JP2002121439A - Ink set for ink jet-recording and method of ink jet- recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set for ink jet-recording capable of obtaining a sufficient preservation stability even printed on paper for exclusive use. SOLUTION: This ink set for ink jet-recording for full color printing comprises a plurality of aqueous recording liquids in which a black ink includes an aqueous liquid including one or more kinds of black metal chelate dyes in forms as free acids expressed by general formula (1) and a cyan ink includes an aqueous liquid including one or more kinds of phthalocyanine dyes in forms as free acids expressed by general formula (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an ink jet recording method. Specifically, the present invention provides a preferable combination of a black recording liquid for forming a color image having excellent storage stability and a cyan recording liquid containing a phthalocyanine dye.

[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 acidic dye are ejected from a fine discharge orifice to perform recording. Regarding the recording liquid used for this, in addition to being capable of stable ejection for a long time,
Fast fixing to C (plain paper copier) paper and fan hold paper (recording paper generally used for general affairs such as continuous paper such as computers) and good print quality of printed matter, that is, bleeding on printing It is required that the contour is clear without any defects and the stability during storage as the recording liquid is also excellent. Therefore, the solvent that can be used for the recording liquid is significantly limited.

On the other hand, dyes for recording liquids have sufficient solubility in the above-mentioned limited solvents and are stable even when stored as recording liquids for a long time.
Further, it is required that the density of the printed image is high, and that it is excellent in water resistance and light resistance. However, it has been difficult to satisfy many of these requirements at the same time. in addition,
In recent years, ink jet recording has been required to be suitable for printing photo-like images, graphic images, and the like (hereinafter abbreviated as photographic images), which have been greatly improved as compared with conventional ink jet recording.

Further, in order to realize a high-definition and clear image in ink jet recording, especially when printing a photographic image, a special coated paper or a special gloss paper (hereinafter abbreviated as a special paper) is used. On such recording media, generally called photo glossy paper or inkjet paper, the action of silicon oxide and aluminum oxide added to form high-definition and clear images, or water-proofing agents represented by polyamines Tends to accelerate the decomposition of the dye by light. As a result, when a photographic image printed matter by an ink jet is displayed indoors and outdoors, there has been a problem that the image is easily discolored and discolored.

Further, unlike character printing which is printed at 100% density, a photographic image has 80% halftone printing, 7
So-called halftone printing such as 0% halftone printing is frequently used. In addition to the black recording liquid,
So-called three-primary-color recording liquids such as yellow, cyan, and magenta, and mixed-color images used in combination thereof have been frequently used, and the delicate color tone of the halftone portion has been reproduced.

[0006] These images are required to have good storage stability, even when stored or posted, with a sufficiently low fading speed due to, for example, light, acid gas, ozone gas, or the like. Generally, the fading of a mixed color image is the sum of the fading speeds of the constituent dyes. However, because the storage stability of the dyes used is specific to the dyes, certain of the constituent dyes faded faster than the other dyes, and as a result, the image lost its initial hue balance It often faded in shape with unsightly discoloration.
Furthermore, catalytic fading (catalytic fading), which is a phenomenon in which a specific dye promotes the decomposition of other dyes, is often added, and the image loses its original color balance and fades with unsightly discoloration. Has been promoted.

In order to evaluate the degree of fading in the halftone area, for example, a "shading" function of commercially available graphic software or word processing software is used to set the print density to an arbitrary value between 0 and 100%. For example, setting to 80%, and setting the printer driver to the color mode, etc., perform shading printing using black ink and three primary color inks.
For example, ultraviolet to visible light is irradiated using a xenon weather o-meter, and the degree of discoloration (ΔE value) before and after irradiation may be measured with a commercially available colorimeter. Alternatively, the printed matter obtained by the above-described printing method is left for a certain period of time in a place exposed to sunlight, and the degree of discoloration (ΔE value) before and after being left is measured by a commercially available colorimeter to preserve the image. Stability can be evaluated.

[0008] The ΔE value is an index indicating the degree of discoloration of an image. In order to impart sufficient storage stability to a photographic image formed on special paper by ink-jet printing, for example, an image giving a value of about 10 or less as a ΔE value before and after irradiation with xenon arc light for 80 hours is required. With the conventional dyes, it is difficult to obtain the above-mentioned target value even with the light resistance of a 100% solid printing portion, and further, so-called half-printing, such as 80% halftone printing and 70% halftone printing, often used in photographic images. In the tone area, the photobleaching of the image was even more pronounced.

Various dyes and recording methods have been proposed to improve the storage stability of images, especially halftone images. However, as described above, the demands of the market, which are complicated and sophisticated, are sufficiently satisfied. I have not been able to. For example,
In JP-A-3-203970, CI reactive blues 14 and 63 corresponding to the phthalocyanine dye represented by the general formula (2) in the present invention are used as a cyan ink, and are used as a specific magenta dye and a yellow dye. Further, it is described that printing is performed in combination with a black dye. However, when printing is performed in combination with this ink, there is a problem that an image loses color balance and deteriorates during long-term storage. This is probably because the magenta dye, the yellow dye, or the black dye is catalytically decomposed by the phthalocyanine dye of the cyan ink. In particular, Japanese Patent Application Laid-Open No.
In the case of printing on so-called inkjet paper, such as photo glossy paper, which has been increasingly used in recent years, with the combination of dyes of PR No. 0, the black dye having a high color density on an image is quickly faded, which is a serious problem. Since this is a dye in which the phthalocyanine dye and the black dye each contain a large number of sulfonic acid groups as water-soluble groups, in the image portion where the cyan ink and the black ink are used in combination,
It is thought that as a result of the similar state of the two dyes being affected by the pH of the paper and the like, the dyes easily interact with each other and the fading of the catalyst proceeds more easily. As described above, the inkjet recording liquid itself using the specific phthalocyanine compound itself used in the present invention is known, but when color recording is performed in combination with a black recording liquid, a combination that provides excellent storage stability is obtained. Was not known.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording method capable of obtaining a recording having sufficient storage stability even when printing and recording on a special paper.

[0011]

Means for Solving the Problems The present inventors have repeatedly studied and found a combination of specific recording liquids having the performance satisfying the above object as recording liquid components, and have achieved the present invention. That is, according to the present invention, a black aqueous recording liquid containing a specific black-based metal chelate dye and a cyan aqueous recording liquid containing a specific phthalocyanine dye are subjected to inkjet recording to achieve high storage stability. Can be achieved.

That is, a first gist of the present invention is an ink set for ink-jet recording for performing full-color recording using a plurality of aqueous recording liquids, wherein the black ink is represented by the following general formula (1) ) Is an aqueous recording liquid containing at least one black metal chelate dye represented by the formula (1), and the cyan ink contains at least one phthalocyanine dye represented by the following general formula (2) as a free acid form: An ink jet recording ink set, which is an aqueous recording liquid containing the ink.

[0013]

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(Wherein the general formula (1) is a compound having at least one hydrophilic group in the molecule, M represents a metal atom, and A, B, C and D each independently represent Represents an aromatic ring optionally substituted with any substituent,
₁ and R ₂ each independently represent a hydrogen atom or any substituent. m is 0-1, n is 0-3, p is 0-2, q is 0-3
Represents an integer. When a plurality of Bs exist, each B may be the same or different from each other.
When p is 2, each R ₁ and R ₂ may be the same or different. Further, M may take a coordination of three or more coordinations, in which case, M may be an arbitrary ligand or a bonding moiety in the general formula (1) or an arbitrary ligand pair by an arbitrary ligand. It may be coordinated at a metal ratio. )

[0015]

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(Wherein, Cu-Pc represents copper phthalocyanine, X is an alkylene group having 1 to 6 carbon atoms or a phenylene group which may be substituted, R ₁ and R ₂ each independently represent a hydrogen atom, Represents an alkyl group which may be substituted, an alkoxyalkyl group which may be substituted, and Y and Z are each independently a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group which may be substituted, A secondary or tertiary amino group which may be substituted by one or two alkyl groups which may be substituted by a phenoxy group, a hydroxyl group or an alkoxy group; an anilino group which may be substituted; Represents an N-methylanilino group or a morpholino group which may be a and b, a and b are rational numbers of 0 or more and 4 or less, c is a rational number of more than 0 and 4 or less, and a
+ B + c is 2 to 4. Further, a second gist of the present invention is that an aqueous recording liquid containing at least one black metal chelate dye whose free acid is represented by the general formula (1), An ink jet recording method characterized by using an aqueous recording liquid containing at least one phthalocyanine dye represented by the general formula (2) in combination.

The reason why the present invention can exert excellent effects is that the specific phthalocyanine cyan dye used in the present invention and the specific black metal chelate dye used in the present invention are more robust than other dyes. In addition to being improved, the specific phthalocyanine cyan dye used in the present invention is less susceptible to catalytic decomposition by the specific black metal chelate dye used in the present invention, and the specific black metal used in the present invention This is considered to be due to the synergistic reason of the fact that the chelate dye is less susceptible to catalytic decomposition by the specific phthalocyanine cyan dye used in the present invention.

Although the mechanism of the development of the fastness is not clear, the phthalocyanine dye has a bulky triazinyl group as a reactive group, which is sterically dye-colored, that is, the azo portion of a black metal chelate dye or phthalocyanine. It is considered that the phthalocyanine portion of the system dye is protected. In addition, while the metal atom of the black metal chelate dye is likely to be coordinated by a plurality of dye molecules or a dye and a ligand other than the dye, that is, a plurality of ligands, the copper atom of the phthalocyanine dye is It appears to be coordinated within a single molecule. That is, the coordination between the metal of the black metal chelate dye and the metal of the phthalocyanine dye is different, the existing state of both dyes on paper is different, the energy transfer between molecules is less likely to occur, and the catalytic discoloration of both is reduced. It is also possible that they are mutually suppressed.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The aqueous recording liquid containing a black metal chelate dye used in the present invention is a black ink. As the black metal chelate dye, a dye whose free acid form is represented by the general formula (1) is used.

The black metal chelate dye used in the present invention is a dye whose free acid form is represented by the general formula (1).
The dye represented by the general formula (1) is disazo or a polyazo compound having a larger number of azo groups than the azo group, wherein phenol, naphthol, or a similar hydroxyl-containing aromatic ring is introduced into a series of aromatic ring chains linked by the azo group. It is a complex compound of a form molecule and any metal.

The dye represented by the general formula (1) is a water-soluble dye.
Has two hydrophilic groups. The hydrophilic group is not particularly limited as long as it is a water-soluble hydrophilic group usually used as an inkjet recording liquid, and examples thereof include sulfonic acid, carboxylic acid, and phosphoric acid. The number of these hydrophilic groups is preferably 2 to 6 as a whole molecule, which is preferable as the performance of the ink jet recording liquid.

A, B, C and D in the general formula (1)
Represents an aromatic ring which may be substituted with an optional substituent, at least one of which may have a heterocyclic ring, preferably a benzene ring or a substituted Is a naphthalene ring which may be substituted.
Among them, D is preferably a naphthalene ring. These aromatic rings A, B, C and D may have a suitable substituent depending on the use of the dye. For example, A represents a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted amino group,
At least one substituent selected from the group consisting of an optionally substituted acylamino group, an optionally substituted sulfonylamino group, an optionally substituted phenylazo group, and an optionally substituted naphthylazo group May be substituted. B is a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted amino group, At least one group selected from the group consisting of an optionally substituted acylamino group and an optionally substituted sulfonylamino group.
May be substituted with a single substituent. C is a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted amino group,
It may be substituted with at least one substituent selected from the group consisting of an optionally substituted acylamino group and an optionally substituted sulfonylamino group. D may further have a substituent in addition to the substituent defined in the general formula (1), and may be a halogen atom, a carboxyl group, a nitro group, an optionally substituted alkyl group, May be substituted with any substituent such as a substituent selected from the group consisting of good alkoxy groups. Among them,
When at least one of A, B and C has a substituent, the substituent may be a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, an optionally substituted alkyl group, And a substituent selected from an optionally substituted alkoxy group, an optionally substituted amino group, an optionally substituted acylamino group and an optionally substituted sulfonylamino group.

M, n, p, and q may be any numbers as long as they are as defined above, in which m is 0,
Those in which n is 1 or 2 and those in which p is 1 are preferably used. Further, it is preferable that q = 1, that is, the case where the dye of the general formula (1) is a trisazo dye. M can also be selected from any metal depending on the purpose, but is preferably a divalent or trivalent transition metal, for example, preferably copper, nickel, iron, cobalt or the like, and particularly preferably copper or nickel.

Specific examples of the black metal chelate dye having a free acid form represented by the above general formula (1) used in the present invention are shown in Table 1 below. It is not limited.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

The other aqueous recording liquid used in the present invention is:
This is a cyan ink, and uses a specific phthalocyanine dye represented by the general formula (2) as an essential component. The phthalocyanine dye represented by the general formula (2) is characterized in that it has a specific triazylaminophenyl group in the molecule. It is considered that the recorded matter can exhibit extremely excellent fastness when the recording is performed in combination with the black disazo dye represented.

In the general formula (2), Cu-Pc represents copper phthalocyanine. X represents a C1-C6 alkylene group or a phenylene group which may be substituted. Preferred examples of the alkylene group for X include an ethylene group, and preferred examples of the optionally substituted phenylene group include a phenylene group substituted with a sulfonic acid group. R ₁ and R ₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted alkoxyalkyl group. Preferred examples of R ₁ and R ₂ include a hydrogen atom and a hydroxyethyl group. Y and Z each independently represent a fluorine atom, a chlorine atom, a hydroxyl group, an optionally substituted alkoxy group, an optionally substituted phenoxy group, a hydroxyl group or an alkoxy group;
Represents a secondary or tertiary amino group which may be substituted by one or two kinds of alkyl groups, an anilino group which may be substituted, an N-methylanilino group which may be substituted, or a morpholino group. Preferred examples of Y and Z include an anilino group substituted with a chlorine atom, a hydroxyl group, an amino group, a methoxy group, and a sulfonic acid group. Groups are more preferable, and a chlorine atom and a 2,5 disulfoanilino group are more preferable. a and b are rational numbers from 0 to 4 inclusive, c is a rational number from 0 to 4 inclusive, and a +
b + c is 2-4. A) and b are rational numbers from 0 to 4, and c is a rational number from 0 to 4 inclusive. Here, each of a and b is preferably about 1 to 2. c is 0.2
~ 2, preferably about 0.5-1.5. However, in any case, a + b + c will be in the range of 2-4. d represents an integer of 0 or more and 2 or less, and is more preferably 1.

Specific examples of the phthalocyanine dye corresponding to the general formula (2) are listed in Table 2 below, but the present invention is not limited to such dyes. Table 2 below
Among them, the No. 1 dye was CI Reactive Blue 7 (Cibacron TurquoiseBlue GE, manufactured by Ciba Geigy), and the No. 2 dye was CI Reactive Blue 15 (Hayashi Chemical High-R).
eact Turquoise Blue). Among the phthalocyanine dyes corresponding to the general formula (2), C.I.
I. Reactive Blue 7, C.I. I. Reactive Blue 14, C.I. I. Reactive Blue 15 and the like are preferred, and CI Reactive Blue 14 is most preferred.

[0035]

[Table 8]

[0036]

[Table 9]

[0037]

[Table 10]

The phthalocyanine dye represented by the general formula (2) may be used as an aqueous recording liquid by using at least one kind of the phthalocyanine dye represented by the general formula (2).
A dye represented by the general formula (2) is mixed with another general phthalocyanine compound, and the mixture is prepared so as to have a composition of the phthalocyanine compound represented by the general formula (2). It may be a liquid. Specific examples of such phthalocyanine dyes other than the general formula (2) include C.I. I. Direct Blue 86 and C.I. I. Direct Blue 199 and the like are preferable, and C.I. I. It is preferable to mix with Direct Blue 199. in this case,
The compounding ratio of the dye represented by the general formula (2) is preferably at least 40% by weight, more preferably at least 60% by weight, based on other dyes. I. Direct Blue 86
A dye corresponding to a = 2, b = 0 and c = 0 in the general formula (2); I. Direct Blue 199 corresponds to a = 2, b = 1 and c = 0 in the general formula (2), and the dye alone is out of the range of the general formula (2).

As an aqueous recording liquid containing the phthalocyanine dye of the general formula (2), CI
Reactive Blue 14 alone or C.I. I. Most preferred is a mixture with Direct Blue 199. Further, a cyan dye having a skeleton other than phthalocyanine may be added to the aqueous recording liquid containing the general formula (2) as long as the performance is not impaired.

To obtain the color image of the present invention by ink-jet recording, (1) ink-jet recording is performed using a full-color ink set including black, magenta, cyan, yellow, etc., depending on the type of ink-jet printer. , (2) each of which can be obtained by a method of performing full-color recording with an inkjet printer using a single-color ink cartridge of black, magenta, cyan, yellow or the like.

Further, in forming a color image, a black ink containing the black metal chelate dye of the present invention,
There is no particular limitation on the magenta ink or yellow ink used in combination with the cyan ink containing the phthalocyanine compound. Examples of the magenta ink include H-acid and γ-acid monoazo dyes and bisazo dyes, xanthene dyes, etc., which are usually used for ink jet recording. I. Acid Red 8, C.I. I. Acid Red 3
7, C.I. I. Acid Red 50, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I.
I. Acid Red 93, C.I. I. Acid Red 9
5, C.I. I. Acid Red 98, C.I. I. Acid Red 287, C.I. I. Acid Red 35, C.I. I. Reactive Red 23, C.I. I. Reactive Red 1
80, C.I. I. Hydrolyzate of Reactive Red 180, C.I. I. Direct violet 107 or the like is preferably used.

As the yellow ink, a yellow dye usually used for ink jet recording, specifically, C.I. I. Acid Yellow 17: 1, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 49,
C. 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 194, C.I. I. Direct Yellow 86, C.I. I.
Direct Yellow 106, C.I. I. Direct Yellow 132, C.I. I. Direct Yellow 142 and the like are preferably used.

The dye represented by the general formula (1) of the present invention is
A method known per se [for example, Yutaka Hosoda, "New Dye Chemistry"
(Published by Gihodo on December 21, 1973) 396-4
As described above, the compound is synthesized through the diazotization and coupling steps. For example, an aromatic amine having a partial structure of A is diazotized and condensed to an aromatic amine having a partial structure of B, and the obtained compound is further diazotized and condensed to an aromatic amine having a partial structure of C; Further, by diazotizing the obtained compound and condensing it with an aromatic compound having a partial structure of D, that is, by reacting a desired metal salt with a compound obtained by sequentially repeating diazotization and condensation, can get.

Examples of the aromatic amine having the partial structure of A include 4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-cyano-4-nitroaniline, 4-chloroaniline, sulfanilic acid, 2-aminobenzene-1,
4-disulfonic acid, C-acid, dahlic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminoterephthalic acid, 3-aminoisophthalic acid, 2,5-diaminobenzoic acid, 5-amino-2-nitrobenzoic acid Aromatic amines such as 2-amino-3-aminocarbonyl-5-formylthiophene, 2-amino-6-carboxybenzothiazole, 2-amino-6-sulfobenzothiazole, 2-amino-4,5 dicyanoimidazole, 2-amino-4 Heterocyclic aromatic amines such as 5-dicarboxyimidazole, and derivatives thereof.

Examples of the aromatic amine having a partial structure of B include 1-naphthylamine, 1,6-clave acid, 1,7-clave acid, 2-methoxyaniline, 2-ethoxyaniline, 2-amino-paracresidine, Aromatic amines such as 5-dimethoxyaniline, 2,5-diethoxyaniline, and 5-acetylamino-2-methoxyaniline;
And heterocyclic aromatic amines such as -amino-3-cyanothiophene, and derivatives thereof.

Examples of the aromatic amine having the partial structure of C include 8-amino-7-hydroxy-2-naphthalenesulfonic acid, 2-hydroxyaniline, and 2-hydroxy-5
And aromatic amines such as 2-methylaniline, 2-hydroxy-5-methoxyaniline, 2-hydroxy-5-ethoxyaniline, and 5-acetylamino-2-hydroxyaniline. These are obtained by repeating the above-mentioned sequential diazotization and condensation with a precursor in which a portion of a hydroxyl group to be interacted with a metal is in an alkoxy form, and then reacting the metal salt with an appropriate amine. ,
The alkoxy group may be obtained by a reaction that converts the alkoxy group into a hydroxyl group coordinated to a metal.

Examples of the aromatic compound having the partial structure of D include α-naphthol derivatives represented by Shoelkof's acid, Videt's acid, L-acid, chromotropic acid, nevirwinteric acid and ε-acid, γ-acid, phenyl γ-acid, 3-sulfophenyl gamma acid, 4-carboxyphenyl gamma acid, RR
Acid, J acid, phenyl J acid, methyl J acid, di J acid, carbonyl J acid, H acid, benzoyl H acid, phenylsulfonyl H acid, M acid, S acid, SS acid, amino acid represented by K acid α-naphthol derivative, R acid, G acid, Crocein
Acid, shephuric acid, F acid, oxynaphthoic acid, β-naphthol derivative represented by 3-hydroxy-1,8-naphthalic acid, amino-β naphthol derivative represented by Boeniger acid, heterocyclic aromatic represented by 8-hydroxy-5-sulfoquinoline And the like. Among them, J acid, γ acid, RR acid, 4-carboxyphenyl gamma acid and 3-sulfophenyl gamma acid are preferred.

Specific examples of R ₁ and R ₂ include a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group,
-Carboxyethyl group, phenyl group, 3-sulfophenyl group, 4-carboxyphenyl group, acetyl group, benzoyl group, 4-methylphenylsulfonyl group, 3-bis (2-hydroxyethyl) amino-5- (2-sulfoethyl) amino-2,4 , 6-triazino groups and the like.

The phthalocyanine dye represented by the general formula (2) of the present invention can be prepared by a method known per se [for example, see Yutaka Hosoda, “Dye Chemistry”, published by Gihodo on July 15, 1968, pp. 385-392. Can be synthesized through substitution reactions such as chlorosulfonation, amidation and hydrolysis, cyanuration, amination and alkoxylation of copper phthalocyanine, but desalting and purifying using a commercially available dye. May be adjusted by

In preparing the recording solution used in the present invention, a black metal chelate dye whose free acid form is represented by the general formula (1) and a phthalocyanine whose free acid form is represented by the general formula (2) The dye may be used as it is in the form of a free acid, or may be used after converting a part or all of the acid group into a desired salt form. One or more ions selected from the group consisting of alkali metal ions such as lithium, sodium, and potassium, ammonium ions, and substituted amines are used as counter ions that form a salt. Specific examples of the substituted amines include mono-, di-, and tri-substituted amines in which the substituent is an alkyl group having 1 to 4 carbon atoms and / or a hydroxyalkyl group having 1 to 4 carbon atoms. Further, different types of counter ions may be used in combination.

In the recording liquid used in the present invention, a black metal chelate dye having a free acid form represented by the general formula (1) and a phthalocyanine dye having a free acid form represented by the general formula (2) The pigment content is preferably 1 to 10% by weight, particularly preferably about 2 to 7% by weight, based on the total amount of the recording liquid. As the solvent used in the recording liquid used in the present invention, as water and a water-soluble organic solvent, for example, ethylene glycol, propylene glycol, butylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 400), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide,
It preferably contains ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropanol, and the like. These water-soluble organic solvents are usually used in the range of 1 to 50% by weight based on the total amount of the recording liquid. On the other hand, water is used in the range of 45 to 95% by weight based on the total amount of the recording liquid.

The recording liquid used in the present invention may contain a compound selected from urea, thiourea, biuret and semicarbazide in an amount of 0.1 to 10% by weight, preferably 2 to 8% by weight based on the total amount thereof. 0.001 to 5.0% by weight
By adding the above surfactant, the quick drying property after printing and the printing quality can be further improved. According to the recording method of the present invention, when ink jet recording is performed on special paper, an image having good storage stability can be obtained.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. The dye N in the examples
o. Is the dye No. in Table 1. Corresponding to “Parts” means “parts by weight” unless otherwise specified. Production Example 1 (Production Example of Dye No. 1 in Table 1) 173 parts of sulfanilic acid were suspended in 800 parts of water, and 35%
260 parts of hydrochloric acid were added. This was cooled to 5 ° C. and 73 parts of sodium nitrite were added. The above-mentioned solution was added to 600 parts of water to which 91 parts of 35% hydrochloric acid had been previously added at 0 to 5 ° C. to diazotize sulfanilic acid. Thereafter, 5 parts of sulfamic acid was added to obtain a diazo liquid of sulfanilic acid.

Separately, 245 parts of 1,7 clavic acid were added to water 6
000 parts, the solution was cooled, the above-mentioned diazo solution of sulfanilic acid was added, and the resulting solid was collected by filtration.
This was suspended in 6000 parts of water, and the pH was adjusted to 12 with a 25% aqueous sodium hydroxide solution to obtain a uniform monoazo compound solution. To this monoazo compound solution, 73 parts of sodium nitrite was added and dissolved. This was added to 6000 parts of water at 0-5 ° C while adjusting the pH to 3 with 35% hydrochloric acid.
By dropwise addition, diazotization of the monoazo compound was performed. 5 more
Then, part of sulfamic acid was added to obtain a diazo solution of a monoazo compound.

Separately, 153 parts of 2,5-dimethoxyaniline hydrochloride were dissolved in 1500 parts of water, the liquid was cooled, the diazo liquid of the above monoazo compound was added, and the resulting solid was collected by filtration. This was suspended in 6000 parts of a 50% aqueous solution of N-methylpyrrolidone, and the pH was adjusted to 12 with a 25% aqueous solution of caustic soda to obtain a uniform disazoazo compound solution.

To this disazo compound solution, 73 parts of sodium nitrite was added and dissolved. This is 6000 copies of 50
% N-methylpyrrolidone aqueous solution at 0-5 ° C.
While the pH was adjusted to 3 with 3% hydrochloric acid, the disazo compound was diazotized by dropping. Further, 5 parts of sulfamic acid was added to obtain a diazo solution of a monoazo compound. 359 parts of 4-carboxyphenyl gamma acid were suspended in 3000 parts of water, and the pH was adjusted to 11 with sodium hydroxide to obtain a uniform solution. The solution was cooled, and the above-mentioned diazo solution of the monoazo compound was added dropwise at 0 to 5 ° C. to perform coupling. At the time of dropping, the pH of the coupling bath was adjusted to 10 to 11 using a 25% aqueous sodium hydroxide solution. 900 parts of common salt was added to the obtained liquid, and the generated crystals were collected by filtration and dried.

The obtained trisazo compound (66 parts) was mixed with 700 parts.
In water, 24 parts of copper sulfate anhydride and 61 parts of diethanolamine were added, and the temperature was raised to 95 to 100 ° C.
The reaction was performed for 2 hours. After insoluble matter in the obtained liquid was collected by filtration, the liquid was cooled to 25 ° C., 70 parts of sodium chloride was added, and the generated solid was collected by filtration. The obtained wet cake was dissolved in 1000 parts of water, 1000 parts of isopropyl alcohol was added, and the resulting crystals were collected by filtration. The obtained pigment was dried, and No. 2 of Table 1 was dried. 31 parts of one dye were obtained in the form of the sodium salt.

The maximum absorption wavelength of the obtained dye in water is 6
63 nm. Production Example 2 (Production Example of Dye No. 1 in Table 2) I. Reactive Blue 7 (Ciba Geigy, C
ibacron Turquoise Blue G-
E) 70 parts were dissolved in 1000 parts of water, 150 parts of sodium chloride was added, and the resulting solid was collected by filtration. The obtained wet cake was dissolved in 1000 parts of water, 1500 parts of isopropyl alcohol was added, and the resulting crystals were collected by filtration. The obtained dye was dried, and No. 2 of Table-2 was dried. 30 parts of one dye are obtained in the form of the sodium salt. The maximum absorption wavelength of the obtained dye in water was 610 nm. Example 1 Preparation of recording liquid 10 parts of diethylene glycol monobutyl ether, 10 parts of glycerin, 5 parts of 2-pyrrolidone, 70 parts of sophthanol
(Surfactant, Nippon Shokubai Co., Ltd.) 0.5 part, No. 1 in Table 1 obtained in Production Example 1 above. Add water to 5 parts of 1 dye,
Adjust the pH to 9 with aqueous sodium hydroxide and adjust the total amount to 1
00 parts. 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 deaerated with a vacuum pump and an ultrasonic cleaner to prepare a black recording liquid.

On the other hand, 10 parts of diethylene glycol monobutyl ether, 10 parts of glycerin, and 2-pyrrolidone 5
Part, sophthanol 70 (surfactant, Nippon Shokubai Co., Ltd.)
No. of Table-2 obtained in Preparation Example 2).
Water is added to 5 parts of the dye of Example 1, and p
H was adjusted to 9 to make the total amount 100 parts. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon filter having a pore size of 1 μm, and then deaerated by a vacuum pump and an ultrasonic cleaner to prepare a cyan recording solution. (2) Printing Inkjet printer (trade name BJC-420J,
2 obtained by the above procedure using Canon Inc.)
Using the recording liquid of the kind, the genuine yellow recording liquid of the printer, and the magenta recording liquid, solid-color solid ink jet recording was performed on photo glossy paper GP-201 (manufactured by Canon Inc.). At this time, using a shading function of MS-Word (word processing software, manufactured by Microsoft Corporation), the printing density is the highest density solid printing, and 80%, 60%, and 40% of the highest density solid printing, for a total of four levels. To obtain a halftone black print. The printed matter was observed with a magnifying glass, and it was confirmed that not only the black recording liquid but also each of the yellow, cyan, and magenta recording liquids was used in the light-colored portion. (3) Image storage stability test Evaluation 1 Using a xenon fade meter (manufactured by Atlas), irradiate the recording paper for 80 hours, measure the degree of discoloration before and after that with a Gretag Macbeth SPM50, and determine the ΔE value. Quantified in form. Here, the ΔE value is a numerical value indicating the degree of discoloration and fading. A larger value indicates a larger degree of discoloration and fading, that is, the light fastness of the image is low. In the evaluation, an 80% density printed portion, of which the fading behavior is conspicuous, was used.

As a result of the test, the light fastness of this dye to photo glossy paper for ink-jet was set to ΔE value,
1, which was a good value. Evaluation 2 The printed matter obtained by the above procedure was displayed on a panel installed in parallel with a south-facing window, and left at 28 ° C. for 45 days. A difference was visually observed while comparing the obtained printed matter after the exposure test with a standard printed matter which was simultaneously printed and then sealed and stored in a cool dark place, but the difference was hardly felt. Example 2 Instead of Dye No. 1 in Table 1 used in Example 1,
Black recording solution prepared in the same manner as in Example 1 using Dye No. 2 in Table 1 and Dye N in Table 2 used in Example 1
Printing evaluation and storability evaluation were carried out in the same manner as in Example 1 except that cyan recording liquid was used in place of o.1 and dye No. 9 in Table 2 was used. As a result, ΔE in Evaluation 1 was 8.9, which was a good result as in Example 1, and the visual determination result in Evaluation 2 was also good. Comparative Example 1 In place of Dye No. 1 in Table 1 used in Example 1, C.I. I.
Example 1 except that 5 parts of Food Black 2 were used.
A recording liquid was prepared in the same manner as in the above method, and printing and storage stability were evaluated. The result of Evaluation 1 was insufficient at ΔE of 21.3, and also in Evaluation 2, the discoloration of the image, particularly in the halftone portion, was remarkable, and only the result of insufficient storage stability was obtained.

[0061]

Embedded image

Comparative Example 2 In place of Dye No. 9 in Table 2 used in Example 2, C.I. I. A recording solution was prepared in the same manner as in Example 1 except that three parts of Direct Blue 199 were used, and printing and storage evaluation were performed. The result of evaluation 1 is $ E
In the evaluation 2, the brown discoloration of the image, particularly in the halftone portion, was remarkable, and only the result of insufficient storage stability was obtained.

[0063]

According to the present invention, even when printing and recording on special paper, ink jet recording with sufficient storage stability becomes possible.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 45/32 C09B 67/22 F 67/22 B41J 3/04 101Y F-term (Reference) 2C056 EA13 FC02 2H086 BA01 BA53 BA57 4J039 BC03 BC33 BC39 BC42 BC52 BC53 BC54 BC59 BC60 BC65 BC72 BC73 BC75 BC77 BC78 BC79 BE02 CA03 CA06 EA16 EA19 EA44 GA24

Claims (26)

[Claims] 1. An ink set for inkjet recording comprising a plurality of aqueous recording liquids for performing full-color recording, wherein the black ink is a black metal chelate represented by the following general formula (1) in the form of a free acid: It is an aqueous recording liquid containing at least one dye, and the cyan ink is an aqueous recording liquid containing at least one phthalocyanine dye represented by the following general formula (2) in the form of a free acid. Characteristic ink set for inkjet recording. Embedded image (Wherein, the general formula (1) is a compound having at least one hydrophilic group in a molecule, M represents a metal atom, and A, B, C and D each independently represent an arbitrary R ₁ and R ₂ each independently represent a hydrogen atom or an arbitrary substituent, and m represents 0 to 0.
1, n represents 0 to 3, p represents 0 to 2, and q represents 0 to 3, each representing an integer. When a plurality of Bs exist, each B may be the same or different from each other. Also, p is 2
In the case, R ₁ and R ₂ may be the same or different from each other. Further, M can take a coordination of tridentate or more, in which case M is represented by any substituent or bonding moiety in the general formula (1) or any ligand.
It may be coordinated at any ratio of ligand to metal. ) (In the formula, Cu-Pc represents copper phthalocyanine, X is an alkylene group having 1 to 6 carbon atoms or a phenylene group which may be substituted, and R ₁ and R ₂ are each independently a hydrogen atom or a substituted phenylene group. And Y and Z each independently represent a fluorine atom, a chlorine atom, a hydroxyl group, an optionally substituted alkoxy group, or an optionally substituted phenoxy group. A secondary or tertiary amino group which may be substituted by one or two alkyl groups which may be substituted by a group, a hydroxyl group or an alkoxy group; an anilino group which may be substituted; Represents a good N-methylanilino group or a morpholino group, a and b are rational numbers of 0 or more and 4 or less, c is a rational number of more than 0 and 4 or less, and a + b + c is 2-
4. ) 2. The ink jet recording ink set according to claim 1, wherein in the general formula (1), D is a naphthalene ring. 3. In the general formula (1), A independently represents a phenyl group which may be substituted or a naphthyl group which may be substituted, and B and C each independently represent a substituted Represents an optionally substituted phenylene group or an optionally substituted naphthylene group, and when A, B or C has a substituent, the substituent may be a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, Group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted amino group,
The ink set for inkjet recording according to any one of claims 1 to 2, which is an acylamino group which may be substituted or a sulfonylamino group which may be substituted. 4. In the general formula (1), m = 0 and n = 1
2 and p = 1.
3. The ink set for inkjet recording according to any one of 3. 5. The ink set for ink jet recording according to claim 1, wherein q in Formula (1) is 1. 6. The compound according to claim 1, wherein in formula (1), one of R ₁ and R ₂ is a hydrogen atom, and the other is a phenyl group which may be substituted. The ink set for inkjet recording according to any one of the above. 7. The ink set for ink jet recording according to claim 1, wherein in the general formula (1), R ₁ and R ₂ are both hydrogen atoms. 8. The general formula (1), wherein M is copper, nickel, iron or cobalt.
8. The ink set for inkjet recording according to any one of items 1 to 7. 9. In the general formula (2), X is an ethylene group, Y is an anilino group substituted by a sulfonic acid group, and Z is a chlorine atom or a hydroxyl group. 9. The ink set for inkjet recording according to any one of 8. 10. In the general formula (2), X is a phenylene group, Y is a methoxy group or an amino group, and Z is a chlorine atom or a hydroxyl group.
An ink set for inkjet recording according to any one of claims 1 to 8. 11. In the general formula (2), c is 0.2 to 0.2.
The ink set for inkjet recording according to claim 1, wherein the number is 2. 12. The phthalocyanine dye represented by the general formula (2) is C.I. I. Reactive Blue 7, C.I. I. Reactive Blue 14, or C.I. I. The ink set for inkjet recording according to any one of claims 1 to 11, wherein the ink set is at least one dye selected from the group consisting of Reactive Blue 15. 13. A phthalocyanine dye represented by the general formula (2): I. Reactive Blue 7, C.I. I. Reactive blue 14, and C.I. I. At least one dye selected from the group consisting of Reactive Blue 15 and C.I. I. Direct Blue 86 and C.I. I. A mixture with at least one dye selected from the group consisting of Direct Blue 199.
10. The ink set for inkjet recording according to any one of 9. 14. An aqueous recording liquid containing at least one black metal chelate dye whose free acid is represented by the following general formula (1), and a free acid having the following general formula (2)
An ink jet recording method characterized by using a combination of an aqueous recording liquid containing at least one phthalocyanine dye represented by the formula: Embedded image (Wherein, the general formula (1) is a compound having at least one hydrophilic group in a molecule, M represents a metal atom, and A, B, C and D each independently represent an arbitrary R ₁ and R ₂ each independently represent a hydrogen atom or an arbitrary substituent, and m represents 0 to 0.
1, n represents 0 to 3, p represents 0 to 2, and q represents 0 to 3, each representing an integer. When a plurality of Bs exist, each B may be the same or different from each other. Also, p is 2
In the case, R ₁ and R ₂ may be the same or different from each other. Further, M can take a coordination of tridentate or more, in which case M is represented by any substituent or bonding moiety in the general formula (1) or any ligand.
It may be coordinated at any ratio of ligand to metal. ) (In the formula, Cu-Pc represents copper phthalocyanine, X is an alkylene group having 1 to 6 carbon atoms or a phenylene group which may be substituted, and R ₁ and R ₂ are each independently a hydrogen atom or a substituted phenylene group. And Y and Z each independently represent a fluorine atom, a chlorine atom, a hydroxyl group, an optionally substituted alkoxy group, or an optionally substituted phenoxy group. A secondary or tertiary amino group which may be substituted by one or two alkyl groups which may be substituted by a group, a hydroxyl group or an alkoxy group; an anilino group which may be substituted; Represents a good N-methylanilino group or a morpholino group, a and b are rational numbers of 0 or more and 4 or less, c is a rational number of more than 0 and 4 or less, and a + b + c is 2-
4. ) 15. The ink jet recording method according to claim 14, wherein in the general formula (1), D is a naphthalene ring. 16. In the general formula (1), A independently represents a phenyl group which may be substituted or a naphthyl group which may be substituted, and B and C each independently represent a substituted Represents an optionally substituted phenylene group or an optionally substituted naphthylene group, and when A, B or C has a substituent, the substituent may be a halogen atom, a sulfonic acid group, a carboxyl group, a hydroxyl group, a nitro group, Group, an alkyl group which may be substituted, an alkoxy group which may be substituted, an amino group which may be substituted, an acylamino group which may be substituted or a sulfonylamino group which may be substituted The ink jet recording method according to any one of claims 14 to 15, wherein: 17. In the general formula (1), m = 0 and n =
2. The method according to claim 1, wherein p = 1 and p = 1.
An ink jet recording method according to any one of Items 4 to 16. 18. The ink jet recording method according to claim 14, wherein in the general formula (1), q is 1. 19. A compound according to claim 14, wherein in formula (1), one of R ₁ and R ₂ is a hydrogen atom and the other is a phenyl group which may be substituted.
The inkjet recording method according to any one of the above. 20. In the general formula (1), R ₁ and R ₂ are both hydrogen atoms.
9. The ink jet recording method according to any one of items 8. 21. The ink jet recording method according to claim 14, wherein in the general formula (1), M is copper, nickel, iron or cobalt. 22. In the general formula (2), X is an ethylene group, Y is an anilino group substituted by a sulfonic acid group, and Z is a chlorine atom or a hydroxyl group. 22. The inkjet recording method according to any one of 21. 23. In the general formula (2), X is a phenylene group, Y is a methoxy group or an amino group, and Z is a chlorine atom or a hydroxyl group.
23. The inkjet recording method according to any one of 4 to 22. 24. In the general formula (2), c is 0.2 to 0.2.
24. The ink jet recording method according to claim 14, wherein: 25. A phthalocyanine dye represented by the general formula (2): I. Reactive Blue 7, C.I. I. Reactive Blue 14, or C.I. I. 25. The ink jet recording method according to claim 14, wherein the ink is at least one kind of dye selected from the group consisting of Reactive Blue 15. 26. A phthalocyanine dye represented by the general formula (2): I. Reactive Blue 7, C.I. I. Reactive blue 14, and C.I. I. At least one dye selected from the group consisting of Reactive Blue 15 and C.I. I. Direct Blue 86 and C.I. I. 15. A mixture with at least one dye selected from the group consisting of Direct Blue 199.
26. The ink jet recording method according to any one of items 25 to 25.