The ink of the present invention is prepared using each dye of the above dye set, that is, magenta, yellow, cyan, and, if necessary, black. The content of the dye in the recording liquid (ink) is as follows. The total amount is preferably 0.1 to 10% by weight, preferably 0.5 to 7% by weight, particularly preferably about 2 to 5% by weight based on the total amount of the recording liquid. When a light-colored ink is used, the content of the pigment is preferably about 0.1 to 2% by weight, and more preferably about 0.1 to 1.5% by weight. Further, a plurality of dyes may be contained in any ink. Further, in the magenta ink of the present invention, the dye represented by the general formula (1) is contained as a chelate compound with a metal element, but forms a partially free dye without forming a chelate compound in the recording liquid. It also includes coexistence. In some cases, the presence of a free dye allows the chelate compound to be stably present. On the other hand, if the content is too large, the original performance as a metal chelate compound is diminished. Therefore, when it is present, the content is usually about 1 to 5% by weight in the recording liquid.

The aqueous medium used for the recording liquid (ink) of the present invention is a medium comprising water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, and the like.
Diethylene glycol, triethylene glycol, polyethylene glycol (weight average molecular weight of about 190 to 40
0), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane ,Ethyl alcohol,
It is preferable that water contains isopropanol and the like.
These water-soluble organic solvents are usually used in the range of 1 to 45% by weight based on the total amount of the recording liquid. On the other hand, water is used in the range of 50 to 95% by weight based on the total amount of the recording liquid.

In the recording liquid of the present invention, 0.1% of the total amount of the recording liquid was used.
1 to 10% by weight, preferably 0.5 to 5% by weight of urea,
By adding a compound selected from thiourea, biuret and semicarbazide, or by adding 0.001 to 5% by weight of a surfactant, quick drying after printing and print quality can be further improved.

The ink set of the present invention is a combination of at least two kinds of inks containing the above-mentioned dyes, or a combination of two or more kinds of inks having different dye concentrations in each dye. A suitable ink set can be obtained by combining the inks prepared based on the above-described preferable combinations of the dyes.

[0097]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

Reference Example-I Production of Dye (1) 1: Synthesis of Azo Compound (Diazotization Coupling Example 1) 206 ml of water, 20 ml of 35% hydrochloric acid, 2-amino-4,
Cooling a solution of 10.0 g of 5-dicyanoimidazole;
5.5 g of sodium nitrite was added to 12 ml of water at 5 to 10 ° C.
An aqueous solution dissolved in was added for diazotization.

Excess sodium nitrite was decomposed with sulfamic acid to obtain a diazo liquid. Dissolve 27.5 g of disodium 2-naphthol-3,6-disulfonate in 284 ml of water and adjust the pH to 8.0 with an aqueous NaOH solution at 0 to 5 ° C.
The above diazo solution was added dropwise while adjusting to 9.0. The resulting solid was collected by filtration, washed with water, and dried to obtain 34.1 g of a compound represented by the following structural formula (L1).

[0100]

Embedded image

2: Synthesis of Metal Chelate Dye (Reference Example 1) Preparation of Nickel Chelate Dye To 3.0 g of the azo dye of the structural formula (L1), 45 ml of water was added, adjusted to pH 10.0 with an aqueous NaOH solution, and dissolved. Nickel (II) chloride hexahydrate 0.72g / water 7ml
Was added dropwise at 15-25 ° C. During the reaction, the pH was adjusted to 9.0 to 10.0 with an aqueous NaOH solution. 1.0 g of sodium chloride was added, and the solid content was collected by filtration. To the obtained wet cake, 45 ml of water was added, heated to 50 to 55 ° C. to dissolve, and filtered. 130 ml of isopropyl alcohol was added to the obtained filtrate, and the precipitate was collected by filtration, dried and dried.
1, No. 1.1 g of a nickel chelate compound of 1-5 was obtained. The maximum absorption wavelength (in water) of the obtained nickel chelate dye was 529.0 nm.

Reference Example 2 Preparation of Copper Chelate Dye To 10.0 g of the azo dye of the structural formula (L1) was added 300 ml of water, adjusted to pH 10.0 with an aqueous NaOH solution, and dissolved. Next, 1.73 g of copper (II) chloride dihydrate / 33 m of water
of solution were added dropwise. During the reaction, the pH was adjusted to 9.0 to 10.0 with an aqueous NaOH solution. 20 g of sodium chloride was added, and the solid content was collected by filtration. The obtained wet cake was dissolved in water, isopropyl alcohol was added, and the precipitate was collected by filtration and dried to obtain 5.0 g of a copper chelate dye No. 1-6 in Table 1. The maximum absorption wavelength (in water) of the obtained copper chelate dye was 544.0 nm.

(Reference Examples 3 to 19) Preparation of Nickel Chelate Dye 1-9, N
o. 1-10, no. 1-14, No. 1-15, N
o. No. 1-34, No. 1; No. 1-36, No. 1; 1-38, N
o. No. 1-44, no. No. 1-45, No. No. 1-46, No. 1
-48, No. No. 1-51, No. 1; No. 1-52, No. 1; 1-53,
No. of Table-5. 5-5, No. 5; No. 5-8, No. 5 in Table-6.
A 6-8 nickel chelate dye was prepared.

The maximum absorption wavelength of these chelate dyes in water was measured. Table 15 below shows the chelate dyes prepared in the respective reference examples and their maximum absorption wavelengths in water.
Shown in

[0105]

[Table 43]

No. The mass spectrum of 1-34 was measured by a magnetic field type mass spectrum (JMS-700 manufactured by JEOL) by an electrospray ion method. A main peak, m / e = 791, was observed. 1-34 metal: azo compound = 1: 2 complex (molecular weight 792 58
Ni).

(Reference Example 20) Preparation of Copper Chelate Dye A copper chelate dye of 1-35 was prepared. The maximum absorption wavelength (in water) of the obtained copper chelate dye was 549.5 nm.

II. Production of Dye (2) 1: Synthesis of Azo Compound (Diazotization Coupling Example 2) Acetic acid 40 m in 2.96 g of 2-aminothiazole sulfate
15 ml of l, n-propionic acid was added and cooled to -5 ° C. Nitrosylsulfuric acid (43.8) was stirred at 0-5 ° C.
%) Was added and stirred to obtain a diazo liquid. 7.0 g of disodium 2-naphthol-3,6-disulfonate
Was dissolved in 300 ml of ice water, and the diazo solution obtained above was added. At 5 ° C. or lower, a 20% aqueous NaOH solution is added, and p
Neutralized and coupled to H3. Sodium chloride 40
g was added and the solids were filtered off.

The obtained wet cake was redispersed in water (volume, 200 ml), and the pH was adjusted to 9.0 with an aqueous NaOH solution.
And add 300 ml of isopropyl alcohol,
The precipitated dye was collected by filtration, and water / isopropyl alcohol = 1.
Then, the resultant was washed with a mixture of / 1 and dried to obtain 7.48 g of an azo dye represented by the following structural formula (L2).

[0110]

Embedded image

2: Synthesis of Metal Chelate Dye (Reference Example 21) Preparation of Nickel Chelate Dye To 1.53 g of the dye of structural formula (L2), 40 ml of water was added, adjusted to pH 10.0 with an aqueous NaOH solution, and dissolved. Next, an aqueous solution of 0.792 g of nickel (II) chloride hexahydrate was added dropwise. During the reaction, the pH is adjusted to 5.0 to 6.0 with acetic acid.
And stirred. After the disappearance of the raw materials, the reaction solution was added to 80 ml of isopropyl alcohol, and the precipitated pigment was filtered off.
Washed and dried with a mixture of isopropyl alcohol = 1/2, and 3-1 Nickel chelate dye
63 g were obtained. The maximum absorption wavelength (in water) of the obtained nickel chelate dye was 545.5 nm.

Reference Examples 22 to 29 Preparation of Nickel Chelate Dyes 2-6, Table-3
No. No. 3-12 and No. 3 in Table-4. 4-1. 4-
2, No. No. 4-15 and No. 4 in Table-5. 5-1. 5
-2, No. 2; A 5-3 nickel chelate dye was prepared. The maximum absorption wavelength of the obtained nickel chelate dye in water was measured. Table 16 below shows the chelate dyes prepared in Reference Examples and their maximum absorption wavelengths in water.

[0113]

[Table 44]

Reference Example-II Preparation of Recording Liquid Preparation of Recording Liquid (Ink-1) 10 parts by weight of diethylene glycol, 3 parts by weight of diethylene glycol monobutyl ether, and the N obtained in Reference Example 1
o. Water was added to 3.0 parts by weight of the 1-5 nickel chelate dye, and the pH was adjusted to 9 with an aqueous sodium hydroxide solution to make the total amount 100 parts by weight. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon (registered trademark) filter having a pore size of 1 μm, and then degassed with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid. The pH of the recording liquid was 7.5.

Evaluation of Saturation of Printed Material Using the obtained recording liquid, an electrophotographic paper (product name: 4024 paper, product of Xerox Co., Ltd.) using an inkjet printer (product name: PM-750C, manufactured by Seiko Epson Corporation) Super Fine Paper (Product name MJA4S
P1, manufactured by Seiko Epson), glossy paper for Super Fine (trade name: MJA4SP3, manufactured by Seiko Epson), dedicated photo print paper (trade name: PMA4SP1,
Inkjet recording was performed on each of the printers (manufactured by Seiko Epson Corporation), and the saturation of the obtained printed matter was measured with a Macbeth densitometer (Gretag Macbeth SPM50, manufactured by Macbeth).
* Quantified in the form of values. Here, the C * value is a numerical value representing the level of high or low chroma of the image, and the larger the numerical value, the higher the chroma. For special photo print paper,
As a result of the above measurement, a good result was obtained in which the C * value was 77.6. Various evaluations were made by the following methods (a) to (c).

(A) Light fastness of recorded image: Recording paper (printed matter) using a xenon fade meter (manufactured by Atlas).
Was irradiated at an irradiation energy of 150 to 160 KJ / m 2 for 80 hours, and the degree of discoloration before and after the irradiation was measured with a Macbeth densitometer (Gretag Macbeth SPM50, manufactured by Macbeth) and quantified in the form of ΔE value. Here, the ΔE value is a numerical value representing the degree of discoloration and fading, and a larger value indicates a larger degree of discoloration and fading, that is, lower light fastness of the image. In the case of the exclusive photo print paper, the ΔE value obtained as a good result of 2.0 was obtained by the above measurement.

(B) Indoor discoloration and discoloration of the recorded image (ozone resistance): The printed matter was left in a light-shielded ozone concentration 3 ppm tank under an environment of 50 to 60% humidity for 2 hours. The degree of fading was measured with a Macbeth densitometer (Gretag Macbeth SPM50, manufactured by Macbeth) and quantified in the form of ΔE value. In the case of the special photo print paper, the ΔE value was 11.0, which was a good result by the above measurement. (C) Storage stability of the recording solution: When the recording solution was sealed in a Teflon (registered trademark) container and stored at 5 ° C. and 60 ° C. for one month, precipitation of insoluble matter was observed. Did not.

Preparation of Recording Liquid Reference Example 1 was used instead of the dye used in the preparation of Ink-1.
Preparation of a recording liquid, actual printing, in the same manner except that the azo metal chelate compound produced in 2, 13, 14, 15 was used.
When the saturation of the printed matter was measured, good results were obtained as shown in Table 9 in the case of the special photo print paper. Similarly, when various evaluations were made by the methods (a) to (c), as shown in Table 17, good results were obtained in the case of the dedicated photo print paper.

[0119]

[Table 45]

[Control Example] A commercially available inkjet printer (trade name: PM-750C, manufactured by Seiko Epson Corporation)
Was used to perform inkjet recording on photo print paper exclusively for inkjet (PR-101, manufactured by Canon Inc.). For printing, two colors, magenta and black,
Solid printing was carried out so that the printing density was set to an OD value and was around 1. In the printer used here, the two color inks of magenta and cyan are a set of dark color ink and light color ink, respectively, and the ink set consisting of a total of six colors of ink, including black and yellow, is a genuine ink set. It is used as This genuine ink is used as a comparative control ink.

Evaluation of printed matter Lightfastness of printed matter Using a xenon fade meter (manufactured by Atlas), the printed matter obtained by the above-described recording was irradiated with xenon light for 80 hours, and the degree of discoloration before and after the xenon light was measured using a Gretag. Macbeth S
It was measured by PM50 and quantified in the form of ΔE value and OD residual ratio of magenta. Here, the ΔE value is a numerical value representing the overall degree of discoloration and fading of an image, and a larger value indicates a larger degree of discoloration and fading, that is, lower light fastness of the image. On the other hand, the magenta OD residual ratio is a numerical value for quantifying the degree of fading of the magenta component of the color components constituting the image. The closer the value is to 100%, the lower the degree of fading of the magenta component is, that is, the magenta component is decomposed. , Indicating that the light fastness of the magenta component of the image is high.

In this comparative example, the printing density of the magenta printing portion obtained an OD value of 1.1. As a result of the light resistance test, ΔE was 15.5, and the magenta OD residual ratio was 69%. On the other hand, the print density of the black print portion obtained an OD value of 1.1. As a result of the light resistance test, ΔE was 36.4 and magenta O
The D residual ratio was 49%. That is, the magenta component in the mixed color portion was more fading than the printed portion of magenta alone. It was considered that magenta fading accelerated due to the catalytic action of the surrounding other color dye, that is, a catalytic fade.

Example Preparation of recording liquid (magenta) Diethylene glycol 10 parts by weight, diethylene glycol monobutyl ether 3 parts by weight, Table 1 Water was added to 2.4 parts by weight of the nickel chelate dye 1-34, and the pH was adjusted to 9 with an aqueous sodium hydroxide solution to adjust the total amount to 100.
Parts by weight were used. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon (registered trademark) filter having a pore size of 1 μm, and then degassed with a vacuum pump and an ultrasonic cleaner.
A thick magenta recording solution was prepared. The same operation was performed except that the amount of the same dye was changed to 0.6 part by weight to prepare a light magenta recording liquid. At this time, the concentration of each dye was adjusted so that the optical density (OD value) of the ink became equal to the value of the genuine ink of the printer used.

The dark and light magenta recording liquids prepared as described above were used in place of the dark and light magenta inks of the genuine ink used in the printer shown in the control example, and the same conditions as in the control example were used. A printing test and a light fastness evaluation were performed. As a result, the printing density of the magenta printing section was 0.9 O
The D value was obtained. As a result of the light resistance test, ΔE was 3.6, and the magenta OD residual ratio was as good as 92%. On the other hand, the print density of the black print portion obtained an OD value of 1.1. As a result of the light resistance test, ΔE was 12.1, and the magenta OD residual ratio was 93.
% Was obtained. That is, even in a black image obtained by overprinting with other colors such as yellow and cyan, the degree of fading of magenta is not large,
The undesired behavior that redness was quickly lost and color balance was lost in the mixed color portion did not occur as in the conventional system.

Instead of the magenta recording solution, the recording solution prepared in Reference Example-II was used, and CIDirect Blue 199 was used as a cyan dye, and 13-3 shown in Table 13 was used as a yellow dye. It can be expected that a similar good recorded image can be obtained when combined with a recording liquid using a dye. Similarly, it is expected that a good recorded image can be obtained by using each of the recording liquids including the combinations of the dyes shown in Table 14.

[0126]

When the dye set, ink set or recording method of the present invention is used, a printed matter having good fastness even in a mixed color portion or a light color portion can be obtained, and when recorded on plain paper or special paper, A clear recorded matter can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomohiro Chino 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Corporation (72) Inventor Tomio Yoneyama 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation F term (reference)

Claims (24)

[Claims] 1. A dye unit comprising at least one magenta dye and at least one yellow dye which are water-soluble azo metal chelate compounds formed from an azo compound represented by the following general formula (1) and a metal element: , And at least one cyan dye. Embedded image (The general formula (1) is an azo compound having at least one or more hydrophilic groups in the molecule, and X ₁ is a plurality of compounds necessary for forming at least one 5- to 7-membered heterocyclic ring. Represents an atom, but the heterocyclic ring containing X ₁ is a heterocyclic ring other than a pyridine ring, and the heterocyclic ring containing X ₁ may have a substituent on the heterocyclic ring. fused .Ar ₁ fused heterocyclic ring may be substituted including good .X ₁ also to form a fused ring represents a naphthyl group selected from the following formulas (2) ~ (4) .Y 1 Represents a chelating group; Z ₁ represents an optional substituent which may be different from each other;
a represents an integer of 0 to 6. ) 2. In the general formula (1), the heterocyclic ring containing X ₁ is an imidazole ring, a pyrazole ring, an isoxazole ring, a thiazole ring, a thiadiazole ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a benzothiazole ring,
The dye set according to claim 1, which is a benzoxazole ring or a benzimidazole ring. 3. In the general formula (1), the heterocyclic ring containing X ₁ may have one or more substituents, and the substituents on the heterocyclic ring may be each independently substituted. An alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted allyl group,
An optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted acyloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, An optionally substituted carbamoyl group, an optionally substituted acyl group, a carboxyl group, a hydroxyl group, a cyano group, an optionally substituted acylamino group, a nitro group,
Halogen atom, phosphono group, sulfo group, mercapto group,
3. A group selected from the group consisting of an optionally substituted alkylthio group, an optionally substituted alkylsulfoxy group, an optionally substituted alkylsulfonyl group, and a thiocyanato group. The dye set as described. 4. In the general formulas (2) to (4), Y
₁ is a hydroxyl group, a carboxyl group, an optionally substituted amino group, a sulfo group, a carbamoyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted alkylsulfonylamino The dye set according to any one of claims 1 to 3, wherein the dye set is a group or an arylsulfonylamino group which may be substituted. 5. In the general formulas (2) to (4), Z
₁ is each independently an optionally substituted alkoxy group,
Optionally substituted aryloxy group, optionally substituted acyloxy group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, carboxyl group, optionally substituted carbamoyl Group, hydroxyl group, optionally substituted amino group, ureido group, optionally substituted acylamino group, optionally substituted alkylsulfonylamino group, optionally substituted arylsulfonylamino group, phosphono group, The dye set according to any one of claims 1 to 4, wherein the dye set is a group selected from a sulfo group and a sulfamoyl group which may be substituted. 6. The dye set according to claim 1, wherein the heterocyclic ring containing X ₁ in the general formula (1) is represented by the following general formula (5). Embedded image (In the formula, R ₁ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, Optionally substituted aryloxy group, optionally substituted acyloxy group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, carboxyl group, optionally substituted carbamoyl Group, hydroxyl group, optionally substituted acyl group, cyano group, optionally substituted acylamino group, nitro group, halogen atom, sulfo group, mercapto group, optionally substituted alkylthio group, and thiocyanato group Group of choice, R
₁ may further form a condensed ring together with the imidazole ring. c represents an integer of 0 to 2. R ₂ is a hydrogen atom,
Represents an alkyl group which may be substituted, an aryl group which may be substituted, or an allyl group which may be substituted. ) 7. The dye set according to claim 6, wherein the general formula (5) is the following general formula (5 ′). Embedded image (Wherein, R ₂ ′ represents a hydrogen atom or an optionally substituted alkyl group) 8. The dye set according to claim 7, wherein Ar ₁ is represented by the following general formula (5 ″). (Wherein, R ₂ ″ represents a sulfo group and an optionally substituted sulfamoyl group) 9. The dye set according to claim ₁ , wherein in the general formula (1), the heterocyclic ring containing X ₁ is represented by the following general formula (6). Embedded image (In the formula, R ₃ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxycarbonyl group. An optionally substituted aryloxycarbonyl group, a carboxyl group, an optionally substituted carbamoyl group, a hydroxyl group, a cyano group,
Or a sulfo group. d represents an integer of 0 to 2. R ₄
Represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. ) 10. The dye set according to claim 1, wherein the heterocyclic ring containing X ₁ in the general formula (1) is represented by the following general formula (7). Embedded image (In the formula, R ₅ may be different from each other, and may be an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, Optionally substituted aryloxy group, optionally substituted acyloxy group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, carboxyl group, hydroxyl group, optionally substituted A good acyl group, a cyano group, an optionally substituted acylamino group, a nitro group,
Represents a halogen atom, a sulfo group, an optionally substituted alkylthio group, or an optionally substituted arylthio group, and R ₅ may further form a condensed ring together with a thiazole ring. e represents an integer of 0 to 2. ) 11. The dye set according to claim 1, wherein the heterocyclic ring containing X ₁ in the general formula (1) is represented by the following general formula (8). Embedded image (In the formula, R ₆ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, a mercapto group, an optionally substituted alkylthio group, Represents an alkylsulfoxy group which may be substituted, or an alkylsulfonyl group which may be substituted.) 12. The method according to claim 1, wherein the water-soluble azo metal chelate compound is a water-soluble azo metal chelate compound formed from a metal element selected from nickel, copper and cobalt. Dye set. 13. The yellow dye is represented by the following general formula (9):
At least one selected from compounds represented by (12)
Containing yellow dyes of azo compounds
The dye set according to claim 1. Embedded image(Where R^Y1Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^Y1Are the same even if they are different
And n represents 1 or 2. )(Where R^Y2Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^Y2Are the same even if they are different
And n represents 1 or 2. )(Where R^Y3Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^Y3Are the same even if they are different
Is also good. )(Where R^Y4Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^Y4Are the same even if they are different
Is also good. ) 14. In each of formulas (9) to (12), at least one of R ^{Y1 to} R ^Y4 is a halogen atom, a carboxyl group, a sulfo group, a phosphono group, a sulfamoyl group, or a sulfonyl which may be substituted. group, may be substituted carbonyl group, may triazinyl group which may be substituted, an optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy groups, substituted The dye set according to claim 13, which is any one of a phenyl group which may be substituted and an amino group which may be substituted. 15. A cyan dye represented by the following general formula (13):
At least one selected from the compounds represented by (14)
Characterized by containing a class of cyan dyes.
5. The dye set according to any one of 4. Embedded image(Where R^C1Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^C1Are the same even if they are different
M represents a metal atom. )(Where R^C2Is a hydrogen atom, a halogen atom, or any
Represents a substituent; ^C2Are the same even if they are different
Is also good. ) 16. In each of formulas (13) to (14), at least one of R ^C1 and R ^C2 is a halogen atom,
Carboxyl group, sulfo group, phosphono group, sulfamoyl group, optionally substituted sulfonyl group, optionally substituted carbonyl group, optionally substituted triazinyl group, optionally substituted C ₁ -C ₄ Alkyl group,
Optionally substituted C ₁ -C ₄ alkoxy group, an optionally substituted phenyl group, a dye according to claim 15, characterized in that either of the amino group which may be substituted set. 17. The dye unit according to claim 1, further comprising at least one kind of black dye.
A dye set according to any one of claims 1 to 16. 18. The dye set according to claim 17, wherein the black dye contains at least carbon black. 19. The black dye according to the following general formula (15)
The dye set according to claim 17, comprising at least one type of black dye represented by (16) and having at least one hydrophilic group in the molecule. Embedded image (Wherein, B, C and D each independently represent an aromatic ring and may further have an optional substituent. M is 0 to 1, n is 0 to 3, p is 0 to 2, q represents an integer of 0 to 4. When there are a plurality of B, each B may be the same or different, and R ^B1 and R ^B2 each independently represent a hydrogen atom or an arbitrary substituent. )) (In the formula, B′C ′ and D ′ each independently represent an aromatic ring, and may further have an arbitrary substituent.
1, n ′ represents an integer of 0 to 3, p ′ represents an integer of 0 to 2, and q ′ represents an integer of 0 to 4. When there are a plurality of B's, each B 'may be the same or different. R ^B1 and R ^B2 each independently represent a hydrogen atom or an optional substituent. M may also be in a tridentate or higher coordination, in which case M can be any ligand to metal, from any substituent or binding moiety in general formula (16), or by any ligand. May be coordinated. In the case where a plurality of B atoms are present, a metal ion may be further coordinated in the form of -OMOO- between B atoms adjacent to each other across the azo group, or B 'and C'. ) 20. In each of the general formulas (15) to (16), at least one of R ^B1 and R ^B2 is a hydrogen atom, an optionally substituted sulfonyl group, an optionally substituted carbonyl group, which may be triazinyl group, optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy group, any of a phenyl group which may be substituted 20. The dye set according to claim 19, wherein: 21. The dye set according to claim 1, wherein the magenta dye of the water-soluble azo metal metal chelate further has an azo dye represented by the general formula (1). 22. Each of the dye units in the dye set according to any one of claims 1 to 21, comprising a yellow dye, a magenta dye, a cyan dye, and, in some cases, a black dye. An ink set, characterized in that: 23. An ink set including yellow, magenta and cyan dye inks, wherein at least one of the inks comprises a combination of a dark color ink and a light color ink, the magenta color light ink is added to the light color ink. ~
The ink set according to claim 22, wherein the magenta dye according to any one of (12) and (21) is contained. 24. An ink jet recording method using the ink set according to claim 22.