JP2002265828A - Inkjet recording ink and method for forming inkjet image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recoding ink suitable for a thermal, piezoelectric, electric field or acoustic inkjet system, having excellent handleability, smell and safety, excellent dispersion and storage stabilities, little in the clogging of a nozzle chip, free from paper dependency, excellent in color developing properties, especially color tone (hue) when printed on an arbitrarily selected paper, excellent in the permeability of the ink into a photographic image quality paper, excellent in water resistance, especially light resistance, and abrasion resistance after printing, and capable of recording an image in high density and high quality. SOLUTION: The inkjet recording ink comprises at least water, a water-soluble organic solvent and a dispersion of colored fine particles. The dispersion of colored fine particles contains a water-insoluble coloring agent and a UV- absorbing polymer molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink for ink jet recording and an ink jet recording method using the ink for ink jet recording.

[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, aqueous inks using water-soluble dyes have the advantages of high transparency and high color density,
When printed on so-called plain paper, the water resistance is poor, and there is a problem in that bleeding occurs and the print quality is reduced, and the light resistance is poor. Therefore, attempts have been made to use water-insoluble colorants such as pigments and disperse dyes for the purpose of solving the above problems,
When the particle size of the colorant is reduced to improve transparency and print quality, light resistance deteriorates, and the use of porous inorganic materials on the surface has been used due to the recent increase in image quality of inkjet technology. When a recording paper provided with an ink receiving layer containing fine particles (hereinafter sometimes referred to as "photographic quality paper") is used, there is a problem that the abrasion resistance is not sufficient. In the case of conventionally well-known dyes and pigments to which a color index (C.I.) number is assigned, an appropriate absorption wavelength effective for improving color reproducibility on an image receiving material is used. It is poor in colorants having a half-value width, in particular, has a good magenta color tone or cyan color tone, and it is difficult to achieve both color tone and fastness.

There has been proposed a method using an ultraviolet absorber for the purpose of improving light fastness. For example, JP-A-6-733
No. 67, 6-73369, JP-A-2000-1097
Each publication of No. 397 discloses a high molecular weight substance containing an ultraviolet absorbing group and a hydrophilic group which are dissolved or dispersed in water, but the ejection stability in an aqueous medium recording liquid for ink jet recording as in the present invention. There is no disclosure of any improvement in storage stability, print density, and the like. Also, Japanese Patent Application Laid-Open
No. 0-160072 discloses an ink using a water-soluble resin containing an ultraviolet absorbing group. However, since the viscosity of the ink tends to increase, the amount of the resin added is limited, and the light resistance is not sufficient. The color tone is not sufficiently satisfactory. Japanese Patent Application Laid-Open No. H11-148034 discloses a recording liquid using a high molecular weight substance having an ultraviolet absorbing group and a hydrophilic group, but the rubbing resistance, ejection stability, and color tone are not sufficient. On the other hand, in order to improve the color tone, Japanese Patent Application No. 11-366.
No. 571 describes an ink jet recording ink containing a dye capable of forming a J-aggregate. However, according to the study of the present inventors, when ink-jet recording is performed with an ink containing a J-aggregate of such a dye, although a vivid color tone is obtained, depending on an image receiving paper, short-waves which are considered to be due to aggregation of particles are considered. It has been found that components may appear or a metallic gloss, that is, a phenomenon called bronze, due to specular reflection of the pigment particle surface may be strongly observed.

[0005] As described above, there is no clogging at the nozzle tip, excellent in ejection stability, excellent in color development and color tone (hue) without dependence on paper, and water resistance after printing even when the photographic quality paper is used. At present, there is no ink jet recording ink which is excellent in light resistance, scratch resistance, and enables high-density, high-quality recording.

[0006]

SUMMARY OF THE INVENTION The present invention provides a thermal,
Suitable for piezoelectric, electric field or acoustic ink jet system, it has handleability, odor and safety, excellent dispersion stability and storage stability of dispersion, less occurrence of clogging at the nozzle tip, and paper dependence Excellent in color development when printing on arbitrarily selected paper, especially excellent in color tone (hue), excellent in ink penetration into photographic quality paper, excellent in water resistance after recording, especially excellent in light resistance and scratch resistance, An object of the present invention is to provide an inkjet recording ink capable of recording with high density and high image quality. In addition, the present invention has handleability, odor, and safety, eliminates ejection failure due to clogging at the nozzle tip, and has no color dependency when printing on arbitrarily selected paper, particularly color tone ( Hue), excellent ink penetration into photographic quality paper, excellent water resistance after recording, particularly excellent light resistance and abrasion resistance, and an ink jet recording method capable of recording with high density and high image quality. Aim.

[0007]

Means for solving the above problems are as follows. That is, <1> an inkjet recording ink containing at least water, a water-soluble organic solvent, and a colored fine particle dispersion, wherein the colored fine particle dispersion contains a water-insoluble colorant and an ultraviolet absorbing polymer. Ink for inkjet recording. <2> adding the water to an organic solvent phase in which the colored fine particle dispersion contains a water-insoluble colorant and an ultraviolet absorbing polymer, or adding the organic solvent phase to water;
The inkjet recording ink according to <1>, which is produced by any one of the above. <3> adding an acid to an aqueous dispersion in which the colored fine particle dispersion contains a water-insoluble colorant and a neutralized product of a UV-absorbing polymer containing a carboxylic acid group or a sulfonic acid group, or , The aqueous dispersion of an acid or an aqueous solution of an acid.
> The ink-jet recording ink described in the above. <4> The maximum absorbance of the ultraviolet absorbing polymer in the range of 300 to 400 nm is 0.1 to 2 when a polymer solution having a concentration of 10 mg / l is measured at an optical path length of 1 cm. The ink for inkjet recording according to any one of 1> to <3>. <5> The inkjet recording ink according to any one of <1> to <4>, wherein the water-insoluble colorant is a dye that forms a J-aggregate. <6> An image is formed using an ink jet recording ink according to any one of <1> to <5>, using an image receiving paper having an image receiving layer containing white inorganic pigment particles on a support. Inkjet image forming method.

[0008] In the present invention, the following means are preferably mentioned. <7> The ultraviolet absorbing polymer contains an ionic group,
0.2 to 4.0 mmol / g.
The ink for inkjet recording according to any one of 1> to <6>. <8> The glass transition temperature of the ultraviolet absorbing polymer is-
<1> characterized by being at least 50 ° C and not more than 150 ° C.
The ink for inkjet recording according to any one of <7> to <7>. <9> The colored fine particle dispersion has an average particle size of 2 nm to 2
The inkjet recording ink according to any one of <1> to <8>, which has a thickness of 00 nm.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an ink-jet ink and an ink-jet recording method of the present invention will be described.
The inkjet ink of the present invention contains a water-insoluble colorant, an ultraviolet absorbing polymer, water, and a water-soluble organic solvent. Hereinafter, the constituent components will be specifically described. Hereinafter, the constituent components will be specifically described.

-Water-insoluble colorant- As used herein, the term "water-insoluble colorant" means a colorant which is almost insoluble or hardly soluble in water, and examples thereof include oil-soluble dyes and disperse dyes. And the like, a dye forming a J-aggregate, a disperse dye, a pigment, a dye forming a J-aggregate is preferable, and a disperse dye and a dye forming a J-aggregate are more preferable. Are particularly preferred.

The oil-soluble dye is not limited to the following, but particularly preferred specific examples are CI Solvent Black Series; CI Solvent Yellow Series;
CI Solvent Red Series; CI Solvent
Bio Red Series; CI Solvent Blue Series; CI Solvent Green Series; and CI Solvent Orange Series.

The disperse dye is not limited to the following, but particularly preferred specific examples are CI Disperse Yellow Series; CI Disperse Orange Series;
CI Dispers Bio Series; CI Dispers Blue Series; and CI Dispers Green Series.

The type of the pigment is not particularly limited, and all conventionally known organic and inorganic pigments can be used. For example, azo lake, azo pigment, phthalocyanine pigment, perylene and perinone pigment, anthraquinone pigment,
Polycyclic pigments such as quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments, and dye lakes such as basic dye lakes and acid dye lakes; nitro pigments; nitroso pigments; aniline black; Organic pigments such as light fluorescent pigments are exemplified. Among the above pigments, it is particularly preferable to use azo pigments, phthalocyanine pigments, anthraquinone pigments, and carbon black pigments.

The dye forming the J-aggregate refers to a dye having a λmax of 20 nm with respect to λmax in a molecular dispersion state in a solution (solvent is, for example, dimethylformamide or dimethylsulfoxide) by forming the J-aggregate. These are dyes that can shift to the long-wave side. For details of J-aggregates of dyes, see “Theory of Photographic Process” (TH James)
Authors), pp. 216-222. Among the dyes forming the J-aggregate, it is preferable to use a dye whose λmax is different from the molecular dispersion state by 20 nm or more and 150 nm or less between the aggregate and the aggregate because the hue and color reproducibility of the formed image become better. Preferably, the dyes differ in λmax from 30 nm to 120 nm). As the dye, any dye that forms a J-aggregate may be used, and a dye having desired absorption characteristics can be appropriately selected. For example, Dye Handbook (edited by The Society of Synthetic Organic Chemistry, Maruzen, published in 1978), Colorant 61
[4], pages 215 to 226 (1988), and Chemical Industries, page 43 to 53 (1986, May) represented by the following general formulas (1) to (11). Various dyes can be used.

[0015]

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In the general formulas (1) to (11), A ¹ and A ² each represent an acidic nucleus, and A ³ represents a substituted or unsubstituted phenol, a substituted or unsubstituted naphthol, or an acidic nucleus; B ¹ represents a basic nucleus, B ² represents an onium form of the basic nucleus, Q ¹ and Q ² each independently represent an aryl group or a heterocyclic group, and Q ³ represents an aryl group or L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ each represent a methine group, m, s and u represent 0,
1, 2 and n and p represent 0, 1, 2, and 3, respectively, q
Represents 0, 1, 2, 3, 4, and r, t1 and t2 are
They represent 1 and 2, respectively. X ^y- represents an anion; y represents 1 or 2; W ¹ and W ² each independently represent an atom necessary to form a 5- or 6-membered carbocyclic or heterocyclic group; Represents a group.

The acidic nucleus represented by A ¹ , A ² or A ³ is preferably an acidic nucleus derived from a cyclic ketomethylene compound or an acidic nucleus derived from a compound having a methylene group sandwiched between electron-withdrawing groups. . Examples of the cyclic ketomethylene compound include 2-pyrazolin-5-one, rhodanin, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid,
Thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, pyrrolin-2
-On. The cyclic ketomethylene compound may have a substituent.

A methylene group sandwiched between the electron-withdrawing groups
Is a compound having Z¹-CH_Two-Z ^TwoCan be represented by
You. Z¹And Z^TwoAre -CN and -SO, respectively._TwoR¹, -CO
R¹, -COOR^Two, -CONHR^Two, -SO_TwoNHR^Two,
-C [= C (CN)_Two] NHR¹It is preferred to represent R
¹Represents an alkyl group, an aryl group, or a heterocyclic group.
Then R^TwoRepresents a hydrogen atom, an alkyl group, an aryl group, or
It preferably represents a heterocyclic group. R¹Or R^TwoRepresented by
Alkyl, aryl, or heterocyclic groups are each a substituent
May be provided.

[0019] basic nucleus represented by B ¹ includes, pyridine, quinoline, indolenine, oxazole - le, imidazo - le, thiazole - Le, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole pyrrole is preferable . The basic nucleus may have a substituent. B ² represents an onium of a basic nucleus which may have a substituent, and among these, the onium of a basic nucleus listed as a preferable example of B ¹ is preferable.

The aryl groups represented by Q ¹ and Q ² include:
It includes an unsubstituted aryl group and an aryl group having a substituent. As the aryl group, a phenyl group and a naphthyl group are preferable. The aryl group represented by Q ¹ preferably has a dialkylamino group, a hydroxyl group, or an alkoxy group as a substituent. The aryl group represented by Q ² preferably has an electron-withdrawing group such as a nitro group, a cyano group, a sulfonyl group, or a halogen atom as a substituent. Q
^The heterocyclic group represented by ¹ and Q ² includes an unsubstituted heterocyclic group and a substituted heterocyclic group. Specifically, pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, indoline, thiazole,
Pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman are preferred.

As the onium of the aryl group or heterocyclic group represented by Q ³ , an aryl group such as a phenyl group and a naphthyl group, or the heterocyclic group enumerated as the heterocyclic group represented by Q ¹ and Q ² described above. An onium compound in which an onium group such as a quaternary ammonium group is substituted on the ring group is exemplified. In addition, those in which a hetero atom constituting a heterocyclic ring becomes a cation to form an onium compound are also included. The aryl group and the heterocyclic group may have a substituent.

Examples of the substituent include a hydrogen atom, a hydroxyl group, a halogen atom (eg, chlorine, bromine, fluorine, iodine), a cyano group, a nitro group, a carboxyl group, a sulfo group, and a chain having 1 to 8 carbon atoms. Or cyclic alkyl groups (e.g., methyl, ethyl, isopropyl, n-butyl, n-hexyl, cyclopropyl, cyclohexyl,
2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl, allyl,
-Hexenyl), an alkynyl group having 2 to 8 carbon atoms (e.g., ethynyl, 1-butynyl, 3-hexynyl), an aralkyl group having 7 to 12 carbon atoms (e.g., benzyl,
Phenethyl), an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, 4-carboxyphenyl,
-Acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), having 1 to 10 carbon atoms (Eg, acetyl, benzoyl, propanoyl, butanoyl), an alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), and a carbon atom of 7
Aryloxycarbonyl group (for example, phenoxycarbonyl, naphthoxycarbonyl) having 1 to 12 carbon atoms
10 carbamoyl groups (for example, unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl), alkoxy groups having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy, methoxyethoxy), and 6 to 12 carbon atoms Aryloxy group (e.g., phenoxy, 4-carboxyphenoxy, 3-methylphenoxy, naphthoxy), acyloxy group having 2 to 12 carbon atoms (e.g., acetoxy, benzoyloxy), sulfonyloxy group having 1 to 12 carbon atoms ( For example, methylsulfonyloxy, phenylsulfonyloxy), an amino group having 0 to 10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, 2-carboxyethylamino), an acylamino group having 1 to 10 carbon atoms ( For example, Ase Amide, benzamide), a sulfonylamino group having 1 to 8 carbon atoms (eg, methylsulfonylamino, phenylsulfonylamino, butylsulfonylamino, n-octylsulfonylamino), a ureido group having 1 to 10 carbon atoms (eg, ureido) , Methylureido), a urethane group having 2 to 10 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino), an alkylthio group having 1 to 12 carbon atoms (for example, methylthio, ethylthio, octylthio), 6 to 6 carbon atoms 12 arylthio groups (eg, phenylthio, nephthylthio), alkylsulfonyl groups having 1 to 8 carbon atoms (eg, methylsulfonyl, butylsulfonyl), and arylsulfonyl groups having 7 to 12 carbon atoms (eg, phenylsulfonyl, 2-phenyl) Naphthyl Ruhoniru), a sulfamoyl group having a carbon number of 0-8 (e.g.,
Unsubstituted sulfamoyl, methylsulfamoyl and the like, and a heterocyclic group (for example, 4-pyridyl, piperidino, 2-furyl, furfuryl, 2-thienyl, 2-pyrrolyl, 2-quinolylmorpholino) and the like can be mentioned.

The methine groups represented by L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ include unsubstituted methine groups and substituted methine groups. Further, the substituents of the methine group may be connected to each other to form a 4, 5, 6 or 7-membered ring (for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene).

The anion represented by X ^y- is represented by the general formula (7)
Represents an anion capable of supplying a negative charge necessary for neutralizing the charge of the cation in the compound represented by Preferably y is 1 or 2, ie X is a monovalent or divalent anion. The anion represented by X ^y- is Cl
^-, Br ^-, I ^- halogen ions, such as, SO ₄ ^2-, HSO
₄ ^-, CH ₃ OSO ₃ ^- alkyl sulfate ion such as p-toluenesulfonic acid ion, naphthalene-1,5-disulfonic acid ion, methanesulfonate ion, trifluoromethanesulfonate ion, ion sulfonic acids such as octanoic acid ion , Acetate ion, p-chlorobenzoate ion, trifluoroacetate ion, oxalate ion,
Carboxylate ions such as succinate ion, PF ₆ ⁻ , BF
_{^{4 -, ClO 4 -, IO}} 4 -, tungstate ion, heteropolyacids ion such as tungstophosphoric acid ions, H ₂ PO ₄
^-, NO ₃ ^-, etc. phenolate ions such as picrate ion.

W ¹ and W ² each independently represent a group of atoms necessary to form a 5- or 6-membered carbocyclic or heterocyclic group.

There are no particular restrictions on the substituents that each of the above groups may have, and specific substituents are the same as those described above.
A ¹ , A ² , A ³ ,
B ¹ , B ² , Q ¹ , Q ² , Q ³ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ ,
And L ⁶ may be linked to each other to form a ring.

Specific examples of the dye forming the J-aggregate are shown below, but the dye used in the present invention is not limited to the following compounds. The cation in the formula may be any of a proton, ammonium, an organic cation (such as triethylammonium, hydroxyethylammonium, and pyridinium) and a metal cation other than those described above.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[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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Among the dyes represented by the general formulas (1) to (11), the dyes represented by the general formulas (1), (2),
The dyes represented by (4), (5), and (6) are preferable because they can form a J-aggregate stably, and the dyes represented by the general formulas (2) and (5) are preferable. Is more preferred. Particularly preferred is a dye represented by the general formula (2).

The cyanine dye represented by the general formula (5) is described in "Theory of Photographic Process" (HJ James), No. 216.
It is described on pages from page 222 to page 222 that a J-aggregate can be formed, which is preferable as the dye for inkjet recording of the present invention. The oxonol dye represented by the general formula (2) is also described in JP-A-9-179246, EP 778493, US Pat. No. 5,922,593, US Pat. No. 5,988,849, and US Pat. No. 5,965,333. It is described that the compounds described in (1) and (2) can form an aggregate having an increased absorption wavelength, and are preferred as a dye of the ink for inkjet recording of the present invention.

The dyes represented by formulas (1) to (11) are described in WO 88/04794, EP 274,723.
No., 276,556, 299,435, US
2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429, 4,040,841, and Nos. 48-68,623, 52-92,716, 55-155,350, 55-155,351,
No. 61-205,934, JP-A-2-173,630
No. 2-230,135 and 2-277,044
Nos. 2-282, 244, 3-7,931, 3-167,546, 3-13,937, 3-
Nos. 206,443, 3-208,047, 3-1
Nos. 92,157, 3-216,645 and 3-27
4,043, 4-37,841, 4-45,4
No. 36, No. 4-138, 449, No. 5-197, 0
No. 77, Japanese Patent Application Nos. 5-273,811 and 6-7,76
No. 1, No. 6-155,727, and the like, or can be synthesized by a method analogous thereto.

In the present invention, the water-insoluble colorant may be used alone, or a plurality of colorants may be used in combination.

-Ultraviolet absorbing polymer- The ultraviolet absorbing polymer can be obtained by polymerization of a conventionally known ultraviolet absorbing monomer.

Examples of the ultraviolet absorbing portion of the ultraviolet absorbing monomer include those selected from the group consisting of triazine derivatives, benzotriazole derivatives, benzophenone derivatives, phenylsalicylic acid derivatives, cyanoacrylate derivatives, and hindered phenol derivatives. , A triazine derivative, a benzotriazole derivative, a benzophenone derivative, and a hindered phenol derivative are preferable, and a triazine derivative and a benzotriazole derivative are more preferable. Examples of the polymerizable portion of the monomer having an ultraviolet absorbing portion include an ethylenically unsaturated group (for example,
A methacryloyl group, an acroyl group, a vinyl group or a vinyl ether group), an epoxy group and the like, and an ethylenically unsaturated group is preferable. Specific examples of the ultraviolet absorbing monomer are described in JP-A-58-111942,
-53543, JP-A-3-161742, JP-A-6
-73367, JP-A-7-209787, JP-A-8-208
JP-A-234364, JP-A-2000-273347 and the like can be used.

The ultraviolet absorbing monomer preferably used in the present invention is represented by the following formula U-1.

[0059]

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In the formula U-1, L represents a group —COO—, —CONH—, — (CH_Two)_m-,-(CH_Two)_m-CO-, -CONH- (CH_Two)_m-, -COO- (CH_Two)_m-, -CO- (CH_Two)_m-, -COO- (CH_Two)_m-NHCO-O- (CH_Two)_n-, -COO- (CH_Two)_m-(CH (OH))_n− (CH_Two)
_p-O-CO- (CH_Two)_q-O-, -Ar- (CH_Two)_m-NHCOO-, -COO- (CH_Two)_m-(CH (OH))_n− (CH_Two)
_p-O-, -O-CO- (CH_Two)_m-O-, -COO- (CH_Two)_m-O-, -COO- (CH_Two)_m-Ar-, -COO- (CH_Two)_m-NH-COO- (CH_Two)_p-O
-CO- (CH _Two)_q-S- or -COO- (CH_Two)_m-NH-CO-NH- (CH_Two)_p
-O-CO- (CH_Two)_q-(Where m, n, p and q are each independently
Represents an integer of 1 to 6, and Ar may have a substituent.
Represents an arylene group).

X represents an ultraviolet ray absorbing site, and the following (X
1) to (X13).

[0062]

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[0063]

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Wherein R ² , R ^{2 ′} and R ^{2 ″} are a hydrogen atom,
Represents an alkyl group, an aryl group, a halogen atom, a substituted alkyl group, a substituted aryl group, an alkanoyloxy group, or a substituted alkoxy group. Among them, a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a substituted alkyl group, and a substituted aryl group are preferable. R ² , R ^{2 ′} and R ^{2 ″} may be the same or different from each other. R ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, or an alkanoyloxy group. Among them, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and an alkanoyloxy group are preferred. R ⁴ is an alkyl group, an aryl group,
Represents a substituted alkyl group or a substituted aryl group. Among them, an alkyl group and a substituted alkyl group are preferable. R ⁵ , R
^{5 ′} , R ^{5 ″} and R ^{5 ″ ″} represent a branched alkyl group (t-butyl group, t-amyl group, α-cumyl group, t-octyl group, neopentyl group, etc.). Preferred are a t-butyl group, a t-amyl group, an α-cumyl group and a t-octyl group. R ⁵ , R ^{5 ′} , R ^{5 ″} and R ^{5 ″ ″} may be the same or different from each other. R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, or a substituted alkoxy group. Among them, a hydrogen atom, a halogen atom, an alkyl group,
Substituted alkyl groups are preferred. R ⁷ and R ^{7 ′} represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, or an alkanoyloxy group. Among them, hydroxy group,
An alkoxy group, a substituted alkoxy group and an alkanoyloxy group are preferred. R ⁷ and R ^{7 ′} may be the same or different from each other.

X represents (X1), (X2), (X3),
(X4), (X5), (X10), (X11), (X1
2) or (X13), preferably (X13)
More preferably, it is (1), (X2), (X5) or (X12).

The ultraviolet absorbing polymer is a water-insoluble type,
Any of a water-dispersed (self-emulsifying) type and a water-soluble type may be used, but a water-dispersed type is preferred in terms of ease of production of colored fine particles, dispersion stability, and the like.

The water-dispersible ultraviolet absorbing polymer may be any of an ion dissociation type, a nonionic dispersing group-containing type, and a mixture of these. The ion dissociation type ultraviolet absorbing polymer includes an ultraviolet absorbing polymer containing a cationic ionic group such as a tertiary amino group, and an anionic ionic group such as a carboxylic acid and a sulfonic acid. UV absorbing polymer. Examples of the non-ionic dispersing group-containing type ultraviolet absorbing polymer include an ultraviolet absorbing polymer containing a non-ionic dispersing group such as a polyethylene oxy chain. Among these, ion-dissociative UV-absorbing polymers containing anionic ionic groups and UV-absorbing polymers containing nonionic dispersible groups have high absorbance in terms of ease of production and dispersion stability of colored fine particles. Molecule, and a mixed type ultraviolet absorbing polymer of both is preferable, an ion dissociation type ultraviolet absorbing polymer containing an anionic ionic group,
The mixed type ultraviolet absorbing polymer is more preferable.

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, itaconic acid monoester, maleic acid monoester, acrylic acid Sodium acrylate, ammonium methacrylate, potassium itaconate and the like.

Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkanesulfonic acid (for example, acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid, etc.), and methacryloyloxyalkanesulfonic acid (for example, 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-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl) Such as a single-sulfonic acid), and the like.

Examples of the phosphoric acid monomer include vinylphosphonic acid and methacryloyloxyethanephosphonic acid.

Of these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, 2 carboxyethyl acrylate, acrylamidoalkyl sulfonic acid, and methacrylamidoalkyl sulfonic acid are preferable, and acrylic acid, methacrylic acid, and 2 carboxyethyl acrylate are preferable. 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 dispersing 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 1 to 20,
1-12 are more preferable.

The ultraviolet absorbing polymer may be formed by copolymerizing a monomer having no ultraviolet absorbing property with an ultraviolet absorbing monomer. As the monomer having no ultraviolet absorbing property which can be copolymerized with the ultraviolet absorbing monomer (hereinafter, referred to as a copolymerized monomer), a monomer having the same polymerization site as that of the ultraviolet absorbing monomer is preferable. Examples of the copolymerizable monomer having an ethylenically unsaturated group as a polymerizable site are shown below. Incidentally, the aliphatic group described in the following examples of the copolymerizable monomer, the aromatic group may be substituted,
Examples of the substituent include an aliphatic group, an aromatic group, a halogen or a cyano group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, and the like. The ester group represents the aliphatic group or the aromatic group.

Acrylic esters, methacrylic esters, vinyl esters of aliphatic or aromatic carboxylic acids, acrylamides and methacrylamides (specifically, acrylamide, N-monosubstituted acrylamide,
N-disubstituted acrylamide, methacrylamide, N-monosubstituted methacrylamide, N-disubstituted methacrylamide (substituents are the aliphatic groups and the aromatic groups), olefins (eg, ethylene, propylene, 1-butene) , 1
-Pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and the like, styrenes (for example, styrene, substituted styrene) and the like.

Further, vinyl ethers (specifically, the above-mentioned aliphatic vinyl ether and the above-mentioned aromatic vinyl ether), and other monomers such as acrylonitrile, methacrylonitrile, crotonic acid ester, itaconic acid diester, Maleic diester, fumaric diester, methyl vinyl ketone, phenyl vinyl ketone, N-
Vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylenemalononitrile, vinylidene and the like.

The aliphatic group is a chain or cyclic alkyl group, alkenyl group or alkynyl group, each of which may be substituted. Examples of the substituent include an aromatic group, a halogen atom, a cyano group, a hydroxy group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group. The aromatic group is an aryl group and may have a substituent. Examples of the substituent include the above-mentioned aliphatic group, halogen atom, cyano group, hydroxy group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, carbamoyl group and the like.

In the case of using the copolymerized monomer, various purposes (for example, control of acid content, control of Tg, improvement of solubility,
A plurality can be copolymerized depending on the (stability of dispersion).

The ultraviolet absorbing polymer is 300 to 40.
The maximum absorbance in the range of 0 nm corresponds to the polymer solution 10
When the mg / L is measured with a 1 cm cell, it is 0.1 to 2, preferably 0.2 to 2, and more preferably 0.5 to 2. If the absorbance is less than 0.1, the effect of improving the light resistance becomes poor. In order to improve the color tone of the ink, the absorbance in the range of 440 to 650 nm is preferably less than 0.2, more preferably less than 0.1. However, when exhibiting an absorption wavelength similar to the colorant used, the absorbance may be 0.2 or more. The absorbance can be adjusted by changing the copolymerization ratio according to the ultraviolet absorbing property of the ultraviolet absorbing monomer.

The content of the ionic group in the ultraviolet absorbing polymer is preferably from 0.2 to 4.0 mmol / g, more preferably from 0.3 to 3.0 mmol / g. It is particularly preferred that it is 0.5 to 2.0 mmol / g. If the content of the ionic group is too small, the dispersion stability of the colored fine particles deteriorates, and if it is too large, the water solubility increases and the suitability for producing the colored fine particles decreases.
When the ultraviolet absorbing polymer contains an anionic ionic group, an alkali metal ion (for example, Na
⁺ , K ^+, etc.) and ammonium ions.

The molecular weight (weight average molecular weight) of the ultraviolet absorbing polymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, still more preferably from 4,000 to 80,000.
It is particularly preferably from 000 to 50,000. If the molecular weight is less than 1000, it tends to be difficult to obtain a stable dispersion, and if it is more than 200,000, the solubility in a dispersion medium tends to decrease, and the suitability for producing colored fine particles tends to decrease. .

The glass transition temperature of the ultraviolet absorbing polymer is preferably from -50 ° C to 150 ° C,
The temperature is more preferably from 30 ° C to 110 ° C, and -1
It is particularly preferred that the temperature be 0 ° C or higher and 100 ° C or lower. Here, the glass transition temperature is a value obtained by measuring the ultraviolet absorbing polymer with DCS at a temperature change of 10 ° C./min. When the glass transition temperature is less than -50 ° C, the printing surface is sticky or the gas permeability is high, so that the color fading to an oxidizing gas such as ozone tends to be poor. When the glass transition temperature is higher than 150 ° C, This is not preferable because the gloss of the printed matter is inferior and the scratch resistance tends to deteriorate.

Specific examples of the ultraviolet absorbing polymer (P-1)
To 22) are listed below. The ultraviolet absorbing polymer used in the present invention is not limited to these specific examples. The following ratios represent mass ratios, and molecular weights represent weight average molecular weights.

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[Table 1]

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Next, an example of a method for producing an ultraviolet absorbing polymer will be described. The present invention is not limited to this production example. In the following, “parts” indicates “parts by mass”. <Production Example> Ultraviolet absorbing monomer (M1-5) 4.45
Part, AMPS 0.55 part, dimethyl 2,2'-azobis (2-methylpropionate) 0.05 part, THF1
0 parts and 10 parts of DMF were charged into a flask, and the mixture was heated to 65 ° C. while stirring under a nitrogen blanket, and then the above mixture was added dropwise over 10 hours. After dropping, 2,2'-
Azobis (2,4-dimethylvaleronitrile) was added to 0.0
Add 5 parts, react at the same temperature for 5 hours, and further add 2,2'-
Azobis (2,4-dimethylvaleronitrile) was added to 0.0
Two parts were added and the mixture was heated at 70 ° C. for 2 hours. The obtained polymer solution was reprecipitated in acetone and dried at 40 ° C. under reduced pressure to obtain 5.0 parts of a target vinyl polymer P-2. The weight average molecular weight was 7,800 (GPC, PS conversion).

-Preparation of Colored Fine Particle Dispersion- The colored fine particle dispersion of the present invention disperses colored fine particles containing a water-insoluble colorant and an ultraviolet absorbing polymer in an aqueous medium (aqueous liquid containing at least water). It is manufactured by Specifically, for example, (i) a method in which a dispersion of the water-insoluble colorant is prepared in advance and the UV-absorbing polymer is adsorbed thereto, or (ii) the water-insoluble colorant and the UV-absorbent A method of adjusting the dispersion in a state in which the polymer coexists is exemplified.

Hereinafter, (i) a method of preparing a dispersion of the water-insoluble colorant in advance and adsorbing the ultraviolet absorbing polymer on the dispersion will be described. A first example of this method includes a first step of dispersing the water-insoluble colorant in an organic solvent phase and a second step of mixing the ultraviolet absorbing polymer in a solid state or in an organic solvent solution. And a third step of pouring water into an organic solvent phase containing the water-insoluble colorant and the ultraviolet absorbing polymer, or pouring the organic solvent phase into water. A second example of the method includes a first step of dispersing the water-insoluble colorant in an aqueous medium phase,
A second step of mixing the ultraviolet absorbing polymer in a solid state or in an aqueous solution (including a dispersed state), and an aqueous medium phase containing the water-insoluble colorant and the ultraviolet absorbing polymer And a third step of charging the aqueous medium phase into water containing an acid or a base. If necessary, a fourth step of adjusting the dispersion by adding a base or an acid may be provided after the third step. In this case, the ultraviolet absorbing polymer contains an ionic group, and when the ionic group is an acid, it is neutralized with a base before use, and in the third step, an acid is used, and the ionic group is a base. In the case of the above, it is used after being neutralized with an acid in advance, and a base is used in the third step.

Next, (ii) a method of preparing a dispersion in a state where the water-insoluble colorant and the ultraviolet absorbing polymer are present together will be described. A first example of this method is a first step of dispersing the water-insoluble colorant and the ultraviolet absorbing polymer in an organic solvent phase, and adding water to the organic solvent phase,
Or a second step of charging the organic solvent phase into water. A second example of this method includes a first step of dispersing the water-insoluble colorant and the ultraviolet absorbing polymer in an aqueous medium phase, and adding an acid or a base to the aqueous medium phase, or Or a second step of charging the aqueous medium phase into water containing a base. If necessary, a third step of adjusting the dispersion by adding a base or an acid may be provided after the second step. The ultraviolet absorbing polymer in this case contains an ionic group, and when the ionic group is an acid, it is neutralized with a base before use, and in the second step, an acid is used,
If the ionic group is a base, neutralize it with an acid before use.
In the second step, a base is used.

To disperse the medium containing the water-insoluble colorant, a disperser (eg, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ong mill) It is preferable to use

In the colored fine particle dispersion, the amount of the ultraviolet absorbing polymer to be used is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 600 parts by mass, based on 100 parts by mass of the water-insoluble colorant. 30-400
Part by weight is particularly preferred. When the amount of the ultraviolet absorbing polymer used is less than 10 parts by mass, the stability of the dispersion is inferior, and the effect of improving the light resistance tends to decrease.
When the amount exceeds 0 parts by mass, the proportion of the water-insoluble colorant in the colored fine particle dispersion is reduced, and when the colored fine particle dispersion is used as an aqueous ink, there is a tendency that there is no room for formulation design.

The content of the water-insoluble colorant in the ink for ink jet recording is preferably 0.2 to 10% by mass, more preferably 0.5 to 30% by mass, and more preferably 0.5 to 30% by mass.
10% by weight is particularly preferred.

The average particle size of the colored fine particles is 1 to
500 nm is preferable, 3 to 300 nm is more preferable, furthermore, 5 to 150 nm is preferable, and 5 to 100 nm.
Is particularly preferred. The average particle size can be adjusted by centrifugation, filtration, or the like.

The organic solvent used for producing the colored fine particle dispersion is not particularly limited, and is appropriately selected based on the solubility and wettability of the water-insoluble colorant and the solubility of the ultraviolet absorbing polymer. For example, methyl ethyl ketone, diethyl ketone, ketone solvents such as cyclohexanone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, tert-butanol, chloroform, chlorine solvents such as methylene chloride, Aromatic solvents such as benzene and toluene; ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether System solvent, and the like. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, but may be 1 to 100 parts by mass of the water-insoluble colorant.
The amount is preferably from 0 to 2,000 parts by mass, more preferably from 100 to 1,000 parts by mass. 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.

The solubility of the organic solvent in water is 10%
In the case of the following, or when the vapor pressure of the organic solvent is higher than that of water, it is preferable to remove part or all of the organic solvent from the viewpoint of the stability of the colored fine particle dispersion. The removal of the organic solvent is preferably performed by evaporation or ultrafiltration. Evaporation can be carried out at 10 to 100 ° C. under normal pressure to reduced pressure conditions.
It is preferably carried out at 0 to 100 ° C. or 10 to 50 ° C. under reduced pressure.

-Water-Soluble Organic Solvent- Next, a water-soluble organic solvent is used in the ink jet recording ink of the present invention for the purpose of forming a dispersion medium of the colored fine particle dispersion or a drying inhibitor or a penetration enhancer. contains.

The water-soluble organic solvent used in the present invention 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, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin , Polyhydric alcohols represented by 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-2 -Imidazolidinone, N-
Examples include heterocycles such as ethyl morpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 3-sulfolene, and polyfunctional compounds such as diacetone alcohol and diethanolamine. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-mentioned water-soluble organic solvents may be used alone or in combination of two or more. These water-soluble organic solvents are preferably contained in the ink in an amount of 10 to 50% by mass.

-Other Additives- As additives other than the water-soluble organic solvent, an anti-drying agent for preventing clogging due to a dry operation at an ink ejection port, and an additive for facilitating penetration of ink into paper. Additives such as penetration enhancers, antioxidants, viscosity regulators, surface tension regulators, dispersants, dispersion stabilizers, fungicides, rust inhibitors, pH regulators, defoamers, chelating agents, and ultraviolet absorbers Can be appropriately selected and used in an appropriate amount.

Examples of the anti-drying agent include urea derivatives in addition to the water-soluble organic solvents. As the penetration enhancer, other than the water-soluble organic solvent, an anionic surfactant such as sodium lauryl sulfate and sodium oleate, a nonionic surfactant and the like can be used.
These have sufficient effects when contained in the ink in an amount of 10 to 30% by mass, and are preferably used within the range of an addition amount that does not cause printing bleeding or paper loss (print-through).

As the antioxidant used for improving the storability of the image, various organic and metal complex-based antifading agents can be used. Hydroquinones, alkoxyphenols,
Examples include dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No. No. 17643, Nos. VII, I to J; 15162; No. 18716, left column, page 650; Page 527 of 36544, N
o. No. 307105, page 872; The compounds described in the patent cited in US Pat.
No. 272, pages 127 to 137, the general formulas of typical compounds and the compounds included in the compound examples can be used.

Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. For example, as anionic surfactants, fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates,
Examples thereof include alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensate, and polyoxyethylene alkyl sulfate salts. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene alkyl allyl ether. Examples thereof include an ethylene fatty acid ester, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene alkylamine, a glycerin fatty acid ester, and an oxyethyleneoxypropylene block copolymer. SURFYNOLS, an acetylene-based polyoxyethylene oxide surfactant (Air
Products & Chemicals) are also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Japanese Patent Application Laid-Open No. 59-157,636, pages (37) to (38), Research Disclosure No.
308119 (1989) can also be used. The surface tension of the ink of the present invention may be 20 to 60 with or without these.
mN / m is preferred. Furthermore, 25 to 45 mN / m is preferable.

The viscosity of the ink of the present invention is preferably 30 mPa · s or less. The viscosity is more preferably adjusted to 20 mPa · s or less, and a viscosity modifier may be used for the purpose of adjusting the viscosity. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants.

Examples of the dispersant and the dispersion stabilizer include various cationic, anionic and nonionic surfactants mentioned as examples of the above-mentioned surface tension modifier.

Examples of the fungicides used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, and 1,2-benzisothiazoline-3-.
And its salts. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass. still,
Details of these are described in "Encyclopedia of Bacterial and Fungicides" (edited by the Japanese Society of Bacteria and Fungi).

Examples of the rust preventive used in the present invention include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, benzotriazole and the like. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.

The pH adjuster used in the present invention can be suitably used in terms of pH adjustment of the water-insoluble colorant-containing fine particle dispersion, imparting dispersion stability, and the like.
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. Examples of the pH adjuster include basic ones such as organic bases and inorganic alkalis, and acidic ones such as organic acids and inorganic acids. 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. In addition, examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.

Fluoro- and silicone-based compounds as antifoaming agents and compounds represented by EDTA as chelating agents can be used as required.

In the present invention, the light resistance of an image is excellent because the above-mentioned ultraviolet absorbing polymer is used, but a generally used ultraviolet absorbing agent may be added. Examples of the ultraviolet absorber which can be added include JP-A-58-185677, JP-A-61-190537, and JP-A-2-782.
JP-A-5-1970075, JP-A-9-34057
Benzotriazole compounds described in JP-A-46-2784, JP-A-5-194483, benzophenone-based compounds described in U.S. Pat. No. 3,214,463, and JP-B-48-30492. ,
Cinnamic acid-based compounds described in JP-A-56-21141 and JP-A-10-88106;
Nos. 503, 8-53427, 8-239
No. 368, No. 10-182621, Tokuheihei 8
Triazine compounds described in JP-A-501291 and the like, Research Disclosure No. Compounds described in Japanese Patent No. 24239 and compounds emitting fluorescent light by absorbing ultraviolet rays, represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners and the like.

The ink-jet recording ink of the present invention comprises:
It can be used not only for monochromatic image formation but also for full-color image formation. To form a full-color image,
Magenta color ink, cyan color ink, and yellow color ink can be used, and further black color ink may be used to adjust the color. It is preferable that at least one of these various hue inks is the ink for inkjet recording of the present invention because a full-color image having a good hue can be formed. Further, it is more preferable that all of these various hue inks are the ink jet recording inks of the present invention because a full-color image having an excellent hue can be formed.

-Image-Receiving Material- Examples of the image-receiving material used in the ink jet recording method using the ink of the present invention include plain paper, coated paper, plastic film and the like. It is preferable to use coated paper as the image receiving material because image quality and image storage durability are improved.

The ink of the present invention is a known recording material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, and JP-A-7-276789. Gazette, pp. 9-323475
JP-A-62-238783, JP-A-10-153
Nos. 989, 10-217473, 10-
No. 235995, No. 10-337947, No. 10-217597, No. 10-337947, etc. Ink-jet dedicated paper, film, electrophotographic paper, fabric, glass, metal, ceramic, etc. It can be used to form images.

The recording paper and recording film used for ink-jet printing using the ink of the present invention will be described below. Supports for recording paper and film are chemical pulp such as LBKP and NBKP, GP, P
It consists of mechanical pulp such as GW, RMP, TMP, CTMP, CMP and CGP, waste paper pulp such as DIP, etc., and if necessary, conventionally known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength And various additives such as a fourdrinier paper machine, a round paper machine, etc., into which an additive such as an agent is mixed can be used. In addition to these supports, any of synthetic paper and plastic film sheets may be used. The support has a thickness of 10 to 250 μm and a basis weight of 10 to 250 g / m
² is preferred. The support may be provided with the ink receiving layer and the back coat layer as they are, or 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. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, as the support, paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin polyolefin.

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

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivative. Such as water-soluble polymers, styrene butadiene latex,
A water-dispersible polymer such as an acrylic emulsion can be used. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.

The ink receiving layer contains a mordant, a water-proofing agent, a light-resistance improving agent, a surfactant,
Hardeners and other additives can be included.

The mordant added to the ink receiving layer is preferably immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325 and JP-A-54-74430.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
Nos. 0-23851, 60-23852, 60-2
No. 3853, No. 60-57836, No. 60-6064
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236
Nos. 2,484,430 and 25,485.
Nos. 64, 3148061, 3309690, 4115124, 4124386, 41938
No. 00, No. 4,273,853, No. 4,282,305, and No. 4,450,224. JP 1
An image receiving material containing a polymer mordant described on pages 212 to 215 of 161236 is particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant,
As these waterproofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, based on the total solid content of the ink receiving layer.
It is preferably 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.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent. The surfactants are described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil), and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin).
About the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. (columns 8 to 17), JP-A No. 61-20994, 6
It is described in each gazette of 2-135826.

As the hardener, the materials described on page 222 of JP-A-1-161236 can be used.

Other additives to be added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners and the like. Is mentioned. The ink receiving layer may be a single layer or two layers.

The recording paper and the recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica,
White inorganic pigments such as colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, melamine Organic pigments such as resins are exemplified.

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

A polymer latex may be added to the constituent layers (including the back layer) of the ink jet recording paper and the recording film. Polymer latex is dimensionally stable,
It is used for the purpose of improving film physical properties such as curling prevention, adhesion prevention and film cracking prevention. Polymer latex is described in JP-A-62-245258 and JP-A-62-1100.
No. 66 describes each of the publications. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back layer.

The ink of the present invention is not limited to an ink jet recording method, and is 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 ( Pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam and the ink is irradiated to the ink to emit the ink using a radiation pressure, and a pressure is generated by heating the ink to form bubbles. Used for thermal ink jet (bubble jet (registered trademark)) system and the like. The ink jet recording method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0129]

EXAMPLES The present invention will be described below in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Ink 01> The following composition was dispersed and mixed at 1200 rpm for 8 hours using a sand grinder mill to obtain a colored fine particle dispersion. Coloring agent (J-associated dye 2-20) 4.0 g Polymer (P-2) 4.0 g pt-octylphenylpolyoxyethylene sulfonate soda 1.6 g 1N sodium hydroxide 6.6 mL MEK 61 mL isopropano -Rule 10mL 0.3mm Zirconia beads 75mL

While stirring 50 g of the above dispersion at 70 ° C., 120 g of water was slowly added thereto.
Heat to 0 ° C, remove solvent until 62.5 g,
The solution was filtered through a 0.4 μm filter. When the particle size of this dispersion was measured using Honeywell Microtrac UPA150,
The average particle size was 67 nm.

Using this dispersion, an inkjet recording liquid (ink 01) having the following composition was prepared. The above dispersion 12.5 g Ethylene glycol 1.3 g Glycerin 1.3 g Water Amount of 25 g in total

<Preparation of Inks 02 to 13>
Ink Preparation Inks 1 to 13 were prepared in the same manner as in Preparation of Ink 01, except that the coloring agent and the polymer were changed to the compounds shown in Table 3 in Preparation 1.

<Preparation of Ink 14> An ink 14 for ink-jet recording was prepared in the same manner as in the preparation of Ink 01, except that the coloring agent was changed to the compound shown in Table 3 and no polymer was used. did.

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[Table 2]

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[Table 3]

-Image recording and evaluation- The prepared inks 01 to 14 are filled in a cartridge of an ink jet printer PM-770C (manufactured by EPSON), and plain paper for PPC and ink jet paper 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 the cartridge was set in the printer and the ejection of ink from all the nozzles was confirmed, an image was output on five A4 sheets, 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 the two images was large.

<Color Tone> The color tone of the image formed on the photo glossy paper was visually observed, and was evaluated on a three-point scale, with A being excellent, B being good, and C being poor.

<Evaluation of Water Resistance> The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in water for 30 seconds, 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.

<Evaluation of Light Fastness> The photo glossy paper on which the image was formed was irradiated with xenon light (85000 lx) for 10 days using a weather meter (Atlas CI65), and the image before and after the xenon irradiation was irradiated. Use a densitometer (X-Ri
te310TR) and evaluated as the residual dye ratio. The case where the dye residual ratio was 90% or more was evaluated as A, the case where the color retention ratio was 80% or more and less than 90% as B, and the case where it was less than 80% as C.

<Evaluation of Scratch Resistance> The photo glossy paper on which the image was formed was dried at room temperature for 1 hour and at 80 ° C. for 1 minute, rubbed five times with a plastic eraser, and observed discoloration.
A sample having little discoloration was evaluated as A, B having discoloration but hardly seeing a white background as B, and C showing discoloration and having a lot of white background as C.

Example 2 <Preparation of Ink 20> Colorant (J-associated dye 2-20)
A solution prepared by dissolving 2.0 g of the polymer (P-21) 2.0 g in dimethylformamide 10 g is prepared. The dissolved liquid was added dropwise to a mixture of 89 g of water and 1.16 g of a 10% aqueous sodium hydroxide solution little by little while stirring to prepare water-insoluble colored fine particles. Water 1 is added to the obtained dispersion.
000 g was added, ultrafiltration was performed until 1000 g of the liquid flowed out, and this was repeated three times, followed by filtration with a 0.4 μm filter. The particle size of this dispersion is measured using Honeywell Microtr.
The average particle size as measured by ac UPA150 was 68 nm. Using this dispersion, an inkjet recording liquid (ink 20) having the following composition was prepared. The above dispersion liquid 12.5 g Ethylene glycol 1.3 g Glycerin 1.3 g Water Amount of 25 g in total-Image recording and evaluation-The produced ink 20 was evaluated in the same manner as in Example 1.

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[Table 4]

As is clear from the results in Table 4, the ink jet recording inks of the examples were excellent in printing suitability, excellent in color development and color tone, independent of paper, and excellent in water resistance and light resistance. At this time, P-22C whose absorbance is less than 0.1
Ink 09 using the compound has little effect of improving light resistance.
The absorbance needs to be 0.1 or more.

Incidentally, the ink 01 using the dye 2-20 was used.
~ 03, 20 are very vivid magenta images, λmax is 550nm, half width is 60nm
And a sharp absorption. Dye 2-20
When the absorption spectrum is measured by dissolving in
x was 490 nm. The image obtained with the ink 04 using the dye 2-42 was a very vivid magenta image, having a λmax of 558 nm and a half-value width of 49 n.
m and a sharp absorption. The dye 2-42 was converted to DM
When dissolved in F and the absorption spectrum was measured,
ax was 493 nm. Therefore, the above-mentioned dye 2-2
The image with the ink using 0, 2-42 is 60-
This is due to a 65-nm long-wave shifted J-aggregate.

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

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA04 EA13 FC01 FC02 2H086 BA01 BA15 BA33 BA53 BA55 BA59 BA60 4J039 AD01 AD03 AD06 AD09 AD11 AD12 AD13 AD14 AD15 AD23 AE04 AE05 AE06 AE07 AF07 BA04 BC03 BC16 BC17 BC20 BC29 BC32 BC32 BC32 BC32 BC52 BC53 BC54 BC60 BC66 BC69 BC76 BE01 BE07 BE08 BE12 BE24 BE33 CA02 CA03 CA05 CA06 EA14 EA35 EA36 EA38 EA41 EA45 GA24

Claims (6)

[Claims] 1. An ink jet recording ink containing at least water, a water-soluble organic solvent and a dispersion of colored fine particles, wherein the dispersion of colored fine particles contains a water-insoluble colorant and an ultraviolet absorbing polymer. Ink for inkjet recording. 2. The method according to claim 1, wherein the colored fine particle dispersion comprises: adding water to an organic solvent phase containing a water-insoluble colorant and an ultraviolet absorbing polymer; or adding the organic solvent phase to water. The ink for inkjet recording according to claim 1, which is produced by any one of the above. 3. The method according to claim 1, wherein the colored fine particle dispersion is prepared by adding an acid to an aqueous dispersion containing a water-insoluble colorant and a neutralized UV-absorbing polymer having a carboxylic acid group or a sulfonic acid group. The inkjet recording ink according to claim 1, wherein the aqueous dispersion is prepared by adding the aqueous dispersion into an acid or an aqueous solution of an acid. 4. The ultraviolet absorbing polymer of 300 to 400.
The maximum absorbance in the range of nm is 0.1 mg when a polymer solution having a concentration of 10 mg / l is measured at an optical path length of 1 cm.
The inkjet recording ink according to any one of claims 1 to 3, wherein 5. The ink jet recording ink according to claim 1, wherein the water-insoluble colorant is a dye forming a J-aggregate. 6. An image-receiving paper having an image-receiving layer containing white inorganic pigment particles on a support, wherein an image is formed using the ink for inkjet recording according to any one of claims 1 to 5. Inkjet image forming method.