JP2003292844A - Inkjet cyan ink and inkjet recording process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To give an image excellent in weathering resistance in an inkjet recording. <P>SOLUTION: The inkjet cyan ink is one having a phthalocyanine-based colorant component and using an ink solvent comprising water and a water- miscible solvent, wherein the ink satisfies the relationship: ε<SB>1</SB>/ε<SB>2</SB><0.95 (wherein ε<SB>1</SB>is the extinction coefficient of the ink in the cyan region as determined by directly measuring the spectrum of the light that has passed a thin-layer cell of a thickness of 1×10<SP>-6</SP>m, and ε<SB>2</SB>is the extinction coefficient of the ink in the cyan region as determined by measuring the spectrum of the light that has passed a 1 cm-thick cell after the ink is diluted with water by 10,000 times). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inkjet cyan ink excellent in weather resistance of an image, and an inkjet recording method using an ink set containing the cyan ink.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink jet printers have been widely used for printing on paper, film, cloth, etc. not only in offices but also at home. The inkjet recording method includes a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, or droplets by electrostatic force. There is a method of sucking and discharging. As the ink composition for inkjet recording, a water-based ink, an oil-based ink, or a solid (melting type) ink is used. Among these inks, water-based inks are predominant in terms of production, handleability, odor, safety and the like.

The colorants used in these ink jet recording inks have high solubility in solvents, high density recording is possible, good hue, light, heat, air and water. It has excellent fastness to chemicals and chemicals, has good fixability with respect to the image receiving material and does not bleed easily, has excellent storage stability as an ink, has no toxicity, has high purity, and is inexpensive. Required to be available. However, it is extremely difficult to find a colorant that meets these requirements at a high level. Although various dyes and pigments have already been proposed and actually used for ink jet, a colorant that satisfies all the requirements has not yet been found. It is difficult to achieve both the hue and the fastness required for the ink jet recording ink with dyes and pigments that have been conventionally well known such as those having a color index (CI) number. So far, we have been studying dyes and pigments that have good hue and are robust, and have been developing excellent pigments for inkjet. In particular, a colorant having a good cyan hue and excellent in ozone fastness is strongly desired.

[0004]

The problem to be solved by the present invention is to provide an ink jet cyan ink which gives a cyan image having high image quality and excellent weather resistance such as light fastness, heat fastness and ozone fastness. Another object of the present invention is to provide an inkjet recording method.

[0005]

The problems of the present invention are as follows.
It was achieved by the cyan ink for inkjet and the inkjet recording method described in 3 above. 1) An inkjet cyan ink having phthalocyanine as a main coloring component and using water and a water-miscible solvent as an ink solvent, the ink is directly transmitted through a thin layer cell having a thickness of 1 × 10 ⁻⁶ m. Extinction coefficient in the cyan region (ε ₁ ) determined by measuring the spectrum
However, with respect to the extinction coefficient (ε ₂ ) in the cyan region obtained by diluting the ink 10,000 times with water and measuring the transmission spectrum using a cell having a thickness of 1 cm, ε ₁ / ε ₂ <0.9.
5. A cyan ink for inkjet, which is No. 5. 2) The inkjet cyan ink according to the above 1, wherein ε ₁ / ε ₂ <0.9. 3) An inkjet recording method, wherein an image is formed by using the inkjet ink set containing the inkjet cyan ink described in 1 or 2 above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The cyan ink of the present invention is characterized in that the absorbance in the cyan region (590 to 720 nm) changes depending on whether the dye has a high concentration or a diluted state. In particular, when comparing the absorbance at the diluted low concentration and the absorbance at the high concentration state, there is a feature that the absorbance at the high concentration is lower than the value obtained by multiplying the concentration ratio for achieving the high concentration state. Specifically, the absorption coefficient (ε ₁ ) in the cyan region obtained by measuring the transmission spectrum of the ink directly using a thin layer cell (high concentration) having a thickness of 1 × 10 ⁻⁶ m, and the ink In 10
The extinction coefficient (ε ₂ ) in the cyan region obtained by measuring the transmission spectrum using a cell (low concentration) diluted 000 times with a thickness of 1 cm indicates that ε ₁ / ε ₂ <0.95 (preferably ε The feature is that ₁ / ε ₂ <0.9). That is, in a high concentration state, the interaction between dye molecules is large, and the molecules themselves show the absorbance (absorption coefficient) shown in the diluted state.
Further, it is characterized by using a dye whose apparent absorbance (absorption coefficient) in a high concentration state decreases. The inventor has found that in order to improve the fastness of the phthalocyanine dye, a dye having an increased intermolecular interaction in such a high concentration range is preferable.

As a dye having such characteristics, a phthalocyanine dye represented by the following general formula (I) is preferable. General formula (I)

[0008]

[Chemical 1] The general formula (I) _{in; X 1, X 2, X} 3 and X ₄ are each _{independently, -SO-Z, -SO 2 -Z} , -SO 2 NR 1
R _2, a sulfo group, a -CONR ₁ R ₂ or -CO ₂ R _1,. Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted Represents a heterocyclic group. R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted It represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. When there are a plurality of Zs, they may be the same or different.
Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a monovalent substituent. When a plurality of X _{1 to} X ₄ and Y _{1 to} Y ₄ are present, they may be the same or different. a _{1 to} a ₄ and b _{1 to} b ₄ are X _{1 to} X ₄ and Y, respectively.
_{1 to} Y ₄ represents the number of substituents, a _{1 to} a ₄ are each independently an integer of 0 to 4, and all are not 0 at the same time, and b _{1 to} b ₄ are each independently, It is an integer of 0-4. M is a hydrogen atom, a metal atom or its oxide, hydroxide or halide.

Phthalocyanine dyes have been known as fast dyes, but when used as ink jet recording dyes, they are known to have poor fastness to ozone gas. In the present invention, in order to reduce the reactivity with ozone, which is an electrophile, it is desirable to introduce an electron-withdrawing group into the phthalocyanine skeleton to make the oxidation potential nobler than 1.0 V (vs SCE). The more preferable the oxidation potential is, the more preferable the oxidation potential is 1.1 V (vs SCE), and the most preferable the oxidation potential is 1.2 V (vs SCE).

The oxidation potential value (Eox) can be easily measured by those skilled in the art. For this method, see P.
“New Instrument” by Delahay
Methods in Electrochemis
try ”(1954 Interscience P
Publishers Inc.), A. J. Bard et al., "E
electrical chemical methods ”(1
980, John Wiley & Sons),
It is described in Aki Fujishima et al., “Electrochemical Measurement Method” (published by Gihodo Publishing Co., Ltd. in 1984).

Specifically, the oxidation potential of the test sample was 1 × 10 ^-4 to 1 × in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. It is dissolved in a concentration of 10 ⁻⁶ mol / liter and measured as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography. This value is
Due to the influence of the potential difference between the liquids and the liquid resistance of the sample solution, there may be a deviation of about several tens of mil volts. However, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone). In order to uniquely define the potential, in the present invention, a direct current polar is used in dimethylformamide containing 0.1 moldm ^-3 tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 0.001 moldm ^-3 ). Values measured by lography (vs SCE)
Is the oxidation potential of the dye.

The value of Eox (oxidation potential) represents the ease with which electrons are transferred from the sample to the electrode. The larger the value (the higher the oxidation potential is), the more difficult it is for electrons to transfer from the sample to the electrode. Indicates that it is hard to be done. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing the electron-withdrawing group, and the oxidation potential becomes less by introducing the electron-donating group. In the present invention, in order to reduce the reactivity with ozone, which is an electrophile, it is desirable to introduce an electron-withdrawing group into the phthalocyanine skeleton to make the oxidation potential more noble. Therefore, if the Hammett's substituent constant σp value, which is a measure of the electron withdrawing property or electron donating property of a substituent, is used, it is possible to introduce a substituent having a large σp value such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group. It can be said that the oxidation potential can be made more noble. It is preferable to use the phthalocyanine dye represented by the general formula (I) for the reason of adjusting the potential as described above.

In the general formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each independently --SO--Z or --SO _2-.
Z, represents -SO ₂ NR ₁ R _2, a sulfo group, a -CONR ₁ R ₂ or -CO ₂ R _1,. Among these substituents, -S
_{O-Z, -SO 2 -Z,} -SO 2 NR 1 R 2 and -CON
R ₁ R ₂ are preferable, -SO ₂ -Z and -SO ₂ NR
₁ R ₂ is preferred, and —SO ₂ —Z is most preferred. Here, when any of a _{1 to} a ₄ representing the number of substituents represents a number of 2 or more, a plurality of X _{1 to} X ₄ may be the same or different, and each of them is independently the above. Represents any of groups. Further, X ₁ , X ₂ , X ₃ and X ₄ may be the same substituents, or, for example, X 1
₁ , X ₂ , X ₃ and X ₄ are all —SO ₂ —Z, and each Z is a substituent of the same type but partially different from each other, as in the case where Z includes different ones. Or different substituents, for example, —SO ₂ —
Z and may include -SO ₂ NR ₁ R _2.

The Z's are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl. Represents a group or a substituted or unsubstituted heterocyclic group. Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are most preferred. R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are more preferable. However, it is not preferable that both R ₁ and R ₂ are hydrogen atoms.

The substituted or unsubstituted alkyl group represented by R ₁ , R ₂ and Z is preferably an alkyl group having 1 to 30 carbon atoms. In particular, a branched alkyl group is preferable because it improves the solubility of the dye and the ink stability.
Particularly, those having an asymmetric carbon (use in a racemic form) are particularly preferable. Examples of the substituent include Z, R ₁ , R ₂ and
The same substituents as Y ₁ , Y ₂ , Y ₃ and Y _{4 in the case} where Y ₁ , Y ₂ , Y ₃ and Y ₄ can have a substituent can be mentioned. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association property of the dye and improve the fastness. In addition, it may have a halogen atom or an ionic hydrophilic group. The number of carbon atoms in the alkyl group does not include carbon atoms in the substituent, and the same applies to other groups.

The substituted or unsubstituted cycloalkyl group represented by R ₁ , R ₂ and Z has 5 to 30 carbon atoms.
Is preferred. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferable, because the solubility of the dye and the stability of the ink are enhanced. Examples of the substituent include the same substituents as those described below when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can further have a substituent. Among them, hydroxyl group, ether group,
An ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association property of the dye and improve the fastness. In addition, it may have a halogen atom or an ionic hydrophilic group.

The substituted or unsubstituted alkenyl group represented by R ₁ , R ₂ and Z is preferably an alkenyl group having 2 to 30 carbon atoms. Particularly, a branched alkenyl group is preferable for the reason of increasing the solubility of the dye and the stability of the ink, and particularly when it has an asymmetric carbon (use in a racemic form).
Is particularly preferable. Examples of the substituent include Z, which will be described later,
The same substituents as R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can be used. Among them, hydroxyl group, ether group, ester group, cyano group,
An amide group and a sulfonamide group are particularly preferable because they enhance the association property of the dye and improve the fastness. In addition, it may have a halogen atom or an ionic hydrophilic group.

The substituted or unsubstituted aralkyl group represented by R ₁ , R ₂ and Z is preferably an aralkyl group having 7 to 30 carbon atoms. In particular, a branched aralkyl group is preferable because it enhances the solubility of the dye and the stability of the ink, and particularly when it has an asymmetric carbon (use in a racemic form).
Is particularly preferable. Examples of the substituent include Z, which will be described later,
The same substituents as R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can be used. Among them, hydroxyl group, ether group, ester group, cyano group,
An amide group and a sulfonamide group are particularly preferable because they enhance the association property of the dye and improve the fastness. In addition, it may have a halogen atom or an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by R ₁ , R ₂ and Z is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent include Z and R described later.
_The same substituents as ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ may have the same substituents. Among them, the electron-withdrawing group is particularly preferable because it makes the oxidation potential of the dye noble and improves the fastness. As the electron-withdrawing group,
Hammett's substituent constant σp value is positive.
Of these, a halogen atom, a heterocyclic group, a cyano group, a carboxyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, an acyl group, a sulfo group and a quaternary ammonium group are preferable, and a cyano group is preferable. Further, a carboxyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, an acyl group, a sulfo group, and a quaternary ammonium group are more preferable.

The heterocyclic group represented by R ₁ , R ₂ and Z is preferably a 5- or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. Below, R ₁ , R ₂ and Z
The heterocyclic group represented by is exemplified in the form of a heterocycle by omitting the substitution position, but the substitution position is not limited, and for example, in the case of pyridine, it is substituted at the 2-position, 3-position and 4-position. It is possible to Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole. , Benzothiazole, isothiazole, benzisothiazole, thiadiazole,
Examples thereof include isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline. Among them, aromatic heterocyclic groups are preferable, and when the preferable examples are exemplified in the same manner as above, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole,
Examples include triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole. They may have a substituent, and as examples of the substituent, Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ described later can further have a substituent. In this case, the same substituents can be used. Preferred substituents are the same as the substituents of the aryl group, and more preferred substituents are the same as the more preferred substituents of the aryl group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group or a hydroxyl group. Group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, acylamino group, arylamino group, ureido group,
Sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy Group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxyl group, or a sulfo group, each of which may further have a substituent. Good.

Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group,
A sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group are preferable, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group are particularly preferable, and a hydrogen atom is most preferable.

When Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ are groups capable of further having a substituent, they may further have the following substituents. .

A linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms,
Linear or branched alkynyl group having 2 to 12 carbon atoms, linear or branched cycloalkyl group having 3 to 12 carbon atoms, linear or branched cycloalkenyl group having 3 to 12 carbon atoms (each of the above groups is branched. Those having a chain are preferable from the reason that the solubility of the dye and the stability of the ink are improved, and those having an asymmetric carbon are particularly preferable.Specific examples of the above groups: for example, methyl, ethyl, propyl, isopropyl, sec- Butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example,
Chlorine atom, bromine atom), aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2 -Thienyl, 2-
Pyrimidinyl, 2-benzothiazolyl),

Cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (eg, phenoxy, 2- Methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamide, benzamide, 4- (3-t-butyl-4-). Hydroxyphenoxy) butanamide), an alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino,
2-chloroanilino, ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio) , 2-phenoxyethylthio), an arylthio group (eg, phenylthio, 2-
Butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (eg, methoxycarbonylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide) ,

Carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N)
-Dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy Group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propa). Noylphenylazo), an acyloxy group (for example,
Acetoxy), a carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy),

A silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, N-succinimide,
N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,
5-triazole-6-thio, 2-pyridylthio), sulfinyl group (e.g. 3-phenoxypropylsulfinyl), phosphonyl group (e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (e.g. , Phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl), and an ionic hydrophilic group (eg, carboxyl group, sulfo group, phosphono group and quaternary ammonium group).

When the phthalocyanine dye represented by the general formula (I) is water-soluble, it preferably has an ionic hydrophilic group. The ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion,
Sodium ion, potassium ion) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium)
Is included. Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it enhances the solubility of the dye and improves the ink stability. The number of ionic hydrophilic groups is preferably at least two in one molecule of the phthalocyanine dye, and particularly preferably at least two sulfo groups and / or carboxyl groups.

A _{1 to} a ₄ and b _{1 to} b ₄ are each X ₁
To X ₄ and Y _{1 to} Y ₄ represent the number of substituents. a _{1 to} a ₄ are
Each independently represents an integer of 0 to 4, but not all are 0 at the same time. b _{1 to} b ₄ are each independently 0.
Represents an integer of 4; When any _{one of} a _{1 to} a ₄ and b _{1 to} b ₄ is an integer of 2 or more, X _{1 to} X ₄ and Y
There will be a plurality of any one of _{1 to} Y ₄ , which may be the same or different.

A ₁ and b ₁ satisfy the relationship of a ₁ + b ₁ = 4. Particularly preferred, a ₁ represents 1 or 2, b ₁ is the combination that represents a 3 or 2, Among them, a
₁ represents 1, b ₁ is the most preferred combination representing the three. The respective combinations of a ₁ and b ₁ , a ₁ and b ₁ , and a ₁ and b ₁ have the same relationship as the combination of a ₁ and b ₁ , and the preferred combinations are also the same.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof. Preferred as M is L as a metal element in addition to hydrogen atom.
i, Na, K, Mg, Ti, Zr, V, Nb, Ta, C
r, Mo, W, Mn, Fe, Co, Ni, Ru, Rh,
Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, C
d, Hg, Al, Ga, In, Si, Ge, Sn, P
b, Sb, Bi and the like. As an oxide, V
O, GeO and the like are preferable. Further, as the hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH)
_{2 and the} like are preferable. Further, as the halide, AlCl, SiCl ₂ , VCl, VCl ₂ , VOC
1, FeCl, GaCl, ZrCl and the like. Among them, Cu, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

In addition, Pc is bonded via L (divalent linking group).
(Phthalocyanine ring) is a dimer (for example, Pc-ML
-M-Pc) or a trimer may be formed, and Ms at that time may be the same or different.

The divalent linking group represented by L is an oxy group-
O-, thio group -S-, a carbonyl group -CO-, a sulfonyl group -SO ₂ -, imino group -NH-, a methylene group -CH ₂
-, And groups formed by combining these are preferable.

With respect to the preferable combination of the substituents of the compound represented by the general formula (I), the compound in which at least one of the various substituents is the above preferable group is preferable, and more various substituents are the above. The compound which is a preferable group is more preferable, and the compound in which all the substituents are the preferable groups is the most preferable.

Among the phthalocyanine dyes represented by the general formula (I), a phthalocyanine dye having a structure represented by the following general formula (II) is more preferable. General formula (II)

[0036]

[Chemical 2]

In the above general formula (II); X _{11 to} X ₁₄ , Y ₁₁ to
Y ₁₈ and M are respectively X _{1 to} X ₄ and Y in the general formula (I).
It is synonymous with _{1 to} Y ₄ and M. a _{11 to} a ₁₄ are each independently an integer of 1 or 2.

The phthalocyanine dye represented by formula (II) of the present invention will be described in detail below. In the general formula _{(II), X 11 ~X 14} , Y 11 ~Y 18 is X ₁ to X in the general formula (I) _4, and Y ₁ to Y ₄ are respectively the same, preferred examples are also the same is there. M is a general formula (I)
It has the same meaning as M in the above, and the preferred examples are also the same.

In the general formula (II), a _{11 to} a ₁₄ are each independently an integer of 1 or 2, preferably 4 ≦ a ₁₁
+ A ₁₂ + a ₁₃ + a ₁₄ ≦ 6 is satisfied, and particularly preferably a ₁₁
= A ₁₂ = a ₁₃ = a ₁₄ = 1.

X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may each be the same substituent, or, for example, X ₁ ,
X ₂ , X ₃ and X ₄ are all —SO ₂ —Z, and each Z is
Are the same kind of substituents but partially different from each other, or different substituents such as --SO ₂ --Z and-
It may contain SO ₂ NR ₁ R ₂ . Among the phthalocyanine dyes represented by formula (II), particularly preferable combinations of substituents are as follows.

X _{11 to} X ₁₄ are independently-
_{SO-Z, -SO 2 -Z,} -SO 2 NR 1 R 2 or -CO
NR ₁ R ₂ is preferred, especially —SO ₂ —Z or —SO ₂ N.
R ₁ R ₂ is preferred, and —SO ₂ —Z is most preferred.

Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group and a substituted aryl group are preferable. Heterocyclic groups are most preferred. In particular, it is preferable to have an asymmetric carbon atom in the substituent (use in a racemic form) for the reason of improving the solubility of the dye and the stability of the ink. Further, it is preferable that the substituent has a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group for the reason of increasing the association property and improving the fastness.

R ₁ and R ₂ are each independently a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group are preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are more preferable. However, R ₁ ,
It is not preferable that both R ₂ are hydrogen atoms. In particular, it is preferable to have an asymmetric carbon atom in the substituent (use in a racemic form) for the reason of improving the solubility of the dye and the stability of the ink. Further, it is preferable that the substituent has a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group for the reason of increasing the association property and improving the fastness.

Y _{11 to} Y ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or an alkoxycarbonyl group. A group, a carboxyl group, and a sulfo group are preferable, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfo group is particularly preferable, and a hydrogen atom is most preferable. It is preferable that each of a _{11 to} a ₁₄ is independently 1 or 2, and it is particularly preferable that all of them are 1. M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, Ni, Zn and Al are preferable, and Cu is particularly preferable.

When the phthalocyanine dye represented by the general formula (II) is water-soluble, it preferably has an ionic hydrophilic group. The ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion,
Sodium ion, potassium ion) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium)
Is included. Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it enhances the solubility of the dye and improves the ink stability. The number of ionic hydrophilic groups is preferably at least two in one molecule of the phthalocyanine dye, and particularly preferably at least two sulfo groups and / or carboxyl groups.

With respect to the preferable combination of the substituents of the compound represented by the general formula (II), the compound in which at least one of the various substituents is the above preferable group is preferable, and more various substituents are the above. The compound which is a preferable group is more preferable, and the compound in which all the substituents are the preferable groups is the most preferable.

The chemical structure of the phthalocyanine dye of the present invention includes at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group or a sulfamoyl group in each of the four benzene rings of the phthalocyanine and a substituent of the entire phthalocyanine skeleton. It is preferable to introduce such that the sum of the σp values is 1.6 or more.

Here, the Hammett's substituent constant σp value will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L.A. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp values and σm values, and these values can be found in many general textbooks. A. Dean, "L
angle's Handbook of Chemis
try ”, 12th Edition, 1979 (McGrow-Hi
ll) and "Chemical Area" special edition, No. 122, 96-103
Details on page 1979 (Nankodo).

The phthalocyanine derivative represented by the general formula (I) is unavoidably a substituent Xn depending on its synthetic method.
(N = 1 to 4) and Ym (m = 1 to 4) are generally analog mixtures having different introduction positions and introduction numbers. Therefore, the general formula statistically averages these analog mixtures. Is often expressed as In the present invention, it has been found that when these analog mixture is classified into the following three types, a specific mixture is particularly preferable. That is, the phthalocyanine dye analog mixture represented by the general formulas (I) and (II) is classified into the following three types based on the substitution position and defined.

(1) β-position substitution type: 2 and / or 3
1st, 6th and / or 7th, 10th and / or 11th, 1st
A phthalocyanine dye having a specific substituent at the 4- and / or 15-position. (2) α-position substitution type: 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 1
A phthalocyanine dye having a specific substituent at the 6-position. (3) α, β-position mixed substitution type: a phthalocyanine dye having a specific substituent in the 1st to 16th positions without regularity.

In the present specification, when a derivative of a phthalocyanine dye having a different structure (in particular, a different substitution position) is described, the above β-position substitution type, α-position substitution type, α, β
-Use mixed substitution type.

The phthalocyanine derivative used in the present invention is, for example, Shirai-Kobayashi co.
C. C. Leznoff-A. B. P. Lever co-authored, VCH issue'Phthalocyanines-P
properties and Application
s' (P.1 to 54) and the like, and can be synthesized by quoting or combining methods similar thereto.

The phthalocyanine compound represented by the general formula (I) of the present invention is a compound of the world patents 00/17275 and 00.
/ 08103, 00/08101, 98/41
As described in JP-A No. 853 and JP-A No. 10-36471, for example, it can be synthesized by subjecting an unsubstituted phthalocyanine compound to sulfonation, sulfonyl chloride, and amidation reactions. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonates is also difficult to control. Therefore, when the sulfo group is introduced under such reaction conditions, the position and the number of the sulfo group introduced into the product cannot be specified, and a mixture having different numbers of substituents and different substitution positions is always provided. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and the substitution position of the heterocyclic-substituted sulfamoyl group cannot be specified.Therefore, the compound of the present invention includes some compounds having different numbers of substituents and different substitution positions. It is obtained as an α, β-position mixed substitution type mixture.

As mentioned above, when a large number of electron-withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and the ozone resistance is enhanced.
According to the above-mentioned synthetic method, it is inevitable that a phthalocyanine dye having a small number of electron-withdrawing groups introduced, that is, a phthalocyanine dye having a more base oxidation potential, is mixed. Therefore,
In order to improve the ozone resistance, it is more preferable to use a synthetic method that suppresses the formation of a compound having a more base oxidation potential.

The phthalocyanine compound represented by the general formula (II) of the present invention is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula. 4) represented by the following formula:
-Sulfophthalonitrile derivative (Compound R) and general formula (I
It can be derived from a tetrasulfophthalocyanine compound obtained by reacting the metal derivative represented by II).

[0056]

[Chemical 3]

In each of the above formulas, Xp corresponds to X ₁₁ , X ₁₂ , X ₁₃ or X ₁₄ in the above general formula (II). Also, Y
q, Yq 'is, Y ₁₁ in the general formula (II), _{respectively, Y 1 2, Y 13,} Y 14, Y 15, Y 16, Y 17 or Y ₁₈
Equivalent to. In the compound R, M ′ represents a cation. Examples of the cation represented by M ′ include alkali metal ions such as Li, Na and K, and organic cations such as triethylammonium ion and pyridinium ion.

General formula (III): M- (Y) d In the general formula (III), M is the above general formula (I) and (II).
Is synonymous with M of, Y is a halogen atom, acetate anion,
A monovalent or divalent ligand such as acetylacetonate or oxygen is shown, and d is an integer of 1 to 4.

That is, according to the above synthesis method, a desired number of substituents can be introduced. In particular, when it is desired to introduce a large number of electron-withdrawing groups in order to make the oxidation potential noble as in the present invention, the above synthetic method is the same as the above-described method for synthesizing the phthalocyanine compound of the general formula (I). It is extremely superior to

The thus obtained phthalocyanine compound represented by the general formula (II) is usually an isomer at each substitution position of Xp, represented by the following general formulas (a) -1 to (a)-.
It is a mixture of compounds represented by 4, that is, β-position substitution type.

[0061]

[Chemical 4]

[0062]

[Chemical 5]

[0063]

[Chemical 6]

[0064]

[Chemical 7]

In the above synthetic method, if all the same Xp are used, a β-position substituted phthalocyanine dye in which X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ have the same substituent can be obtained. On the other hand, if different Xp's are used in combination, it is possible to synthesize dyes having the same kind of substituents but partially different substituents or dyes having different kinds of substituents. ..
Among the dyes of the general formula (II), those dyes having different electron-withdrawing substituents from each other are particularly preferable because they can adjust the solubility of the dye, the association property, the stability of the ink over time, and the like.

In the present invention, it was found that it is extremely important for the oxidation potential to be nobler than 1.0 V (vs SCE) in any of the substitution types, and it is very important to improve the fastness. This was completely unpredictable from the prior art. The cause is unknown in detail, but among them, the β-position substitution type tends to be obviously superior in hue, light fastness, ozone gas resistance, etc. to the α, β-position mixed substitution type. there were.

Specific examples of the phthalocyanine dyes represented by the above general formulas (I) and (II) (exemplified compounds I-1 to I-
12 and 101 to 190) are shown below, but the phthalocyanine dye used in the present invention is not limited to the following examples.

[0068]

[Chemical 8]

[0069]

[Chemical 9]

[0070]

[Chemical 10]

[0071]

[Chemical 11]

[0072]

[Chemical 12]

[0073]

[Chemical 13]

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

[0084]

[Table 11]

In addition, M-Pc (Xp ₁ ) in Tables 8 to 11
The structure of the phthalocyanine compound represented by m (Xp ₂ ) n is as follows.

[0086]

[Chemical 14]

The phthalocyanine dye represented by the general formula (I) can be synthesized according to the above-mentioned patents. Further, the phthalocyanine dye represented by the general formula (II) can be produced by the method described in JP-A 2001-226.
275, 2001-96610, 2001-4
It can be synthesized by the method described in each publication of No. 7013 and 2001-193638. The starting materials, dye intermediates, and synthetic routes are not limited to these.

The cyan ink for ink jet of the present invention preferably contains the phthalocyanine dye in an amount of 0.2 to 20.
It is contained in an amount of 0.5% by mass, more preferably 0.5 to 15% by mass.

In the present invention, an ink set containing the above cyan ink (hereinafter, the cyan ink of the present invention and the ink contained in the ink set containing the cyan ink may be simply referred to as the ink of the present invention) is used. Is preferred. In the ink of the present invention, in order to adjust the color tone to obtain a full-color image together with the phthalocyanine dye,
Other dyes may be used in combination. The following can be given as examples of dyes that can be used in combination.

Examples of yellow dyes include aryl or heterylazo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, and open-chain active methylene compounds as coupling components; for example, open-chain active methylenes as coupling components. Azomethine dyes having compounds; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other quinophthalone dyes, Examples thereof include nitro / nitroso dyes, acridine dyes and acridinone dyes. These dyes may be those that show yellow for the first time after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or may be a polymer cation having a partial structure thereof.

Examples of magenta dyes include aryl or heterylazo dyes having phenols, naphthols and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes and styryls. Methine dyes such as dyes, merocyanine dyes, oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone, such as dioxazine dyes Examples thereof include condensed polycyclic dyes. These dyes may be those that exhibit magenta only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or may be a polymer cation having a partial structure thereof.

Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carboniums such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes. Dyes; phthalocyanine dyes; anthraquinone dyes; for example, aryl or heterylazo dyes having phenols, naphthols, anilines as coupling components, and indigo / thioindigo dyes can be mentioned. These dyes may be those that show cyan only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or may be a polymer cation having a partial structure thereof. Also, black dyes such as polyazo dyes can be used.

The dyes used in the present invention, including the phthalocyanine dyes, are substantially water-soluble or water-dispersible. Specifically, the solubility of the dye in water at 20 ° C. is preferably 2% by mass or more, more preferably 5% by mass or more. The phthalocyanine dye used in the present invention is 20 ° C.
It is preferable that the solubility of the dye in 2 in water is 2% by mass or more.

Further, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes and reactive dyes can be used in combination. Among them, CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, CI Direct Red
63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 11
1, 173, 184, 207, 211, 212, 214, 218, 21, 223, 22
4, 225, 226, 227, 232, 233, 240, 241, 242, 243, 24
7 CI Direct Violet 7, 9, 47, 48, 51, 6
6, 90, 93, 94, 95, 98, 100, 101 CI Direct Yellow 8, 9, 11, 12, 27, 28, 2
9, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 8
7, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 1
32, 142, 144, 161, 163 CI Direct Blue 1, 10, 15, 22, 25, 55, 67, 6
8, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 10
8, 109, 151, 156, 158, 159, 160, 168, 189, 192, 19
3, 194, 199, 200, 201, 202, 203, 207, 211, 213, 21
4, 218, 225, 229, 236, 237, 244, 248, 249, 251, 25
2,264,270,280,288,289,291 CI Direct Black 9,17,19,22,32,51,5
6, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 11
4, 117, 118, 121, 122, 125, 132, 146, 154, 166, 16
8,173,199 CI Acid Red 35, 42, 52, 57, 62, 80, 82, 11
1, 114, 118, 119, 127, 128, 131, 143, 151, 154, 15
8, 249, 254, 257, 261, 263, 266, 289, 299, 301, 30
5,336,337,361,396,397 CI Acid Violet 5,34,43,47,48,90,10
3,126 CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 4
4, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 15
1, 159, 169, 174, 190, 195, 196, 197, 199, 218, 21
9,222,227 CI Acid Blue 9,25,40,41,62,72,76,78,
80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 13
8,143,175,181,205,207,220,221,230,232,24
7, 258, 260, 264, 271, 277, 278, 279, 280, 288, 29
0,326 CI Acid Black 7,24,29,48,52: 1,172 CI Reactive Red 3,13,17,19,21,22,23,
24, 29, 35, 37, 40, 41, 43, 45, 49, 55 CI Reactive Violet 1, 3, 4, 5, 6, 7, 8,
9, 16, 17, 22, 22, 23, 24, 26, 27, 33, 34 CI Reactive Yellow 2, 3, 13, 14, 15, 17, 1
8,23,24,25,26,27,29,35,37,41,42 CI Reactive Blue 2,3,5,8,10,13,14,1
5, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38 CI Reactive Black 4, 5, 8, 14, 21, 23, 26,
31, 32, 34 CI Basic Red 12, 13, 14, 15, 18, 22, 23, 2
4, 25, 27, 29, 35, 36, 38, 39, 45, 46 CI Basic Violet 1, 2, 3, 7, 10, 15, 1
6, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48 CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 1
9, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 4
5, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71 CI Basic Black 8, etc.

Further, a pigment may be used in combination. As the pigment that can be used in the ink of the invention, commercially available pigments and known pigments described in various documents can be used. For the literature, Color Index (The Soc
Society of Dyers and Colorists), "Revised New Edition Pigment Handbook" edited by Japan Pigment Technology Association (1989), "Latest Pigment Application Technology" CMC Publishing (1986), "Printing Ink Technology" CMC Publishing (1
984), W. Herbst, K. Hunger, Industrial
Organic Pigments (VCH Verlagsgesellschaft, published in 1993) and others. Specifically, organic pigments include azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, quinacridone. Pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, etc.), dyeing lake pigments (lake pigments of acidic or basic dyes), azine pigments, etc. CI Pigment Yellow 3
CI Pigment Red101, which is a red pigment such as 4, 37, 42, 53, etc.
CI Pigment Blue 27, 29,17: 1 for blue pigments such as 108
Examples thereof include CI Pigment Black 7, which is a black pigment, and magnetite, and CI Pigment White 4,6,18,21, which is a white pigment.

Pigments having a preferable color tone for image formation include phthalocyanine pigments for blue or cyan pigments and indanthrone pigments of anthraquinone type (for example, CI
Pigment Blue 60, etc., and triarylcarbonium pigments of dyed lake pigment type are preferable, and particularly phthalocyanine pigments (preferred examples are CI Pigment Blue 1
Copper phthalocyanine such as 5: 1, 15: 2, 15: 3, 15: 4, 15: 6, monochloro or low chlorinated copper phthalocyanine,
In the aluminum phthalocyanine, the pigment described in European Patent 860475, a metal-free phthalocyanine that is CI Pigment Blue 16, a phthalocyanine that has a central metal of Zn, Ni, and Ti, among which CI Pigment Blue 15: 3,
15: 4, aluminum phthalocyanine) is most preferred.

Among red to purple pigments, azo pigments (preferred examples are CI Pigment Red 3, 5, 11, 11;
D22, D38, D48: 1, D48: 2, D48: 3, D48: 4, D49:
1, the same 52: 1, the same 53: 1, the same 57: 1, the same 63: 2, the same 144, the same 146,
184), etc., among which CI Pigment Red is preferable.
57: 1, 146, 184), quinacridone pigments (preferred examples are CI Pigment Red 122, 192, 202,
The same 207, 209, CI Pigment Violet 19, 42, among which CI Pigment Red 122 is preferable, and a triarylcarbonium pigment of a dyeing lake pigment type (a preferable example is a xanthene type CI Pigment Red 81:
1, CI Pigment Violet 1, same 2, same 3, same 27, same 3
9), dioxazine pigments (eg CI Pigment Viole
t 23, ibid. 37), a diketopyrrolopyrrole pigment (for example, C.
I. Pigment Red 254), perylene pigments (eg CI P
igment Violet 29), anthraquinone pigment (for example, C.
I. Pigment Violet 5: 1, ibid 31, ibid 33) and thioindigo (eg CI Pigment Red 38, ibid 88) are preferably used.

As a yellow pigment, an azo pigment (a preferable example is a monoazo pigment type CI Pigment Yellow 1, 3,
74, 98, CI Pigment Yellow 12, which is a disazo pigment type
13,14, 16, 17, 83, CI Pigment Yello of general azo system
w 93, 94, 95, 128, 155, benzimidazolone C.
I. Pigment Yellow 120, 151, 154, 156, 180 and the like, among them, preferable ones are those in which a benzidine-based compound is not used as a raw material), isoindoline / isoindolinone-based pigments (as a preferable example, CI Pigment Yellow 109, 110,
137, 139, etc.), quinophthalone pigment (preferred examples are CI Pigment Yellow 138 etc.) and flapantron pigments (eg CI Pigment Yellow 24 etc.) are preferably used.

As the black pigment, inorganic pigments (preferably, carbon black and magnetite) and aniline black can be mentioned as preferable ones. Besides, orange pigments (CI Pigment Orange 13, 16 and the like) and green pigments (CI Pigment Green 7 and the like) may be used.

The pigment that can be used in the ink of the present invention may be the above-mentioned naked pigment or a surface-treated pigment. The surface treatment method includes a method of coating a surface of resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, a radical generated from a diazonium salt) as a pigment. A method of binding to the surface is considered and is described in the following documents and patents. Properties and Applications of Metal Soap (Koshoubou) Printing Ink Printing (CMC Publishing 1984) Latest Pigment Application Technology (CMC Publishing 1986) US Patents 5,554,739, 5,571,311 JP 9-151342, 10-140065, 10 -292143
No. 11-166145, in particular, a self-dispersible pigment prepared by acting the diazonium salt described in the above-mentioned U.S. patent on carbon black, and the encapsulation prepared by the method described in the above-mentioned Japanese patent. The pigment is particularly effective because dispersion stability can be obtained without using an extra dispersant in the ink.

In the ink of the present invention, the pigment may be dispersed using a dispersant. As the dispersant, various known dispersants can be used depending on the pigment to be used, for example, a surfactant type low molecular dispersant or a polymer type dispersant. Examples of dispersants include JP-A-3-69949 and European Patent 549.
Examples thereof include those described in No. 486. In addition, a pigment derivative called synergist may be added in order to promote adsorption of the dispersant to the pigment when the dispersant is used. The particle size of the pigment that can be used in the ink of the present invention is preferably in the range of 0.01 to 10 μm after dispersion,
It is more preferably 0.05 to 1 μm. As a method for dispersing the pigment, a known dispersion technique used at the time of ink production or toner production can be used. As a disperser,
Vertical or horizontal agitator mill, attritor,
Examples thereof include a colloid mill, a ball mill, a three roll mill, a pearl mill, a super mill, an impeller, a despurser, a KD mill, a dynatron and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

Next, the surfactant which can be contained in the ink-jet ink of the present invention will be described. By containing a surfactant in the inkjet recording ink of the present invention and adjusting the liquid properties of the ink, it is possible to improve the ejection stability of the ink, improve the water resistance of the image, and prevent bleeding of the printed ink. It can have an excellent effect. Examples of the surfactant include anionic surfactants such as sodium dodecylsulfate, sodium dodecyloxysulfonate, sodium alkylbenzenesulfonate, and cationic surfactants such as cetylpyridinium chloride, trimethylcetylammonium chloride and terrabutylammonium chloride. , Polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene octyl phenyl ether, and other nonionic surfactants. Of these, nonionic surfactants are particularly preferably used.

The content of the surfactant is 0.
001 to 15% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass.

The cyan ink for ink jet of the present invention can be prepared by dissolving or dispersing a phthalocyanine dye and preferably a surfactant in an ink solvent. In the present invention, the ink solvent includes water and a water-miscible organic solvent, and preferably contains 20% by mass or more of water as the ink solvent. If necessary, additives such as a wetting agent, a stabilizer and a preservative can be added to the ink of the present invention.

When preparing the ink liquid of the present invention, it is preferable that the water-soluble ink is first dissolved in water. After that, various solvents and additives are added, dissolved and mixed to form a uniform ink liquid. As the dissolution method at this time, various methods such as dissolution by stirring, dissolution by irradiation with ultrasonic waves, and dissolution by shaking can be used. Among them, the stirring method is particularly preferably used. When performing stirring, various methods such as fluidized stirring known in the art and stirring utilizing shearing force using an inversion agitator or dissolver can be used. On the other hand, like a magnetic stirrer, a stirring method utilizing a shearing force with the bottom of the container can also be preferably used.

Examples of the water-miscible organic solvent that can be used in the present invention include alcohols (eg, methanol, ethanol, propanol, isopropanol,
Butanol, isobutanol, sec-butanol, t
-Butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol) Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate,
Ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg, ethanolamine, diethanolamine, triethanolamine,
N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg formamide, N, N-dimethylformamide). , N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N
-Vinyl-2-pyrrolidone, 2-oxazolidone, 1,
3-dimethyl-2-imidazolidinone, acetonitrile, acetone) and the like. Two or more kinds of the water-miscible organic solvents may be used in combination.

When the phthalocyanine dye is an oil-soluble dye, it can be prepared by dissolving the oil-soluble dye in a high boiling point organic solvent and emulsifying and dispersing it in an aqueous medium. The high boiling organic solvent used in the present invention has a boiling point of 1
It is preferably 50 ° C. or higher, more preferably 1
It is 70 ° C or higher. As the high boiling point organic solvent, for example,
Phthalate esters (eg, dibutyl phthalate,
Dioctyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphones (eg, diphenyl phosphate) , Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Di-2-ethylhexylphenyl phosphate), benzoic acid ester acid (for example, 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate),

Amides (for example, N, N-diethyldodecaneamide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivative (N , N-dibutyl-2-
Butoxy-5-tert-octylaniline and the like), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols ( For example, 2,4-di-te
rt-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-
(4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (eg, 2- (2,4-di-te)
Examples thereof include rt-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid). The high boiling point organic solvent can be used in a mass ratio of 0.01 to 3 times, preferably 0.01 to 1.0 times the amount of the oil-soluble dye. These high-boiling organic solvents may be used alone or in a mixture of several kinds [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2
-Ethylhexyl) sebacate, dibutyl phthalate and poly (Nt-butyl acrylamide)].

Examples of compounds other than the above high boiling point organic solvents used in the present invention and methods for synthesizing these high boiling point organic solvents are described in, for example, US Pat. Nos. 2,322,027 and 2,533,514.
No. 2,772,163, No. 2,835,579, No. 3,594,17
No. 1, No. 3,676,137, No. 3,689,271, No. 3,700,4
No. 54, No. 3,748,141, No. 3,764,336, No. 3,765,
No. 897, No. 3,912,515, No. 3,936,303, No. 4,00
4,928, 4,080,209, 4,127,413, 4,1
No. 93,802, No. 4,207,393, No. 4,220,711, No. 4,
239,851, 4,278,757, 4,353,979, and
4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657,
No. 4,684,606, No. 4,728,599, No. 4,745,049
No. 4,935,321, No. 5,013,639, European Patent No. 27
6,319A, 286,253A, 289,820A, 309,
158A, 309,159A, 309,160A, 509,31
1A, 510,576A, East German Patent 147,009, 15
No. 7,147, No. 159,573, No. 225,240A, British Patent No.
2,091,124A, JP-A-48-47335, 50-26530, 51
-25133, 51-26036, 51-27921, 51-27922
No. 51, No. 51-149028, No. 52-46816, No. 53-1520, No. 53
-1521, 53-15127, 53-146622, 54-91325
54-106228, 54-118246, 55-59464,
56-64333, 56-81836, 59-204041, 61-8464
No. 1, 62-118345, 62-247364, 63-167357,
63-214744, 63-301941, 64-9452, 64-94
No. 54, No. 64-68745, JP-A No. 1-101543, No. 1-102454.
No. 2, No. 2-792, No. 2-4239, No. 2-43541, No. 4-29237
No. 4, No. 4-30165, No. 4-232946, No. 4-346338, etc.

In the present invention, the oil-soluble dye and the high boiling point organic solvent are used by emulsifying and dispersing in an aqueous medium. When emulsifying and dispersing, a low boiling point organic solvent may be used in combination from the viewpoint of emulsifying property. The low boiling point organic solvent that can be used in combination is an organic solvent having a boiling point of about 30 ° C. or more and 150 ° C. or less at normal pressure. For example, esters (eg ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (eg methyl isobutyl). Ketones, methyl ethyl ketone, cyclohexanone), amides (eg dimethylformamide, N-methylpyrrolidone), ethers (eg tetrahydrofuran, dioxane) and the like are preferably used, but not limited thereto.

In the emulsification dispersion, an oil phase in which a dye is dissolved in a mixed solvent of a high-boiling organic solvent and a low-boiling organic solvent in some cases is dispersed in an aqueous phase mainly composed of water to form fine oil droplets of the oil phase. Is done for. At this time, in either or both of the water phase and the oil phase, a surfactant, a wetting agent, a dye stabilizer, which will be described later,
Additives such as an emulsion stabilizer, an antiseptic agent and an antifungal agent can be added if necessary. As an emulsification method, a method of adding an oil phase to a water phase is generally used, but a so-called phase inversion emulsification method of dropping an aqueous phase into the oil phase can also be preferably used.

In emulsifying and dispersing in the present invention, various surfactants can be used. Anionic interfaces such as fatty acid salts, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfate ester salts, etc. Activator, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer Nonionic surfactants such as In addition, SURFYNOLS (A which is an acetylene-based polyoxyethylene oxide surfactant)
irProducts & Chemicals) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Furthermore, JP-A-59-157,63
No. 6, pages (37)-(38), Research Disclosure No. What was mentioned as a surfactant of 308119 (1989) can also be used. The surfactant used for emulsification has a different purpose from the surfactant added to adjust the liquid physical properties of the ink jet recording ink described above, but the same kind can be used, resulting in It can also fulfill the function of adjusting the physical properties of the ink.

Further, for the purpose of stabilizing immediately after emulsification, a water-soluble polymer may be added in combination with the above surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof are preferably used. Also polysaccharides, casein,
It is also preferable to use natural water-soluble polymers such as gelatin. Furthermore, for stabilizing the dye dispersion, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, which are substantially insoluble in an aqueous medium,
Polyvinyl, polyurethane, polyester, polyamide, polyurea, polycarbonate and the like obtained by polymerizing methacrylamides, olefins, styrenes, vinyl ethers and acrylonitriles can also be used in combination. It is preferable that these polymers contain —SO ₃ ⁻ and —COO ⁻ . When these polymers that are substantially insoluble in an aqueous medium are used in combination, it is preferably used in an amount of 20% by mass or less of the high boiling point organic solvent, and more preferably 10% by mass or less.

When an oil-soluble dye or a high-boiling organic solvent is dispersed by emulsification to form an aqueous ink, what is particularly important is the particle size controller. It is essential to reduce the average particle size in order to increase color purity and density when an image is formed by inkjet. The volume average particle size is preferably 1 μm or less, more preferably 5 to 100 nm. The methods for measuring the volume average particle size and particle size distribution of the dispersed particles include static light scattering method, dynamic light scattering method, and centrifugal sedimentation method, as well as Experimental Chemistry Course 4th Edition 41.
Using the method described on pages 7-418,
It can be easily measured by a known method. For example, it may be diluted with distilled water so that the particle concentration in the ink may be 0.1 to 1% by mass, and easily used with a commercially available volume average particle size measuring device (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Can be measured. Furthermore, the dynamic light scattering method utilizing the laser Doppler effect is particularly preferable because it can measure the particle size up to a small size. The volume average particle diameter is an average particle diameter weighted by particle volume, and is the sum of diameters of individual particles multiplied by the volume of the particles in a set of particles divided by the total volume of the particles. The volume average particle size is described in “Chemistry of Polymer Latex” (Soichi Muroi, Polymer Publishing Association), page 119.

Further, it was revealed that the presence of coarse particles also plays a very important role in printing performance. That is, it was found that the coarse particles clog the nozzles of the head, or even if they do not clog, they form stains, resulting in non-ejection of ink or misalignment of ejection, which seriously affects printing performance. In order to prevent this, 10 or less particles of 5 μm or more are used in 1 μL of ink when made into ink and 1 μL or less.
It is important to suppress the number of particles of m or more to 1000 or less. As a method for removing these coarse particles, a known centrifugation method, microfiltration method or the like can be used. These separating means may be carried out immediately after the emulsification and dispersion, or after adding various additives such as a wetting agent and a surfactant to the emulsified dispersion,
It may be just before filling the ink cartridge. A mechanical emulsifying device can be used as an effective means for reducing the average particle size and eliminating coarse particles.

As the emulsifying device, known devices such as a simple stirrer or impeller stirring system, in-line stirring system, mill system such as colloid mill, ultrasonic system and the like can be used, but use of a high pressure homogenizer is particularly preferable. is there. A high pressure homogenizer is described in US Pat.
The detailed mechanism is described in Japanese Patent No. 254, JP-A-6-47264 and the like, but as a commercially available device, there is a Gaulin homogenizer (APV GAULIN IN
C. ), Microfluidizer (MICROFLUI
DEX INC. ), And ultimizer (Sugino Machine Co., Ltd.). Also, in recent years, US Pat.
A high-pressure homogenizer having a mechanism for atomizing in an ultra-high pressure jet stream, as described in 20551, is particularly effective for the emulsion dispersion of the present invention. As an example of an emulsifying device using this ultra-high pressure jet flow, DeBEE2
000 (BEE INTERNATIONAL LT
D. ) Is mentioned.

The pressure at the time of emulsification with the high-pressure emulsification disperser is 5
It is 0 MPa or more, preferably 60 MPa or more, and more preferably 180 MPa or more. For example, it is a particularly preferable method to use two or more kinds of emulsifiers together by a method of passing the mixture through a high-pressure homogenizer after emulsifying with a stirring emulsifier. Also, once emulsified and dispersed with these emulsifying devices,
It is also a preferable method to add an additive such as a wetting agent or a surfactant and then pass through the high pressure homogenizer again while the ink is filled in the cartridge. When the low boiling point organic solvent is contained in addition to the high boiling point organic solvent, it is preferable to remove the low boiling point solvent from the viewpoint of stability of the emulsion and safety and health. As a method for removing the low boiling point solvent, various known methods can be used depending on the kind of the solvent. That is, there are an evaporation method, a vacuum evaporation method, an ultrafiltration method and the like. The step of removing the low boiling point organic solvent is preferably carried out as soon as possible immediately after emulsification.

The ink of the present invention includes an anti-drying agent for preventing clogging due to dry operation at the ink ejection port, a penetration accelerator for better penetrating the ink into paper, an ultraviolet absorber and an antioxidant. , A viscosity modifier, a surface tension adjusting agent, a dispersant, a dispersion stabilizer, an antifungal agent, a rust preventive agent, a pH adjusting agent, an antifoaming agent, and a chelating agent can be appropriately selected and used in appropriate amounts. ..

The anti-drying agent used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol,
Thiodiglycol, dithiodiglycol, 2-methyl-
Polyhydric alcohols represented by 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N
-Heterocycles such as ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. It is preferable that the drying inhibitor is contained in the ink in an amount of 10 to 50% by mass.

Penetration enhancers used in the present invention include ethanol, isopropanol, butanol and di (tri).
Alcohols such as ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants can be used. If these are contained in the ink in an amount of 10 to 30% by mass, sufficient effects can be obtained, and it is preferable to use them in an addition amount range that does not cause bleeding of printing and print through.

The ultraviolet absorber used for improving the storability of images in the present invention is disclosed in JP-A-58-1856.
77, 61-190537, JP-A-2-
No. 782, No. 5-97075, and No. 9-34.
No. 057, benzotriazole compounds, JP-A-46-2784, JP-A-5-1944
83, U.S. Pat. No. 3,214,463 and the like, benzophenone compounds, JP-B-48-30492, JP-A-56-21141, JP-A-10-881.
Cinnamic acid-based compounds described in JP-A No. 06, etc.
No. 298503, No. 8-53427, No. 8-
239368, No. 10-182621, and Japanese Patent Publication No. 8-501291, triazine compounds, Research Disclosure No. 2423
Compounds described in No. 9 and stilbene-based and benzoxazole-based compounds that absorb ultraviolet rays to emit fluorescence, so-called fluorescent brighteners can also be used.

In the present invention, various kinds of organic type and metal complex type anti-fading agents can be used as the antioxidant used for improving the image storability. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromanes,
There are alkoxyanilines, heterocycles and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No. 17643
VII, I through J, No. 15162, same N
o. 18716, page 650, left column, same No. 36544, page 527, ibid. 307105, page 872, ibid.
The compounds described in the patent cited in 15162 and the compounds included in the general formulas and the compound examples of the representative compounds described on pages 127 to 137 of JP-A No. 62-215272 can be used.

Antifungal agents used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazoline-3-.
ON, its salt, etc. are mentioned. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass. The details of these are described in "Encyclopedia of Antibacterial and Antifungal Agents" (edited by the Encyclopedia Editorial Committee of the Antibacterial and Antifungal Society of Japan).
Examples of the rust preventive agent include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and benzotriazole. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.

The pH adjuster used in the present invention can be preferably used in terms of pH adjustment and dispersion stability imparting, and the pH of the ink at 25 ° C. is adjusted to 8 to 11. preferable. If the pH is less than 8, the solubility of the dye is lowered and the nozzles are likely to be clogged, and if it exceeds 11, the water resistance tends to be deteriorated. Examples of the pH adjuster include basic ones such as organic bases and inorganic alkalis, and acidic ones such as organic acids and inorganic acids. Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include alkali metal hydroxides (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogencarbonate, etc.), ammonium and the like. Examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, alkylsulfonic acid and the like. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like.

In the present invention, a nonionic, cationic or anionic surfactant may be mentioned as a surface tension adjusting agent in addition to the above-mentioned surfactant. For example, as the anionic surfactant, a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, a dialkylsulfosuccinate, an alkyl phosphate ester salt, a naphthalene sulfonate formalin condensate,
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid. Examples thereof include esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block copolymers and the like. SURFYNOLS (AirProduct) which is an acetylene-based polyoxyethylene oxide surfactant.
s & Chemicals) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, JP-A-59-157,636 (37)
~ (38), Research Disclosure No. Three
The compounds listed as the surfactant described in 08119 (1989) can also be used. The surface tension of the ink of the present invention is 20-60 with or without them.
mN / m is preferred. Furthermore, 25 to 45 mN / m is preferable.

The viscosity of the ink of the present invention is preferably 30 mPa · s or less. Since it is more preferable to adjust the viscosity to 20 mPa · s or less, a viscosity modifier may be used for the purpose of adjusting the viscosity. Examples of the viscosity modifier include celluloses, water-soluble polymers such as polyvinyl alcohol, and nonionic surfactants. For more details, "Viscosity adjustment technology" (Technical Information Association, 1999)
Chapter 9 and "Chemicals for Inkjet Printers (Supplement to 98) -Development Trends and Prospect Survey of Materials-" (CMC, 1997), pp. 162-174.

Further, in the present invention, the above-mentioned various cationic, anionic and nonionic surfactants are used as the dispersant and the dispersion stabilizer, and fluorine-based compounds, silicone compounds and ED as the defoaming agent.
A chelating agent represented by TA and the like can also be used if necessary.

The recording paper and recording film used in the image recording method of the present invention will be described. The support for recording paper and recording film is chemical pulp such as LBKP, NBKP, GP, PGW, RMP, TMP, CTMP, CM.
P, CGP, etc. mechanical pulp, DIP, etc. waste paper pulp, etc., and if necessary, conventional known pigments, binders, sizing agents, fixing agents, cation agents, paper strengthening agents, and other additives are mixed. Those manufactured by various devices such as a fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 1
0 to 250 g / m ² is desirable. The support may be directly provided with an image receiving layer and a back coat layer as an image receiving material, or a size press or an anchor coat layer may be provided with starch, polyvinyl alcohol or the like, and then an image receiving layer and a back coat layer may be provided as an image receiving material. Good. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. In the present invention, as the support, a paper or plastic film having both surfaces laminated with polyolefin (eg, polyethylene, polystyrene, polybutene and their copolymers) or polyethylene terephthalate is more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The image-receiving layer provided on the support contains a porous material and an aqueous binder. Further, the image receiving layer preferably contains a pigment, and the pigment is preferably a white pigment. As white pigments, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. Porous white inorganic pigments are particularly preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either silicic acid anhydride obtained by a dry production method (gas phase method) or hydrous silicic acid obtained by a wet production method can be used.

The recording paper containing the above pigment in the image receiving layer is specifically described in JP-A-10-81064 and 10-104.
No. 119423, No. 10-157277, No. 10-2
No. 17601, No. 10-348409, JP-A-2001
138621, 2000-43401, 20
00-212135, 2000-309157,
2001-96897, 2001-138627
No. 11-91242, No. 8-2087, No. 8-2090, No. 8-2091, and No. 8-2093.
No. 8, No. 8-174992, No. 11-192777,
What was disclosed by Unexamined-Japanese-Patent No. 2001-301314 etc. can be used.

As the aqueous binder contained in the image-receiving layer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative, etc. And water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion.
These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the image receiving layer.

The image-receiving layer may contain a mordant, a water-proofing agent, a light resistance improver, a gas resistance improver, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder.

The mordant added to the image-receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used. Regarding the polymer mordant, JP-A-48-28325, JP-A-54-74430 and JP-A-5-74430.
No. 4-124726, No. 55-22766, No. 55-
142339, 60-23850, 60-23.
No. 851, No. 60-23852, No. 60-23853
No. 60, No. 60-57836, No. 60-60643, No. 60-118834, No. 60-122940, No. 6
0-122941, 60-122942, 60
-235134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430 and 2,548,564;
No. 3148061, No. 3309690, No. 4115
No. 124, No. 4124386, No. 4193800,
No. 4273853, No. 4282305, No. 4450
There is a description in each specification of No. 224. JP-A 1-1612
Image receiving materials containing the polymer mordant described on pages 212 to 215 of JP-A No. 36 are particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The waterproofing agent is effective for waterproofing the image,
A cationic resin is particularly preferable as the water-proofing agent. Examples of such cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide and the like. The content of these cationic resins is preferably 1 to 15% by mass, and particularly preferably 3 to 10% by mass, based on the total solid content of the image receiving layer.

As the light resistance improver and the gas resistance improver,
Phenol compounds, hindered phenol compounds, thioether compounds, thiourea compounds, thiocyanate compounds, amine compounds, hindered amine compounds, TEMP
O compounds, hydrazine compounds, hydrazide compounds, amidine compounds, vinyl group-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinic acid compounds, sugars, water-soluble reducing compounds, organic acids,
Examples thereof include inorganic acids, hydroxy group-containing organic acids, benzotriazole compounds, benzophenone compounds, triazine compounds, heterocyclic compounds, water-soluble metal salts, organic metal compounds and metal complexes. Specific examples of these compounds include JP-A Nos. 10-182621 and 2001-26.
No. 0519, Japanese Patent Laid-Open No. 2000-260519, Japanese Patent Publication No. 4
-34953, Japanese Patent Publication No. 4-34513, Japanese Patent Publication No. 4-
34512, JP-A-11-170686, JP-A-6
0-67190, JP-A-7-276808, JP-A-2
000-94829, JP-A-8-512258, JP-A-11-3219090 and the like.

The surface active agent is a coating aid, a peelability improving agent,
Functions as a slipperiness improver or antistatic agent. The surfactant is described in JP-A-62-173463 and JP-A-62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil) and a solid fluorine compound resin (eg, tetrafluoroethylene resin).
Regarding organic fluoro compounds, Japanese Patent Publication No. 57-9053
No. 8 (columns 8 to 17), JP-A Nos. 61-20994 and 6;
It is described in each publication of JP-A No. 2-135826.

Examples of the hardener include JP-A-1-161236, page 222, JP-A-9-263036, and JP-A-1.
0-119423, JP 2001-310547 A,
It is possible to use the materials and the like described in.

Other additives to be added to the image-receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners,
Preservatives, pH adjusters, matting agents, hardeners and the like can be mentioned. The image receiving layer may be either one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, white inorganic pigments such as magnesium hydroxide, styrene Examples thereof include organic plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, organic pigments such as urea resins and melamine resins.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the ink jet recording paper and recording film. The polymer fine particle dispersion is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. For the polymer fine particle dispersion, see JP-A Nos. 62-245258 and 62-1.
It is described in each publication of No. 36648 and No. 62-110066. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking or curling of the layer can be prevented. Curling can also be prevented by adding a polymer particle dispersion having a high glass transition temperature to the back layer.

In the present invention, the ink jet recording system is not limited, and known systems such as a charge control system for ejecting ink by using electrostatic attraction and a drop-on-demand system (pressure system) for utilizing vibration pressure of a piezo element are used. Pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink and the ink is ejected by using radiation pressure, and a thermal ink jet method in which the ink is heated to form bubbles and the generated pressure is used. It is used in a bubble jet (registered trademark) method or the like. The inkjet recording method uses a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink. Method is included.

The ink of the present invention can be used for purposes other than ink jet recording. For example, it can be used as a display image material, an image forming material of an interior decoration material, an image forming material of an outdoor decoration material, and the like.

Materials for display images include posters, wallpaper, decorative accessories (figures, dolls, etc.), commercial advertisement leaflets, wrapping paper, wrapping materials, paper bags, plastic bags, packaging materials, signs, transportation (automobiles, buses). , Trains, etc.) refers to various objects such as images drawn or attached to the side, clothes with a logo, etc. When the dye of the present invention is used as a material for forming a display image, the image includes not only an image in a narrow sense but also all patterns such as abstract designs, characters, geometric patterns and the like which are perceptible to humans.

The interior decoration materials include various materials such as wallpaper, decorative accessories (figures and dolls), lighting equipment members, furniture members, floor and ceiling design members. When the dye of the present invention is used as an image forming material, the image includes not only an image in a narrow sense, but also all patterns of the dye that can be recognized by humans such as abstract designs, characters, and geometric patterns.

The outdoor decoration materials include various materials such as wall materials, roofing materials, signboards, gardening materials, outdoor decoration accessories (figures and dolls), members of outdoor lighting equipment, and the like. When the dye of the present invention is used as an image-forming material, the image includes not only an image in a narrow sense, but also all patterns of the dye recognizable by humans such as abstract designs, characters, and geometric patterns.

In the above-mentioned applications, various media such as paper, fibers, cloth (including non-woven fabric), plastics, metals, ceramics, etc. can be mentioned as media on which patterns are formed. As the dyeing form, mordant, printing,
Alternatively, the dye can be immobilized in the form of a reactive dye having a reactive group introduced therein. Among these, it is preferable that the dye is dyed in a mordant form.

[0148]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited thereto.

(Preparation of Ink Liquid) Deionized water was added to the following components to make 1 liter, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. This ink liquid has an average pore size of 0.25
An ink liquid for light cyan (LC-1) was prepared by vacuum filtration with a micrometer of μm.

[0150] [Light cyan ink LC-1 prescription] Phthalocyanine dye (154) 17.5g / l Diethylene glycol 150g / l Urea 37g / l Glycerin 130g / l Triethylene glycol monobutyl ether                                      130 g / l Triethanolamine 6.9g / l Benzotriazole 0.08g / l PROXEL XL2 3.5g / l Surfynol STG 10g / l

Further, 68 g of the cyan dye (154) was prepared according to the above formulation.
An ink liquid for cyan (C-1) whose amount was increased to / l was prepared.

First, this ink (C-1), a cyan ink of Epson Inkjet Printer PM-950C, and a cyan ink of Canon Inkjet Printer BJF900 were used as a thin layer cell having a cell thickness of 1 × 10 ⁻⁶ m. Absorbance was measured using to determine the extinction coefficient ε ₁ at λmax. Next, these inks were diluted 10000 times with water, and the absorbance was measured using a cell having an optical path length of 1 cm to obtain an absorption coefficient ε ₂ at λmax. At this time, in each case, water was added to the control cell for measurement. The results of calculating ε ₁ / ε ₂ are shown in Table 12 below.

[0153]

[Table 12]

Next, these inks were filled in a cyan / light cyan ink portion of a cartridge of an ink jet printer, and an image was printed on the ink jet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. by the same machine to evaluate image fastness. I went. However, C-1 and LC-1 were tested by loading them in the Epson PM-950C cartridge and Canon BJF900 cartridge, and using the Epson PM-950C cyan ink and the Canon BJF900 cartridge. The cyan ink was loaded into the cartridge of each in-house printer and tested.

Regarding the image storability, a cyan solid image printed sample was prepared and evaluated as follows. The light fastness was measured by measuring the image density Ci immediately after printing with the X-rite 310, irradiating the image with xenon light (85,000 lux) for 10 days using a weather meter manufactured by Atlas, and then again measuring the image density Cf. Was measured to obtain the dye residual ratio Cf / Ci * 100 and evaluated. Regarding the afterimage rate of the dye, the reflection density is 1,
Evaluation was made with 3 points of 1.5 and 2, A at a dye residual rate of 70% or more at any concentration, B at a point of 2 points less than 70%, and at a rate of less than 70% at all concentrations. It was set to C. For heat fastness, 1 at 80 ° C and 70% RH
The concentration before and after storing the sample for 0 days was determined by X-rite 310
The residual dye rate was measured and evaluated. Dye residual ratio was evaluated at three points of reflection density of 1, 1.5 and 2, and A was used when the residual dye rate was 90% or more, and B was used when all the points were less than 90%. The case where the concentration was less than 90% was designated as C. Regarding ozone fastness, the photo glossy paper on which the image was formed was left in a box in which the ozone gas concentration was set to 0.5 ppm for 7 days, and the image density before and after being left under ozone gas was measured by a reflection densitometer (X-Rite310TR). Was used to evaluate the dye residual rate. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor manufactured by APPLICS (model: OZG-EM-01). When the residual dye ratio is 80% or more at any concentration, A,
1 or 2 points were evaluated as three levels, with B being 80% or less and C being 70% or less at all concentrations. The obtained results are shown in Table 13.

[0156]

[Table 13]

From Table 13, it can be seen that the ink of the present invention is excellent in weather resistance (fastness to light, heat and ozone) and particularly improved in fastness to ozone.

[0158]

According to the present invention, an image having high image quality and excellent weather resistance can be provided in ink jet recording.

Claims (3)

[Claims] 1. A cyan ink for inkjet which has phthalocyanine as a main coloring component and uses water and a water-miscible solvent as a solvent for the ink, the ink is directly formed into a thin layer cell having a thickness of 1 × 10 ⁻⁶ m. The extinction coefficient (ε ₁ ) in the cyan region obtained by measuring the transmission spectrum of the ink was diluted 10000 times with water to obtain a thickness of 1
ε ₁ / ε _{2 with} respect to the extinction coefficient (ε ₂ ) in the cyan region obtained by measuring the transmission spectrum using a cell of cm
<Cyan ink for inkjet characterized by being 0.95. 2. The cyan ink for inkjet according to claim 1, wherein ε ₁ / ε ₂ <0.9. 3. An ink jet recording method, which comprises forming an image using the ink jet ink set containing the cyan ink for ink jet according to claim 1 or 2.