JP2001247787A - Coloring fine-particle dispersoid, ink-jet ink, and ink jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring fine-particle dispersoid excellent in dispersion stability, excellent in color development and color tone, water resistance and light stability without depending upon the kind of paper when printed in an optional paper, and suitable for water-based writing ink, water-based printing ink, information recording ink, etc. SOLUTION: This coloring fine-particle dispersoid contains fine particles each of which comprises the following components: one or more kinds of polymers selected from the group consisting of a polyurethane, a polyester, a polyamide, a polyurea and a polycarbonate; and an oil-soluble dye represented by general formula I, e.g. formula I-8. Such a mode that each of the polymers has 0.01-3.0 mmol/g of a dissociative group, and the dissociative group is at least either of carboxyl group and sulfonic group, is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous colored fine particle dispersion containing an oil-soluble dye, an inkjet ink containing the colored fine particle dispersion, and an inkjet recording method using the inkjet ink.
More specifically, a color fine particle dispersion having good color reproduction and suitable for writing aqueous inks, aqueous printing inks, information recording inks, etc., and ink jet inks suitable for thermal, piezoelectric, electric field or acoustic ink jet systems And an ink jet recording method.

[0002]

[Prior art]

In recent years, with the spread of computers, ink jet printers have been widely used not only in offices but also in homes for printing on paper, film, cloth 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, most of the aqueous inks use a water-soluble dye that dissolves in a molecular state, and thus have the advantage of high transparency and color density. However, since the dye is water-soluble, the water resistance is poor. When printing on so-called plain paper, there is a problem that bleeding occurs and the printing quality is remarkably deteriorated, and light resistance is poor.

Therefore, aqueous inks using pigments or disperse dyes for the purpose of solving the above problems have been disclosed in, for example,
157468, JP-A-4-18468 and 8-18
No. 3920, No. 10-110126, No. 10-195
No. 355 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, and clogging at the ink ejection port is likely to occur. There is a problem. Further, in the case of these aqueous inks, the hue is generally not sufficient, particularly the hue of the magenta component is not sufficient, and there is a problem in color reproducibility based on insufficient color tone.

On the other hand, JP-A-58-45272, JP-A-6-340835, JP-A-7-268254, and 7-2.
JP-A-68257 and JP-A-7-268260 propose a method of enclosing a dye in polyurethane or polyester dispersion particles. However, the dispersions described above have not only the problem of color reproducibility due to insufficient color tone as described above, but also the dispersion stability of the dye-containing polymer dispersion when the dye is included at a desired concentration. Also, there is a problem that the water resistance is not always sufficient.

On the other hand, JP-A-9-59552 and 9-1
No. 11163, No. 9-255887, No. 10-367
In each publication of No. 28, by using a dye obtained by coupling an aromatic diamine to pyrazolotriazole,
It has been proposed to improve the color tone. However,
In these cases, there are problems that the color tone changes depending on the type of the image receiving paper and that the water resistance is not sufficient.

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 the dispersion stability of the colored fine particles, has no paper dependence, is excellent in color development and color tone when printed on arbitrarily selected paper, and is excellent in water resistance and light resistance,
Aqueous ink for writing, aqueous printing ink, colored fine particle dispersion suitable for ink for information recording, etc., and thermal, piezoelectric, suitable for electric or acoustic ink jet system, when performing printing using a nozzle or the like, An ink-jet ink and an ink-jet recording method which do not cause clogging at the nozzle tip, have no dependence on paper, have excellent coloring and color tone when printed on arbitrarily selected paper, and have excellent water resistance and light resistance. The purpose is to provide.

[0008]

Means for solving the above problems are as follows. That is, <1> at least one selected from polyurethane, polyester, polyamide, polyurea and polycarbonate
A colored fine particle dispersion comprising colored fine particles containing one kind of polymer and an oil-soluble dye represented by the following general formula (I).

[0009]

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In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a 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 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 Represents an 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. R ³ and R ⁴ may combine to form an aromatic ring or a hetero ring. R ⁵ represents an unsaturated heterocyclic group. M represents a hydrogen atom, a dissociated inorganic base, a primary amine, a secondary amine or a tertiary amine. <2> The above <1 wherein the oil-soluble dye is dispersed in the polymer.
The colored fine particle dispersion described in (1) above. <3> The colored fine particle dispersion according to <1> or <2>, wherein the polymer contains 0.01 to 3.0 mmol / g of a dissociable group. <4> The colored fine particle dispersion according to <3>, wherein the dissociable group is at least one of a carboxyl group and a sulfonic acid group. <5> From the above <1> obtained by either adding water to an organic solvent containing a polymer and an oil-soluble dye and emulsifying the same, or adding the organic solvent to water and emulsifying the same. 4> The colored fine particle dispersion according to any one of the above. <6> An inkjet ink comprising the colored fine particle dispersion according to any one of <1> to <5>. <7> An ink jet recording method characterized by performing recording using the ink for ink jet described in <6>.

[0011]

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 dispersing colored fine particles containing an oil-soluble dye and at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate in an aqueous medium. Be done.

-Oil-soluble dye- The oil-soluble dye is a compound represented by the following general formula (I). The compounds represented by formula (I) may be used alone or in combination of two or more.

[0014]

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In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a 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 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 Represents an 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. R ³ and R ⁴ may combine to form an aromatic ring or a hetero ring. R ⁵ represents an unsaturated heterocyclic group. M represents a hydrogen atom, a dissociated inorganic base, a primary amine, a secondary amine or a tertiary amine.

Hereinafter, specific examples (I-1 to 30) of the oil-soluble dye represented by formula (I) are listed. Note that the present invention is not limited to these specific examples.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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-Polymer- The polymer is at least one selected from polyurethane, polyester, polyamide, polyurea and polycarbonate. The polymers may be used alone or in combination of two or more.

Examples of the polymer include conventionally known polymers, which may be any of a water-insoluble polymer, a water-dispersed (self-emulsifying) polymer, and a water-soluble polymer. In terms of easiness, water-insoluble polymers and water-dispersed (self-emulsifying) polymers are preferred,
From the viewpoint of dispersion stability, an aqueous dispersion (self-emulsifying) polymer is particularly preferred.

The water-dispersible (self-emulsifying) polymer includes, for example, an ion dissociation polymer, a nonionic dispersible group-containing polymer, or a mixed polymer thereof.
And the like.

Examples of the ion dissociation type polymer include a polymer having a cationic dissociation group such as a tertiary amino group and a polymer having an anion dissociation group such as carboxylic acid and sulfonic acid. Examples of the nonionic dispersible group-containing polymer include a polymer containing a nonionic dispersible group such as a polyethyleneoxy group.

Among these, from the viewpoint of the dispersion stability of the colored fine particles, an ion-dissociative polymer containing an anionic dissociable group, a nonionic dispersible group-containing polymer, and a mixed polymer are preferred.

-Polyurethane-The polyurethane is generally synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials.

Examples of the diol compound include non-dissociable diols and dissociable diols.

As the non-dissociable diol, for example,
Ethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,2-butanediol, 1,
3-butanediol, 2,3-butanediol, 2,2-
Dimethyl-1,3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2- Ethyl-2-methyl-1,3-propanediol, 1,2-hexanediol,
1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-
Pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5 -Dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4 -Cyclohexanedimethanol,
Hydroquinone, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 2
00, 300, 400, 600, 1000, 1500,
4000), polypropylene glycol (average molecular weight =
200, 400, 1000), polyester polyols, 4,4'-dihydroxydiphenyl-2,2-propane, 4,4'-dihydroxyphenylsulfone, and the like.

The dissociable diol has a dissociable group,
It is used for the purpose of imparting productivity and dispersing stability of colored fine particles. Preferable examples of the dissociable group in the dissociable diol include a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, —OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, Na, K and the like). Anionic groups such as alkali metal salts, ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine and trimethylamine) or cationic groups such as primary, secondary, tertiary amine and quaternary ammonium salts Is mentioned. Among these, an anionic group is preferable, and a carboxyl group is particularly preferable.

The diol having an anionic group includes, for example, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid,
5,6-trimethoxy-3,4-dihydroxyhexanoic acid, 2,3-dihydroxy-4,5-dimethoxypentanoic acid, 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid and salts thereof, and the like. No.

As the diisocyanate, for example,
Methylene diisocyanate, ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m -Phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, dicyclohexyl methane diisocyanate, methylene bis (4-cyclohexyl isocyanate ), And the like.

The diol compound and the diisocyanate compound may be used each alone or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer, solubility, phase with the dye, etc.). (Solubility, stability of dispersion), two or more of them may be used in combination at any ratio.

--Polyester-- The polyester is generally synthesized by dehydration condensation of a dicarboxylic acid compound and a diol compound.

Examples of the dicarboxylic acid compound include dicarboxylic acids having no dissociable group other than carboxylic acids and derivatives thereof, and dicarboxylic acids having dissociable groups other than carboxylic acid.

Examples of the dicarboxylic acid having no dissociable group other than the carboxylic acids and derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α- Dimethyl succinic acid, acetone dicarboxylic acid, sebacic acid, 1,9-nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butylterephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Ω-poly (ethylene oxide) dicarboxylic acid, p-xylylene dicarboxylic acid, and the like. These compounds may be used in the form of an alkyl ester of a dicarboxylic acid (for example, dimethyl ester) or an acid chloride of a dicarboxylic acid when conducting a polycondensation reaction with the diol compound, or may be used in the form of maleic anhydride or maleic anhydride. It may be used in the form of an acid anhydride such as succinic acid and phthalic anhydride.

Examples of the dicarboxylic acid having a dissociable group other than the carboxylic acid include those having an anionic group and / or a cationic group as the dissociable group. Examples of the anionic group include a sulfonic acid group, a sulfuric acid monoester group, —OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, alkali metal salts such as Na and K, ammonia, dimethylamine, and the like). , Ethanolamine, diethanolamine, triethanolamine, and ammonium salts such as trimethylamine). Examples of the cationic group include primary, secondary, and tertiary amines, and quaternary ammonium salts. Among these,
Anionic groups are preferred, and sulfonic acid groups are particularly preferred.

Preferred examples of the dicarboxylic acid and diol compound having a sulfonic acid group include sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, and 2-sulfoterephthalic acid). ), Sulfosuccinic acid, sulfonaphthalenedicarboxylic acids (4-sulfo-1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5-naphthalenedicarboxylic acid, etc.), 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfone Acids and salts thereof.

Examples of the diol compound include the same diol compounds as those described above as the raw material of the polyurethane.

Representative synthetic methods of the polyester include a method by a condensation reaction of the diol compound with the dicarboxylic acid or a derivative thereof, and a hydroxycarboxylic acid such as a hydroxycarboxylic acid (eg, 12-hydroxystearic acid). , Ring-opening polymerization of cyclic ethers and lactones (Lecture on Polymerization Reaction 6 Ring-Opening Polymerization (I) by Takeo Saegusa (Kagaku Doujin, 1971))
And the like. The dicarboxylic acid compound and the diol compound may be used each alone or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer, solubility, compatibility with the dye, dispersion of the dye, and the like). Two or more may be used in combination at any ratio depending on the stability of the product).

-Polyamide-The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, ring-opening polymerization of monomers such as lactams, and the like.

Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, Piperazine,
Examples thereof include 2,5-dimethylpiperazine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, and xylylenediamine.

Examples of the dicarboxylic acid compound include the same compounds as the dicarboxylic acid compounds described as the raw materials for the polyester.

Examples of the aminocarboxylic acid compound include glycine, alanine, phenylalanine, ω-aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid.

The monomers used for the ring-opening polymerization include, for example, ε-caprolactam, azetidinone, pyrrolidone and the like.

The diamine compound, the dicarboxylic acid compound, the aminocarboxylic acid compound and the monomer are
Each of these may be used alone, or depending on various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer, solubility, compatibility with the dye, and stability of the dispersion).
Two or more kinds may be used in combination at an arbitrary ratio.

-Polyurea- The polyurea can be generally obtained by a polyaddition reaction between a diamine compound and a diisocyanate compound, or a deammonification reaction between a diamine compound and urea. Examples of the diamine compound include those similar to the diamine compounds described as the raw materials for the polyamide. Examples of the diisocyanate compound include the same as the diisocyanate compound described as the raw material of the polyurethane.

-Polycarbonate- The polycarbonate can be generally obtained by reacting a diol compound with a phosgene or carbonate derivative (eg, an aromatic ester such as diphenyl carbonate).

Examples of the diol compound include the same diol compounds as those described above as the raw material of the polyurethane.

The diol compound and the phosgene or carbonate derivative may be used alone or for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer, solubility, (Compatibility, stability of dispersion), two or more kinds may be used in combination at any ratio.

In the synthesis of the above-mentioned polymer, “Polymer Experiment
(Vol. 5) Polycondensation and polyaddition (edited by Shu Kamihara, published by Kyoritsu Shuppan Co., Ltd. (1980)), "Polyester Resin Handbook (Eiichiro Takiyama, published by Nikkan Kogyo Shimbun (1988))", "Polyurethane resin" Handbook (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)), "Experimental Methods for Polymer Synthesis (Takashi Otsu and Masayoshi Kinoshita, published by Kagaku Doujinshi (1972))", Tokubo 33-1
141, 37-7641, 39-5989,
Nos. 40-27349, 42-5118, 42-
No. 24194, No. 45-10957, No. 48-254
No. 35, No. 49-36942, No. 52-81344
JP-A-56-88454, JP-A-6-34083
A known method described in No. 5, etc. can be employed.

Among the above polymers, a polymer having the dissociable group is preferable, a polymer having at least one of a carboxyl group and a sulfonic acid group as the dissociable group is more preferable, and a polymer having a carboxyl group is particularly preferable.

The dissociable group in the polymer having a dissociative group may be introduced as a substituent from the polymer main chain, like a dissociable diol at the time of the synthesis of the polyurethane, or a dicarboxylic acid may be added to the terminal of the polyester. The compound may remain as an unreacted terminal of the compound, or may react with an acid anhydride (for example, maleic anhydride) with respect to a reactive group such as an —OH group or an amino group remaining at the terminal after polymerization of the polymer. Acid) may be introduced by reacting a compound capable of introducing a dissociating group by a reaction such as
There is no limitation on the mode of its introduction.

The content of the dissociative group in the polymer having a dissociative group is preferably from 0.1 to 3 mmol / g, more preferably from 0.2 to 2 mmol / g. When the content of the dissociable group is less than 0.1 mmol / g,
The self-emulsifiability of the polymer decreases, and 3 mmol /
If the amount exceeds g, the water solubility tends to be high and the dye tends to be unsuitable for dispersion.

Among the above-mentioned polymers, polyurethane and polyester are particularly preferable in consideration of the easiness of introducing a dissociating group from the viewpoint of imparting compatibility with the oil-soluble dye and giving excellent dispersion stability.

Hereinafter, specific examples of the polymer (P-1 to P-1)
38) in the form of a raw material monomer (however, P-23
And P-34 and thereafter are exemplified in the form of a polymer). In addition,
The present invention is not limited to these specific examples. All acidic groups in each polymer are described in a non-dissociable form, and those formed by a condensation reaction such as polyester and polyamide are all composed of dicarboxylic acids, diols, and irrespective of raw materials. Diamine,
It was represented by hydroxycarboxylic acid, aminocarboxylic acid and the like. The ratio in parentheses means the molar percentage ratio of each component.

P-1 Toluene diisocyanate / ethylene glycol / 1,4-butanediol (50/15/3
5) P-2 4,4'-diphenylmethane diisocyanate /
1,3-propanediol / polypropylene glycol (Mw = 1000) (50/45/5) P-3 toluene diisocyanate / hexamethylene diisocyanate / ethylene glycol / polyethylene glycol (Mw = 600) / 1,4-butanediol (40 / 10
/ 20/10/20) P-4 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / diethylene glycol / 1,
6-hexanediol (25/25/35/15)

P-5 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20 /
20/10) P-6 4,4'-diphenylmethane diisocyanate /
Hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/20/10) P-7 1,5-naphthylene diisocyanate / butanediol / 4,4 ' -Dihydroxydiphenyl-2,
2'-propane / polypropylene glycol (Mw = 400) /
2,2-bis (hydroxymethyl) propionic acid (50
/ 20/5/10/15) P-8 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid / polybutylene oxide (Mw = 500) (35
/ 15/25/25) P-9 Isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2-bis (hydroxymethyl) propionic acid (50/20/20/10) P-10 Toluene diisocyanate / 2,2-bis (Hydroxymethyl) butanoic acid / polyethylene glycol (Mw = 1000) / cyclohexanedimethanol (50/1
0/10/30) P-11 diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol /
Butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10/10
/ 33/7) P-12 diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) butanoic acid /
2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10/20/15/10/5)

P-13 Terephthalic acid / isophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/10) P-14 Terephthalic acid / isophthalic acid / 4,4′- Dihydroxydiphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20/20 /
15/15) P-15 terephthalic acid / isophthalic acid / cyclohexanedimethanol / neopentyl glycol / diethylene glycol (20/30/25/15/10) P-16 terephthalic acid / isophthalic acid / 4,4'-benzenedimethanol / Diethylene glycol / neopentyl glycol (25/25/25/15/10)

P-17 Terephthalic acid / isophthalic acid / 5
-Sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2/25/25) P-18 terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (22/22/6/25/15 /
10) P-19 isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / ethylene glycol (40/1
0/40/10) P-20 cyclohexanedicarboxylic acid / isophthalic acid /
2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid / cyclohexanedimethanol / ethylene glycol (30/20/5/25/20)

P-21 11-aminoundecanoic acid (1
00) P-22 12-Aminododecanoic acid (100) P-23 Reaction product of poly (12-aminododecanoic acid) and maleic anhydride P-24 11-Aminoundecanoic acid / 7-aminoheptanoic acid (50/50) ) P-25 hexamethylenediamine / adipic acid (50 /
50) P-26 tetramethylenediamine / adipic acid (50 /
50) P-27 hexamethylenediamine / sebacic acid (50 /
50) P-28 N, N-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20/30)

P-29 Toluene diisocyanate /
4,4'-diphenylmethane diisocyanate / hexamethylenediamine (30/20/50) P-30 nonamethylenediamine / urea P-31 hexamethylenediamine / nonamethylenediamine / urea (25/25/50) P-32 toluenediisocyanate / Hexamethylenediamine / 2,2-bis (hydroxymethyl) propionic acid (50/40/10) P-33 11-aminoundecanoic acid / hexamethylenediamine / urea (33/33/33)

[0066]

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The molecular weight (Mw) of the polymer is usually from 1,000 to 200,000, and from 2,000 to 200,000.
50,000 is preferred. When the molecular weight is less than 1,000, it tends to be difficult to obtain a stable colored fine particle dispersion, and when the molecular weight exceeds 200,000, the solubility in an organic solvent deteriorates, There is a tendency that the viscosity increases and dispersion becomes difficult.

-Production of Dispersion of Colored Fine Particles- The dispersion of colored fine particles is produced by dispersing the oil-soluble dye and the polymer in an aqueous medium (a liquid containing at least water) in the form of colored fine particles. Is done. Specifically, for example, a method in which a latex of the polymer is prepared in advance and the oil-soluble dye is impregnated in the latex, or a coemulsification dispersion method is used. Among these, the co-emulsification dispersion method is preferable. As the co-emulsification dispersion method, water is added to an organic solvent containing the polymer and the oil-soluble dye, and the organic solvent is added to water. And a method in which the organic solvent is emulsified into fine particles by any one of the above methods.

The latex means a polymer in which a water-insoluble polymer is dispersed as fine particles in an aqueous medium. As the state of dispersion, those in which the polymer is emulsified in the aqueous medium, micelle-dispersed, or those in which the polymer chains have a partially hydrophilic structure and molecular chains themselves are molecularly dispersed , And so on.

Here, a method of preparing the polymer latex in advance and impregnating the polymer latex with the oil-soluble dye will be described. A first example of this method is a first step of preparing a polymer latex, a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution and the polymer latex, And a third step of preparing a colored fine particle dispersion. A second example of this method is a first step of preparing a polymer latex, and preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, mixing the dye solution with a liquid containing at least water to form a dye. A second step of preparing a fine particle dispersion; and a third step of mixing the polymer latex and the dye fine particle dispersion to prepare a colored fine particle dispersion. As a third example of this method,
The method described in JP-A-55-139471 is exemplified.

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

The content of the polymer in the colored fine particle dispersion is preferably from 10 to 1,000 parts by mass, more preferably from 50 to 600 parts by mass, per 100 parts by mass of the oil-soluble dye. When the content of the polymer is less than 10 parts by mass, fine and stable dispersion tends to be difficult, and when the content is more than 1000 parts by mass, the proportion of the oil-soluble dye in the colored fine particle dispersion is reduced, and When the fine particle dispersion is used as an aqueous ink, there is a tendency that there is no room for formulation design.

--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 polymer. For example, ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone, methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, tert
-Alcohol solvents such as butanol, chlorine 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, diethyl ether, tetrahydrofuran and dioxane. And ether solvents, glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether. The organic solvents may be used alone or in combination of two or more. Further, depending on the solubility of the dye or polymer, it may be used by mixing with water.

The use amount of the organic solvent is not particularly limited as long as the effect in the present invention is not impaired.
The amount is preferably from 10 to 2,000 parts by mass, more preferably from 100 to 1,000 parts by mass, based on 100 parts by mass of the polymer. When the amount of the organic solvent is less than 10 parts by mass, the fine and stable dispersion of the colored fine particles tends to be difficult due to the increase in the viscosity of the organic phase, and when the amount exceeds 2,000 parts by mass, the organic solvent is removed. There is a tendency that the steps of desolvation and concentration for the purpose are indispensable and complicated, and 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 preferably at 40 to 100 ° C. under normal pressure or 10 to 50 ° C. under reduced pressure.

--Additive-- The colored fine particle dispersion may contain an additive 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 neutralizer, a dispersant, and a dispersion stabilizer.

In the case where the polymer has an unneutralized dissociable group, the neutralizing agent has a pH of the colored fine particle dispersion.
It can be suitably used in terms of control, self-emulsification control, and dispersion stability. The neutralizing agent may be added at the time of taking out as a polymer before preparing a dispersion, or may be added in any process of performing dispersion or after completion of dispersion.

Examples of the neutralizing agent include organic bases and inorganic alkalis for anionic dissociation groups, and organic acids and inorganic acids for cationic dissociation groups.

Among the neutralizing agents for the anionic dissociable groups, the organic bases include triethanolamine,
Diethanolamine, N-methyldiethanolamine,
Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.) and carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.). , Ammonia and the like.

Among the neutralizing agents for the cationic dissociable groups, the organic acids include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid, and the inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid. Acids and the like.

The neutralizing agent has a pH of 4.5 to 1 from the viewpoint of improving the dispersion stability of the colored fine particle dispersion.
It is preferable to add so as to be 0.0, and the pH is 6 to 1
More preferably, it is added to be 0.0.

The dispersant and the dispersion stabilizer may be added to any of a polymer latex, a polymer solution, a dye solution, a solution containing at least water, and the like. It is preferably added to any one of the polymer solution, the dye solution, and the solution containing water in the process before preparing the solution. Examples of the dispersant and dispersion stabilizer include various cationic, anionic and nonionic surfactants, water-soluble or water-dispersible low molecular compounds, oligomers and the like. The dispersant, the addition amount of the dispersion stabilizer, with respect to the total amount of the oil-soluble dye and the polymer,
It is 0 to 100% by mass, preferably 0 to 20% by mass.

—Colored Fine Particles— The content of the colored fine particles in the colored fine particle dispersion is preferably from 1 to 45% by mass, more preferably from 2 to 30% by mass. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration and the like.

The particle diameter of the colored fine particles is from 1 to 50.
0 nm is preferable, and 3 to 300 nm is more preferable.
~ 200 nm is particularly preferred. The particle size distribution is not particularly limited, and may have a broad particle size distribution or a monodispersed particle size distribution. The particle size and the particle size distribution can be adjusted by means such as centrifugation and filtration.

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

When the colored fine particle dispersion is used as an ink such as a water-based ink for writing, a water-based printing ink, an information recording ink, etc., the recording material of the ink may be plain paper, resin-coated paper, ink jet paper, film And electrophotographic paper, cloth, glass, metal, ceramics and the like.

(Inkjet Ink and Inkjet Recording Method) The inkjet ink of the present invention contains the colored fine particle dispersion of the present invention and further contains other components appropriately selected as necessary. .
In the ink-jet recording method of the present invention, recording is performed using the ink-jet ink of the present invention. There are no particular restrictions on the ink nozzles and the like used at that time, and they can be appropriately selected according to the purpose.

-Other components- The other components are contained within a range that does not impair the effects of the present invention. As the other components, for example, an anti-drying agent, a penetration enhancer, an ultraviolet absorber, an antioxidant,
Cultivated land additives such as viscosity adjusters, surface tension adjusters, dispersants, dispersion stabilizers, fungicides, rust inhibitors, pH adjusters, defoamers, chelating agents, and the like.

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

The drying inhibitor is preferably a water-soluble organic solvent having a lower vapor pressure than water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, and the like.
Polyhydric alcohols represented by dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-
Heterocycles such as 2-imidazolidinone and N-ethylmorpholine; 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 in combination of two or more.
The content of the drying inhibitor in the inkjet ink is preferably from 10 to 50% by mass.

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, sodium oleate and nonionic surfactants. And the like. 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. As the ultraviolet absorber,
For example, JP-A-58-185677 and JP-A-61-19
0537, JP-A-2-782, 5-19
Benzotriazole compounds described in JP-A Nos. 7075, 9-34057 and the like;
JP, JP-A-5-194483, U.S. Pat.
Benzophenone compounds described in JP-A-214463, JP-B-48-30492, JP-B-56-2114.
No. 1, cinnamic acid-based compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, The triazine compounds described in JP-T-8-501291 and the like, Research Disclosure No. Compounds described in No. 24239 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. As the antioxidant, for example, various organic and metal complex antifading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines,
Indans, chromans, alkoxyanilines, heterocycles and the like can be mentioned. Examples of the metal complex anti-fading agent include a nickel complex and a zinc complex. No. 17643, Sections VII I through J; 15162;
No. 18716, left column, page 650; 36544 of 52
No. 7, ibid. No. 307105, page 872; Fifteen
162, the compound described in the patent cited in
The compounds included in the general formulas and examples of the typical compounds described on pages 127 to 137 of JP-A-2-215272 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,
Cationic or anionic surfactants are included.

The surface tension of the ink-jet ink of the present invention is preferably 25 to 70 mPa · s,
60 mPa · s 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 or a chelating agent represented by EDTA can be used if necessary.

The ink-jet ink of the present invention can be suitably used for printing on a known recording material. The recording material is not particularly limited, but is preferably ink jet paper. Examples of the inkjet paper include, for example, JP-A-8-169172 and 8-2769.
No. 3, No. 2-276670, No. 7-2767
No. 89, 9-323475, JP-A-62-2
No. 2,388,783, JP-A Nos. 10-153989, 10-217473, 10-23599
No. 5, No. 10-337947, No. 10-21
No. 7597, No. 10-337947 and the like.

As the recording material, the following recording paper and recording film are preferably used in addition to the ink jet paper. 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. In addition,
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
Examples thereof include mechanical pulp such as MP, CMP, and CGP, and waste paper pulp such as DIP. In the pulp,
If necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers and the like may be added and mixed. The support can be manufactured by using various apparatuses such as a fourdrinier paper machine and a round paper machine. The support may further be a synthetic paper, a plastic film sheet or the like.

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

The support may be provided with the ink receiving layer and, if necessary, a back coat layer directly.
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 and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferable, and a white pigment (eg, oxidized) is contained in the polyolefin. It is more preferable that a tinting dye (eg, cobalt blue, ultramarine, neodymium oxide) is added.

The ink receiving layer contains a pigment, an aqueous binder, a mordant, a waterproofing agent, a light fastness improving agent, a surfactant and other additives.

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,
Inorganic white pigments such as aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate; and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. Can be Among these, porous inorganic pigments are preferred, and synthetic amorphous silica having a large pore area is particularly preferred. As the synthetic amorphous silica, either silicic anhydride obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but hydrous silicic acid is particularly preferable.

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. Polymers, water-dispersible polymers such as styrene butadiene latex and acrylic emulsions, and the like. These may be used alone or in combination of two or more. Among these, adhesion to the pigment,
In view of the peel resistance of the ink receiving layer, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferred.

The mordant is preferably immobilized, and for that purpose, a polymer mordant is preferred. Examples of the polymer mordant include, for example, JP-A-48-283.
No. 25, No. 54-74430, No. 54-124726
No. 55-22766, No. 55-142339,
No. 60-23850, No. 60-23851, No. 60
-23852, 60-23853, 60-57
No. 836, No. 60-60643, No. 60-11883
No. 4, No. 60-122940, No. 60-122941
No. 60-122942, No. 60-235134
JP-A-1-161236, U.S. Pat.
No. 84430, No. 2548564, No. 3148061
Nos. 3309690, 4115124, 41
24386, 4193800, 4273753
Nos. 4,282,305 and 4,450,224. Among these, Japanese Patent Application Laid-Open No. 1-1612
The polymer mordants described on pages 212 to 215 of JP-A No. 36 are preferred. Use of the polymer mordant described in the publication is preferable in that an image with excellent image quality is obtained and the light fastness of the image is improved.

The water-proofing agent is used for the purpose of making an image water-resistant. As the water-proofing agent, a cationic resin is preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferred. The content of the cationic resin is preferably from 1 to 15% by mass, and particularly preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzophenone and benzotriazole ultraviolet absorbers. Among 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. Note that an organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil) and a solid fluorine compound resin (eg, ethylene tetrafluoride resin). (Columns 8 to 17), JP-A-61-2
Nos. 0994 and 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 brightening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to each layer of the recording paper and the recording film.
The polymer latex has dimensional stability, curl prevention,
It is used for the purpose of improving film properties such as preventing adhesion and cracking of the film. As the polymer latex, JP-A Nos. 62-245258 and 62-131648,
JP-A-62-10066 can be mentioned. When a polymer latex having a low glass transition temperature (40 ° C. or less) is added to a layer containing a 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 layer, curling can be prevented.

The ink-jet ink of the present invention can be applied to any ink-jet recording system, for example, a charge control system for discharging ink by utilizing electrostatic attraction,
Drop-on-demand method (pressure pulse method) using the oscillating pressure of a piezo element, acoustic ink jet method in which an electric signal is converted into an acoustic beam, and the ink is radiated to the ink to discharge the ink using a radiation pressure, and heating the ink Thermal inkjet that generates bubbles and uses the generated pressure
(Bubble Jet (registered trademark)) system or the like.

Incidentally, the ink jet recording method includes the following:
Examples include a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different densities, and a method of using colorless and transparent ink.

[0120]

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.

<Synthesis Example 1 (Synthesis of Polymer P-5)
> In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 39.1 g of 4,4'-diphenylmethane diisocyanate, 6.6 g of hexamethylene diisocyanate, 15.2 g of tetraethylene glycol, 4.9 g of ethylene glycol, 5.3 g of 2,2-bis (hydroxymethyl) propionic acid and 150 ml of N, N-dimethylacetamide were added and dissolved at room temperature with stirring. 0.2 g of di-n-butyltin dilaurate was added, the mixture was heated to 90 ° C., and heated and stirred for 6 hours.
After diluting with 50 ml of dimethylacetamide and further cooling to room temperature, a solution prepared by dissolving 2.2 g of sodium methoxide in 100 ml of methanol was added. The obtained polymer was precipitated by pouring into 5 liters of ethyl acetate / hexane (80/20 by volume), and dried by filtration to obtain 69.5 g of the polymer P-5. The obtained polymer P
-5 has a dissociable group content of 0.58 mmol / g
And its weight average molecular weight was 9,800.

<Synthesis Example 2 (Synthesis of Polymer P-17)> 46.5 g of dimethyl terephthalate, 46.5 g of dimethyl isophthalate, and sodium 5-sulfo were placed in a 300 ml three-necked flask equipped with a stirrer and a distillation tube. 6.0 g of dimethyl isophthalate, ethylene glycol 3
0 g, neopentyl glycol 26.0 g, calcium acetate 0.05 g as a condensation catalyst, antimony oxide (II
I) 30 g at 150 ° C. while distilling off methanol and ethylene glycol produced in a nitrogen stream by adding 0.05 g.
Then, the mixture was heated and stirred at 190 ° C. for 1 hour. Next, the temperature was lowered to about 150 ° C., and the pressure of the reaction system was gradually increased with a pump under stirring, and the temperature was raised while distilling off ethylene glycol in the range of 10 to 40 Pa to obtain a temperature of 250 ° C.
The reaction was further performed at 2.5 ° C. for 2.5 hours. The reaction product was taken out as it was and cooled to obtain 120 g of the polymer P-17. The obtained polymer P-17 had a dissociable group content of 0.37 mmol / g and a weight average molecular weight of 5,600.

<Production Example 1 (Colored fine particle dispersion (A-1))
Preparation >> A mixture of 10 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol, 4.8 g of the polymer (P-5: sodium salt), and 1.2 g of the oil-soluble dye (I-8) was heated to 75 ° C. Then, with stirring, water 6
0 parts were added. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 20%. The particle diameter of the colored fine particles in the colored fine particle dispersion is 28 nm in volume average diameter.
Met. Hereinafter, this is abbreviated as colored fine particle dispersion (A-1).

<Production Example 2 (Colored fine particle dispersion (A-2))
Preparation>) 10 parts of methyl ethyl ketone, 5 parts of isopropyl alcohol, the polymer (P-5: sodium salt)
After heating a mixed solution of 3 g and 1.2 g of the oil-soluble dye (I-9) to 60 ° C., 1 part of a 25% aqueous solution of a surfactant (manufactured by Kao Corporation; Emal 20C), 60 ° C. Water 5
0 parts were added, and 5000 minutes for 1 minute using a homogenizer.
The mixture was stirred at a high speed for 3 minutes. The obtained liquid was concentrated at 40 ° C. under reduced pressure to prepare a colored fine particle dispersion having a solid content of 20%. The particle diameter of the colored fine particles in the colored fine particle dispersion was 58 nm in volume average diameter. Hereinafter, this is referred to as colored fine particle dispersion (A-2).

<Production Example 3 (Colored fine particle dispersion (A-4))
Preparation> 5 parts of tetrahydrofuran, 15 parts of isopropyl alcohol, 4.8 g of the polymer (P-17: sodium salt), 1.2 g of the oil-soluble dye (I-16)
After the mixture was heated to 65 ° C., 60 parts of water was added dropwise with stirring over 30 minutes. This solution is heated at 40 ° C under reduced pressure.
To prepare a colored fine particle dispersion having a solid content of 20%. 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 (A-4).

<Production Examples 4 to 7 (Colored fine particle dispersion (A-
Preparation of 3 and 5 to 7)> In the same manner as in Production Examples 1 to 3, the types of the polymer and the oil-soluble dye were changed as shown in Table 1, and the colored fine particle dispersions (A-3) and ( A-
5) to (A-7) were prepared.

<Production Example 8 (Preparation of comparative colored fine particle dispersion (B-1))> In Production Example 3, the oil-soluble dye (I-16) was replaced with the following compound (H-1). A colored fine particle dispersion having a solid content of 20% was prepared in the same manner as in Production Example 3 except for the above. The particle diameter of the colored fine particle dispersion was 42 nm in volume average diameter. Hereinafter, this is referred to as a colored fine particle dispersion (B-1).

[0128]

Embedded image

Example 1 10 parts of diethylene glycol, 8 parts of glycerin, 8 parts of triethylene glycol monobutyl ether, and 25% of a surfactant were added to 62 parts of the colored fine particle dispersion (A-1) prepared in Production Example 1 above. An aqueous inkjet ink was prepared by mixing 4 parts of an aqueous solution (manufactured by Kao Corporation; Emal 20C) and 8 parts of ion-exchanged water and filtering through a 0.2 μm filter.

(Examples 2 to 7)
Instead of the colored fine particle dispersion (A-1), the colored fine particle dispersions (A-2) to (A-7) were added so that the amount of the oil-soluble dye became constant, and 10 parts of diethylene glycol, 8 parts of glycerin, 8 parts of triethylene glycol monobutyl ether and 4 parts of a 25% aqueous solution of a surfactant (manufactured by Kao Corporation; Emal 20C) (when the surfactant is used in advance when dispersing the dye, the total amount of the surfactant is the same) The amount of addition was adjusted so that the total amount became 10%).
0 parts were added. Further, the mixture was filtered through a 0.2 μm filter to prepare an aqueous inkjet ink.

Comparative Example 1 The procedure of Example 1 was repeated, except that the colored fine particle dispersion (A-1) was replaced with the colored fine particle dispersion (B-1) prepared in Production Example 8. An ink-jet ink was prepared as in Example 1.

Comparative Example 2 10 parts of diethylene glycol, 8 parts of glycerin, 10 parts of tetraethylene glycol monobutyl ether, 1 part of diethanolamine, and 67 parts of ion-exchanged water were mixed with 4 parts of the following comparative dye (H-2). The mixture was filtered through a 0.2 μm filter to prepare an inkjet ink.

[0133]

Embedded image

(Image Recording and Evaluation) The following evaluations were performed on the ink jet inks of the above Examples and Comparative Examples. The results are shown in Table 1. In Table 1, "color tone", "paper dependence", "water resistance" and "light fastness" indicate that each ink-jet ink was subjected to photo gloss by an ink-jet printer (manufactured by EPSON Corporation; PM-700C). This was evaluated after an image was recorded on paper (manufactured by Fuji Photo Film Co., Ltd .; inkjet paper, photo grade).

<Color Tone> The recorded image was visually checked for A
(Good) and B (Bad) were evaluated in two stages.

<Paper Dependency> The color tone between the image formed on the photo glossy paper and the image separately formed on the plain paper for PPC is compared. The case where the difference was large was evaluated as B (poor) and evaluated in two steps.

<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, allowed to dry 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.

<Light fastness> Xenon light (85,000 lux) was irradiated on the photo glossy paper on which the image was formed using a weather meter (Atlas CI65) for 3 days.
Image densities before and after xenon irradiation are measured with a reflection densitometer (X-Rite3).
10TR) and evaluated as the residual dye ratio. The reflection density is 1, 3 and 1.5.
Measured in points. In any of the concentrations, the case where the residual ratio of the dye was 70% or more was A, and 1 or 2 points were less than 70% as B, and the case where all the concentrations were less than 70% was C.

[0139]

[Table 1]

As is clear from Table 1, the ink-jet ink of the present invention was excellent in color developability and color tone, independent of paper, and excellent in water fastness and light fastness.

[0141]

According to the present invention, the above-mentioned conventional problems can be solved, the dispersion stability of the colored fine particles is excellent, there is no paper dependency, and the coloring property when printing on arbitrarily selected paper is improved. Excellent color tone, and excellent water resistance and light resistance, suitable for aqueous fine ink for writing, aqueous printing ink, information recording ink, etc., and suitable for thermal, piezoelectric, electric field or acoustic ink jet system. When printing using a nozzle or the like, there is no clogging at the nozzle tip, there is no dependence on paper, excellent color development and color tone when printing on arbitrarily selected paper, and water resistance And an ink jet ink and an ink jet recording method which are excellent in light resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/00 B41J 3/04 101Y (72) Inventor Takahiro Ishizuka 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. In-house (72) Inventor Kazue Sano 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd.F-term (reference) 2C056 EA13 FA03 FA04 FA07 FB01 FC02 FC06 2H086 BA53 BA56 BA59 BA60 4J039 AE03 AE04 AE06 AE08 BC05 BC12 BC20 BC29 BC33 BC40 BC50 BC51 BC53 BC55 BC65 BC66 BC72 BC73 BC74 BC77 BE01 BE02 BE07 BE12 CA06 EA35 EA38 EA41 EA44 GA24

Claims (7)

[Claims] Claims: 1. It comprises colored fine particles containing at least one polymer selected from polyurethane, polyester, polyamide, polyurea and polycarbonate, and an oil-soluble dye represented by the following general formula (I). Colored fine particle dispersion to be used. Embedded image In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group. , Hydroxy, nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide Group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio Group, sulfinyl group, phosphoryl group, A carboxyl group or a sulfo group. R ³ and R ⁴ may combine to form an aromatic ring or a hetero ring. R ⁵ represents an unsaturated heterocyclic group. M represents a hydrogen atom, a dissociated inorganic base, a primary amine, a secondary amine or a tertiary amine. 2. The colored fine particle dispersion according to claim 1, wherein the oil-soluble dye is dispersed in a polymer. 3. A polymer containing 0.01 to 3.0 mmol /
The colored fine particle dispersion according to claim 1, comprising g of a dissociable group. 4. The colored fine particle dispersion according to claim 3, wherein the dissociable group is at least one of a carboxyl group and a sulfonic acid group. 5. The method according to claim 1, wherein water is added to an organic solvent containing a polymer and an oil-soluble dye to emulsify, and the organic solvent is added to water to emulsify the water. 5. The colored fine particle dispersion according to any one of 4. 6. An ink-jet 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-jet ink according to claim 6.