JP2007224276A - Ink composition, ink set and method of recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition excellent in penetrating property, without damaging ozone resistance and light fastness, an ink set and a method of recording. <P>SOLUTION: This ink composition containing at least an azo dyestuff obtained by bonding azo group with a heterocyclic ring group or a phthalocyanine dyestuff having an associative group, a water miscible organic solvent and water is provided by further containing citric acid and/or its salt. The ink set is provided by containing the ink composition, and the method of recording by using them is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink composition, an ink set, and a recording method.

In recent years, with the spread of computers, inkjet printers are widely used for printing on paper, film, cloth, etc. not only in offices but also at home.
Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these ink compositions for inkjet recording, water-based inks, oil-based inks, or solid (melted type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

The colorant used in these inks for ink jet recording has high solubility in solvents, high density recording, good hue, light, heat, air, water and chemicals. Excellent fastness, good fixability to image-receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, and availability at low cost It is requested. However, it is extremely difficult to search for colorants that meet these requirements at a high level.
Various dyes and pigments have already been proposed and actually used for inkjet, but no colorant that satisfies all the requirements has yet been discovered. Conventionally well-known dyes and pigments to which color index (CI) numbers are assigned are difficult to achieve both the hue and fastness required for ink jet recording inks.

In view of the above, the applicant has developed specific azo dyes and phthalocyanine dyes in order to improve the ozone resistance and light resistance of the dyes.
These dyes are characterized in that the oxidation potential of the dye is increased, and that ozone resistance and light resistance can be improved by promoting association of the dye molecules.
However, there is a problem that due to the association of the dye molecules, the permeability of the ink to the image receiving paper is deteriorated and bronze gloss appears on the surface of the image receiving paper.
In order to prevent the bronze gloss of the image receiving paper surface, it is effective to improve the penetrability of the dye. For this purpose, for example, the amount of the surfactant in the ink is increased to improve the ink permeability to the image receiving paper. The technique to make is mentioned. However, an increase in the amount of the surfactant causes deterioration such as bleeding and water resistance.
That is, an additive that improves the permeability of the ink without deteriorating the various performances of the ink has been desired.

By the way, conventionally, it has been proposed that a polycarboxylic acid is contained in an ink as a metal chelating agent to improve the ejection stability of the ink (for example, Patent Documents 1 to 4).
However, the above prior art has room for improvement in the permeability improvement effect.

JP 11-315238 A Japanese Patent Laid-Open No. 2003-231446 JP 2003-231847 A JP 2004-99825 A

  The problem to be solved by the present invention is to provide an ink composition, an ink set, and a recording method excellent in permeability without impairing ozone resistance and light resistance.

The present invention is as follows.
1) In an ink composition comprising at least an azo dye having an azo group bonded to a heterocyclic group, or a phthalocyanine dye having an associative group, a water-miscible organic solvent, and water, citric acid and / or its An ink composition comprising a salt.
2) The ink composition as described in 1) above, wherein the content of citric acid and / or a salt thereof is 0.01 to 1% by mass in the ink composition.
3) The ink composition as described in 1) or 2) above, wherein the azo dye having an azo group bonded to the heterocyclic group is an azo dye having a heterocyclic group at both ends of the azo group.
4) An oxidation potential of an azo dye having an azo group bonded to the heterocyclic group or a phthalocyanine dye having the associative group is nobler than 1.0 V (vs SEC). ).
5) An ink set comprising the ink composition according to any one of 1) to 4) above.
6) A recording method comprising using the ink composition according to any one of 1) to 4) above or the ink set according to 5) above.
7) The recording method as described in 6) above, which is an ink jet recording method.

  According to the present invention, there are provided an ink composition, an ink set, and a recording method excellent in permeability without impairing ozone resistance and light resistance.

  The present invention is described in detail below.

  The present inventors have found that addition of a polyvalent carboxylic acid containing a hydroxyl group and / or a salt thereof is effective as a means for improving the permeability of an ink using an associative dye to an image receiving paper. . Among polyvalent carboxylic acids and / or salts thereof containing a hydroxyl group, citric acid and / or salts thereof are desirable because they are stable against evaporation of ink and pH change even when added to ink. Trisodium citrate is preferred. In the case of a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among which alkali metals are preferred, especially Sodium, lithium and / or potassium salts are preferred. In the case of citric acid, the trisodium salt is desirable.

  Although the mechanism by which polyvalent carboxylic acid having a hydroxyl group such as citric acid improves the permeability of the ink to the image receiving paper is not clear, the hydroxyl group and the associative dye interact with each other. It is thought that citric acid is present near the dye.

  The amount of citric acid and / or salt thereof added is preferably 0.01 to 1% by mass in the ink composition, more preferably 0.02 to 0.5% by mass, and 0.05 to 0.1% by mass. % Is more preferable. If the amount of citric acid and / or its salt added is too small, the effect of improving the permeability will be insufficient, and if it is too large, the solid content concentration in the ink will increase and the storage stability of the ink over time will deteriorate. There are concerns.

(Azo dye having an azo group bonded to a heterocyclic group, or a phthalocyanine dye having an associative group)
The yellow dye useful in the present invention will be described in detail as an azo dye having an azo group bonded to a heterocyclic group.
The ink composition of the invention preferably contains a compound represented by the following general formula (Y-I).

Formula (Y-I):

In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y,
Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z
, Q and G each represent a monovalent, divalent or trivalent substituent, and at least two represent a divalent substituent or at least one represents a trivalent substituent.
The compound represented by the general formula (Y-I) functions as a yellow dye. The ink composition of the present invention is preferably a yellow ink composition.

The compound represented by the general formula (Y-I) functions as a yellow dye. The ink composition of the present invention is preferably a yellow ink composition. In the general formula (Y-I), preferred examples of the substituent for G are preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group. Are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole,
Isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline,
Examples include sulfolane.

When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butyl) Phenyl, 2,4-di-t-amylphenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl,
2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group ( For example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- (3-t-butyl) -4-hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino,
Diethylamino, methylbutylamino), arylamino group (for example, phenylamino,
2-chloroanilino), ureido groups (eg phenylureido, methylureido, N,
N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2- Butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and arylsulfonylamino groups (eg methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N
-Dibutylcarbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N
, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl) A heterocyclic oxy group (for example, 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-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, Butyl methyl silyloxy), an aryloxycarbonylamino group (e.g., phenoxycarbonylamino), an imido group (e.g., N- succinimido, N- phthalimido), a heterocyclic thio group (e.g., 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), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3
-Phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg carboxyl groups,
Sulfo group, phosphono group and quaternary ammonium group).

  In the general formula (Y-I), examples of preferred substituents of Q, R, X, Y and Z will be described in detail.

When Q, R, X, Y and Z represent a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

  Hereinafter, Q, R, X, Y, and Z will be described in more detail.

The halogen atom represented by Q, R, X, Y and Z represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

The alkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is preferable. Examples of the alkyl group include methyl, ethyl, butyl, t-butyl, n-
Octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl or 4-
Sulfobutyl can be mentioned.

The cycloalkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

The aralkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aralkyl include benzyl and 2-phenethyl.

The alkenyl group represented by Q, R, X, Y and Z represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferably a C2-C30 substituted or unsubstituted alkenyl group such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopentene-1-
Yl, 2-cyclohexen-1-yl and the like.

The alkynyl group represented by Q, R, X, Y and Z is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

The aryl group represented by Q, R, X, Y and Z is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoyl. Aminophenyl. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent.

The heterocyclic group represented by Q, R, X, Y and Z is a 5- or 6-membered substituted or unsubstituted,
It is a monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine,
Quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, Pyrrolidine,
Examples include piperidine, piperazine, imidazolidine, thiazoline and the like.

The alkoxy group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxy group include
Mention may be made of methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

The silyloxy group represented by Q, R, X, Y and Z is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group represented by Q, R, X, Y and Z is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An oxy group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups.
Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-
Examples include octylaminocarbonyloxy and Nn-octylcarbamoyloxy.

The alkoxycarbonyloxy group represented by Q, R, X, Y and Z has 2 to 30 carbon atoms.
Is preferably a substituted or unsubstituted alkoxycarbonyloxy group, and examples of the substituent include
Examples thereof include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of the group include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

The acylamino group represented by Q, R, X, Y and Z is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms.
And the same substituents as those exemplified when is a group capable of further having a substituent. Examples of the aminocarbonylamino group include, for example, carbamoylamino, N, N
-Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like can be mentioned.

The alkoxycarbonylamino group represented by Q, R, X, Y and Z has 2 to 30 carbon atoms.
Is preferably a substituted or unsubstituted alkoxycarbonylamino group, and examples of the substituent include
Examples thereof include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups represented by Q, R, X, Y and Z are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the alkylsulfonylamino group and arylsulfonylamino group include
Examples thereof include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

The alkylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. As an example of the substituent, the G may further have a substituent. And the same substituents as mentioned when they are small groups. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

The alkyl and arylsulfinyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfinyl groups include, for example, methylsulfinyl, ethylsulfinyl,
Examples thereof include phenylsulfinyl and p-methylphenylsulfinyl.

The alkyl and arylsulfonyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by Q, R, X, Y and Z is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable, and examples of the substituent include a group in which G can further have a substituent. Examples are the same as the substituents sometimes mentioned. Examples of the acyl group include, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-
And furylcarbonyl.

The aryloxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned.
Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned.
Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

Examples of the azo group represented by Q, R, X, Y, and Z include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. Can do.

Examples of the imide group represented by Q, R, X, Y, and Z include N-succinimide and N-phthalimide.

When Q, R, X, Y and Z represent a divalent group, the divalent group includes an alkylene group (e.g.,
Methylene, ethylene, propylene, butylene, pentylene), alkenylene groups (eg, ethenylene, propenylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups ( Example, 6-chloro-1,3,5
-Triazine-2, 4-diyl group, pyrimidine-2, 4-diyl group, pyrimidine-4, 6
-Diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-
, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group or an aryl group), -S-, -S
O ₂ —, —SO— or a combination thereof (eg —NHCH ₂ CH ₂ NH—, —NHC
ONH- etc.) is preferable.

An alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group,
The alkyl group or aryl group of R may have a substituent.

  Examples of the substituent are the same as the substituent described in G above.

  The alkyl group and aryl group for R ′ have the same meanings as the examples of the substituent for G.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- SO—, —SO ₂ — or a combination thereof (eg, —SCH ₂ CH
₂ S-, -SCH ₂ CH ₂ CH ₂ S-, etc.) are more preferable.

The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group,
A trivalent heterocyclic group,> N-, or a combination thereof with a divalent group (eg> NCH ₂ CH ₂
NH-,> NCONH-, etc.).

The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (Y-I), preferred examples of n are 1 or 2, with 2 being particularly preferred.

  In the general formula (Y-I), a preferred example of the substituent for X is an electron-withdrawing group. In particular, it is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and more preferably an electron-withdrawing group having a σp value of 0.30 or more. The upper limit is 1.0 or less electron withdrawing group.

Specific examples of X which is an electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group,
Cyano group, nitro group, dialkylphosphono 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 alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, σ
An aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with another electron-withdrawing group having a p value of 0.20 or more.

Preferred examples of X include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, nitro group, carbon number 1-12
Alkylsulfinyl group, arylsulfinyl group having 6 to 18 carbon atoms, and 1 to 12 carbon atoms
Alkylsulfonyl group, C6-18 arylsulfonyl group, C0-12 sulfamoyl group, C1-12 halogenated alkyl group, C1-12 halogenated alkyloxy group, C1 A halogenated alkylthio group of -12, a halogenated aryloxy group of 7-18 carbon atoms, an aryl group of 7-18 carbon atoms substituted with two or more other electron-withdrawing groups of σp0.20 or more, and nitrogen 5 having atoms, oxygen atoms, or sulfur atoms
An 8-membered ring and a C1-C18 heterocyclic group can be mentioned.

More preferably, a cyano group, a C1-C12 alkylsulfonyl group, a C6-C18
An arylsulfonyl group or a sulfamoyl group having 0 to 12 carbon atoms.

Particularly preferable as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and the most preferable one is a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms. It is.

  In the general formula (YI), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;

Detailed examples of the substituent represented by Z are the same as the corresponding examples of the substituent described in the example of the heterocyclic group represented by G, and preferred examples are also the same.

A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In the general formula (YI), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted group. The arylsulfonyl group is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group, and particularly preferably a hydrogen atom.

  In general formula (Y-I), R represents a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number. A C4-C12 heterocyclic group is preferred, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1 to C8 is preferred, a secondary or tertiary alkyl group is particularly preferred, and a t-butyl group is most preferred. preferable.

  In general formula (YI), Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted group. A heterocyclic group having a total carbon number of C4 to C12 is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1 to C8 and / or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

  Regarding the preferred combination of substituents of the dye represented by the general formula (Y-I) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferred combination as the dye represented by the general formula (Y-I) of the present invention includes the following (A) to (G).

(I) G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) R is a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C4.
Among them, 12 heterocyclic groups are preferred, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, a secondary or tertiary alkyl group is particularly preferred, and a t-butyl group is most preferred.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Among these, a hydrogen atom and the total number of carbon atoms C1 to C are preferable.
8 linear alkyl groups or branched alkyl groups are preferred, especially hydrogen atoms, or C1-C
An alkyl group of 8 is preferred, and a hydrogen atom is most preferred.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,
A substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted aryl group or a substituted heterocyclic group. Substituent aryl groups are preferred.

(F) Q is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, particularly a hydrogen atom, A substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

(G) n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 2.
The compound represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y-4) or general formula ( A compound represented by any one of Y-5) is preferred.

General formula (Y-1):

In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation.
m ₁ represents an integer of 0 to 3.

General formula (Y-2):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group,
L ₁ represents a divalent linking group, G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3.

General formula (Y-3):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group,
L ₂ represents a divalent linking group, G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.

General formula (Y-4):

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group,
L ₃ represents a divalent linking group, G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.

General formula (Y-5):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group,
L ₄ represents a divalent linking group, G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

The compound represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y-4) or general formula ( In Y-5), the nitrogen-containing heterocycle composed of G, G ₁ and G ₂ is preferably an S-triazine ring.
Specific examples of the dyes represented by formulas (Y-1) to (Y-5) (exemplified dyes 1 to 26)
) Is shown below, but the dye used in the present invention is not limited to the following examples.

Moreover, although the structure of the following specific examples is shown in the form of a free acid, it cannot be overemphasized that you may use in the form of arbitrary salts.

Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, or organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

The compound represented by the general formula (Y-I) can be synthesized, for example, by a synthesis method (Japanese Patent Laid-Open No. 2001-279145).
JP, 2003-277661, JP 2003-277661, JP 2004-8.
3903) can be synthesized.
As a representative example, a synthesis method of a dye (DYE-11) will be described.
[Synthesis of DYE-11]

(1) Synthesis of compound b1:
18.5 g of NaHCO ₃ and 185 ml of H ₂ O were heated to 40 ° C., a solution of 18.4 g of compound a1 (Tokyo Chemicals) and 48 ml of acetone was added and stirred for 1 hour. After concentrating the acetone, 40 g of hydrazine was added and stirred at room temperature for 3 hours.
4 g of compound b1 (mp> 300 ° C.) was obtained.
(2) Synthesis of compound c1:
Compound b1 10.5 g, pivaloyl acetonitrile (Tokyo Chemicals) 20 g and H ₂
10 ml of 1N-NaOH was added to 330 ml of O and heated for 3 hours. The filtrate was filtered, the filtrate was acidified with acetic acid, and the precipitated crystals were filtered. 4 g of compound c1 (mp = 233-235)
C). ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.2 to 1.3 (18H
, S)
(3) Synthesis of compound e1:
90.57 g of compound d1 was suspended in 500 ml of H ₂ O, and 130 ml of concentrated hydrochloric acid was injected, and then cooled until the internal temperature became 5 ° C. or lower. Next, sodium nitrite 36.23g and 7
0 ml of an aqueous solution was added dropwise at an internal temperature of 4 to 6 ° C., and the mixture was further stirred at an internal temperature of 5 ° C. or lower for 30 minutes.
Next, 159 g of sodium sulfite and 636 ml of H ₂ O were injected while maintaining the internal temperature at 20 ° C. or lower, and 250 ml of concentrated hydrochloric acid was injected at an internal temperature of 25 ° C., followed by stirring at an internal temperature of 90 ° C. for 1 hour. After cooling the internal temperature to room temperature, filtration, washing with 200 ml of water, air drying, and 80.0 g of compound e1
Got.

(4) Synthesis of compound f1:
28 ml of triethylamine in an ethanol suspension of 23.3 g of compound e1 and 209 ml
After dropwise addition at room temperature, 12.2 g of ethoxymethylenemalononitrile (ALDRICH product) was added in portions, refluxed for 3 hours, cooled to room temperature, filtered, washed with 400 ml of isopropyl alcohol and dried to obtain 23.57 g of compound f1. .
(5) Synthesis of DYE-11:
5.4 g of compound f1 was dissolved in 43 ml of phosphoric acid at room temperature and stirred at an internal temperature of 0 ° C. for 3 m.
1 ml of isoamyl nitrite (Tokyo Chemicals) was added dropwise and stirred at the same temperature for 10 minutes, and then dropped into a solution of 3 g of compound c1 suspended in 100 ml of methanol at an internal temperature of −3 to 5 ° C. After stirring at the same temperature for 20 minutes, the reaction solution was poured into 500 ml of H ₂ O, stirred at room temperature for 10 minutes, filtered, washed with H ₂ O, and air-dried to obtain 5.5 g of Dye 62 crude crystals. The obtained crude crystals were adjusted to 10 wt% aq (at 25 ° C .: pH≈8.3: KOHaq preparation) and then gel chromatography (H ₂ O; Sephadex LH-20; Amersham Biosc
purification) to obtain 2.8 g of DYE-11.
λmax = 436 nm (H ₂ O), ε: 3.38 × 10 ⁴ (dm ³ .cm / mol)

The ink composition of the present invention can be used in combination with a yellow dye other than the compounds represented by the general formulas (Y-1) to (Y-5).
Examples of the yellow dye used in combination include International Patent Publication WO2005 / 075573 and JP2004-83.
No. 903 (paragraph numbers [0024] to [0062]), 2003-277661 (paragraph number [0021]
] To [0050]), 2003-277262 (paragraph numbers [0042] to [0047]), 200
3-128953 (paragraph numbers [0025] to [0076]), 2003-41160 (paragraph number [00
28] to [0064]), those described in US Application Publication No. US2003 / 0213405 (paragraph number [0108]), and C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 2
9, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96
, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161,
163, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44,
49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 15
9, 169, 174, 190, 195, 196, 197, 199, 218, 219, 22
2,227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 2
3, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29
, 32, 36, 39, 40 and the following general formula (Y-6), general formula (Y-7), and the like, but are not limited thereto.

General formula (Y-6):

General formula (Y-7):

(In the general formulas (Y-6) and (Y-7), K ₁ , K ₂ , K ₁₁ , and K ₂₁ independently represent CH ₃ , OCH ₃ , and Z and Z ′ represent independently Represents a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, which may be further condensed, and Z and Z ′ are the same as each other. Or different.

A magenta dye useful in the present invention will be described as an azo dye having an azo group bonded to a heterocyclic group.
In the ink set of the present invention, the magenta dye used in the magenta ink composition includes, for example, an aryl or heteryl azo dye having phenols, naphthols, anilines, etc. as a coupler component; for example, pyrazolones, pyrazolotriazoles as a coupler component Azomethine dyes having methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes,
For example, quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes can be exemplified, but the invention is not limited thereto.
As the magenta dye, a heterocyclic azo dye is preferable, and International Application Publication No. 2002/8379.
5 (pages 35-55), 2002-83626 (pages 27-42), JP 2004-1
49560 (paragraph numbers [0046] to [0059]), 2004-149561 (
And those described in paragraphs [0047] to [0060]).

A black dye useful in the present invention will be described as an azo dye having an azo group bonded to a heterocyclic group.

As the black dye, at least one is a compound selected from the group consisting of a compound represented by formula (S-1) and a salt thereof (hereinafter also referred to as “water-soluble shortwave dye S”), and at least One is a compound selected from the group consisting of compounds represented by (L-1), (L-2), (L-3) and (L-4) and salts thereof (hereinafter referred to as “water-soluble long wave dye L”). Also described.
And a combination thereof.

(Water-soluble short wave dye S)
The water-soluble short wave dye S has a maximum absorption spectrum in an aqueous solvent (absorption maximum: λmax) of 440.
It is preferable that the dye has a broad absorption at ˜540 nm and a full width at half maximum of 90 nm to 200 nm. Here, the water solvent means a medium in which water is a main solvent and a dye that may appropriately contain a water-miscible organic solvent is dissolved or dispersed. Also, the absorption spectrum is usually 1cm
It is measured with a spectrophotometer using the cell. The same applies to the water-soluble long wave dye L described later.
The absorption spectrum of the water-soluble short wave dye S is measured using a single compound. That is, when measuring an absorption spectrum in an aqueous solvent, the water-soluble short-wave dye S does not exhibit physical properties such as a desired absorption maximum and half width by combining a plurality of compounds, but exhibits such physical properties by a single compound. Means. It is obvious that compounds having different structures may be used in combination as the water-soluble short wave dye S (hereinafter also referred to as “short wave dye S”). Furthermore, in the present invention, a dye other than the compound represented by the general formula (S-1) may be used in combination.
Since the short wave dye S has such absorption characteristics, it can absorb a wide range of light from blue to green, which tends to be insufficient in the absorption spectrum of the water-soluble long wave dye L, and is preferable as a complementary dye. Have
The absorption maximum of the short wave dye S is preferably between 440 and 520 nm, and particularly preferably between 460 and 500 nm.
The full width at half maximum of the absorption maximum of the short wave dye S is preferably between 100 nm and 180 nm, and particularly preferably between 110 nm and 160 nm.

Further, the short wave dye S preferably does not have a dissociable phenolic hydroxyl group present in a general pigment. With such a structure, there is little change in color tone depending on the image receiving material used, and oxidation such as ozone in the air. It has a preferable performance such as low reactivity with reactive gas and excellent gas resistance.
Here, the dissociable phenolic hydroxyl group means a dissociable hydroxyl group substituted with an aryl group. This aryl group may be substituted with other substituents.
Furthermore, it is preferable that the short wave dye S has four or more azo groups in one molecule. With such a structure, the color developability is enhanced, and an image with good fixability can be obtained because the dye plane is greatly expanded. Can be given.

The black ink composition of the present invention preferably contains a compound selected from the compound represented by formula (S-1) and a salt thereof.

Formula (S-1):

In the general formula (S-1), B _{1 to} B ₃₀ represent a hydrogen atom or an ionic hydrophilic group,
Contains at least one ionic hydrophilic group.

Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable. Among them, a carboxyl group and a sulfo group are preferable, and a sulfo group is most preferable from the viewpoint of increasing the solubility in an aqueous solvent. The carboxyl group, phosphono group, and sulfo group may be in a salt state, and examples of the counter salt include ammonium, alkali metals (eg, lithium, sodium, potassium) and organic cations (eg, tetramethylammonium, Tetramethylguanidinium, tetramethylphosphonium) and the like. As the counter salt, ammonium, lithium, sodium, and potassium are preferable. Among them, sodium and lithium are more preferable, and lithium is most preferable.

Furthermore, although the example of the compound represented with general formula (S-1) preferably used by this invention below is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

Among these, the compound of Compound Example 1 is more preferable. As described above, it may be used as a salt, and a sodium salt is commercially available as CIDirect Red 84 and is useful because it is available as a commercial dye. In addition, when the counter salt is lithium, the dye is less likely to precipitate because it is more water-soluble than other counter cations. Therefore, it is particularly preferable in terms of storage stability in a solution and obtaining a bronze-free image.
In addition to the short-wave dyes S other than the commercially available dyes, Color Index Vol. 4 (The Soc
It can be easily synthesized from commercially available raw materials according to the CIDirect Red84 synthesis route described in the IETY of Dyers and Colorists).

The black ink composition of the present invention preferably contains 0.1 to 3% by mass, preferably 0.2 to 2.5% by mass, particularly preferably 0.3 to 2.0% by mass of the short wave dye S. Is also possible.

(Water-soluble long wave dye L)
In the present invention, the water-soluble long wave dye L has an absorption spectrum maximum (absorption maximum) in an aqueous solvent of 550 to 700 nm and a half-value width of 100 nm or more (preferably 120 to 500 nm, more preferably 120 to
350 nm).
The absorption spectrum of the water-soluble long wave dye L is measured using a single compound. That is, when the water-soluble long wave dye L of the present invention measures an absorption spectrum in an aqueous solvent,
By combining a plurality of compounds, it does not indicate physical properties such as a desired absorption maximum and half width, but it means that such physical properties are exhibited by one compound. In the present invention, as long as the water-soluble long wave dye L (hereinafter also referred to as “long wave dye L”) satisfies the absorption spectrum, it is clear that compounds having different structures may be used in combination. It is. Furthermore, in the present invention, a dye other than the long wave dye L exhibiting the absorption spectrum characteristic may be used in combination.
The long wave dye L preferably has 2 to 4 azo groups conjugated to each other in one molecule.

Further, the long wave dye L is more preferably one having an associative property and a property capable of physically suppressing the reaction.
To determine whether the dye is in an associated state, measure the visible absorption spectrum while changing the dye concentration, and determine whether the dye has an association property by examining the absorption maximum wavelength, molar extinction coefficient, and waveform change. It can be easily judged from a comparison between the physical properties of the solution and the absorption spectrum of the dye on the image receiving material.
Specifically, as defined in JP-A-2004-307831, an aqueous solution of 0.1 mmol / l dye has an optical path length of 1 cm.
The molar extinction coefficient (ε1) at the maximum wavelength of visible absorption measured using the cell of
Between the molar extinction coefficient (ε2) when measuring a l / l aqueous solution using a liquid crystal cell with an optical path length of 5 μm,
Dyes that satisfy the relationship of ε1 / ε2> 1.2 are preferred.

In this invention, it is preferable to contain either of the following general formula (L-1), (L-2), (L-3) and (L-4).
In the following general formula, the dye is represented by the structure of a free acid, but it goes without saying that it may be used in the form of a salt in actual use.

Formula (L-1):

In the general formula (L-1), W, R ₄₃ and R ₄₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, hetero Ring group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group)
An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, a heterocyclic sulfonylamino group, a nitro group, an alkyl and arylthio group, a heterocyclic thio group, Represents an alkyl and arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl and arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group;
Each group may be further substituted. R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R ₄₂ described above. Also, R ₄₃ and R ₄₁ , R ₄₁ and R ₄₂ or R _4
5 and R ₄₆ may combine to form a 5- to 6-membered ring. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ ,
X ₆ and X ₇ represent a monovalent group. However, general formula (L-1) contains at least one ionic hydrophilic group.

  The general formula (L-1) of the present invention will be described in detail.

In general formula (L-1), preferred X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group, An alkynyl group,
Aralkyl group, aryl group, heterocyclic group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group) Represents an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, and a heterocyclic thio group, and each group may be further substituted.

Preferred X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom,
An alkyl group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group), Represents an acylamino group, and among them, a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferable, and an amino group having a substituent is particularly preferable, and an ionic hydrophilic group An amino group substituted with an aryl group having a substituent (such as a substituted anilino group) is most preferred.

Preferred W in the general formula (L-1) is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, a thiophene ring, an imidazole ring, a thiazole ring, a benzothiazole ring, A pyridine ring or a pyridazine ring), particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-
A naphthyl group, a pyridine ring or a thiazole ring;

In General Formula (L-1), R ₄₁ and R ₄₂ each independently represent a hydrogen atom or a carbon number of 1 to 4.
Alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group,
Represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, and a sulfamoyl group, and each group may further have a substituent, among which a hydrogen atom, an alkyl group, an aryl Group, heterocyclic group, acyl group, alkyl group or arylsulfonyl group are preferable, hydrogen atom, alkyl group, aryl group and heterocyclic group are more preferable, especially hydrogen atom, aryl group having a substituent and heterocyclic ring having a substituent. Group is preferable, and a hydrogen atom and an aryl group having a substituent are most preferable. However,
R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , R ₄₁ and R
₄₂ or R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

In the general formula (L-1), R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R ₄₂ , and preferred examples are also the same.

In general formula (L-1), an ionic hydrophilic group is synonymous with general formula (S-1), and its preferable example is also the same.

A particularly preferable combination as the compound represented by the general formula (L-1) of the present invention includes the following (A) to (E).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a heterocyclic group, a cyano group, An alkoxy group, an amide group,
Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) , Hydroxyl (
Salt), phosphono group (may be salt) or quaternary ammonium, among which hydrogen atom, halogen atom, alkyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof), hydroxyl (which may be a salt thereof) (including salts thereof) are preferred, further (including salts thereof) hydrogen atom, a sulfo group, a carboxyl group (including salts thereof) are preferred, X _1,
It is preferable that at least one of X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including a salt thereof) or a carboxyl group (including a salt thereof).

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group, an aryl group, and a heterocyclic group are preferable, particularly a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. Also,
R ₄₃ and _{R 41,} or _{R 41} and _{R 42} may combine to form a 5- or 6-membered ring.

(D) Preferred examples of R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group, and each group may be further substituted.

More preferred R ₄₃ represents a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, among which a cyano group, A carboxyl group, a carbamoyl group, and an alkoxycarbonyl group are preferable, and a cyano group is particularly preferable.

R ₄₄ is more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an amino group (an alkylamino group, an arylamino group). Group, including a heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, among them A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
An alkenyl group, an alkynyl group, an aralkyl group and an aryl group are preferable, and a methyl group is particularly preferable.

(E) R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group, an aryl group, and a heterocyclic group are preferable, particularly a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms. Also,
R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

For preferred combinations of substituents of the dye represented by formula (L-1) of the present invention,
A compound in which at least one of various substituents is the preferred group is preferred, a compound in which more various substituents are the preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred. .

Specific examples of the azo dye represented by the general formula (L-1) are shown below, but the present invention is not limited to the following examples, and in the following specific examples, a carboxyl group, a phosphono group, and The sulfo group may be in a salt state, and examples of the counter ion forming the salt include an ammonium ion,
Alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium) are included. Among these, ammonium ion, sodium ion, potassium ion, and lithium ion are preferable, and lithium ion is most preferable.

(L-2):

In general formula (L-2), R ₁₁ and R ₁₂ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. May be substituted with a good sulfamoyl group, phosphate group, nitro group, acyl group, ureido group, hydroxyl group or a C1-4 alkoxy group, a hydroxyl group, a carbon number of 1 Is an alkoxy group having 1 to 4 carbon atoms or an acylamino group which may be substituted with an alkoxy group of -4, sulfo group or carboxyl group, A represents a phenyl group or a naphthyl group, a halogen atom, a cyano group, a carboxyl group, A sulfo group,
It may be substituted with a sulfamoyl group, phosphoric acid group, nitro group, acyl group, ureido group, hydroxyl group, or alkoxy group having 1 to 4 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group. C1-C4 alkyl group, hydroxyl group, C1-C4
May be substituted by an alkoxy group having 1 to 4 carbon atoms or an acylamino group which may be substituted with an alkoxy group, a sulfo group or a carboxyl group. n1 is 0 or 1.

Of the compounds represented by the general formula (L-2), compounds represented by the following general formula (L-6) are preferred.

(L-6):

In general formula (L-6), R <_13> , R <_14> and R <_15> are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Optionally substituted sulfamoyl group, phosphate group, nitro group, acyl group, ureido group,
Carbon which may be substituted with a hydroxyl group or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfo group or a carboxyl group An alkoxy group or an acylamino group of formulas 1 to 4, and R
_13, at least one of R ₁₄ and R ₁₅ are sulfo groups or carboxyl groups. n1 is 0 or 1.

Specific examples of preferred compounds of the compound represented by formula (L-2) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

Details of the compound represented by formula (L-2) and a salt thereof are described in JP-A-2005-2853.
No. 51 publication, and the compounds described in the publication can be preferably used.

(L-3):

In general formula (L-3), E and F each independently represent a phenyl group, a naphthyl group, or an azo group, which is a 5-membered or 6-membered aromatic heterocyclic group bonded to a carbon atom; Each component contains at least one carboxyl group or sulfo group. One of X and Y is a hydroxyl group and the other is an amino group, and l ₂ , m ₂ and n ₂ are each independently 1 or 2
Represents.

Of the compounds represented by the general formula (L-3), the compounds represented by the following general formula (L-7) are preferred.

Formula (L-7):

In General Formula (L-7), E and G each independently represent a phenyl group, a naphthyl group, or an azo group, which is a 5-membered or 6-membered aromatic heterocyclic group bonded to a carbon atom; Each component contains at least one carboxyl group or sulfo group. a and b each represent a single bond, the bond position of the bond a is the 2nd or 3rd position, and the bond position of the bond b is the 6th or 7th position. One of X and Y is a hydroxyl group, the other is an amino group, l ₃ , m ₃ , n ₃
And each independently represents 0 or 1.

In general formula (L-7), it is preferable that E and G are each independently a phenyl group or a naphthyl group which may be substituted with a substituent containing at least one carboxyl group and / or sulfo group. . Examples of substituents for substituting E and G include halogen atoms,
Alkyl group, amino group, carboxyl group, sulfo group, nitro group, alkyl group, alkoxy group, acyl group, phenyl group, ureido group, hydroxyl group, alkoxy group, alkyl group substituted with sulfo group or carboxyl group, hydroxyl group Group, alkoxy group,
Examples thereof include an alkoxy group substituted with a sulfo group or a carboxyl group, an amino group substituted with a phenyl group, an alkyl group, or an acyl group, which may be further substituted with a carboxy group or a sulfo group.

In the general formula (L-7), E and G are each independently a phenyl group having a sulfo group at the o-position with respect to the azo group and further substituted with a nitro group, an alkoxy group, or a sulfo group. Preferably there is.

Specific examples of preferred compounds of the compound represented by formula (L-3) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

The details of the compound represented by the general formula (L-3) and a salt thereof are described in JP-A-2004-2853.
No. 51 publication, and the compounds described in the publication can be preferably used.

(L-4):

In the formula (L-4), R ₂₁ represents a phenyl group having a substituent or a naphthyl group having a substituent, R ₂₂ represents a phenylene group having a substituent or a naphthylene group having a substituent, and R ₂₃ represents It represents a 5- to 7-membered heterocyclic group having at least one double bond and a substituent.
Further, the substituents in R _{21 to} R ₂₃ are independently OH, SO ₃ H, PO ₃ H ₂ , C
O ₂ H, NO ₂ , NH ₂ , an alkyl group having 1 to 4 carbon atoms, an alkyl group having a substituent, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having a substituent, an amino group, an amino having a substituent It is selected from the group consisting of a group and a phenyl group having a substituent.

In this invention, the compound represented by the following general formula (L-5) is preferable among the compounds represented by the said general formula (L-4).

(L-5):

In the formula (L-5), R _{31 to} R ₃₉ are independently H, OH, SO ₃ H, PO ₃ H ₂ , CO
Represents a group selected from the group consisting of ₂ H, NO ₂ , and NH ₂ .

Specific examples of preferred compounds of the compounds represented by the general formulas (L-4) and (L-5) and salts thereof are shown below, but are not limited thereto. Moreover, although the following specific example is shown with the structure of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

Detailed explanations of the compounds represented by the general formulas (L-4) and (L-5) and salts thereof are described in International Application Publication WO 03/106572 pamphlet and Japanese Patent Application Laid-Open No. 2005-2271. The compounds described in the publication can be preferably used.

Next, a cyan dye useful in the present invention will be described as a phthalocyanine dye having an associative group.
The cyan dye is preferably a dye represented by the general formula (C).

General formula (C)

General formula (CI)

In general formula (C), M represents a hydrogen atom, a metal atom, or an oxide, hydroxide, and halide thereof. Pc represents a phthalocyanine nucleus represented by the general formula (CI) of (k + l + m + n) valence. X ₁ , X ₂ , X ₃ , and X ₄ are each independently —SO—R ₁ , —SO ₂ —R ₁ , —S
Represents a substituent selected from O ₂ NR ₂ R ₃ , —CONR ₂ R ₃ , —CO ₂ —R ₁ , or CO—R ₁ , and four benzene rings in the phthalocyanine nucleus {in the general formula (CI) A, B, C, D}
There are at least one each. However, X ₁ , X ₂ , X ₃ and X ₄ are not all the same, and at least one of X ₁ , X ₂ , X ₃ and X ₄ has an ionic hydrophilic group as a substituent. . R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. k, l, m, and n represent integers of 0 <k <8, and 0 ≦ l <8
An integer of 0 ≦ m <8 is represented, and an integer of 0 ≦ n <8 is represented. Where k and / or l
And / or m and / or n independently represent a number satisfying 4 ≦ k + 1 + m + n ≦ 8. Y
₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom and / or a monovalent substituent. Each of the monovalent substituents may further have a substituent. The general formula (C) has at least one associative group.

The phthalocyanine nucleus represented by the general formula (CI) is preferably represented by the following general formula (CIa).

General formula (CIa)

In the dye represented by the general formula (C), X ₁ , X ₂ , X ₃ and X ₄ are each independently-
Represents a substituent selected from SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃ , and the substituent is four benzene rings in the phthalocyanine nucleus {general formula (CI) or general formula ( A in CIa)
B, C, D} each has at least one.

  The dye represented by the general formula (C) is preferably represented by the following general formula (Ca).

General formula (Ca)

In general formula (Ca), M represents a hydrogen atom, a metal atom, or an oxide, hydroxide, and halide thereof. Pc represents a (k + l) -valent phthalocyanine nucleus represented by the above general formula (CIa). X ₁ and X ₂ are each independently —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃
And four benzene rings in the phthalocyanine nucleus {general formula (C
At least one each exists in A, B, C, D} in Ia). However, X ₁ , X ₂
Are not the same, and at least one of X ₁ and X ₂ has an ionic hydrophilic group as a substituent. R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. k and l represent an integer of 0 <k <8, and represent an integer of 0 ≦ l <8. However, k and / or l each independently represents a number satisfying 4 ≦ k + l ≦ 8.

The associative group of the phthalocyanine dye having an associative group means a group having at least a bonding site (or functional group) capable of hydrogen bonding between molecules in the group. One or more binding sites can be contained in one group. Examples of the bonding site include a hydroxyl group, an amino group, an amide bond, an oxide bond, and the like, and a hydrogen bond is formed between the same species or different species.
The associative group may be capable of hydrogen bonding between the phthalocyanine dye and any additive.
Examples of the substituent that can be an associative group include a hydroxyl group, an ether group, and an ester as a substituent when R ₁ , R ₂ , R _3, and Y in the general formula (C) can further have a substituent. Group, cyano group, amide group, sulfonamide group and the like.

In general, it is known to use various phthalocyanine compounds as an ink composition. The phthalocyanine compound represented by the following general formula (XI) is inevitably defined as a substitution position (R ₁ : 1 position to R ₁₆ : 16 position) of the substituent Rn (n = 1 to 16) during the synthesis thereof. In some cases, these substitution position isomers are regarded as the same derivative without being distinguished from each other. Further, even when isomers are included in the substituent of R, they are often regarded as the same phthalocyanine compound without distinction.

The compounds represented by the general formula (C) include those having different structures. Here, the case where the structures are different from each other is described by the general formula (XI), and the substituent Rn (n = 1 to 16) This is either when the constituent atomic species are different, when the number of substituents Rn is different, or when the position of the substituent Rn is different.

The structure of the phthalocyanine compound represented by the general formula (XI) is different (especially the substitution position).
Derivatives are defined and classified into the following three types.

(1) β-position substitution type: (phthalocyanine compound having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position).
(2) α-position substitution type: (phthalocyanine compound having a specific substituent at the 1- and / or 4-position, 5- and / or 8-position, 9- and / or 12-position, 13- and / or 16-position).
(3) α, β-position mixed substitution type: (phthalocyanine compound having a specific substituent without regularity at positions 1 to 16).

In the present specification, when describing phthalocyanine derivatives having different structures (particularly substitution positions), the above (1) β-position substitution type, (2) α-position substitution type, (3) α, β-position mixture Use substitution type.

The phthalocyanine derivative thus obtained (for example: in the case of k = 1 = m = n = 1) is usually introduced at each X ₁ , X ₂ , X ₃ , X ₄ substituent (the introduction position is β-position). It is a mixture of compounds represented by the following general formulas (a) -1 to (a) -4, which are isomers in common).

That is, the compounds represented by the general formulas (a) -1 to (a) -4 are represented by β-position substitution type (2
And / or phthalocyanine compounds having specific substituents at the 3-position, 6- and / or 7-position, 10- and / or 11-position, 14- and / or 15-position, and α-substituted type (1 and / or 4 position, 5 and / or 8)
Phthalocyanine compounds having specific substituents at the 9th, 9th and / or 12th, 13th and / or 16th positions) and α, β-position mixed substitution type (the phthalocyanine compounds having specific substituents at the 1st to 16th positions without regularity) ) Is a compound having a completely different structure (the position of introduction of a specific substituent is different), and is a structural feature that is extremely important as a means for achieving the object of the present invention.

Derivatives in which a soluble group is introduced only at the β-position are compared to other types in hue, light fastness,
It tends to be overwhelmingly superior in ozone gas resistance.
Specifically, (1) good spectral absorption characteristics (acceleration of association state of phthalocyanine compound by introduction of specific solubility group at β-position); (2) high image fastness (high oxidation potential and promotion of strong association state) (For example, suppressing discoloration due to an oxidation reaction between a phthalocyanine compound and ozone gas as an electrophilic reagent); (3) high solubility in an ink composition; (4) providing good ink liquid temporal stability; The phthalocyanine compound of the invention is selectively incorporated by a specific number of specific dissolving groups into a specific substitution position (β position), that is, a strong association of a fully β-position substituted phthalocyanine compound with a high oxidation potential And a specific number of specific soluble groups can be selectively introduced.

In this case, it is preferable in terms of synthesis that a substituent having a large electron-withdrawing property is selected as the soluble group X, and Y is a hydrogen atom.

The improvement effect of hue, light fastness, ozone gas resistance, etc. brought about by the structural characteristics of these specific substituents and the addition of the required properties to the colored composition (ink) cannot be predicted from the above prior art. Is.

Hereinafter, although the specific example (Exemplary compounds 1-155) of the dye represented by general formula (C) is given, this invention is not necessarily limited to these specific examples.

In the following Tables 1 to 9, the general formula (XII) represents a (k + 1) -valent phthalocyanine nucleus (the introduction position of the substituent R is a β-position substitution type as defined in the present invention). R represents R ₁ and / or R _2, t is an integer of 1-2. It represents an integer of 0 <k <8, and represents an integer of 0 <l <8. However,
k and l each independently represent a number satisfying 4 ≦ k + l ≦ 8.

In the following Table 10, the general formula (XIII) represents a (k + l + m) -valent phthalocyanine nucleus (the introduction position of the substituent R is a β-position substitution type as defined in the present invention). R is R ₁ and / or R ₂ and / or
Or an R _3, t is an integer of 1-2. It represents an integer of 0 <k <8, represents an integer of 0 <l <8, and represents an integer of 0 <m <8. However, k and / or l and / or m are each independently 4
Represents a number satisfying ≦ k + 1 + m ≦ 8.

In the following Table 11, the general formula (XIV) is a (k + l + m + n) -valent phthalocyanine nucleus (substituent R).
Represents the β-position substitution type defined in the present invention. R represents R ₁ and / or R ₂ and / or R ₃ and / or R ₄ , and t represents an integer of 1 to 2.
Represents an integer of 0 <k <8, represents an integer of 0 <l <8, represents an integer of 0 <m <8, 0 <n
<An integer of 8 is represented. However, k and / or l and / or m and / n are each independently 4 ≦ k
It represents a number satisfying + l + m + n ≦ 8.

  In a compound represented by the general formula (C) (a phthalocyanine derivative having a specific structure in which a specific number of specific substituents are selectively introduced at specific positions), the performance exerted by the specific structure is highly functional. It is extremely useful as an ink-jet dye imparted with the above and a dye synthesis intermediate.

  Examples of the water-miscible organic solvent that can be used in the present invention include a drying inhibitor for preventing clogging due to dry operation at the ink jetting port, a penetration accelerator for allowing the ink to penetrate well into paper, and the like. There is.

The drying inhibitor used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, Hexanediol, pentanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, polyhydric alcohols typified by glycerol, trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether , Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl -Heterocycles such as 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulfolene, polyfunctionality such as diacetone alcohol and diethanolamine Examples of the compound include urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.
Examples of penetration enhancers used in the present invention include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, 1,2-hexanediol, and the like. Alcohols, 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, triethylene glycol monobutyl ether, ethylene Glycol derivatives such as ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethylene glycol monophenyl ether can be used. If these are contained in the ink in an amount of 10 to 30% by mass, the effect is sufficient, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  In addition, as a water-miscible organic solvent, in order to increase the solubility of the dye, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylene Amines such as tetramine, polyethyleneimine, tetramethylpropylenediamine, and formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N- Other polar solvents such as vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and acetone can also be used. In addition, the said water miscible organic solvent may use 2 or more types together. The amount of these water-miscible organic solvents used is 0.1 to 80% by mass, preferably 1 to 50% by mass in the ink composition of the present invention.

The ink composition of the present invention includes an ultraviolet absorber, an antioxidant, a viscosity modifier, a surface tension modifier, a dispersant, a dispersion stabilizer, an antifungal agent, a rust inhibitor, a pH adjuster, an antifoaming agent, and a chelate. An appropriate amount of an additive such as an agent can be selected and used.

  Examples of the ultraviolet absorber used for improving the storability of the image in the present invention include JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194443, US Pat. No. 3,214,463, etc. 48-30492, 56-21114, and cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, and 8-239368. And triazine compounds described in JP-A-10-182621, JP-A-8-501291, etc. Jar No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based compounds and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  In the present invention, various kinds of organic and metal complex anti-fading agents can be used as the antioxidant used to improve image storage stability. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

The ink of the present invention preferably further contains a preservative in the ink from the viewpoint of preventing corrosion. In the present invention, the preservative refers to those having a function of preventing the generation and growth of microorganisms, particularly bacteria and fungi (molds) (also referred to as antifungal agents).
The following can be effectively used as preservatives useful in the present invention.

  Examples of inorganic preservatives include heavy metal ions (such as silver ion-containing materials and copper complex compounds) and salts thereof. Organic preservatives include quaternary ammonium salts (tetrabutylammonium chloride, diisopropylammonium nitrite, cetylpyridinium chloride, dicyclohexylammonium nitrite, benzyltrimethylammonium chloride, etc.), phenol derivatives (phenol, cresol, butylphenol, xylenol, bisphenol). ), Phenoxy ether derivatives (phenoxyethanol, etc.), heterocyclic compounds (benzotriazole, proxel (PROXEL), 1,2-benzisothiazolin-3-one, etc.), acid amides, carbamic acids, carbamates, amidine / guanidines , Pyridines (sodium pyridinethione-1-oxide, etc.), diazines, triazines, pyrrole / imidazoles, oxazols・ Oxazines, pentaerythritol tetranitrate, benzotriazoles, thiazole / thiadiazines, thioureas, thiosemicarbazides, dithiocarbamates, sulfides, sulfoxides, sulfones, sulfamides, antibiotics (penicillin, tetracycline, etc.) ), Sodium dehydroacetate, sodium benzoate, p-hydroxybenzoic acid ethyl ester, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, 1,2-benzisothiazolin-3-one and its salts Is possible. As the antiseptic, those described in the antibacterial and microscopic handbook (Technical Hall: 1986), the antibacterial and antifungal encyclopedia (edited by the Japanese Society for Antibacterial and Antifungal Society), etc. can be used.

Various compounds such as those having an oil-soluble structure and a water-soluble structure can be used, but a water-soluble compound is preferable. Particularly preferably, proxel and benzotriazole can be used.
In particular, in the present invention, when two or more of these preservatives are used in combination, the ejection stability of the ink over a long period of time is remarkably improved, and the effects of the present invention are further improved. When two or more types are combined, the preservative species preferably have a skeleton having a different chemical structure. Moreover, when it contains 2 or more types of preservatives, it is preferable that at least 1 type of preservatives is a heterocyclic compound. For example, the combination of a heterocyclic compound and an antibiotic, the combination of a heterocyclic compound and a phenol derivative, etc. are mentioned preferably. The content ratio in the case of combining two kinds of preservatives is not particularly limited, but a range of preservative A / preservative B = 0.01 to 100 (mass ratio) is preferable.
The addition amount of the preservative can be used in a wide range, but is 0.001 to 10% by mass, preferably 0.02 to 5.00% by mass, and more preferably 0.1 to 5% by mass.

  The pH adjuster used in the present invention can be suitably used in terms of pH adjustment, imparting dispersion stability, etc., and the pH of the ink at 25 ° C. is preferably adjusted to 4-11. When the pH is less than 4, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 11, the water resistance tends to deteriorate. As a pH adjuster, an organic base, an inorganic alkali, etc. are mentioned as a basic thing, An organic acid, an inorganic acid, etc. are mentioned as an acidic thing.

  Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, and dimethylethanolamine. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, and potassium hydroxide), carbonates (for example, sodium carbonate, sodium hydrogen carbonate, and the like), ammonium, and the like. 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.

(Surfactant)
The ink composition of the present invention may contain a surfactant. Surfactants improve ink ejection stability by adjusting ink physical properties such as surface tension, improve media permeability, improve water resistance of images, and prevent bleeding of printed ink. Can have an excellent effect.
Surfactants include, for example, fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, cationic surfactants such as fatty amine salts, quaternary ammonium salts and alkylpyridinium salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan Fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer, acetylene Nonionic surfactants polyoxyethylene oxide, etc., amino acids and amphoteric surfactants betaines, fluorine, and the like silicon compound. These can be used alone or in combination of two or more.
From the viewpoint of the above effects, nonionic surfactants are more preferable from the viewpoints of ink ejection stability and paper permeability. In particular, compounds represented by the following general formula (I) or (II) or general formula (III) are more preferable.
Polyhydric alcohol mono- or dialkyl ethers (eg, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc.) also have surface activity. However, in the present invention, these are regarded as penetrants and not as surfactants.

  First, the compound represented by formula (I) will be described.

In the general formula (I), R ²¹ represents an alkyl group having 5 to 40 carbon atoms, preferably 8 to 18 carbon atoms, which may be linear or branched and may be substituted.
Examples of the group that can be substituted for the alkyl group represented by R ²¹ include an aryl group (for example, phenyl, o-tolyl, p-tolyl, pt-butylphenyl), an alkoxy group (for example, methoxy, ethoxy, n-butoxy). Etc.), halogen atoms (for example, chlorine atom, bromine atom) and the like.
Specific examples of the alkyl group represented by R ²¹ include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl. 1-n-butylpentyl, 1-n-pentylhexyl, 1-n-hexylheptyl, 1-n-heptyloctyl, 1-n-octylnonyl, 6-methoxyhexyl, 2-phenylethyl and the like. it can.
m ₁ represents the average number of moles of ethylene oxide added, and is 2 to 40, preferably 3 to 30, and particularly preferably 3 to 20.
Of the compounds represented by the general formula (I), a compound represented by the following general formula (I-1) is particularly preferable.

In General Formula (I-1), R ²² and R ²³ each represent a saturated hydrocarbon having 4 to 10 carbon atoms, and the total number of carbon atoms of R ²² and R ²³ is 8 to 18. m ₁₁ represents an average addition mole number of ethylene oxide is 3 to 20. Examples of the saturated hydrocarbon having 4 to 10 carbon atoms represented by R ²² and R ²³ include n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl and the like can be mentioned. The total number of carbon atoms of R ²² and R ²³ is 8 to 18, and 8 to 16 is more preferable. m ₁₁ is 3 to 20, more preferably from 5 to 20, more preferably from 6 to 18.
Although the specific example of a compound represented by general formula (I) below is shown, it is not limited to these.

  Specific examples of the compound represented by the general formula (I-1) are shown in Table 12 below, but are not limited thereto.

  Next, the compound represented by formula (II) will be described.

In the general formula (II), R ²⁴ represents an alkyl group having 5 to 40 carbon atoms, preferably 5 to 30 carbon atoms, which may be linear or branched, and may be substituted.
Examples of the group capable of substituting for the alkyl group represented by R ²⁴ include an aryl group (eg, phenyl, o-tolyl, p-tolyl, pt-butylphenyl), an alkoxy group (eg, methoxy, ethoxy, n-butoxy). Etc.), halogen atoms (for example, chlorine atom, bromine atom) and the like. Specific examples of the alkyl group represented by R ²⁴ include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl. 1-n-butylheptyl, 1-n-hexylnonyl, 1-n-heptyldecyl, 1-n-octyldodecyl, 1-n-decyltetradecyl, 6-methoxyhexyl, 2-phenylethyl, etc. it can.
m ₂ represents an average addition number of ethylene oxide, 2 to 40, preferably from 3 to 30, particularly preferably from 4 to 20.
Of the compounds represented by the general formula (II), a compound represented by the following general formula (II-1) is particularly preferable.

In general formula (II-1), R ²⁵ and R ²⁶ are each a saturated hydrocarbon group having 2 to 20 carbon atoms, preferably 4 to 13 carbon atoms. Examples of the saturated hydrocarbon group having 2 to 20 carbon atoms represented by R ²⁵ and R ²⁶ include ethyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl. , N-nonyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl and the like. m ₂₁ represents an average addition mole number of ethylene oxide, 2 to 40, 3 to 30 are preferred.
Although the specific example of a compound represented by general formula (II) below is shown, it is not limited to these.

  Examples of the compound represented by the general formula (II-1) include a polyethylene oxide adduct of one-terminal ester of 2-butyloctanoic acid polyethylene oxide and undecan-6-ol. Specific examples of the compound represented by the general formula (II-1) are shown in Table 13 below, but are not limited thereto.

The compound represented by the general formula (I) or the general formula (II) can be synthesized using a known method. For example, Takehiko Fujimoto's revised edition “Introduction to New Surfactant” (1992) ) It can be obtained by the method described in pages 94 to 107.
Next, the acetylene glycol surfactant represented by the general formula (III) will be described.

In the formula, R ³¹ and R ³² each independently represents an alkyl group having 1 to 18 carbon atoms.
More specifically, R ³¹ and R ³² each independently represents an alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, n-propyl, butyl, hexyl, octyl, decyl, dodecyl, etc.) and substituted. It may be. Examples of the substituent include an alkyl group (for example, methyl, ethyl, isopropyl and the like), an alkoxy group (for example, methoxy, ethoxy and the like), a halogen atom (for example, a chlorine atom and a bromine atom) and the like. Among these, as R ³¹ and R ³² , an unsubstituted linear alkyl group having 1 to 12 carbon atoms or an unsubstituted branched alkyl group is preferable, and particularly preferable specific examples thereof include methyl, ethyl, n-butyl, 2- Examples include methylbutyl and 2,4-dimethylpentyl.
R ³² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and the alkyl group and the phenyl group may be substituted.
Examples of the substituent for the alkyl group represented by R ³³ include an alkyl group (for example, methyl, ethyl, isopropyl and the like), an alkoxy group (for example, methoxy, ethoxy and the like), and a phenyl group. Examples of the substituent of the phenyl group of R ³³ include an alkyl group (eg, methyl, ethyl, isopropyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), etc. Can be mentioned. Among R ³³ , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom is particularly preferable.
X is a hydrogen atom,

R ³⁴ and R ³⁵ each independently represents an alkyl group having 1 to 18 carbon atoms. Preferable substituents and specific examples of R ³⁴ and R ³⁵ are substituents and specific examples selected from the same group as R ³¹ and R ³² described above. R ³⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and preferred specific examples thereof are substituents and specific examples selected from the same group as R ³³ described above.
m ₃ and m ₄ each represents the average number of moles of ethylene oxide added, and m ₃ + m ₄ is 0 to 100, preferably 0 to 50, particularly preferably 0 to 40.
Here, when m ₃ = 0, R ³³ represents a hydrogen atom, and when m ₄ = 0, R ³⁶ represents a hydrogen atom. When X represents a hydrogen atom, m ³ represents 1 to 100, preferably 1 to 50, particularly preferably 1 to 40.
Of the compounds represented by the general formula (III), a compound represented by the following general formula (III-1) is particularly preferable.

In the formula, R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ each independently represent an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. m ₃₁ and m ₄₁ each represent the number of moles of ethylene oxide added, and the sum thereof is 0 to 40, preferably 2 to 20.
Although the specific example of a compound represented by general formula (III) or general formula (III-1) below is shown, it is not limited to these.

The compound represented by the general formula (III) or the general formula (III-1) can be synthesized using a known method. For example, Takehiko Fujimoto's revised edition “Introduction to New Surfactant” ( (1992), pages 94 to 107, and the like.
Moreover, the compound represented by general formula (III) or general formula (III-1) can also be easily obtained as a commercial item, and as the specific brand name, it is Surfinol 61,82,104,420. , 440, 465, 485, 504, CT-111, CT-121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF-58, DF -75, DF-110D, DF-210, GA, OP-340, PSA-204, PSA-216, PSA-336, SE, SE-F, Dinol 604 (above, Nissin Chemical Co., Ltd. and Air Products & Chemicals) ), Orphine A, B, AK-02, CT-151W, E1004, E1010, P, SPC, STG, Y, 32W Science Co., Ltd.).
Examples of the compound represented by the general formula (III-1) include ethylene oxide adducts of acetylene-based diols (SURFYNOL series (Air Products & Chemicals)) and acetylene-based diols such as 2,4,7,9-tetra Methyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol and the like are preferable, and molecular weight is particularly preferable. Having a molecular weight of 300 to 900 is more preferable, and a molecular weight of 400 to 900 is particularly preferable.
As the surfactant to be contained in the ink composition in the present invention, it is preferable that precipitation and separation from the ink hardly occur and the foaming property is small. From this viewpoint, the hydrophobic part is double-stranded or the hydrophobic part is branched. Anionic surfactants, anionic or nonionic surfactants having a hydrophilic group in the vicinity of the center of the hydrophobic site, and nonionic surfactants in which the hydrophobic site is double-stranded or the hydrophobic site is branched A surfactant is preferred. Of these, nonionic surfactants are preferred, and from this viewpoint, the nonionic surfactants having a hydrophobic portion double-stranded or a branched hydrophobic portion are represented by the general formula (I-1) or the general formula (II-1). The acetylene glycol surfactant represented by the general formula (III-1) is preferred as the nonionic surfactant having a hydrophilic group near the center of the hydrophobic moiety.

  Examples of the surfactant include an ethylene oxide adduct of polypropylene glycol. For example, a compound represented by the following general formula (IV) is preferable.

  In the formula, x, y and z represent integers, and y is preferably an integer of 12 to 60, and x + z is preferably an integer of 5 to 25.

  As the compound represented by the general formula (IV), Adeka Pluronic L61, Adeka Pluronic L62, Adeka Pluronic L63, Adeka Pluronic L64, Adeka Pluronic L42, Adeka Pluronic L43, Adeka Pluronic L44, Adeka Pluronic L31, manufactured by Asahi Denka Co., Ltd. Examples include Adeka Pluronic L34, but the present invention is not limited to these.

  The content of the surfactant in the ink composition of the present invention is 0.05 to 50 g / L, preferably 0.05 to 30 g / L, and more preferably 0.1 to 20 g / L. Within the above-mentioned range, the printing failure due to the deterioration of ejection stability, the occurrence of bleeding at the time of color mixing, the degradation of printing quality such as the generation of whiskers, the adhesion of ink to the hard surface during ejection, etc. is further improved.

  In the present invention, a solid wetting agent can also be used. The solid wetting agent is a wetting agent that is solid at room temperature, and urea, ethylene urea, trimethylolpropane, or trimethylolethane is particularly preferable. By using a solid wetting agent, it is possible to provide an ink composition and a recording method which can suppress bronze gloss and have excellent ejection stability without impairing ozone resistance and light resistance.

  In addition to the specific dye according to the present invention described above, other dyes may be added to the ink composition of the present invention for the purpose of adjusting the color tone. Further, in order to constitute a full color ink set, a yellow ink and a black ink are used in combination with the ink composition of the present invention, and each of these dyes is also used. Examples of the dyes that can be used in combination are as follows.

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

  Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, and merocyanines Dyes, methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; And ring dyes. These dyes may exhibit magenta only after a part of the chromophore is dissociated, and the counter cation in that case 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, and further may be a polymer cation having them in a partial structure.

Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanines Dye; anthraquinone dye; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes can be mentioned. These dyes may be those that exhibit cyan only after part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal, an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.
Black pigments such as polyazo dyes can also be used.

As other water-soluble dyes, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes can be used in combination.
Among these, CI Direct Red 1, 2, 4, 9, 11, 23, 26, 31, 37, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 87, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 219, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, 254, CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101 C.I.Direct Blue 1, 10, 15, 22, 25, 55, 67, 68 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200 , 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 290, 291
CI Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132 , 146, 154, 166, 168, 173, 199
CI Acid Red 1, 8, 35, 42, 52, 57, 62, 80, 81, 82, 87, 94, 111, 114, 115, 118, 119, 127, 128, 131, 143, 144, 151, 152 , 154, 158, 186, 245, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397 C.I. Acid Violet 5, 34, 43, 47 48, 90, 103, 126, CI Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 87, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 185, 205, 207, 220, 221, 230, 232, 247, 249, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326C.I. Acid Black 7, 24, 29, 48, 52: 1, 172C.I.Reactive Red 3, 6, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43 45, 49, 55, 63, 106, 107, 112, 113, 114, 126, 127, 128, 129, 130, 131, 137, 160, 161, 174, 180 C.I.Reactive violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34C.I.Reactive Blue 2, 3, 5, 7, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, 82, 89, 158 , 182, 190, 203, 216, 220, 244
CI Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34 C.I.Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46 C.I.Basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48
CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71 C.I.Basic Black 8, etc. It is done.

In addition to the dye represented by the above formula, dyes described in the following publications can also be preferably used.
JP-A-10-130557, JP-A-9-255906, JP-A-6-234944, JP-A-7-97541, European Patent 982371, WO 00/43450, WO 00/43451, WO 00/43452, WO 00 / 43453, WO 03/106572, WO 03/104332, JP 2003-238862, JP 2004-83609, JP 2002-302619, JP 2002-327131, JP 2002-265809, WO 04 / 087815, WO 02/090441, WO 03/027185, WO 04/088551, JP 2003-321627, JP 2002-332418, JP 2002-332419, WO 02/059216, WO 02/059215, WO 04/0887814 , WO 04/0 6252, WO 04/046265, US Patent 6652637B, WO 03/106572, WO 03/104332, Special Table 2002-540281, Patent 3558213, Patent 3558212, Patent 3558211, JP 2004-285351, JP 2004-323605, WO 04/104108, JP-A-2003-192930, WO 99/48981, European Patent Publication No. 1063268A, etc., anthrapyridone dye, European Patent No. 682088B1, WO 94 / 16021A, WO 96 / 24636A, US Patent 6468338, WO 03 / 106572A, JP-A-9-124965, JP-A-6-220377, JP-A-6-234944, WO 98/44053, WO 00/58407, European Patent Publications 1378549A, 755984A Azo dyes described in JP 1052274A and JP 1048701, JP 2000-160079, JP 10-130557, WO 01 / 48090A, WO 01 / 62854A, WO 2004 / 7622A, European Patent Publication 1086999A, Key described in 982371A Toazo dye, European Patent Publication No. 1243627A No., same 1243626A issue, same 1394227A JP, JP-A No. 2003-34758, WO 02 / 34844A, WO No. 04/87815.

(Pigment)
As the pigment that can be used in the present invention, commercially available pigments and known pigments described in various documents can be used. Regarding the literature, the Color Index (Edited by The Society of Dyers and Colorists), “Revised New Handbook of Pigments” edited by the Japan Pigment Technology Association (published in 1989), “Latest Pigment Applied Technology” published by CMC (published in 1986), “Printing Ink Technology” CMC Publishing (1984), W. Herbst, K.M. Hunger co-authored Industrial Organic Pigments (VCH Verlagsgesellschaft, published in 1993). Specifically, as organic pigments, azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, quinacridone Pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dyed lake pigments (acid or basic dye lake pigments), azine pigments, etc. C.I. of yellow pigment I. Pigment Yellow 34, 37, 42, 53, and other red pigments such as C.I. I. Pigment Red 101, 108, C.I. I. Pigment Blue 27, 29, 17: 1, etc., black pigments such as C.I. I. Pigment Black 7, magnetite, and other white pigments such as C.I. I. Pigment White 4, 6, 18, 21 and the like.

  As a pigment having a preferable color tone for image formation, a phthalocyanine pigment, an anthraquinone-based indanthrone pigment (for example, CI Pigment Blue 60), and a dyed lake pigment-based triarylcarbonium pigment are preferable for a blue or cyan pigment. Phthalocyanine pigments (preferred examples include copper phthalocyanine such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, monochloro or low chlorinated copper) Among the phthalocyanines and alnium phthalocyanines, the pigments described in European Patent No. 860475, the metal-free phthalocyanine which is CI Pigment Blue 16, the phthalocyanines whose central metals are Zn, Ni and Ti, among them, CI pigment is preferable. Bl e 15: 3, 15: 4 and aluminum phthalocyanine) are most preferred.

  For red to purple pigments, azo pigments (preferred examples include CI Pigment Red 3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146, and 184). I. Pigment Red 57: 1, 146, 184), quinacridone pigments (preferred examples include CI Pigment Red 122, 192, 202, 207, 209, CI Pigment Violet 19, 42, particularly preferred are CI Pigment Red 122), dyed lake pigment-based triarylcarbonium pigments (preferred examples include xanthene-based CI Pigment Red 81: 1, CI Pigment Violet). 1, 2, 3, 27, 39), dioxazine pigments (for example, CI Pigment Violet 23, 37), diketopyrrolopyrrole pigments (for example, CI Pigment Red 254), perylene Pigments (e.g. CI Pi ment Violet 29), anthraquinone pigments (e.g., C.I. Pigment Violet 5: 1, the 31, the 33), thioindigo (e.g. C.I. Pigment Red 38, the 88) is preferably used.

  Examples of yellow pigments include azo pigments (preferred examples include monoazo pigment-based CI Pigment Yellow 1, 3, 74, 98, disazo pigment-based CI Pigment Yellow 12, 13, 14, 16, 17, 83, synthetic azo-based CI Pigment Yellow 93, 94, 95, 128, 155, benzimidazolone-based CI Pigment Yellow 120, 151, 154, 156, 180, etc. That are not used as raw materials), isoindoline / isoindolinone pigments (preferred examples include CI Pigment Yellow 109, 110, 137, and 139), and quinophthalone pigments (preferred examples include CI). Pigment Yellow 13 Etc.), etc. flavanthrone pigments (e.g., C.I. Pigment Yellow 24) are preferably used.

Preferred examples of the black pigment include inorganic pigments (preferably carbon black and magnetite as examples) and aniline black.
In addition, an orange pigment (such as CI Pigment Orange 13, 16) or a green pigment (such as CI Pigment Green 7) may be used.

The pigment that can be used in the ink composition of the present invention may be the above-mentioned bare pigment or a surface-treated pigment. Surface treatment methods include resin or wax surface coating, surfactant deposition, reactive substances (eg radicals derived from silane coupling agents, epoxy compounds, polyisocyanates, diazonium salts, etc.) pigments A method of bonding to the surface is conceivable and is described in the following documents and patents.
(1) Properties and applications of metal soap (Sachishobo)
(2) Printing ink printing (CMC Publishing 1984)
(3) Latest pigment application technology (CMC Publishing 1986)
(4) U.S. Pat. Nos. 5,554,739, 5,571,311 (5) JP-A-9-151342, 10-140065, 10-292143, 11-166145 Self-dispersing pigments prepared by allowing a diazonium salt described in US Patent 4) to act on carbon black and encapsulated pigments prepared by the method described in Japanese Patent (5) above are used in inks. In particular, the dispersion stability can be obtained without using an extra dispersant.

In the ink composition of the present invention, the pigment may be further dispersed using a dispersant. Various known dispersants can be used in accordance with the pigment to be used, for example, a surfactant-type low-molecular dispersant or a polymer-type dispersant. Examples of the dispersant include those described in JP-A-3-69949, European Patent 549486 and the like. In addition, when a dispersant is used, a pigment derivative called a synergist may be added to promote adsorption of the dispersant to the pigment.
The particle size of the pigment that can be used in the present invention is preferably in the range of 0.01 to 10 μm after dispersion, and more preferably 0.05 to 1 μm.
As a method for dispersing the pigment, a known dispersion technique used in ink production or toner production can be used. Examples of the dispersing machine include vertical or horizontal agitator mills, attritors, colloid mills, ball mills, three roll mills, pearl mills, super mills, impellers, dispersers, KD mills, dynatrons, and pressure kneaders. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

  The ink composition of the present invention can be used for various image recording because of its high image durability. The dye for imaging can be used, for example, in photographic photosensitive materials, in thermal transfer materials, in thermal and pressure sensitive recording materials, in ink jet recording, etc. Is suitable for use as an ink composition for inkjet recording.

  The method for preparing the ink composition is described in detail in JP-A-5-295212, JP-A-7-97541, and JP-A-7-82515 in addition to the aforementioned patent documents, and the ink composition of the present invention. It can also be used to prepare products.

[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. To do. As the image receiving material, an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support is preferable. The description of paragraph numbers 0093 to 0105 of JP-A No. 2003-306623 can be applied as the ink jet recording method of the present invention.

  In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638, JP 2002-121440, JP 2002-154201, JP 2002-144696, JP 2002-080759, Japanese Patent Application 2000-299465, and Japanese Patent Application 2000. The method described in -297365 can be preferably used.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066. When a polymer latex 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 latex having a high glass transition temperature to the backcoat layer.

As described above, the ink composition of the present invention may be an ink set containing the ink composition for forming a color image. In the present invention, the ink jet recording method is not limited, and a known method, for example, a charge control method in which ink is ejected using an electrostatic attraction force, a drop-on-demand method (pressure pulse using a vibration pressure of a piezo element), or the like. Method), an acoustic ink jet method in which an electrical signal is converted into an acoustic beam and applied to the ink and the ink is ejected using the radiation pressure, and a thermal ink jet method in which bubbles are formed by heating the ink and the generated pressure is used. Used for etc.
Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
First, dyes used in the following examples are described.

Y-1

M-1

C-1

In the formula, three of the four Xs are —SO ₂ (CH ₂ ) ₃ SO ₃ Li, and one X is —SO ₂ (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (CH ₃ ) OH. It is.

BK-1

Y-2

<Creation of IS-01>
(Preparation of ink composition)
Each component having the composition shown in Table 14 was stirred and dissolved for 1 hour while being heated at 30 to 40 ° C. Thereafter, each ink composition was prepared by filtration under reduced pressure through a microfilter having an average pore diameter of 0.25 μm, and ink set IS-01 was obtained.

  In the above table, Orphin E1010 is an acetylene glycol surfactant manufactured by Nissin Chemical Co., Ltd., and PROXEL XL II (S) is an Avecia preservative.

<Creation of IS-02>
An ink set IS-02 (Comparative Example) was obtained in the same manner as described above except that tricarballylic acid was added instead of 3Na citric acid as an additive.

  Next, the ink tank BCI-7 for an inkjet printer manufactured by Canon Inc. was filled with the ink, and the following evaluation was performed using an inkjet printer PIXUS iP8600 manufactured by Canon Inc. In addition, genuine ink was used as it was for red ink and green ink.

(Image quality evaluation)
A solid image of yellow, magenta, cyan, and black is printed on an inkjet paper photo glossy paper “Fuji Photo Film” manufactured by Fuji Photo Film Co., Ltd. in an environment of 35 ° C. and 80% RH. After drying overnight in an environment of% RH, it was visually evaluated according to the following criteria.
A: No dye deposition or bronze gloss is observed on the surface of the image receiving paper.
B: Precipitation of dye and bronze gloss are observed in some places on the image receiving paper surface.
C: Precipitation of dye and bronze gloss are observed in a wide range on the image receiving paper surface.

(Evaluation of image preservation)
A solid image of yellow, magenta, cyan, and black was printed on an inkjet paper photo glossy paper “Fuji Photo Film” manufactured by Fuji Photo Film Co., Ltd. in an environment of 23 ° C. and 60% RH. The following evaluation was performed after drying overnight.
(1) Light fastness is measured after the image density Ci is measured with a reflection densitometer X-rite 310, and the image is irradiated with xenon light (85,000 lux) for 14 days using a weather meter manufactured by Atlas. The image density Cf was measured again, and the dye residual ratio (Cf / Ci) × 100 was determined and evaluated.
The evaluation was performed by the dye residual ratio at a reflection density of 0.9 to 1.1.
(2) For ozone resistance, the image is left in a box where the ozone gas concentration is set to 0.5 ppm for 7 days, and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR). It was measured and evaluated as a dye residual ratio. The evaluation was performed based on the dye residual ratio at a reflection density in the range of 0.9 to 1.1. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.

  The above evaluation results are shown in Tables 15 and 16 below.

From the results of the examples, in the printing method according to the present invention, it is possible to obtain a high-quality image without impairing the image preservability such as light resistance and ozone resistance of the ink, and without dye precipitation and bronze gloss. I understood.
In addition, although it carried out using PR101 made from Canon, and the photographic paper made from Epson, the same result was obtained in any case.

Claims (7)

  In an ink composition comprising at least an azo dye having an azo group bonded to a heterocyclic group, or a phthalocyanine dye having an associative group, a water-miscible organic solvent, and water, citric acid and / or a salt thereof is further added. An ink composition comprising the ink composition.   2. The ink composition according to claim 1, wherein the content of citric acid and / or a salt thereof is 0.01 to 1% by mass in the ink composition.   The ink composition according to claim 1 or 2, wherein the azo dye having an azo group bonded to the heterocyclic group is an azo dye having a heterocyclic group at both ends of the azo group.   The oxidation potential of an azo dye having an azo group bonded to the heterocyclic group or a phthalocyanine dye having the associative group is nobler than 1.0 V (vs SEC). An ink composition according to any one of the above.   An ink set comprising the ink composition according to claim 1.   A recording method using the ink composition according to claim 1 or the ink set according to claim 5.   The recording method according to claim 6, wherein the recording method is an inkjet recording method.