JP2002154201A - Method of recording ink jet image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of recording an ink jet image wherein ejection stability can be raised and there is any weak point in hue, weatherability, water resistance and image quality. SOLUTION: There is disclosed the method of recording an ink jet image wherein an ink composition for ink jet including a water-soluble dye and a polymer fine particle dispersion material is ejected on an image receiving material to form an image and then the image receiving material is heated to form a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet image recording method which has high quality of recorded images, excellent ejection stability, and excellent preservation of the obtained images.

[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. Various dyes and pigments have already been proposed and actually used for inkjet. 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 jet recording ink.

On the other hand, forming a film on an image surface
With colorant and water, oxygen, ozone, NO _xCut off contact with etc.
In addition, methods for improving the robustness are being studied. JP
7-237348 and JP-A-8-2090
Has a latex layer on the alumina hydrate layer,
After forming an image with ink on the sodium hydrate layer,
A method for coating a coating layer is described. But on
When the latex layer is heated to form a film by the method described above,
Ink or solvent remains in latex layer
Cracks occur in the coating, and weather resistance and water resistance
The problem that the property falls is arisen.

[0005]

Accordingly, the problem to be solved by the present invention is that the ejection stability is high, the hue, weather resistance,
An object of the present invention is to provide an ink jet image recording method free from defects in water resistance and image quality.

[0006]

The above object has been attained by the following invention. <1> An inkjet method comprising: discharging an inkjet ink composition containing a water-soluble dye and a polymer fine particle dispersion onto an image receiving material to form an image; and heating the image receiving material to form a coating. Image recording method. <2> The inkjet image recording method according to <1>, wherein the ink composition contains a water-soluble dye represented by the general formula (AI). General formula (AI)

[0007]

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In the formula, 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 group 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.

<3> The ink jet image recording method according to <1> or <2>, wherein the polymer fine particle dispersion has a glass transition temperature (Tg) of 40 to 160 ° C. <4> The inkjet image recording according to any one of <1> to <3>, wherein the solid content concentration of the polymer fine particle dispersion is 0.1 to 10% by mass relative to the ink composition. Method.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. -Water-soluble dye- 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, JA Dean, “Lange's
Handbook of Chemistry, 12th Edition, 1979 (Mc Gr
aw-Hill) and “Chemical Field”, No. 122, 96-1
See page 03, 1979 (Nankodo). In the present invention, each substituent is defined or described by Hammett's substituent constant σ _p value, but this is limited to only those substituents having a known value found in the above-mentioned books. This does not mean 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 (AI) 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, the σ _p value is used in such a meaning.

The ink for ink jet recording used in the present invention preferably contains the compound represented by the general formula (AI). Hereinafter, the azo dye represented by the general formula (AI) will be described in detail. General formula (AI)

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In the general formula (AI), X is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, it is a 0.30 to 1.0 electron-withdrawing group. 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 group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group,
Thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkyloxy group, halogenated alkylthio group, and other electron-withdrawing groups having a σ _p value of 0.20 or more And an aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group.

X may further have a substituent, and examples of the substituent include the following. A halogen atom (eg, chlorine atom, bromine atom), a linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl,
Propyl, isopropyl, t-butyl), having 7 to 1 carbon atoms
8 aralkyl groups (eg, benzyl, phenethyl);
An alkenyl group having 2 to 12 carbon atoms (for example, vinyl or allyl), a linear or branched alkynyl group having 2 to 12 carbon atoms (for example, ethynyl), a linear or branched cycloalkyl group having 3 to 12 carbon atoms ( For example, cyclopropyl, cyclohexyl), a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (eg, cyclopentenyl, cyclohexenyl), an aryl group (eg, phenyl, 4-t-)
Butylphenyl, 2,4-di-t-amylphenyl),
Heterocyclic group (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 group (for example, phenoxy, 2-methylphenoxy,
4-tert-butylphenoxy, 3-nitrophenoxy, 3
-T-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino group (for example, methylamino, butyl Amino, diethylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, ureido group (for example, phenylureide, methylureide, N, N-dibutylureido), sulfamoylamino group (for example,
N, N-dipropylsulfamoylamino), an alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), an arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenyl) Thio), an alkyloxycarbonylamino group (eg, methoxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N -Dibutylcarbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl), a sulfonyl group (eg, methanesulfonyl, octanesulfonyl, Zensulfonyl, toluenesulfonyl), alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (eg, , Phenylazo, 4-methoxyphenylazo, 4-
Pivaloylaminophenylazo, 2-hydroxy-4-
Propanoylphenylazo), acyloxy group (eg, acetoxy), 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-phthalimide), a heterocyclic thio group (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (For example, phenoxycarbonyl), an acyl group (for example, acetyl, 3
-Phenylpropanoyl, benzoyl) and the like.

X is preferably a compound having 2 to 1 carbon atoms.
2, 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 12 carbon atoms
Alkylsulfinyl group, an arylsulfinyl 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, 0 carbon atoms
To 12 sulfamoyl groups, halogenated alkyl groups having 1 to 12 carbon atoms, halogenated alkyloxy groups having 1 to 12 carbon atoms, halogenated alkylthio groups having 1 to 12 carbon atoms,
A halogenated aryloxy group having 7 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms substituted by two or more other electron-withdrawing groups having a σ _p value of 0.20 or more, and a nitrogen atom and an oxygen atom Or a 5- to 8-membered ring having 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 (AI), 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,
Aralkyl group, aryl group, heterocyclic group, 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 group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, 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, 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 groups represented by R _{1 to} R ₆ and Y include:
It includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms. 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
-Sulfobutyl.

The cycloalkyl group represented by R _{1 to} R ₆ and Y includes a cycloalkyl group having a substituent 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:
An aryl group having a substituent and an unsubstituted aryl group are included. The aryl group has 7 to 7 carbon atoms.
Twelve aryl groups are preferred. Examples of the substituent 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:
It includes 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 2-
Examples include a 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 groups represented by R _{1 to} R ₆ and Y include 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 3,
5-disulfobenzamide groups.

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:
It includes a substituted ureido group and an unsubstituted ureido group. The ureido group has 1 to 1 carbon atoms.
Twelve ureido groups are preferred. Examples of the substituent 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 group represented by R _{1 to} R ₆ and Y includes 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 an N, N-dipropylsulfamoylamino group.

The alkylthio groups represented by R _{1 to} R ₆ and Y include an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms. 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. As the arylthio group,
An arylthio group having 6 to 12 carbon atoms is preferred. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group 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 group 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 groups represented by R _{1 to} R ₆ and Y include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include 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 1 carbon atoms.
Two 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. As the acyloxy group,
An acyloxy group having 1 to 12 carbon atoms is preferred. 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. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms. 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 groups represented by R _{1 to} R ₆ and Y include a substituted heterocyclic thio group and an unsubstituted heterocyclic thio group. As the heterocyclic thio group,
It preferably has a 5- or 6-membered hetero 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 sulfinyl group having a substituent 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 preferable, and a sulfo group is particularly preferable. 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 (AI), R ₁ and R ₂ ,
R ₃ and R ₁ , and 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 (AI), A is 5 to
Represents a group of non-metallic atoms necessary to form an 8-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.

Examples of the ring A include a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a pyridine ring, a piperazine ring, an oxane ring, a thiane ring, a sulfolane ring, a thiazole ring and a benzothiazole. Ring, oxazole ring, benzoxazole ring, imidazole ring, benzimidazole ring, thiophene ring, furan ring, pyrrole ring, pyrimidine ring, pyrazine ring, triazine ring, pyridazine ring and the like. The group which can be possessed may be further substituted by the groups exemplified as the above 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, and an ionic hydrophilic group at the 4-position to the N atom of the pyrazole ring (in addition to the N atom, Z ₁ and Z ₂ of the pyrazole ring) A benzene ring substituted with a benzene ring.

In the general formula (AI), Z ₁ and Z
₂ is each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group,
Heterocyclic group, 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, alkoxy Carbonylamino 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, It represents 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 (AI), azo dyes having a structure represented by the following general formula (A-II) are preferable. The general formula (A-II) used in the present invention below
The azo dye represented by the formula is described in detail. General formula (A-
II)

[0061]

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In the general formula (A-II), X, Y, Z
₁, Z_Two, R₁, R_Two, R_Three, R_Four, R_Five, R₆Is the general formula
X, Y, Z in (A-I)₁, Z_Two, R₁, R_Two, R_Three, R_Four,
R_Five, R₆Synonymous with X, Y, and Z₁, Z_Two, R
₁, R_Two, R_Three, R_Four, R_Five, R ₆Is the same.

In the general formula (A-II), Z ₃ , Z ₄ and Z ₅ each independently represent a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, 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 group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy Represents 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, 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 (AI) 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. It is a hydrophilic group, and among them, a hydrogen atom, an alkyl group and an ionic hydrophilic group are particularly preferred, and an ionic hydrophilic group is most preferred.

Particularly preferred combinations of substituents for the azo dye represented by formula (A-II) used in 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 or an ionic hydrophilic group, and among them, an ionic hydrophilic group is particularly preferable.

In addition, as for the preferable combination of the substituents of the compound represented by the general formula (A-II), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable. Compounds in which the substituents are the preferred groups are more preferred, and compounds in which all the substituents are the preferred groups are most preferred.

However, in the general formula (AI),
At least _{one of} R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A. In the general formula (A-II), R ₁ , R _{2, R 3, R 4,} R 5, R 6, X, Y, Z 1,
At least one of Z ₂ , Z ₃ , Z ₄ and Z ₅ represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. The general formula (AI) and the general formula (AI
Since the azo dye represented by I) has at least one ionic hydrophilic group in the molecule, it has good solubility or dispersibility in an aqueous medium. R _{1 to} R ₆ , X, Y
And the ionic hydrophilic group as a substituent of Z _{1 to} Z ₅ include a sulfo group, a carboxyl group and a quaternary ammonium. Among them, a sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). Is mentioned.

The azo dye represented by formula (A-II) more preferably has a structure represented by the following formula (A-III). General formula (A-III)

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In the general formula (A-III), X, Y, Z ₁ , Z
₂ , Z ₄ , R ₁ , R ₂ and R ₆ represent X,
Each of Y, Z ₁ , Z ₂ , Z ₄ , R ₁ , R ₂ and R ₆ has the same meaning, and preferred examples are also the same.

Among the azo dyes represented by formula (A-III), particularly preferred combinations of substituents include
X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or an arylsulfonyl group having 6 to 18 carbon atoms, and 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 each} represent 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)
It is. 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,
They are 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.

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

The formula (AI) and the formula (A-II)
Specific examples of the azo dye represented by (Exemplified compounds 101 to 14)
3) is shown below, and the azo dye used in the present invention includes:
It is not limited to the following example.

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In 100 parts by mass of the ink composition for ink jet recording used in the present invention, the azo dye is contained in an amount of 0.2%.
It is preferably contained in an amount of from 20 to 20 parts by mass. Further, the ink composition for inkjet recording used in 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. Examples of dyes that can be used in combination 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 dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone; and dioxazine dyes And condensed polycyclic dyes. These dyes may be those that exhibit magenta 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 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; for example, aryl or hetenylazo dyes having phenols, naphthols, and anilines as coupling components; indigo / thioindigo dyes. These dyes may be those that exhibit cyan only after a part of the chromophore dissociates, and in that 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.

-Polymer fine particle dispersion-The polymer fine particle dispersion (polymer latex) used in the present invention is prepared by a so-called emulsion polymerization method using a vinyl monomer, and is obtained by dispersing a polymer in an aqueous medium into fine particles. It is.

In order to improve the hue when forming an image by the ink jet recording method and to improve the printing performance (prevention of nozzle clogging and ejection distortion), the particle diameter of the dispersed particles should be 0 in volume average particle diameter. 0.001 to 1 μm, and more preferably 0.01 to 0.5 μm.
The volume average particle size is an average particle size weighted by the particle volume, and is a value obtained by dividing the sum of the diameters of individual particles multiplied by the volume of the particles in the set of particles and dividing the total volume of the particles. The volume average particle size is described in "Chemistry of Polymer Latex" (published by Soichi Muroi, Polymer Publishing Association), page 119. The method of measuring the volume average particle size of the dispersed particles includes a static light scattering method, a dynamic light scattering method, a centrifugal sedimentation method, and a method described in Experimental Chemistry Course, 4th edition, pages 417 to 418. For example, it can be easily measured by a known method such as use. For example, the ink is diluted with distilled water so that the particle concentration in the ink becomes 0.1 to 1% by mass, and easily diluted with a commercially available volume average particle size analyzer (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Can be measured. Further, the dynamic light scattering method using the laser Doppler effect is preferable because the particle size can be measured down to a small size.

The structure of the polymer constituting the polymer fine particle dispersion may be a homopolymer of any monomer selected from the group of monomers shown below as typical examples or a copolymer obtained by freely combining them. 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 (a) Olefins: ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, cyclopentadiene, 4-pentenoic acid, methyl 8-nonenoate, vinyl sulfonic acid , Trimethylvinylsilane, trimethoxyvinylsilane, butadiene, pentadiene, isoprene, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane and the like.

(B) 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.

(C) Derivatives of α, β-unsaturated carboxylic acids: alkyl acrylates (for example, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylates (for example, 2-chloroethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, allyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, etc.), substituted alkyl methacrylate (eg, 2- Hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-
Acetoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (addition moles = 2 to 100), polyethylene glycol monomethacrylate (polyoxyethylene addition moles = 2 to 100) ), Polypropylene glycol monomethacrylate (polyoxypropylene having an added mole number of 2 to 100), 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate,
-Oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, etc.), derivatives of unsaturated dicarboxylic acids (eg, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.), polyfunctional esters (For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol Hexaacrylate, 1,2,4-cyclohexanetetramethacrylate, etc.)

(D) Amides of α, β-unsaturated carboxylic acids: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert Butylacrylamide, N-tert
Octyl methacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetoneacrylamide, itaconic diamide, N-methylmaleimide, 2-acrylamide-2- Methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine and the like.

(E) Styrene and its derivatives: styrene, vinyltoluene, p-tertbutylstyrene, vinylbenzoic acid, methyl vinylbenzoate, α-methylstyrene, p-chloromethylstyrene, vinylnaphthalene,
p-hydroxymethylstyrene, p-styrenesulfonic acid sodium salt, p-styrenesulfinic acid potassium salt, 1,4-divinylbenzene, 4-vinylbenzoic acid-
2-acryloyl ethyl ester and the like.

(F) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether and the like. (G) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate and vinyl chloroacetate. (H) Other polymerizable monomers: N-vinylpyrrolidone,
2-vinyloxazoline, 2-isopropenyloxazoline, divinylsulfone, and the like.

The polymer which is synthesized by copolymerization of these monomers and is preferably selected in the polymer fine particle dispersion used in the present invention is mainly composed of acrylic resin.
A methacrylic resin, a styrene resin, a conjugated diene resin, a vinyl acetate resin, a homopolymer or a copolymer of a polyolefin resin and the like, and among these, a polymer having an ethylenically unsaturated group in a main chain or a side chain, that is, a conjugated polymer. Dienes or polymers having at least two non-conjugated ethylenically unsaturated groups, and more preferably a polymer having at least one monomer having a different polymerizability of each unsaturated group as a constituent monomer component, are preferably conjugated dienes. Is particularly preferable.

The above-mentioned preferred monomers having at least two 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. Further, 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-diene. 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-
Trichloro-1,3-butadiene and 2-cyano-1,
Examples thereof include 3-butadiene, 1,4-hexadiene, cyclopentadiene, and ethylidene norbornene.

The following are specific examples of preferred polymer fine particle dispersions used in the present invention, but the present invention is not limited to these. Here, unless otherwise specified, the numerical value indicating the composition ratio of each monomer represents a mass percentage.

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

The emulsion polymerization method used for synthesizing the polymer latex of the present invention will be described below. The emulsion polymerization method uses at least one emulsifier and water or an organic solvent miscible with water (eg, methanol,
In a mixed solvent of ethanol, acetone, etc., about 5 to 150% by mass of the monomer with respect to the dispersion medium is emulsified using an emulsifier of 0.1 to 20% by mass with respect to the monomer. Using from 0.02 to 5% by weight of a radical polymerization initiator, generally from 30 ° C. to about 100 ° C., preferably 4 ° C.
The reaction is carried out at a temperature of 0 ° C. to 90 ° C. with stirring. 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, Sodium salt of 2′-azobiscyanovaleric acid, 2,2′-azobis (2-amidinopropane) hydrochloride,
2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis {2-methyl-N- [1,1'-bis (hydroxymethyl)- Azo compounds such as [2-hydroxyethyl] propionamide}. Among them, potassium persulfate,
Ammonium persulfate is 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, emulsifiers described in JP-B-53-6190, and water-soluble polymers.

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) ”. Particularly, those known as soap-free latex can also be preferably used.

As another example of the water-dispersible polymer fine particles that can be used in the present invention, a water-insoluble polymer having a dissociating group can be mentioned. The water-insoluble polymer containing a dissociating group refers to a polymer having an ionic dissociating group. The ionic dissociating group includes a cationic dissociating group such as a tertiary amino group and a quaternary ammonium group, and an anionic dissociating group such as carboxylic acid, sulfonic acid and phosphoric acid. Examples of the dissociative group-containing polymer include a vinyl polymer and a condensation polymer (polyurethane, polyester, polyamide, polyurea, polycarbonate). It is preferable that the water-insoluble polymer having a dissociating group is a polymer having water dispersibility, that is, self-emulsifying property.

Examples of the dissociating group contained in the dissociating group-containing vinyl polymer include a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, -OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, Na, K, etc.). Alkali metal salts, or ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine,
Anionic groups such as ammonium salts such as trimethylamine, or primary, secondary, tertiary amines, or salts thereof (eg, organic acids (eg, acetic acid, propionic acid,
Examples thereof include cationic groups such as methanesulfonic acid), inorganic acids (such as hydrochloric acid and sulfuric acid), and quaternary ammonium salts. Of these, anionic groups are preferable, and carboxyl groups are particularly preferable.

Examples of the monomer containing the carboxylic acid as a dissociating group include acrylic acid, methacrylic acid,
Itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl ester (for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc., and monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).

Examples of the monomer containing the sulfonic acid as a dissociating group include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc.), methacryloyloxy Alkylsulfonic acid (for example, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamidoalkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2 -Acrylamide-2-methylbutanesulfonic acid, etc.), methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-meth Riruamido -2, methyl propane sulfonic acid) and the like.

Examples of the monomer containing phosphoric acid as a dissociating group include monoacryloyloxyethyl phosphate and monomethacryloyloxyethyl phosphate.

Of these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable, and acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamide-2-acrylic acid are preferable. Methylpropanesulfonic acid and 2-acrylamido-2-methylbutanesulfonic acid are particularly preferred.

Examples of the monomer having a cationic dissociating group include dialkylaminoethyl methacrylate and dialkylaminoethyl acrylate.
Monomers having a quaternary ammonium group, and monomers having a quaternary ammonium group such as N-2-acryloyloxyethyl-N, N, N-trimethylammonium chloride and N-vinylbenzyl-N, N, N-triethylammonium chloride. No.

The above-mentioned monomer containing a dissociating group may be copolymerized with a monomer having no dissociating group, and the following monomers can be used as the monomer. That is, acrylic acid esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl Acrylate,
tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxy Ethyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, Glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 2,2,2-tetrafluoroethyl acrylate, H, IH, 2H, 2H-perfluoro-decyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, and the like.

Methacrylic esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate,
Lauryl methacrylate, stearyl methacrylate,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate,
Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl Methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-tetrafluoroethyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate, dioctyl-2-methacryloyl Oxyethyl phosphate and the like can be mentioned.

Vinyl esters, specifically, vinyl acetate, vinyl propionate, vinyl butyrate,
Examples include vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate.

Acrylamides, specifically, acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, tert-butylacrylamide, tert-
Octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxymethylacrylamide, butoxymethylacrylamide, methoxyethylacrylamide,
Examples include phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide, and the like.

Methacrylamides, specifically, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacryl Amide, methoxyethyl methacrylamide, phenyl methacrylamide, β
-Cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like.

Olefins, specifically, styrenes such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene; For example, styrene, methyl styrene,
Examples include dimethylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and methyl vinylbenzoate.

Vinyl ethers, specifically, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like can be mentioned.

Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl Ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N
-Vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene and the like.

It is also preferable to copolymerize a monomer containing a nonionic dispersing group as described below. Examples of such a monomer include an ester of a polyethylene glycol monoalkyl ether and a carboxylic acid monomer, Contains esters of polyethylene glycol monoalkyl ether and sulfonic acid monomer, esters of polyethylene glycol monoalkyl ether and phosphoric acid monomer, vinyl group-containing urethane formed from polyethylene glycol monoalkyl ether and isocyanate group-containing monomer, and polyvinyl alcohol structure Macromonomer and the like. The repeating number of the ethyleneoxy moiety of the polyethylene glycol monoalkyl ether is preferably from 8 to 50, and more preferably from 10 to 30. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably from 1 to 20, and more preferably from 1 to 12.

Next, the above-mentioned condensation group-containing condensation polymer will be described in detail. The dissociative group-containing polyurethane is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. Specific examples of the diol compound include, as non-dissociable diols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2,2-dimethyl -1,3-propanediol, 1,4-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol,
-Ethyl-2-methyl-1,3-propanediol,
1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2-
Diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-
2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 2,2,4
Trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 200 to 4000), polypropylene glycol (average molecular weight = 200) ~ 1000), polyester polyol, 4,4'-dihydroxydiphenyl-2,2
-Propane, 4,4'-dihydroxyphenylsulfone and the like.

Preferred examples of the diisocyanate include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylylene diisocyanate,
1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate)
And the like.

The dissociative group-containing polyurethane can be obtained, for example, by using a diol containing a dissociative group at the time of synthesizing the polyurethane. In that case, the dissociating group is introduced into the polyurethane as a substituent from the polymer backbone. As a diol having a dissociation group, particularly an anionic group,
2,2-bis (hydroxymethyl) propionic acid, 2,2
-Bis (hydroxymethyl) butanoic acid, 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid, 2,3-
Dihydroxy-4,5-dimethoxypentanoic acid, 3,5
-Di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid and salts thereof,
It is not particularly limited to these.

Examples of the dissociating group contained in the dissociating group-containing polyurethane include a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, —OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, Na, K and the like). Alkali metal salts,
Or an anionic group such as ammonium, dimethylamine, ethanolamine, diethanolamine, triethanolamine, and trimethylamine, or a cationic group such as primary, secondary, tertiary amine, and quaternary ammonium salts. Among them, an anionic group is preferable, and a carboxyl group is particularly preferable.

The polyester is basically synthesized by a condensation reaction between a diol compound and a dicarboxylic acid compound. Specific examples of dicarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, 9-nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butylterephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Ω-poly (ethylene oxide) dicarboxylic acid, p-xylylene dicarboxylic acid and the like. These compounds may be used in the form of an alkyl ester of a dicarboxylic acid (for example, dimethyl ester) or an acid chloride of a dicarboxylic acid when performing a polycondensation reaction with a diol compound,
It may be used in the form of an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride.

The polyester containing a dissociating group includes, in addition to carboxylic acid, sulfonic acid groups, sulfuric acid monoester groups, -OPO
(OH) ₂ , a sulfinic acid group, or an anion such as a salt thereof (for example, an alkali metal salt such as Na or K, or an ammonium salt such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, or trimethylamine). Or a cationic group such as a tertiary amine or a salt thereof (eg, a salt of an organic acid (eg, acetic acid, propionic acid, methanesulfonic acid) or an inorganic acid (eg, hydrochloric acid, sulfuric acid)) or a quaternary ammonium salt It is obtained by synthesizing using a dicarboxylic acid compound having a dissociating group as described above. As the dissociating group other than the carboxylic acid contained in the dissociating group-containing polyester, an anionic group is preferable, and a sulfonic acid group is particularly preferable.

A dicarboxylic acid having a sulfonic acid group,
Preferred examples of the diol raw materials include sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, and 2-sulfoterephthalic acid), sulfosuccinic acid, and sulfonaphthalenedicarboxylic acids (4- Sulfo-1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5-naphthalenedicarboxylic acid, etc.), 3,5-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof.

As the diol compound, a compound selected from the same group as the diols described in the above polyurethane can be used. A typical synthetic method of the polyester is a condensation reaction of the above diol compound with a dicarboxylic acid or a derivative thereof, which is obtained by condensing a hydroxycarboxylic acid such as a hydroxycarboxylic acid (eg, 12-hydroxystearic acid). And ring-opening polymerization of cyclic ethers and lactones.
Polyesters obtained by a method such as ring-opening polymerization (I) written by Takeo Saegusa (detailed in Kagaku Dojin, 1971) can also be suitably used in the present invention.

The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, or ring-opening polymerization of lactams. Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, and 2,5-diamine. Examples thereof include dimethylpiperazine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, xylylenediamine, and the like. Examples of the aminocarboxylic acid include glycine, alanine, phenylalanine, and ω-.
Examples include aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. Examples of the monomer that can be used for ring-opening polymerization include ε-caprolactam, azetidinone, and pyrrolidone. As the dicarboxylic acid compound, a compound selected from the same group as the dicarboxylic acids described in the polyester can be used.

The polyurea can be obtained basically by the polyaddition of a diamine compound and a diisocyanate compound or the deammonification reaction of a diamine compound and urea. The diamine compounds used as raw materials are the diamines and diisocyanate compounds described in the above polyamide. Compounds selected from the same group as the diisocyanates described in the above polyurethane can be used.

The polycarbonate can be basically obtained by reacting a diol compound with a phosgene or a carbonate derivative (eg, an aromatic ester such as diphenyl carbonate), and the diol compound as a raw material is described in the above polyurethane. Compounds from the same group as the diols can be used.

The dissociating group can be introduced into each of the polymers by various methods. For example, in the case of polyurethane, as described above, a diol containing a dissociating group can be used during synthesis and introduced as a substituent from the polymer main chain. Further, as in the case of using a polyester as the oil-soluble polymer, it can be introduced by leaving a dicarboxylic acid unreacted terminal at the terminal of the polymer. Furthermore, after the polymerization of each of the above polymers, a compound capable of introducing a dissociating group by a reaction such as an acid anhydride (for example, maleic anhydride) may be allowed to act on a reactive group such as a hydroxy group or an amino group. .

For the above-mentioned polymer containing a dissociating group, both the vinyl polymer and the condensed polymer may be used as necessary constituent materials one by one, or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer). And the solubility, the compatibility with the dye, and the stability of the dispersion).

Also, among the polymers having a dissociating group,
Those having at least one of a carboxyl group and a sulfonic group as the dissociable group are preferable, and those having a carboxyl group as the dissociable group are particularly preferable.

The content of the dissociable group in the polymer containing a dissociative group is preferably from 0.1 to 3.0 mmol / g, more preferably from 0.2 to 2.0 mmol / g. If the content of the dissociable group is too small or too large, the self-emulsifying property of the dissociative group-containing polymer tends to be small, and the effect of stabilizing the fine particle dispersion of the dye tends to be small.

As the dissociating group, the anionic dissociating group further includes an alkali metal (for example, Na,
K) or a salt of an ammonium ion. The tertiary amine serving as the cationic dissociating group may further include an organic acid (eg, acetic acid, propionic acid, methanesulfonic acid) or an inorganic acid (hydrochloric acid, Salt).

In view of the above-mentioned dissociative group-containing polymer, considering excellent dispersion stability, ease of dissociation group introduction, and the like,
More preferred are vinyl polymers, polyurethanes and polyesters, particularly preferred are vinyl polymers.

Specific examples of the vinyl polymer having a dissociating group are listed below. The ratio in parentheses means the mass ratio. Note that the present invention is not limited to these specific examples.

[0144]

[Table 2]

Specific examples of the condensation polymer among the polymers having a dissociating group are listed below, but the present invention is not limited thereto. All acidic groups in each polymer are shown in non-dissociated form. Also polyester,
For those produced by condensation reaction such as polyamide,
The components are all dicarboxylic acids, regardless of the raw materials,
It is represented by diol, diamine, hydroxycarboxylic acid, aminocarboxylic acid and the like. The ratio in parentheses means the molar percentage ratio of each component.

[0146]

[Table 3]

Regarding the synthesis of the condensation polymer containing a dissociating group, “Polymer Experiments (Vol. 5) Polycondensation and polyaddition (edited by Shu Kanbara, published by Kyoritsu Shuppan Co., Ltd. (1980))” and “Polyester Resin Handbook (Eiichiro Takiyama, published by Nikkan Kogyo Shimbun (1988)), "Polyurethane Resin Handbook (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987))", "Experimental method for polymer synthesis (Takayuki Otsu and Kinoshita) Masaetsu co-authored, published by Kagaku Doujin (19
72)) ”, JP-B No. 33-1141, 37-7641
Nos. 39-5989, 40-27349, 4
Nos. 2-5118, 42-24194, 45-10
No. 957, No. 48-25435, No. 49-36942
No. 52-81344, JP-A-56-88454.
And known methods described in each gazette such as JP-A-6-340835.

The polymer fine particle dispersion used in the present invention is used to prevent the solution containing the polymer fine particle dispersion from being clogged at the nozzle when forming an image. Glass transition temperature (T
g) is preferably higher. Those having Tg higher than the discharge temperature by about 10 ° C are more preferable, and those having Tg of 40 to 160 ° C are most preferable.

The solid content concentration of the polymer fine particle dispersion is preferably 0.1 to 10% by mass relative to the ink composition.
0.2-8 mass% is more preferable.

After the image formation, the heat treatment for forming a film of the polymer fine particle dispersion may be carried out at a temperature higher than the glass transition temperature (Tg) of the polymer fine particle dispersion, preferably at about 10 ° C. higher than Tg. Good to do. The heating means is not particularly limited, and hot air, an iron, a heated roller, infrared rays, or the like can be used. The time from application to heating is not particularly limited, but a shorter time is better. Preferably it is 1 second to 3 minutes, more preferably 1 second to 1 minute.

-Preparation Method of Ink Composition- The ink composition for ink jet recording used in the present invention can be prepared by dissolving and / or dispersing the above water-soluble dye in an aqueous medium. The “aqueous medium” in the present invention refers to 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. A method for preparing an aqueous ink composition for inkjet recording is described in JP-A-5-148436 and JP-A-5-295512.
Nos. 7-97541, 7-82515, 7-
The details are described in each of JP-A Nos. 118584 and can also be used for preparing the ink composition for inkjet recording used in the present invention.

Examples of the water-soluble organic solvent that can be used in the present invention include alcohols (eg, methanol,
Ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (for example,
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), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine) , N- ethyl diethanolamine,
Morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine,
Polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide,
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 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.

-Additive- In the present invention, an anti-drying agent for preventing the ink composition for ink-jet recording from being clogged due to a drying operation at an ink ejection port, and for preventing the ink from penetrating into paper. Addition of penetration enhancers, ultraviolet absorbers, antioxidants, viscosity modifiers, surface tension regulators, dispersants, dispersion stabilizers, fungicides, rust inhibitors, pH regulators, defoamers, chelating agents, etc. The agent can be appropriately selected and used in an appropriate amount.

As the drying inhibitor 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, 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-ethyl Heterocycles such as morpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 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 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.

Examples of the penetration enhancer used in the present invention include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate and the like. The nonionic surfactants listed as surfactants for emulsification and dispersion 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 to J in I. 15162; 187
No. 16 at page 650, left column. 36544, page 527;
No. No. 307105, page 872; 15162
Compounds described in the patent cited in JP-A-62-297
The compounds included in the general formulas and the compound examples of the representative compounds described on pages 127 to 137 of JP 15272 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-oxide.
And its salts. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass. still,
Details of these are described in "Encyclopedia of Bacterial and Fungicides" (edited by the Japanese Society of Bacteria and Fungi). Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, benzotriazole and the like. These are preferably used in the ink in an amount of 0.02 to 5.00% 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 an alkali metal hydroxide (for example, sodium carbonate, sodium hydrogen carbonate, and the like), ammonia, and the like. 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.

Examples of the surface tension modifier used in the present invention include 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 an alkylamine, a glycerin fatty acid ester, and an 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 Unexamined Patent Publication No.
No. 9-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) may be used as the surfactant. The surfactant used here preferably has a solubility in water at 25 ° C. of 0.5% or more. The surface tension of the inks of the present invention is 20 with or without these.
６０60 mN / m is preferred. 25-45 mN / m
Is preferred.

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.

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.

In forming an image by the ink jet image recording method of the present invention, a known recording material, that is, plain paper,
Resin-coated paper, for example, JP-A-8-169172,
JP-A-8-27693, JP-A-2-276670,
Nos. 7-276789, 9-323475, 62-238783, and 10-15398
No. 9, No. 10-217473, No. 10-23
No. 5995, No. 10-337947, No. 10
JP-A-217597 and JP-A-10-337947, etc., paper for exclusive use of ink jet, film, paper for electrophotography, fabric, glass, metal, ceramics and the like can be used.

The recording paper and recording film used for forming an image by the ink jet image recording method 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. The support may be provided with the ink receiving layer and the back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, the ink receiving layer and the back coat layer may be provided. 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, paper and plastic films laminated on both sides with a polyolefin (eg, 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 derivatives. 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 improver, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder (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. When the polymer mordant described in the publication is used, an image having 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-based 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 (for example, fluorine oil), and a solid fluorinated compound resin (for example, ethylene tetrafluoride resin). For organic fluoro compounds, see
No. 9053 (columns 8 to 17), JP-A-61-20994
And JP-A-62-135826.

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

Other additives 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. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica,
Colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, white inorganic pigments such as magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea Organic pigments such as resin and melamine resin.

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-jet recording method used in the present invention is not limited, and a known method, for example, a charge control method in which ink is ejected 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 (registered trademark)) system. 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.

[0178]

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

(Preparation of Ink Set 101) Deionized water was added to the following components to make 1 liter.
While stirring for 1 hour. Then KOH 10
mol / l to pH = 9, average pore size 0.25μ
The mixture was filtered under reduced pressure with a micro filter of m to prepare an ink liquid for light magenta. Magenta dye in the description 3.75 g Diethylene glycol 150 g Urea 37 g Glycerin 130 g Triethylene glycol monobutyl ether 130 g Triethanolamine 6.9 g Benzotriazole 0.08 g PROXEL XL2 3.5 g Polymer dispersion (P-1) 50 g (solid content) in the description Further, by changing the type of dye, the type of additive, and the amount of addition, magenta ink, light cyan ink, cyan ink, yellow ink, and black ink were prepared, and ink set 101 shown in Table 4 was prepared.

[0180]

[Table 4]

[0181]

Embedded image

[0182]

Embedded image

Similarly, according to Table 5, the ink sets 102 to
109 was created. The two types of polymer fine particle dispersions were combined at an equal mass ratio. Further, a comparative ink set 109 was prepared in the same manner as the ink set 101 except that the polymer fine particle dispersion was not contained.

[0184]

[Table 5]

Next, these ink sets 101 to 10
9 to an inkjet printer PM670C (EPSO
N Co., Ltd.), and the image was printed on the inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine. After printing, the polymer fine particle dispersion was formed into a film through a roller heated to 100 ° C.
01 to 109).

Separately, as a comparative example, a comparative example ink set having the same formulation as the ink set 101 except that a polymer fine particle dispersion P′-1 (styrene / butadiene = 75/25) having a glass transition temperature Tg of less than 40 ° C. was mixed. 110 was created and the image was printed as with the other ink sets. No heat treatment was performed after printing, and the remaining pull 110 was obtained.

The following evaluation was performed on the prepared samples. After setting the cartridge in the printer and confirming the ejection of ink from all nozzles, A4
Disturbance in printing was evaluated for outputs on 20 sheets. A: There is no printing disorder from the start to the end of printing. B: Output with disorder of the printing occurs. C: There is the disorder of printing from the start to the end of printing. The printed portion of the sample was touched with a finger, and the stickiness was evaluated. A: No stickiness B: Slight stickiness C: Severe stickiness The light fastness was measured using X-rite 310 image density Ci immediately after printing. After irradiating with xenon light (85,000 lux) for 10 days, the image density Cf was measured again to determine and evaluate the dye remaining ratio Cf / Ci * 100. The dye remaining rate was evaluated at three points where the reflection density was 1, 1.5, and 2. When the dye remaining rate was 70% or more at any density, A, 2
The case where the point was less than 70% was B, and the case where the point was less than 70% at all concentrations was C. Regarding the heat preservability, the concentration before and after storing the sample for 10 days under the condition of 80 ° C was determined by X-rite 31.
The measurement was performed at 0, and the residual dye ratio was determined and evaluated. The dye remaining rate was evaluated at three points where the reflection density was 1, 1.5, and 2. When the dye remaining rate was 90% or more at any density, A, 2
When the point was less than 90%, it was B, and when it was less than 90% at all concentrations, it was C. The water resistance was evaluated by immersing the sample in still water for 10 seconds. A: no change, B: slight bleed, C: severe bleed and poor image quality.
Was evaluated. Table 6 shows the obtained results.

[0188]

[Table 6]

The ink jet image recording method of the present invention comprises:
It can be seen that the ejection stability of the ink is excellent, and the obtained image is excellent in water resistance and excellent in image storability such as light fastness and heat fastness.

[0190]

According to the ink jet image recording method of the present invention, the ejection stability is high, the hue is good, and especially, the water resistance and
Image recording with excellent weather resistance can be performed.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2C056 FC01 HA44 HA46 2H086 BA05 BA56 BA59 BA60 BA62 4J039 AD01 AD02 AD05 AD06 AD08 AD09 AD10 AD12 AD16 AD22 AE04 AE06 AE08 BC07 BC08 BC09 BC10 BC11 BC13 BC14 BC15 BC18 BC34 BC35 BC36 BC40 BC50 BC51 BC54 BC72 BC75 BC76 BC79 BE06 BE12 CA06 DA05 EA34 EA37 EA38 EA41 EA44 EA46 GA24

Claims (4)

[Claims] 1. An ink jet ink composition containing a water-soluble dye and polymer fine particle dispersion is discharged onto an image receiving material to form an image, and the image receiving material is heated to form a film. Inkjet image recording method. 2. The ink composition according to claim 1, wherein the ink composition contains a water-soluble dye represented by the general formula (AI).
3. The ink-jet image recording method described in 1. above. General formula (AI) In the formula, 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 are each 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,
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, heterocycle Oxy group, azo group, acyloxy group, carbamoyloxy group,
Represents 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; R ₁ and R ₂ , R ₃ and R ₁ and R ₂ and R ₅ may be combined with each other to form a ring.
Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, 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 group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy Represents 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. 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 , R ₅ , R ₆ , X,
At least one of Y, Z ₁ , Z ₂ and A represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. 3. The ink jet image recording method according to claim 1, wherein the polymer fine particle dispersion has a glass transition temperature (Tg) of 40 to 160 ° C. 4. The ink-jet image recording according to claim 1, wherein the solid content concentration of the polymer fine particle dispersion is 0.1 to 10% by mass based on the ink composition. Method.