JPH10217597A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image having excellent optical fastness by a rapid ink jet printer by forming the image on a recording medium having a mordant layer containing polymer mordant of a specific amount of a unit to be represented by a predetermined formula on a support. SOLUTION: Ink containing dye represented by a formula I [R<1> , R<2> each indicates alkyl group, heterocyclic group, (n) indicates 1 or 2, A indicates a formula II (R<3> , R<4> , R<5> , R<6> each indicates a hydroxyl group, alkyl group) and B indicates -CH=CH] is prepared. Meanwhile, a recording medium obtained by laminating one or more mordant layers each containing polymer mordant of 60mol% or more at a unit represented by a formula III (R<1> to R<4> indicates H, alkyl group, L indicates a bivalent linkage group, and (p) indicates 0 or 1) is formed on a support. The prepared ink is printed by ink jet on the medium to form an image having excellent optical fastness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method excellent in light fastness of an image. Furthermore, the present invention relates to an image forming method using an ink jet recording and an ink jet printer.

[0002]

2. Description of the Related Art In recent years, with the spread of personal computers, printers such as ink-jet printers have rapidly become widespread. Further, with the spread of photo-quality scanners, photo CDs, and digital cameras, demand for a printing system for printing digitized photo images is rapidly increasing. Particularly, the spread of simple and inexpensive ink jet printers is remarkable, and the demand for image quality of the image is increasing year by year.

As an ink jet system, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. Many new methods have been proposed and put into practical use, such as a method using the above ink. In particular, recently, there is a tendency to eject a large amount of ink having a high print speed and a low density.

[0004] As a recording medium used in the ink jet recording method, a recording sheet having an ink receiving layer provided on a support called a normal paper or an ink jet recording sheet has conventionally been used. However, when these recording sheets are used, none of them can be used in the field of photographic image quality where high resolution and gloss are required, such as a lot of ink bleeding and low gloss.

In order to solve such a problem, a technique of an ink jet recording sheet using gelatin as an ink receiving layer on a resin-coated paper in which both sides of the paper are coated with a resin, that is, a so-called RC (resin-coated) paper as a support, is used. Kaihei 4-21
No. 6990, and No. 6-64306. Japanese Patent Application Laid-Open No. H7-179032 discloses a method for making the appearance and feel of an image output by an ink jet printer similar to those of a conventional photograph, in which a recording medium containing a synthetic hydrophilic resin in an ink receiving layer and an ink jet recording method using the same. A method is disclosed. Further, as a method of improving the image quality and stability of the image, Japanese Patent Application Laid-Open No.
No. 36 discloses a method of using a resin-coated support containing gelatin and a basic latex in an ink receiving layer.

[0006] With these improvements in systems and recording media, the image quality of ink jets has approached that of photographs.
For this reason, the performance other than the image quality has come to be compared with the photograph, and there has been a problem that the light fastness of the image is particularly poor.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming an image having excellent light fastness. In addition, printers that print digital image information such as inkjets, inkjet printers that have improved performance and increased printing speed, and inkjet printers that have improved image quality by ejecting many ink drops with low density, Another object of the present invention is to provide a method for forming an excellent image.

[0008]

The above object has been achieved by the following means. (1) Using an ink containing the dye of the following general formula (1) and / or the dye of the general formula (2) and / or the dye of the general formula (3), at least the following general formula An image forming method for forming an image on a recording medium having at least one mordant layer containing a polymer mordant containing at least 60 mol% of the unit represented by (I).

[0009]

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In the formula, R ¹ and R ² are each a substituent selected from a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an acylamino group, a sulfamoyl group, a sulfo group and a carboxyl group. Represents a group. n represents 1 or 2. A represents a monovalent group selected from the following general formula.

[0011]

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Where R^Three, R^Four, R^Five, R⁶Are each
Hydrogen atom, hydroxyl group, alkyl group, halogen atom, alcohol
Xy group, acylamino group, carbamoyl group, aryla
Substituents selected from zo, sulfo and carboxyl groups
Represent or R^Three, R^Four, R ^Five, R⁶Next to each other
Two groups may form a condensed ring. The fused ring is
They may further have a substituent. R⁷Is an alkyl group,
Reel group, carboxyl group, carbamoyl group, ester
Group, acylamino group, cyano group, alkoxy group, hydroxyl group
Represents a substituent selected from R⁸, R⁹, R^Ten, R¹¹,
R¹²Represents a hydrogen atom, an alkyl group, an alkoxy group,
Selected from halogen atom, sulfo group, carboxyl group
Represents a substituent. When n is 1, B is selected from the following general formula.
Represents a monovalent group.

[0013]

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In the formula, X and Y are each a chlorine atom, -N
L ¹ L ² and —OL ³ are represented. L ¹ , L ² and L ³ represent a hydrogen atom, an alkyl group or an aryl group. M represents a hydrogen atom, ammonium or an alkali metal. When n is 2, B represents a divalent group selected from the following general formula. The two azo dye portions may be the same or different.

[0015]

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In the formula, L ⁴ , L ⁵ and L ⁶ represent a hydrogen atom or an alkyl group. L ⁵ and L ⁶ may combine with each other to form a 5- or 6-membered ring. X has the same meaning as described above.

[0017]

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Where R^{twenty one}Is hydrogen atom, hydroxyl group, alkyl
Group, halogen atom, alkoxy group, amino group, acyl group
Mino group, sulfonylamino group, carbamoyl group, sulf
Amoyl group, arylazo group, sulfo group, carboxyl
Represents a substituent selected from the group^{twenty two}, R^{twenty three}, R^{twenty four}Is it
Hydrogen atom, alkyl group, alkoxy group, arylo
Xy group, amino group, aryl group, alkylsulfonyl
Group, arylsulfonyl group, nitro group, halogen atom,
Selected from sulfo, carboxyl, and arylazo groups
Represents a substituent. B and M have the same meanings as described above. m is 0
Represents an integer from 1 to 2. n represents 1 or 2. n is 2
The two naphthol azo dyes are the same
Or different. A substituent in the general formula (2)
R^{twenty one}, SO _ThreeM, arylazo group is 2 to 8 of naphthol
Any of the positions may be substituted.

[0019]

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In the formula, M has the same meaning as described above. p represents an integer from 1 to 4, and q represents an integer from 0 to 3.

[0021]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, and may be linear or branched. L represents a divalent linking group. p represents 0 or 1. (2) The image forming method according to (1), wherein an image is formed on the recording medium by using an ink jet printer with the ink.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Among the dyes represented by the general formula (1), those in which n is 2 are preferable, and among them, those in which B is as follows are preferable.

[0024]

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In the formula (1), particularly preferred dyes are as follows.

[0026]

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R ² , R ³ and M are as defined above.

Among the dyes represented by the general formula (2), when n is 1, B is as follows:

[0029]

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When n is 2, the following is obtained.

[0031]

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Particularly preferred in the general formula (2) are as follows.

[0033]

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The dye used in the present invention has the general formula (1)
And / or an ink containing a dye of the general formula (2) and / or a dye of the general formula (3) on a support,
At least 60 mol% of the unit represented by the general formula (I)
By forming an image on a recording medium having at least one mordant layer containing the above-described polymer mordant, a robust image can be obtained. In particular, when a dye represented by the general formula (2) is used, Great effect. Preferred compounds of the present invention are shown below.

[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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[0052]

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[0053]

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[0054]

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These dyes can be used as inks as they are, or by dissolving them in aqueous and / or organic solvents, or by emulsifying and dispersing, or by encapsulating and dispersing with polymers to form liquids. The amount of these dyes added to the ink is determined in relation to the recording medium. For this reason, in the adjustment of the yellow, magenta, cyan and black inks, it is preferable to add 0.2 to 15% by weight, preferably 0.5 to 10% by weight, of each color ink.

Examples of solvents that can be used in the ink containing the dye of the present invention are described below. The following solvents can be used as a mixture. For example; water, methyl alcohol,
Carbon such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, etc. Numbers 1 to 10
Alkyl alcohols; for example, aliphatic or aromatic hydrocarbons represented by cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecanone, tetralin, decalin, benzene, toluene, xylene and the like solvent,;
For example, halogenated hydrocarbon solvents such as carbon tetrachloride, trichloroethylene, tetrachloroethane, and dichlorobenzene; ether solvents such as ethyl ether, butyl ether, ethylene glycol diethyl ether, and ethylene glycol monoethyl ether; , Acetone, methyl ethyl ketone, methyl propyl ketone, methyl amyl ketone, cyclohexanone, and other ketone solvents; for example, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, phenyl acetate, phenyl acetate, ethylene glycol monoethyl ether acetate, lactic acid Ester solvents such as ethyl; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; other amines Amides, nitrogen-containing heterocyclics such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and oxycarboxylic acids such as valerolactone and caprolactone. Is mentioned.

The method for forming an image on a recording medium containing the mordant of the present invention using the ink containing the dye of the present invention is not particularly limited. For example, the recording medium may be directly immersed in the ink, the ink may be sprayed onto the recording medium from the outside (for example, an ink jet printing method), or a coating containing the ink may be used. A dye may be transferred to the recording medium by forming a film and using heat or an alkali or a solvent (eg, sublimation type thermal transfer printing, dye diffusion printing, etc.). Among them, the effect of the present invention is greatly exerted particularly when used for inkjet printing.

When the image of the present invention is formed by using the ink jet printing method, the ink containing the coloring matter of the present invention may contain a humectant and a solubilizer as needed. As these humectants and solubilizers, those described in JP-B-58-27762 are suitable. Specifically, a combination of at least one of a 5- to 7-membered nitrogen-containing heterocyclic ketone compound and at least one of an aliphatic sulfone compound, an alicyclic sulfone compound or an alicyclic sulfoxide compound is desirable.

These compounds have remarkable effects as humectants and solubilizers, and include conventionally known hydrophilic organic solvents such as alkylene glycols, alkyl ethers of alkylene glycol, carboxylic acid amide derivatives, lactones, Ethylene, sulfur compounds, alcoholamines, monohydric, dihydric or trihydric alcohols, carbonates, urea derivatives, ethylene oxide adducts, N-vinyl-2-pyrrolidone oligomers, cellulose derivatives such as hydroxypropylcellulose, etc. Do not show a decrease in their effect. Further, the humectant has an effect of preventing solidification of the dye and other compounds due to drying as one of causes of nozzle clogging.

Further, another cause of the clogging of the nozzle is considered to be the generation of mold and the generation of aggregates due to the generation of fungi, and a fungicide is also added. Molds and bacteria live in all parts of the ink jet printer, such as ink channels, storage tanks, and nozzles.
If conditions such as humidity are met, molds or bacteria will proliferate significantly, forming colonies, forming aggregates incorporating dyes and other compositions, and causing clogging.

The polymer mordant which can be used in the present invention contains at least 60 mol% of the unit represented by the general formula (I). In the general formula (I), R ₁ , R ₂ , R ₃ and R
₄ each independently represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, An atom or a methyl group or an ethyl group is particularly preferred. L represents a divalent linking group having 1 to about 20 carbon atoms, for example, an alkylene group, a phenylene group, an arylene group and the like. Preferred specific examples of these divalent linking groups are shown below.

[0062]

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Preferred specific examples of the monomer unit represented by the general formula (I) of the present invention are shown below. However, it is not limited to these.

[0064]

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The polymer mordant which can be used in the present invention may contain a monomer unit other than the general formula (I). Preferred monomer units include, for example, pyrrolidones, acrylates (eg, n-butyl acrylate), Examples include methacrylic acid esters (for example, n-butyl methacrylate), acrylamides (for example, diacetone acrylamide), methacrylamides (for example, n-butyl methacrylamide), and styrenes (for example, styrene sulfinic acid). Further, JP-A-59-169042, JP-A-62-244036
May be contained. Further, two or more of these monomer units may be used.

The molecular weight of the polymer mordant which can be used in the present invention is preferably from 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer tends to move, and if the molecular weight is too large, coating may be hindered.

Preferred specific examples of the polymer mordant used in the present invention are shown below, but the present invention is not limited to these. Also, two or more kinds may be used in combination.

[0068]

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[0069]

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[0070]

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[0071]

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The synthesis method of the present invention is disclosed in
No. 44043, etc., and can be easily synthesized. The amount of the polymer mordant to be applied can be easily determined by those skilled in the art according to the amount of the dye, the type and composition of the polymer mordant, but is preferably about 0.2 to about 30 g / m ² . Among them, it is preferable to use 0.5 to 15 g / m ² . The recording medium of the present invention may have at least one mordant layer.If necessary, a protective layer, a layer having a fluorescent whitening agent for improving a white background, and an auxiliary layer such as an anti-curl layer may be provided. it can. In particular, it is effective to provide a protective layer and a layer having a fluorescent whitening agent for improving a white background. The total thickness of the coating layer including the mordant layer and the auxiliary layer is 3 μm
It is preferably from 50 to 50 μm, more preferably from 5 to 25 μm. Further, the coating layer may be provided not only on one side but also on both sides of the support.

The swelling ratio of the entire coating layer with water is 100%
It is desirably at least 1000% and preferably at most 150% and not more than 500%. Here, the swelling ratio is a value obtained by dividing the swelling value when water is dropped by the dry film thickness and multiplying by 100. Controlling the swelling behavior is extremely important in controlling ink seepage and spreading, and in preventing scratches and the like in the printer. The film surface pH of the recording medium is preferably 9 or less from the viewpoint of storage stability and safety of the recording medium. Here, the film surface pH is a value obtained by dropping 40 μl of water on the coated surface of the recording medium and measuring the pH one minute later.

As the binder of the mordant-containing layer and other layers constituting the recording medium, hydrophilic binders are preferably used. An example thereof is disclosed in JP-A-62-253159.
No. (26) to (28). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A-62-245260 and the like, that is, -COOM or-
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more kinds.

A binder may be added to the mordant layer of the recording medium of the present invention. As the binder used,
Although the above hydrophilic binder can be widely used,
Polyvinyl alcohol and derivatives thereof are preferred, and the degree of saponification of polyvinyl alcohol is particularly preferably 90% or less.

A matting agent can be used in the recording medium of the present invention. A conventionally known matting agent can be used. Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfate, calcium carbonate, etc.), and silver halide grains which do not form an image ( Silver chloride, silver bromide, etc., and a small amount of iodine atoms may be contained as a halogen component) or glass. In addition, West German Patent 2,529,321, British Patent 760,
Nos. 775 and 1,260,772, U.S. Pat.
01,905, 2,192,241, 3,05
3,662, 3,062,649, 3,25
7,206, 3,322,555, 3,35
No. 3,958, No. 3,370,951, No. 3,41
1,907, 3,437,484, 3,52
No. 3,022, No. 3,615,554, No. 3,63
5,714, 3,769,020, 4,02
Inorganic matting agents described in JP-A Nos. 1,245 and 4,029,504 can also be used.

Examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose, etc.), and synthetic resin. Examples of synthetic resins are water-insoluble or poorly soluble synthetic polymers, such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycysilyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), Acrylonitrile, olefins (eg, ethylene, etc.), styrene, benzoguanamine, formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl ( A polymer having a monomer component of a combination of (meth) acrylate, styrene sulfonic acid and the like can be used. In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole, polyvinylidene chloride, and the like can also be used. In addition, British Patent Nos. 1,055,713, U.S. Pat. Nos. 1,939,213 and 2,221,873
No. 2,268,662 and 2,322,037
No. 2,376,005, 2,391,181
Nos. 2,701,245 and 2,992,101
No. 3,079,257 and 3,262,782
No. 3,443,946, No. 3,516,832
Nos. 3,539,344 and 3,591,379
Nos. 3,754,924 and 3,767,448
And JP-A-49-106821 and 57-14835.
And the like.

Among them, polymethyl methacrylate, benzoguanamine / formaldehyde condensed polymer (for example, trade name Eposter; manufactured by Nippon Shokubai Chemical Co., Ltd .: existing chemical substance 7-31, etc.), polyolefin (for example, flow beads LE-1080, trade name) CL-2080, HE-
5023; manufactured by Iron and Steel Chemical or trade name Chemipearl V-1
00; Mitsui Petrochemical), polystyrene beads (Moltex), nylon beads (Mortex),
AS resin beads (manufactured by Mortex), epoxy resin beads (manufactured by Mortec), polycarbonate resins (manufactured by Mortec) and the like are preferable. JP-A-53-7231 and JP-A-58-66937 as alkali-soluble matting agents,
Alkali-soluble matting agents such as an alkyl methacrylate / methacrylic acid copolymer described in JP-A-60-8894 and an alkali-soluble polymer having an anionic group described in JP-A-58-166341 can also be used. These matting agents may be used in combination. For example, a combination of two or more kinds of fine particle powders having different Mohs hardness, a combination of two or more kinds of spherical matting agents having different average particle diameters, an amorphous matting agent such as silica for the mordant layer and a polymethyl methacrylate for the back layer. Such a spherical matting agent is used in combination.

The constituent layers (including the back layer) of the recording medium of the present invention contain silica, particularly colloidal silica, for the purpose of improving adhesion resistance, improving film strength, and improving curl balance. You may. The colloidal silica has an average particle diameter of 7 μm to 500 μm, the main component is silicon dioxide, and may contain alumina or sodium aluminate as a small component. In addition, these colloidal silicas may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide or an organic salt such as tetramethylammonium ion as a stabilizer. In particular, as a stabilizer for colloidal silica, colloidal silica comprising potassium hydroxide or ammonium hydroxide is preferable. These colloidal silicas are described, for example, in Egon, Matjevic, Ed., Surface and Colloid Science, Surface and Colloid Science.
Vol. 6, 3-1
Page 00 (1973, John Wiley & Sons). Specific examples of colloidal silica include DuPont [E. I. do point Nemou
rs & Co, (USA)] to Ludox AM,
Ludox AS, Ludox LS, Ludox T
M, Ludox HS, etc. under the trade name of Nissan Chemical Co., Ltd.
(Japan, Tokyo) from Snowtex 20, Snowtex C, Snowtex N, Snowtex O, etc., from Monsant Co, (USA)
nC-30, Syton 200, etc., and Nalco Chem, CO (USA)
oag 1030, Nalcoag 1060, Nal
Coag ID-21-64 and the like are commercially available. The preferred use amount of the colloidal silica is 0.05 to dry weight ratio based on the solid content of the constituent layer.
5.0, particularly preferably 0.2 to 2.5.

In the present invention, it is preferable to use a germicidal and antibacterial agent for the recording medium in order to prevent decay of the dispersion or coating solution of various chemicals. The antibacterial and antibacterial agent used in the present invention may be any water-soluble one,
Specifically, thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothianoic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, Alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds,
Various antibacterial agents and antibacterial agents such as cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, active halobene compounds such as chlorinated isocyanuric acid, sodium, chelating agents, sulfite compounds, and penicillins. There are fungicides. In addition, other L. E West (LE Wes)
t), Water Quality Criteria (Wat
er Quality Criteria) Photo.
Sci. and Eng., Vol 9, No. 6 (196
5) The disinfectant described in JP-A-57-8542 and JP-A-58-8542.
No. 105145, No. 59-126533, No. 55-1
Various antibacterial agents described in Nos. 11942 and 57-157244; antibacterial antibacterial agents described in Hiroshi Horiguchi, "Chemistry of antibacterial and fungicide" (published by Sankyo Publishing Co., Ltd. in 1982) can be used.

The hardener used in the recording medium of the present invention is not particularly limited, and known hardeners such as aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and aziridines (for example, PB Report 19) , 9
21, U.S. Pat. Nos. 2,950,197 and 2,96
No. 4,404, No. 2,983,611, No. 3,2
Nos. 71,175, JP-B-46-40898
And isoxazole-based compounds (for example, those described in U.S. Pat.
1,609), epoxy type (for example, U.S. Pat. No. 3,047,394, West German Patent 1,0).
No. 35,663, British Patent No. 1,033,518, JP-B-48-35495, vinyl sulfones (for example, 1,3,5-triacrylonitrile-hexahydro-s) -Triazine,
Bis (vinylsulfonyl) methyl ether, N, N-ethylene-bis (vinylsulfonylacetamide) ethane,
N, N′-trimethylene-bis (vinylsulfonylacetamide) and the like, for example, PB reports 19, 920,
West German Patent Nos. 1,100,942 and 2,337,41
2, 2,545,722, 2,635,518
Nos. 2,742,308 and 2,749,260
No., UK Patent No. 1,251,091, Japanese Patent Application No. 45-5
Nos. 4236 and 48-110996, U.S. Pat.
Nos. 539,644 and 3,490,911), acryloyl-based (for example, Japanese Patent Application No.
8-27949, U.S. Pat. No. 3,640,720), carbodiimide-based (for example,
U.S. Pat. Nos. 2,938,892 and 4,043,818
Nos. 4,061,499, JP-B-46-
No. 38715, Japanese Patent Application No. 49-15095, triazines (for example, 2,4-dichloro-6-).
Hydroxy-S-triazine and the like, and also, for example, German Patent Nos. 2,410,973 and 2,553,915
No. 3,325,287, those described in JP-A-52-12722), N-methylols (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3 -Dihydroxydioxane), mucohalic acid (mucochloric acid, mucophenoxycyclolic acid, etc.), dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, maleimide-based, acetylene-based, metasulfonate-based hardened Membrane agents can be used. Examples of the polymer hardener include polymers having an aldehyde group described in U.S. Pat. No. 3,396,029 (e.g., copolymers of acrolein);
Research Disclosure No. 17333 (197
8) and the like, a polymer having a dichlorotriazine group described in US Pat. No. 3,623,878, a polymer having an epoxy group described in US Pat. No. 3,623,878, Research Disclosure 1
6725 (1978), U.S. Pat. No. 4,161,40.
7, JP-A-54-65033 and JP-A-56-14252.
4, a polymer having an active vinyl group or a group which can be a precursor thereof, and JP-A-56-66.
No. 841 discloses a polymer having an active ester group. The addition amount of the hardener is optional, but usually, about 0.0% of the constituent materials capable of reacting with the hardener is used.
1 to 30 wt%, particularly 0.1 to 10 wt%, is suitable.

In the constituent layers of the recording medium, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, and preventing static charge. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-18345.
No. 7, etc. Further, an organic fluoro compound may be included for the above purpose. Representative examples of the organic fluoro compound include JP-B-57-9053, Nos. 8-17.
Column, JP-A-61-20994, 62-135826
And hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

In the constituent layers of the recording medium, a high-boiling organic solvent can be used for the purpose of coating aid, improving releasability, improving slipperiness and preventing static charge. Specifically, JP-A-62-2
No. 53159, pp. (25) and 62-245253. Further, for the above purpose,
Various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. JP-A-62-215953 and 63-46
No. 449 is also effective.

The constituent layers (including the back layer) of the recording medium may contain various polymer latexes for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. . Specifically, Japanese Patent Application Laid-Open No. Sho 62
-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass point transition (40 ° C. or less) is used for the mordant layer, the mordant layer can be prevented from cracking and curl can be improved, and if a polymer latex having a high glass transition point is used for the back layer, An anti-curl effect is obtained.

In the constituent layers of the recording medium, an anti-fading agent may be used. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Antioxidants include, for example, chroman compounds, Craman compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Unexamined Patent Publication No.
The compound described in -159644 is also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), and benzophenone-based compounds (Japanese Unexamined Patent Publication No. 2784) and JP-A Nos. 54-48535 and 62-136641.
And the compounds described in JP-A-61-88256 and the like.
Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. As metal complexes, U.S. Pat. Nos. 4,241,155 and 4,245,018 Nos. 3 to
Column 36, column 4, 254, 195 columns 3 to 8, JP-A-62-174741, JP-A-61-88256 (27)
To (29), JP-A-63-199248, JP-A-1-7
5568 and 1-74272.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). The anti-fading agent for preventing fading of the dye formed on the recording medium may be contained in the recording medium in advance, or may be contained in ink or the like and supplied from the outside to the recording medium. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

The recording medium may use a fluorescent whitening agent. In particular, it is preferable that a fluorescent whitening agent is incorporated in the recording medium, or it is contained in ink or the like and supplied from outside to the recording medium. As an example, K.K. Weenkataram
an "The Chemistry of Synt
Hetic Dyes ”, Vol. V, Chapter 8, JP-A-61-1
And the compounds described in US Pat. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor.

In the present invention, the support for the recording medium is not particularly limited.
Synthetic polymers (films) are mentioned. Specifically, it is made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Synthetic paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper),
Metals, cloths, glasses and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, Japanese Patent Application Laid-Open No. 62-253159
The supports described in pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

In the present invention, a particularly preferred support is a paper or plastic support laminated on both sides with a polyolefin (for example, a homopolymer such as polyethylene, polystyrene, polyethylene terephthalate, or polybutene, or a copolymer of any combination thereof). However, a white pigment such as titanium oxide and zinc oxide, and a coloring dye such as cobalt blue, ultramarine blue and neodymium oxide are preferably contained in the polyolefin.

The thickness of the polyolefin layer is not particularly limited, but is preferably from 10 to 100 microns, particularly preferably from 15 to 50 microns, more preferably from 20 to 35 microns. The surface shape of the polyolefin can be any shape, such as a mirror surface, one with regular irregularities, one with irregular irregularities, etc., but the surface on which the constituent layers of the recording medium are applied is particularly a mirror surface. Is preferred. The surface of the polyolefin layer is subjected to a surface activation treatment such as a corona discharge treatment or a flame treatment, and if necessary, an undercoat layer is provided, and a constituent layer is applied thereon and used. There is no particular limitation on the white pigment that can be contained in the polyolefin on the coating surface side, but titanium oxide and zinc oxide are preferred, and anatase type titanium oxide is particularly preferred.
It is preferable to use it together with 0% or less of zinc oxide. The amount of the white pigment contained in the polyolefin is preferably 5% by weight or more, more preferably 10 to 50% by weight, and particularly preferably 15% to 30%.

The coloring pigment which can be contained in the surface-side polyolefin is not particularly limited.
300 ° C for cobalt blue, ultramarine, neodymium oxide, etc.
Those that can withstand the above coating temperatures are desirable.
The amount of the tinting pigment used is 0.1 to 3% by weight based on the white pigment. In order to control the surface reflection characteristics, the selection and the amount of the tinting pigment are particularly important. Even in pigments referred to as ultramarine blue, colors vary greatly depending on the manufacturer and the production number. Therefore, it is desirable to mix and use various pigments so as to obtain necessary surface reflection characteristics. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer is preferably designed to have an antistatic function and to have a surface resistivity of 10 ¹² Ω · cm or less.

The image forming method of the present invention can be used for all systems including the release and reception of dyes, including ink jet printing, sublimation type thermal transfer printing, and dye diffusion transfer printing. Among them, the effect of the present invention is greatly exerted when used for inkjet printing. There is no limitation on the type of inkjet printing, and the image forming method of the present invention can be used regardless of whether it is a continuous type or an on-demand type. The type of the ink jet head is not limited, and is preferably used for all printers including a piezo type, a bubble jet type, a thermal jet type, and a type using ultrasonic waves. Recent advances in ink-jet systems have been remarkable, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, a colorless method Many new methods, such as a method using transparent ink, have been proposed and put into practical use. The image forming method of the present invention is preferably used for any of these methods, but particularly has a high print speed,
In a printer that ejects a large amount of low-density ink to form an image close to a photograph, the improvement effect is remarkably exhibited.

[0093]

Embodiments of the present invention will be described below. In the examples, parts mean parts by weight. <Preparation of Ink-01> Dye 2-4 5 parts N-methylpyrrolidone 20 parts Diethylene glycol 20 parts Polyethylene glycol (PEG-300) 5 parts Water 50 parts The above composition mixture was heated and dissolved at 50 ° C, and the average pore size was adjusted to 0.
The mixture was filtered through an 8 μm microfilter to obtain 100 parts of the desired ink.

<Preparation of Recording Medium 101> Pulp Mixing Ratio L
BKP / NBSP = 6/4 high quality paper (density 1.053,
Polyethylene was laminated on both sides (thickness: 152 μm) at 300 ° C. by an extrusion coating method to form a reflective support. On the back surface, a mixture of titanium having a surface treatment as a white pigment in polyethylene having a density of 0.923 and ultramarine (blue mouth and red mouth) manufactured by Daiichi Kasei Co., Ltd. as a coloring pigment was used. The thickness of the front polyethylene was 36 μm, and the thickness of the back polyethylene was 27 μm. A sample 101 was prepared by coating the following coating layer on the above resin-coated support. The main purpose of addition of each compound is shown in parentheses, but the purpose of addition is not limited thereto.

First layer: alkali-treated gelatin 1.0 g / m ² compound UV-01 (fluorescent brightener) 0.03 g / m ² compound H-02 (hardener) 0.08 g / m ² metaboric acid Tetrahydrate salt (thickener) 0.10 g / m ² Compound W-04 (surfactant) 0.02 g / m ² Compound F-08 (preservative) 0.001 g / m ²

Second layer: Compound P-17 (polymer mordant) 5.0 g / m ² polyvinyl alcohol PVA405 (binder) manufactured by Kuraray Co., Ltd. 3.5 g / m ² Compound W-04 (surfactant) 0.06 g / M ²

Third layer: alkali-treated gelatin 0.3 g / m ² SG-6 (matting agent) manufactured by Soken Chemical Co., Ltd. 0.18 g / m ² Compound W-04 (surfactant) 0.02 g / m 2 ² Compound W-07 (surfactant) 0.02 g / m ² Compound F-08 (preservative) 0.002 g / m ²

[0098]

Embedded image

The dye 2-1 of the ink-01 was changed to 2-31, 2
Ink-2, ink-03, ink-04, and ink-05 were prepared in the same manner except that -32, 2-33, and 2-34 were used. Second layer compound P of recording medium 101
-17 to P-1, P-5, P-20, P-21 (P-2
Recording media 102, 103, 104, and 105 were prepared in the same manner except that (0, P-21 are described below).

[0100]

Embedded image

After the recording media 101 to 105 were applied, they were allowed to stand at room temperature for one week, cut into a postcard size of 14.5 cm in length and 10 cm in width, and using an ink jet printer PM-700C manufactured by Epson Corporation using ink-01 to 05 Was used to print a solid image.

The printed sample was obtained from Atlas C. I
Xenon light (85,000 lux) was irradiated for one week using a 65 weather meter. The image density before and after the irradiation with xenon light was measured using a reflection densitometer (X-Rite310TR), and the light fastness of the image was evaluated by determining the residual ratio of the dye. The residual dye ratio was determined according to the following equation. The results are shown in Table 1.

[0103]

[Table 1]

As described above, according to the present invention, an image having excellent light fastness can be obtained. In particular, with respect to an ink jet printer capable of obtaining image quality close to a photograph, the performance other than the image quality is compared with that of the photograph, and the excellent light fastness is a great invention result.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 7/04 C08J 7/04 H C09D 11/00 C09D 11/00

Claims (2)

[Claims] 1. A dye represented by the following general formula (1):
Including the dye of the general formula (2) and / or the dye of the general formula (3)
Using a black ink, on a support, at least the following general
Polymer containing 60 mol% or more of the unit represented by the formula (I)
Recording medium having at least one mordant layer containing a mordant
An image forming method for forming an image on a body. Embedded imageWhere R¹, R^TwoAre hydrogen, hydroxyl, and alkyl, respectively.
Group, aryl group, heterocyclic group, halogen atom, alkoxy
Si group, acylamino group, sulfamoyl group, sulfo group,
Represents a substituent selected from a carboxyl group. n is 1 or
Represents 2. A is a monovalent group selected from the following general formula:
Represent. Embedded imageWhere R^Three, R^Four, R^Five, R⁶Are hydrogen atoms and water, respectively.
Acid group, alkyl group, halogen atom, alkoxy group, acid
Amino group, carbamoyl group, arylazo group, sulfo
Group, represents a substituent selected from a carboxyl group, or
R^Three, R^Four, R ^Five, R⁶Of two adjacent groups
It may form a ring. The fused ring further has a substituent.
You may have. R⁷Represents an alkyl group, an aryl group,
Ruboxyl group, carbamoyl group, ester group, acyl group
Selected from mino group, cyano group, alkoxy group, hydroxyl group
Represents a substituent. R⁸, R⁹, R^Ten, R¹¹, R¹²Each
Hydrogen, alkyl, alkoxy, halogen
Displays the substituents selected from substituents, sulfo groups, and carboxyl groups.
You. When n is 1, B is monovalent selected from the following general formula:
Represents a group. Embedded imageIn the formula, X and Y are each a chloro atom, -NL¹L^Two, −
OL^ThreeRepresents L¹, L^Two, L^ThreeIs hydrogen atom, alkyl
Represents an aryl group or an aryl group. M is a hydrogen atom, ammo
Represents the metal or alkali metal. When n is 2, B
Represents a divalent group selected from the following general formula. And 2
Some azo dyes are the same but different.
May be. Embedded imageWhere L^Four, L^Five, L⁶Is a hydrogen atom or an alkyl group
Represents L^Five, L⁶Are bonded to each other to form a 5- or 6-membered ring
It may be formed. X has the same meaning as described above. Embedded imageWhere R^{twenty one}Is hydrogen atom, hydroxyl group, alkyl group, halogen
Atom, alkoxy group, amino group, acylamino group, sulf
Honylamino group, carbamoyl group, sulfamoyl group,
Selected from arylazo, sulfo, and carboxyl groups
Represents a substituent represented by^{twenty two}, R^{twenty three}, R^{twenty four}Are hydrogen sources
, An alkyl group, an alkoxy group, an aryloxy group,
Mino group, aryl group, alkylsulfonyl group, aryl
Sulfonyl group, nitro group, halogen atom, sulfo group,
Lists the substituents selected from ruboxyl and arylazo groups.
You. B and M have the same meanings as described above. m is an integer from 0 to 2
Represents a number. n represents 1 or 2. When n is 2, two
Certain naphthol azo dye moieties are the same but different
May be. In the general formula (2), the substituent R^{twenty one}, SO _Three
M and the arylazo group may be any of the 2- to 8-positions of naphthol.
The position may be replaced. Embedded imageIn the formula, M has the same meaning as described above. p is an integer from 1 to 4
And q represents an integer of 0 to 3. Embedded imageWhere R₁, R_Two, R_Three, And R_FourAre independent of each other
Represents a hydrogen atom or an alkyl group.
You may. L represents a divalent linking group. p is 0 or 1
Represent. 2. The image forming method according to claim 1, wherein an image of the ink is formed on a recording medium using an ink jet printer.