JP2003292849A - Inkjet recording ink and inkjet recording process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording ink capable of forming a high-quality image and excellent in storability, not drying at an inkjet head, and showing high ejection stability. <P>SOLUTION: The inkjet recording ink is one prepared by dissolving or dispersing at least one dye represented by formula (I) and containing an antifoam. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has high discharge stability,
The present invention relates to an inkjet recording ink and an inkjet recording method, which are excellent in hue of an obtained image and are excellent in image storability under severe conditions.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, inkjet printers have been used not only in offices but also at home.
Widely used for printing on film, cloth, etc.

The ink jet recording method includes a method of applying pressure by a piezo element to eject droplets, a method of generating bubbles in ink by heat to eject droplets, a method of using ultrasonic waves, or an electrostatic force. There is a method of sucking and ejecting liquid droplets by means of. As these inkjet recording inks, water-based inks, oil-based inks, or solid (melting type) inks are used. Among these inks, water-based inks are predominant in terms of manufacturing, handling, odor, safety and the like.

The dyes used in these ink jet recording inks have high solubility in solvents, high density recording is possible, good hue, light, heat, air, water and It has excellent fastness to chemicals, has good fixability to the image receiving material and does not easily bleed, has excellent storage stability as an ink, has no toxicity, has high purity, and is available at low cost. It is required to be able to do it. However, it is extremely difficult to search for a dye that meets these requirements at a high level. In particular, a dye having a good cyan hue and excellent weather fastness is strongly desired.

On the other hand, it is important to remove minute bubbles in the ink when preparing the ink. If the removal of minute bubbles in the ink is insufficient, there is a problem that ejection stability is impaired due to ink clogging in the inkjet head. A surfactant is often added to the ink for the purpose of adjusting the physical properties of the ink and improving the penetrability of the paper, but in this case, the surfactant becomes one of the factors that cause bubbles, which causes a problem of bubble removal. Will be more important.

[0006]

SUMMARY OF THE INVENTION Therefore, the problems to be solved by the present invention are for ink jet recording which gives a high quality image having excellent ejection stability, good hue of the obtained image, and excellent storability. An ink and an inkjet recording method are provided. It is another object of the present invention to provide an inkjet recording ink and an inkjet recording method, which have good ejection stability under severe conditions for a long period of time and have high image storability.

[0007]

The above object of the present invention is achieved by an ink jet recording ink and an ink jet recording method having the following constitutions. (1) An ink for ink-jet recording, comprising at least one dye represented by the following general formula (I) dissolved or dispersed in an aqueous medium and containing an antifoaming agent. . General formula (I)

[0008]

[Chemical 3]

In the general formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each independently --SO--Z, --SO ₂ --Z,
-SO ₂ NR ₁ R _2, 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 Alternatively, it represents an unsubstituted heterocyclic group. The above 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 aryl group, or a substituted Alternatively, it represents an 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 each X ₁
To X ₄ and Y _{1 to} Y ₄ represent the number of substituents, and a _{1 to} a ₄ are
Each is independently an integer of 0 to 4, and all are 0 at the same time.
And b _{1 to} b ₄ are each independently 0 to
It is an integer of 4.

M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. (2) The inkjet recording ink according to (1) above, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (II). General formula (II)

[0015]

[Chemical 4]

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. (3) The ink for inkjet recording as described in (1) or (2) above, wherein the content of the defoaming agent is 0.001 to 5 mass%. (4) The inkjet recording ink according to any one of (1) to (3) above, which contains a betaine-based surfactant. (5) An inkjet recording method comprising using the inkjet recording ink according to any one of (1) to (4) above. (6) The inkjet recording ink according to any one of (1) to (4) above, from a nozzle on a surface of an image receiving layer of an image receiving material having an image receiving layer containing white inorganic pigment fine particles on a support. Is ejected in accordance with a recording signal to form an ink image on the image receiving layer.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The dye contained in the ink jet recording ink of the present invention is a phthalocyanine dye represented by the above general formula (I).

The phthalocyanine dye has been known as a fast dye, but when it is used as a recording dye for ink jet, it is known that it has poor fastness to ozone gas.

In the present invention, an electron withdrawing group is introduced into the phthalocyanine skeleton to make the oxidation potential nobler than 1.0 V (vs SCE) in order to reduce the reactivity with ozone which is an electrophile. Is desirable. The more preferable the oxidation potential is, the more preferable the oxidation potential is 1.1 V (vs SCE), and the more preferable is 1.2 V (vs SCE).
Those that are more noble are most preferred.

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 define the potential uniquely, in the present invention, 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 direct current polarography at
E) 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 the transfer of electrons from the sample to the electrode is.
In other words, it means that it is difficult to be oxidized. 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.

The phthalocyanine dye represented by the general formula (I) is preferably used also 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.

Z is 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, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
And a substituted or unsubstituted heterocyclic group, 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.

R₁, R₂And the substitution or non-positioning represented by Z
An alternative alkenyl group is an alkenyl group having 2 to 30 carbon atoms.
The lucenyl group is preferred. Especially dye solubility and ink stability
A branched alkenyl group is preferred because it enhances
Especially when it has an asymmetric carbon (use in racemic form)
Is particularly preferable. Examples of the substituent include Z, which will be described later,
R ₁, R₂, Y₁, Y₂, Y₃And Y_FourHas further substituents
The same as the substituents when possible are mentioned. Na
In any case, hydroxyl group, ether group, ester group, cyano group,
Amide group and sulfonamide group enhance the dye's association and are robust
It is particularly preferable because it improves the property. In addition, halogen source
It may have a child or an ionic hydrophilic group.

R₁, R₂And the substitution or non-positioning represented by Z
An alternative aralkyl group is an aralkyl group having 7 to 30 carbon atoms.
The aralkyl group is preferred. Especially dye solubility and ink stability
Branched aralkyl groups are preferred because they increase
Especially when it has an asymmetric carbon (use in racemic form)
Is particularly preferable. Examples of the substituent include Z, which will be described later,
R ₁, R₂, Y₁, Y₂, Y₃And Y_FourHas further substituents
The same as the substituents when possible are mentioned. Na
In any case, hydroxyl group, ether group, ester group, cyano group,
Amide group and sulfonamide group enhance the dye's association and are robust
It is particularly preferable because it improves the property. In addition, halogen source
It may have a child 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 examples of the substituent include Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ described later, which may further have a substituent. The same as the substituents in this case can be mentioned. 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 (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, Phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy,
3-methoxycarbamoyl), an acylamino group (for example, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (for example, methylamino, butylamino,
Diethylamino, methylbutylamino), anilino groups (eg, phenylamino, 2-chloroanilino, ureido groups (eg, phenylureido, methylureido,
N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (eg, methoxycarbonylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfone) Amide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl),
Sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, 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-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg,
Trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg, phenoxycarbonylamino), 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 (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example,
Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic group (for example, 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 its oxide, hydroxide or halide.

Preferred as M is Li, Na, K, Mg, Ti, Z as a metal element in addition to hydrogen atom.
r, V, Nb, Ta, Cr, Mo, W, Mn, Fe, C
o, Ni, Ru, Rh, Pd, Os, Ir, Pt, C
u, Ag, Au, Zn, Cd, Hg, Al, Ga, I
Examples thereof include n, Si, Ge, Sn, Pb, Sb, and Bi. Preferable examples of the oxide include VO and GeO.

As the hydroxide, Si (O
H) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like are preferable. Further, as the halide, AlCl,
SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, G
Examples thereof include aCl and ZrCl. Among them, Cu, N
i, 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), the phthalocyanine dye having the structure represented by the general formula (II) is more preferable. The phthalocyanine dye represented by formula (II) of the present invention is described in detail below.

In the general formula (II), X₁₁~ X₁₄,
Y₁₁~ Y₁₈Is X in the general formula (I) ₁~ X_Four, Y₁~ Y_FourWhen
Each has the same meaning, and the preferred examples are also the same. Also,
M has the same meaning as M in formula (I), and preferred examples are also the same.
It is like.

In the general formula (II), a₁₁~ A₁₄Respectively
Independently, it is an integer of 1 or 2, preferably 4 ≦ a₁₁
+ A₁₂+ A₁₃+ A₁₄Satisfying ≦ 6, particularly preferably a₁₁
= A ₁₂= A₁₃= A₁₄= 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 the general formula (II), particularly preferable combinations of substituents are as follows.

X _{11 to} X ₁₄ are each 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, and 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.

Regarding the preferred combination of substituents of the compound represented by the general formula (II), a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are 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.

As the chemical structure of the phthalocyanine dye of the present invention, at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group is provided 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.

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.
35 years L. 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, "Lang
e's Handbook of Chemistr
y ”12th edition, 1979 (McGraw-Hil
l) and "Chemical Area" special edition, No. 122, 96-103
Details on page 1979 (Nankodo).

The phthalocyanine derivative represented by the general formula (I) is inevitably substituted by the 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: a phthalocyanine dye having a specific substituent at the 2- and / or 3-position, 6- and / or 7-position, 10- and / or 11-position, 14- 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, by Shirai-Kobayashi, published by IPC, "Phthalocyanine-Chemistry and Function-" (P.1-62),
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 World Patent Nos. 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 described 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 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).

[0073]

[Chemical 5]

In each of the above formulas, Xp corresponds to X ₁₁ , X ₁₂ , X ₁₃ or X ₁₄ in the 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.

The cation represented by M'includes Li, Na,
Examples thereof include alkali metal ions such as K and organic cations such as triethylammonium ion and pyridinium ion. General formula (III): M- (Y) d In general formula (III), M is said 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.

[0078]

[Chemical 6]

[0079]

[Chemical 7]

[0080]

[Chemical 8]

[0081]

[Chemical 9]

In the above synthetic method, all Xp are the same.
If you use the one X₁₁, X₁₂, X ₁₃And X₁₄Is totally
Obtained β-position substituted phthalocyanine dye having the same substituent
You can On the other hand, combine different Xp
If used together, they are the same kind of substituents but partially
Dyes with different substituents or different dyes
Dyes with certain types of substituents can be synthesized.
Among the dyes of general formula (II), different electron withdrawing
These dyes that have a functional substituent are
Properties, ink stability over time, etc.
Good

In the present invention, it was found that it is very important that the oxidation potential is nobler than 1.0 V (vs SCE) in any of the substitution types, which is very important for improving the fastness, and the effect is large. 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) (exemplary 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.

[0085]

[Chemical 10]

[0086]

[Chemical 11]

[0087]

[Chemical 12]

[0088]

[Chemical 13]

[0089]

[Chemical 14]

[0090]

[Chemical 15]

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

[Table 5]

[0096]

[Table 6]

[0097]

[Table 7]

[0098]

[Table 8]

[0099]

[Table 9]

[0100]

[Table 10]

[0101]

[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.

[0103]

[Chemical 16]

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

For the purpose of obtaining a full-color image together with the cyan dye, the ink-jet ink of the present invention comprises
You may use together other dyes in order to adjust a color tone. Examples of dyes that can be used in combination are as follows.

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 methylene 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, anthrapyridone, etc., 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; carbonium such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes. Dyes; phthalocyanine dyes; anthraquinone dyes; examples include aryl or heterylazo dyes having phenols, naphthols, anilines as coupling components, and indigo / thioindigo dyes. 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.

Black dyes such as polyazo dyes can also be used.

Examples of water-soluble dyes include direct dyes, acid dyes, food dyes, basic dyes and reactive dyes. Preferred are CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62,
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.

The phthalocyanine dye used in the present invention and the above 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.

As the pigment used in the present technology, commercially available pigments and known pigments described in various documents can be used. For the literature, the Color Index (The Socie
ty 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 so on. 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 Red 10 such as 4, 37, 42, 53
CI Pigment Blue 27, 29,1 for blue pigments such as 1, 108
CI Pigment Black 7, which is a black pigment such as 7: 1, and CI Pigment White 4,6,18,21 which is a white pigment, such as magnetite.

Pigments having a preferable color tone for image formation include phthalocyanine pigments for blue to 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 the 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.

In addition, orange pigment (CI Pigment Or
ange 13, 16) or a green pigment (such as CI Pigment Green 7) may be used.

The pigment that can be used in the present technology 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 (Koshobo) Printing Ink Printing (CMC Publishing 1984) Latest Pigment Application Technology (CMC Publishing 1986) US Patents 5,554,739, 5,571,311 JP-A-9-151342, 10-140065 , Ibid 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 present invention, the pigment may be dispersed using a dispersant. As the dispersant, various known dispersants can be used according to the pigment used, for example, a surfactant type low molecular dispersant or a polymer type dispersant. Examples of the dispersant include those described in JP-A-3-69949, European Patent 549486 and the like. 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 present technology is preferably in the range of 0.01 to 10 μ after dispersion,
More preferably, it is 05 to 1 μ.

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 the disperser, a vertical or horizontal agitator mill, attritor, colloid mill, ball mill, three roll mill, pearl mill, super mill, impeller,
Examples include 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 that can be contained in the ink according to the present invention will be described.

By adjusting the liquid properties of the ink by containing a surfactant in the ink jet recording ink of the present invention, the ejection stability of the ink is improved, the water resistance of the image is improved, and the bleeding of the printed ink is prevented. It is possible to give excellent effects such as prevention.

In the present invention, various kinds of surfactants can be used for the above purpose, but betaine surfactants are preferably used. Here, the betaine-based surfactant also includes, for example, the one used for dispersing the oil-soluble dye.

The betaine-based surfactant referred to here is a compound having both a cationic site and an anionic site in the molecule and having surface activity. Examples of the cationic moiety include an amine nitrogen atom, a nitrogen atom of a heteroaromatic ring, a boron atom having four carbon bonds, and a phosphorus atom. Of these, an amine nitrogen atom or a nitrogen atom of a heteroaromatic ring is preferable. Of these, a quaternary nitrogen atom is particularly preferable. As the anionic moiety, a hydroxyl group, a thio group, a sulfonamide group, a sulfo group, a carboxyl group, an imide group,
Examples thereof include a phosphoric acid group and a phosphonic acid group. Among these, a carboxyl group and a sulfo group are particularly preferable. The charge of the surfactant molecule as a whole may be cation, anion, or neutral, but is preferably neutral.

The preferable addition amount of the betaine-based surfactant (including the amount used for dispersing the dye) has a wide range, but preferably 0.001 to 50% by mass in the ink composition, more preferably It is 0.01 to 20 mass%.

Specific examples of the betaine-based surfactant are shown below, but the present invention is not limited thereto.

[0130]

[Chemical 17]

[0131]

[Chemical 18]

[0132]

[Chemical 19]

The ink jet recording ink of the present invention comprises
It can be prepared by dissolving and / or dispersing a phthalocyanine dye and a surfactant in an aqueous medium. The “aqueous medium” in the present invention means water or a mixture of water and a small amount of a water-miscible organic solvent, to which additives such as a wetting agent, a stabilizer and a preservative are added, if necessary.

When preparing the ink liquid of the present invention, in the case of a water-soluble ink, it is preferable to first dissolve it 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 ultrasonic irradiation, 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.

Regarding the method for preparing the water-based ink-jet ink, JP-A-5-148436 and JP-A-5-295 have been used.
No. 312, No. 7-97541, No. 7-82515,
7-118584, Japanese Patent Application 2000-200080
No. 2000-249799 and the details thereof are described, and it can be used for the preparation of the inkjet recording ink of the present invention.

Examples of water-miscible organic solvents that can be used in the present invention include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol).
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 boiling point of the high boiling point organic solvent used in the present invention is preferably 150 ° C. or higher, more preferably 170 ° C. or higher.

Examples of the high boiling point organic solvent include phthalic acid 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), phosphoric acid or phosphonic esters (eg diphenyl phosphate, triphenyl) Phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-
Ethylhexyl phenyl phosphate), benzoic acid ester acid (for example, 2-ethylhexyl benzoate,
2,4-dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl). alcohol,
2,4-di-tert-amylphenol, etc., aliphatic esters (eg, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, iso Stearyl lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesin Acid esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert)
-Amylphenol, 4-dodecyloxyphenol,
4-dodecyloxycarbonylphenol, 4- (4-
Dodecyloxyphenylsulfonyl) phenol), carboxylic acids (eg, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid)), alkylphosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid) , Diphenylphosphoric acid) and the like.

The high-boiling point organic solvent is 0.01 to 3 times by mass ratio, preferably 0.01 to 1.0, with respect to the oil-soluble dye.
Can be used in double dose.

These high-boiling organic solvents may be used alone or in a mixture of several kinds [eg, 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 the emulsification has the same purpose as that of the surfactant added for adjusting the liquid physical properties of the ink jet recording ink, but the same kind can be used. As a result, 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.

Further, for stabilizing the dye dispersion, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, which are substantially insoluble in an aqueous medium, Polyvinyl, polyurethane, polyester obtained by polymerization of vinyl ethers and acrylonitrile,
Polyamide, polyurea, polycarbonate, etc. can also be used together. These polymers are -SO ^2- , -CO
It is preferable to contain O ⁻ . When these polymers which 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,
It is more preferably used in an amount of 10% by mass or less.

When an oil-soluble dye or a high boiling point organic solvent is dispersed by emulsification to form an aqueous ink, what is particularly important is a controller having a particle size. 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, and are described on pages 417 to 418 of Experimental Chemistry Course 4th Edition. It can be easily measured by a known method such as using a known method.

For example, the particle concentration in the ink is 0.1-1.
Diluted with distilled water to a mass% and commercially available volume average particle size measuring device (for example, Microtrac UPA
(Manufactured by Nikkiso Co., Ltd.) for easy measurement. 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 the particle volume, and is the sum of the diameter of each particle multiplied by the volume of the particle in the aggregate of particles divided by the total volume of the particle. is there. For volume average particle size, refer to “Chemistry of Polymer Latex” (Souichi Muroi, Polymer Society) 1
There is a description on page 19.

It was also found 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 separation means may be carried out immediately after the emulsified dispersion, or immediately after the addition of various additives such as a wetting agent and a surfactant to the emulsified dispersion and immediately before the filling into 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.).

In addition, in recent years, US Pat. No. 5,720,55
A high-pressure homogenizer having a mechanism of atomizing in an ultra-high pressure jet stream as described in No. 1 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, DeBEE2000
(BEE INTERNATIONAL LTD.).

The pressure during 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. It is also a preferable method to emulsify and disperse in one of these emulsifying devices, add additives such as a wetting agent and 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 hygiene. 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 jet recording ink of the present invention contains an antifoaming agent.

The defoaming agent in the present invention refers to a compound which, instead of the causative agent of foaming, exists on the liquid surface by itself and has no repulsive force for resisting thinning of the foam film. . Specific examples include alcohols, ethers, fatty acid esters, metal stones, phosphoric acid esters, silicons, nonionic surfactants and the like.

As alcohols, for example, methanol,
Examples include ethanol, butanol, and octanol.

Examples of the fatty acid esters include isoamyl stearate, succinic acid diester, diethylene glycol distearate, oxyethylene sorbitan monolauric acid ester, and the like.
There is Nopco KF manufactured by Nopco Chem.Co.

Examples of ethers include di-t-amylphenoxyethanol, 3-heptylcellosolve, nonylcellosolve and 3-heptylcarbitol. Commercially available products include, for example, Bionin K-1 manufactured by Takemoto Yushi Co., Ltd.
7, Nopco DF122-NS manufactured by San Nopco Ltd. may be mentioned.

Examples of metal soaps include aluminum stearate and potassium oleate, and commercially available products include Nopco DF122-NS manufactured by San Nopco KK.

As silicones, for example, silicone oil,
There are silicone emulsion, organic modified silicone oil, etc., and as commercial products, SN Deformer 5016 manufactured by San Nopco Co., Ltd., Surfynol D manufactured by Air Products Co., Ltd.
F-58, Surfynol DF-695, SM-5513 manufactured by Toray Dow Corning Silicone Co., Ltd. and the like can be mentioned.

Examples of the nonionic surfactants include the following. 1) alkyl allyl ether ethylene oxide adduct _{2) HO- (C 2 H 4} O) n - (C 3 H 6 O) m - ( molecular weight _{C 2 H 4 O) n -OH} 500
10000, C ₂ H ₄ O content is 0 to 55% 3) Alkyl ester type: R ₁ (R ₂ ) CHCOO (C ₂ H ₄ O) _n R ₁ , R ₂ : C _{1 to} C ₁₀ alkyl group
n: 1 to 8 4) acetylene diols and their ethylene oxides 0 to
8-Mole Adduct As the defoaming agent used in the present invention, silicons and nonionic surfactants are preferable among them, and nonionic surfactants having an HLB value of about 1 to 4 are particularly preferable.

The antifoaming agents listed above can be used alone or in combination of two or more kinds.

The addition amount of the defoaming agent in the ink is preferably 0.001 to 5% by mass, and 0.0
It is more preferably 1 to 3% by mass. If the added amount is too small, the defoaming effect does not sufficiently appear, and if the added amount is too large, the ink liquid causes layer separation, which is not preferable.

In addition to the above defoaming agent, the ink-jet recording ink obtained in the present invention may contain an anti-drying agent for preventing clogging due to dry operation at the ink ejection port and an ink on paper. Permeation enhancer for penetration, ultraviolet absorber, antioxidant, viscosity modifier, dispersant, dispersion stabilizer,
Additives such as antifungal agents, rust preventives, pH adjusters and chelating agents can be appropriately selected and used in appropriate amounts.

The ink viscosity of the present invention is 1 at 25 ° C.
It is preferably ˜30 mPa · s. It is more preferably 2 to 15 mPa · s, and particularly preferably 2 to 10
It is mPa · s. When it exceeds 30 mPa · s, the fixing speed of the recorded image becomes slow and the ejection performance also deteriorates. 1 mPa
If it is less than s, the recorded image is bleeding and the quality is degraded.

The viscosity can be adjusted by adjusting the amount of the ink solvent added. As the ink solvent, for example, glycerin, diethylene glycol, triethanolamine, 2
-Pyrrolidone, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and the like.

The inkjet recording ink used in the present invention preferably has a static surface tension at 25 ° C. of 25 to 50 mN / m. Furthermore, it is preferable that the static surface tension at 25 ° C. is 30 to 40 mN / m. If the static surface tension of the ink exceeds 50 mN / m, the ejection stability will deteriorate, bleeding will occur at the time of color mixing, and whiskers will occur (for example, when black characters are printed on cyan solid, the bleeding from black characters becomes stringy). , Etc.) and the print quality is remarkably deteriorated. In addition, the static surface tension of the ink is 25
If it is less than mN / m, ink may adhere to the hard surface at the time of ejection, resulting in defective printing.

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, as the antioxidant used for improving the storability of the image, various organic and metal complex type anti-fading agents can be used. 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.

Examples of the fungicide used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester and 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.

Details of these are described in "Encyclopedia of Antibacterial and Antifungal Agents" (edited by the Japanese Society for Antibacterial and Antifungal Encyclopedia Editorial Committee).

Examples of rust preventives 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.

In the present invention, the above-mentioned cation, anion and nonionic surfactants and chelating agents typified by EDTA can be used as the dispersant and dispersion stabilizer, 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.

An image receiving layer and a back coat layer may be directly provided on the support to serve 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. It may be used as a material. Furthermore, for the support, machine calendar,
The flattening treatment may be performed by a calendar device such as a TG calendar or a soft calendar.

In the present invention, a paper and a plastic film, both sides of which are laminated with polyolefin (eg, polyethylene, polystyrene, polybutene and their copolymers) or polyethylene terephthalate, are more preferably used as the support. 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, polyvinyl pyrrolidone, 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-
No. 28325, No. 54-74430, No. 54-124
No. 726, No. 55-22766, No. 55-14233.
No. 9, No. 60-23850, No. 60-23851,
No. 60-23852, No. 60-23853, No. 60
-57836, 60-60643, 60-11
8834, 60-122940, 60-122
No. 941, No. 60-122942, No. 60-2351.
34, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, and 31,480.
No. 61, No. 3309690, No. 4115124, No. 4124386, No. 4193800, No. 42738.
No. 53, No. 4282305, and No. 4450224. Image receiving materials containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 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 are described in JP-A-10-182621 and JP-A-2001-260519.
No. 2000-26019, Japanese Patent Publication No. 4-349.
No. 53, Japanese Patent Publication No. 4-34513, Japanese Patent Publication No. 4-3451
2, JP-A-11-170686, JP-A-60-67.
190, JP-A-7-276808, and JP-A-2000-
94829, Tokuyohei 8-512258, JP-A-11
No. 321090 and the like are mentioned.

The surfactant 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). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-29944 and JP-A-62-135826.

As the hardener, page 222 of JP-A-1-161236, JP-A-9-263036, 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. , White inorganic such as aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide Examples include pigments, styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, organic pigments such as urea resins and melamine resins.

Examples of the aqueous binder contained in the back coat layer include 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 316648 and 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) 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 ink jet recording method is a method of ejecting a large number of low density ink 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 method. A method using ink is included.

The ink jet recording ink of the present invention comprises
It can also 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 material includes 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 material includes 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 applications, examples of the medium on which the pattern is formed include various materials such as paper, fibers, cloth (including non-woven fabric), plastic, metal and ceramics. 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.

[0213]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited thereto. Example 1 (Preparation of Ink Liquid) Deionized water was added to the following components to make 1 liter, and the mixture was stirred and dissolved for 1 hour while heating at 30 to 40 ° C. After that, vacuum filtration was performed with a microfilter having an average pore size of 0.25 μm to prepare an ink liquid for light cyan. (Components of Ink Liquid for Light Cyan) Cyan Dye (Exemplified Compound 154) 17.5 g Triethylene glycol monobutyl ether 119.0 g Glycerin 123 g Diethylene glycol 164 g PROXEL XL2 [Zeneca] 1.0 g Benzotriazole 0.07 g Antifoam (A- 1) 10.0 g Surfactant (W-1) 6 g Surfactant (W-1): 2-butyloctanoic acid ester at one end of polyethylene glycol (average ethylene oxide repeating number 10) Also, deionized water is added to the following components. Was added to make 1 liter, and the mixture was stirred and dissolved for 1 hour while heating at 30 to 40 ° C.
Then, vacuum filtration was performed using a microfilter having an average pore size of 0.25 μm to prepare a cyan ink liquid. (Components of Cyan Ink Liquid) Cyan Dye (Exemplary Compound 154) 68.0 g Triethylene glycol monobutyl ether 127.0 g Glycerin 110 g Diethylene glycol 107 g PROXEL XL2 [Zeneca] 4.0 g Benzotriazole 0.09 g Defoamer (A-) 1) 10.0 g Surfactant (W-1) 10.0 g Next, except that the above-mentioned dye species, defoaming agent species and defoaming agent addition amounts, and surfactant species were changed in accordance with Table 1 below. , Examples 2 to 4 and Comparative Examples 1 and 2 were made in the same manner.

[0214]

[Table 12]

The antifoaming agents used in the above table are as follows. _{A-1: R 1 (R} 2) CHCOO (C 2 H 4 O) n ( _{wherein, R 1 = C 4 H 9} , R 2 = C 4 H 9, n = 4) A-2: 2,4 , 7,9-Tetramethyl-5-decyne-
4,7-diol ethylene oxide 4 mol adduct Also, comparative dye C-1 used in the above table, surfactant W-
The structural formula of 19 is shown below.

[0216]

[Chemical 20]

(Inkjet recording) The ink for light cyan and the ink for cyan produced above were packed in a cartridge of an inkjet printer PM920C (manufactured by Seiko Epson Co., Ltd.), and the inkjet paper Photo Gloss manufactured by Fuji Photo Film Co., Ltd. was used in the same machine. Paper E
An image was printed on X and the following evaluations were performed. The results are shown in Table 15. (1) Discharge stability The cartridge was set in a printer, and a continuous discharge test of ink from nozzles was performed to evaluate discharge stability.

Further, the ejection stability was evaluated after the printer was left at room temperature for 2 weeks with the cartridge set in the printer.

◯: Stable Δ: Slightly unstable X: Unstable (2) Image storability For the evaluation of the image storability, a solid image print sample of cyan was prepared and the following evaluation was performed. Light fastness Image density Ci immediately after printing is measured by a reflection densitometer (X-Rite31
(0TR), the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter manufactured by Atlas, and the image density Cf was measured again to measure the residual dye ratio Ci / Cf *.
100 was obtained and evaluated. Image density Ci of 1, 1.5, 2
The dye residual rate was 85 at any concentration.
%, A was given, B was given when two points were less than 85%, and C was given when all the concentrations were less than 85%. Thermal fastness The reflection densitometer (X-Rite310TR) measures the density before and after storing the sample for 7 days under the condition of 70 to 80% RH.
The residual dye rate was measured and evaluated. The image density Ci was evaluated at three points of 1, 1.5, and 2, and in any of the densities, the dye residual rate was 90% or more, A, and when the two points were less than 90%, B, and all the densities. The case of less than 90% was designated as C. Ozone resistance The ozone gas concentration was left in a box set to 0.5 ppm for 7 days, and the concentration before and after ozone gasification was measured with a reflection densitometer (X-Rite 310TR) to obtain and evaluate the residual dye ratio. The image density Ci was evaluated at three points of 1, 1.5 and 2, and A in all the cases where the dye residual rate was 80% or more, and 1 in the case where 1 or 2 points were less than 85%, and B in all cases. The case where the concentration was less than 70% was designated as C. The results obtained are shown in Table 15.

[0220]

[Table 13]

From the results shown in Table 15, when the ink of the present invention was used for ink jet recording, excellent storage stability was exhibited as compared with Comparative Example. In particular, it showed excellent performance in ozone resistance. In addition, it can be seen from the evaluation of printing performance that good ejection stability is exhibited. Furthermore, the ink of the present invention showed significantly superior performance to the comparative example in ejection stability after being left for 2 weeks.

The image receiving paper used in the present invention is EP
The same effect as the above result can be seen even when the SON PM photo paper and Canon PR101 are used.

The same ink prepared in Example 1 was packed in a cartridge of an ink jet printer BJ-F850 (manufactured by Canon Inc.), and the image was printed on the ink jet paper photo glossy paper EX manufactured by Fuji Photo Film by the same machine. When the same evaluation as in Example 1 was performed, Example 1
Similar results were obtained. Similar effects were observed when the image receiving paper was PM photo paper manufactured by EPSON and PR101 manufactured by Canon.

[0224]

According to the present invention, it is possible to provide an ink jet recording ink and an ink jet recording method which are excellent in ejection stability and image storability, give high quality images, and have good performance even under severe conditions.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 47/073 C09B 47/24 47/24 B41J 3/04 101Y F term (reference) 2C056 EA05 EA13 FC01 FC06 2H086 BA56 BA59 BA62 4J039 BC19 BC32 BC33 BC49 BC51 BC54 BC56 BC58 BC60 BE02 BE12 BE16 BE22 CA03 CA06 EA41 EA44 EA46 GA24

Claims (6)

[Claims] 1. An ink-jet recording comprising at least one dye represented by the following general formula (I) dissolved or dispersed in an aqueous medium and containing an antifoaming agent. Ink. General formula (I) 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. 2. The ink for inkjet recording according to claim 1, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (II). General formula (II) In the general formula (II) above, X _{11 to} X ₁₄ , Y _{11 to} Y ₁₈ , and M are
Each has the same meaning as X _{1 to} X ₄ , Y _{1 to} Y ₄ , and M in the general formula (I). a _{11 to} a ₁₄ are each independently an integer of 1 or 2. 3. The ink for ink jet recording according to claim 1, wherein the content of the defoaming agent is 0.001 to 5 mass%. 4. The ink for ink jet recording according to claim 1, which contains a betaine-based surfactant. 5. An ink jet recording method using the ink for ink jet recording according to claim 1. 6. The ink jet recording ink according to claim 1, which is formed on a surface of an image receiving material of an image receiving material having an image receiving layer containing fine white inorganic pigment particles on a support through a nozzle. An ink jet recording method, wherein an ink image is formed on the image receiving layer by ejecting in accordance with a recording signal.