JP2002114930A - Ink for ink jet recording and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for ink jet recording, which has no paper dependence, is excellent in the density of recording, color tone, and penetration into a paper of a photographic image quality, is free from staining immediately after printing, and gives an image excellent in water resistance, particularly in color fastness to ozone. SOLUTION: The ink for ink jet recording contains a colored fine particle dispersion containing at least a hydrophobic high-boiling organic solvent having a boiling point of 150 deg.C or above, a coloring agent and an olefinic polymer. The olefinic polymer preferably comprises one containing a poly-1,2-butadiene structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-jet ink containing a water-based dispersion of colored fine particles and an ink-jet recording method using the ink-jet ink. The present invention relates to an ink-jet ink and an ink-jet recording method which are excellent in temporal stability and ejection stability of a fine particle dispersion ink, and have excellent image water resistance and image fastness, and are suitable for a thermal, piezoelectric, electric field or acoustic ink jet system.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink-jet printers have been used not only in offices but also at home as paper,
It is widely used for printing on films, cloths and the like.
Oil-based, water-based, and solid inks are known as ink-jet inks, but water-based inks are mainly used in terms of manufacturing, handling, odor, safety, and the like. However, since many of the aqueous inks use water-soluble dyes that dissolve in a molecular state, they have the advantage of high transparency and color density.However, since the dyes are water-soluble, they have poor water resistance and are used on so-called plain paper. When printing, there is a problem that bleeding occurs and the printing quality is remarkably deteriorated, and light resistance is poor.

For the purpose of solving the above problems, aqueous inks using pigments or disperse dyes have been disclosed in, for example, JP-A-56-1.
57468, JP-A-4-18468, 8-183
No. 920, No. 10-110126 and No. 10-195
No. 355 and other publications. However, in the case of these water-based inks, the water resistance is improved to some extent, but it is difficult to say that it is sufficient.In the case of the pigment ink, the coloring is inferior to that of the dye ink, and the storage stability of the dispersion of each of the dispersed inks is lacking. Therefore, it has a drawback such as easy clogging at the discharge port. In addition, recording paper provided with an ink receiving layer containing a porous inorganic pigment on its surface (hereinafter referred to as “photo-quality paper”) has emerged due to the recent trend toward higher image quality in inkjet technology.
There is that. It has been found that the use of the above (1) has a drawback that the aqueous ink using the above-mentioned pigment or disperse dye has poor penetrability, and that the dye and pigment easily peel off from the surface when rubbed by hand.

Japanese Patent Application Laid-Open No. 58-45272,
-340825, 7-268254, 7-26
JP-A-8257 and JP-A-7-268260 propose a method of enclosing a dye in polyurethane or polyester dispersion particles. However, the dispersions described above have a drawback that if the dye is included at a desired concentration, it is difficult to obtain colored particles having excellent dispersion stability. This has the problem that the color tends to fade.

On the other hand, Japanese Patent Publication No. 5-76977 discloses that
An ink composition is disclosed in which an oil-soluble dye is dissolved and dispersed in an organic solvent having a low water solubility and a specific gravity close to that of water.However, when photographic quality paper is used, there is a problem that the color is easily discolored by ozone. Was.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention is excellent in recording density, color tone, and ink permeability to photographic quality paper when printing on arbitrarily selected paper, eliminates stains immediately after printing, and provides water resistance of an image, particularly, color to ozone. An object of the present invention is to provide an ink jet ink and an ink jet recording method which are excellent in image fastness.

[0007]

Means for solving the above problems are as follows. That is, <1> a hydrophobic high-boiling organic solvent having a boiling point of 150 ° C. or more;
An inkjet ink comprising a colored fine particle dispersion containing at least a colorant and an olefin-containing polymer. <2> The olefin-containing polymer is poly-1,2-
The inkjet ink according to <1>, which has a butadiene structure. <3> An ink jet recording method characterized by performing recording using the ink for ink jet described in <1> or <2>.

[0008] In the present invention, the following means are preferably mentioned. <4> The inkjet ink according to <1> or <2>, wherein the colorant is an oil-soluble dye. <5> The oil-soluble dye is represented by the following general formula (1) or (2)
The inkjet ink according to any one of <1> to <2>, which is a compound represented by the formula:

[0009]

Embedded image

In the general formulas (1) and (2), R
¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group,
Hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group,
Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group , An aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, a carboxyl group or a sulfo group. A
Represents -NR ⁵ R ⁶ or a hydroxy group, the R ⁵ and R ⁶ are independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, bonded to each other and R ⁵ and R ⁶ It may form a ring. B ¹ represents = C (R ³⁾ - or = N- and represents, B ² is -C (R ⁴⁾ = or represent -N =. Any of R ¹ and R ⁵ , R ³ and R ^6, and R ₁ and R ² may be bonded to each other to form an aromatic ring or a heterocyclic ring. X represents a residue of a color photographic coupler, and Y represents an unsaturated heterocyclic group.

<6> The content of the olefin-containing polymer is at least 5% by mass of the colorant.
The inkjet ink according to any one of <1>, <2>, and <4> to <5>. <7> The hydrophobic high-boiling organic solvent has a relative dielectric constant at 25 ° C. of 3 to 12, <1>, <2>
> And <4> to <6>. <8> An average particle diameter of dispersed particles in the colored fine particle dispersion is 100 nm or less.
>, <2> and <4> to <7>. <9> An image receiving material in which an ink receiving layer containing a porous inorganic pigment is provided on a support may be used in any of <1>, <2> and <4> to <8>
An ink jet recording method characterized by performing recording using the ink for ink jet described in any one of the above (1) to (4).

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an ink-jet ink and an ink-jet recording method will be described. [Inkjet Ink] The inkjet ink of the present invention is characterized by containing a colored fine particle dispersion containing at least a hydrophobic high-boiling organic solvent having a boiling point of 150 ° C. or higher, a colorant, and an olefin-containing polymer. (Colored Fine Particle Dispersion) In the present invention, the colored fine particle dispersion is obtained by adding a colored fine particle containing at least one each of a hydrophobic high-boiling organic solvent having a boiling point of 150 ° C. or higher, a colorant, and an olefin-containing polymer to an aqueous medium. It is a dispersion obtained by dispersion. More specifically, the colored fine particle dispersion of the present invention is a so-called emulsified dispersion in which a hydrophobic high-boiling organic solvent, a colorant, and an olefin-containing polymer are dispersed as fine oil droplets in an aqueous medium. It is in a physical state. The `` aqueous medium '' in the present invention is a mixture of water or a mixture of water and a small amount of a water-miscible organic solvent, if necessary, to which additives such as a surfactant, a wetting agent, a stabilizer, and a preservative are added. Means

—Hydrophobic High Boiling Point Organic Solvent— In the present invention, the colored fine particle dispersion contains a hydrophobic high boiling point organic solvent. As the hydrophobic high-boiling organic solvent,
It is preferably hydrophobic and has a boiling point of 150 ° C. or higher,
Those having a temperature of 170 ° C. or higher are more preferable. Where "hydrophobic"
Means that the solubility in distilled water at 25 ° C. is 3% or less. The hydrophobic high-boiling organic solvent preferably has a dielectric constant of 3 to 12, and more preferably 4 to 10. Here, the dielectric constant means a relative dielectric constant with respect to vacuum at 25 ° C.

The hydrophobic high-boiling organic solvent is disclosed in US Pat. No. 2,322,027, Japanese Patent Application No.
Compounds described in JP-A-203857 can be used. Specifically, high-boiling organic solvents such as phosphoric acid esters, fatty acid esters, phthalic acid esters, benzoic acid esters, phenols, and amides are preferable, but not limited thereto. These are, depending on the purpose,
Both liquid and solid at room temperature can be used.

The amount of the high-boiling organic solvent is not particularly limited as long as the effect of the present invention is not impaired.
The amount is preferably from 0 to 1,000 parts by mass, more preferably from 0 to 300 parts by mass.

—Olefin-Containing Polymer— In the present invention, the term “olefin-containing polymer” refers to a polymer having a carbon-carbon double bond in its structure, and the “carbon-carbon double bond” as used herein means an aromatic compound such as benzene. A carbon-carbon double bond excluding a cyclic conjugated double bond such as a hydrocarbon. The carbon-carbon double bond may be contained in either the main chain or the side chain of the polymer, and when the carbon-carbon double bond is contained in the side chain, either at the terminal of the side chain or inside. Good. The olefin-containing polymer can be produced by subjecting a monomer having a carbon-carbon double bond that does not participate in the polymerization reaction to vinyl polymerization or condensation polymerization. In addition, polymers that do not contain carbon-carbon double bonds,
It can also be produced by introducing a carbon-carbon double bond site.

When the content ratio of the carbon-carbon double bond in the olefin-containing polymer is determined by a unit (monomer unit) constituting the olefin-containing polymer (that is, in a polymer comprising one or more N monomers, When n / N × 100 when n monomers having the carbon-carbon double bond are contained), it is preferable that the carbon-carbon double bond is contained in at least 10% to 100% of the structural units. , 30% to 100% more preferably contain the carbon-carbon double bond.
% To 100% more preferably contains the carbon-carbon double bond, and particularly preferably 60% to 100% contains the carbon-carbon double bond. When the content of the carbon-carbon double bond is less than 10%, the effect of suppressing fading due to oxidizing gas such as ozone is poor, which is not preferable.

The molecular weight (weight average molecular weight) of the olefin-containing polymer is preferably from 1,000 to 500,000, more preferably from 1500 to 300,000, more preferably from 2,000 to 200,000, and more preferably from 2,000 to 100,000. Is particularly preferred. If it is smaller than 1000, it tends to be difficult to obtain the effects of the present invention.
It is not preferable because dispersion tends to be difficult due to an increase in viscosity and a decrease in solubility.

The amount of the olefin-containing polymer used is not particularly limited as long as the effect of the present invention is not impaired.
0 parts by mass is preferable, 10 to 500 parts by mass is more preferable, and 20 to 300 parts by mass is particularly preferable. When the amount is less than 5 parts by mass, it is difficult to obtain the effects of the present invention, and when the amount is more than 1000 parts by mass, it is affected by the type and content of the hydrophobic high boiling point organic solvent, but becomes difficult to be dispersed. In addition, the use of photographic quality paper is not preferable because the penetrability tends to deteriorate. The olefin-containing polymer may have a single monomer unit or a plurality of monomer units, and two or more olefin-containing polymers may be used in combination.

Specific examples of the olefin-containing polymer (P
-1 to 37) are listed below. The olefin-containing polymer used in the present invention is not limited to these specific examples. The molecular weight indicates a mass average molecular weight. Specific examples Olefin-containing polymer (molar ratio of constituent units) P-1) Polyallyl methacrylate, molecular weight 12000 P-2) Poly (allyl methacrylate-co-butyl acrylate) (80:20), molecular weight 5600 P-3) Chain transfer Polyallyl methacrylate using mercaptoacetic acid as an agent, molecular weight 5300 P-4) polyallyl methacrylate using 2-mercaptosuccinic acid as a chain transfer agent, molecular weight 5300 P-5) poly [allyl methacrylate-co-diphenyl phosphate ( 2-methacryloyloxyethyl) ester] (70:
30), molecular weight 23000 P-6) allyl methacrylate / methacrylic acid copolymer (92: 8), molecular weight 23000 P-7) poly (allyl methacrylate-co-2-carboxyethyl acrylate) (80:20), molecular weight 18000 P-8) Poly [allyl methacrylate-co-methacrylic acid monoester of polyethylene glycol (about 23 repeats of ethyleneoxy chain)] (97: 3), molecular weight 28000 P-9) Poly (N-allylacrylamide-co-N , N-diphenylacrylamide) (90:10), molecular weight 23000 P-10) poly [2- (allyloxy) ethyl acrylate-co-methacrylic acid] (95: 5), molecular weight 7800 P-11) poly (styrene-co -Maleic anhydride-co-maleic acid monoallyl ester) (30: 5: 65), molecular weight 20000 P-12) Poly (styrene-co-maleic acid monoallyl ester) (30:70), molecular weight 12000 P-13 ) Poly [styrene-co-maleic acid mono (diallyl)
Amide] (50:50), molecular weight 18000 P-14) polyallyl methacrylate-block-polybutyl methacrylate (70:30), molecular weight 5600 P-15) polyallyl methacrylate-block-polymethacrylic acid (60:40), Molecular weight 5300 P-16) polymethacrylic acid-block-polyallyl methacrylate-block-polymethacrylic acid (25:50:25), molecular weight 6
700 P-17) Polybutadiene (1,4-type 100%), molecular weight 2300 P-18) Polybutadiene (1,4-type 9%, 1,2-type 91%), molecular weight 3100 P-19) Polybutadiene (1 , 4-type 10%, 1,2-type 90%),
Molecular weight 1420 P-20) polybutadiene (1,4-type 9%, 1,2-type 91%), molecular weight 12000 P-21) polybutadiene (1,4-type 9%, 1,2-type 91%), Molecular weight 105000 P-22) polybutadiene (1,2-type 100%), molecular weight 1300 P-23) polybutadiene (1,2-type 100%), molecular weight 4200 P-24) poly (butadiene-co-styrene) (80 : 20), molecular weight 53000 P-25) polyisoprene (1,4-type 100%), molecular weight 6500 P-26) polynorbornene, molecular weight 17000 P-27) poly [(1- (2,4-hexadienoyl) Oxy)
Ethylene) -co- (1-hydroxyethylene)] (60:40),
Molecular weight 24000 P-28) poly [(2-hexadienyl-1,3-dioxane-4,6-diyl) methylene) -co- (1-hydroxyethylene)] (70:30), molecular weight 31000 P-29) poly [(1- (2-methylpropanoyloxy) ethylene) -co- (1-hydroxyethylene)] (72:28), molecular weight 23000 P-30) poly [(1-propinoylaminoethylene) -co-
(1-aminoethylene)] (50:50), molecular weight 5400 P-31) poly [(1- (2,4-hexadienoyl) aminoethylene) -co- (1-aminoethylene)] (70:30), Molecular weight 5400 P-32) Poly [oxy (1-propenoyloxymethylethylene)], molecular weight 8400 P-33) Poly [imino (1,6-dioxo-2,4-hexadienylene) iminohexamethylene], molecular weight 3200 P -34) Poly [imino (1,4-dioxo-2-methylidenebutylene) iminotetramethylene], molecular weight 4200 P-35) Poly [allyloxymethylimino (1-oxohexamethylene)], molecular weight 13200 P-36 ) Partially maleated polybutadiene (1,2-type 100
%), Molecular weight 1100 P-37) Partially maleated polybutadiene (1,2-type 100
%), Molecular weight 3000

Next, an example of a method for producing the olefin-containing polymer will be described. The present invention is not limited to this production example. In the following, “parts” represents “parts by mass”. <Production example of olefin-containing polymer (P-2)> 79.8 parts of allyl methacrylate, 20.
A mixed solution comprising 2 parts, 0.2 part of dodecyl mercaptan, 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 40 parts of isopropanol (IPA) and 40 parts of tetrahydrofuran (THF) was prepared. . Next, 20 parts of THF and 0.1 part of dimethyl 2,2′-azobis (2,4-dimethylvaleronitrile) were charged into the flask, and the mixture was heated to 65 ° C. while stirring under a nitrogen blanket. The mixture was added dropwise over 3 hours, and after completion of the addition, 0.05 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further reacted at the same temperature for 5 hours. The obtained polymer solution was concentrated under reduced pressure to obtain 100 parts of the target olefin-containing polymer P-2. The weight average molecular weight was 5,600 (GPC measurement, in terms of polystyrene).

-Colorant- In the present invention, as the colorant, oil-soluble dyes, pigments, colored polymers, colored waxes and the like can be used. Among these, it is preferable to use an oil-soluble dye. Hereinafter, the oil-soluble dye will be described.

Among the oil-soluble dyes applicable to the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or hetenylazo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Methine dyes such as benzylidene dyes and monomethine oxonol dyes; for example, naphthoquinone dyes,
Quinone-based dyes such as anthraquinone dyes; and other dyes include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

Of the oil-soluble dyes applicable to the present invention, any magenta dye can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; Such methine dyes;
Carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dye; .

Among the oil-soluble dyes applicable to the present invention, any dye can be used as the cyan dye. For example, indanianiline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes;
Carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye; phthalocyanine dyes; anthraquinone dyes; for example, aryl or hetenylazo dyes having phenols, naphthols, and anilines as coupling components; indigo / thioindigo dyes; be able to.

Each of the above dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an inorganic metal such as an alkali metal or ammonium. It may be a cation, an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having such a partial structure.

Although not limited to the following, preferable specific examples include C.I. I. Solvent Black 3,7,27,29 and 34; I. Solvent Yellow 14, 16, 19, 29, 30, 56,
82, 93 and 162; I. Solvent Red
1,3,8,18,24,27,43,49,51,7
2, 73, 109, 122, 132 and 218;
I. Solvent Violet 3; I. Solvent Blue 2,11,25,35,38,67 and 7
0; I. Solvent Green 3 and 7; I. Solvent Orange 2;
Particularly preferred among these are Nubian Bl
ack PC-0850, Oil Black HBB
, Oil Yellow 129, Oil Yellow
w 105, Oil Pink 312, Oil Red
5B, Oil Scarlet 308, Vali
Fast Blue 2606, Oil Blue
BOS (manufactured by Orient Chemical Co., Ltd.), Aizen Sp
ilon Blue GNH (Hodogaya Chemical Co., Ltd.)
Made), Neopen Yellow 075, Neop
en Mazenta SE1378, Neopen
Blue 808, Neopen Blue FF
4012, Neopen Cyan FF4238 (B
ASF).

In the present invention, a disperse dye can be used within a range that dissolves in a water-immiscible organic solvent.
Preferred specific examples thereof include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,9
3,99,100,119,122,124,126,
160, 184: 1, 186, 198, 199, 20
1,204,224 and 237; I. Disperse Orange 13, 29, 31: 1, 33, 49, 54,
55, 66, 73, 118, 119 and 163;
I. Disperse Red 54, 60, 72, 73, 8
6,88,91,92,93,111,126,12
7,134,135,143,145,152,15
3,154,159,164,167: 1,177,1
81, 204, 206, 207, 221, 239, 24
0,258,277,278,283,311,32
3,343,348,356 and 362; I. Disperse Violet 33; I. Disperse Blue 56, 60, 73, 87, 113, 128, 14
3,148,154,158,165,165: 1,1
65: 2,176,183,185,197,198,
201, 214, 224, 225, 257, 266, 2
67, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;

Particularly preferred oil-soluble dyes include azo or azomethine dyes represented by the following formulas (1) or (2). A dye represented by the following general formula (2) is known as a dye formed from a coupler and a developing agent by oxidation in a photographic material.

[0030]

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In the general formulas (1) and (2), R
¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group,
Hydroxy, nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino,
Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group , An aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, a carboxyl group or a sulfo group.

In the above general formulas (1) and (2), particularly, R ² is a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an amide group, an ureido group, a sulfo group, It is preferably a famoylamino group, an alkoxycarbonylamino group or a sulfonamide group.

In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The aliphatic group may have a branch or may form a ring. The aliphatic group preferably has 1 to 20 carbon atoms, and preferably has 1 to 20 carbon atoms.
-18 is more preferable. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, and phenyl is particularly preferable. Examples of the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include:
The substituents described in the description of R ^{1 to} R ⁴ can be exemplified.
Examples of the substituent of the aryl portion of the substituted aralkyl group are the same as the following examples of the substituent of the substituted aryl group.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, and phenyl is particularly preferred. The aryl part of the substituted aryl group is the same as the above-mentioned aryl group. Examples of the substituent of the substituted aryl group include the substituents described in the description of R ^{1 to} R ⁴ .

In the general formulas (1) and (2), A
Represents -NR ⁵ R ⁶ or a hydroxy group, R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. A is preferably -NR ⁵ R ^6. R ⁵ and R ⁶ may combine with each other to form a ring. R ⁵ and R ⁶ are more preferably a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and more preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or 1 carbon atom. Most preferably, it is a substituted alkyl group of .about.18.

In the general formulas (1) and (2), B
¹ = C (R ³⁾ - or = N- and represents, B ² is -C
(R ⁴ ) = or -N =. B ¹ and B ² are simultaneously -
Preferably When not N =, B ¹ is = C (R ³⁾ - in and B ² is -C (R ⁴⁾ If = become more preferably.
Any of R ¹ and R ⁵ , R ³ and R ^6, and R ¹ and R ² may combine with each other to form an aromatic ring or a heterocyclic ring.

In the above formula (1), Y represents an unsaturated heterocyclic group. Y is preferably a 5- or 6-membered unsaturated heterocyclic ring. An aliphatic ring, an aromatic ring, or another heterocyclic ring may be fused to the heterocyclic ring. Examples of heteroatoms in the heterocycle include N, O, and S. Examples of the unsaturated heterocyclic ring include, for example, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a thiophene ring, a benzothiazole ring, a benzoxazole ring, a benzoisothiazole ring, a pyrimidine ring, a pyridine ring, and quinoline. Rings and the like are preferred. Also,
The unsaturated heterocyclic group may have the substituents described above for R ^{1 to} R ⁴ .

In the general formula (2), X represents a residue of a color photographic coupler. The followings are preferred as the residue of the color photographic coupler. Yellow coupler: U.S. Pat. Nos. 3,933,501 and 4,022,
Nos. 620, 4,326,024, 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,47
No. 6,760, U.S. Pat.
Couplers represented by formulas (I) and (II) in 314,023 and 4,511,649, and EP 249,473A and 502,424A.
No. 6A, couplers represented by formulas (1) and (2) (especially Y-28 on page 18), 568,037A couplers represented by formula (I) in claim 1; U.S. Pat.
No. 6,576, column 1, lines 45 to 55, general formula (I)
A coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425,
Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18);
No. 969A1, couplers represented by formula (Y) on page 4 (especially Y-1 (page 17), Y-54 (page 41));
U.S. Pat. No. 4,476,219, column 7, 36-58.
Couplers represented by the formulas (II) to (IV) in the row (particularly II-
17, 19 (column 17), II-24 (column 1)
9)).

Magenta coupler: US Pat. No. 4,310,
Nos. 619 and 4,351,897, European Patent 73,6
No. 36, U.S. Pat. Nos. 3,061,432 and 3,72
No. 5,067, Research Disclosure No. 2
No. 4220 (June 1984); 24230 (1
Jun. 984), JP-A-60-33552,
No. 43659, No. 61-72238, No. 60-357
No. 30, No. 55-118034, No. 60-18595
No. 1, U.S. Pat. Nos. 4,500,630 and 4,540,
No. 654, No. 4,556,630, International Publication WO88
/ 04795, JP-A-3-39737 (L-57)
(Page 11, lower right), L-68 (page 12, lower right), L-77
(Page 13, lower right)), [A-
4] -63 (p. 134), [A-4] -73, -75
(P. 139) and M-4, -6 (2
6), M-7 (page 27), and M of 571,959A.
-45 (p. 19), M of JP-A-5-204106.
-1 (p. 6), paragraph 023 of JP-A-4-362631.
7, M-22, U.S. Pat. No. 3,061,432;
No. 725,067.

Cyan coupler: US Pat. No. 4,052,2
No. 12, No. 4,146,396, No. 4,228,23
No. 3, No. 4,296,200, European Patent 73,636
CX-1,3,3 of JP-A-4-208443.
4, 5, 11, 12, 14, 15 (pages 14 to 16); JP-A-4-43345, C-7, 10 (page 35), 34,
35 (p. 37), (I-1), (I-17) (42-4)
3) a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

In addition, Japanese Patent Application Laid-Open No. Sho 62-215272.
(Page 91), JP-A-2-33144 (page 3, 30
P.), EP 355, 660A (p. 4, p. 5, p. 45,
The couplers described on page 47) are also useful.

Among the oil-soluble dyes represented by the general formula (1), a dye represented by the following general formula (3) is particularly preferably used as the magenta dye.

[0043]

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In the general formula (3), Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ¹ is preferably an electron-withdrawing group having a σp value of 0.30 or more and 1.0 or less. Preferred specific substituents include the electron-withdrawing substituents described below. Among them, acyl groups having 2 to 12 carbon atoms and 2 to 12 carbon atoms are preferable.
12 alkyloxycarbonyl groups, nitro groups, cyano groups, alkylsulfonyl groups having 1 to 12 carbon atoms, 6 carbon atoms
Preferred are an arylsulfonyl group having 1 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms. Particularly preferred are a cyano group and carbon number 1
To 12 alkylsulfonyl groups and arylsulfonyl groups having 6 to 18 carbon atoms, most preferably a cyano group.

In the general formula (3), Z ² represents a hydrogen atom, an aliphatic group or an aromatic group. In the general formula (3), R ^{1 to} R ⁶ have the same meaning as those in the general formula (1).

In the general formula (3), Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them,
Q is preferably a group consisting of a group of nonmetallic atoms necessary to form a 5- to 8-membered ring. Among them, an aromatic group or a heterocyclic group is particularly preferable. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond.
Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom. Specific examples of such a ring structure include, for example, benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring And a benzimidazole ring, an oxazole ring, a benzoxazole ring, an oxane ring, a sulfolane ring, a thiane ring, and the like. When these rings further have a substituent, the substituent may be a substituent represented by the general formula (1). Group R
Illustrated group with ¹ to R ^4.

The preferred structure of the compound represented by formula (3) is described in Japanese Patent Application No. 2000-220649.
It is described in the specification.

Among the dyes represented by the general formula (2),
As the magenta dye, a dye represented by the following general formula (4) is particularly preferably used.

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In the general formula (4), G represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an ester group, an amino group, Represents a carbamoyl group, a sulfonyl group, a sulfamoyl group, a ureido group, a urethane group, an acyl group, an amide group or a sulfonamide group.

In the general formula (4), R ¹ , R ² ,
A, B ¹ and B ² have the same meanings as those in the formula (2), and their preferred ranges are also the same.

In the general formula (4), L represents an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an ester group, an amino group, a carbamoyl group, Sulfonyl group,
Represents an atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be substituted with at least one of a sulfamoyl group, a ureido group, a urethane group, an acyl group, an amide group and a sulfonamide group; May further form a condensed ring with another ring.

In the compound represented by the general formula (4), A is preferably -NR ⁵ R ⁶ , and L is preferably a 5-membered nitrogen-containing heterocyclic ring, and is preferably a 5-membered nitrogen-containing heterocyclic ring. Includes an imidazole ring, a triazole ring and a terazole ring.

Among the dyes represented by the general formulas (1) and (2), examples of magenta dyes (M-1 to 16, D-1 to 27, 1 to 5 to 13) , 1-
16-19, 1-21, 1-23-24, 1-27-2
9, 1-33 to 34, 1-36), which are
The present invention is described in detail, and the present invention is not limited by these.

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Other examples of the colorant compound usable in the present invention include Japanese Patent Application Nos. 2000-78491, 11-365190 and 2000-2206.
No. 49, but is not limited thereto.

The compound represented by the general formula (3) is
For example, Japanese Patent Application No. 2000-220649,
The compound can be synthesized with reference to the method described in JP-A-5-161856. Compounds represented by the general formula (4) are disclosed in, for example, JP-A-4-126772 and JP-B-7-94180, and Japanese Patent Application No.
It can be synthesized with reference to the method described in 0-78491.

Among the dyes represented by the general formula (2),
As the cyan dye, a pyrrolotriazoleazomethine dye represented by the following general formula (5) is particularly preferably used.

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In the general formula (5), A, R ¹ ,
R ² , B ^1, and B ² have the same meanings as those in Formula (2), and their preferred ranges are also the same.

In the general formula (5), Z ³ and Z ⁴ each independently have the same meaning as G in the general formula (4). Z ³ and Z ⁴ may be bonded to each other to form a ring structure. When Z ³ is an electron-withdrawing group having a Hammett substituent constant σp value of 0.30 or more, the absorption is sharp, and it is more preferable. Further, Z ³ is more preferably an electron withdrawing group having a Hammett substituent constant σp value of 0.45 or more, and most preferably an electron withdrawing group having a Hammett substituent constant σp value of 0.60 or more. Those having a sum of the Hammett substituent constant σp values of Z ³ and Z ⁴ of 0.70 or more exhibit an excellent hue as a cyan color, and are more preferable.

In the general formula (5), M is an atomic group forming a 1,2,4-triazole ring fused to the 5-membered ring in the general formula (5), and Part 2
One of the atoms B ³ and B ⁴ is a nitrogen atom, and the other is a carbon atom.

The compound represented by the general formula (5) is preferably used as a cyan dye, but can also be used as a magenta dye by changing the substituent.

Here, the Hammett's substituent constant σp value used in the present specification will be described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of a substituent on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constants determined by Hammett's rule include σp and σm values, and these values can be found in many general books. For example, JA Dean,
"Lange's Handbook of Chemistry", 12th edition, 197
9 (Mc Graw-Hill) and extra edition of "Chemistry", 122
No. 96-103, 1979 (Nankodo).
In the present invention, each substituent is defined as Hammett's substituent constant σ.
p is limited or explained by p, but this does not mean that it is limited to only certain substituents found in the above-mentioned books, and that the value is unknown in the literature. Needless to say, it also includes a substituent that will be included in the range when measured based on the rule. Although the general formulas (1) to (5) include those that are not benzene derivatives, the σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense.

Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)). Examples of the electron-withdrawing group having a Hammett σp value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), and an aryloxycarbonyl group (for example, m -Chlorophenoxycarbonyl), an alkylsulfinyl group (eg, n-propylsulfinyl), an arylsulfinyl group (eg, phenylsulfinyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogen Alkyl group (eg If, it can be exemplified trifluoromethyl).

Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.30 or more include an acyloxy group (eg, acetoxy) and a carbamoyl group (eg, N
-Ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (for example, trifluoromethyloxy), a halogenated aryloxy group (for example,
Pentafluorophenyloxy), a sulfonyloxy group (eg, methylsulfonyloxy group), a halogenated alkylthio group (eg, difluoromethylthio), and two or more aryl substituted with an electron-withdrawing group having a σp value of 0.15 or more. Groups (eg, 2,4-dinitrophenyl, pentachlorophenyl), and heterocycles (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2)
-Benzimidazolyl). Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include a halogen atom in addition to the above.

The following are specific examples of the dye represented by the general formula (5) that can be used in the present invention.
The present invention is described in detail, and the present invention is not limited by these.

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The oil-soluble dyes usable in the present invention include:
Further, there are exemplified compounds described in Japanese Patent Application No. 11-365188, but are not limited thereto.

-Production of Colored Fine Particle Dispersion- In the present invention, the colored fine particle dispersion is obtained by dispersing a colored fine particle containing at least the colorant, the hydrophobic high-boiling organic solvent, and the olefin-containing polymer in an aqueous medium. It can be manufactured by Specifically, a method of co-emulsifying and dispersing the colorant, the hydrophobic high-boiling point organic solvent and the olefin-containing polymer (co-emulsification dispersion method) may be mentioned. As the coemulsification dispersion method, adding water to the organic solvent phase containing the colorant, the hydrophobic high-boiling organic solvent and the olefin-containing polymer, and adding the organic solvent phase to water, By either
A preferred method is to emulsify the organic solvent phase to form fine particles.

The emulsifying apparatus used in the co-emulsifying dispersion method includes a simple stirrer, an impeller stirring method, an in-line stirring method, a mill method such as a colloid mill,
Although known devices such as an ultrasonic system can be used, the use of a high-pressure homogenizer is particularly preferable. The high-pressure homogenizer is described in detail in U.S. Pat. No. 4,533,254 and JP-A-6-47264, but as a commercially available apparatus, a Gorin homogenizer (APV GAULIN) is used. IN
C. ), Microfluidizer (MICROFLUI
DEX INC. ), An Ultimateizer (Sugino Machine Co., Ltd.) and the like can be used. In recent years, US-
A high-pressure homogenizer having a mechanism for forming fine particles in an ultrahigh-pressure jet stream, such as that described in JP-A-5720551, is particularly effective for the emulsification and dispersion of the present invention. As an example of an emulsifying apparatus using this ultra-high pressure jet stream, DeBEE20
00 (BEE INTERNATIONAL LT)
D. ).

The pressure at the time of emulsification with a high-pressure emulsifying dispersion device is 5
At least 00 bar, preferably at least 600 bar,
More preferably, it is 1800 bar or more. For example, it is a particularly preferable method to use two or more emulsifiers in combination, for example, by emulsifying with a stirring emulsifier and then passing through a high pressure homogenizer. Further, a method is also preferable in which, once emulsified and dispersed by these emulsifying apparatuses, an additive such as a wetting agent or a surfactant is added, and the ink is again passed through a high-pressure homogenizer while the cartridge is filled with ink. When a low-boiling organic solvent is contained in addition to the hydrophobic high-boiling organic solvent, it is preferable to remove the low-boiling solvent from the viewpoint of stability of the emulsion and safety and health. Various known methods can be used to remove the low-boiling solvent depending on the type of the solvent.
That is, there are an evaporation method, a vacuum evaporation method, an ultrafiltration method and the like. This step of removing the low boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

For emulsification and dispersion, various surfactants can be used. For example, fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates,
Anionic surfactants such as alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, and sorbitan fatty acids Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene oxypropylene block copolymers are preferred. In addition, SURFYNOLS (AirPro), which is an acetylene-based polyoxyethylene oxide surfactant, is used.
ducts & Chemicals) are also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Japanese Unexamined Patent Application Publication No.
7) to (38), Research Disclosure No. 30
Those mentioned as surfactants described in 8119 (1989) can also be used.

In the case of dispersing colored fine particles containing a colorant and a hydrophobic high-boiling organic solvent in an aqueous medium by co-emulsification dispersion to form an aqueous ink, it is particularly important to control the particle size. In order to increase color purity and density when an image is formed by inkjet, it is preferable to reduce the average particle diameter of the colored fine particles. In particular,
The volume average particle diameter of the colored fine particles is preferably 100 nm or less, more preferably 1 nm or more and 80 nm or less. Further, if the colored fine particles include coarse particles, the printing performance may be reduced. For example, printing performance may be adversely affected, for example, when coarse particles clog the nozzles of the head, or even when they are not clogged, they may form a stain, resulting in non-ejection of the ink or ejection distortion. Therefore, it is preferable that the proportion of the coarse particles is low, and when preparing the ink, it is preferable that the number of particles having a size of 5 μm or more is 10 or less and the number of particles having a size of 1 μm or more is 1000 or less in 1 μl of the ink. As a method for removing coarse particles, a known centrifugal separation method, a microfiltration method, or the like can be used. These separation means may be performed immediately after emulsification and dispersion, or after adding various additives such as a wetting agent and a surfactant to the emulsified dispersion and immediately before filling the ink cartridge. In order to reduce the average particle diameter of the colored fine particles and to reduce the coarse particles, it is effective to use a mechanical emulsifying device.

The content of the hydrophobic high-boiling point organic solvent in the colored fine particle dispersion is not particularly limited. However, from the viewpoint of good penetration of the ink into the recording paper, the content in the colored fine particles may be reduced. It is preferably at least 25% by mass. From the viewpoint of maintaining good solubility of the oil-soluble dye, it is preferable to use 30% by mass or more with respect to the colorant. On the other hand, if the amount of the hydrophobic high-boiling organic solvent used is too large, the ratio of the oil phase is too large, and stable and fine dispersion tends to be difficult. In this respect, the amount of the hydrophobic high-boiling organic solvent to be used is preferably 50 to 1500% by mass relative to the colorant,
More preferably, it is 100 to 1000% by mass.

In the ink-jet ink of the present invention, the colored fine particles are preferably contained in an amount of 1 to 45% by mass, more preferably 2 to 30% by mass. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration and the like.

-Organic solvent- The organic solvent used for preparing the colored fine particle dispersion other than the hydrophobic high-boiling organic solvent is not particularly limited, and may be appropriately determined based on the solubility and wettability of the colorant. For example, ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone, methanol, ethanol, 2-propanol, 1-propanol, 1-
Butanol, alcohol solvents such as tert-butanol, chloroform, chlorine solvents such as methylene chloride, benzene, aromatic solvents such as toluene, ethyl acetate, butyl acetate, ester solvents such as isopropyl acetate, diethyl ether, tetrahydrofuran, Ether solvents such as dioxane, ethylene glycol monomethyl ether,
Examples thereof include glycol ether solvents such as ethylene glycol dimethyl ether. The organic solvents may be used alone or in combination of two or more. Further, depending on the solubility and wettability of the colorant and the solubility of the polymer, a mixed solvent with water may be used.

The amount of the organic solvent used is not particularly limited as long as the effect of the present invention is not impaired.
It is preferably 2,000 parts by mass or less, more preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the dye. When the amount of the organic solvent used exceeds 2000 parts by mass, the steps of removing the solvent and concentrating the organic solvent are indispensable and complicated, and there is a tendency that there is no room for formulation.

When the solubility of the organic solvent in water is 10% or less, or when the vapor pressure of the organic solvent is higher than water, the organic solvent is removed from the viewpoint of the stability of the colored fine particle dispersion. Preferably. The removal of the organic solvent can be performed at 10 to 100 ° C. under normal pressure or reduced pressure, and is preferably performed at 40 to 100 ° C. under normal pressure or 10 to 50 ° C. under reduced pressure.

—Water-Insoluble Polymer Additive— A water-insoluble polymer other than the olefin-containing polymer (hereinafter referred to as a water-insoluble polymer) may be added.
As a first addition method, the colorant during co-emulsification dispersion,
In addition to the hydrophobic high-boiling organic solvent and the olefin-containing polymer, by adding a water-insoluble polymer,
The water-insoluble polymer is contained in the colored fine particles, and the second addition method is a case where the water-insoluble polymer is converted into an aqueous dispersion and mixed with the colored fine particle dispersion. The water-insoluble polymer used may be a nonionic polymer or a polymer having an ionic group. The ionic group includes a cationic group such as a tertiary amino group and an anionic group such as carboxylic acid and sulfonic acid. Examples of the ionic group-containing polymer include a vinyl polymer and a condensation polymer (polyurethane, polyester, polyamide, polyurea, polycarbonate). A method of co-emulsifying and dispersing these nonionic polymers or ionic group-containing polymers with a colorant and a hydrophobic high-boiling organic solvent, a method of separately dispersing and adding them, and a method of adding the nonionic polymer and the ionic group-containing polymer. For specific examples, see Japanese Patent Application No. 2000-2.
03856, 2000-203857, Japanese Patent Application No. 20
It is described in detail in each specification of 00-238817.

—Other Components— The ink-jet ink of the present invention contains the above-mentioned colored fine particle dispersion, and may further contain other components appropriately selected as necessary.

The other components are contained within a range that does not impair the effects of the present invention. Examples thereof include a drying inhibitor, a penetration enhancer, an ultraviolet absorber, an antioxidant, a fungicide, a pH adjuster, and a surface tension. Modifier, defoamer, viscosity modifier, dispersant,
Known additives such as a dispersion stabilizer, a rust inhibitor, a chelating agent and the like can be mentioned.

The above-mentioned anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the above-mentioned ink-jet ink at the ink jet opening of a nozzle used in an ink-jet recording system.

As the drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol,
Thiodiglycol, dithiodiglycol, 2-methyl-
Polyhydric alcohols represented by 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl)
Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine And the like, a sulfur-containing compound such as sulfolane, dimethyl sulfoxide and 3-sulfolene, a polyfunctional compound such as diacetone alcohol and diethanolamine, and a urea derivative. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. These may be used alone or in combination of two or more. These anti-drying agents may be present in the inkjet ink in an amount of 10 to 50% by mass.
It is preferred to contain.

The penetration enhancer is suitably used for the purpose of better penetrating the ink-jet ink into paper.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, and the like.
Examples thereof include sodium oleate and a nonionic surfactant. The penetration enhancer is contained within a range that does not cause bleeding of printing, paper dropout (print-through), and the like, and generally exhibits a sufficient effect when contained in the inkjet ink at about 5 to 30% by mass.

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

The antioxidant is used for the purpose of improving the storability of an image. For example, various organic and metal complex antifading agents can be used. Examples of the organic fading inhibitor include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans,
Alkoxyanilines, heterocycles, and the like. Examples of the metal complex-based anti-fading agent include a nickel complex, a zinc complex, and the like. 17643, Sections I-J of VII, N
o. 15162; 18716, page 650, left column,
No. No. 36544, page 527; 307105
No. 872, ibid. Compounds described in the patent cited in US Pat. No. 15,162, and the compounds represented by the general formulas and examples of typical compounds described on pages 127 to 137 of JP-A-62-215272 can be used. .

Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Can be These are contained in the ink at 0.02-1.
It is preferable to use 00% by mass.

As the surface tension adjusting agent, nonionic,
Preference is given to cationic or anionic surfactants. Incidentally, the surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m.
N / m is more preferred. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used if necessary.

The above-mentioned pH adjuster is used in the dispersion of the colored fine particle dispersion.
It can be suitably used in terms of H adjustment and dispersion stability imparting, and is preferably added so as to have a pH of 4.5 to 10.0, and more preferably added so as to have a pH of 6 to 10.0. . The pH adjuster is preferably a basic one such as an organic base or an inorganic alkali, and an acidic one is preferably an organic acid or an inorganic acid. In the basic pH adjuster, among the organic bases, triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like are more preferable, and among the inorganic alkalis, alkali metal hydroxides, carbonates, Ammonia and the like are more preferred. Of the alkali metal hydroxides, sodium hydroxide, lithium hydroxide, potassium hydroxide and the like are particularly preferred, and among the carbonates, sodium carbonate and sodium hydrogen carbonate are particularly preferred. In the acidic pH adjuster, among the organic acids, acetic acid, propionic acid, trifluoroacetic acid, alkylsulfonic acid and the like are more preferable, and among the inorganic acids, hydrochloric acid, sulfuric acid, phosphoric acid and the like are more preferable.

[Ink-Jet Recording Method] In the ink-jet recording method of the present invention, recording is performed on an image receiving material using the ink for ink-jet recording. The ink nozzles and the like used at that time are not particularly limited. It can be appropriately selected depending on the situation.

The image receiving material is not particularly limited, and includes known recording materials such as plain paper, resin-coated paper, paper dedicated to ink jet, film, electrophotographic common paper, fabric, glass, metal, and ceramics. . Among the recording materials, inkjet-only paper is preferable, and examples thereof include JP-A-8-169172 and JP-A-8-27693.
JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-28787.
No. 83, Japanese Unexamined Patent Publication No. 10-153989,
JP-217473, JP-A-10-235995,
Those described in JP-A-10-337947, JP-A-10-217597, JP-A-10-337947, and the like are more preferable.

In the present invention, among the above-mentioned image receiving materials, the following recording paper and recording film are particularly preferable.

The recording paper and the recording film are formed by laminating a support and an ink receiving layer, and if necessary, laminating other layers such as a back coat layer. Each layer including the ink receiving layer may be a single layer, or may be two or more layers.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
MP, CMP, mechanical pulp such as CGP, waste paper pulp such as DIP, etc., if necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. Those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used. In addition, synthetic paper, plastic film sheets, and the like may be used.

The thickness of the support is 10 to 250.
It is about μm, and the basis weight is desirably 10 to 250 g / m ² .

The support may be provided with the ink receiving layer or the back coat layer. Further, after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, The ink receiving layer and the back coat layer may be provided. The support may be subjected to a flattening process using a calender such as a machine calender, a TG calender, and a soft calender.

Among the above-mentioned supports, paper laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) and plastic films are preferably used. It is more preferable to add a white pigment (for example, titanium oxide, zinc oxide, etc.) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide, etc.) to the polyolefin.

The ink receiving layer contains a pigment, an aqueous binder, a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant,
Other additives are included.

The pigment is preferably a white pigment.
Examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite,
Inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, styrene pigment, acrylic pigment, urea resin, melamine resin,
And the like. Among these white pigments, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is more preferable. 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 include water-soluble binders such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. These aqueous binders may be used alone or may be used alone.
More than one species may be used in combination. Among these, polyvinyl alcohol, silanol modified polyvinyl alcohol,
It is preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.

It is preferable that the mordant is immobilized. For this purpose, a polymer mordant is preferably used. As the polymer mordant, JP-A-Showa 4
8-28325, 54-74430, 54-1
No. 24726, No. 55-22766, No. 55-142
No. 339, No. 60-23850, No. 60-23851
Nos. 60-23852, 60-23853, 60-57836, 60-60643, 60-
No. 118834, No. 60-122940, No. 60-1
No. 22941, No. 60-122942, No. 60-23
5134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, and 314.
No. 8061, No. 3309690, No. 4115124
Nos. 4,124,386, 4,193,800, 42
No. 73853, No. 4282305, No. 4450224
No. is described in each specification. Polymer mordants described on pages 212 to 215 of JP-A-1-161236 are particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

The water-resistant agent is effective for making the image water-resistant, and cationic resins are preferred. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone,
Examples thereof include a dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Of these, polyamide polyamine epichlorohydrin is particularly preferred. The content of the cationic resin is 1 to 15 with respect to the total solid content of the ink receiving layer.
% By mass is preferable, and 3 to 10% by mass is more preferable.

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

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. Examples of the surfactant include JP-A-62-17346.
No. 3, No. 62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound,
Preferably, it is hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil) and a solid fluorine compound resin (for example, ethylene tetrafluoride resin). The organic fluoro compound is described in
No. 9053 (columns 8 to 17), JP-A-61-20994
And JP-A-62-135826.

Examples of the other additives include a pigment dispersant, a thickener, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, a pH adjuster, a matting agent, and a hardening agent.

The back coat layer contains a white pigment, an aqueous binder, and other components.

Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc,
Calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo boehmite, hydroxylated White inorganic pigments such as aluminum, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, and magnesium hydroxide; organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin. Can be

As the aqueous binder, styrene /
Water-soluble polymers such as maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, and styrene Water-dispersible polymers such as butadiene latex and acrylic emulsion are exemplified.

Examples of the other components include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

Incidentally, a polymer latex may be added to the constituent layers (including the back coat layer) in the recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-131648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing the mordant, cracking and curling of the layer can be prevented. When a polymer latex having a high glass transition temperature is added to the back coat layer, curling can be prevented.

In the ink jet recording method of the present invention, the image receiving material to be used is not particularly limited. However, when an ink receiving layer is laminated on a support, and the ink receiving layer uses a recording material containing a white pigment. This is preferable because the formed image has high image quality. Also, in many conventional dispersion inks, when a recording material having an ink receiving layer containing a porous inorganic pigment such as a white pigment is used, the penetration property to the recording material is poor, and There is a problem that the dye is peeled off from the surface when rubbing is performed by hand. However, since the ink of the present invention is excellent in soaking properties, such a problem has been solved. Therefore, when the recording material is used, an image with high image quality and high intensity can be formed.

The ink-jet recording method of the present invention is not particularly limited, and is a known method, for example, a charge control method for discharging ink using electrostatic attraction, a drop-on-demand using vibration pressure of a piezo element. A method (pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate ink to discharge ink using radiation pressure, a thermal method that heats ink to form bubbles and uses the generated pressure Any of an ink jet (bubble jet (registered trademark)) method or the like may be 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.

[0136]

The present invention will be described below with reference to examples.
The present invention is not limited by the following examples. [Example 1] (Preparation of colorant-dispersed ink) Oil-soluble dye (M-1)
5 g, 1.6 g of sodium dioctyl sulfosuccinate,
2.0 g of the olefin-containing polymer (P-2), 1.8 g of the high boiling point organic solvent (S-1), and 3.2 g of (S-2) were dissolved at 75 ° C. in 75 ml of ethyl acetate. 75 ml of deionized water heated to 75 ° C. was put into the solution, and emulsification was performed at 10,000 rpm using a homogenizer. After emulsification for 4 minutes, stop for 1 minute was repeated for a total of 6 cycles. The obtained emulsion was concentrated under a nitrogen flow until the odor of ethyl acetate disappeared, and filtered to obtain a fine emulsion of a hydrophobic dye. Diethylene glycol, glycerin and deionized water were added to the obtained emulsion, and 10
An oil-soluble dye-dispersed ink (ink 01) composed of an oil-soluble dye concentration of 2% by mass, a diethylene glycol concentration of 5% by mass, and glycerin of 5% by mass per 0 ml was prepared. The volume average particle size of the obtained emulsified dispersion ink was measured by using Microtrac UPA (Nikkiso Co., Ltd.) and found to be 75 nm.

[0137]

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Further, in the above-described ink production process,
Except for the type of the olefin-containing polymer, the amount of the olefin-containing polymer added, and the dye, the oil-soluble dye-dispersed ink (Ink 02 to
3) was produced. The olefin-containing polymer and colorant used are shown in Table 1 below. In addition, the polymer used as a comparative example was the following, and was a polymer containing no olefin moiety. PH-1: polybutyl acrylate, molecular weight 32000

[0139]

[Table 1]

As is clear from the results in Table 1, the ink 0
The dispersibility of each of Nos. 1 to 13 was good (normal or higher). Further, in the ink 12, an ink was also prepared in which the addition amount of the olefin-containing polymer (P-37) was increased to 1100 parts by mass (to the dye in a mass ratio of 11) with respect to 100 parts by mass of the oil-soluble dye. It was found that when the added amount of the contained polymer exceeded 1000 parts by mass, the dispersibility of the ink was reduced. Therefore, in order to maintain good dispersibility of the ink, it was found that the amount is preferably 1,000 parts by mass or less based on 100 parts by mass of the oil-soluble dye.

<Preparation of Ink 14> Water-soluble dye A-1
2 g was dissolved in 40 g of ion-exchanged water, and 5 g of diethylene glycol, 5 g of glycerin, and 0.5 g of sodium sodium hexaethylene glycol monododecyl ether sulfate were used.
g, 0.5 g of sodium di (2-ethylhexyl) sulfosuccinate and 37 g of ion-exchanged water.
The mixture was filtered through a 45 μm filter to prepare an aqueous inkjet ink 14.

[0142]

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-Image Recording and Evaluation- The prepared inks 01 to 14 are filled in a cartridge of an ink jet printer PM-670C (manufactured by EPSON Corporation), and plain paper for PPC and ink jet paper photo glossy paper are used by using the same machine. An image was recorded on EX (manufactured by Fuji Photo Film Co., Ltd.), and the following evaluation was performed. Table 2 shows the evaluation results.

<Evaluation of Printing Performance> After setting the cartridge in the printer and confirming the ejection of ink from all nozzles, an image was output on 10 sheets of A4 paper, and the disturbance of printing was evaluated according to the following criteria. A: There was no printing disorder from the start to the end of printing. B: Printing disorder sometimes occurred from the start to the end of printing. C: Printing disorder was observed from the start to the end of printing.

<Evaluation of Paper Dependency> The color tone of the image formed on the photo glossy paper and the image formed on the plain paper for PPC were compared. The case where the difference between the two images was small was “B”, and the case where the difference between the two images was large was “C”.

<Evaluation of Water Resistance> The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in water for 30 seconds, dried naturally at room temperature, and observed for bleeding. A sample without bleeding was evaluated as "A", a sample with slight bleeding as "B", and a sample with much bleeding as "C".

<Evaluation of Scratch Property> The image aged for 30 minutes after printing the image was rubbed with an eraser, and the presence or absence of a density change in the image area was visually evaluated. “A” indicates a good result with little change in density, and “B” indicates a bad result with a change in density. <Image Storage> Inkjet Paper Photo Glossy Paper E
The following evaluation was performed on the print sample of X. As the ozone storage resistance, the ratio of the concentration before and after storing the sample for 7 days under the condition of an ozone concentration of 0.3 ppm and 25 ° C. was determined as a dye residual ratio (%) by the following method, and the following rank was given. . Dye residual ratio (%) = density after standing for 7 days / density immediately after printing * 100 Dye residual ratio is 71 to 100% A 41 to 70% B 40% or less C

[0148]

[Table 2]

As is clear from the results shown in Table 2, the ink-jet inks of the examples were excellent in printability, water resistance, and abrasion resistance, and particularly excellent in image preservability by ozone.
In particular, when the olefin-containing polymer contains a poly-1,2-butadiene structure, it can be seen that a remarkable effect is exhibited by adding a small amount.

[Example 2] (Preparation of ink set 101) Magenta dye (M-6)
5 g, 1.25 g of the olefin-containing polymer (P-2), 3.8 g of a hydrophobic high-boiling organic solvent (S-1), 6.3 g of a hydrophobic high-boiling organic solvent (S-2), and sodium dioctylsulfosuccinate. 13 parts, UV1 to UV5 (mass ratio =
3.12 g of a 1: 2: 2: 3: 1 mixture) and 50 ml of ethyl acetate at 70 ° C. 5 in this solution
00 ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is added to a microfluidizer.
600 bars at (MICROFLUIDEX INC)
The particles were made to pass through five times at a pressure of 5 μm to form fine particles. Further, the emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate was eliminated to obtain a colored fine particle dispersion. To the obtained fine emulsion, 100 parts of diethylene glycol, 40 parts of glycerin, SURFYNOL4
65 (Air Products & Chemicals)
5.5 parts, urea 46.0 parts, triethanolamine 7.
5 parts, benzotriazole 0.075 parts, preservative 2.5
Parts and deionized water to make a total of 1000 parts to prepare a light magenta ink.

In the preparation of the light magenta ink, the amount of the oil-soluble dye, the amount of the hydrophobic high-boiling organic solvent, the amount of the vinyl polymer, and the amount of the sodium dioctyl sulfosuccinate were changed as shown in Table 3 below. An ink, a cyan ink, a yellow ink, and a black ink were respectively manufactured, and an ink set 101 including six types of inks was manufactured. The structural formula of the dye (Y-1) used in the yellow ink and the black ink is shown below.

[0152]

[Table 3]

[0153]

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[0154]

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-Preparation of Ink Sets 102 to 106- Next, in preparing the ink set 101, the ink sets 102 to 106 were prepared by changing the oil-soluble dye and the olefin-containing polymer as shown in Tables 4 and 5 below. . Table 6 shows a comparative ink set using a water-soluble dye.
An ink set 107 according to the above was prepared. The dyes (YY-2, MM-2 to MM-2) used in the ink sets 102 to 107 were used.
3, CC-2 to 3, and A-1 to 7) are shown below.

[0156]

[Table 4]

[0157]

[Table 5]

[0158]

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[0159]

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[0160]

[Table 6]

[0161]

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[0162]

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<Image Recording and Evaluation> The prepared ink sets 101 to 107 were evaluated in the same manner as in Example 1. The following methods were used for the evaluation of stability over time, evaluation of dryness, and evaluation of bleeding of fine lines. Tables 7 and 8 show the evaluation results.
Shown in

<Evaluation of stability over time> The prepared dispersion ink was aged at 80 ° C., and the particle diameter after 5 days of aging was measured.
Evaluation was made based on the value of particle diameter after day / particle diameter immediately after preparation. Those with a value of less than 1.1 were rated "A", and those with a value of 1.1 or more were rated "B". <Evaluation of Drying Property> Immediately after printing the image, the image portion was touched with a finger, and the generated stain was visually evaluated. "O" indicates that no stain was generated. <Evaluation of bleeding of fine line> A thin line pattern of yellow, magenta, cyan and black was printed and evaluated visually.
“○” indicates that no bleeding was confirmed, and “△” indicates that slight bleeding was not confirmed.

[0165]

[Table 7]

[0166]

[Table 8]

As is clear from the results in the table, the inks of the examples were excellent in printability, did not depend on paper, and were excellent in water resistance, scratch resistance and image storability.

Example 3 The same ink prepared in Example 2 was used in an ink jet printer BJ-F850 (CA
NON Corporation), the image was printed on inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine, and the same evaluation as in Example 2 was performed. The same result as in Example 2 was obtained. Was.

[0169]

According to the present invention, when printing is performed using a nozzle or the like, clogging does not occur at the nozzle tip, there is no dependence on paper, and water resistance when printing on arbitrarily selected paper is achieved. The present invention can provide an ink-jet ink and an ink-jet recording method which are excellent in the properties, abrasion, and image storability.

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Claims (3)

[Claims] 1. An ink-jet ink comprising a colored fine particle dispersion containing at least a hydrophobic high-boiling organic solvent having a boiling point of 150 ° C. or higher, a colorant, and an olefin-containing polymer. 2. The method according to claim 1, wherein the olefin-containing polymer is poly-
The inkjet ink according to claim 1, having a 1,2-butadiene structure. 3. An ink-jet recording method comprising performing recording using the ink-jet ink according to claim 1.