JP2000094826A - Ink jet recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording body which is free from printing bleeding, has excellent print gloss, has good image quality, has no stickiness, and has excellent ink drying properties. In an ink jet recording medium provided with an ink receiving layer on a sheet-like support, a cellulose derivative having at least (A) a methoxyl group and / or a hydroxypropoxyl group in the ink receiving layer, and (B) N-vinylpyrrolidone And / or a copolymer resin of N-vinylpyrrolidone and another polymerizable monomer, and (C) a cationic resin, and a mixture of (A), (B) and (C). A / B / C = 100/5 to 100/1 by weight
20. An ink jet recording material, which is 20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording medium, and more particularly, to an ink jet recording medium which is free from printing bleeding and stickiness, has good water resistance, has excellent printing gloss, and has good ink drying properties. It relates to an excellent ink jet recording medium.

[0002]

2. Description of the Related Art An ink-jet recording system in which an aqueous ink is ejected from a fine nozzle onto a recording medium to form an image,
Terminal printers, facsimile machines, plotters, form printing, etc., because there is little noise during recording, color printing is easy, high-speed recording is possible, and it is cheaper than other printing devices. Widely used in Until now, high-quality paper and ink-coated paper with a porous pigment applied to the surface have been used as inkjet recording paper, and many of these have a so-called matte tone with low surface gloss. However, with the rapid spread of ink-jet printers and higher image quality, ink-jet papers with high surface gloss and photographic image quality have been demanded. OHP
There is also an increasing demand for light-transmitting recording sheets for use as signs, signboards and show windows.

Therefore, in order to obtain a glossy or transparent sheet, an ink receiving layer made of a hydrophilic polymer resin such as a water-soluble cellulose derivative, polyvinyl alcohol or polyvinylpyrrolidone is provided on paper or a plastic film. (Japanese Patent Laid-Open No. 56-80)
No. 489, JP-A-61-63474, JP-A-61-193879, JP-A-63-237983.
JP-A-6-316146, JP-B 2-3-3
No. 4792). However, copolymer resins of polyvinylpyrrolidone or N-vinylpyrrolidone and other polymerizable monomers have problems such as stickiness on the sheet surface and poor ink drying property as the blending portion increases. Was. JP-A-61-63474 discloses that a protective layer made of a substance having a lower hydrophilicity than a copolymer of vinylpyrrolidone and vinyl acetate is provided on a receiving layer made of a copolymer of vinylpyrrolidone and vinyl acetate. Although it has been proposed, although such a receiving layer can suppress stickiness,
There is a drawback that printing blur occurs because the absorption speed is reduced. Further, a cellulose derivative having a hydroxyethyl group is inferior in ink absorbency and causes printing bleeding, so that a desired image quality cannot be obtained (Japanese Patent Application Laid-Open No. 61-0761).
No. 8687).

On the other hand, various performances are required for an ink jet recording sheet, one of which is water resistance. Specifically, it is required that even if water is applied to a recording portion of a character or an image, the ink is eluted and no bleeding occurs. In order to solve this problem, a cationic substance is contained in the recording layer provided in the sheet or on the sheet-like support,
Many techniques for imparting water resistance have been proposed. For example,
JP-A-53-49113 discloses an ink jet recording paper in which a water-soluble polymer is impregnated into a sheet containing a urea-formalin resin powder, and JP-A-55-53591 discloses a sheet containing a water-soluble metal salt. Japanese Patent Application Laid-Open No.
No. 9-20696 discloses that dimethyldiallylammonium chloride is used in combination.
Japanese Patent Application Laid-Open No. 59-146889, Japanese Patent Application Laid-Open No. 60-161188, and Japanese Patent Application Laid-Open No.
8, JP-A-7-149038, JP-A-9-1990
JP-A-104167 and JP-A-9-254529 describe that a dicyandiamide-based resin is used in combination, and JP-A-6-92012 describes that an addition polymer of a secondary amine and epihalohydrin is used in combination. .

It has been proposed to impart water resistance to the ink receiving layer containing a glossy cellulose derivative or polyvinylpyrrolidone as a main component by blending a cationic resin. However, as the amount of the cationic resin increases, there is a problem that the ink drying property at the time of printing is reduced, or the glossiness is reduced, so that it is necessary to limit the amount of the cationic resin. There (60
-96067, JP-A-61-293886, JP-A-63-160875, and JP-A-7-25
No. 7023). For example, JP-A-63-160875
In the publication, (A) 10 to 90% by weight of a cationic synthetic resin, (B) 1 to 30% by weight of a cellulose derivative, and (C) 20 to 100% by weight of partially saponified polyvinyl alcohol or vinyl acetate and other polymerization 80 to 0% by weight monomer
0 to 89% by weight of a partially or completely saponified copolymer resin and / or 0 to 89% by weight of a (D) homopolymer resin of N-vinylpyrrolidone or a copolymer resin with another polymerizable monomer (However, the sum of the components (C) and (D) is 9 to 89% by weight.)
A recording sheet is disclosed in which a composition mainly composed of a mixture of is coated on the surface of a support sheet and dried to provide a resin coating layer on the support. However, the glossiness was insufficient and the ink drying property was poor, which was not satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and provides an ink jet recording medium which is free from printing bleeding and stickiness, has excellent printing water resistance, and provides excellent image quality with glossiness. It is intended to provide.

[0007]

Means for Solving the Problems In an ink jet recording material having an ink receiving layer provided on a sheet-like support, the present inventors have provided at least (A) a methoxyl group and / or a hydroxypropoxyl group on the ink receiving layer. A cellulose derivative, (B) a homopolymerized resin of N-vinylpyrrolidone and / or a copolymerized resin of N-vinylpyrrolidone and another polymerizable monomer, and (C) a cationic resin. By limiting the number of blending portions, a recording medium which does not cause printing blur or stickiness and can obtain excellent image quality with glossiness was found, and the present invention was completed. Further, (A) is hydroxypropyl methylcellulose, (B) is an average molecular weight of 500,000 or less, and a copolymer resin of N-vinylpyrrolidone and another polymerizable monomer is a vinylpyrrolidone / vinyl acetate copolymer or a sheet-like resin. By using resin-coated paper as the support, the printing glossiness is improved, which is more preferable.

[0008] The present invention includes the following embodiments. [1] In an ink jet recording medium provided with an ink receiving layer on a sheet-like support, (A) a cellulose derivative having at least (A) a methoxyl group and / or a hydroxypropoxyl group in the ink receiving layer, and (B) N-vinylpyrrolidone A homopolymer resin and / or a copolymer resin of N-vinylpyrrolidone and another polymerizable monomer, and (C)
An ink jet recording material comprising a cationic resin, wherein the mixing ratio of (A), (B) and (C) is A / B / C = 100/5 to 100/1 to 20 by weight. [2] The ink jet recording material according to [1], wherein the cellulose derivative having a methoxyl group and / or a hydroxypropoxyl group is hydroxypropylmethylcellulose. [3] (B) A homopolymer resin of N-vinylpyrrolidone and / or a copolymer resin of N-vinylpyrrolidone and another polymerizable monomer has an average molecular weight of 5,000 to 500,000.
A homopolymerized resin of N-vinylpyrrolidone which is 0 and / or
Alternatively, the inkjet recording material according to [1] or [2], which is a copolymer resin of N-vinylpyrrolidone having an average molecular weight of 5,000 to 500,000 and another polymerizable monomer. [4] The ink jet recording material according to claim 1, 2 or 3, wherein the copolymer resin of N-vinylpyrrolidone and another polymerizable monomer is a vinylpyrrolidone / vinyl acetate copolymer. [5] The ink jet recording medium according to any one of claims 1 to 4, wherein the sheet-shaped support is a resin-coated paper.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The recording medium of the present invention comprises a sheet-like support and a receptor layer mainly composed of an ink-absorbing resin. The cellulose derivative of the component (A) used in the receiving layer has a methoxyl group and / or a hydroxypropoxyl group, such as methylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. These cellulose derivatives are excellent in glossiness and ink absorptivity and give recording without blurring and unevenness. In the present invention, it is particularly preferable to use hydroxypropyl methylcellulose having excellent image quality.

However, the receiving layer made of the specific (A) cellulose derivative described above may be formed after recording depending on the type of ink.
When the recording medium is moved to, for example, a low-temperature or high-humidity environment, a phenomenon that the recording partially whitens occurs. In the present invention, (B)
The whitening phenomenon can be prevented by adding a homopolymer resin of N-vinylpyrrolidone and / or a copolymer resin of N-vinylpyrrolidone and another polymerizable monomer. As the homopolymer resin of N-vinylpyrrolidone as the component (B) and / or the copolymer resin of N-vinylpyrrolidone and other polymerizable monomers, various commercially available resins can be used. From the viewpoint of good properties, preferred are a homopolymer of vinylpyrrolidone, a copolymer of vinylpyrrolidone and vinyl acetate, a copolymer of vinylpyrrolidone and a cationic monomer, and the like. Particularly, a copolymer of vinylpyrrolidone and vinyl acetate is preferred, and the monomer molar ratio thereof is preferably 20/80 to 70/30, and particularly 60/40 to 70/70, which is excellent in solubility in water.
30 is more preferred.

The molecular weight of the resin (B) is 50.
5,000 or less, preferably 5,000 to 500,00
0 is more preferred. If the molecular weight is less than 5,000, printing bleeding is likely to occur, and if it exceeds 500,000, (A)
Poor compatibility with the components may result in a decrease in print gloss. The amount of the homopolymer resin of N-vinylpyrrolidone and / or the copolymer resin of N-vinylpyrrolidone and another polymerizable monomer is 5 to 100 parts by weight of the component (A).
To 100 parts by weight, preferably 10 to 80 parts by weight. If the amount is less than 5 parts by weight, a satisfactory level in print gloss cannot be obtained. If the amount exceeds 100 parts by weight, (A)
The compatibility with the components deteriorates, and the gloss also decreases. In particular, when recording with an ink in which the coloring material is a dye, 10 to 40
Parts by weight are preferred.

The cationic resin as the component (C) is not particularly limited, but various resins which form an insoluble salt with a sulfone group, a carboxyl group and the like of an ink jet dye, secondary amine, tertiary amine Cationic resins containing amines, quaternary ammonium salts, and the like are included. The water resistance of the recording can be improved by the cationic resin.

As specific examples, polyethyleneimine, polyvinylpyridine, polyvinylamine, a polymer of monoallylamine hydrochloride, a polymer of diallylamine hydrochloride, a copolymer of monoallylamine hydrochloride-diallylamine hydrochloride, (meth) acrylamidoalkyl 4 Examples of such compounds include polymers of quaternary ammonium salts, polyalkylene polyamine / dicyandiamide condensates, secondary amine / epichlorohydrin addition polymers, and polyepoxyamines. Preferred is a cationic resin obtained by copolymerizing a polyalkylene polyamine and dicyandiamide, for example, because it has excellent water resistance and a high print density compared to other cationic resins. Is mentioned. Further, an allylamine diallylamine copolymer which is effective for improving printing moisture resistance, and an addition polymer of a secondary amine and epihalohydrin which are particularly effective for improving water resistance can also be used in combination.

The amount of the cationic resin is (A) component 10
1 to 20 parts by weight, preferably 1 to 0 parts by weight.
To 10 parts by weight. When the amount is less than 1 part by weight, sufficient water resistance cannot be obtained, and when the amount is more than 20 parts by weight, problems such as a decrease in print gloss and ink drying property occur. For the purpose of adjusting the gloss and transparency of the recording sheet, various inorganic or organic pigments or particles can be added. Examples of inorganic pigments include silica, clay, talc, calcium carbonate, aluminum silicate, zeolite, and alumina.Examples of organic pigments and particles include various plastic particles such as styrene resin, acrylic resin, and urethane resin, and cellulose fine particles. Examples include powder and starch particles. The amount of the pigment or particle is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the component (A). If it exceeds 20 parts by weight, glossiness and print density may be reduced, and a desired image quality may not be obtained.

In the coating composition constituting the ink receiving layer of the present invention, resin emulsions such as polyolefin resin, acrylic resin, polyester resin, polyurethane resin, vinyl acetate resin, etc. Latex can also be blended. In the coating composition constituting the ink receiving layer of the present invention, a dispersant, a crosslinking agent, a thickener, a defoamer, a wetting agent, a fluorescent dye, a colorant, an antistatic agent, a preservative, and an ultraviolet absorber And the like are appropriately added as necessary. Next, the sheet-like support used in the present invention is not particularly limited.
Papers such as medium paper, coated paper, art paper, cast coated paper, synthetic paper, white plastic film, transparent plastic film, translucent plastic film, resin-coated paper, and the like can be used. The thickness of the sheet-shaped support is not particularly limited, but is preferably 25 to 500 μm, more preferably 50 to 500 μm from the viewpoint of ease of handling and cost.
It is 300 μm. The support is preferably a laminated paper (resin-coated paper) obtained by coating a base paper with a thermoplastic resin composition or the like, a white plastic film, or the like.

In order to express gloss more effectively,
A substrate having a high barrier property with respect to the aqueous composition of the ink receiving layer is preferable, and a pigment such as titanium oxide or barium sulfate is blended, or polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyimide, poly made opaque by making it porous. A white plastic film such as acetate, polyethylene, polypropylene, and polystyrene, and a so-called resin-coated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene on a paper base are preferable. The most preferred support in terms of the balance between quality and cost is a base paper and a polyolefin resin-coated paper coated on at least one surface on which the ink receiving layer is provided. The thickness of the base paper is not particularly limited.
Preferably it is 500 μm. When the thickness is less than 30 μm, the rigidity of the ink jet recording sheet is low, and inconveniences such as a decrease in feel, texture, and opacity when the hand is held arise. On the other hand, if it is thicker than 500 μm, it becomes rigid and difficult to handle, which may cause a trouble in paper feed running in the printer. More preferred range 50 μm to 3
00 μm. Also not specifically limited to the weight of the base paper, but is preferably in the range of ^{30g / m 2 ~500g / m 2} .

The base paper is a pulp sheet composed mainly of wood pulp. As wood pulp, LBK
Chemical pulp such as P, NBKP, GP, PGW, RM
Various pulp such as mechanical pulp such as P, TMP, CTMP, CMP and CGP, and waste paper pulp such as DIP are exemplified. Furthermore, various conventionally known papermaking additives can be blended as needed. As papermaking additives,
Examples include various papermaking pigments, binders, sizing agents, fixing agents, retention agents, cationizing agents, dry paper strength agents, wet paper strength agents, pH adjusters, conductive agents, dyes, and the like. One or more kinds can be blended. As the paper machine, a known fourdrinier paper machine, a cylindrical paper machine, a twin wire paper machine, or the like can be used. Further, any of acidic, neutral and alkaline papermaking may be used. The base paper may be subjected to a tab size or size press with starch or polyvinyl alcohol, or a surface smoothness treatment such as a machine calender, a heat calender, a soft calender, or a super calender, following the paper making.

The polyolefin resin coating layer is formed by melt-coating a resin composition containing a polyolefin resin as a main component and, if necessary, a white pigment and various additives. Examples of the polyolefin resin include homopolymers and copolymers such as ethylene and propylene.
Species or a mixture of two or more can be used.
Among them, low density polyethylene, medium density polyethylene,
High-density polyethylene, linear low-density polyethylene, and polypropylene are easy to process and easily available, so they can be suitably used. Although the physical properties of the polyolefin resin are not particularly limited, the molecular weight is preferably 20,0 due to suitability for processing and curl.
00-200,000, density 0.915-0.950
g / m ³ and the melt index are preferably in the range of 2 to 40 g / 10 min (JIS K-6760).
Further, a white pigment and various additives can be blended in the polyolefin resin coating layer. Above all, it is preferable to mix a white pigment in the polyolefin resin coating layer on the front side in order to increase whiteness and opacity.

Examples of the white pigment include anatase-type white titanium, rutile-type titanium dioxide, zinc oxide, calcium carbonate, talc and the like, and one kind or a mixture of two kinds can be used. The amount of the white pigment is 0.1 to 30 parts by weight based on 100 parts by weight of the polyolefin resin.
If the amount is less than 0.1 part by weight, the effect of increasing whiteness and opacity is small, and if it exceeds 30 parts by weight, dispersion in an olefin resin becomes difficult. The preferred range is 1 to 15 parts by weight. From the viewpoint of whiteness and opacity, anatase-type white titanium and rutile-type titanium dioxide are preferable.

In addition to white pigments, additives such as colored pigments, dyes, optical brighteners, antioxidants, plasticizers, and dispersants can be added as appropriate. Mixing of polyolefin resin and white pigments and additives, extruder for kneading,
This is performed using a heating roll kneader, a Banbury mixer, a pressure kneader, or the like. The polyolefin resin coating layer is formed by a melt extrusion coating method. That is, the polyolefin resin composition is cast on a running base paper from a slit die into a film by using a melt extruder and coated. At that time, the temperature of the molten film varies depending on the type of the resin, but is generally from 200C to 350C. As the slit die, a flat die is preferable for a T-type die, an L-type die, and a fish-type die, and the opening diameter of the slit is desirably 0.1 to 2 mm. Further, in order to obtain the desired center line surface roughness of the present invention, it is preferable to use a cooling roll having a highly smooth surface such as a mirror-finished surface as a cooling roll for cooling the molten resin film on the front side. Further, as the cooling roll for cooling the molten resin film on the back side, a cooling roll similar to the surface or having a roughened surface may be used. Alternatively, a polyolefin resin coating layer can be provided also on the surface on the opposite side of the surface on which the ink receiving layer is provided, from the curl property of the ink jet recording sheet. The coating amount of the polyolefin resin coating layer, with each of the front and rear surfaces of the base member, a ^{5g / m 2 ~50g / m 2} . 5g / m
^If it is less than ² , the desired gloss cannot be obtained or the adhesion to the base paper is insufficient. On the other hand, if it exceeds 50 g / m ² , the sheet-like support becomes thick, and disadvantages such as unnecessarily raising the cost arise. The preferred range is 10 g /
a m ² ~30g / m ^2. The ink receiving layer and the back layer of the present invention can be applied directly on the sheet-like substrate, but for the purpose of improving the adhesion with the sheet-like substrate,
A surface activation treatment such as a corona discharge treatment or a flame treatment may be performed, or an undercoat layer may be provided. Also,
By adjusting the surface roughness of the base paper or the roughness of the resin coating layer, it is possible to impart a semi-gloss texture.

The coating composition for an ink receiving layer composed of the above-mentioned materials can be coated on a sheet-like support by, for example, a bar coater, a blade coater, or the like by various known coating methods.
Coating and drying are performed by various publicly known coating devices such as an air knife coater, a roll coater, a gravure coater, a curtain coater, and a die coater. The coating amount is ² to 50 g / m ² , preferably 5 to 30 g / m ² in dry weight. When the amount is less than 2 g / m ² , the ink absorption tends to be insufficient, and the ink tends to bleed or dry slowly. If it exceeds 50 g / m ² , the obtained effect is not only saturated, but also disadvantages such as a disadvantage in cost and a strong curl are caused. The glossiness of the printed portion of the ink jet recording medium thus obtained (JIS-P814
2: 75 ° gloss) is 7 depending on the printer and ink.
It is preferably at least 0%, more preferably at least 85%. Further, in order to suppress the occurrence of curling, a curl preventing layer may be provided on the side of the substrate opposite to the surface on which the ink receiving layer is provided. The curl prevention layer in this case is not particularly limited, but it is considered that curl occurs due to the absorption and release of moisture of the ink receiving layer due to a change in humidity. Therefore, it is effective to use a material having a composition similar to that of the ink receiving layer. It is.

[0022]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted thereto.
In addition, parts,% and viscosity in Examples are parts by weight and% by weight, respectively, unless otherwise specified. Example 1 Softwood bleached kraft pulp (NBKP) beaten to 250 ml by CSF (JIS P-8121) and bleached kraft pulp (LB) beaten to 280 ml by CSF
KP) at a weight ratio of 2: 8 and a concentration of 0.5
% Pulp slurry was prepared. To this pulp slurry, 2.0% of cationized starch, 0.4% of alkyl ketene dimer, 0.1% of anionized polyacrylamide resin, and 0.7% of polyamide polyamine epichlorohydrin resin were added based on the absolute dry weight of the pulp. To disperse. The pulp slurry having the above composition was paper-made by a fourdrinier machine and passed through a drier, a size press, and a machine calender to produce base paper having a basis weight of 128 g / m ² and a tightness of 1.0 g / m ³ . The size press liquid used in the size press step was prepared by mixing carboxyl-modified polyvinyl alcohol and sodium chloride at a weight ratio of 2: 1, adding the mixture to water, and heating and dissolving to a concentration of 5%. This was applied to both sides of the paper in an amount of 25 cc.

After subjecting both sides of the base paper to corona discharge treatment, the following polyolefin resin composition 1 mixed and dispersed with a Banbury mixer was applied to the felt side of the base paper so that the coating amount was 25 g / m ^2. Then, the polyolefin resin composition 2 (resin composition for the back side) is applied to the wire side by a melt extruder (melting temperature of 320 ° C.) having a T-type die so that the coating amount is 25 g / m ^2. Then, the surface was cooled and solidified by a cooling roll having a mirror surface to produce a sheet-like support. The antioxidant in the polyolefin resin composition 1 prevents the polyethylene from being oxidized in the melt extrusion step, and the ultramarine blue and the fluorescent whitening agent have a bluish and apparent whiteness in the polyolefin resin-containing layer. To improve the visual feeling.

(Polyolefin resin composition 1) Long chain type low
Density polyethylene resin (density 0.926g / m^Three, Mel
Index 20 g / 10 min) 35 parts by weight, low density
Polyethylene resin (density 0.919g / m ^Three, Melt-in
Dex 2 g / 10 min) 50 parts by weight, anatase type diacid
15 parts by weight of titanium oxide (A-220; manufactured by Ishihara Sangyo)
0.1 parts by weight of zinc phosphate, antioxidant (Irgano
x1010; Ciba-Geigy) 0.03 parts by weight, ultramarine
(Blue mouth ultramarine No. 2000; manufactured by Daiichi Kasei) 0.09 weight
Part, optical brightener (UVITEX OB; Ciba-Geigy)
0.3 parts by weight (polyolefin resin composition 2) high-density polyethylene
Fat (density 0.954g / m^Three, Melt index 20
g / 10 minutes) 65 parts by weight, low density polyethylene resin (dense
Degree 0.924g / m^Three, Melt index 4g / 10
Min.) 35 parts by weight.
On the side where the composition 1 was provided, the following coating liquid for an ink receiving layer was
15 g / m dry weight^Two With a die coater
Coated and dried. (Coating solution for ink receiving layer) (A) Hydroxypropyl methylcellulose (Metro
60SH15: 100 parts by weight, manufactured by Shin-Etsu Chemical Co., Ltd.
(B) Polyvinylpyrrolidone / vinyl acetate copolymer (P
VP / VA S-630, average molecular weight 45,000: I
SP) (30 parts by weight) and (C) as Amigen NF (Polyal)
Condensation product of kylene polyamine and dicyandiamide, Daiichi Kogyo
Pharmaceutical) 3 parts and PAA-D11 (allylamine di
Allylamine copolymer, manufactured by Nitto Bo) 2 parts, blocking
Amorphous silica (Fine Seal X-45:
1 part by weight, 12% paint concentration.

Example 2 In the coating liquid for an ink receiving layer of Example 1, (B) was replaced with polyvinylpyrrolidone (PVP K-30, average molecular weight 6).
000: ISP), white polyester film as base material (Crispar G2323, Toyobo, thickness 125)
μm) to obtain an ink jet recording material in the same manner as in Example 1. Example 3 In the same manner as in Example 1 except that in the coating liquid for an ink receiving layer of Example 1, (B) was changed to polyvinylpyrrolidone (PVP K-120, average molecular weight 1,200,000: manufactured by ISP). An ink jet recording medium was obtained.

Example 4 In the coating liquid for an ink receiving layer of Example 1, (B) was converted to an alkylated polyvinyl pyrrolidone (ANTARON P-9).
04, average molecular weight 66,000: manufactured by ISP) to obtain an ink jet recording material in the same manner as in Example 1. Example 5 An ink jet recording material was obtained in the same manner as in Example 1 except that in the coating liquid for an ink receiving layer of Example 1, (A) was changed to methylcellulose (MC25: manufactured by Shin-Etsu Chemical).

Example 6 An ink jet recording material was obtained in the same manner as in Example 1 except that the blending amount of (B) was changed to 7 parts by weight in the coating liquid for an ink receiving layer of Example 1. Example 7 An ink jet recording material was obtained in the same manner as in Example 1 except that the blending amount of (B) was changed to 85 parts by weight in the coating liquid for an ink receiving layer of Example 1. Example 8 In the coating liquid for an ink receiving layer of Example 1, the compounding part of (C) was 1.0 part by weight of Amigen NF and PAA-D110.
An ink jet recording material was obtained in the same manner as in Example 1 except that the amount was changed to 5 parts by weight.

Example 9 Ink jet was carried out in the same manner as in Example 1 except that in the coating liquid for the ink receiving layer of Example 1, (C) was changed to 12 parts by weight of Amigen NF and 6 parts by weight of PAA-D11. A recording was obtained. Example 10 Synthetic paper (trade name: YUPO FPG-110, Oji Oil) having the sheet-like support of Example 1 in a three-layer structure containing polypropylene and an inorganic pigment and having a central base material layer and paper-like layers on both front and back surfaces An ink-jet recording material was obtained in the same manner as in Example 1 except that the thickness was 110 μm.

Comparative Example 1 An ink jet recording medium was obtained in the same manner as in Example 1 except that the coating liquid for the ink receiving layer of Example 1 was changed from (A) to hydroxyethyl cellulose (SP200: manufactured by Daicel). Comparative Example 2 An ink jet recording material was obtained in the same manner as in Example 1 except that the blending amount of (B) was changed to 120 parts by weight in the coating liquid for an ink receiving layer of Example 1. Comparative Example 3 An ink jet recording material was obtained in the same manner as in Example 1 except that the blending part of (B) was changed to 2 parts by weight in the coating liquid for an ink receiving layer of Example 1.

Comparative Example 4 An ink jet recording material was obtained in the same manner as in Example 1 except that the blending amount of (C) was changed to 25 parts by weight in the ink receiving layer coating liquid of Example 1. Comparative Example 5 An ink jet recording material was obtained in the same manner as in Example 1 except that the amount of the amigen NF (C) was changed to 0.3 part by weight in the coating liquid for an ink receiving layer of Example 1.

Table 1 shows the evaluation results of the ink jet recording paper thus obtained. In addition, about the said evaluation, evaluation was performed by the following methods. (Suitable for inkjet recording) inkjet printer,
Printing was performed using NOVA JET PRO (GA ink, manufactured by ENCAD). [Print bleeding] The printing unevenness (shading unevenness) of the solid printing portion of each color was visually evaluated based on the following criteria. ：: Good level with almost no bleeding. Δ: Slight bleeding, but not practically problematic. ×: Bleeding is noticeable, which is a practically problematic level.

[Print Gloss] The glossiness at 75 ° of a green solid print portion was measured according to JIS-P8142. [Stackiness of Printed Section in High Humidity Atmosphere] The recording sheet after printing was allowed to stand for 24 hours in an atmosphere of 35 ° C. and 80% relative humidity, and evaluated by touching the printed section with a finger. ：: No sticky feeling. Δ: Somewhat sticky. ×: A level at which stickiness is strong and poses a problem in practical use. [Ink drying property] After a certain period of time after printing, the printed portion was rubbed with a finger to evaluate the drying condition of the ink. ：: Dried within 10 minutes after printing. Δ: Dried 10 to 30 minutes after printing. X: It did not dry 30 minutes after printing.

[Water resistance to printing] The printed portion was immersed in a water bath for 10 seconds, and the ink flow after air drying was visually evaluated according to the following criteria. A: No ink flow was observed or slight ink flow was observed, but the image was sufficiently maintained. ：: The ink flow is slightly observed, but does not cause a problem in practical use. Δ: Ink is flowing, but barely practical. X: A level at which practically a problem occurs in which ink almost flows.

[0034]

[Table 1]

As apparent from Table 1, (A) a cellulose derivative having a methoxyl group and / or a hydroxypropoxyl group, (B) a homopolymer resin of N-vinylpyrrolidone and / or N-vinylpyrrolidone and other It contains a copolymer resin with a polymerizable monomer and (C) a cationic resin, and the mixing ratio of (A), (B) and (C) is A / B by weight.
Example 1 where / C = 100/5 to 100/1 to 20
10 was a favorable result in all the evaluation items.
In particular, Example 1 in which (A) is hydroxypropylmethylcellulose and (B) uses vinylpyrrolidone / vinyl acetate copolymer is compared with Example 5 in which methylcellulose is used and Example 4 in which alkylated PVP is used. Was better. Example 2 in which the average molecular weight of (B) was less than 500,000 was also excellent in all evaluation items. As for the sheet-like support, Example 1 in which the receiving layer was the same and resin-coated paper was used was superior to Example 10 in which no resin-coated paper was used. On the other hand, in Comparative Example 1 using a cellulose derivative having no methoxyl group and / or hydroxypropoxyl group, printing bleeding was observed, whereas in Comparative Example 2 in which the blending amount of vinylpyrrolidone / vinyl acetate copolymer exceeded 100 parts by weight, glossiness was low. Stickiness, poor ink drying properties. Comparative Example 3 containing less than 5 parts by weight of the vinylpyrrolidone / vinyl acetate copolymer and Comparative Example 4 containing more than 20 parts by weight of the cationic resin are inferior in glossiness. Comparative Example 5 in which the content of the cationic resin is less than 1 part by weight
Were inferior in water resistance and were not practical levels.

[0036]

Industrial Applicability The present invention relates to an ink jet recording medium, in particular, an ink jet recording medium having no print bleeding or stickiness, having print water resistance and excellent print gloss, and having good image quality.

Claims (5)

[Claims] 1. An ink jet recording material comprising a sheet-like support provided with an ink receiving layer, wherein said ink receiving layer has at least (A) a cellulose derivative having a methoxyl group and / or a hydroxypropoxyl group, and (B) N-vinyl. A homopolymerized resin of pyrrolidone and / or a copolymerized resin of N-vinylpyrrolidone and another polymerizable monomer, and (C) a cationic resin, and (A), (B) or (C). A / B / C = 100/5 to 100/1 by weight
20. An ink jet recording material, which is 20. 2. The ink jet recording material according to claim 1, wherein the cellulose derivative (A) having a methoxyl group and / or a hydroxypropoxyl group is hydroxypropylmethylcellulose. (B) The average molecular weight of the homopolymer resin of N-vinylpyrrolidone and / or the copolymer resin of N-vinylpyrrolidone and another polymerizable monomer is 5,000 to 50.
A homopolymer resin of N-vinylpyrrolidone having an average molecular weight of 5,000 to 500,000
3. The ink jet recording material according to claim 1, which is a copolymer resin of N-vinylpyrrolidone, which is 0, and another polymerizable monomer. 4. The ink-jet recording material according to claim 1, wherein the copolymer resin of N-vinylpyrrolidone and another polymerizable monomer is a vinylpyrrolidone / vinyl acetate copolymer. 5. The ink jet recording medium according to claim 1, wherein the sheet support is resin-coated paper.