JP2002114927A - Process for producing pigment dispersion, and ink for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and easy process for producing a pigment dispersion, and an ink for ink jet recording, having a good color hue and excellent in light and water resistances. SOLUTION: The process for producing a pigment dispersion has steps of supplying a first liquid comprising a solution of a water-soluble metal salt and a second liquid comprising a solution of a dye of general formula 1 or 2, and mixing under stirring the supplied first and second liquids to convert the dye into a pigment to thereby form dispersed pigment particles. The ink for ink jet recording contains a pigment obtained by converting a dye of general formula 1 or 2 into a pigment. A concrete example of the dye is a compound represented by formula 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a pigment dispersion and an ink-jet ink.

[0002]

2. Description of the Related Art Ink jet recording methods include a method in which small droplets of ink are caused to fly on recording paper by utilizing the electric deformation of a piezoelectric element or the pressure of foaming during heating. Is becoming widely used due to the spread of the Internet, especially due to the influence of the Internet. As a colorant for these printers, a dye ink used by dissolving a dye in a medium and a pigment ink obtained by solid-dispersing a pigment in a medium are used. Most commercially available printers use a dye ink in which a water-soluble dye is dissolved in a glycol-based solvent and water. When a dye ink is used, the hue of the printed image becomes good, but there is a problem that the water resistance of the image is low and the light resistance is low because the dye is water-soluble. On the other hand, when the pigment ink is used, the water resistance and the light resistance of the printed image are good, but the hue is inferior to the case where the dye ink is used, and the light resistance and the water resistance and the hue are compatible. The development of a new ink is desired.

[0003] Oxonol compounds are known as dyes having good hue. The oxonol compound is important as a dye, a sensitizing dye for photography, a dye for recording optical information, a stain for a biological sample such as a cell, or a drug, and its absorption spectrum in a solution is often characterized by a sharp one. is there. However, the oxonol compound has a sharp absorption in a solution, but is water-soluble because the chromophore has a negative charge and is hydrophilic. If an oxonol compound having low solubility in water can be developed, it can be expected as a colorant having good hue, water fastness and light fastness. However, in reality, oxonol compounds satisfying various performances have not yet been found.

On the other hand, when preparing a pigment ink, a compound which is hardly soluble in water, such as a pigment, is dispersed in an aqueous medium.
Pigments produced by various methods are ground with a disperser together with water and a dispersant. However, with inkjet inks,
In order to prevent nozzle clogging at the time of ink ejection, it is necessary to atomize the pigment, and this method requires several hours to several tens of hours for grinding and dispersion. Therefore, a method for preparing a pigment ink more simply is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a pigment dispersion capable of easily producing a pigment dispersion having good hue, light fastness and water fastness. Another object of the present invention is to provide an inkjet ink which can be produced by a simple method and can form an image having good hue, light fastness and water fastness.

[0006]

Means for solving the above problems are as follows. <1> A first liquid which is a solution of a water-soluble metal salt and a second liquid which is a solution of a dye represented by the following general formula (1) or (2) are supplied and supplied. The first
A method for producing a pigment dispersion, comprising a step of producing a pigment particle by pigmentizing the dye by stirring and mixing the liquid and the second liquid.

General formula (1)

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General formula (2)

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Wherein A and B each have a conjugated double bond chain
Y and Z each represent an atomic group necessary for completion.
Lists the atomic groups required to form a carbocyclic or heterocyclic ring.
You. L ¹, L^Two, L^Three, L^FourAnd L^FiveAre each replaced
Represents an optional methine group, and P, P ', Q and Q' are
Stands for a substituent. X and X 'are each an oxygen atom,
Sulfur atom or C (CN)_TwoAnd G⁺Is a proton,
Represents triethylammonium or pyridinium. m1
And n1 represent 0, 1 or 2, respectively, and x and y are each
Represents 0 or 1, respectively.

<2> The pigment according to <1>, wherein an anionic surfactant and / or a nonionic surfactant are contained in at least one of the first liquid and the second liquid. This is a method for producing a dispersion. <3> The method for producing a pigment dispersion according to <1> or <2>, wherein the average volume particle size of the pigment particles is 0.2 μm or less.

<4> An inkjet ink containing a pigment, water, and a hydrophilic organic solvent, wherein the pigment is a first liquid which is a solution of a water-soluble metal salt, and a first liquid represented by the following general formula (1): Or a second pigment, which is a solution of the dye represented by (2), and a pigment that has been pigmented by stirring and mixing the supplied first liquid and the second liquid. And the volume average particle size of the pigment is 0.2
It is an ink for inkjet characterized by being below μm.

General formula (1)

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General formula (2)

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Wherein A and B each represent a conjugated double bond chain
Y and Z each represent an atomic group necessary for completion.
Lists the atomic groups required to form a carbocyclic or heterocyclic ring.
You. L ¹, L^Two, L^Three, L^FourAnd L^FiveAre each replaced
Represents an optional methine group, and P, P ', Q and Q' are
Stands for a substituent. X and X 'are each an oxygen atom,
Sulfur atom or C (CN)_TwoAnd G⁺Is a proton,
Represents triethylammonium or pyridinium. m1
And n1 represent 0, 1 or 2, respectively, and x and y are each
Represents 0 or 1, respectively.

In the production method of the present invention, pigment dispersion particles are formed by converting a dye solution into a pigment. Therefore, it is necessary to grind a solid pigment with a disperser, which is required in the conventional production method. A pigment dispersion can be easily and simply manufactured. Further, since the pigment contains a pigment obtained by converting a dye into a pigment, the resulting pigment dispersion has excellent hue and excellent water resistance and light resistance. Further, since the inkjet ink of the present invention contains pigment particles obtained by converting a dye into a pigment,
An image having not only excellent hue but also excellent water resistance and light resistance can be formed. Further, by producing a pigment by pigmentation of the dye using a dye solution, it is not necessary to grind the solid-state pigment required for the conventional pigment ink production with a disperser, It can be easily manufactured.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION [Method for Producing Pigment Dispersion] In the method for producing a pigment dispersion according to the present invention, a first liquid which is a solution of a water-soluble metal salt is prepared by the following general formula (1) or (2). And a second liquid which is a solution of the dye represented by
The method further comprises a step of mixing the supplied first liquid and the second liquid with stirring to convert the dye into a pigment to generate pigment dispersed particles. In addition, the method for producing a pigment dispersion of the present invention may include, before the step, a step of preparing the first liquid and a step of preparing the second liquid.

It is preferable to continuously supply the first liquid and the second liquid, and to continuously mix and stir the supplied liquids, because the production efficiency is further improved. Further, it is more preferable to supply each liquid continuously at an equal flow rate.

In the method for producing a pigment dispersion of the present invention, for example, a container provided with a supply port capable of supplying the first liquid and the second liquid, and the liquid in the container are mixed and stirred. It can be carried out using a stirrer provided with a stirring means. It is preferable that the stirring means has high stirring and mixing efficiency of the liquid in the container. When the stirring and mixing efficiency of the stirring means is high, the production efficiency can be improved, and the primary particles of the aqueous pigment to be produced can be made finer and the particle size can be averaged. As a stirrer provided with a stirrer having high stirring and mixing efficiency, for example, JP-A-10-4
The stirring device described in Japanese Patent No. 3570 is preferably used in the present invention.

The average volume particle diameter of the pigment-dispersed particles formed in the above step is preferably 0.2 μm or less in terms of improving the hue. Further, when the average volume particle diameter of the pigment-dispersed particles is in the above-mentioned range, the ejection stability of the ink is improved even when the pigment is used in an inkjet ink without being finely divided, which is preferable. The particle size of the pigment-dispersed particles can be adjusted by production conditions, for example, a solution addition speed, a stirring speed, and the like. Usually, the addition speed (supply flow rate per unit time) of the first and second liquids is increased and The particle size of the pigment particles generated decreases as the stirring speed increases.

[0020] The first liquid can be prepared by dissolving a water-soluble metal salt in a predetermined solvent. As the solvent, water is preferable. In addition, a mixed solvent obtained by mixing a hydrophilic organic solvent with water can be used according to the solubility of the water-soluble metal salt, the affinity for the second liquid, and the like. The water-soluble metal salt may be dissolved in water and dissolved in water.
A metal salt that can exist as a metal cation having a valency or higher can be used. As the water-soluble metal salt, any of the typical metals of Groups 2 and 12 to 15 and transition metals of Groups 3 to 11 of the periodic table can be used. Of these, salts of typical metals of Groups 2, 12, and 13 are more preferable, salts of magnesium, calcium, strontium, barium, zinc and aluminum are more preferable, and salts of magnesium, calcium, zinc and aluminum are most preferable. preferable.

The metal valence of the water-soluble metal salt is preferably 2 to 6, more preferably 2 to 4, and preferably 2 to 4.
Or 3 is particularly preferred.

The second liquid can be prepared by dissolving the dye represented by the general formula (1) or (2) in a predetermined solvent. As the solvent,
Hydrophilic organic solvents are preferred, for example, dimethylformamide (DMF), dimethylsulfoxide (DMSO),
Dimethylacetamide (DMAc), N-methyl-2-
Pyrrolidone, N, N, N ', N'-tetramethylurea,
Preferred are 1,3-dimethyl-2-imidazolidinone, sulfolane and the like.

Hereinafter, the dyes represented by formulas (1) and (2) will be described. In the general formula (1), Y
-C- (A) _x -C (= X)-which binds to Z and -C = (B) _y = C (-X'H)-which binds to Z are in a conjugate state. Therefore, Y and -C- (A) bonded thereto
a carbocyclic or heterocyclic ring represented by _x- C (= X)-, and Z and -C = (B) _y = C (-X '
The carbocycle or heterocycle represented by H)-is considered as one of the resonance structures. In the following, for convenience, Y and Z and -C- (A) _x -C (=
X)-and -C- (B) _y -C (-X'H)-and carbocycles and heterocycles (hereinafter referred to as "resonance-structure carbocycle" and "resonance-structure heterocycle", respectively) May be)
Will be described together.

The carbocycle and heterocycle of the resonance structure include
A 4- to 7-membered carbocyclic or heterocyclic ring is preferred. Particularly preferred is a 5- or 6-membered carbocyclic or heterocyclic ring. These rings may be further condensed with another ring, and the condensed ring is preferably a 4- to 7-membered ring. Further, the carbocycle or heterocycle may have a substituent.

As the substituent, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group),
Alkenyl group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and aryl Ruhoniru group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group,
Examples include carbamoyl, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups.

The substituents will be described in more detail. A halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [shows a linear, branched, or cyclic substituted or unsubstituted alkyl group. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, For example, cyclohexyl, cyclopentyl,
4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms) For example, bicyclo [1,2,2] heptane-
2-yl, bicyclo [2,2,2] octan-3-yl), and a tricyclo structure having many ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below represents an alkyl group having the same concept. ],

Alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group; An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted 3 to 30 carbon atoms); A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-
Cyclopenten-1-yl, 2-cyclohexen-1-
Yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 to 30 carbon atoms)
Is a substituted or unsubstituted bicycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,
2,1] hept-2-en-1-yl, bicyclo [2,
2,2] oct-2-en-4-yl)], alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group), aryl group ( A substituted or unsubstituted aryl group having preferably 6 to 30 carbon atoms,
For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),

Heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 5 or 6 of number 3 to 30
Membered aromatic heterocyclic group. For example, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms)
A substituted or unsubstituted alkoxy group such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy) and an aryloxy group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Aryloxy group, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably having 3 to 20 carbon atoms)
Silyloxy group, for example, trimethylsilyloxy,
t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-
Oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, having 2 to 3 carbon atoms)
0 substituted or unsubstituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy ),

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyl Oxyphenoxycarbonyloxy), an amino group (preferably,
An amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, Diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example,
Formylamino, acetylamino, pivaloylamino,
Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),

An aminocarbonylamino group (preferably,
A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino),
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-
Octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxy) Carbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino;
N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino),

Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonyl Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted arylthio such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 3 carbon atoms)
0 substituted or unsubstituted heterocyclic thio group, for example, 2-
Benzothiazolylthio, 1-phenyltetrazole-5
-Ylthio), a sulfamoyl group (preferably having 0 carbon atoms)
To 30 substituted or unsubstituted sulfamoyl groups, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoyl Sulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 3
0 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl),

Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl) , P-methylphenylsulfonyl), an acyl group (preferably 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, for example, acetyl , Pivaloyl, 2-
Chloroacetyl, stearoyl, benzoyl, pn-
Octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example,
Phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, Ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-
Octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazole-2
-Ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methyl) Phenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 to 30 carbon atoms); A substituted or unsubstituted phosphinylamino group, for example, Dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) .

Among the substituents exemplified above, those having a hydrogen atom may be obtained by removing the hydrogen atom contained in the substituent and further substituting with the above exemplified substituent. Examples of the substituent containing a hydrogen atom include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples of the substituent having a dissociable hydrogen atom include a hydroxyl group, a carboxyl group, an imide group, a sulfo group, a carbamoyl group (such as an acylcarbamoyl group and a sulfonylcarbamoyl group).

The heterocyclic ring may contain one kind of hetero atom or two or more kinds of hetero atoms different from each other. Preferred as a hetero atom forming a heterocyclic ring having a resonance structure is an atom selected from a boron atom, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Among them, an atom selected from a nitrogen atom, an oxygen atom and a sulfur atom is preferable.

In the general formula (1), x and y each independently represent 0 or 1, and preferably 0.

In the above general formula (1), X and X 'represent an acid
Elemental atom, sulfur atom or C (CN) _TwoRepresents Among them,
An oxygen atom is preferred.

The carbocycles having the above resonance structure include the following carbocycles I-1 to I-4. x and y each independently represent 0 or 1, but preferably 0.

[0039]

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Among them, the carbocycle having the resonance structure includes
Carbocycles I-1 and I-4 are preferred.

The heterocyclic ring having the resonance structure includes the following heterocyclic rings I-5 to I-41.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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Among the above, as the heterocyclic ring having the resonance structure,
I-5, I-6, I-7, I-8, I-9, I-18,
I-35, I-36 and I-40 are preferred, and I-
5, I-6 and I-7 are more preferred, and I-6 is most preferred.

In the above carbocyclic and heterocyclic rings, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a substituent, and the substituent is the same as the substituent for the carbocyclic and heterocyclic rings in the resonance structure. R ¹ ,
Any two of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be linked to form a condensed ring.

In the general formula (1), L ¹ , L ² , L ³ , L ⁴
And methine groups represented by L ⁵ represents may be each independently selected from the same. The methine group includes an unsubstituted methine group and a methine group having a substituent. The substituent has the same meaning as the substituent for the carbocyclic and heterocyclic rings in the resonance structure. Among them, preferred substituents are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, a halogen atom, an amino group, a carbamoyl group or a heterocyclic group. Further, two or more substituents are linked to form a 5-
7-membered ring (for example, cyclopentene ring, 1-dimethylaminocyclopentene ring, 1-diphenylaminocyclopentene ring, cyclohexene ring, 1-chlorocyclohexene ring, isophorone ring, 1-morpholinocyclopentene ring,
A cycloheptene ring).

In the general formula (1), m1 and n1 each represent 0, 1 or 2. In particular, the sum of m1 and n1 is preferably 0, 1, 2, or 3, and m1 and n1
Is particularly preferably 0, 1 or 2.

In the general formula (1), G ⁺ represents a proton, triethylammonium or pyridinium.

In the general formula (2), L ¹ , L ² , L ³ ,
L ⁴ , L ⁵ , X, X ′, G ⁺ , m1 and n1 have the same meanings as those defined in the formula (1), and the preferred ranges are also the same.

In the general formula (2), the substituents represented by P, P ', Q and Q' have the same meanings as the substituents on the carbocyclic and heterocyclic rings of the resonance structure.

The substituent represented by P or P 'is preferably a substituent having a Hammett's substituent constant σp value of 0.2 or more. Hammett's substituent constant is described, for example, in Chem. Re
v. 91, 165 (1991).
Particularly preferred substituents include cyano, nitro, alkoxycarbonyl, acyl, carbamoyl, sulfamoyl and sulfonyl groups.

Preferred examples of the substituent represented by Q or Q ′ include an alkyl group, an aryl group, an alkoxy group and an amino group.

Hereinafter, the general formula (1) or the general formula (2)
Specific examples of the compound represented by Although shown together, the dye used in the present invention is not limited to the following specific examples.

[0057]

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[0058]

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[0059]

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[0060]

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[0065]

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[0070]

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It is preferable that at least one of the first liquid and the second liquid contains a dispersant. Addition of a dispersing agent is preferred because aggregation of primary particles of the produced aqueous pigment can be prevented. As the dispersant,
Anionic and nonionic surfactants are preferred. As the anionic surfactant, for example,
Fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters,
Preferred are naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate, and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, and glycerin. Fatty acid esters, oxyethylene oxypropylene block copolymers and the like are preferred. As the anionic surfactant and the nonionic surfactant, one type may be used alone, or two or more types may be used in combination. The amount of the dispersant added is preferably not more than 50 parts by mass, based on 100 parts by mass of the resulting aqueous pigment. Preferably, the dispersant is contained in the first liquid.

The method for producing a pigment dispersion of the present invention can be used, for example, for producing various inks.
For example, various inks can be manufactured by adding a step of mixing the pigment dispersion and other components after manufacturing a pigment dispersion by the manufacturing method of the present invention.

[Ink for Ink Jet] The ink for ink jet of the present invention contains a pigment, water and a hydrophilic organic solvent, and the pigment comprises a dye represented by the general formula (1) or (2). It is characterized by becoming. The average volume particle size of the pigment is preferably 0.2 μm or less. It is preferable that the average volume particle diameter of the pigment is in the above range because the ink ejection stability is improved.

The pigment is a pigment formed by supplying the first liquid and the second liquid, respectively, and stirring and mixing the supplied first liquid and the second liquid. Preferably it is. That is, a pigment obtained by using the method for producing a pigment dispersion of the present invention is preferable.

The ink-jet ink is ink 1
When the solid content of the dispersion is 0.2 parts by mass or more and 10 parts by mass
It is preferably at most part by mass.

The water is preferably water from which various ions have been removed, for example, ion-exchanged water, distilled water, pure water, ultrafiltration water and the like. In addition, it is also preferable to devise measures such as suppressing the generation of mold and bacteria by irradiating the water with ultraviolet rays.

As the hydrophilic organic solvent, alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl) Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,
Triethylene glycol monophenyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine) , Diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (for example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane,
2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-
Dimethyl-2-imidazolidinone, acetonitrile, acetone) is preferred. The hydrophilic organic solvents may be used alone or in combination of two or more.

The ink-jet ink of the present invention preferably has a viscosity of not more than 20 mPa · s at room temperature.
More preferably, it is not more than mPa · s. Further, the surface tension is preferably 20 mN / m or more and 100 mN / m or less, and more preferably 20 mN / m or more and 45 mN / m or less. The viscosity and surface tension of various additives,
For example, it can be adjusted by adding a viscosity adjusting agent, a surface tension adjusting agent and the like. Further, the ink-jet ink of the present invention,
Contains additives other than the above additives, for example, pH adjusters, anti-drying agents, penetration enhancers, ultraviolet absorbers, antioxidants, stabilizers, fungicides, rust inhibitors, bactericides, defoamers, etc. It may be.

The ink-jet ink of the present invention can be prepared from known recording materials, that is, plain paper and resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, and JP-A-7-276670. -276789,
JP-A-9-323475, JP-A-62-238873
Gazette, JP-A-10-1538989, and 10-2
No. 17473, No. 10-235995, No. 1
Japanese Patent Application Laid-Open Nos. 0-337947, 10-217597, 10-337947, and the like, for forming an image on ink jet dedicated paper, film, electrophotographic common paper, fabric, glass, metal, ceramics, and the like. Can be used.

The recording paper and recording film which can be used for forming an image using the ink-jet ink of the present invention will be described below. The recording paper and recording film can be composed of a support, an ink receiving layer formed on the surface thereof, a back coat layer formed on the back surface thereof, and the like. The support is a chemical pulp such as LBKP or NBKP,
GP, PGW, RMP, TMP, CTMP, CMP, C
It consists of mechanical pulp such as GP, waste paper pulp such as DIP, etc., and if necessary, mixes known additives such as pigments, binders, sizing agents, fixing agents, cationic agents, paper strength agents, etc. Those manufactured by various devices such as a net paper machine and a circular net paper machine can be used. In addition to the above-described supports, synthetic paper and plastic film sheets may be used as the supports. The thickness of the support is 10 to 250 μm.
m and the basis weight are desirably 10 to 250 g / m ² .

The support may be provided directly with an ink receiving layer and a back coat layer, or may be provided with a size press or an anchor coat layer using starch, polyvinyl alcohol or the like, followed by an ink receiving layer and a back coat layer. May be provided. Further, a machine calendar, T
The flattening process may be performed by a calendar device such as a G calendar or a soft calendar. As the support,
Paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferred. Further, it is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

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

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide. Water-soluble polymers such as derivatives, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion are exemplified. One of these aqueous binders may be used alone, or two or more thereof may be used in combination.
Among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferred in terms of adhesion to the pigment and peel resistance of the ink receiving layer.

The ink receiving layer may contain, in addition to the pigment and the aqueous binder, a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant and other additives. It is preferable that the mordant is immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325 and JP-A-54-28325.
No. 74430, No. 54-124726, No. 55-22
No. 766, No. 55-142339, No. 60-2385
No. 0, No. 60-23851, No. 60-23852,
No. 60-23853, No. 60-57836, No. 60
No. 60643, No. 60-118834, No. 60-1
No. 22940, No. 60-122941, No. 60-12
Nos. 2942 and 60-235134, JP-A-1-16
1236, U.S. Pat. Nos. 2,484,430 and 2,
No. 548564, No. 3148061, No. 330969
0, 4115124, 4124386, 4
193800, 4273753, 428230
Nos. 5 and 4450224. An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

As the water-proofing agent, a cationic resin is particularly preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably from 1 to 15% by mass, particularly preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer. As the light resistance improver, zinc sulfate, zinc oxide,
Hindered amine antioxidants, benzotriazole-based ultraviolet absorbers such as benzophenone and the like can be mentioned. Of these, zinc sulfate is particularly preferred. The addition of the surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil), and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin). Regarding the organic fluoro compound, Japanese Patent Publication No. 57-9053 (No.
17), JP-A-61-20994 and 62-135.
826 is described in each publication.

Other additives to be added to the ink receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener, a preservative, a pH adjuster, a matting agent, and a hardener. And the like. Incidentally, even if the ink receiving layer is a single layer,
It may have more than one layer.

The recording paper and the recording film may be provided with a back coat layer. In the back coat layer,
It is preferable to include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and silicic acid. Aluminum, diatomaceous earth,
White inorganic pigments such as calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloisite, magnesium carbonate, magnesium hydroxide, etc., styrene-based plastic pigment And organic pigments such as acrylic plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin.

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

A polymer latex may be added to the constituent layers (including the back coat layer) of the recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Polymer latex is described in JP-A-62-245258 and JP-A-62-13166.
Nos. 48 and 62-11066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, even if a polymer latex having a high glass transition temperature is added to the back layer,
Can prevent curl

The ink-jet ink of the present invention can be used for various ink-jet recording image forming methods, and the recording method is not particularly limited. Known recording methods, for example, a charge control method in which ink is ejected using electrostatic attraction, a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element, and irradiation of ink by converting an electric signal into an acoustic beam The method can be used in an image forming method using an acoustic ink jet method in which ink is ejected using radiation pressure and a thermal ink jet method in which ink is heated to form bubbles and the generated pressure is used. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. A method using ink is included.

[0100]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In the following examples,% means mass% unless otherwise specified. (Preparation of Pigment Dispersion A) As a solution (first liquid) of a water-soluble metal salt, the following liquids I to III in Table 1 were prepared. Further, as solutions (second solutions) of the dye represented by the general formula (1) or (2), solutions IV to VI in Table 2 below were prepared.

[0101]

[Table 1]

[0102]

[Table 2]

Next, a stirrer having the same structure as the stirrer 10 shown in columns 0010 to 0021 of JP-A-10-43570 and shown in FIG.
The pair of stirring blades was stirred at 1500 revolutions per minute, and the solution I of Table 1 and the solution IV of Table 2 were supplied into the reaction vessel at an equal flow rate for 10 minutes. The solution I and the solution IV are stirred and mixed in a reaction vessel,
370 g of a pigment dispersion A in which the dye in the IV liquid was converted to a pigment to form pigment particles was obtained. About the obtained pigment dispersion A, the volume average particle diameter of the dispersed particles (pigment particles) was measured with a UPA analyzer, and the particle diameter was 0.15 μm.

(Preparation of Pigment Dispersion B) A pigment dispersion B was prepared in the same manner except that the liquid V was used in place of the liquid IV used for preparing the pigment dispersion A. When the volume average particle size of the dispersed particles (pigment particles) of the obtained pigment dispersion B was measured with a UPA analyzer, the particle size was 0.13.
μm.

(Preparation of Pigment Dispersion C) A pigment dispersion C was prepared in the same manner except that the liquid VI was used instead of the liquid IV used for preparing the pigment dispersion A. When the volume average particle size of the dispersed particles (pigment particles) of the obtained pigment dispersion C was measured with a UPA analyzer, the particle size was 0.13.
μm.

(Preparation of Pigment Dispersion D) Pigment Dispersion D was prepared in the same manner except that Liquid II was used instead of Liquid I used for preparing Pigment Dispersion A. About the obtained pigment dispersion D, the volume average particle diameter of the dispersed particles (pigment particles) was measured with a UPA analyzer, and the particle diameter was 0.11.
μm.

(Preparation of Pigment Dispersion E) Pigment Dispersion E was prepared in the same manner except that Liquid III was used in place of Liquid I used for preparing Pigment Dispersion A. About the obtained pigment dispersion E, the volume average particle diameter of the dispersed particles (pigment particles) was measured with a UPA analyzer to find that the particle diameter was 0.16.
μm.

(Preparation of Pigment Dispersion F) In the preparation of Pigment Dispersion A, the rotation of the stirring blade during stirring and mixing was increased by 30 minutes per minute.
Pigment dispersion F was prepared in the same manner except that the rotation was 00. When the volume average particle diameter of the dispersed particles (pigment particles) of the obtained pigment dispersion F was measured with a UPA analyzer, the particle diameter was 0.09 μm.

(Preparation of Pigment Dispersion G) A pigment dispersion G was prepared in the same manner except that the supply of the liquids I and IV during the production of the pigment dispersion A was carried out at an equal flow rate for 5 minutes. When the volume average particle size of the dispersed particles (pigment particles) of the obtained pigment dispersion G was measured with a UPA analyzer, the particle size was 0.08 μm.

(Preparation of Pigment Dispersions H and I) 7.84 g of Exemplified Compound D-110 was ground, added to a solution of 5.0 g of calcium chloride dissolved in 500 ml of water, and heated and stirred on a steam bath for 1 hour. did. After cooling to room temperature, the crystals were filtered, washed with water, and dried with a blast drier (yield 7.0 g). Elemental analysis of this crystal revealed that the crystal was a salt crystal of the anion and calcium cation of Exemplified Compound D-110 at a molar ratio of 2: 1 and contained 4 mol of water molecules per mol (hereinafter, referred to as “ Compound C-1 ").

11.3 g of the compound C-1, 4.5 g of a dispersant having the following structure and 59 ml of ion-exchanged water were added to a sand grinder mill (IMEX Co., Ltd.).
) For 10 minutes and 6 hours, respectively, to obtain Pigment Dispersion H and Pigment Dispersion I, respectively. Note that zirconia was used as a hard grinding medium. With respect to the obtained pigment dispersions H and I, the volume average particle diameter of the dispersed particles (pigment particles) was measured with a UPA analyzer, and the particle diameters were each 0.1.
45 μm and 0.18 μm.

[0112]

Embedded image

(Preparation of Pigment Dispersions J and K) Pigment dispersions J and K were prepared in the same manner except that Exemplified Compound D-57 was used instead of Exemplified Compound D-55 used for preparing Pigment Dispersions H and I. A product J and a pigment dispersion K were obtained. The pigment dispersion having a grinding time of 10 minutes was designated as Pigment Dispersion J, and the pigment having a grinding time of 6 hours was designated as Pigment Dispersion K. With respect to the obtained pigment dispersions J and K, the volume average particle diameter of the dispersed particles (pigment particles) was measured with a UPA analyzer, and the particle diameters were each 0.1.
53 μm and 0.21 μm.

(Preparation of Inkjet Ink) Inkjet ink 1 having the following composition was prepared. Pigment dispersion A 30% Diethylene glycol 12% Glycerin 8% Dispersant 3% Deionized water 47%

Ink jet inks 2 to 7 were prepared in the same manner as in the preparation of ink jet ink 1 except that pigment dispersions B to G were used instead of the pigment dispersion A.
Were each produced.

An ink-jet ink 8 having the following composition was prepared. Pigment dispersion H 12% Diethylene glycol 12% Glycerin 8% Dispersant 3% Deionized water 65%

The ink-jet inks 9 to 1 were prepared in the same manner as in the preparation of the ink-jet ink 8, except that the pigment dispersions I to K were used instead of the pigment dispersion H.
1 was produced.

(Image Recording and Evaluation) An ink-jet printer (“PM-770C”, Seiko Epson Corporation) was manufactured using the ink-jet inks 1 to 11 thus prepared.
Magenta solid images were recorded on photo glossy paper (ink jet paper, photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd.). The resulting image was evaluated for hue, light fastness, and water fastness. Hue was evaluated visually by relative evaluation. The light resistance was measured by irradiating the image receiving material on which the image was recorded with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.I65), and measuring the image density before and after the xenon irradiation with a reflection densitometer (X-Rite310TR). ). The image density before and after storage at 80 ° C. and 70% humidity for 7 days as a part of the light resistance was measured in the same manner. The results are shown in Table 3 below. In Table 3 below, those having a residual dye ratio of more than 90% are indicated by “○”. Regarding the water resistance, the image was dried for 1 hour and then immersed in 1 liter of water for 1 hour to evaluate whether or not the density of the solid image was reduced. In Table 3 below, those having no decrease in concentration were indicated by “○”. Table 3 below also shows the evaluation of the simplicity of the method for producing the pigment dispersion used.

[0119]

[Table 3]

From the results shown in Table 3, it was found that the ink-jet ink of the present invention can be prepared by a simple method and is excellent in hue, light fastness and water fastness.

[0121]

According to the present invention, it is possible to provide a method for producing a pigment dispersion capable of easily producing a pigment dispersion having good hue, light fastness and water fastness. Further, according to the present invention, it is possible to provide a novel ink jet ink capable of forming an image having good hue, light fastness and water fastness.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 67/20 C09D 11/00 C09D 11/00 B41J 3/04 101Y F-term (Reference) 2C056 EA13 FC02 2H086 BA55 BA59 BA60 4H056 CA01 CC02 CC08 CE03 DD07 FA01 4J039 BA30 BA31 BA32 BC16 BC31 BC32 BC33 BC36 BC50 BC51 BC53 BC54 BC55 BC65 BC68 BC72 BC74 BE01 BE02 BE12 BE22 CA06 EA35 EA38 GA24

Claims (4)

[Claims] 1. A first liquid which is a solution of a water-soluble metal salt;
A solution of a dye represented by the following general formula (1) or (2)
A second liquid is supplied, and before the second liquid is supplied,
The first liquid and the second liquid are mixed by stirring.
Producing a pigment-dispersed particle by pigmentizing the dye
A method for producing a pigment dispersion, comprising: General formula (1)General formula (2)Wherein A and B each complete a conjugated double bond chain
And Y and Z each represent a carbon ring or
Represents an atomic group necessary for forming a heterocyclic ring. L ¹,
L^Two, L^Three, L^FourAnd L^FiveEach may be substituted
Represents a methine group, and P, P ', Q and Q' are independently substituted
Represents a group. X and X 'each represent an oxygen atom, a sulfur atom,
Or C (CN)_TwoAnd G⁺Is proton, triethyla
Represents ammonium or pyridinium. m1 and n1 are
Each represents 0, 1 or 2; x and y each represent 0 or
Represents 1. ) 2. The pigment dispersion according to claim 1, wherein an anionic surfactant and / or a nonionic surfactant is contained in at least one of the first liquid and the second liquid. Method of manufacturing a product. 3. The pigment-dispersed particles having an average volume particle size of 0.1.
The method for producing a pigment dispersion according to claim 1, wherein the pigment dispersion is 2 μm or less. 4. It contains a pigment, water and a hydrophilic organic solvent.
An inkjet ink, wherein the pigment is water-soluble.
A first liquid that is a solution of a metal salt, and a compound represented by the following general formula (1) or
Represents a second solution which is a solution of the dye represented by (2).
Supplying the first liquid and the second liquid
With a pigment that has been pigmented by stirring and mixing
And the pigment has a volume average particle size of 0.2 μm or less.
An ink-jet ink, characterized in that: General formula (1)General formula (2)Wherein A and B each complete a conjugated double bond chain
And Y and Z each represent a carbon ring or
Represents an atomic group necessary for forming a heterocyclic ring. L ¹,
L^Two, L^Three, L^FourAnd L^FiveEach may be substituted
Represents a methine group, and P, P ', Q and Q' are independently substituted
Represents a group. X and X 'each represent an oxygen atom, a sulfur atom,
Or C (CN)_TwoAnd G⁺Is proton, triethyla
Represents ammonium or pyridinium. m1 and n1 are
Each represents 0, 1 or 2; x and y each represent 0 or
Represents 1. )