JP2002046349A - Recording medium and water-based recording ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording medium, a water-based ink and an ink jet recording method which are excellent in light resistance and resistance to gas and with which a recorded matter allowing to preserve for a long period of time can be provided. SOLUTION: In the recording medium including an ink accepting layer, a porous pigment and a binder, the ink accepting layer includes a benzotriazole- based compound represented by formula (I). The water-based recording ink includes a coloring material, water and 0.01 to 2 wt.% of the benzotriazole-based compound represented by formula (I), wherein R represents a hydrogen atom, sodium, potassium or amine and the amine may be either monovalent or bivalent or trivalent amine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, a water-based recording ink, and an ink-jet recording method which are excellent in light resistance and gas resistance and can provide recorded matter which can be stored for a long time.

[0002]

2. Description of the Related Art In recent years, the revolutionary progress of ink jet recording technology has resulted in high quality images output to a recording medium by ink jet recording, and high image quality comparable to silver halide photography. Can be output. However, the dye is a colorant which is used in the output of high-quality images, ultraviolet light, light or ozone such as visible light, NO X, _SO X, easily deteriorated by gas such as _H 2 _S, i.e., lightfastness And the gas resistance is poor. For this reason, the recorded matter inkjet-recorded using the ink containing the dye (dye ink) is inferior in light fastness and gas fastness, not to mention in an environment where strong light is applied, but also in a room or the like. Even in an environment where strong light hardly shines, there is a problem that the recorded image undergoes discoloration with time, that is, the storage stability is poor, and this point is still inferior to silver halide photography.

On the other hand, as a recording medium for ink jet recording, a so-called “swelling type” having an ink receiving layer containing a polymer such as polyvinyl alcohol as a main component, and a fine porous pigment such as amorphous silica and the like. There is a so-called “void type” (also referred to as an absorption type) having an ink receiving layer containing a binder as a main component, but a void type recording medium is superior in terms of ink absorption (quick drying). For this reason, in particular, the gap type recording medium is often used for outputting a high-quality image in which the amount of ejected ink is large. However, since the dye is buried in the polymer, the printed matter recorded by inkjet recording on the swelling-type recording medium using the dye ink discolors the dye due to air oxidation and the light deterioration of the dye mediated by air. (Determination of singlet oxygen by light and decomposition of dye by singlet oxygen) hardly causes discoloration and discoloration caused by deterioration of the dye mediated by air, whereas the dye ink is applied to a void-type recording medium. Since the ink-receiving layer has an infinite number of voids and has high contact with the outside air, the ink-recorded matter recorded using the ink jet recording is liable to cause deterioration of the dye mediated by air and to be easily discolored. Thus, the deterioration of the dye mediated by air is a problem peculiar to the void type recording medium.

[0004] As a method for improving the preservability (in-room preservability) of the recorded matter, a method is known in which a benzotriazole-based ultraviolet absorber is contained in ink or a recording medium. However, the benzotriazole-based ultraviolet absorber,
In order to exhibit the effect, it is necessary to add a large amount, and when the benzotriazole-based ultraviolet absorber is contained in the recording medium, the recording medium base becomes yellowish, and thus is not practical. .

Japanese Patent Application Laid-Open No. 9-1922 discloses a problem peculiar to a recording medium having an ink receiving layer containing gelatin as a main component (a swelling type recording medium). In order to solve the problem described above, the image tends to be spotted and the resolution of the image is reduced ”(see paragraph No. [0006] in the publication), the benzotriazole-based ultraviolet absorber is added to the ink receiving layer. Techniques for containing different benzotriazole-based compounds have been disclosed. However, there is still a technique for preventing `` air-mediated deterioration of the dye '' which is a problem peculiar to the gap type recording medium, and improving the preservability of a recorded matter obtained by using the gap type recording medium. Not provided.

Accordingly, it is an object of the present invention to provide a recorded matter which is excellent in light resistance and gas resistance and which can prevent deterioration of dyes mediated by air which is peculiar to a void type recording medium, particularly, a recorded image when stored indoors. An object of the present invention is to provide a recording medium and a water-based recording ink capable of providing a recorded matter which hardly causes discoloration and can be stored for a long period of time.

The inventors of the present invention have conducted various studies on a recording material in which characters and / or images have been formed with a dye ink on a void type recording medium. As a result, the ink receiving layer and / or the dye ink have a specific structure. By containing the benzotriazole-based compound, it is possible to prevent deterioration of the dye mediated by air peculiar to the void-type recording medium and to improve the storage stability (light fastness and gas fastness) of the recorded matter in the room. I learned that I can do it. In addition, in the ink jet recording method using a benzotriazole-based compound having such a specific structure, it has been found that by using a specific magenta dye as a coloring material, it is possible to obtain a recorded matter having more excellent light resistance.

[0008]

Means for Solving the Problems The present invention has been made based on the above findings. In a recording medium in which the ink receiving layer contains a porous pigment and a binder, the ink receiving layer has the following general formula (I) The present invention provides a recording medium containing a benzotriazole-based compound represented by the following formula:

[0009]

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Further, the present invention relates to an aqueous recording ink containing at least a coloring material and water, wherein
A benzotriazole compound represented by the formula:
The present invention provides an aqueous recording ink containing 1% by weight.

Further, the present invention provides an ink containing the dye represented by the following general formula (II) on the recording medium:
It is an object of the present invention to provide an ink jet recording method for forming characters and / or images, or an ink jet recording method in which droplets of the aqueous recording ink are ejected, and the droplets are attached to a recording medium to perform printing.

[0012]

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[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the recording medium of the present invention will be described in detail. The recording medium of the present invention is a so-called “void-type” recording medium in which the ink receiving layer contains a porous pigment and a binder, and the ink receiving layer further includes a benzol represented by the general formula (I). Contains a triazole compound.

In the general formula (I), R represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a substituted or unsubstituted methyl group and a substituted or unsubstituted ethyl group. R is particularly preferably a hydrogen atom.

In the general formula (I), X represents a hydrogen atom, sodium, potassium or amine. The amine may be any of primary, secondary, and tertiary. Specifically, examples of the primary amine include methylamine, ethylamine, and propylamine. Examples of the secondary amine include dimethylamine and Examples include diethylamine and N-methylethylamine, and examples of the tertiary amine include trimethylamine, triethylamine, N, N-dimethylethylamine, and N, N-diethylmethylamine. X is particularly preferably a hydrogen atom.

Preferred specific examples of the benzotriazole-based compound represented by the general formula (I) include, for example, benzotriazole, benzotriazole sodium salt,
One or more selected from the group consisting of 4-methylbenzotriazole, 4-methylbenzotriazole sodium salt and benzotriazoleamine salt. Among them, it is particularly preferable to use benzotriazole from the viewpoint of solubility.

The benzotriazole compound represented by the general formula (I) is used in the ink receiving layer in an amount of 0.01 to 5%.
% By weight, more preferably 0.1 to 3% by weight. Content is 0.01% by weight
If it is less than 1, there is no effect on light resistance and gas resistance, and there is a possibility that air-borne deterioration of the coloring material cannot be sufficiently prevented.
If the content exceeds 5% by weight, the ink absorbency may be reduced.

Examples of the porous pigment contained in the ink receiving layer include, for example, a silica type such as a precipitation method, a gel type and a gas phase method, as well as smectite clay, calcium carbonate,
Examples thereof include calcium sulfate, barium sulfate, titanium dioxide, kaolin, clay, talc, magnesium silicate, and calcium silicate, and one or more of these are used. Of these, the use of silica pigments in particular,
It is preferable in terms of high purity, price, and availability, and among the silica-based pigments, a precipitation method or gel type silica is particularly preferable.

The specific surface area of the porous pigment determined by BET is determined by the balance between image quality such as color development and resolution of characters and / or images formed on the ink receiving layer and storability. From the viewpoint of, preferably 100 to 500 m ² /
g, more preferably 200 to 400 m ² / g. B
If the specific surface area by ET is less than 100 m ² / g, the image density may be reduced. If it is more than 500 m ² / g, deterioration of the coloring material mediated by air cannot be sufficiently prevented, and the storage quality of the recorded matter is poor. There is a risk.

The average particle size of the porous pigment may be any range as long as it can be generally used as a pigment. 05 to 15 μm, more preferably 0.1 to 1
0 μm.

The content of the porous pigment is preferably 40 to 90% by weight in the ink receiving layer.
More preferably, it is from about 80% by weight. Content is 40
If the amount is less than 90% by weight, the ink absorbency may decrease. If the amount exceeds 90% by weight, the coating strength of the ink receiving layer may decrease.

As the binder contained in the ink receiving layer, any binder having binding ability and capable of increasing the strength of the ink receiving layer may be used. Examples thereof include polyvinyl alcohol, silanol-modified polyvinyl alcohol, and vinyl acetate. , Starch, cellulose derivatives such as carboxymethylcellulose, casein, gelatin, conjugated diene copolymer latex such as styrene-butadiene copolymer, vinyl copolymer latex such as ethylene-vinyl acetate copolymer, acrylic acid and methacrylic acid An acrylic copolymer latex such as an acid polymer may be used, and one or more of these may be used. In particular, it is preferable to use polyvinyl alcohol.

The content of the binder is preferably 5 to 60% by weight of the total amount of the porous pigment.
More preferably, it is 50 wt%. If the content is less than 5% by weight, the strength of the ink receiving layer may be reduced. If the content is more than 60% by weight, the absorbability of the ink or the adsorptivity of the coloring material may be reduced.

In the ink receiving layer of the recording medium of the present invention, if necessary, a dye fixing agent, a fluorescent whitening agent, a water-proofing agent, a fungicide, a preservative, a dispersant, a surfactant, a thickener may be used. ,
Additives such as a pH adjuster, an antifoaming agent and a water retention agent can be contained, and one or more of these are used.

The dye fixing agent that can be contained in the ink receiving layer includes, for example, cationic organic substances, polyvalent metal ions, and cationic surfactants. Examples of the cationic organic substance include low-molecular compounds such as primary to tertiary amine compounds, primary to tertiary amine salts, and quaternary ammonium salts, and primary to tertiary amino groups and primary to tertiary amines. Oligomer having base or quaternary ammonium base or polymer having these groups, and the like, specifically, diallyldimethylammonium chloride polymer, epihalohydrin-secondary amine copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethyl Ammonium chloride-acrylamide copolymer, diallylmethyl ammonium salt polymer, diallylamine hydrochloride-sulfur dioxide copolymer, dimethylmethylamine hydrochloride copolymer, polyallylamine, polyethyleneimine, polyethyleneimine 4
Quaternary ammonium salt compounds, (meth) acrylamidoalkylammonium salt polymers, ionicenes containing quaternary ammonium bases, and the like. Examples of the polyvalent metal ion include Al ³⁺ , Ca ²⁺ , and Mg ²⁺ .
Examples of the cationic surfactant include benzalkonium chloride. One or more of these are used, and it is particularly preferable to use a polymer having a quaternary ammonium base.

The content of the dye fixing agent is preferably 0.5 to 15% by weight in the ink receiving layer.
More preferably, it is 10 to 10% by weight. Content is 0.
If it is less than 5% by weight, there is no effect on improving the color development and water resistance of the recorded matter, and if it is more than 15% by weight, there is a possibility that high gloss (bronzing) may occur due to a decrease in ink absorbency or deposition of a coloring material. .

The substrate on which the ink receiving layer is provided is, for example, paper (including sized paper), resin-coated paper obtained by coating polyethylene, polypropylene, polyester or the like on paper, baryta paper, RC paper, or other photographic paper. Examples include a substrate, a thermoplastic resin film such as polyethylene terephthalate, polyethylene, and polypropylene, a synthetic paper, and a sheet-like material formed of synthetic fibers.

The basis weight of the substrate is 50 to 120 g / m ^2.
And more preferably 70 to 100 g / m ² . Further, the thickness of the base material is 100 to
240 μm, preferably 140 to 200 μm
Is more preferable.

The recording medium of the present invention is manufactured, for example, as follows. First, an aqueous coating solution containing the components described above (the benzotriazole-based compound represented by the general formula (I), a porous pigment, a binder, a dye fixing agent, and other various additives) is prepared. Then, the aqueous coating solution is
Known methods, for example, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, coated on the surface of the substrate by a size press method,
Drying is performed using a known drying means such as a hot air dryer or a far infrared dryer. Further, from the viewpoint of improving the surface strength and smoothness of the ink receiving layer, a calendering treatment or the like can be performed to such an extent that the ink absorbing ability is not reduced. In the recording medium of the present invention thus manufactured, the coating amount of the ink receiving layer is preferably 10 to 40 g / m ² , and more preferably ²⁰ to 30 g / m ² in terms of solid content. More preferred. If the coating amount is less than 10 g / m ² , there is no effect in terms of the coloring property of the dye as compared with the case where the ink receiving layer is not provided, and if it exceeds 40 g / m ² , powder dropping of the ink receiving layer occurs. There is a risk. Incidentally, the thickness of the ink receiving layer itself is preferably from 10 to 40 μm, and from 20 to 3 μm.
0 μm is more preferred.

The ink receiving layer has a porosity of 30 to 30.
It is preferably 80%, more preferably 40 to 70%. If the porosity is less than 30%, the quick drying property, absorption speed, absorption capacity, etc. of the ink may decrease,
If it exceeds 80%, the porous pigment may fall off, causing slip on the paper feed roll and clogging of the head. Examples of a method for setting the porosity of the ink receiving layer within the above range include the above-described calender treatment. The porosity of the ink receiving layer is described in J. Org. TAPPI No. 48-85
Measured according to

The ink used for recording characters and / or images on the recording medium of the present invention may be any ink used in a recording method such as an ink jet recording method. Is usually
An aqueous recording ink containing a coloring material such as a dye or a pigment and water. In the recorded matter on which characters and / or images are formed on the recording medium of the present invention using the aqueous recording ink, air is interposed by the action of the benzotriazole-based compound represented by the general formula (I). Since the deterioration of the color material is prevented, the color material is excellent in light resistance and gas resistance, and hardly causes discoloration and fading of the recorded image especially during indoor storage, and long-term storage is possible. In particular, a recorded matter on which a character and / or an image is formed by using an ink containing the dye represented by the general formula (II) (described later) in the recording medium of the present invention is particularly excellent in light resistance. . Further, since the recording medium of the present invention is a so-called void type recording medium, it has excellent ink absorbency (quick drying property) and can sufficiently cope with a large amount of ink ejection.

Next, the aqueous recording ink of the present invention will be described in detail. The water-based recording ink of the present invention is a water-based recording ink containing at least a coloring material and water, wherein the benzotriazole-based compound represented by the general formula (I) is used in an amount of 0.0.
The content is 1 to 2% by weight, preferably 0.1 to 1% by weight. When the content is less than 0.01% by weight, there is no effect on light resistance and gas resistance. When the content is more than 2% by weight, the flying characteristics of ink droplets may be changed or nozzles may be clogged.

The coloring material contained in the aqueous recording ink of the present invention includes dyes and pigments. It is preferable to use dyes from the viewpoint of high color density per unit weight and vivid color. As the dye, a water-soluble dye is preferable.Specifically, those which are classified into an acid dye, a direct dye, a mordant dye, a reactive dye, a soluble vat dye, a sulfur dye and an edible dye in a color index are exemplified. Can be The effect of the present invention of "providing a recorded matter excellent in gas fastness and light fastness" is particularly exhibited when a dye having essentially poor light fastness and gas fastness is used.

The aqueous recording ink of the present invention can provide a recorded matter having excellent light fastness and gas fastness by the action of the benzotriazole compound represented by the general formula (I). When the dye represented by the general formula (II) is used as the material, it is possible to provide a recorded matter having more excellent light resistance. The dye represented by the general formula (II) is a dye for magenta ink (magenta dye).

Preferred examples of the dye represented by the general formula (II) include the following dyes M-1 to M-10, and one or more of these dyes can be used.

[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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As the water (main solvent) contained in the aqueous recording ink of the present invention, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water can be used. In particular, it is preferable to use water that has been sterilized by ultraviolet irradiation, addition of hydrogen peroxide, or the like, in order to prevent generation of mold and bacteria and to enable long-term storage of the ink.

The aqueous recording ink of the present invention may contain, if necessary, a penetration enhancer, a surfactant, a wetting agent, a nozzle clogging inhibitor, a preservative / antifungal agent, a pH adjuster, a dissolution aid,
An antioxidant, a surface tension adjuster, a viscosity adjuster, a dielectric constant adjuster, an oxygen absorber and the like can be contained.
Species or two or more species are used.

As a recording medium on which characters and / or images are formed by the aqueous recording ink of the present invention, a recording medium in which the ink receiving layer contains a porous pigment and a binder,
A so-called “gap type” recording medium is preferable. Using the aqueous recording ink of the present invention, characters and / or
Alternatively, the recorded matter on which an image is formed has excellent light resistance and gas resistance, and can be stored for a long period of time.

The recording medium and the aqueous recording ink of the present invention are:
It is mainly used as recording paper or recording liquid in an ink jet recording method. The ink jet recording method may be any method as long as it is a method of discharging ink droplets and attaching the liquid droplets to a recording medium to perform printing, but an on-demand type ink jet recording method is particularly preferable. Examples of the on-demand type ink jet recording method include, for example,
A piezoelectric element recording method of performing recording by using a piezoelectric element disposed in a printer head, a thermal jet recording method of performing recording by using thermal energy by a heater or the like of a heating resistance element disposed in a printer head, and the like. However, according to the recording medium and the aqueous recording ink of the present invention, excellent effects are exhibited when recording is performed using any recording method.

The present invention can be variously modified without departing from the spirit thereof. For example, the ink receiving layer in the recording medium of the present invention may be provided on one side of the substrate, or may be provided on both sides. Further, the production of the recording medium of the present invention is carried out by a water-based coating method containing components (porous pigment, binder, dye fixing agent and other various additives) other than the benzotriazole-based compound represented by the general formula (I). A method of preparing a liquid, applying the aqueous coating liquid to a substrate, drying the substrate, and then immersing the substrate in an aqueous solution containing the benzotriazole-based compound represented by the general formula (I); Alternatively, the method can be carried out by applying the aqueous solution to the substrate by a size press method or spraying it with a spray or the like.

Further, the aqueous recording ink of the present invention contains the benzotriazole-based compound represented by the general formula (I) in the above-mentioned predetermined amount, and, if necessary, a coloring material of the general formula (II). Except for using the dye represented by the formula, the composition is the same as that of this type of ink, and other components that can be contained in the ink are not particularly limited.

[0052]

Examples of the present invention will be described below. Example 1,
Examples 2 and 6 are examples of the recording medium of the present invention, and Examples 3 to 5 are examples of the aqueous recording ink of the present invention. Comparative Examples 1 to 4 are comparative examples of a recording medium and an aqueous recording ink. However, it goes without saying that the present invention is not limited to such an embodiment.

Examples 1 and 6 A coating solution having the following composition was prepared. The obtained coating liquid is applied to a substrate (trade name “Lumirror 1”).
25T "(manufactured by Toray Industries, Inc.) using an air knife coater so that the coating amount after drying is 20 g / m ^2, and drying using a hot air dryer (140 ° C., 3 minutes) ) To provide a recording medium 1.

<Composition of coating liquid>-100 parts by weight of silica (trade name "Fine Seal X37B", manufactured by Tokuyama Corporation)-400 parts by weight of polyvinyl alcohol (10% aqueous solution) (trade name "Gosenal T-330") , Manufactured by Nippon Synthetic Chemical Co., Ltd.)-25 parts by weight of cationic polymer (trade name "Neofix RP-70", manufactured by Nika Chemical Co., Ltd.)-3 parts by weight of benzotriazole-600 parts by weight of water

Example 2 A recording medium 2 was manufactured in the same manner as in Example 1 except that 3 parts by weight of 4-methylbenzotriazole was used instead of 3 parts by weight of benzotriazole in the coating solution of Example 1. did.

Example 3 A three-color water-based recording ink having the following composition was prepared, and an ink set 1 including three-color water-based recording inks of cyan (C), magenta (M), and yellow (Y) was manufactured. did. The aqueous recording ink was prepared by mixing and dissolving the respective components, and performing pressure filtration with a membrane filter having a pore size of 1 μm.

<Composition of Cyan Ink> C.I. I. Direct Blue 199 3 parts by weight-Benzotriazole 1 part by weight-Triethylene glycol monobutyl ether 10 parts by weight-Diethylene glycol 10 parts by weight-Glycerin 10 parts by weight-Triethanolamine 1 part by weight-Disodium ethylenediaminetetraacetate 0.01 part by weight- Olfin E1010 1 part by weight ・ Proxel XL-2 0.3 part by weight ・ Ion exchange water 65 parts by weight

<Composition of Magenta Ink> C.I. I. Acid Red 52 1.5 parts by weight C.I. I. Acid Red 249 1.5 parts by weight-Benzotriazole 1 part by weight-Triethylene glycol monobutyl ether 10 parts by weight-Diethylene glycol 10 parts by weight-Glycerin 10 parts by weight-Triethanolamine 1 part by weight-Disodium ethylenediaminetetraacetate 0.01 part by weight Parts 1 part by weight of Olphin E1010 0.3 parts by weight of Proxel XL-2 65 parts by weight of ion-exchanged water

<Composition of Yellow Ink> C.I. I. Acid Yellow 32 2 parts by weight-Benzotriazole 1 part by weight-Triethylene glycol monobutyl ether 10 parts by weight-Diethylene glycol 10 parts by weight-Glycerin 10 parts by weight-Triethanolamine 1 part by weight-Disodium ethylenediaminetetraacetate 0.01 part by weight- Olfin E1010 1 part by weight ・ Proxel XL-2 0.3 part by weight ・ Ion exchange water 65 parts by weight

Example 4 In place of benzotriazole in each ink in ink set 1 of Example 3, 4-
An ink set 2 provided with three color aqueous recording inks having the same composition as the ink set 1 except that methylbenzotriazole was used (at the same concentration as benzotriazole).

Example 5 Ink provided with three color aqueous recording inks having the same composition as ink set 1 except that magenta ink 2 having the following composition was used instead of magenta ink in ink set 1 of Example 3. Set 3 was manufactured.

<Composition of Magenta Ink 2> 4 parts by weight of the dye M-1 1 part by weight of benzotriazole 10 parts by weight of triethylene glycol monobutyl ether 10 parts by weight of diethylene glycol 10 parts by weight of glycerin 1 part by weight of triethanolamine Parts-Disodium ethylenediaminetetraacetate 0.01 parts by weight-Olphin E1010 1 part by weight-Proxel XL-2 0.3 parts by weight-Deionized water 65 parts by weight

Comparative Example 1 A recording medium 3 was manufactured in the same manner as in Example 1 except that benzotriazole was not used in the coating solution of Example 1. In addition, an ink set 4 was prepared which had the same composition as the ink set 1 except that the ink set 1 of Example 3 did not contain benzotriazole.

Comparative Example 2 An ink set 5 was prepared having the same composition as the ink set 3 except that the ink set 3 of Example 5 did not contain benzotriazole. .

[Comparative Example 3] Instead of the coating liquid of Example 1,
A recording medium 4 was manufactured in the same manner as in Example 1 except that a coating solution having the following composition was used.

<Composition of coating liquid>-100 parts by weight of silica (trade name "FINE SEAL X37B", manufactured by Tokuyama Corporation)-400 parts by weight of polyvinyl alcohol (10% aqueous solution) (trade name "Gosenal T-330")・ Nippon Synthetic Chemical Co., Ltd.) ・ Cation polymer 25 parts by weight (trade name “Neofix RP-70”, manufactured by Nika Chemical Industry Co., Ltd.) ・ Benzotriazole ultraviolet absorber (solid content 30%) 10 parts by weight (Product name “ADK STAB LX-301”, manufactured by Asahi Denka Kogyo Co., Ltd.) ・ Water 600 parts by weight

[Comparative Example 4] Instead of the coating liquid of Example 1,
A recording medium 5 was produced in the same manner as in Example 1 except that a coating solution having the following composition was applied so that the coating amount after drying was 10 g / m ² .

<Composition of coating liquid> ・ 70 parts by weight of lime-treated gelatin ・ 70 parts by weight of polyvinylpyrrolidone (trade name “PVP-90”, manufactured by BASF) ・ 25 parts by weight of cationic polymer (trade name “Neofix RP- 70, manufactured by Nichika Chemical Industry Co., Ltd.)-Benzotriazole 3 parts by weight-Surfactant 1 part by weight (trade name "Megafax F-120", manufactured by Dainippon Ink and Chemicals, Inc.)-Water 1800 weight Department

[Evaluation of Light Resistance, Indoor Storage Property and Ozone Resistance] Using an ink jet printer (trade name “MJ-930C”, manufactured by Seiko Epson Corporation) equipped with each of the ink sets 1 to 5, the following [ Table 1] shows the combinations of the ink set and the recording medium, and
Then, composite black and solid printing of each color of C, M, and Y were performed to produce recorded matter. This recorded matter was evaluated by the following [Method for evaluating light resistance], [Method for evaluating indoor storage stability] and [Method for evaluating ozone resistance]. The results are shown in Table 1 below. In addition, the printing method was prepared so that the composite black was composed of the aqueous recording inks of three colors of C, M and Y.

[Evaluation Method of Light Resistance] Using a Xenon weatherometer Ci35A (manufactured by Atlas Electric Devices Co., Ltd.), a temperature of 40 ° C., a relative humidity of 50% RH, a black panel temperature of 63 ° C. and an illuminance of 0.25 W / at 340 nm were obtained.
Under the condition of m ^2, the recording material was subjected to light irradiation treatment (light irradiation time: 50 hours). The optical density (OD) of each of the C, M, and Y color portions in the recorded matter before and after the light irradiation treatment was measured using a Gretag densitometer (manufactured by Gretag), and the optical density residual ratio (ROD) was calculated by the following equation. I asked. ROD (%) = (D / D ₀ ) × 100 D: OD D ₀ of the recorded matter after the light irradiation treatment: OD of the recorded matter before the light irradiation treatment The larger the numerical value of the ROD, the better the light resistance. .

[Evaluation Method of Room Storage Property] The recorded matter was stuck on a wall in a room (room temperature 24 ° C., relative humidity 60% RH).
Left for months. The color difference (ΔE ^* ab) of the Bk color portion immediately after printing of this recorded matter was determined (JIS Z).
8730). The smaller the value of ΔE ^* ab, the more
Shows excellent room storage stability.

[Evaluation criteria for ozone resistance]
Temperature 24 ° C, relative humidity 60% RH, ozone concentration 10pp
The ozone treatment was carried out by leaving the container for 120 minutes in a light-shielded tank maintained at m. Bk before ozone treatment of this recorded matter
The color difference (ΔE ^* ab) for the color portion was determined (JIS
Z 8730). The smaller the value of ΔE ^* ab, the better the ozone resistance.

[Evaluation of ink absorptivity] Using the above-mentioned ink jet printer, a combination of an ink set and a recording medium shown in the following [Table 1] was used to obtain cyan, magenta,
Printing was performed so that the reflection density of yellow was 2.0 or more, and immediately after printing, PPC paper was overlaid on the printing portion and lightly pressed. The degree of the amount of ink transferred to the PPC paper was visually observed and evaluated according to the following evaluation criteria. <Evaluation criteria> A: No transfer at all. Δ: Transfer slightly. ×: Transfer considerably.

[0074]

[Table 1]

As is clear from the results shown in Table 1, the recorded matter obtained by using the recording medium 1 or 2 containing the benzotriazole compound represented by the general formula (I) (Examples 1 and 2) And 6), and an ink set 1 including an aqueous recording ink containing the benzotriazole-based compound.
Recorded matter obtained using any one of Examples 3 (Examples 3 to 5)
Are recorded materials obtained using the recording media 3 to 5 containing no benzotriazole-based compound and the ink set 4 or 5 including an aqueous recording ink containing no benzotriazole-based compound (Comparative Examples 1 to 5). It turns out that it is excellent in light resistance, indoor storage stability and ozone resistance as compared with 4). The recorded matter of Comparative Example 3 was obtained by using the recording medium 4 containing a normal benzotriazole-based ultraviolet absorber, but was inferior in each of the above-described characteristics as compared with each recorded matter of Example. Thus, the effectiveness of the benzotriazole-based compound represented by the general formula (I) according to the present invention is clear. In the first place, the surface of the ink receiving layer of this recording medium 4 was slightly yellowish, so that it could not be used practically. Further, solid printing of magenta in the recorded matter of Examples 5 and 6 obtained using the ink set 3 or 5 provided with the magenta ink containing the dye (M-1) represented by the general formula (II) It can be seen that the portion has better light fastness than the solid printed portion of magenta in other recorded materials. Further, since the recorded matter of Comparative Example 4 was obtained by using the so-called swelling type recording medium 5, the ink absorbing property was higher than that of the void type recorded matter of the Examples and other Comparative Examples. The result was inferior.

[0076]

According to the recording medium, the aqueous recording ink and the ink jet recording method of the present invention, a recorded matter having excellent light fastness and gas fastness, in particular, almost no discoloration and fading of the recorded image during indoor storage, A recorded matter that can be stored for a long time can be provided. Further, the recording medium and the aqueous recording ink of the present invention are particularly suitably used for an ink jet recording method. In particular, the recording medium of the present invention is excellent in ink absorbency, and thus is optimal for outputting a high-quality image in which the amount of ejected ink is large.

Continued on the front page (72) Inventor Hiroko Hayashi 3-3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Corporation (72) Inventor Miharu Kanaya 3-3-5 Yamato Suwa City, Nagano Prefecture Seiko Epson Corporation F-term (reference) 2C056 FC01 FC06 2H086 BA01 BA15 BA19 BA33 BA35 BA38 BA53 BA56 BA59 BA62 4J039 AB01 AB07 AD06 AD08 AD09 AD15 BA21 BC52 BC69 BC72 BC73 BC79 BE01 BE02 BE24 CA03 CA06 EA35 EA44 GA24

Claims (13)

[Claims] 1. A recording medium in which the ink receiving layer contains a porous pigment and a binder, wherein the ink receiving layer contains a benzotriazole-based compound represented by the following general formula (I). Embedded image 2. The benzotriazole compound represented by the general formula (I) is a group consisting of benzotriazole, benzotriazole sodium salt, 4-methylbenzotriazole, 4-methylbenzotriazole sodium salt and benzotriazoleamine salt. 2. The recording medium according to claim 1, wherein the recording medium is at least one member selected from the group consisting of: 3. The ink-receiving layer according to claim 1, wherein the benzotriazole-based compound represented by the general formula (I)
3. The recording medium according to claim 1, which contains 5% by weight. 4. The recording medium according to claim 1, wherein the porous pigment is a silica pigment. 5. The recording medium according to claim 1, which is used in an ink jet recording method. 6. An aqueous recording ink containing at least 0.01 to 2% by weight of a benzotriazole compound represented by the general formula (I) in an aqueous recording ink containing at least a coloring material and water. 7. The benzotriazole compound represented by the general formula (I) is a group consisting of benzotriazole, benzotriazole sodium salt, 4-methylbenzotriazole, 4-methylbenzotriazole sodium salt and benzotriazoleamine salt. The aqueous recording ink according to claim 6, which is one or more kinds selected from the group consisting of: 8. The color material according to claim 6, wherein the color material is a dye.
The aqueous recording ink as described in the above. 9. The aqueous recording ink according to claim 8, wherein the dye is a dye represented by the following general formula (II). Embedded image 10. The aqueous recording ink according to claim 6, which is used in an ink jet recording method. 11. The aqueous recording ink according to claim 6, wherein the ink receiving layer is used when forming characters and / or images on a recording medium containing a porous pigment and a binder. 12. An ink jet recording method for forming a character and / or an image on the recording medium according to claim 1 with an ink containing the dye represented by the general formula (II). 13. An ink jet recording method for discharging a droplet of the aqueous recording ink according to claim 6 and attaching the droplet to a recording medium to perform printing.