JP2002080759A - Ink composition for ink jet printing and method for ink jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for ink jet printing, excellent in handleability, odor, safety or the like, having high issue stability after the lapse of long period of time under severe conditions, giving images of good hue, light stability and water resistance, having no image defect such as fine line blotting and improved in image preservability under severe conditions. SOLUTION: This ink composition for ink jet printing is obtained by including a water-soluble azo dye of general formula I [X is an electron-withdrawing group having >=0.20 Hammett's substituent constant σp; R1 to R6, Y, Z1 and Z2 are each independently H, a halogen or a (substituted) organic group; A is a group of nonmetal atoms required for forming a five to eight-membered ring and the ring may be a saturated ring or may have unsaturated bond] and a water-miscible organic solvent, and the ink composition for ink jet printing also contains dispersed polymeric microparticles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for ink jet recording, which has high image quality, excellent storage stability, and excellent ejection stability, and an ink jet recording method using the same.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink-jet printers have been used not only in offices but also at home as paper,
It is widely used for printing on films, cloths and the like.
Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, or a method in which droplets are applied by electrostatic force. There is a method of sucking and discharging. As these inkjet recording inks,
Water-based ink, oil-based ink, or solid (melt-type) ink is used. Among these inks, aqueous inks are predominant in terms of production, handling, odor, safety, and the like.

The colorants (dyes and pigments) used in these inks for ink jet recording have high solubility in solvents, enable high-density recording, have good hue, It has excellent fastness to heat, air, water and chemicals, has good fixability to the image receiving material and does not easily spread, has excellent storage stability as ink, has no toxicity, and has high purity. Furthermore, it is required that it be available at low cost. However, it is extremely difficult to search for a coloring agent that satisfies these requirements at a high level. In particular, a colorant having a good magenta hue and excellent light fastness is strongly desired.

[0004] Various dyes and pigments have already been proposed and actually used for ink jet. However, at present, a colorant satisfying all requirements has not been found yet. With well-known dyes and pigments to which a color index (CI) number is assigned, it is difficult to achieve both the hue and the fastness required for an ink for ink jet recording. As a dye for improving fastness, an azo dye derived from an aromatic amine and a 5-membered heterocyclic amine described in JP-A-55-161856 has been proposed. However, these dyes have unfavorable hues in the yellow and cyan regions, and thus have a problem of deteriorating color reproducibility. JP-A-61-36362 and JP-A-2-221566.
In each publication, an ink jet recording ink containing a water-soluble pyrazolylazo dye for the purpose of achieving both hue and light fastness is disclosed. However, the dyes used in each publication have insufficient improvement in hue, and when used as a water-soluble ink, have insufficient solubility in water. Further, when the dyes described in the respective publications are used as water-soluble inks for ink jet, there is a problem in fastness to wet heat. As means for solving these problems, JP-A-11-504958 proposes, in addition to the same dye structure as described above, a compound containing an interactive group and an ink composition. However, it has been found that all of these inks for ink jet recording have poor hues, and image deterioration may occur under severe conditions such as long-term storage at a high temperature.
The image deterioration under such severe conditions is particularly remarkable in the image receiving paper containing the white inorganic pigment in the image receiving layer, and the reaction with the white inorganic pigment itself and the gas adsorbed on the white inorganic pigment other than the deterioration reaction due to heat. It is estimated that there is an effect of the components.

[0005]

Accordingly, an object of the present invention is to provide a water-based ink having advantages in handling, odor, safety, etc., which has high ejection stability, and furthermore, the hue and light fastness of the obtained image. An object of the present invention is to improve the image storability under severe conditions without excellence in image quality, such as excellence in water resistance and water resistance, and without defects such as blurring of fine lines. It is still another object of the present invention to provide an inkjet ink composition having high ejection stability even for an ink that has been maintained for a long period of time or under severe conditions.

[0006]

The above object has been attained by the following inventions. (1) In an ink composition for ink jet recording containing at least a water-soluble dye and a water-soluble organic solvent, the water-soluble dye is an azo dye represented by the following general formula (I), and further contains a polymer fine particle dispersion. An ink composition for ink-jet recording, comprising:

[0007]

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(In the general formula (I), X represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group. , Nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl Group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl Group, phosphoryl group, acyl group Or an ionic hydrophilic group,
R ₁ and R ₂ , R ₃ and R ₁ , and R ₂ and R ₅ may be bonded to each other to form a ring. Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, and an alkoxy group. Group, aryloxy group, amide 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, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, Represents a phosphoryl group, an acyl group, or an ionic hydrophilic group. A is
Represents a group of non-metallic atoms necessary to form a 5- to 8-membered ring,
May be a saturated ring or may have an unsaturated bond, at least three of the non-metallic atoms forming A are substituted with N atoms of the pyrazole ring, Z ₁ and Z ₂ respectively; The atom substituted with the N atom of the pyrazole ring is adjacent to both the Z ₁ and Z ₂ substituted atoms. Where R ₁ , R ₂ ,
At least one of R ₃ , R ₄ , R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. (2) In (1), an ink composition for inkjet recording, wherein the average particle size of the polymer fine particle dispersion is 1 μm or less. (3) In (1) or (2), the solid content of the polymer fine particle dispersion in the ink is 0.05 to 30% by mass.
The use of an ink composition for inkjet recording characterized by the following.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Here, the Hammett's substituent constant σ _p value used in the present specification will be described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constants determined by Hammett's rule include σ _p and σ _m values, and these values can be found in many general books. For example, JADean, “Lange's Ha
ndbook of Chemistry ", 12th edition, 1979 (Mc Gra
w-Hill) and “Chemical Field”, No. 122, 96-1
See page 03, 1979 (Nankodo). In the present invention, each substituent is limited or described by Hammett's substituent constant σ _p, but this is limited to only those substituents having a value known in the literature, which can be found in the above-mentioned books. Not to mention the meaning, but it goes without saying that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I) of the present invention is not a benzene derivative, the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. Hereinafter, in the present invention, σ _p
The value is used in this sense.

The ink jet recording ink of the present invention contains the compound represented by the above general formula (I). Hereinafter, the azo dye represented by formula (I) of the present invention will be described in detail.

[0011]

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In the general formula (I), X is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, it is 0.30 or more electron-withdrawing group.
The upper limit is an electron-withdrawing group of 1.0 or less. Specific examples of X which is an electron-withdrawing group having a σ _p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkyl phosphono group. Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide group, Halogenated alkyloxy group, halogenated aryloxy group,
A halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more, a heterocyclic group, a halogen atom, an azo group,
Or a selenocyanate group.

The group in which X may further have a substituent may further have the following substituents. Halogen atom (for example, chlorine atom, bromine atom), carbon number 1
~ 12 linear or branched alkyl groups (e.g. methyl,
Ethyl, propyl, isopropyl, t-butyl), an aralkyl group having 7 to 18 carbon atoms (eg, benzyl, phenethyl), an alkenyl group having 2 to 12 carbon atoms (eg, vinyl, allyl), A chain or branched alkynyl group (e.g., ethynyl, 1-butynyl), a linear or branched cycloalkyl group having 3 to 12 carbon atoms (e.g., cyclopropyl, cyclohexyl), a carbon number of 3 to 1
Two linear or branched cycloalkenyl groups (eg, cyclopentenyl, cyclohexenyl), aryl groups (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups ( For example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-
Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxyl group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy Groups (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg, acetamido, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino,
-Chloroanilino, a ureido group (e.g., 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-toluenesulfonamide), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, , N-succinimide, N-phthalimime),
Heterocyclic thio group (for example, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), a sulfinyl group (eg, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl) , An acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl) and the like.

X As a preferable one, a compound having 2 to 2 carbon atoms
An acyl group having 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, a cyano group, and a nitro group , Having 1 to 1 carbon atoms
2, an alkylsulfinyl group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms, carbon A halogenated alkyl group having 1 to 12 carbon atoms, a halogenated alkyloxy group having 1 to 12 carbon atoms, a halogenated alkylthio group having 1 to 12 carbon atoms, a halogenated aryloxy group having 7 to 18 carbon atoms, 2
An aryl group having 7 to 18 carbon atoms substituted with one or more σ _p 0.20 or more other electron-withdrawing groups, and a 5- to 8-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom, and having 1 carbon atom
To 18 heterocyclic groups. More preferably, an alkyloxycarbonyl group having 2 to 12 carbon atoms,
A nitro group, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms. Particularly preferred as X are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and the most preferred is a cyano group.

In the general formula (I), R ₁ , R ₂ , R
₃ , R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Amino group, alkylamino group,
Alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl A heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group,
Represents a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, an ureido group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group and an alkoxycarbonyl group are particularly preferred. .

Examples of the halogen atom represented by R _{1 to} R ₆ and Y include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by R _{1 to} R ₆ and Y includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group has 1 to 1 carbon atoms.
Twelve alkyl groups are preferred. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t
-Butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

Examples of the cycloalkyl group represented by R _{1 to} R ₆ and Y include a substituted cycloalkyl group and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group represented by R _{1 to} R ₆ and Y includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl groups represented by R _{1 to} R ₆ and Y include:
Examples include an aryl group having a substituent and an unsubstituted aryl group. The aryl group has 7 carbon atoms.
~ 12 aryl groups are preferred. Examples of the substituent include:
Examples include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic groups represented by R _{1 to} R ₆ and Y include:
Examples include a substituted heterocyclic group and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include:
A 2-pyridyl group, a 2-thienyl group and a 2-furyl group.

The alkylamino group represented by R _{1 to} R ₆ and Y includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by R _{1 to} R ₆ and Y includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.

The aryloxy group represented by R _{1 to} R ₆ and Y includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group and an o-methoxyphenoxy group.

The amide group represented by R _{1 to} R ₆ and Y includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamido group, a propionamido group, a benzamido group, and a 3,5-disulfobenzamido group.

The arylamino groups represented by R _{1 to} R ₆ and Y include an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido groups represented by R _{1 to} R ₆ and Y include:
Examples include a ureido group having a substituent and an unsubstituted ureido group. The ureido group has 1 carbon atom.
~ 12 ureido groups are preferred. Examples of the substituent include:
Examples include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino groups represented by R _{1 to} R ₆ and Y include a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino.

The alkylthio groups represented by R _{1 to} R ₆ and Y include an alkylthio group having a substituent and an unsubstituted alkylthio group. As the alkylthio group,
An alkylthio group having 1 to 12 carbon atoms is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio groups represented by R _{1 to} R ₆ and Y include an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include:
Examples include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R _{1 to} R ₆ and Y includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide groups represented by R _{1 to} R ₆ and Y include a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide groups include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by R _{1 to} R ₆ and Y includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by R _{1 to} R ₆ and Y includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include:
And an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Examples of the sulfonyl group represented by R _{1 to} R ₆ and Y include a methanesulfonyl group and a phenylsulfonyl group.

The alkoxycarbonyl group represented by R _{1 to} R ₆ and Y includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group has 2 to 2 carbon atoms.
Twelve alkoxycarbonyl groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R _{1 to} R ₆ and Y includes a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5- or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by R _{1 to} R ₆ and Y includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy groups represented by R _{1 to} R ₆ and Y include an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms.
Examples of the substituent include an ionic hydrophilic group.
Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by R _{1 to} R ₆ and Y includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy groups represented by R _{1 to} R ₆ and Y include a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by R _{1 to} R ₆ and Y includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group,
An aryloxycarbonyl group having 7 to 12 carbon atoms is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include:
A phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R _{1 to} R ₆ and Y includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide groups represented by R _{1 to} R ₆ and Y include an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimido group and an N-succinimido group.

The heterocyclic thio group represented by R _{1 to} R ₆ and Y includes a substituted heterocyclic thio group and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5- or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The sulfinyl groups represented by R _{1 to} R ₆ and Y include a substituted sulfinyl group and an unsubstituted sulfinyl group. Examples of the sulfinyl group include phenylsulfinyl.

The phosphoryl group represented by R _{1 to} R ₆ and Y includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl groups represented by R _{1 to} R ₆ and Y include an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic groups represented by R _{1 to} R ₆ and Y include a carboxyl group, a sulfo group, and a quaternary ammonium group. As the ionic hydrophilic group,
A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. The carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). ).

In the general formula (I), R ₁ and R ₂ , R
Each of ₃ and R ₁ , R ₅ and R ₂ may form a ring. Preferred examples for forming a ring are shown below.

[0052]

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In the general formula (I), A is 5 to 8
Represents a group of non-metallic atoms necessary for forming a membered ring (hereinafter, the ring represented by A may be referred to as “ring A”). Ring A
May be a saturated ring or may have an unsaturated bond. The non-metallic atom group is preferably a group of one or more selected from a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and particularly preferably only a carbon atom.

The ring A includes, for example, benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, piperazine ring, oxane ring, and thiane ring. Among them, the group which can have a substituent may be further substituted with the groups exemplified as the substituents R _{1 to} R ₆ , Y and Z _{1 to} Z ₂ .

At least three of the nonmetallic atoms forming the ring A are the N atoms of the pyrazole ring, Z ₁ and Z ₂
And the atom substituted by the N atom of the pyrazole ring is adjacent to both the Z ₁ and Z ₂ substituted atoms.

The ring A is preferably a benzene ring,
In particular, a benzene ring substituted with an ionic hydrophilic group (which may be substituted by the aforementioned substituent) at the 4-position to the N atom of the pyrazole ring other than the N atom of the pyrazole ring and Z ₁ and Z ₂ is particularly preferable. preferable.

In the general formula (I), Z ₁ and Z ₂
Is independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an alkoxy group, an aryloxy group Amide 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, It represents an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Among them, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group and ionic hydrophilic group Are particularly preferable, and a halogen atom, an alkyl group and an alkoxy group are particularly preferable, and a halogen atom is most preferable.

For each group represented by Z ₁ and Z ₂ , R ₁
And the same as the respective groups represented by R ₆ and Y, and the preferred ranges are also the same.

Among the azo dyes represented by the general formula (I), an azo dye having a structure represented by the following general formula (II) is preferable. Hereinafter, the azo dye represented by formula (II) of the present invention will be described in detail.

[0061]

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In the general formula (II), X, Y,
Z₁, Z_Two, R₁, R_Two, R_Three, R_Four, R_Five, R₆Is the general
X, Y, Z in the formula (I)₁, Z_Two, R₁, R_Two, R_Three, R_Four,
R_Five, R ₆Synonymous with X, Y, and Z₁, Z_Two, R
₁, R_Two, R_Three, R_Four, R_Five, R₆Is the same.

In the general formula (II), Z ₃ , Z ₄ and Z ₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group , Carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonyl, aryloxycarbonylamino, imide, heterocyclic thio , Sulfinyl group, phos Lil group, an acyl group or an ionic hydrophilic group.

Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, an ureido group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and an ionic group Hydrophilic groups are particularly preferred.

Specific examples of Z ₃ , Z ₄ and Z ₅ include the substituents R _{1 to} R ₆ in the general formula (I) and the groups described above for Y.

More preferably, Z ₃ and Z ₅ are a hydrogen atom, a halogen atom and an alkyl group, and among them, a hydrogen atom is particularly preferred.

More preferably, Z ₄ is 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, an alkoxycarbonyl group and an ionic group. A hydrophilic group is particularly preferable, and among them, a hydrogen atom, an alkyl group, and an ionic hydrophilic group are particularly preferable, and an ionic hydrophilic group is most preferable.

Particularly preferred combinations of the substituents for the azo dye represented by formula (II) of the present invention are: X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms,
To 18 arylsulfonyl groups, particularly preferably a cyano group. Y is a hydrogen atom, an alkyl group, or an aryl group, and particularly a hydrogen atom. R ₁ and R ₂ are an alkyl group (which may have an ionic hydrophilic group as a substituent) or an aryl group (which may have an ionic hydrophilic group as a substituent).
R ₃ , R ₄ and R ₅ are hydrogen atoms, and R ₆ is an amide group (which may have an ionic hydrophilic group as a substituent). Z ₁ and Z ₂ are a halogen atom or an alkyl group. Z ₃ and Z ₅ are a hydrogen atom, a halogen atom, and an alkyl group, among which a hydrogen atom is particularly preferred. Z ₄
Is a hydrogen atom, a halogen atom, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an ionic hydrophilic group, and among them, an ionic hydrophilic group is particularly preferable.

As for the preferable combination of the substituents of the compound represented by the general formula (II), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and more various substituents are preferable. Is more preferable, and a compound in which all the substituents are the preferable groups is most preferable.

However, in the general formula (I), R
₁, R_Two, R_Three, R_Four, R_Five, R₆, X, Y, Z₁, Z_Twoand
At least one of A in the general formula (II)
Is R ₁, R_Two, R_Three, R_Four, R_Five, R₆, X, Y, Z₁,
Z_Two, Z_Three, Z_Four, And Z_FiveAt least one of the
Represents an ionic hydrophilic group or an ionic hydrophilic group as a substituent
Have In the general formula (I) and the general formula (II)
The azo dye represented has at least one ion in the molecule.
Dissolves in aqueous media because it has a hydrophilic group
Good dispersibility or property. R₁~ R₆, X, Y and
Z₁~ Z_FiveThe ionic hydrophilic group as a substituent of
Contains e-group, carboxyl group and quaternary ammonium
You. Of these, sulfo groups and carboxyl groups are preferred.
And a sulfo group is particularly preferred. Carboxyl group
The ruho group may be in the form of a salt,
Examples of ions include alkali metal ions (eg, sodium ions).
And potassium ions) and organic cations (eg, tetra
Methylguanidium ion).

The azo dye represented by the general formula (II) is
More preferably, the structure is represented by the following general formula (III).

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In the general formula (III), X, Y, Z ₁ ,
Z ₂ , Z ₄ , R ₁ , R ₂ and R ₆ have the same meanings as X, Y, Z ₁ , Z ₂ , Z ₄ , R ₁ , R ₂ and R _{6 in} formula (II), Preferred examples are also the same.

Among the azo dyes represented by formula (III), particularly preferred combinations of substituents include X
Is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms,
An arylsulfonyl group having 6 to 18 carbon atoms is particularly preferable, and a cyano group is particularly preferable. Y is a hydrogen atom, an alkyl group or an aryl group, and among them, a hydrogen atom is particularly preferred. R ₁ and R ₂ are an alkyl group (which may have an ionic hydrophilic group as a substituent) or an aryl group (which may have an ionic hydrophilic group as a substituent). R ₆ is an amide group (which may have an ionic hydrophilic group as a substituent). Z ₁ and Z ₂ are a halogen atom or an alkyl group. Z ₄ is a hydrogen atom, a halogen atom, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an ionic hydrophilic group, of which an ionic hydrophilic group is particularly preferable.

As for the preferred combination of the substituents of the compound represented by the general formula (III), a compound in which at least one of the various substituents is the above-mentioned preferable group is preferable. Is more preferable, and a compound in which all the substituents are the preferable groups is most preferable.

Specific examples of the azo dyes represented by the formulas (I) and (II) (exemplified compounds 101 to 143)
Is shown below, but the azo dye used in the present invention is not limited to the following examples.

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The ink for ink jet recording 10 of the present invention
In 0 parts by mass, the content of the azo dye is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.
Further, the inkjet ink of the present invention may be used in combination with the azo dye, in order to obtain a full-color image or to adjust the color tone. Other dyes that can be used in combination include a yellow dye, a magenta dye, a cyan dye and a black dye, and specific examples thereof include the following.

The yellow dyes include, for example, phenols, naphthols, anilines, pyrazolones, pyridones, and open-chain active methylene compounds as phenols, naphthols, anilines, pyrazolones, and open-chain active methylene compounds; Azomethine dyes having compounds; for example, methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes, anthraquinone dyes and the like; other dyes include quinophthalone dyes; Examples include nitro / nitroso dyes, acridine dyes, and acridinone dyes. These dyes may be those that exhibit a yellow color only after a part of the chromophore dissociates, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, Organic cations such as quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.

Examples of magenta dyes include aryl or hetenylazo dyes having phenols, naphthols and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes and styryl Methine dyes such as dyes, merocyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; And condensed polycyclic dyes. These dyes may exhibit magenta only after a part of the chromophore is dissociated, and in that case, the counter cation may be an alkali metal or an inorganic cation such as ammonium, or pyridinium, Organic cations such as quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.

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; and carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye Dyes; Phthalocyanine dyes; Anthraquinone dyes; Examples of the coupling component include aryl or hetenylazo dyes having phenols, naphthols, and anilines, and indigo / thioindigo dyes. These dyes may be those that exhibit cyan only after a part of the chromophore dissociates, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, Organic cations such as quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used. Also, a black dye such as a polyazo dye can be used.

The polymer fine particle dispersion in the present invention is a product prepared by a so-called emulsion polymerization method using a vinyl monomer, in which a polymer is dispersed in an aqueous medium in a fine particle state (sometimes called a polymer latex). In order to improve the hue when forming an image by the inkjet recording method and to improve the printing performance (prevention of nozzle clogging and ejection distortion), the particle diameter of the dispersed particles is preferably 1 μm or less in volume average particle diameter. , More preferably 0.001 to 1 μm, particularly preferably 0.01 to 1 μm.
0.5 μm.

The methods for measuring the volume average particle diameter and the particle size distribution of the dispersed particles include static light scattering method, dynamic light scattering method, centrifugal sedimentation method and the methods described in Experimental Chemistry Course, 4th edition, pp. 417-418. It can be easily measured by a known method, for example, by using a known method. For example, dilution with distilled water so that the particle concentration in the ink is 0.1 to 1% by mass,
It can be easily measured with a commercially available volume average particle size analyzer (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Further, the dynamic light scattering method using the laser Doppler effect is particularly preferable because the particle size can be measured down to a small size. The volume average particle size is the average particle size weighted by the particle volume, and is obtained by dividing the sum of the diameters of the individual particles multiplied by the volume of the particles in the aggregate of the particles by the total volume of the particles. The volume average particle diameter is described in “Chemistry of Polymer Latex” (published by Soichi Muroi, Polymer Publishing Association), page 119.

The structure of the polymer constituting the polymer latex can be a homopolymer of any monomer selected from the group of monomers shown below as typical examples or a copolymer of any combination thereof. There is no particular limitation on the monomer unit that can be used, and any monomer unit can be used as long as it can be polymerized by a usual radical polymerization method.

Monomer group olefins: ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, cyclopentadiene, 4-pentenoic acid, 8-nonenoic acid methyl, vinylsulfonic acid, trimethylvinylsilane , Trimethoxyvinylsilane, pentadiene, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane and the like.

Α, β-unsaturated carboxylic acids and salts thereof: acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate and the like.

Derivatives of α, β-unsaturated carboxylic acids: alkyl acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylates (eg, 2-chloro Ethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, allyl acrylate, etc., alkyl methacrylate (for example,
Methyl methacrylate, butyl methacrylate, 2-
Ethylhexyl methacrylate, dodecyl methacrylate, etc., substituted alkyl methacrylate (for example, 2-
Hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, ω-
Methoxy polyethylene glycol methacrylate (addition mole number = 2 to 100), polyethylene glycol monomethacrylate (addition mole number of polyoxyethylene = 2 to 100), polypropylene glycol monomethacrylate (addition mole number of polyoxypropylene = 2) To 100), 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, etc.) and unsaturated dicarboxylic acid derivatives (for example, monobutyl maleate). Dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.) and polyfunctional esters (eg, ethylene glycol diacrylate, ethylene glycol) Methacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2,4-cyclohexane Tetramethacrylate).

Amides of α, β-unsaturated carboxylic acids: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-
Methyl-N-hydroxyethyl methacrylamide, N-
tert-butylacrylamide, N-tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetoneacrylamide, itaconic diamide, N-methylmaleimide , 2-acrylamide-
Styrene and its derivatives such as 2-methylpropanesulfonic acid, methylenebisacrylamide and dimethacryloylpiperazine: styrene, vinyltoluene, p-ter
t-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, α-methylstyrene, p-chloromethylstyrene, vinylnaphthalene, p-hydroxymethylstyrene, sodium p-styrenesulfonate, potassium p-styrenesulfinate, 1 , 4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester and the like.

Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether and the like. Vinyl esters: vinyl acetate, vinyl propionate,
Vinyl benzoate, vinyl salicylate and vinyl chloroacetate. Other polymerizable monomers: N-vinylpyrrolidone, 2-vinyloxazoline, 2-isopropenyloxazoline,
Divinyl sulfone and the like.

The polymer preferably selected from the polymer fine particle dispersion of the present invention synthesized by copolymerization of these monomers is mainly composed of acrylic / methacrylic resin, styrene resin, conjugated diene resin, vinyl acetate resin, It is composed of a homopolymer or a copolymer such as a polyolefin resin. Among these, polymers having an ethylenically unsaturated group in the main chain or side chain, that is, monomers having conjugated dienes or at least two non-conjugated ethylenically unsaturated groups, and having different polymerizabilities of the respective unsaturated groups. Is more preferably a polymer having at least one of the following as a constituent monomer component, and particularly preferably a polymer having a conjugated diene as a constituent component.

The above-mentioned preferred monomers having at least two types of non-conjugated ethylenically unsaturated groups and having different polymerizabilities of the unsaturated groups include allyl acrylate, allyl methacrylate, N-allyl acrylamide, N-allyl methacrylamide and the like can be mentioned. Specific examples of the conjugated diene monomer which is a particularly preferred monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, and 2-n-propyl-1,3-butadiene. , 2,
3-dimethyl-1,3-butadiene, 2-methyl-1,
3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-
Naphthyl-1,3-butadiene, 2-chloro-1,3-
Butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene,
2,3-dichloro-1,3-butadiene, 1,1,2-
Trichlorol 1,3-butadiene and 2-cyano 1,
Examples thereof include 3-butadiene, 1,4-hexadiene, cyclopentadiene, and ethylidene norbornene.

Specific examples of the preferred polymer fine particle dispersion of the present invention are shown below, but the present invention is not limited thereto. Here, unless otherwise specified, the numerical value indicating the composition ratio of each monomer represents a mass percentage.

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[Table 1]

These polymer fine particle dispersions may be used alone or, if necessary, in combination of two or more.

The emulsion polymerization method used for synthesizing the polymer fine particle dispersion of the present invention will be described below.
The emulsion polymerization method uses at least one emulsifier in water or a mixed solvent of water and a water-miscible organic solvent (eg, methanol, ethanol, acetone, etc.) in an amount of 5 to 150% by mass based on the dispersion medium. Of the monomers is emulsified using 0.1 to 20% by weight of the emulsifier with respect to the monomers and 0.02 to 5% by weight of the monomers with the radical polymerization initiator, generally at 30 ° C to about 1%.
It is carried out with stirring at a temperature of 00 ° C., preferably 40 ° C. to 90 ° C. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

Examples of the polymerization initiator include azobis compounds, peroxides, hydroperoxides, redox catalysts and the like. For example, inorganic peroxides such as potassium persulfate and ammonium persulfate, t-butyl peroctoate,
Organic peroxides such as benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, 2,2′-azobisisobutyrate, 2, 2'-
Sodium salt of azobiscyanovaleric acid, 2,2′-azobis (2-amidinopropane) hydrochloride,
2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl ) -2-hydroxyethyl] propionamide} and the like. Of these, potassium persulfate and ammonium persulfate are particularly preferred.

As the emulsifier, anionic, cationic and
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. Specific examples thereof include sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyl Examples thereof include trimethylammonium chloride, N-2-ethylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, an emulsifier described in JP-B-53-6190, and a water-soluble polymer.

In the emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed. In addition, the emulsion polymerization reaction may be carried out by putting a monomer, a surfactant, and an aqueous medium in advance in a reaction vessel in a total amount and adding an initiator, or, if necessary, any of a monomer and an initiator solution,
Alternatively, it may be carried out while dropping part or all of the two. The latex of the present invention can be easily synthesized by using a usual emulsion polymerization method. The general method of emulsion polymerization is detailed in the following books. "Synthetic Resin Emulsion (Edited by Tadashi Okuda and Hiroshi Inagaki, published by Polymer Publishing Association (1978))", "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Published by Polymer Publishing Association (1993)" ) ”,“ Synthesis of Synthetic Latex (Souichi Muroi, Published by The Society of Polymer Publishing (1970)) ”. In the present invention, the preferable range of the solid content of the polymer fine particle dispersion in the ink is 0.05 to 30% by mass, more preferably 0.1 to 10% by mass.

The ink composition for ink jet recording of the present invention can be prepared by dissolving and / or dispersing the above water-soluble dye or polymer fine particle dispersion 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-soluble organic solvent to which additives such as a wetting agent, a stabilizer, and a preservative are added as necessary. Methods for preparing aqueous ink compositions for inkjet recording are described in JP-A-5-148436, JP-A-5-295121, JP-A-7-97541, and JP-A-7-82.
The details are described in JP-A Nos. 515 and 7-118584, and can be used for preparing the ink composition for inkjet recording of the present invention.

Examples of water-soluble organic solvents which can be used in the present invention include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol).
Butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentane Diol, 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). The water-miscible organic solvent may be used in combination of two or more.

When the ink composition for ink-jet recording obtained in the present invention is used as an ink for ink-jet recording, an anti-drying agent for preventing clogging due to a dry operation at an ink ejection port, and an ink using a paper. Penetration enhancers, UV absorbers, antioxidants, viscosity modifiers, surface tension regulators, dispersants, dispersion stabilizers, fungicides, rust inhibitors, pH regulators, defoamers, chelates for good penetration An additive such as an agent can be appropriately selected and used in an appropriate amount.

As the anti-drying agent used in the present invention, a water-soluble organic solvent having a lower vapor pressure than water is preferable. 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, etc., 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-ethylmorpholine And the like, a sulfur-containing compound such as sulfolane, dimethyl sulfoxide and 3-sulfolene, a polyfunctional compound such as diacetone alcohol and diethanolamine, and a urea derivative. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-mentioned drying inhibitors may be used alone or in combination of two or more. These anti-drying agents are preferably contained in the ink in an amount of 10 to 50% by mass.

As the penetration enhancer used in the present invention, ethanol, isopropanol, butanol, di (tri)
Alcohols such as ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate and nonionic surfactants can be used. These have sufficient effects when contained in the ink in an amount of 10 to 30% by mass, and are preferably used within the range of an addition amount that does not cause printing bleeding or paper loss (print-through).

The ultraviolet absorber used in the present invention to improve the storability of an image is disclosed in JP-A-58-1856.
Nos. 77, 61-90537 and JP-A-2-
No. 782, No. 5-1970075, No. 9-34
Benzotriazole compounds described in JP-A-557 / 057, JP-A-46-2784, JP-A-5-1944
No. 83, U.S. Pat. No. 3,214,463, benzophenone-based compounds described in JP-B-48-30492, JP-B-56-21141, and JP-A-10-881.
No. 06, etc., cinnamic acid-based compounds,
298503, 8-53427 and 8-
Nos. 339368, 10-182621, and JP-A-8-501291, and the like. 2423
Compounds described in No. 9 and compounds that absorb ultraviolet rays and emit fluorescence, typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents can also be used.

As the antioxidant used for improving the storability of an image in the present invention, various organic and metal complex-based antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes. More specifically, Research Disclosure No. VI of 17643
Nos. I through J of I. 15162; 18
No. 716, page 650, left column, ibid. 527 of 36544
Page, the same No. No. 307105, page 872; 151
Compounds described in the patents cited in JP-A-6-62
The compounds included in the general formulas and examples of the typical compounds described on pages 127 to 137 of JP-A-215272 can be used.

The fungicides used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazoline-3-
And its salts. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

The pH adjusting agent used in the present invention can be suitably used in terms of pH adjustment, dispersion stability imparting, etc., and is preferably added so as to have a pH of 4.5 to 10.0. More preferably, it is added so as to have a pH of 6 to 10.0. As the pH adjuster, organic bases as basic ones, inorganic alkalis and the like, organic acids as acidic ones,
And inorganic acids. Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.), and ammonia. In addition, examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.

The surface tension modifier used in the present invention includes nonionic, cationic and anionic surfactants. For example, anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer. SUR, an acetylene-based polyoxyethylene oxide surfactant
FYNOLS (Air Products & Chemic
als) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Japanese Patent Application Laid-Open
No. 9-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) may be used as the surfactant.
The surface tension of the ink of the present invention is preferably 20 to 60 mN / ms with or without these. Further, it is preferably 25 to 45 mN / m.

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

In the present invention, the above-mentioned various cationic, anionic and nonionic surfactants are used as dispersants and dispersion stabilizers, and fluorine-based, silicone-based compounds and EDs are used as defoamers.
A chelating agent represented by TA and the like can be used as needed.

The ink of the present invention is a known recording material, that is, plain paper or resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, and JP-A-7-276789. Gazette, pp. 9-323475
JP-A-62-238783, JP-A-10-153
Nos. 989, 10-217473, 10-
No. 235995, No. 10-337947, No. 10-217597, No. 10-337947, etc. Ink-jet dedicated paper, film, electrophotographic paper, fabric, glass, metal, ceramic, etc. It can be used to form images.

The recording paper and recording film used for ink-jet printing using the ink of the present invention will be described below. Supports for recording paper and film are chemical pulp such as LBKP and NBKP, GP, P
Consists of mechanical pulp such as GW, RMP, TMP, CTMP, CMP and CGP, waste paper pulp such as DIP, etc., and if necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, and paper strength And various additives such as a fourdrinier paper machine, a round paper machine, etc., into which an additive such as an agent is mixed can be used. In addition to these supports, any of synthetic paper and plastic film sheets may be used. The support has a thickness of 10 to 250 μm and a basis weight of 10 to 250 g / m.
² is preferred. An image receiving material may be provided by directly providing an ink receiving layer and a back coat layer on a support, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol, etc., and then providing an ink receiving layer and a back coat layer. It may be. Further, the support may be subjected to a flattening treatment by a calender device such as a machine calender, a TG calender, and a soft calender. In the present invention, as the support, both surfaces are polyolefin (eg,
Paper and plastic films laminated with polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine, neodymium oxide) to the polyolefin polyolefin.

In the ink receiving layer provided on the support,
Contains a pigment and an aqueous binder. As the pigment, a white pigment is good, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica,
Aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide,
Examples include inorganic white pigments such as zinc sulfide and zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and in particular, synthetic amorphous silica having a large pore area is preferable. As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, and it is particularly preferable to use hydrous silicic acid. Two or more of these pigments may be used in combination.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivative. Such as water-soluble polymers, styrene butadiene latex,
A water-dispersible polymer such as an acrylic emulsion can be used. 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 peel resistance of the ink receiving layer.

The ink receiving layer may contain a mordant, a water-proofing agent, a light fastness improving agent, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325 and JP-A-54-74430.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
Nos. 0-23851, 60-23852, 60-2
No. 3853, No. 60-57836, No. 60-6064
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236
Nos. 2,484,430 and 25,485.
Nos. 64, 3148061, 3309690, 4115124, 4124386, 41938
No. 00, No. 4,273,853, No. 4,282,305, and No. 4,450,224. JP 1
An image receiving material containing a polymer mordant described on pages 212 to 215 of 161236 is particularly preferred. By using the polymer mordant described in the publication, an image with excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant,
As these waterproofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, based on the total solid content of the ink receiving layer.
It is preferably 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone.
Of these, zinc sulfate is particularly preferred.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent. The surfactants are described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil), and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin).
About the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. (columns 8 to 17), JP-A No. 61-20994, 6
It is described in each gazette of 2-135826.

As the hardener, the materials described on page 222 of JP-A-1-161236 can be used.

Other additives to be added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners, and the like. Is mentioned. The ink receiving layer may be a single layer or two layers.

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

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin And water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the ink jet recording paper and the recording film. The polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Polymer fine particle dispersions are described in JP-A-62-245258 and JP-A-62-1.
It is described in the respective publications 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 and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer fine particle dispersion having a high glass transition temperature to the back layer.

The ink of the present invention is not limited to an ink jet recording method, and is a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method using vibration pressure of a piezo element ( Pressure-pulse method), acoustic ink-jet method in which an electric signal is converted into an acoustic beam to irradiate the ink to discharge ink using radiation pressure, and thermal ink-jet that heats the ink to form bubbles and uses the generated pressure (Bubble jet)
It is used for the method. The ink jet recording method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0136]

The present invention will be described below with reference to examples.
It is not limited to this.

(Example 1) Deionized water was added to the following components to make 1 liter.
Stir for hours. Then, at 10 mol / l of KOH, p
H was adjusted to 9 and filtered under reduced pressure through a micro filter having an average pore diameter of 0.25 μm to prepare an ink liquid for light magenta. Magenta dye in the specification (101) 3.75 g Diethylene glycol 150 g Urea 37 g Glycerin 130 g Triethylene glycol monobutyl ether 130 g Surfynol 465 (Air Products & Chemicals) 10.5 g Compound of the present invention Polymer fine particle dispersion P-1 30 g (as solid content) Ethanolamine 6.9 g Benzotriazole 0.08 g PROXEL XL2 3.5 g Magenta ink, light cyan ink, cyan ink, yellow ink, and black ink are prepared by changing the dye type and additives, and ink set 101 shown in Table 2 is made. did.

[0138]

[Table 2]

[0139]

Embedded image

[0140]

Embedded image

Next, for each of the light magenta, magenta, light cyan, cyan, yellow, and black inks of the ink set 101, the dye type and the type and amount of the polymer fine particle dispersion of the present invention were changed as shown in Table 3. 102-112. When the dyes were used in combination, they were used in equimolar amounts, and when the polymer fine particle dispersion of the present invention was used in combination, they were used in equal amounts. The volume average particle diameter of the polymer fine particle dispersion
As a result of measurement with PA (manufactured by Nikkiso Co., Ltd.), each was 0.2 μm or less.

[0142]

[Table 3]

[0143]

Embedded image

Next, these ink sets 101-112
To the inkjet printer PM770C (EPSON
And the image was printed on inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine, and the following evaluation was performed. 1) For printing performance, after setting the cartridge in the printer and confirming the protrusion of ink from all nozzles,
Sheets were output, and the printing disorder was evaluated. A: There is no printing disturbance from the start to the end of printing. B: Output with printing disturbance occurs. C: There is the printing disturbance from the printing start to the end. 2) The printing performance is as follows. Disorder of printing was evaluated by the same method as the printing performance. 3) Immediately after printing, the stainability when touching with a finger was evaluated visually. 4) Regarding bleeding of fine lines, yellow, magenta, cyan and black fine line patterns were printed and evaluated visually. As for black, after printing solid magenta ink, a black thin line was printed, and bleeding due to contact between two colors was also evaluated. 5) Regarding water resistance, the obtained image was immersed in deionized water for 5 seconds, and then the blur of the image was visually evaluated. 6) Regarding image storability, print samples of yellow, magenta, cyan and black were prepared and evaluated as follows. Light fastness is determined by setting the image density Ci immediately after printing to X-rite 31.
After the measurement at 0, the image was irradiated with xenon light (85,000 lux) for 8 days using an Atlas weather meter, and the image density Cf was measured again to determine and evaluate the residual dye ratio Cf / Ci * 100. Was done. The reflection density is 1
The evaluation was performed at three points of 1.5 and 2, and A was obtained when the dye remaining ratio was 70% or more at any concentration, B was obtained when the point was less than 70%, and B was obtained when the concentration was less than 70% at all concentrations. C. Regarding the heat fastness, the concentration before and after the sample was stored for 10 days under the condition of 80 ° C. was measured with an X-rite 310, and the residual ratio of the dye was determined and evaluated. The reflection density is 1
The evaluation was performed at three points of 1.5 and 2, where the residual ratio of the dye was 80% or more at any concentration, A: when the point was less than 80%, B: when the percentage was less than 80%, and when it was less than 80% at all concentrations. C.

[0145]

[Table 4]

[0146]

[Table 5]

It can be seen that when the ink composition of the present invention is used, excellent ejection stability can be obtained, and that the ink composition exhibits excellent performance in terms of water resistance and fastness (in particular, heat fastness). In addition, the ink composition of the present invention is excellent in the performance of outputting fine lines without blurring. It should be noted that the same effects as those described above can be obtained even when the image receiving paper used in the present invention is changed to PM photo paper manufactured by EPSON and PR101 manufactured by Canon.

(Example 2) The same ink produced in Example 1 was applied to an ink jet printer BJ-F850 (CA
NON Corporation), the image was printed on Fuji Photo Film inkjet paper photo glossy paper EX by the same machine, and the same evaluation as in Example 1 was performed. The same result as in Example 1 was obtained. Was done. In addition, the receiving paper is PM photo paper manufactured by EPSON, PR1 manufactured by Canon.
In the case of 01, the same effect was obtained.

[0149]

According to the present invention, an ink jet recording ink having excellent ejection stability, high light fastness, little bleeding, and capable of forming an image with little deterioration even under severe conditions (excellent weather resistance). And an ink jet recording method.

 ────────────────────────────────────────────────── ─── Continued on front page F term (reference) 2C056 EA13 FC01 FC02 2H086 BA52 BA56 BA62 4J039 AD01 AD02 AD03 AD04 AD05 AD08 AD09 AD10 AD12 AD13 AD14 AD15 AD16 AD22 AD23 BA29 BC05 BC12 BC16 BC19 BC20 BC29 BC31 BC33 BC36 BC37 BC40 BC41 BC44 BC47 BC50 BC51 BC53 BC54 BC55 BC56 BC57 BC65 BC68 BC72 BC75 BC76 BC79 BE06 BE12 EA34 EA35 EA38 EA41 EA42 EA44 EA45 EA47 GA24

Claims (3)

[Claims] 1. An ink-jet recording ink composition containing at least a water-soluble dye and a water-soluble organic solvent,
An ink composition for ink jet recording, wherein the water-soluble dye is an azo dye represented by the following general formula (I), and further contains a polymer fine particle dispersion. Embedded image (In the general formula (I), X represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group , An alkylamino group,
Alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl A heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group,
Represents a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group; R ₁ and R ₂ , R ₃
And R ₁ , and R ₂ and R ₅ may combine with each other to form a ring. Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, and an alkoxy group. Group, aryloxy group, amide 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, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, or ionic hydrophilic Table . A represents a group of nonmetallic atoms necessary for forming a 5- to 8-membered ring, which may be a saturated ring or may have an unsaturated bond, and represents a group of nonmetallic atoms forming A. At least three of them are each substituted with a pyrazole ring N atom, Z ₁ and Z ₂ , and the atom substituted with the pyrazole ring N atom is adjacent to both the Z ₁ and Z ₂ substituted atoms. Where R ₁ , R ₂ , R ₃ , R ₄ ,
At least one of R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. ) 2. The ink composition for ink jet recording according to claim 1, wherein the average particle size of the polymer fine particle dispersion is 1 μm or less. 3. The ink composition for ink jet recording according to claim 1, wherein the solid content of the polymer fine particle dispersion in the ink is 0.05 to 30% by mass.