JP2007070573A - Ink set and method for inkjet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set having good image preservability, preventing dye deposition on images and causing no bronze problem, and to provide a method for inkjet printing. <P>SOLUTION: The ink set comprises magenta ink containing at least one magenta dye and cyan ink containing at least one cyan dye, wherein each of the magenta dye and the cyan dye is an anionic water-soluble dye and each anionic water-soluble dye has a sulfonic group as a water-soluble group and Li<SP>+</SP>ion or quaternary ammonium as the counter ion, and the method for inkjet printing comprises forming full color images for inkjet by using the ink set. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink set and an ink jet recording method.

In recent years, with the spread of computers, ink jet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.
Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these inks for inkjet recording, water-based inks, oil-based inks, or solid (melting type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

For the colorant used in these inks for ink jet recording, it has high solubility in solvents, high density recording is possible, hue is good, light, heat, air, ozone, water, Excellent fastness to chemicals, good fixability to image-receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, and low cost It is required to be able to do it. However, it is extremely difficult to search for colorants that meet these requirements at a high level.
Various dyes and pigments have already been proposed and actually used for inkjet, but no colorant that satisfies all the requirements has yet been discovered. Conventionally well-known dyes and pigments having a color index (CI) number are difficult to achieve both hue and fastness required for ink jet recording inks.

  The inventors of the present invention have been studying ink jet inks using dyes (for example, see Patent Documents 1 and 2). In these documents, it is proposed to improve the light resistance and gas resistance of an image by using a water-soluble dye having a noble oxidation potential or a water-soluble dye having a strong associative property for the ink. However, when the dye is likely to associate, there is a problem in that the solubility of the dye in water decreases at the same time, or the precipitation of the dye occurs on the image, thereby deteriorating the bronze and the like. This problem is particularly remarkable in the case of a cyan ink that has high planarity and easily forms an association state, such as a metal phthalocyanine compound.

In order to increase the water solubility of such a metal phthalocyanine compound, improve bronzing, and at the same time achieve good image fastness, the present inventors have a sulfonic acid group as a water-soluble group and A metal phthalocyanine compound having a high associative and high oxidation potential having Li ⁺ ions or quaternary ammonium ions as ions has been proposed. However, when a full color image is formed with an ink set comprising magenta, cyan, yellow, and black inks, the bronze in the cyan image is improved, but the secondary color, especially blue, is formed by mixing different inks. There was a problem that bronze and the like deteriorated due to the hue. This is due to the exchange of dye counter ions in secondary colors such as blue, green and red mixed with dyes in different inks, and in composite gray formed by mixing yellow, magenta, cyan and black. This is thought to be due to a decrease in the solubility of the dye.

  In recent years, magenta inks using water-soluble dyes having an anthrapyridone skeleton have been described in Patent Documents 3 to 5 as means for improving the gas resistance of magenta dyes. However, since a water-soluble dye having an anthrapyridone skeleton generally has a low molar absorption coefficient, a high dye concentration is required in the ink in order to obtain a predetermined concentration. Therefore, when used for dark magenta ink, etc., there are many cases where ink ejection properties, dye storage stability, and dye deposition on the image become problems, and when used only for light ink with low dye concentration. There are many.

  The Li salt of a magenta dye having an anthrapyridone skeleton is described as one of the counter ions such as K salt, Na salt, quaternary ammonium salt, etc., although it is partially described in the above document. However, the usefulness of the Li salt is not described at all, and is not described at all in the examples.

JP 2003-306623 A JP 2004-115620 A JP 2003-192930 A Japanese Patent Laying-Open No. 2005-8868 JP 2005-41846 A

  The problem to be solved by the present invention is that when forming a full-color image using an ink set, the ink has good storage stability and prevents precipitation of dye on the image and does not cause bronzing problems. It is to provide a set and an ink jet recording method.

The problems of the present invention can be solved by the following means.
1) An ink set having a magenta ink containing at least one magenta dye and a cyan ink containing at least one cyan dye, both the magenta dye and the cyan dye being an anionic water-soluble dye An ink set, wherein any of the anionic water-soluble dyes has a sulfonic acid group as a water-soluble group, and Li ⁺ ion or quaternary ammonium ion is used as a counter ion.
2) The ink set according to 1), wherein the cyan dye is a water-soluble phthalocyanine dye having an oxidation potential nobler than 1.0 V (vs SCE).
3) The ink set according to 1) or 2), further comprising a yellow ink containing at least one kind of yellow dye and a black ink containing at least one kind of black dye.
4) The yellow dye and the black dye are anionic water-soluble dyes, the water-soluble group of the anionic water-soluble dye is a sulfonic acid group, a carboxyl group or a phenolic hydroxyl group, and the water-soluble group is a sulfonic acid group. In this case, Li ⁺ ion or quaternary ammonium ion is used as a counter ion, and when the water-soluble group is a carboxyl group or a phenolic hydroxyl group, K ⁺ ion or Na ⁺ ion is used as a counter ion. The ink set according to 3).
5) The ink set according to any one of 1) to 4), wherein the ink sets have the same hue and have different dye concentrations.
6) 90% by mass or more of the anionic water-soluble dye in each ink of the ink set does not have a sulfonic acid group and a carboxyl group in the molecule at the same time. Ink set.
7) The ink set according to any one of 1) to 6), wherein when the water-soluble group of the anionic water-soluble dye is a sulfonic acid group, Li ⁺ ion is used as a counter ion.
8) The ink set according to any one of 1) to 7), wherein the cyan ink contains at least one water-soluble cyan dye represented by the following general formula (C).

In the general formula (C), X _{1 to} X ₄ and Y _{1 to} Y ₄ each independently represent a carbon atom or a nitrogen atom. A _{1 to} A ₄ are each independently required to form an aromatic ring or a heterocyclic ring (which may form a condensed ring with another ring) together with X _{1 to} X ₄ and Y _{1 to} Y _4. Represents an atomic group. A _{1 to} A ₄ may have a substituent. At least one of A _{1 to} A ₄ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
9) The ink set according to any one of 1) to 8), wherein the magenta ink contains at least one water-soluble magenta dye represented by the following general formula (M).
General formula (M)

In the general formula (M), A ₃₁ represents a 5-membered heterocyclic group.
B ₃₁ and B ₃₂ are each = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - represents a or -CR ₃₂ =. R ₃₅ and R ₃₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group Represents a heterocyclic sulfonyl group or a sulfamoyl group, and each group may further have a substituent.
G ₃ , R ₃₁ and R ₃₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino) Group, including heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl And Arylchi O group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, sulfonic acid group, or heterocyclic thio group, each group may be further substituted .
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- to 6-membered ring.
Note that at least one of A ₃₁ , R ₃₁ , R ₃₂ , R ₃₅ , R _36, and G ₃ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion.
10) The magenta ink is a water-soluble dye having an anthrapyridone skeleton, a sulfonic acid group as a water-soluble group, and a counter ion being Li ⁺ ion. The ink set according to any one of the above.
11) The ink set according to any one of 3) to 10), wherein the yellow ink contains at least one water-soluble yellow dye represented by the following general formula (Y).
General formula (Y) (AN = NB) n-L
In the formula, A and B each independently represent an optionally substituted heterocyclic group. L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different.
12) The ink set according to any one of 3) to 10), wherein the black ink contains at least one water-soluble black dye represented by the following general formula (Bk).
Formula _{(Bk): A 1 -N =} N-A 2 -N = N-A 3
In General Formula (Bk), A ₁ , A _2, and A ₃ each independently represents an optionally substituted aromatic group or an optionally substituted heterocyclic group. A ₁ and A ₃ are monovalent groups, and A ₂ is a divalent group.
13) The ink set according to any one of 1) to 12), which is used for inkjet.
14) An ink jet recording method comprising forming an ink jet full color image using the ink set according to 13).
15) In the recording method described in 14), an image receiving material having an image receiving layer containing inorganic pigment particles on a support is caused to eject ink droplets according to a recording signal to record an image on the image receiving material. An inkjet recording method.

  According to the present invention, since the kind of water-soluble group of the anionic water-soluble dye and the counter ion in the ink set are defined, when a full-color image is formed using the ink set, the image storage stability is good. In addition, it is possible to provide an ink set and an ink jet recording method in which precipitation of a dye on an image is prevented and bronzing does not occur.

The present invention will be further described below.
As described above, the ink set of the present invention includes at least a magenta ink and a cyan ink, and each of the magenta dye and the cyan dye contained therein is an anionic water-soluble dye, and the anionic water-soluble dye. The water-soluble group is a sulfonic acid group, and Li ⁺ ion or quaternary ammonium ion is used as a counter ion.
That is, in the present invention, the water-soluble group of the anionic water-soluble dye in magenta ink and cyan ink is specified as a sulfonic acid group, and the counter ion is specified as Li ⁺ ion or quaternary ammonium ion. The optimal counter ion is the Li ⁺ ion.

Similarly, the ink set of the present invention can further include yellow ink and black ink. In this case, the yellow dye and the black dye contained in the yellow ink and the black ink are both anionic water-soluble dyes, and the water-soluble group of the anionic water-soluble dye is a sulfonic acid group, a carboxyl group or a phenolic hydroxyl group. When the water-soluble group is a sulfonic acid group, a Li ⁺ ion or a quaternary ammonium ion is used as a counter ion, and when the water-soluble group is a carboxyl group or a phenolic hydroxyl group, a K ⁺ ion or Na ^{The +} ion is preferably a counter ion.
As a preferred combination, when the water-soluble group is a sulfonic acid group, the counter ion is a Li ⁺ ion. In the case where the water-soluble group is a carboxyl group or a phenolic hydroxyl group, in order to prioritize the solubility of the dye in water, the counter ion is preferably a K ⁺ ion, and the interaction with a dye having a sulfonic acid group is prioritized. For this purpose, the counter ion is preferably a Na ⁺ ion. These are appropriately selected.

  In this way, there is an optimal combination of water-soluble groups and counter ions, and preferred counter ions for sulfonic acid groups and carboxyl groups are different from each other. Therefore, a sulfonic acid group and a carboxyl group are simultaneously contained in the dye molecule. It is desirable not to.

  The use of the ink set of the present invention is not particularly limited, but it is preferably used for inkjet.

  Each ink in the present invention preferably contains 0.2 to 20% by mass of a dye, and more preferably 0.5 to 15% by mass.

Next, the dye used for the ink set of the present invention will be described.
The dye used in the present invention is not particularly limited as long as it satisfies the relationship between the water-soluble group and the counter ion of the present invention, but the image fastness such as the light resistance, gas resistance, and heat and humidity resistance of the image. A dye having an azo group bonded to a heterocyclic ring (hereinafter also referred to as “heterocyclic azo dye”), an associative phthalocyanine dye and an anthrapyridone dye having a Li ⁺ ion as a counter ion (hereinafter referred to as a heterocyclic azo dye, The phthalocyanine dye and the dye used in the present invention such as an anthrapyridone dye having a Li ⁺ ion as a counter ion are also collectively referred to as a dye for the present invention.) The present invention is a heterocyclic azo dye, the phthalocyanine dye or Li ⁺ Although it is preferable to contain at least one anthrapyridone dye having an ion as a counter ion, other dyes and / or pigments may be used in combination.
The dye for use in the present invention preferably has an oxidation potential of 1.0 V (vs SCE) or more.
A person skilled in the art can easily measure the value of the oxidation potential (Eox). Regarding this method, for example Delahay, “New Instrumental Methods in Electrochemistry” (published by Interscience Publishers, 1954) J. et al. "Electrochemical Methods" by Bard et al. (Published by John Wiley & Sons in 1980) and "Electrochemical Measurement Method" by Akira Fujishima et al. (Published by Gihodo Publishing Co., Ltd. in 1984).

Specifically, the oxidation potential is 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / min in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. It is measured as a value relative to SCE (saturated calomel electrode) using various voltammetry (polarography using a dropping mercury electrode, cyclic voltammetry, a method using a rotating disk electrode, etc.). Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone).
In the present invention, SCE (saturated calomel) is used as a reference electrode in N, N-dimethylformamide (concentration of dye is 0.001 mol / liter) containing 0.1 mol / liter of tetrapropylammonium perchlorate as a supporting electrolyte. Electrode), a value (vs SCE) measured using a graphite electrode as a working electrode and a platinum electrode as a counter electrode was defined as the oxidation potential of the dye.

  The value of Eox represents the ease of transfer of electrons from the sample to the electrode, and the greater the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group. In the present invention, in order to lower the reactivity with ozone as an electrophile, it is desirable to introduce an electron withdrawing group into the dye skeleton to make the oxidation potential more noble.

Moreover, as dye for this invention, (epsilon) 1 / (epsilon) 2 is 1.1 or more by the following associative evaluation method, 1.1-1.5 are still more preferable, 1.2-1.5 are especially preferable.
Assessing method of dye associative property The associating property of a dye can be evaluated as follows. When a 0.01 mmol / L dye solution was measured using a cell with an optical path length of 1 cm, a molecular absorption coefficient (ε1) of the solution absorption spectrum and a 20 mmol / L dye solution with an optical path length of 5 μm were used. The ratio of the solution absorption spectrum to the molecular extinction coefficient (ε2), ε1 / ε2, is an indicator of dye association. The higher this number, the easier the dye will associate. A dye having a value of 1.1 or more exhibits excellent performance in ozone resistance and light resistance due to dye association. Highly associative dyes tend to cause dye precipitation on the formed image. However, in the present invention, the water-soluble group of the dye and its counter ion are specified. Problems are less likely to occur.
As the solvent used in the dye solution, ultrapure water having a specific resistance value of 18 MΩ · cm or more such as deionized water is used.

First, the heterocyclic azo dye will be described.
As used herein, “substituted” used in “substituted alkyl group” and the like indicates that a hydrogen atom present in “alkyl group” or the like is substituted with a specific substituent. The “substituted alkyl group” and the like are also synonymous with the substituted alkyl group and the like. Further, the “optionally substituted alkyl group” means including a normal (unsubstituted) alkyl group and the above substituted alkyl group, and other “optionally substituted heterocyclic groups” and the like This is the same as above.

The heterocyclic azo dye is not particularly limited as long as it has at least one structure in which an azo group is bonded to the heterocyclic ring, but is an azo dye having a structure in which a heterocyclic group is bonded to both ends of the azo group. It is preferable that it is represented by the following general formula (A).
Formula (A): A−N = N−B
[Wherein, A and B each independently represents an optionally substituted heterocyclic group. ]
As the heterocyclic azo dye used in the present invention, a compound represented by the following general formula (Y), a compound represented by the general formula (Bk) and the general formula (M) is preferable. The compound represented by the general formula (Bk) is not necessarily a heterocyclic azo dye as described above.

The compound represented by the general formula (Y) is preferably a yellow dye. The dye preferably has at least one of the above properties (oxidation potential and associability), and more preferably has all the properties. The oxidation potential of the dye is more preferably noble than 1.1 V (vs SCE), and particularly preferably noble than 1.15 V (vs SCE).
General formula (Y) (AN = NB) n-L
In the formula, A and B each independently represent an optionally substituted heterocyclic group. L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different.

  Examples of the dye represented by the general formula (Y) include WO 2005/075753, JP-A No. 2004-83903 (paragraph numbers [0024] to [0062]), JP-A No. 2003-277762 (paragraph numbers [0022] to [0049]. ], JP-A No. 2003-277661 (paragraph numbers [0021] to [0050]), JP-A No. 2003-128953 (paragraph numbers [0025] to [0076]), JP-A No. 2003-41160 (paragraph number [0028] ] To [0064]) and the like, those in which the relationship between the water-soluble group and the counter ion satisfies the present invention. Specific examples of the dye are shown below in the form of a free acid, but the azo dye used in the present invention is not limited to the following examples.

Below, the compound represented by general formula (Bk) is demonstrated. The compound represented by the general formula (Bk) is preferably a black dye. The dye preferably has at least one of the above properties (oxidation potential and associability), and more preferably has all the properties. The oxidation potential of this dye is more preferably a dye noble than 1.1 V (vs SCE), particularly preferably a dye nobler than 1.15 V (vs SCE).
Formula _{(Bk): A 1 -N =} N-A 2 -N = N-A 3
In the formula, A ₁ , A ₂ and A ₃ each independently represents an optionally substituted aromatic group or an optionally substituted heterocyclic group. A ₁ and A ₃ are monovalent groups, and A ₂ is a divalent group. At least one of A ₁ , A ₂ and A ₃ is preferably a heterocyclic group.

  As the dye represented by the general formula (Bk), among the azo dyes described in JP-A Nos. 2004-115620 and 2004-223229, the relationship between the water-soluble group and the counter ion satisfies the present invention. Things.

Moreover, in order that the azo dye represented by the general formula (Bk) has preferable hue, fastness, and storage stability, it is preferable to satisfy the following physical properties, and it is effective for suppressing bronze gloss.
Physical property 1: 680 nm ≧ λmax (DMF) ≧ 570 nm, where λmax (DMF) is the maximum absorption wavelength of the absorption spectrum in DMF.
Physical property 2: When the maximum absorption wavelength of the absorption spectrum in water is λmax (water), | λmax (DMF) −λmax (water) | ≧ 30 nm.
Physical property 3: When the molar extinction coefficient in DMF is ε (DMF) and the molar extinction coefficient in water is ε (water), ε (water) / ε (DMF) ≦ 0.9.
Physical property 4: Absorbance at the maximum absorption wavelength of the aggregate in the absorption spectrum measured in water is Abs (association), and absorbance at the maximum absorption wavelength of the monomer absorption spectrum measured in DMF is Abs (monomer). When, Abs (monomer) / Abs (aggregate) ≦ 0.75.
In addition, about the definition of the said physical property, it is based on Unexamined-Japanese-Patent No. 2005-139427.

  Specific examples of the azo dyes represented by formula (Bk) used in the present invention are shown below in the form of free acids, but the present invention is not limited to the following examples, and the following specific examples In the examples, the ionic hydrophilic group should have the preferred counter ion shown above.

  The azo dye represented by the general formula (Bk) can be synthesized by a coupling reaction between a diazo component and a coupler, and these are described in JP-A Nos. 2003-306623 and 2005-1394278. There is.

Moreover, in this invention, you may adjust to a more preferable hue by using another colorant together with the said dye. Any dye can be used as the dye to be used in combination. For example, in yellow dyes, aryl or heteryl azo dyes having substituted benzenes, substituted naphthalenes, heterocyclic rings such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); Examples include azomethine dyes having open-chain active methylene compounds as coupler components; methine dyes such as benzylidene dyes and monomethine oxonol dyes; and quinone dyes such as naphthoquinone dyes and anthraquinone dyes. Examples of other dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes. Particularly preferred in combination is a dye (S) having a λmax of 350 nm to 500 nm, and the above-mentioned and later-described yellow dyes can be used. Among them, an azo having 2 to 6 azo groups in one molecule is preferable. It is a dye. In the present invention, a yellow pigment can also be used.
In magenta dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocyclic rings such as pyridine and pyrazine, open-chain active methylene compounds, etc. as coupler components; for example open-chain active methylene compounds as coupler components Azomethine dyes having the above; and anthrapyridone dyes. Particularly preferred are azo dyes having a heterocyclic ring in the chromophore or an anthrapyridone dye.
For cyan dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes; Polymethine dyes such as oxonol dyes and merocyanine dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes and the like. Particularly preferred are phthalocyanine dyes.

  In particular, from the standpoint of fastness, a dye having an oxidation potential nobler than 1.0 V or an associative dye is preferable. Specific examples of preferable dyes used in combination include the dyes described in Japanese Patent Application No. 2003-360370.

  The content of the compound represented by the general formula (Bk) in the ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

In addition, it is more preferable to add the following water-soluble short-wave dye S to the black ink. It is particularly preferable that this dye S has an absorption spectrum maximum in an aqueous solvent of 440 to 540 nm and a half width of 90 to 200 nm.
The water-soluble short-wave dye S used in the present invention has a maximum absorption spectrum (absorption maximum: λmax) in an aqueous solvent at 440 to 540 nm and a half width at 90 nm to 200 nm, and achieves broad absorption. .
The absorption spectrum of the water-soluble short wave dye S is measured using a single compound. That is, when measuring the absorption spectrum in an aqueous solvent, the water-soluble shortwave dye S of the present invention does not exhibit physical properties such as a desired absorption maximum and a half-value width by combining a plurality of compounds, but the physical properties of one compound Is meant to indicate In the present invention, it is obvious that compounds having different structures may be used in combination as long as the water-soluble short wave dye S (hereinafter also referred to as “short wave dye S”) satisfies the absorption spectrum. It is. Furthermore, in the present invention, a short wave dye other than the short wave dye S exhibiting the above absorption spectrum characteristics may be used in combination.
Since the short wave dye S has such absorption characteristics, it can absorb a wide range of light from blue to green, which tends to be insufficient in the absorption spectrum of the water-soluble long wave dye L such as disazo dye or trisazo dye. , Have preferable absorption characteristics as a complementary color dye.
The absorption maximum of the short wave dye S is preferably between 450 and 520 nm, particularly preferably between 460 and 500 nm.
The full width at half maximum of the absorption maximum of the short wave dye S is preferably between 100 nm and 180 nm, and particularly preferably between 110 nm and 160 nm.
Furthermore, it is preferable that the short wave dye S of the present invention has 2 to 6 azo groups in one molecule, and this structure enhances color developability and also has a fixing property because the dye plane is greatly expanded. Can give a good picture.
Further, the number of the azo groups is more preferably 4 to 6 per molecule from the viewpoint of color developability and fixability.

As the short wave dye S, among the compounds described in Japanese Patent Application Nos. 2004-206329 and 2004-206330, those having a relationship between the water-soluble group and the counter ion satisfy the present invention. The short wave dye S also preferably has at least one water-soluble group in the molecule. As the water-soluble group, a sulfonic acid group, a carboxyl group, and a phenolic hydroxyl group are particularly preferable. Optimally, the water-soluble group is a sulfonic acid group.
The sulfonic acid group, carboxyl group, and phenolic hydroxyl group are preferably in a salt state. In the case of a sulfonic acid group, a Li ⁺ ion or a quaternary ammonium ion is used as a counter ion, and the water-soluble group is a carboxyl group. In the case of a phenolic hydroxyl group, a K ⁺ ion or a Na ⁺ ion may be used as a counter ion. More preferably, when the water-soluble group is a sulfonic acid group, the counter ion is a Li ⁺ ion.

Examples of the short wave dye S include polyazo dyes represented by the following general formula.
(D) n-Y
In the above general formula, D represents a dye residue composed of 1 to 3 azo groups conjugated to each other and 3 to 4 aromatic rings having a total of 20 or more π electrons. , N is 1 or 2, when n is 1, Y represents a hydrogen atom, and when n is 2, Y represents a divalent linking group. The aromatic ring constituting the chromophore may be a heterocyclic ring or a hydrocarbon ring, but is preferably a hydrocarbon ring. When the aromatic ring constituting the chromophore is a condensed ring, the number of π electrons on the aromatic ring is the number of π electrons as the whole condensed ring. For example, a naphthalene ring has 10 π electrons. It is. The divalent linking group represented by Y is an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, alkyl Group, represents an aryl group), —O—, and a divalent group obtained by combining these linking groups, and further includes an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, and a halogen atom. May have a substituent such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, or a sulfonamide group. Particularly preferred examples of the linking group include —NH—CO—NH—, —NH—CS—NH—, and groups having the following general formula.

  In the above general formula, X represents a hydroxyl group, a sulfo group, an alkoxy group, an aryloxy group, an amino group (including an alkylamino group or an arylamino group), or an alkyl or arylsulfenyl group, and each group further has a substituent. You may have.

  For example, commercially available CIDirect Red 84, Brown 106, and Brown 202 are useful as such short-wave dye S, and CI Direct Red 84, which can be used to adjust the color tone of many black dyes and is excellent in color development, fastness, and fixing properties. Is particularly useful.

  Further, examples of the short wave dye S preferably used in the present invention are shown in the form of a free acid, and it is preferable to use the salt as the salt as described above.

Among them, CIDirect Red 84 (Na salt of the above compound example 2) and Brown 106 (Na salt of the above compound example 14) are preferable because they are available as commercially available dyes. The counter ions of these dyes are Na ⁺ ions. It is preferable to use it by exchanging with Li ⁺ ion. Among them, CI Direct Red 84 Li ⁺ salt, which can be used for adjusting the color tone of many black dyes and is excellent in color development, fastness, and fixing property, is particularly useful.
In addition, the short wave dye S other than the commercially available dye can be easily obtained from commercially available raw materials according to the synthesis route of CI Direct Red 84 or Brown 106 described in Color Index Vol. 4 (issued by The Society of Dyers and Colorists). Can be synthesized.

  The black ink in the present invention preferably contains 0.1 to 4% by mass, preferably 0.5 to 3.0% by mass, particularly preferably 1.0 to 2.5% by mass of the short wave dye S. However, the black ink can be appropriately changed as desired. It is.

  The compound represented by formula (M) (hereinafter also referred to as “compound (M)”) will be described. The dye represented by formula (M) is preferably a magenta dye. The dye preferably has at least one of the above properties (oxidation potential and associability), and more preferably has all the properties. Further, the oxidation potential of this compound is preferably nobler than 1.0 V (vs SCE), more preferably nobler than 1.1 V (vs SCE), and 1.15 V (vs SCE). It is particularly preferred that

  General formula (M)

In the general formula (M), A ₃₁ represents a 5-membered heterocyclic group.
B ₃₁ and B ₃₂ are each = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - represents a or -CR ₃₂ =. R ₃₅ and R ₃₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group Represents a heterocyclic sulfonyl group or a sulfamoyl group, and each group may further have a substituent.
G ₃ , R ₃₁ and R ₃₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino) Group, including heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl And Arylchi O group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, sulfonic acid group, or heterocyclic thio group, each group may be further substituted .
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- to 6-membered ring.
Note that at least one of A ₃₁ , R ₃₁ , R ₃₂ , R ₃₅ , R _36, and G ₃ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion.

Specific examples of the compound (M) include International Patent Publication No. 2002/83795 (pages 35 to 55), 2002-83663 (pages 27 to 42), and JP-A No. 2004-149560 (paragraph numbers [0046] to [0046]. )], 2004-149561 (paragraph numbers [0047] to [0060]), the water-soluble group is only a sulfonic acid group, and the counter ion is Li ⁺ ion or quaternary ammonium ion. Can be mentioned. Specific examples of particularly preferred compound (M) are shown below in terms of the structure of the free acid, and it is preferable to use them as the above-mentioned salts as described above.

  The content of the heterocyclic azo dye in the magenta ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

  In addition, a magenta dye is not restrict | limited to the compound represented by the said general formula (M), The water-soluble magenta dye which has an anthrapyridone skeleton is also mentioned as a preferable example.

The water-soluble magenta dye having an anthrapyridone skeleton is not particularly limited as long as it is a compound having an anthrapyridone skeleton, having only a sulfonic acid group as a water-soluble group, and a counter ion being a Li ⁺ ion. For example, among the compounds described in JP2003-192930, JP2005-8868, JP2005-41846, JP2005-60629, etc., a compound satisfying the relationship between the water-soluble group of the present invention and the counter ion Is mentioned.

  The content of the water-soluble magenta dye having an anthrapyridone skeleton in the magenta ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

Next, the phthalocyanine dye which is the dye for the present invention will be described. As the phthalocyanine dye, those having an associative group are preferable. The associative group means a group having at least a binding site (or functional group) capable of hydrogen bonding between molecules in the group. One or more binding sites can be contained in one group. Examples of the bonding site include a hydroxyl group, an amino group, an amide bond, an oxide bond, and the like, and a hydrogen bond is formed between the same species or different species. The associative group may be capable of hydrogen bonding between the phthalocyanine dye and any additive.
As the phthalocyanine dye, a compound represented by the following general formula (C) (hereinafter also referred to as “compound (C)”) is preferable. The compound represented by the general formula (C) is preferably a cyan dye. The dye preferably has at least one of the above properties (oxidation potential and associability), and more preferably has all the properties.
In the present invention, in order to reduce the reactivity with ozone, which is an electrophile, for example, a carbon atom of a phthalocyanine skeleton is partially substituted with a hetero atom such as azaphthalocyanine, or an electron withdrawing group is replaced with a phthalocyanine skeleton. It is desirable that the oxidation potential be made nobler than 1.0 V (vs SCE). The oxidation potential is preferably as noble, more preferably noble than the oxidation potential of 1.1 V (vs SCE), and particularly preferably noble than 1.15 V (vs SCE).

In the general formula (C), X _{1 to} X ₄ and Y _{1 to} Y ₄ each independently represent a carbon atom or a nitrogen atom. Preferably it is a carbon atom. A _{1 to} A ₄ are each independently required to form an aromatic ring or a heterocyclic ring (which may form a condensed ring with another ring) together with X _{1 to} X ₄ and Y _{1 to} Y _4. Represents an atomic group. The formed heterocyclic ring is preferably a nitrogen-containing 6-membered ring. A _{1 to} A ₄ may have a substituent, and at least one of the substituents of A _{1 to} A ₄ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

  Specific examples of the compound (C) include International Publication Nos. 2002/60994, 2003/811, 2003/62324, JP 2003-213167, 2004-75986, 2004-323605, Among those described in 2004-315758, 2004-315807, and Japanese Patent Application No. 2003-421124, those satisfying the relationship between the water-soluble group and the counter ion of the present invention can be mentioned. Specific examples of particularly preferred cyan dyes are shown below, but the coloring matter used in the present invention is not limited to the following examples.

  The compound (C) of the present invention can be synthesized according to Japanese Patent Application Laid-Open No. 2004-315729, Japanese Patent Application Nos. 2003-411390, and 2004-094413. Further, the starting material, dye intermediate and synthetic route are not limited by these.

  Although the compound (C) can be used alone, it can be used in combination with other dyes, particularly other phthalocyanine dyes.

  In order to form a full color image, the ink set of the present invention can also use two shades of ink with the same hue and different dye concentrations. Furthermore, it is possible to use inks of intermediate colors such as red, green, blue, and violet.

In addition, in the ink set of the present invention, other colorants may be used in combination in order to adjust the color tone in order to obtain a full-color image together with the dye.
Any colorant can be used as the colorant that can be used in the ink set of the present invention or the colorant that can be used in combination with the dye. Examples of colorants that can be used in combination include the dyes described so far, the dyes described in paragraphs [0331] to [0334] of JP-A No. 2004-331871, and [0335] to [0341]. And the like.

In addition to the dye represented by the above formula, dyes described in the following publications can also be preferably used.
JP-A-10-130557, JP-A-9-255906, JP-A-6-234944, JP-A-7-97541, EP 982371, WO 00/43450, WO 00/43451, WO 00/43452, WO 00 / 43453, WO 03/106572, WO 03/104332, JP 2003-238862, JP 2004-83609, JP 2002-302619, JP 2002-327131, JP 2002-265809, WO 01 / 48090, WO 04/087815, WO 02/90441, WO 03/027185, WO 04/085541, JP 2003-321627, JP 2002-332418, JP 2002-332419, WO 02/059215, WO 02 / 059216, WO 0 / 087814, WO 04/046252, WO 04/046265, US Pat. No. 6,652,637, WO 03/106572, WO 03/104332, WO 00/58407, Patent 3558213, Patent 3558212, Patent 3558211, Special No. 2004-285351, WO 04/078860, JP-A No. 2004-323605, WO 04/104108.
In each of the above dyes, the water-soluble group and the counter ion are preferably combined in the present invention.

  The ink of the present invention contains a dye in a medium, preferably an aqueous medium. In the aqueous medium, water or a solvent such as a water-miscible organic solvent is added to water as necessary.

  The water-miscible organic solvent that can be used in the present invention is a material having functions such as an anti-drying agent, a penetration accelerator, and a wetting agent for ink jet recording inks in the field, and is mainly a high-boiling water-miscible material. An organic solvent is used. Specific examples and preferred use amounts of such compounds are described in JP-A No. 2004-331871 (paragraph numbers [0419] to [0423]).

  For the purpose of improving the ejection stability, print quality, image durability, and the like of the ink composition used in the ink set of the present invention, the surfactants and drying inhibitors described in JP-A No. 2004-331871 and the like, penetration Accelerator, urea-based additive, chelating agent, ultraviolet absorber, antioxidant, viscosity modifier, surface tension modifier, dispersant, dispersion stabilizer, antiseptic, antifungal agent, rust inhibitor, pH adjuster, Additives such as an antifoaming agent, a polymer material, and an acid precursor can be appropriately selected and used. The preferred use amounts of these additives are as described in JP-A-2004-331871.

  JP-A-2004-318771 also describes preferred ranges and measuring methods of ink physical properties such as pH, conductivity, viscosity, static surface tension, dynamic surface tension and the like, and methods for adjusting these physical properties of the ink composition. As described in the publication.

  In addition, about the preparation method of the inkjet ink composition, Unexamined-Japanese-Patent No. 5-148436, 5-295312, 7-97541, 7-82515, 7-118584, Unexamined-Japanese-Patent No. 2004-331871. Details are described in each of these methods, and can also be used for the preparation of the ink composition of the present invention.

  As the recording paper and the recording film which are printing media suitably used in the present invention, those described in JP-A-2004-331871 (paragraph numbers [0503] to [0627]) are preferably used.

  The ink set and ink composition of the present invention can also be used for purposes other than inkjet recording. For example, it can be used for display image materials, image forming materials for interior decoration materials, outdoor decoration materials, and the like described in JP-A-2004-318771 [0727] to [0731].

  In the production of ink, as described in Japanese Patent Application Laid-Open No. 2004-331871, ultrasonic vibration can be applied to the dissolution process of additives such as dyes.

  In preparing the ink of the present invention, a step of removing dust that is a solid content by filtration, which is performed after further preparation of liquid, is important. The filtration step is also as described in JP-A-2004-318771.

  The conditions described in [0628] to [0652] of Japanese Patent Application Laid-Open No. 2004-331871 are preferable for the ink ejection onto the recording material in the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

The dyes used in the examples are shown below.
<Cyan dye>

<Magenta dye>

<Yellow dye>

<Black dye>

Example 1
Preparation of Cyan Ink After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / l, and filtration under reduced pressure was performed with a microfilter having an average pore diameter of 0.25 μm to prepare a cyan ink liquid (C-1A).

Dye C-1 60.0g
Glycerin 118.0g
Triethylene glycol 107.0g
91.0 g of triethylene glycol monobutyl ether
1,2-hexanediol 24.0 g
2-Pyrrolidone 35.0g
Urea 24.0g
Surfinol 465 30.0g
Triethanolamine 2.0g
Benzotriazole 0.06g
PROXEL XL2 (Avecia) 1.1g

Preparation of light cyan ink A light cyan ink liquid (LC-1A) was prepared in the same manner as C-1A except that the amount of dye used was changed from 60.0 g to 15.0 g.

Preparation of magenta ink After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / l, and filtration under reduced pressure was performed with a microfilter having an average pore diameter of 0.25 μm to prepare a magenta ink liquid (M-1A).

Dye M-1 35.0g
Glycerin 102.0g
Triethylene glycol 19.0g
Triethylene glycol monobutyl ether 100.0g
1,2-hexanediol 12.0g
2-Pyrrolidone 11.0g
Urea 24.0g
Surfinol 465 10.0g
Triethanolamine 2.0g
Benzotriazole 0.06g
PROXEL XL2 (Avecia) 1.1g

  Further, the cyan ink (C-1B to 1C) and the magenta ink (M-1B to 1F) were processed in the same manner as C-1A and M-1A except that the type and amount of the dye were changed as shown in Table 1. Produced.

(Example 2)
Preparation of print sample Cyan inks C-1A to 1C and magenta inks M-1A to 1F prepared in Example 1 were filled in an ink cartridge of an ink jet printer PM-G800 manufactured by Seiko Epson Corporation in the combinations shown in Table 2. The following evaluation was performed on the same machine.

(Bronze evaluation)
M (magenta) solid, C (on 23 ° C. and 60% RH conditions on Fuji Photo Film Co., Ltd. inkjet paper photo glossy paper “Painted photo finish” and Seiko Epson ink jet paper “Photo paper” Cyan) solid and B (blue) solid images were printed, and after standing overnight under the same conditions, bronzing (metallic gloss on the print surface) was visually evaluated according to the following criteria.
○: No bronze gloss is observed.
Δ: Bronze gloss is slightly observed.
X: Bronze gloss is clearly recognized.
Table 2 shows ink combinations and evaluation results.

  From the results of Table 2, it can be seen that the bronze of the cyan image and the blue image is remarkably improved by using the combination of the magenta ink and the cyan ink of the present invention.

(Example 3)
The same ink prepared in Example 1 is packed in a cartridge of an ink jet printer PIXUS990i (manufactured by Canon) according to the combination of the ink set implemented in Example 2, and the image is printed on the same machine by Fuji Photo Film “Paint Photo Finish”. When printing was performed on PR101 manufactured by Canon Inc. and the same evaluation as in Example 2 was performed, the same result as in Example 2 was obtained.

Example 4
Preparation of Cyan Ink After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 7 and filtration under reduced pressure was performed with a microfilter having an average pore diameter of 0.25 μm to prepare a cyan ink liquid (C-2A).

Dye C-1 60.0g
1,5-pentanediol 50.0g
2-Pyrrolidone 50.0g
100.0 g of trimethylolpropane
Surfinol 465 20.0g
Benzotriazole 0.06g
PROXEL XL2 (Avecia) 1.1g

Preparation of magenta ink After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / l, and the mixture was filtered under reduced pressure through a microfilter having an average pore diameter of 0.25 μm to prepare a magenta ink liquid (M-2A).

Dye M-1 35.0g
1,5-pentanediol 50.0g
2-Pyrrolidone 50.0g
100.0 g of trimethylolpropane
Surfinol 465 20.0g
Benzotriazole 0.06g
PROXEL XL2 (Avecia) 1.1g

  Further, the cyan ink (C-2B to 2C) and the magenta ink (M-2B to 2F) were processed in the same manner as C-2A and M-2A except that the type and amount of the dye were changed as shown in Table 3. Produced.

(Example 5)
Preparation of print sample The cyan inks C-2A to 2C and the magenta inks M-2A to 2F prepared in Example 4 were combined in the combinations shown in Table 4 into an ink cartridge of a Hewlett-Packard composite inkjet printer (HP Photomart 2550). After filling, the following evaluation was performed with the same machine.

(Bronze evaluation)
M (magenta) on Fuji Photo Film Co., Ltd. Inkjet Paper Photo Glossy Paper “Painted Photo Finishing” and Hewlett Packard Inkjet Paper (HP Premium Plus Photo Gloss) at 23 ° C. and 60% RH Solid images, C (cyan) solid images, and B (blue) solid images were printed, and left to stand overnight under the same conditions. The bronzes (metallic luster on the print surface) were visually evaluated according to the following criteria.
○: No bronze gloss is observed.
Δ: Bronze gloss is slightly observed.
X: Bronze gloss is clearly recognized.
Ink combinations and evaluation results are shown in Table 4.

  From the results shown in Table 4, even when the type of the ink solvent was changed and thermal ink jet printing was performed in the same manner as in Example 3, the same effects as in Example 2 and Example 3 could be obtained.

(Example 6)
Preparation of Y, M, C, and Bk ink sets In Example 1, yellow ink, light magenta ink, magenta ink, light cyan ink, cyan ink, and black ink were prepared by changing the dye species and additives. Table 5 An ink set 301 having the density shown in FIG.

  Further, ink sets 302 to 320 were produced in the same manner as ink set 301 except that the type and amount of dye were changed as shown in Table 6.

(Example 7)
Preparation of printing sample The ink sets 301 to 320 prepared in Examples 5 and 6 were filled in an ink cartridge of an ink jet printer PM-G800 manufactured by Seiko Epson Corporation, and the following evaluation was performed using the same machine.

(Bronze evaluation)
Fuji Photo Film Co., Ltd. inkjet paper photo glossy paper “Painting Photographic Finish” and Seiko Epson Inkjet Paper “Photo Paper” under 23 ° C. 60% RH condition, Y (yellow) solid, M ( Magenta) Solid, C (Cyan) Solid, R (Red) Solid, G (Green) Solid, B (Blue) Solid, Bk (Black) Solid Images are printed and left overnight under the same conditions. Evaluation of the metallic luster on the print surface was performed according to the following criteria.
○: No bronze gloss is observed.
Δ: Bronze gloss is slightly observed.
X: Bronze gloss is clearly recognized.
Table 7 shows the evaluation results. In all levels, bronzing with solid Y and solid M was not observed, so it was removed from the table.

  From Table 7, it can be seen that the ink set of the present invention has improved bronzing in all solid images.

(Example 8)
The same ink set prepared in Examples 5 and 6 was packed in a cartridge of an ink jet printer PIXUS990i (made by Canon), and images were printed on Fuji Photo Film's ink jet paper “Paint Photo Finish” and Canon's PR101. When the same evaluation as in Example 7 was performed, the same result as in Example 7 was obtained.

Claims (15)

An ink set comprising a magenta ink containing at least one magenta dye and a cyan ink containing at least one cyan dye, wherein both the magenta dye and the cyan dye are anionic water-soluble dyes; and Any one of the anionic water-soluble dyes has a sulfonic acid group as a water-soluble group, and an Li ⁺ ion or a quaternary ammonium ion is used as a counter ion.   The ink set according to claim 1, wherein the cyan dye is a water-soluble phthalocyanine dye having an oxidation potential nobler than 1.0 V (vs SCE).   The ink set according to claim 1, further comprising a yellow ink containing at least one kind of yellow dye and a black ink containing at least one kind of black dye. When the yellow dye and the black dye are anionic water-soluble dyes, the water-soluble group of the anionic water-soluble dye is a sulfonic acid group, a carboxyl group or a phenolic hydroxyl group, and the water-soluble group is a sulfonic acid group In the method, Li ⁺ ion or quaternary ammonium ion is used as a counter ion, and when the water-soluble group is a carboxyl group or a phenolic hydroxyl group, K ⁺ ion or Na ⁺ ion is used as a counter ion. The ink set according to 3.   The ink set according to any one of claims 1 to 4, wherein the ink sets have the same hue and have different dye concentrations.   The ink according to any one of claims 1 to 5, wherein 90% by mass or more of the anionic water-soluble dye in each ink of the ink set does not have a sulfonic acid group and a carboxyl group in the molecule at the same time. set. The ink set according to claim 1, wherein when the water-soluble group of the anionic water-soluble dye is a sulfonic acid group, Li ⁺ ion is used as a counter ion. The ink set according to claim 1, wherein the cyan ink contains at least one water-soluble cyan dye represented by the following general formula (C).

In the general formula (C), X _{1 to} X ₄ and Y _{1 to} Y ₄ each independently represent a carbon atom or a nitrogen atom. A _{1 to} A ₄ are each independently required to form an aromatic ring or a heterocyclic ring (which may form a condensed ring with another ring) together with X _{1 to} X ₄ and Y _{1 to} Y _4. Represents an atomic group. A _{1 to} A ₄ may have a substituent. At least one of A _{1 to} A ₄ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. The ink set according to claim 1, wherein the magenta ink contains at least one water-soluble magenta dye represented by the following general formula (M).
General formula (M)

In the general formula (M), A ₃₁ represents a 5-membered heterocyclic group.
B ₃₁ and B ₃₂ are each = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - represents a or -CR ₃₂ =. R ₃₅ and R ₃₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group Represents a heterocyclic sulfonyl group or a sulfamoyl group, and each group may further have a substituent.
G ₃ , R ₃₁ and R ₃₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino) Group, including heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl And Arylchi O group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, sulfonic acid group, or heterocyclic thio group, each group may be further substituted .
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- to 6-membered ring.
Note that at least one of A ₃₁ , R ₃₁ , R ₃₂ , R ₃₅ , R _36, and G ₃ has a sulfonic acid group, and has Li ⁺ or a quaternary ammonium ion as a counter ion. The magenta ink is a water-soluble dye having an anthrapyridone skeleton, a sulfonic acid group as a water-soluble group, and a counter ion being Li ⁺ ion. The ink set described in 1. The ink set according to claim 3, wherein the yellow ink contains at least one water-soluble yellow dye represented by the following general formula (Y).
General formula (Y) (AN = NB) n-L
In the formula, A and B each independently represent an optionally substituted heterocyclic group. L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different. The ink set according to claim 3, wherein the black ink contains at least one water-soluble black dye represented by the following general formula (Bk).
Formula _{(Bk): A 1 -N =} N-A 2 -N = N-A 3
In General Formula (Bk), A ₁ , A _2, and A ₃ each independently represents an optionally substituted aromatic group or an optionally substituted heterocyclic group. A ₁ and A ₃ are monovalent groups, and A ₂ is a divalent group.   The ink set according to claim 1, wherein the ink set is used for inkjet.   An ink jet recording method comprising forming a full color image for ink jet using the ink set according to claim 13.   15. The recording method according to claim 14, wherein the image receiving material having an image receiving layer containing inorganic pigment particles on a support is ejected with ink droplets according to a recording signal, and an image is recorded on the image receiving material. Inkjet recording method.