JP2002256192A - Ink composition for ink jet and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for ink jet excellent in handling properties, odor characteristics, safeness and delivering stability, giving an image excellent in hue, light resistance and water resistance, causing no bleeding in a thin line and the like, excellent in image storage property under severe conditions and exhibiting high delivering stability even in the case of an ink kept for a long period of time or under severe conditions. SOLUTION: The ink composition for ink jet recording comprises at least a water-soluble dye of general formula I [wherein X is an electron-withdrawing substituent group having a Hammet's substituent constant of at least 0.2; Y, R1 to R6 , Z1 and Z2 are each H, an alkyl group and the like, provided that anyone of X, Y, R1 to R6 , Z1 and Z2 is an ionic hydrophilic group; and A is a 5 to 8-membered ring] and contains a compound of general formula 1 [wherein X is CO, CS, SO2 ; R1 to R4 are each H, an alkyl group and the like, provided that anyone is a hydrophilic group; and n is 0 or 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

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

[0005]

Accordingly, an object of the present invention is to provide a water-based ink having advantages in handleability, odor, safety and the like, which has high ejection stability, and furthermore, the hue and lightfastness of the obtained image. An object of the present invention is to improve the image storability under severe conditions without excellence in image quality, such as excellence in water resistance and water resistance, and without defects such as bleeding of fine lines. Another object of the present invention is to provide an ink-jet ink composition having high ejection stability even for ink that has been aged for a long period of time or under severe conditions.

[0006]

The above object has been attained by the following inventions. That is, <1> an ink-jet recording ink composition containing at least a water-soluble dye represented by the following general formula (I), which contains a compound represented by the following general formula (1): Recording ink composition. General formula (I)

[0007]

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In the general formula (I), X represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. R _1, R
₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y are each independently
Hydrogen atom, 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 group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, Represents a phosphoryl group, an acyl group, or an ionic hydrophilic group, and R ₁ and R ₂ , R ₃ and R ₁ , and R ₂ and R ₅ may be bonded to each other to form a ring. Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group,
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. 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 ,
At least one of R ₄ , R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. General formula (1)

[0009]

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In the general formula (1), X represents -CO-,-
CS- or -SO ₂ - represents a. R1 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R2, R3, and R4 represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and R2, R3,
R4 may be the same or different. R2 and R3
Alternatively, R1 and R4 may combine to form a ring. n represents 0 or 1. However, the compound of the general formula (1)
In the molecule, a carboxyl group and a salt thereof, a sulfo group and a salt thereof, a hydroxyl group, —O (CH ₂ CH ₂ O) _m H, —O (C
It has at least one hydrophilic group selected from H ₂ CHCH ₃ O) _m H (m is an integer of 1 or more). <2> The ink composition for inkjet recording according to <1>, further comprising a water-soluble organic solvent. <3> The ink composition for inkjet recording according to <2>, wherein the content of the water-soluble organic solvent is 0.1 to 50% by mass. <4> The ink composition for inkjet recording according to <1>, wherein the content of the compound represented by Formula (1) is 0.1 to 30% by mass. <5> An ink jet recording method for recording on an image receiving material by discharging ink according to a recording signal using the ink composition for ink jet recording of <1> to <4>,
An ink jet recording method, wherein the image receiving material has an image receiving layer containing white inorganic pigment particles on a support.

[0011]

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

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

[0013]

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In the general formula (I), X is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, it is an electron-withdrawing group having a σ _p value of 0.30 to 1.0. Specific examples of X which is an electron-withdrawing group having a σ _p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkyl phosphono group. Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group,
Sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, σ _p value of 0 An aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with at least 20 other electron-withdrawing groups.

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

X 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, two or more sigma _p value of 0.20 or more other electron-withdrawing substituted aryl group having 7 to 18 carbon atoms in the group, and a nitrogen atom, 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 (I), R ₁ , R ₂ , R
₃ , R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Amino group, alkylamino group,
Alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl A heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group,
Represents a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Of these, 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.

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

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

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

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

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

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

The alkoxy 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 a 3,5-disulfobenzamido group.

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

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

The sulfamoylamino 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 N, N-dipropylsulfamoylamino.

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

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

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

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

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

The sulfamoyl 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:
And an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0054]

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

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

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

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

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

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

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

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

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

In the general formula (II), Z ₃ , Z ₄ and Z ₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group , Carbamoyl 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, phos Lil group, an acyl group or an ionic hydrophilic group.

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

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

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

More preferably, Z ₄ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and an ionic group. A hydrophilic group is particularly preferable, and among them, a hydrogen atom, an alkyl group, and an ionic hydrophilic group are particularly preferable, and an ionic hydrophilic group is most preferable.

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

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

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

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

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

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

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

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

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

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

Examples of magenta dyes include aryl or hetenylazo dyes having phenols, naphthols and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes and styryl Methine dyes such as dyes, merocyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone; 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 the cyan dye include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; and carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye Dyes; Phthalocyanine dyes; Anthraquinone dyes; Examples of the coupling component include aryl or hetenylazo dyes having phenols, naphthols, and anilines, and indigo / thioindigo dyes. These dyes may be those that exhibit cyan only when 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, It may be an organic cation such as a quaternary ammonium salt, or may be a polymer cation having them in a partial structure. Also, a black dye such as a polyazo dye can be used.

The ink composition for ink jet recording of the present invention contains a compound represented by the following general formula (1). Hereinafter, the compound represented by formula (1) of the present invention will be described. General formula (1)

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In the general formula (1), X represents -CO-,-
CS- or -SO ₂ - represents a. R1 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R2, R3, and R4 represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and R2, R3,
R4 may be the same or different. R2 and R3
Alternatively, R1 and R4 may combine to form a ring. n represents 0 or 1. However, the compound of the general formula (1)
In the molecule, a carboxyl group and a salt thereof, a sulfo group and a salt thereof, a hydroxyl group, —O (CH ₂ CH ₂ O) _m H, —O (C
It has at least one hydrophilic group selected from H ₂ CHCH ₃ O) _m H (m is an integer of 1 or more).

The alkyl groups represented by R1, R2, R3, and R4 may be cyclic, linear, or branched.
The number of carbon atoms is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6. R1, R
The aryl group represented by 2, R3 and R4 has 6 to 1 carbon atoms.
2 are preferable, and 6 to 10 are more preferable. R1
The heterocyclic group represented by preferably contains a hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably contains a nitrogen atom and an oxygen atom. Examples of preferred heterocycles include pyrrole, indole, furan,
Thiophene, quinoline, thiazole, isothiazole,
Examples include pyridine, pyrazine, pyridazine, oxazole, piperidine, and morpholine. Among them, preferred heterocycles are pyrrole, indole, furan, thiophene, quinoline, pyridine, and particularly preferred are
Pyrrole, indole, furan and thiophene.

Examples of the substituent which may be substituted on the alkyl group, the aryl group and the heterocyclic group represented by R1, R2, R3 and R4 include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group and an acyl group. Group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, alkoxy group,
Aryloxy group, hydroxyl group, acyloxy group, sulfonyloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, nitro group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group And a heterocyclic group.

In the present invention, the amount of the compound represented by the general formula (1) is preferably in the range of 0.1 to 30% by mass, and more preferably 0.5 to 20% by mass in 100% by mass of the ink for ink jet recording. More preferably, it is in the range of mass%. In the present invention, two or more compounds represented by the general formula (1) can be used in combination.

Specific examples of the amide compound represented by the general formula (1) are shown below, but the present invention is not limited to the following examples.

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The ink composition for ink jet recording used in the present invention can be prepared by dissolving and / or dispersing the above-mentioned water-soluble dye and amide compound in an aqueous medium. The "aqueous medium" in the present invention means water or a mixture of water and a small amount of a water-soluble organic solvent to which additives such as a wetting agent, a stabilizer and a preservative are added as necessary. A method for preparing an aqueous ink composition for inkjet recording is described in JP-A-5-14.
Nos. 8436, 5-29512, 7-97541
The details are described in JP-A Nos. 7-82515 and 7-118584, 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, tert-butanol).
Butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentane) Diol, glycerin, hexanetriol, thiodiglycol, dithioglycol, 2-methyl-1,3-propanediol, trimethylolpropane), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether) , Diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene Glycol monophenyl ether), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N
-Ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethyl) Acetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-
Pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone,
Acetonitrile, acetone). The water-soluble organic solvent may be used in combination of two or more. The content of the water-soluble organic solvent in the ink composition for inkjet recording of the present invention is preferably 0.1 to 50% by mass, and 5 to 50% by mass.
% Is more preferred. In the present invention, it is preferable to add a water-soluble organic solvent for the purpose of preventing clogging due to drying at the ink ejection port.

When the ink composition for ink jet recording obtained in the present invention is used as an ink for ink jet recording, a penetration enhancer, an ultraviolet absorber, an antioxidant, a viscosity modifier for better penetration of the ink into paper. , Surface tension regulator, dispersant, dispersion stabilizer, fungicide, rust inhibitor, p
Additives such as H adjusters, defoamers and chelating agents can be appropriately selected and used in appropriate amounts.

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

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

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

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

As the surface tension modifier used in the present invention, a nonionic, cationic or anionic surfactant can be used. For example, anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer. SUR, an acetylene-based polyoxyethylene oxide surfactant
FYNOLS (Air Products & Chemic
als) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Japanese Unexamined Patent Publication No.
No. 9-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) may be used as the surfactant. The surface tension of the ink of the present invention is preferably 20 to 60 mN / m with or without using them. 2 more
5-45 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. For more details, "Viscosity adjustment technology" (Technical Information Association, 1999)
Chapter 9 and “Chemicals for Inkjet Printers (98 Supplement) -Material Development Trends and Prospects-” (CMC, 1997), pp. 162-174.

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

In the present invention, a polymer fine particle dispersion can be used for the purpose of improving water resistance and light resistance. For details of the polymer fine particle dispersion, refer to Japanese Patent Application No. 2000-36.
No. 3090. In the present invention,
When a polymer fine particle dispersion is used, the particle diameter of the dispersed particles is preferably from 0.001 to 1 μm, more preferably from 0.01 to 0.5 μm, as a volume average particle diameter. The solid content of the dispersion is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 8% by mass, based on the ink composition.

The ink of the present invention is 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, and JP-A-7-276789. Gazette, pp. 9-323475
JP-A-62-238783, JP-A-10-153
Nos. 989, 10-217473, 10-
No. 235995, No. 10-337947, No. 10-217597, No. 10-337947, etc. Ink-jet dedicated paper, film, electrophotographic paper, fabric, glass, metal, ceramic, etc. It can be used to form images.

The recording paper and recording film used for ink-jet printing using the ink of the present invention will be described below. Supports for recording paper and film are chemical pulp such as LBKP and NBKP, GP, P
It 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, 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 image receiving material may be provided by directly providing an image receiving layer and a back coat layer on the support, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol, or the like, and then providing the image receiving layer and the back coat layer as an image receiving material. Good. Further, the support may be subjected to a flattening treatment using a calender 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 blue, neodymium oxide) to the polyolefin polyolefin.

The image receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, 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,
Examples thereof include inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, 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 image receiving layer, a porous inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly 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 image receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative and the like. And a water-dispersible polymer such as styrene-butadiene latex and acrylic emulsion.
These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the image receiving layer.

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

The mordant added to the image receiving layer is preferably immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325, JP-A-54-74430,
Nos. 4-124726, 55-22766, 55-
Nos. 142339, 60-23850, 60-23
No. 851, No. 60-23852, No. 60-23853
No. 60-57836, No. 60-60643, No. 60-118834, No. 60-122940, No. 6
Nos. 0-122941, 60-122942, 60
-235134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430 and 2,548,564,
No. 3148061, No. 3309690, No. 4115
No. 124, No. 4124386, No. 4193800,
No. 4238353, No. 4282305, No. 4450
No. 224 is described in each specification. JP-A-1-16112
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A No. 36 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, and particularly preferably from 3 to 10% by mass, based on the total solid content of the image receiving layer.

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

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

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

Other additives to be added to the image receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener,
Preservatives, pH adjusters, matting agents, hardening agents and the like can be mentioned. The image 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,
White inorganic pigments such as colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea Organic pigments such as resin and melamine resin.

As the aqueous binder contained in the back coat layer, 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.
Nos. 36648 and 62-110066. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer fine particle dispersion having a high glass transition temperature to the back layer.

The ink of the present invention is not limited to an ink jet recording method, and is a known method such as a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method using vibration pressure of a piezo element ( Pressure pulse method), acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate ink to radiate pressure to eject ink, and thermal ink jet that heats 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.

[0138]

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

(Example 1) Deionized water was added to the following components to make 1 liter, and the mixture was heated at 30 to 40 ° C to obtain 1 liter.
Stir for hours. Then, at 10 mol / l of KOH, p
H was adjusted to 9 and filtered under reduced pressure through a micro filter having an average pore diameter of 0.25 μm to prepare an ink liquid for light magenta. Magenta dye in the specification (114) 4.1 g Diethylene glycol 150 g Urea 37 g Glycerin 50 g Triethylene glycol monobutyl ether 90 g Surfynol 465 (Air Products & Chemicals) 10.5 g Amides Specific examples (I-8) 25 g Triethanolamine 6.9 g Benzotriazole 0.08 g PROXEL XL2 3.5 g Magenta ink, light cyan ink, cyan ink, yellow ink, and black ink were prepared by changing the dye type and additives, and ink set 101 having the density shown in Table 1 was prepared.

[0140]

[Table 1]

[0141]

Embedded image

[0142]

Embedded image

Next, for the light magenta, magenta, light cyan, cyan, yellow, and black inks of the ink set 101, the types and amounts of the dyes and the amide compounds were changed according to Table 2, and the ink set 102-
108 were created. When the dye was used in combination, the dyes were used in equimolar amounts, and when the amide represented by the general formula (1) was used in combination, they were used in equal amounts. When using a dye together,
In all moles, the same amount as the ink set 101 was used.

[0144]

[Table 2]

Next, these ink sets 101-108
To the inkjet printer PM770C (EPSON
The product was packed in a cartridge manufactured by Fuji Photo Film Co., Ltd., and an image was printed on inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd., and the following evaluation was performed. 1) For printing performance, after setting the cartridge in the printer and confirming the protrusion of ink from all nozzles,
Sheets were output, and the printing disorder was evaluated. A: There is no printing disturbance from the start to the end of printing. B: Output with printing disturbance occurs. C: There is the printing disturbance from the printing start to the end. 2) The printing performance is as follows. The printing disorder was evaluated in the same manner as in the printing performance. 3) Immediately after printing, the dryness was evaluated by visual inspection of the stain when touched with a finger. 4) Regarding bleeding of fine lines, yellow, magenta, cyan and black fine line patterns were printed and evaluated visually. As for black, after printing solid magenta ink, a black thin line was printed, and bleeding due to contact between two colors was also evaluated. 5) Regarding water resistance, the obtained image was immersed in deionized water for 5 seconds, and then the blur of the image was visually evaluated. 6) Regarding image storability, print samples of yellow, magenta, cyan and black were prepared and evaluated as follows. The light fastness was determined by measuring the image density Ci immediately after printing with an X-rite 310, irradiating the image with xenon light (85,000 lux) for 8 days using an Atlas weather meter, and then re-evaluating the image density Cf. Was measured to determine a dye residual ratio (Cf / Ci) × 100, and evaluation was performed. Regarding the dye remaining ratio, the reflection density was 1, 1,.
Evaluation was made at three points of 5 and 2, where A indicates that the dye remaining ratio was 70% or more at any concentration, B indicates that the two points were less than 70%, and C indicates that the concentration was less than 70% at all concentrations. did. Regarding the wet heat fastness, the concentration before and after the sample was stored for 6 days under the conditions of 80 ° and 70% RH was measured with an X-rite 310 to obtain and evaluate the dye residual ratio. Regarding the dye remaining rate, the reflection density was evaluated at three points of 1, 1.5, and 2, and at any density, the dye remaining rate was 80% or more, A, and when the point was less than 80%, B, all And C was less than 80%.

[0146]

[Table 3]

[0147]

[Table 4]

It can be seen that when the ink composition of the present invention is used, excellent ejection stability can be obtained without clogging, and that the ink composition exhibits excellent performance in terms of water resistance and fastness. In addition, the ink composition of the present invention is excellent in the performance of outputting fine lines without blurring. Incidentally, the image receiving paper used in the present invention is a PM photo paper manufactured by EPSON,
The same effect as the above result can be obtained even when changing to PR101 manufactured by Canon Inc.

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

[0150]

According to the present invention, there is provided an ink jet recording ink and an ink jet recording method capable of forming an image having particularly excellent ejection stability, high light fastness, little bleeding and little deterioration under severe conditions. Can be provided.

Continued on front page F term (reference) 2C056 EA13 FC01 FC02 2H086 BA15 BA33 BA52 BA53 BA56 BA59 BA62 4J039 BC07 BC08 BC10 BC11 BC13 BC14 BC15 BC18 BC32 BC34 BC35 BC36 BC40 BC49 BC51 BC54 BE06 CA05 CA06 EA29 EA35 EA38 EA41 EA44 EA44 EA44 EA44 EA44 EA44 EA41 FA02 FA04 FA06 FA07 GA24

Claims (5)

[Claims] 1. An ink-jet recording ink composition containing at least a water-soluble dye represented by the following general formula (I), comprising a compound represented by the following general formula (1): Recording ink composition. General formula (I) In the general formula (I), X represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group , An alkylamino group,
Alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl A heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group,
Represents a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group; R ₁ and R ₂ , R ₃
And R ₁ , and R ₂ and R ₅ may combine with each other to form a ring. Z ₁ and Z ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, and an alkoxy group. Group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, or ionic hydrophilic Table . A represents a group of nonmetallic atoms necessary for forming a 5- to 8-membered ring, which may be a saturated ring or may have an unsaturated bond, and represents a group of nonmetallic atoms forming A. At least three of them are each substituted with a pyrazole ring N atom, Z ₁ and Z ₂ , and the atom substituted with the pyrazole ring N atom is adjacent to both the Z ₁ and Z ₂ substituted atoms. Where R ₁ , R ₂ , R ₃ , R ₄ ,
At least one of R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. General formula (1) In the general formula (1), X is -CO -, - CS- or -SO ₂ - represents a. R1 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R2, R
3, R4 represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and R2, R3, and R4 may be the same or different. R2 and R3 or R1 and R4 may combine to form a ring. n represents 0 or 1. However, the compound represented by the general formula (1) has, in the molecule, a carboxyl group and a salt thereof, a sulfo group and a salt thereof, a hydroxyl group, —O (CH ₂ CH ₂ O) _m H, and —O (CH ₂ CHCH _3).
O) _m H (m comprises at least one of one or more hydrophilic groups chosen from an integer). 2. The ink composition for ink-jet recording according to claim 1, further comprising a water-soluble organic solvent. 3. The ink composition for ink-jet recording according to claim 2, wherein the content of the water-soluble organic solvent is 0.1 to 50% by mass. 4. The ink composition according to claim 1, wherein the content of the compound represented by the general formula (1) is 0.1 to 30% by mass. 5. An ink jet recording ink composition according to claim 1, wherein the ink is ejected in accordance with a recording signal.
An ink jet recording method for recording on an image receiving material, wherein the image receiving material has an image receiving layer containing white inorganic pigment particles on a support.