JP2002088294A - Colored fine particle dispersion and ink for ink jet recording, made by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored fine particle dispersion which has good handleability, odor and safety, is suitable for e.g. a water-base ink for writing, a water-base printing ink, and an ink for recording information, and is excellent in dispersion stability and shelf stability since the dispersed particles have each a small diameter. SOLUTION: The dispersion contains colored fine particles containing an oil-soluble dye and a vinyl polymer, wherein the vinyl polymer is derived from a monomer represented by formula (I) (wherein R is H, an aliphatic group, or an alkoxycarbonyl group; L is alkylene or arylene; and m is 0 or 1) and has a cyano group content of 10-49 mass%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous colored fine particle dispersion containing an oil-soluble dye, an ink jet recording ink containing the colored fine particle dispersion, and an ink jet recording using the ink jet recording ink. About the method.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink jet printers have been widely used not only in offices but also at home for printing on paper, film, cloth and the like. As inks for inkjet recording, oil-based inks, aqueous inks, and solid inks are known.Among these, aqueous inks are advantageous in terms of ease of production, handleability, odor, safety, and the like. Water-based inks have become mainstream.

However, most of the aqueous inks use water-soluble dyes that dissolve in a molecular state, and thus have the advantage of high transparency and color density. However, since the dyes are water-soluble, they have poor water resistance. When printing on so-called plain paper, bleeding occurs and the printing quality is significantly reduced,
There is a problem that light resistance is poor.

Therefore, aqueous inks using pigments and disperse dyes for the purpose of solving the above-mentioned problems have been disclosed in, for example, JP-A-56-1981.
157468, JP-A-4-18468, 10-1
Nos. 10126, 10-195355, and the like. However, in the case of these water-based inks, the water resistance is improved to some extent, but it is not sufficient, and the storage stability of the dispersion of the pigment or the disperse dye in the water-based ink is lacking, causing clogging at the ink ejection port. There is a problem that it is easy. In addition, these water-based inks generally have insufficient hue and have a problem in color reproducibility based on insufficient color tone. Furthermore, recording paper provided with an ink receiving layer containing porous inorganic fine particles on the surface thereof (hereinafter, may be referred to as “photo-quality paper”) has been used due to the recent trend toward higher image quality of ink jet technology. )), There is a problem that the ink using the pigment or the dye has poor permeation property, and the pigment or the dye is easily peeled off from the surface when rubbed by hand.

On the other hand, JP-A-58-45272, JP-A-6-340835, 7-268254, and 7-2
Nos. 68257 and 7-268260 propose a method of including a dye in urethane or polyester dispersion particles. JP-A-9-241565 proposes a method of enclosing a dye using a vinyl polymer containing a styrene acrylonitrile copolymer macromer as a constituent monomer. However,
In the case of the inkjet ink obtained by the above method, the color tone is insufficient, the color reproducibility is insufficient, and the prevention of fading is also insufficient. Further, when printing is performed on paper containing inorganic fine particles in the image receiving layer, there is a problem that the rub resistance due to an eraser or the like is insufficient.

[0006] Japanese Patent Application Laid-Open Nos. 9-59552 and 9-1
No. 11163, No. 9-255887, No. 10-367
JP-A Nos. 28 and 11-286637 disclose that the above color tone can be improved by using a dye obtained by coupling an aromatic diamine to a color photographic coupler. However, in these, the particle size or particle size distribution of the dispersion tends to be large, the dispersion stability and printability are not sufficient, the color tone changes depending on the type of image receiving paper, and the scratch resistance is not sufficient. There is a problem.

As described above, in addition to having handleability, odor and safety, the particle size of the dispersed particles is small, and the storage stability of the dispersion is excellent. No clogging, excellent ejection stability, no paper dependence, excellent color development, excellent color tone (hue), excellent ink permeability even when using the photographic quality paper, water resistance after printing,
At present, there has not yet been provided a colored fine particle dispersion which is particularly excellent in light resistance and scratch resistance and enables high-density and high-quality recording.

[0008]

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 has handleability, odor, safety, is suitable for writing aqueous ink, aqueous printing ink, information recording ink, etc., the particle size of the dispersed particles is small, the dispersion stability of the dispersion and An object of the present invention is to provide a colored fine particle dispersion having excellent storage stability. The invention is suitable for thermal, piezoelectric, electric or acoustic ink jet systems,
With handleability, odor and safety, small particle size of dispersed particles, excellent dispersion stability and storage stability of dispersion, less occurrence of clogging at the nozzle tip, no dependence on paper, arbitrarily Excellent color development when printing on selected paper, especially excellent color tone (hue), excellent ink penetration into photographic quality paper,
An object of the present invention is to provide an ink jet recording ink having excellent water resistance, particularly light resistance and scratch resistance after recording, and capable of recording with high density and high image quality. The present invention provides easy handling, odor,
Equipped with safety, eliminates ejection failure due to clogging at the nozzle tip, has no paper dependence, and has excellent color development when printing on arbitrarily selected paper, especially excellent color tone (hue), and is suitable for photo quality paper. An object of the present invention is to provide an ink jet recording method which is excellent in ink permeability, excellent in water resistance after recording, particularly excellent in light resistance and scratch resistance, and capable of recording with high density and high image quality.

[0009]

Means for solving the above problems are as follows. That is, <1> a colored fine particle dispersion containing colored fine particles containing an oil-soluble dye and a vinyl polymer, wherein the vinyl polymer is derived from a monomer represented by the following general formula (I), 10 to 49 cyano groups
A colored fine particle dispersion characterized by mass%. General formula (I)

[0010]

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In the general formula (I), R represents a hydrogen atom, an alkyl group or an alkoxycarbonyl group, L represents an alkylene group or an arylene group, and m is 0 or 1. <2> The oil-soluble dye has the following general formula (II) or (III)
The colored fine particle dispersion of the above <1>, which is represented by the following formula:

[0012]

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In the general formulas (II) and (III),
R¹, R^Two, R^ThreeAnd R^FourIs independently a hydrogen atom,
Halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano
Group, hydroxy group, nitro group, amino group, alkylamido
Groups, alkoxy groups, aryloxy groups, amide groups,
Reelamino group, ureido group, sulfamoylamino
Group, alkylthio group, arylthio group, alkoxycal
Bonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl
Group, heterocyclic oxy group, azo group, acyloxy group,
Rubamoyloxy group, silyloxy group, aryloxy
Carbonyl group, aryloxycarbonylamino group, a
Mido group, heterocyclic thio group, sulfinyl group, phosphoryl
Represents a group, an acyl group, a carboxyl group or a sulfo group. A
Is -NR^FiveR⁶Or a hydroxy group, R^Fiveand
R⁶Each independently represent a hydrogen atom, an aliphatic group or an aromatic group.
Or a heterocyclic group. A is -NR^FiveR⁶Good to be
Good. R^FiveAnd R⁶Are bonded to each other to form a ring
You may. B¹Is = C (R^Three)-Or = N-,
B ^TwoIs -C (R^Four) = Or -N =. B¹, B^TwoBut
At the same time, it is preferable that -N = is not satisfied.¹Is = C
(R^Three)-, B^TwoIs -C (R^Four) = Is better
Good. R¹And R^Five, R^ThreeAnd R⁶And / or R¹And R^TwoIs
May combine with each other to form an aromatic ring or a heterocyclic ring.
No. X is the residue of a color photographic coupler, Y is an unsaturated heterocyclic ring
Represents a group. <3> The colored fine particles are composed of an oil-soluble dye and a vinyl polymer.
Emulsifying by adding water to the organic solvent phase containing
And emulsification by introducing the organic solvent phase into water
The above <1> or
Or the colored fine particle dispersion according to <2>. <4> the colored fine particles are a vinyl polymer and an oil-soluble dye,
Before being characterized by containing a hydrophobic high-boiling organic solvent
The colored fine particle dispersion according to any one of <1> to <3>.
object. <5> As monomers for forming the vinyl polymer,
Contains acrylonitrile or methacrylonitrile
The method according to any one of <1> to <4>, wherein
Colored fine particle dispersion. <6> Coloring according to any one of <1> to <5>.
Ink jet containing a fine particle dispersion
Inkjet recording ink. <7> The inkjet recording ink according to <6>.
Ink-jet recording using ink
Recording method.

In the present invention, the following means are further preferably mentioned. <8> When the content of the ionic group of the vinyl polymer is 0.
The colored fine particle dispersion according to any one of <1> to <5>, which has a concentration of 2 to 4.0 mmol / g. <9> The ionic group of the vinyl polymer is at least one of a carboxyl group and a sulfonic acid group.
5> The colored fine particle dispersion according to any one of the above.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a colored fine particle dispersion, an ink-jet ink and an ink-jet recording method of the present invention will be described.

(Colored Fine Particle Dispersion) The colored fine particle dispersion of the present invention is obtained by mixing colored fine particles containing an oil-soluble dye and a vinyl polymer with an aqueous medium (an aqueous liquid containing at least water).
It becomes dispersed.

-Oil-soluble dye- As the applicable yellow dye, any 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,
There are quinone dyes such as anthraquinone dyes and the like, and other dyes include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

Any applicable magenta dye can be used. For example, aryl or hetenylazo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, merocyanine dyes, and oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye;
Examples thereof include quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone, and condensed polycyclic dyes such as dioxazine dye.

Any applicable cyan dye can be used. For example, indoaniline dye,
Azomethine dyes having pyrrolotriazoles as indophenol dyes or coupling components; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; Dyes; for example, phenols, naphthols as coupling components,
Examples thereof include aryl or hetenylazo dyes having anilines and indigo / thioindigo dyes.

Each of the above-mentioned dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore is dissociated. In this case, the counter cation is 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, preferred specific examples include, for example, CI Solvent Black
3,7,27,29 and 34; CI Solvent Yellow 14,16,19,
29, 30, 56, 82, 93 and 162; CI Solvent Red 1, 3,
8,18,24,27,43,49,51,72,73,109,122,132 and 218; CI
Solvent Violet 3; CI Solvent Blue
2,11,25,35,38,67 and 70; CI Solvent Green 3
And 7; and CI Solvent Orange 2. Particularly preferred among these are Nubian Black P
C-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow
105, Oil Pink 312, Oil Red 5B, Oil Scarlet 308, V
ali Fast Blue 2606, Oil Blue BOS (Orient Chemical Co., Ltd.), Aizen Spilon Blue GNH (Hodogaya Chemical
NeopenYellow 075, Neopen Mazenta SE137
8, Neopen Blue 808, Neopen Blue FF4012, Neopen Cya
n FF4238 (manufactured by BASF) and the like.

In the present invention, a disperse dye can be used within a range that dissolves in a water-immiscible organic solvent.
Preferred examples thereof include CI Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,16.
0,184: 1,186,198,199,201,204,224 and 237; CI Disperse Orange 13,29,31: 1,33,49,54,55,66,73,118,119
And 163; CI Disperse Red 54,60,72,73,86,88,9
1,92,93,111,126,127,134,135,143,145,152,153,154,15
9,164,167: 1,177,181,204,206,207,221,239,240,258,27
7,278,283,311,323,343,348,356 and 362; CI Disperse Violet 33; CI Disperse Blue 56,60,7
3,87,113,128,143,148,154,158,165,165: 1,165: 2,176,1
83,185,197,198,201,214,224,225,257,266,267,287,35
4,358,365 and 368; and CI Disperse Green 6:
1 and 9 and the like.

Particularly preferred oil-soluble dyes include azo and azomethine dyes represented by the following formulas (II) and (III). Dyes of general formula (III) are known as dyes formed from couplers and developing agents by oxidation in photographic materials.

[0024]

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In the general formulas (II) and (III),
R¹, R^Two, R^ThreeAnd R^FourIs independently a hydrogen atom,
Halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano
Group, hydroxy group, nitro group, amino group, alkylamido
Groups, alkoxy groups, aryloxy groups, amide groups,
Reelamino group, ureido group, sulfamoylamino
Group, alkylthio group, arylthio group, alkoxycal
Bonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl
Group, heterocyclic oxy group, azo group, acyloxy group,
Rubamoyloxy group, silyloxy group, aryloxy
Carbonyl group, aryloxycarbonylamino group, a
Mido group, heterocyclic thio group, sulfinyl group, phosphoryl
Represents a group, an acyl group, a carboxyl group or a sulfo group. A
Is -NR^FiveR⁶Or a hydroxy group, R^Fiveand
R⁶Each independently represent a hydrogen atom, an aliphatic group or an aromatic group.
Or a heterocyclic group. A is -NR^FiveR⁶Good to be
Good. R^FiveAnd R⁶Are bonded to each other to form a ring
You may. B¹Is = C (R^Three)-Or = N-,
B ^TwoIs -C (R^Four) = Or -N =. B¹, B^TwoBut
At the same time, it is preferable that -N = is not satisfied.¹Is = C
(R^Three)-, B^TwoIs -C (R^Four) = Is better
Good. R¹And R^Five, R^ThreeAnd R⁶And / or R¹And R^TwoIs
May combine with each other to form an aromatic ring or a heterocyclic ring.
No. X is the residue of a color photographic coupler, Y is an unsaturated heterocyclic ring
Represents a group.

R ⁵ and R ⁶ are preferably each independently a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and are preferably a hydrogen atom, an alkyl group or a substituted alkyl group, an aryl group, or a substituted aryl group. More preferably,
Most preferably, they are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms. R ² is a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group,
An amide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, and a sulfonamide group are preferred.

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 and may form a ring. The aliphatic group preferably has 1 to 20 carbon atoms,
More preferably, it is 18. 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 moiety of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include the substituents described for R ¹ , R ² , R ³ and R ⁴ . 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 for R ¹ , R ² , R ³ and R ⁴ .

The unsaturated heterocyclic group represented by Y in the formula (II) is preferably a 5- or 6-membered unsaturated heterocyclic ring. An aliphatic ring, an aromatic ring or another hetero ring may be condensed to the hetero ring. Examples of heteroatoms on the heterocycle include N, O, and S. Examples of the saturated heterocyclic ring include a pyrrolidine ring and a morpholine ring. Examples of unsaturated heterocycles include 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 a quinoline ring. Is mentioned. The heterocyclic group may have the substituents described above for R ^{1 to} R ⁴ .

As the coupler represented by X in the formula (III), the following couplers are preferred. Yellow coupler: U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024,
4,401,752, 4,248,961, JP-B-58-10739, UK Patent 1,425,020, JP 1,476,760, US Patent 3,973,96
No. 8, No. 4,314,023, No. 4,511,649, European Patent 249,473
No. A, couplers represented by formulas (I) and (II) of No. 502,424A, couplers represented by formulas (1) and (2) of No. 513,496A (especially Y-28 on page 18, 568,037) The coupler of formula (I) of claim 1 of A, the column 1-4 of U.S. Pat. No. 5,066,576.
Coupler represented by the general formula (I) in lines 5 to 55, JP-A-4-27
A coupler represented by the general formula (I) in paragraph 0008 of No. 4425,
Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18), formula (Y) on page 4 of 447,969 A1
(Especially Y-1 (page 17), Y-54 (41
P.)), U.S. Pat.
Couplers represented by (II) to (IV) (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; US Pat. No. 4,310,619;
4,351,897, European Patent 73,636, U.S. Patent 3,061,432
No. 3,725,067, Research Disclosure No.
No. 24220 (June 1984), No. 24230 (June 1984),
33552, 60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Patent 4,500,63
No. 0, 4,540,654, 4,556,630, International Publication WO88 / 04
No. 795, JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13), European Patent 456,257 (A-4) -63
(P. 134), (A-4) -73, -75 (p. 139), M-4, -6 of No. 486,965
(P. 26), M-7 (p. 27), M-45 of P. 571,959A (p. 19),
(M-1) of 5-204106 (p. 6), M- of paragraph 0237 of
22, U.S. Pat. Nos. 3,061,432 and 3,725,067.

Cyan coupler: US Pat. No. 4,052,212,
No. 4,146,396, No. 4,228,233, No. 4,296,200, European Patent 73,636, CX-1,3,4,5,11,12,14,15 of JP-A-4-04843
(Pages 14 to 16); C-7,10 (p. 35), 34, 35 (37
Page 1), (I-1), (I-17) (pages 42 to 43);
A coupler represented by the general formula (Ia) or (Ib):

In addition, JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3 and 30), EP355,660A (pages 4, 5 and 45)
Pp. 47) are also useful.

Among the dyes represented by the general formula (II), a dye represented by the following formula (IV) is particularly preferably used as the magenta dye. Formula (IV)

[0035]

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In the formula, Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ¹ has a σ _p value of 0.
The number of the electron-withdrawing groups is preferably 30 or more and 1.0 or less. Preferred specific substituents include the electron-withdrawing substituents described below.
Acyl group having 12 to 12 carbon atoms, alkyloxycarbonyl group having 2 to 12 carbon atoms, nitro group, cyano group, alkylsulfonyl group having 1 to 12 carbon atoms, arylsulfonyl group having 6 to 18 carbon atoms, carbamoyl having 1 to 12 carbon atoms Group and carbon number 1
~ 12 halogenated alkyl groups are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group. R ^{1 to} R ⁶ have the same meaning as in formula (II). Z ² represents a hydrogen atom, an aliphatic group, or an aromatic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q is 5
A group consisting of a group of nonmetallic atoms necessary for forming an 8-membered ring is preferable. Among them, an aromatic group and a heterocyclic group are 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 nitrogen, oxygen, sulfur or carbon. Specific examples of such a ring structure include, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring,
Cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring,
Examples include a benzimidazole ring, an oxazole ring, a benzoxazole ring, an oxane ring, a sulfolane ring, and a thiane ring.When these rings further have a substituent, the substituent may be any of the above substituents R ^{1 to} R ⁴ The exemplified groups are exemplified. The preferred dye structure represented by formula (IV) is described in Japanese Patent Application No. 2000-80733.

Among the dyes represented by the general formula (III), as the magenta dye, a dye represented by the following formula (V) is particularly preferably used. Expression (V)

[0038]

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In the formula, G is a hydrogen atom, an aliphatic group, an aromatic group,
Heterocyclic group, cyano group, alkoxy group, aryloxy
Group, alkylthio group, arylthio group, ester group,
Mino group, carbamoyl group, sulfonyl group, sulfamoi
Group, ureido group, urethane group, acyl group, amide group,
Or a sulfonamide group. Also R¹, R^Two, A, B
¹And B^TwoIs synonymous with formula (III) and their preference
The same is true for the range. L is an aliphatic group, an aromatic group, a heterocyclic ring
Group, cyano group, alkoxy group, aryloxy group,
Killthio, arylthio, ester, amino,
Carbamoyl, sulfonyl, sulfamoyl, c
Raid group, urethane group, acyl group, amide group, or
It may be substituted with at least one of the sulfonamide groups
A group of atoms that form a 5- or 6-membered nitrogen-containing heterocycle
This heterocyclic ring may form a condensed ring with another ring.
Good.

In the compound represented by the formula (V), A is preferably -NR ⁵ R ⁶ and L is preferably a 5-membered nitrogen-containing heterocyclic ring. Examples of the 5-membered nitrogen-containing heterocycle include an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the magenta dyes represented by the formulas (II) and (III) are described below, but they are for describing the present invention in detail, and the present invention is not limited thereto.

[0041]

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[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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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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Examples of the compounds of the present invention are described in Japanese Patent Application No.
No. 65187, No. 11-365190, and Japanese Patent Application No. 2000-80733, but are not limited thereto.

The dye represented by the formula (IV) of the present invention can be synthesized, for example, by referring to the methods described in Japanese Patent Application No. 2000-80733 and JP-A-55-161856. The dye represented by the formula (V) of the present invention can be synthesized with reference to, for example, the methods described in JP-A-4-126772, JP-B-7-94180 and JP-A-11-365187.

Among the dyes represented by the general formula (III), a pyrrolotriazoleazomethine dye represented by the following formula (VI) is particularly preferably used as a cyan dye. Equation (VI)

[0063]

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In the formula (VI), A, R ¹ , R ² , B ¹ and B ²
Has the same meaning as in formula (III), and their preferred ranges are also the same. Z ³ and Z ⁴ each independently have the same meaning as G in formula (V). Z ³ and Z ⁴ may combine with each other to form a ring structure. M is an atomic group capable of forming a 1,2,4-triazole ring fused to the 6-membered ring of the formula (VI), and one of two atoms B ³ and B ⁴ of the condensed portion is a nitrogen atom, The other is a carbon atom.

Further, the pyrrole represented by the general formula (VI)
Z of rotriazole azomethine compound^ThreeIs Hammett replacement
Base constant σ_pAn electron-withdrawing group having a value of 0.30 or more
Has sharp absorption and is more preferable. Moreover,
Z^ThreeIs the Hammett substituent constant σ_pElectron attraction of 0.45 or more
Is preferred, and the Hammett substituent constant σ_p0.60 or less
The above electron withdrawing groups are most preferred. And Z^Threeand
Z^FourSubstituent constant σ of _pIf the sum of the values is 0.70 or more
Is more preferable as it exhibits an excellent hue as a cyan color.

The pyrrolotriazole azomethine compound of the present invention represented by the general formula (VI) is preferably used as a cyan dye, but may be used as a magenta dye by changing the substituent.

Here, the Hammett's substituent constant σ _p value used in the present specification will be described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constants determined by Hammett's rule include σ _p values and σ _m values, and these values can be found in many general books. For example, JA Dean,
"Lange's Handbook of Chemistry", 12th edition, 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.
_{Although it is} limited or explained by _p , this does not mean that it is limited to only certain substituents known in the literature, and the Hammett rule even if the value is unknown in the literature Needless to say, it also includes a substituent which will be included in the range when measured based on the above.
Although the general formulas (II) to (VI) of the present invention include compounds that are not benzene derivatives, the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. I do. In the present invention, the σ _p value is used in this sense.

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p 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 σ _p value of 0.45 or more include an acyl group (eg, an acetyl group), an alkoxycarbonyl group (eg, a dodecyloxycarbonyl group), and an aryloxycarbonyl group (eg, , M-chlorophenoxycarbonyl), an alkylsulfinyl group (eg, n-propylsulfinyl), an arylsulfinyl group (eg, phenylsulfinyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl) , A halogenated alkyl group (for example, , Trifluoromethyl) having a Hammett substituent constant σ _p value of 0.30.
Examples of the electron-withdrawing group include, in addition to the above, an acyloxy group (eg, acetoxy), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (eg, trifluoromethyloxy). ), A halogenated aryloxy group (for example, pentafluorophenyloxy), a sulfonyloxy group (for example, methylsulfonyloxy group), a halogenated alkylthio group (for example, difluoromethylthio), and two or more σ _p values of 0.15 or more. Aryl groups (for example, 2,4-dinitrophenyl, pentachlorophenyl) and heterocycles (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benz) substituted with the above electron-withdrawing groups. Imidazolyl).

Specific examples of the electron-withdrawing group having a σ _p value of 0.20 or more include a halogen atom and the like in addition to the above.

Specific examples of the cyan dye used in the present invention will be given below, but these are for describing the present invention in detail, and the present invention is not limited thereto.

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[0072]

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The dyes usable in the present invention include, but are not limited to, the exemplified compounds described in Japanese Patent Application No. 11-365188.

-Vinyl polymer- In the present invention, the vinyl polymer is a polymer derived from the monomer A represented by the following general formula (I), and may optionally be copolymerized with another monomer B. General formula (I)

[0076]

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In the general formula (I), R represents a hydrogen atom, an aliphatic group or an alkoxycarbonyl group, L represents an alkylene group or an arylene group, and m represents 0 or 1.
It is.

The high cohesive energy density of the cyano group improves the adhesion between the colored fine particles and the substrate (paper, plastic film, etc.), and the reaction between the oil-soluble dye and the gas or the fading promoting factor contained in the image receiving layer. The contact is prevented and the fading prevention performance is improved.

Next, the preferred range of the monomer A represented by the general formula (I) will be described. Among the above R,
A hydrogen atom, an alkyl group having 1 to 3 carbon atoms and an alkoxycarbonyl group having 1 to 20 carbon atoms are preferable, and a hydrogen atom,
A methyl group and an alkoxycarbonyl group having 1 to 8 carbon atoms are more preferable, and a hydrogen atom and a methyl group are particularly preferable. Among the above L, an alkylene group having 1 to 6 carbon atoms and an arylene group having 6 to 10 carbon atoms are preferable, and an alkylene group having 1 to 4 carbon atoms and a phenylene group are more preferable. preferable. m is preferably 0.

Examples of the monomer A include the following. Acrylonitrile, methacrylonitrile, α-cyanoacrylates (ester groups are aliphatic groups, aromatic groups, for example, methyl group, ethyl group, benzyl group, phenyl group and the like) and the like, among which acrylonitrile, Methacrylonitrile is preferred.

The content of the cyano group in the vinyl polymer is preferably from 10 to 49% by mass, more preferably from 10 to 43% by mass, and particularly preferably from 15 to 38% by mass. When the content of the cyano group is less than 10% by mass, it is difficult to obtain the effects of the present invention. When the content is more than 49% by mass, the solubility of the vinyl polymer in an organic solvent is remarkably reduced, and it is difficult to obtain colored fine particles. Tend.

The vinyl polymer may be any of a water-insoluble type, a water-dispersible (self-emulsifying) type, and a water-soluble type. Are preferred.

Examples of the water-dispersible vinyl polymer include:
Any of an ion dissociation type, a nonionic dispersible group-containing type, and a mixture thereof may be used. Examples of the ion dissociation type vinyl polymer include a vinyl polymer containing a cationic ionic group such as a tertiary amino group and a vinyl polymer containing an anionic ionic group such as a carboxylic acid and a sulfonic acid. . Examples of the nonionic dispersible group-containing vinyl polymer include a vinyl polymer containing a nonionic dispersible group such as a polyethyleneoxy chain. Among these, from the viewpoint of dispersion stability of the colored fine particles, an ion dissociation type vinyl polymer containing an anionic ionic group, a nonionic dispersible group containing type vinyl polymer, and a mixed type vinyl polymer are preferable.

The monomer having an ionic group includes a monomer having an anionic ionic group and a monomer having a cationic ionic group.
Examples of the monomer having an anionic ionic group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, 2 carboxyethyl acrylate, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, and monoalkyl itaconate (eg, monomethyl itaconate, Monoethyl itaconate, monoalkyl maleate (eg, monomethyl maleate, monobutyl maleate, etc.), sodium acrylate, ammonium methacrylate, potassium itaconate, and the like.

Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkanesulfonic acid (eg, acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid, etc.), and methacryloyloxyalkanesulfonic acid (eg, Acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid, etc.), acrylamidoalkanesulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methyl) Butanesulfonic acid and the like, methacrylamide alkanesulfonic acid (for example, 2-methacrylamide-2-methylethanesulfonic acid, 2-methacrylamide-2-methylpropane) Bread sulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid).

The phosphoric acid monomer includes, for example, vinylphosphonic acid, methacryloyloxyethanephosphonic acid and the like.

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

Examples of the monomer having a cationic ionic group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl acrylate.

Examples of the monomer containing a nonionic dispersible group include, for example, an ester of a polyethylene glycol and a carboxylic acid monomer, an ester of a polyethylene glycol and a sulfonic acid monomer, and a mixture of a polyethylene glycol and a phosphoric acid monomer. Examples thereof include vinyl group-containing urethanes formed from esters, polyethylene glycols and isocyanate group-containing monomers, and macromonomers having a polyvinyl alcohol structure. The polyethylene glycols are polyethylene glycol monoalkyl ether and polyethylene glycol whose both terminals are hydroxyl groups. When the polyethylene glycol is polyethylene glycol, the derived vinyl monomer preferably has a polymerizable group at only one terminal and the other terminal is a hydroxyl group. The repeating number of the ethyleneoxy moiety of the polyethylene glycol is preferably 5 to 100, and more preferably 5 to 30.
The number of carbon atoms of the alkyl group of the polyethylene glycol monoalkyl ether is preferably from 1 to 20,
1-12 are more preferable.

The mass ratio of the monomer A in the vinyl polymer is preferably 20 to 100% by mass,
0 mass% is more preferable, 60-100 mass% is still more preferable, and 60-95 mass% is especially preferable.

Examples of the monomer B include the following. Acrylic esters and methacrylic esters (ester groups are aliphatic groups and aromatic groups, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group) Group, tert-butyl group, amyl group, hexyl group, 2-
Ethylhexyl group, tert-octyl group, 2-chloroethyl group, 4-bromobutyl group, cyanoethyl group, 2-
Acetoxyethyl, furfuryl, tetrahydrofurfuryl, 5-hydroxypentyl, cyclohexyl, benzyl, hydroxymethyl, butoxymethyl, 3-methoxybutyl, 2- (2-methoxyethoxy) ethyl, 2 -(2-butoxyethoxy) ethyl group, 2,2,2-tetrafluoroethyl group, 1H, 1
H, 2H, 2H-perfluorodecyl group, phenyl group,
2,4,5-tetramethylphenyl group, 4-chlorophenyl group, etc.);

Vinyl esters, specifically, aliphatic carboxylic acid vinyl esters which may have a substituent (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate) , Vinyl chloroacetate, etc.), optionally substituted aromatic carboxylic acid vinyl esters (eg, vinyl benzoate, vinyl 4-methylbenzoate, vinyl salicylate, etc.);

Acrylamides, specifically, acrylamide, N-monosubstituted acrylamide, N-disubstituted acrylamide (substituents are aliphatic, aromatic, and silyl groups such as methyl, ethyl, n A propyl group,
Isopropyl group, n-butyl group, tert-butyl group,
tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, trimethylsilyl, etc.);

Methacrylamides, specifically, methacrylamide, N-monosubstituted methacrylamide, N-disubstituted methacrylamide (substituents are aliphatic, aromatic and silyl groups; for example, methyl, Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, benzyl group, hydroxymethyl group, alkoxymethyl group,
Phenyl group, 2,4,5-tetramethylphenyl group, 4
-Chlorophenyl group, trimethylsilyl, etc.);

Olefins, specifically, styrenes such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene; For example, styrene, methyl styrene,
Dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, and the like;

Vinyl ethers, specifically, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like; other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, Dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malononitrile, And vinylidene.

The monomers A may be used alone or in combination of two or more. The monomer B may be one kind or two or more kinds. The monomers A and B are selected according to various purposes (for example, acid content control and _Tg control, solubility improvement, dispersion stability).

The content of the ionic group in the vinyl polymer is preferably from 0.2 to 4.0 mmol / g, more preferably from 0.3 to 3.0 mmol / g, and more preferably from 0.5 to 3.0 mmol / g. It is particularly preferred that it is 2.0 mmol / g. If the content of the ionic group is too small, the self-emulsifiability of the polymer will be small, and if it is too large, the water solubility will increase and the dispersibility of the oil-soluble dye will decrease. In the vinyl polymer, the dissociating group may form a salt with an alkali metal ion (for example, Na ⁺ , K ^+, etc.) or an ammonium ion.

The molecular weight (weight average molecular weight) of the vinyl polymer is preferably from 1,000 to 200,000, more preferably from 3,000 to 100,000, still more preferably from 5,000 to 80,000,
It is particularly preferred that it is between 5,000 and 50,000. When the molecular weight is smaller than 1000, it tends to be difficult to obtain a stable dispersion, and when the molecular weight is larger than 200,000,
Even if the solubility in the organic solvent is deteriorated or the organic solvent is dissolved, the viscosity of the solution tends to increase and it is difficult to disperse the solution.

Specific examples of the vinyl polymer (P-1 to P-2)
4) is listed below. The vinyl polymer used in the present invention is not limited to these specific examples. The following ratios represent mass ratios, molecular weights represent mass average molecular weights, and% represents mass% of cyano groups contained in the vinyl polymer.

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[0103]

[Table 2]

Next, an example of a method for producing a vinyl polymer will be described. The present invention is not limited to this production example. In the following, “parts” indicates “parts by mass”. <Production Example> 30 parts of methacrylonitrile, 15 parts of sec-butyl methacrylate, 5 parts of 2-carboxyethyl acrylate, 0.7 part of dodecyl mercaptan, dimethyl 2,2′-azobis (2-methylpropionate)
A mixed solution composed of 1 part, 20 parts of MEK, and 20 parts of DMF was prepared. Next, 10 parts of MEK and 0.05 parts of dimethyl 2,2′-azobis (2-methylpropionate) were charged into a flask, and the temperature was raised to 70 ° C. while stirring under a nitrogen blanket. The solution was added dropwise over 10 hours. After completion of the dropwise addition, 0.05 parts of dimethyl 2,2′-azobis (2-methylpropionate) was added, the mixture was reacted at the same temperature for 2 days, and dimethyl 2,2′-azobis (2-methylpropionate) was further added. ) Was added and reacted at the same temperature for 2 days. The obtained polymer solution was reprecipitated in hexane and dried at 40 ° C. under reduced pressure to obtain 48 parts of a target vinyl polymer P-11. The weight average molecular weight is 100
00 (GPC, PS conversion).

-Preparation of Colored Fine Particle Dispersion- The colored fine particle dispersion of the present invention is obtained by dispersing colored fine particles containing the oil-soluble dye and the vinyl polymer in an aqueous medium (an aqueous liquid containing at least water). Manufactured. Specifically, for example, a method in which a dispersion of the vinyl polymer is prepared in advance and the oil-soluble dye is impregnated in the dispersion, or a coemulsification dispersion method is used. Among them, the co-emulsification dispersion method is preferable, and the co-emulsification dispersion method is such that water is added to an organic solvent phase containing the oil-soluble dye and the vinyl polymer to emulsify, and the organic Emulsification by adding a solvent phase is preferred.

Here, a method of preparing a dispersion of the vinyl polymer in advance and impregnating the dispersion with the oil-soluble dye will be described. A first example of this method includes a first step of preparing the vinyl polymer dispersion, and a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent.
A third step of mixing the dye solution and the vinyl polymer dispersion to prepare a colored fine particle dispersion. In a second example of this method, a first step of preparing the vinyl polymer dispersion, a dye solution in which the oil-soluble dye is dissolved in an organic solvent is prepared, and the dye solution and a liquid containing at least water are mixed. A second step of preparing a dye fine particle dispersion by mixing; and a third step of mixing the vinyl polymer dispersion and the dye fine particle dispersion to prepare a colored fine particle dispersion.

Next, the co-emulsification method will be described. A first example of this method includes a first step of preparing a vinyl polymer dye solution in which the oil-soluble dye and the vinyl polymer are dissolved in an organic solvent, a solution containing the vinyl polymer dye solution, and at least water. And a second step of preparing a colored fine particle dispersion by mixing A second example of this method includes a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent; a second step of preparing a vinyl polymer solution in which the vinyl polymer is dissolved; and A third step of preparing a colored fine particle dispersion by mixing the solution, the vinyl polymer solution, and a liquid containing at least water. A third example of this method is a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution and a liquid containing at least water to prepare a dye fine particle dispersion. And a second step of preparing a vinyl polymer solution in which the vinyl polymer is dissolved, mixing the vinyl polymer solution and a liquid containing at least water to prepare a vinyl polymer fine particle dispersion, and the dye fine particle dispersion. A third step of preparing a colored fine particle dispersion by mixing with the vinyl polymer fine particle dispersion. A fourth example of this method includes a first step of preparing a vinyl polymer solution in which the vinyl polymer is dissolved in an organic solvent, and a dye solution in which the oil-soluble dye is dissolved. And a third step of mixing the vinyl polymer solution and the dye fine particle dispersion to prepare a colored fine particle dispersion.

In the colored fine particle dispersion, the amount of the vinyl polymer to be used is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 100 parts by mass, per 100 parts by mass of the oil-soluble dye.
400 parts by mass is more preferred. When the amount of the vinyl polymer used is less than 10 parts by mass, fine and stable dispersion tends to be difficult.When the amount exceeds 1000 parts by mass, the ratio of the oil-soluble dye in the colored fine particle dispersion is small. When the colored fine particle dispersion is used as an aqueous ink, there is a tendency that there is no room for formulation design.

In the colored fine particles, the oil-soluble dye is preferably dispersed in the vinyl polymer. The content of the colored fine particles in the colored fine particle dispersion is preferably 1 to 45% by mass, and 2 to 30% by mass.
Is more preferred. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration, or the like. The average particle size of the colored fine particles is 1 to 500 n in volume average particle size.
m is preferable, and 3 to 300 nm is more preferable.
50 nm is particularly preferred, and 5-100 nm is most preferred. The average particle size can be adjusted by centrifugation, filtration, or the like. The volume average particle size is the average particle size weighted by the particle volume, and is obtained by dividing the sum of the diameters of the individual particles multiplied by the volume of the particles in the aggregate of the particles by the total volume of the particles. For volume average particle size, see "Chemistry of Polymer Latex" (Souichi Muroi, Polymer Publishing Association)
It is described on page 119.

-Organic Solvent- The organic solvent used for producing the colored fine particle dispersion is not particularly limited, and can be appropriately selected based on the solubility of the oil-soluble dye or the vinyl polymer.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone, methanol, ethanol, 2-propanol and
Alcohol solvents such as -propanol, 1-butanol and tert-butanol; chloroform solvents such as chloroform and methylene chloride; aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; Examples thereof include ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether.
These organic solvents may be used alone or may be used alone.
More than one species may be used in combination.

The amount of the organic solvent used is not particularly limited as long as the effect of the present invention is not impaired, but is preferably from 10 to 2,000 parts by mass, more preferably from 100 to 1000 parts by mass, per 100 parts by mass of the vinyl polymer. Parts by mass are more preferred. When the amount of the organic solvent used is less than 10 parts by mass, the fine and stable dispersion of the colored fine particles tends to be difficult, and when it exceeds 2,000 parts by mass, the solvent removal for removing the organic solvent and There is a tendency that a concentration step is indispensable, and there is no room for formulation design.

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 to reduced pressure, and is preferably performed at 40 to 100 ° C. under normal pressure or 10 to 50 ° C. under reduced pressure.

—Additives— The colored fine particle dispersion of the present invention may contain additives appropriately selected according to the purpose within a range that does not impair the effects of the present invention. Examples of the additive include a neutralizing agent, a hydrophobic high-boiling organic solvent, a dispersant, and a dispersion stabilizer.

When the vinyl polymer has an unneutralized dissociable group, the neutralizing agent may be used to adjust the pH of the colored fine particle dispersion.
It can be suitably used in terms of control, self-emulsification control, and dispersion stability. Examples of the neutralizing agent include an organic base and an inorganic alkali.

Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.), and ammonia. From the viewpoint of improving the dispersion stability of the colored fine particle dispersion, the neutralizing agent is preferably added so as to have a pH of 4.5 to 10.0, and added so as to have a pH of 6.0 to 10.0. Is more preferred.

The hydrophobic high-boiling organic solvent is used for adjusting the viscosity, specific gravity, and printing performance of the colored fine particle dispersion. The hydrophobic high-boiling organic solvent is preferably hydrophobic and has a boiling point of 150 ° C. or higher, more preferably 170 ° C. or higher. Here, “hydrophobic” means 25
It means that the solubility in distilled water at 0 ° C. is 3% or less. The hydrophobic high-boiling organic solvent has a dielectric constant of 3
-12, more preferably 4-10. Here, the dielectric constant means a relative dielectric constant with respect to a vacuum at 25 ° C. The hydrophobic high-boiling organic solvent is preferably contained in the same fine particles as the vinyl polymer and the oil-soluble dye. Therefore, in the case of the co-emulsification dispersion method, it is preferable to add the compound to the oil-soluble dye or the vinyl polymer solution.

Examples of the hydrophobic high-boiling organic solvent include US Pat. No. 2,322,027 and Japanese Patent Application No. 2000-2.
Compounds described in JP-A-038575 can be used. Specific examples include phosphoric acid triesters, phthalic acid diesters, alkylnaphthalenes, and benzoic esters. These can be liquid or solid at room temperature depending on the purpose. The amount of the hydrophobic high-boiling solvent used is not particularly limited as long as the effect of the present invention is not impaired.
0 to 1000 parts by mass, preferably 0 to 1000 parts by mass,
-300 parts by mass is more preferred.

The dispersant and / or the dispersion stabilizer is
The vinyl polymer dispersion, the vinyl polymer solution,
Although it may be added to any of a dye solution, a solution containing at least water, and the like, it is added to a solution containing the vinyl polymer, the dye solution, and water in the previous step of preparing the vinyl polymer and / or dye fine particle dispersion. Is preferred. Examples of the dispersant and dispersion stabilizer include various cationic, anionic and nonionic surfactants, water-soluble or water-dispersible low molecular weight compounds, oligomers and the like. The amount of the dispersant and dispersion stabilizer to be added is preferably 0 to 100% by mass, more preferably 0 to 20% by mass, based on the total of the oil-soluble dye and the vinyl polymer.

Although the colored fine particle dispersion of the present invention can be used in various fields, it is suitable for aqueous inks for writing, aqueous printing inks, information recording inks and the like. It can be particularly preferably used.

(Ink for Inkjet Recording) The ink for inkjet recording of the present invention contains the colored fine particle dispersion of the present invention, and may further contain other components appropriately selected as necessary. .

-Other components- The above-mentioned other components are contained within a range that does not impair the effects of the present invention. Regulator, surface tension regulator, defoamer, viscosity regulator, dispersant, dispersion stabilizer,
Known additives such as a rust inhibitor, a chelating agent and the like can be mentioned.

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

As the anti-drying agent, 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-ethyl Heterocycles such as morpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; and urea derivatives. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. These may be used alone or may be used alone.
More than one species may be used in combination. These anti-drying agents are preferably contained in the inkjet recording ink in an amount of 10 to 50% by mass.

The penetration enhancer is suitably used for the purpose of better penetrating the ink for ink jet recording 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, sodium oleate, and a nonionic surfactant. No.
The permeation enhancer is contained within a range that does not cause bleeding of print, paper dropout (print-through), and the like, and usually exhibits a sufficient effect when contained in the ink for inkjet recording 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-48-3049.
No. 2, No. 56-21141, and JP-A-10-8
No. 8106, cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, and JP-T-8-501291. And the like, Research Disclosure No. 2
Compounds described in No. 4239 and compounds emitting fluorescent light by absorbing ultraviolet rays, represented by stilbene-based and benzoxazole-based compounds, 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-based 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. Nos. 17643, VII, I to J; 15162; No. 18716, left column, page 650; No. 36544, page 527; 3071
No. 05, page 872; 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 pH adjusting agent, the neutralizing agent (organic base, inorganic alkali) can be used. The p
For the purpose of improving the storage stability of the inkjet recording ink, the H adjuster is preferably added so that the inkjet recording ink has a pH of 6 to 10.
It is more preferable to add H7 to H10.

As the surface tension adjusting agent, nonionic,
Preference is given to cationic or anionic surfactants. The surface tension of the inkjet recording ink of the present invention is preferably from 25 mN / m to 25 mN / m.
60 mN / m is more preferred.

The viscosity of the ink for ink-jet recording of the present invention is preferably 30 mPa · s or less,
a · s or less is more preferable. Examples of the viscosity modifier used for adjusting the viscosity include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants.

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

(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 nozzle and the like used at that time are not particularly limited. It can be appropriately selected depending on the situation.

-Image-Receiving Material- The image-receiving material is not particularly limited, and known recording materials, for example, plain paper, resin-coated paper, inkjet-only paper, film, electrophotographic common paper, fabric, glass, metal, Ceramics etc. are mentioned. Among the recording materials, paper dedicated to inkjet is preferable.
Nos. 69172, 8-27693 and 2-2
Nos. 76670, 7-276789, 9-
323475, JP-A-62-28783, JP-A-10-153899, and 10-217
Nos. 473 and 10-235995 and 10-
What is described in 337947, 10-217597, 10-337947, etc. is 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 image receiving layer and, if necessary, by laminating other layers such as a back coat layer. In addition, each layer including the image 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 image 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, An image 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, a paper and a plastic film laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) 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.

In the image receiving layer, a pigment, an aqueous binder,
It contains a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant, and other additives.

As the pigment, a white pigment is preferable.
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 image receiving layer.

The mordant is preferably 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-proofing 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% by mass based on the total solid content of the image receiving layer.
Is preferably, and more preferably 3 to 10% by mass.

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 releasability 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, pseudoboehmite, aluminum hydroxide, alumina,
Examples include white inorganic pigments such as lithopone, zeolite, hydrohaloysite, magnesium carbonate, and magnesium hydroxide, and organic pigments such as styrene-based plastic pigment, acrylic-based plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin.

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 fine particle dispersion (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. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-131648,
It is described in each publication of JP-A-62-10066. 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.

The ink-jet recording method of the present invention is not particularly limited, and may be a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method 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. In addition,
In the inkjet recording method, 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 using colorless and transparent ink are included.

[0154]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified. (Example 1)-Production Example 1 (Preparation of Colored Fine Particle Dispersion (B-1))-4 parts of isopropyl alcohol, 6 parts of tert-butanol, 1.5 parts of vinyl polymer (P-1), and an oil-soluble dye (M-1) 2 mol /
L sodium hydroxide was gradually added in such an amount that the vinyl polymer acid was neutralized, and then the temperature was raised to 80 ° C. Thereafter, while stirring, 30 parts of water was gradually added to carry out phase inversion emulsification. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 16%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 63 nm in volume average diameter (Microtrac UPA150; measured by Nikkiso Co., Ltd.).
Hereinafter, this is abbreviated as colored fine particle dispersion (B-1).

Production Example 2 (Colored fine particle dispersion (B-2)
Preparation)-3 parts of ethyl acetate, 0.5 part of cyclohexanone, 1.4 parts of vinyl polymer (P-3), oil-soluble dye (M-4)
0.6 parts of a mixture was prepared. On the other hand, a mixed solution of 2 mol / L sodium hydroxide, 15 parts of water, and 0.2 parts of sodium di (2-ethylhexyl) sulfosuccinate was prepared in such an amount that the acid of the vinyl polymer was neutralized. The two mixed liquids were combined, mixed and emulsified with a homogenizer, and then concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 13.3%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 74 nm in volume average diameter. Less than,
This is abbreviated as colored fine particle dispersion (B-2).

Production Example 3 (Colored fine particle dispersion (B-3)
Preparation)-6.4 parts of oil-soluble dye (M-1), 8.0 parts of sodium dioctyl sulfosuccinate, vinyl polymer (P-10)
5.1 parts of a hydrophobic high boiling point organic solvent (S-1) 7.7 parts,
And 50 parts of ethyl acetate at 70 ° C. 2m of the amount that acid of vinyl polymer is neutralized during dissolution
ol / L sodium hydroxide was added slowly. 400 parts of deionized water was added to this liquid 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 obtained emulsion was concentrated to 160 parts by a rotary evaporator. The particle diameter of the colored fine particles in the colored fine particle dispersion was 30 nm in volume average diameter. Hereinafter, this is abbreviated as colored fine particle dispersion (B-3).

[0157]

Embedded image

-Production Examples 4 to 9-Production Example 4 is produced in a similar manner to Production Example 1, Production Example 5 is produced in a similar manner to Production Example 2, and Production Example 6 is produced in a similar manner to Production Example 3. Was produced from Table 3 shows the vinyl polymers and oil-soluble dyes used. The polymers used as comparative examples were as follows, and were vinyl polymers containing no monomer A component. PH-1: poly (n-butyl acrylate), molecular weight 32
000 PH-2: n-butyl acrylate / acrylic acid (95:
5) Copolymer, molecular weight 27,000

The dispersibility and storage stability of the prepared colored fine particle dispersion were evaluated as follows. The dispersibility is "good" when there is no sedimentation or large particles at the time of dispersion and the particle size distribution is one peak.
And those in which precipitates and large particles were formed were regarded as "bad".
For storage stability, a solution adjusted to a dye concentration of 2% by mass is 70%.
Heated at ℃ for 5 days, change of particle size within ± 10% is “good”
And

[0160]

[Table 3]

As is clear from the results in Table 3, a dispersion of colored fine particles having no aggregation and a small particle size can be produced. In particular, a vinyl polymer containing an ionic group was excellent in dispersibility.

Example 2 <Preparation of Ink 01> 50 parts of the colored fine particle dispersion (B-1) prepared in Production Example 1 of Example 1 were mixed with 5 parts of diethylene glycol, 5 parts of glycerin, and hexaethylene glycol sulfate. Sodium monododecyl ether 0.
5 parts, 0.5 parts of sodium di (2-ethylhexyl) sulfosuccinate and 39 parts of ion-exchanged water were mixed,
The mixture was filtered through a 0.45 μm filter to prepare an aqueous inkjet recording ink 01.

<Preparation of Inks 02 to 09>
In the preparation of (1), the colored fine particle dispersion (B-1)
Was replaced with the colored fine particle dispersions (B-2) to (B-9) prepared in Production Examples 2 to 10 of Example 1, respectively.
Aqueous inkjet recording inks 02 to 09 were each prepared in the same manner as in the preparation of Ink 01.

<Preparation of Ink 10> Water-soluble dye A-1
2 parts were dissolved in 40 parts of ion-exchanged water, and 5 parts of diethylene glycol, 5 parts of glycerin, 0.5 sodium sodium hexaethylene glycol monododecyl ether sulfate were added.
Parts, 0.5 parts of sodium di (2-ethylhexyl) sulfosuccinate and 37 parts of ion-exchanged water,
The mixture was filtered through a 0.45 μm filter to prepare an aqueous inkjet recording ink 10.

[0165]

Embedded image

-Image Recording and Evaluation- The prepared inks 01 to 10 are filled in a cartridge of an ink jet printer PM-670C (manufactured by EPSON), 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 4 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 evaluation was made in three steps, where B was small when C was small, and C when the difference between both images was large.

<Evaluation of Water Resistance> The photo glossy paper on which the image was formed was dried at room temperature for 1 hour, 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 Light Fastness> Xenon light (85000 lx) was irradiated onto the photo glossy paper on which the image was formed using a weather meter (Atlas CI65) for 4 days, and the image density before and after the xenon irradiation was determined by the reflection density. Total (X-Rit
e310TR) and evaluated as the residual dye ratio. The reflection density is 3, 1.5 and 2.0.
Measured in points. At any of the concentrations, the case where the dye residual ratio was 80% or more was evaluated as A, and the case where 1 or 2 points were less than 80% was B, and the case where the concentration was less than 80% at all concentrations was evaluated as C.

[0171]

[Table 4]

As is evident from the results in Table 4, the ink jet recording ink of the present invention has a small particle size, excellent printability, excellent color development and color tone, has no dependence on paper, and has water resistance and light resistance. Was excellent.

Example 3-Preparation of Ink Set 101-5 parts of magenta dye (M-6), vinyl polymer (P-
3) 1.25 parts of a hydrophobic high-boiling organic solvent (S-1)
63 parts, a hydrophobic high-boiling point organic solvent (S-2) 6.38 parts,
It was dissolved at 70 ° C. in 3.13 parts of sodium dioctylsulfosuccinate and 50 ml of ethyl acetate. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. To this mixed solution, 2 mol / L sodium hydroxide was added until the acid of the vinyl polymer was neutralized.
Next, this coarse particle dispersion was added to a microfluidizer (MI
(CROFLUIDEXINC) at a pressure of 600 bar for 5 times to obtain fine particles. Further, the resulting 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, 110 parts of diethylene glycol, 50 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 amounts of the oil-soluble dye, the hydrophobic high-boiling point organic solvent, the amount of the vinyl polymer, and the amount of sodium dioctyl sulfosuccinate were changed as shown in Table 5, and the magenta ink and the light cyan ink were used. , A cyan ink, a yellow ink, and a black ink, respectively, to prepare an ink set 101 including six types of inks. The structural formula of the dye (YY-1) used in the yellow ink and the black ink is shown below.

[0175]

[Table 5]

[0176]

Embedded image

-Preparation of Ink Sets 102 to 103- Next, in preparing the ink set 101, the oil-soluble dye and vinyl polymer were changed as shown in Tables 6 and 7 below.
Ink sets 102 to 103 were prepared. Further, an ink set 104 according to Table 8 was prepared as a comparative ink set using a water-soluble dye. The ink set 10
The dyes (YY-2, MM-2-3, C
The structural formulas of C-2 to 3 and A-1 to 7) are shown below.

[0178]

[Table 6]

[0179]

[Table 7]

[0180]

Embedded image

[0181]

Embedded image

[0182]

[Table 8]

[0183]

Embedded image

[0184]

Embedded image

(Image Recording and Evaluation) The prepared ink sets 101 to 107 were evaluated in the same manner as in Example 2. The dryness evaluation, fine line bleeding evaluation, abrasion evaluation, and dark heat fastness evaluation were evaluated by the following methods. Tables 9 and 10 show the evaluation results.

<Evaluation of Drying Property> Immediately after printing an 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. <Evaluation of Scratch Property> The image aged for 30 minutes after image printing 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. <Dark heat fastness> The dark heat fastness of an image is 1 at 80 ° C.
The image density before and after storing the sample for 0 days was measured using the X-rite 310
And the residual image ratio of the dye was determined and evaluated. Regarding the dye residual image rate, the reflection density was evaluated at three points of 1, 1.5, and 2, and when any of the densities, the dye residual rate was 90% or more, "A". "B", and the case of less than 90% in all points was "C".

[0187]

[Table 9]

[0188]

[Table 10]

As is clear from the results shown in Tables 9 and 10, the ink of the present invention was excellent in printability, did not depend on paper, and was excellent in water resistance, abrasion resistance, light resistance and dark heat fastness.

[0190]

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. It is possible to provide an ink jet recording ink and an ink jet recording method which are excellent in the properties, scratch resistance and light fastness.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 67/46 C09D 11/00 C09D 11/00 B41J 3/04 101Y F-term (Reference) 2C056 EA13 FC02 2H086 BA52 BA56 BA59 4J037 AA30 CC16 DD23 EE28 EE43 FF03 FF15 FF18 FF22 FF23 FF25 FF29 4J039 AD10 AD11 BC05 BC06 BC12 BC29 BC32 BC33 BC35 BC36 BC40 BC44 BC50 BC51 BC52 BC53 BC54 BC55 BC65 BC72 BC73 BC79 EA37 EA38 EA35 EA35

Claims (7)

[Claims] 1. A colored fine particle dispersion comprising colored fine particles containing an oil-soluble dye and a vinyl polymer, wherein the vinyl polymer is derived from a monomer represented by the following general formula (I): 10 to 4 cyano groups
A colored fine particle dispersion, which is 9% by mass. General formula (I) In the general formula (I), R represents a hydrogen atom, an aliphatic group,
Represents an alkoxycarbonyl group, L represents an alkylene group or an arylene group, and m is 0 or 1. 2. The oil-soluble dye of the following general formula (II) or (II)
The colored fine particle dispersion according to claim 1, which is represented by (I). Embedded image In the general formulas (II) and (III), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom,
Aliphatic group, aromatic group, heterocyclic group, cyano group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group , Alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonyl Group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl group or sulfo group. A is -NR ⁵
R ⁶ represents a hydroxy group; R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; R ⁵ and R ⁶ may combine with each other to form a ring. B ¹ represents = C (R ³⁾ - or = N- and represents, B ² is -C (R ⁴⁾ = or represent -N =. R ¹ and R ⁵ , R ³ and R ⁶ and / or R ¹ and R ² may combine with 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. 3. The method according to claim 1, wherein the colored fine particles are emulsified by adding water to an organic solvent phase containing an oil-soluble dye and a vinyl polymer, and emulsifying by adding the organic solvent phase to water. 2. A method according to claim 1, wherein
Or the colored fine particle dispersion according to 2. 4. The colored fine particle dispersion according to claim 1, wherein the colored fine particles contain a vinyl polymer, an oil-soluble dye, and a hydrophobic high-boiling organic solvent. 5. The colored fine particle dispersion according to claim 1, wherein the monomer forming the vinyl polymer contains acrylonitrile or methacrylonitrile. 6. An ink jet recording ink comprising the colored fine particle dispersion according to claim 1. Description: 7. An ink jet recording method, wherein recording is performed using the ink for ink jet recording according to claim 6.