KR20060007729A - Recording Media for Inkjet Printers - Google Patents

Abstract

The present invention provides a recording medium for an inkjet printer which is excellent in water absorption and moisture resistance as well as ink absorption amount and ink absorption speed.

The present invention and the base layer; And an ink receiving layer coated on one surface of the base layer, wherein the ink receiving layer is made of a zirconium compound containing an inorganic filler, a hydrophilic resin, a styrene-maleimide copolymer, and a halogen element. To provide.

Ink receiving layer, styrene, maleimide, zirconium, halogen

Description

Recording medium for ink jet printers {Recording medium for ink jet printers}

1 is a cross-sectional view showing an embodiment of an inkjet recording medium according to the present invention.

<Brief description of the major symbols in the drawings>

1 ... substrate layer

2. Ink receiving layer

3 ... undercoat layer

4 ... protective layer

5. Back coating layer

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, and more particularly, to a recording medium for an inkjet printer including an ink receiving layer coated on one surface of a substrate layer.

Inkjet printers are widely used due to their high output speed, low printer cost, and the ability to provide high resolution images.

In inkjet printers, various recording media such as general paper, specially coated special paper, and special film are used. In general, a recording medium for an inkjet printer has a hydrophobic base layer made of cellulose acetate or a polyester such as polyethylene terephthalate and a hydrophilic material coated on one surface of the hydrophobic base layer so that the ink can be easily fixed to the recording medium. It consists of an ink receiving layer.

Such recording media for inkjet printers are applied to the printing of digital photographs or images through inkjet printers, such as thermal, piezo or face change, which are used as presentation tools via overhead projectors, It is used in the advertising field.

In recent years, recording by inkjet printers has rapidly improved the picture quality, and thus records that are equivalent to silver chloride photographs, which are the ultimate goals of hard copying, can be obtained.

U.S. Patent No. 5,866,268, Japanese Patent Laid-Open No. 55-144,172, and Japanese Patent Laid-Open No. 62-268,682 use a hydrophilic resin such as cellulose derivative, polyvinyl alcohol, etc. as a binder to improve the absorption rate and absorption capacity of ink. Although a medium is disclosed, problems such as blurring of an image are pointed out because the recording medium in the patent is weak in water resistance.

Japanese Patent Laid-Open No. 59-198,186 and Japanese Patent Laid-Open No. 56-84,992 disclose a recording medium having a coating layer containing an organic acid salt of polyethyleneimine. In the above patent, the water resistance of the recording medium is improved, but there is a problem that yellowing due to ultraviolet rays occurs due to deterioration of heat resistance and light resistance.                         

In recent years, attention has been paid to the alumina capable of forming a high gloss image and an excellent ability to fix dyes in ink as a recording medium as compared with conventional recording media. U.S. Patent No. 4,879,166, U.S. Patent 5,104,730, and Japanese Patent Laid-Open No. 2-276,670, Japanese Patent Laid-Open No. 4-37,576, and Japanese Patent Application Laid-open No. 5-32,037 include records containing alumina hydrates having boehmite structures. Disclosed about the medium.

In addition, it is already known to use a compound containing zirconium atoms in an inkjet recording paper. Japanese Patent Laid-Open No. 55-53,591, Japanese Patent Laid-Open No. 55-150,396, Japanese Patent Laid-Open No. 56-867,789, Japanese Patent Laid-Open No. 58-89,391 and Japanese Patent Laid-Open No. 58-94,491 in combination with a water-soluble dye An ink jet recording paper comprising a polyvalent metal salt forming a poorly soluble salt is described. In addition, Japanese Patent Laid-Open No. 60-67,190, Japanese Patent Laid-Open No. 61-10,584, and Japanese Patent Laid-Open No. 61-57,379 describe an inkjet recording paper to which a cationic polymer and a water-soluble polyvalent metal salt are added. Japanese Patent Laid-Open No. 4-7,189 discloses a method using a porous pigment and an acid zirconium chloride compound. EP 754,560 discloses a patent using a water-soluble binder, a pigment, a zirconium compound and a cationic polymer in combination.

However, in the prior art, although dye fixation and short-term water resistance have been improved a lot, there is a problem in that long-term water resistance is insufficient, and in particular, moisture resistance at a high temperature is deteriorated in some cases.

The technical problem to be solved by the present invention is to solve the above problems and to provide a recording medium for an ink jet printer, which has improved not only moisture resistance at high temperature but also long term water resistance and ink absorption.

In order to achieve the above technical problem, in the present invention, the base layer; And an ink receiving layer coated on one surface of the base layer, wherein the ink receiving layer comprises an inorganic filler, a hydrophilic resin, a styrene-maleimide copolymer, and a zirconium compound. To provide.

The base layer may be a transparent or translucent film selected from polyester-based, polycarbonate-based, cellulose-acetate-based or polyethylene-based films, paper coated with one or two sides of polyethylene or polypropylene, single-sided or double-sided art paper, cast coated paper, It may be one selected from the group consisting of synthetic paper, photo paper and baryta paper.

The inorganic filler may be calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, aluminum silicate, silicate, sodium silicate, magnesium silicate, calcium silicate, silica and alumina. More preferably, at least one selected from alumina represented by Formula 1 may be used.

<Formula 1>

_{Al 2 O 3-p (OH} ) 2p · qH 2 O

In said formula, p is an integer of 3 or less, q is a rational number of quantity of 10 or less, More preferably, it is a rational number of quantity of 5 or less.

Since such alumina has a positive charge on its own, there is an advantage that the dye in the ink is well fixed to the ink receiving layer, and at the same time, the transparency is high, the printing density is high, and the color is good. In addition, since the porous layer is formed, the ink absorption of the ink receiving layer is improved, and the binder-based resin type has a weak water resistance using a hydrophilic polymer, whereas the porous method using the alumina is mainly a pigment-based method as in the present invention. Since the ink receiving layer is formed, the water resistance is also excellent, and surface characteristics such as a phenomenon of eliminating the sticking phenomenon between the films that may occur when the binder is used alone can be controlled.

Here, the inorganic filler preferably has 50 to 95% by weight relative to the total solids in the ink-receiving layer-forming composition.

However, recording media that form a porous ink-receiving layer mainly using pigments, such as alumina, are generally excellent in water resistance, but are also poor in immersion in water for a long time or under high temperature and high humidity.

Accordingly, it is preferable to include a copolymer of styrene-maleimide to not only improve water resistance but also improve moisture resistance under high temperature and high humidity.

Furthermore, the copolymer of styrene-maleimide is preferably a compound consisting of styrene and maleimide having a tertiary amine group.

Generally, dyes used in color inks for inkjet printers are direct dyes or acidic dyes, which have anionic carboxyl groups or sulfonic acid groups in the dye molecules themselves, and thus cationic salt forms and ionic bonds of the copolymers of styrene-maleimide. It is fixed through the film, and the water resistance and fixability of the image formed by the dye are improved.

Here, the copolymer of styrene-maleimide preferably has 0.5 to 20% by weight based on the total solids in the ink-receiving layer-forming composition.

On the other hand, it is preferable to include a zirconium compound in order to further improve the water resistance of the recording medium and the moisture resistance under high temperature and high humidity. Even more preferably, the zirconium compound is a zirconium compound containing a halogen element.

As a result, the zirconium compound not only acts as a crosslinking agent but also has a dye-fixing ability of zirconium as a polyvalent metal, thereby acting as a dye fixing agent such as a copolymer of styrene-maleimide, thereby providing a synergistic effect. Acidic zirconium compounds convert the copolymer of styrene-maleimide into the form of a cationic ammonium salt to render the copolymer of styrene-maleimide water soluble. As a result, the copolymer of styrene-maleimide and the zirconium compound may serve to improve the water resistance and moisture resistance of the coating layer by synergistic effects of structurally stable crosslinking and other forms of dye fixation. In general, if the water resistance is increased too much only through crosslinking, the ink absorbency is lowered or the moisture resistance is weakened. However, the method according to the above does not degrade the moisture resistance.

Here, the zirconium compound preferably has 0.05 to 20% by weight relative to the total solids in the ink-receiving layer-forming composition.                     

The hydrophilic resin may be at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, hydroxypropylmethyl, gelatin, starch and polyethylene oxide. Here, even more preferred hydrophilic resin is polyvinyl alcohol. The polyvinyl alcohol is often used as a main binder because of good ink suitability and excellent adhesive role to pigments.

Here, the hydrophilic resin preferably has 5 to 30% by weight based on the total solids in the ink-receiving layer-forming composition.

The ink receiving layer may further include other additives to improve the physical properties of the recording medium. At this time, the other additive in the ink receiving layer is preferably 0.015 to 10% by weight based on the total solids in the ink receiving layer formation composition.

The recording medium for an inkjet printer may further include an undercoat layer located between the base layer and the ink receiving layer.

The recording medium for the inkjet printer may further include a protective layer located on the ink receiving layer.

The recording medium for an inkjet printer may further include a back coating layer located on one surface of the base layer on which the ink receiving layer is not formed.

Hereinafter, the technical configuration of the present invention in more detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms.

1 is a cross-sectional view showing an embodiment of an inkjet recording medium according to the present invention.                     

Referring to FIG. 1, first, a substrate layer 1 having an upper surface and a lower surface is provided. Here, the base layer is one of a transparent or translucent film selected from polyester-based, polycarbonate-based, cellulose-acetate-based or polyethylene-based film, polyethylene or polypropylene, single-sided or double-sided coated paper, single-sided or double-sided art paper, cast It may be one selected from the group consisting of coated paper, synthetic paper, photo paper and baryta paper. In addition, the thickness of the base layer is preferably 70 to 350㎛ to be easy to handle and to prevent bending when forming a coating layer thereon.

Subsequently, first, the ink receiving layer 2 is formed on the upper surface of the base layer 1 by using the composition for forming an ink receiving layer.

The ink receiving layer-forming composition is formed by mixing an inorganic filler, a polyvinyl alcohol, a copolymer of styrene-maleimide, a zirconium compound containing a halogen element, and a solvent.

In the composition for forming an ink-receiving layer, the inorganic filler may be calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, aluminum silicate, silicate, sodium silicate, magnesium silicate, calcium silicate, Silica and alumina and the like can be used. More preferably, the inorganic filler may be at least one selected from alumina represented by the formula (1).

<Formula 1>

_{Al 2 O 3-p (OH} ) 2p · qH 2 O

In the above formula, p is a natural number of 3 or less and q is a free number of an amount of 10 or less, and more preferably a positive number of 5 or less. In many cases, hydrated water (H ₂ O) exhibits a detachable aqueous phase that is not involved in the formation of the crystal lattice. Therefore, q in Formula 1 may take a value that is not an integer multiple. More preferably, the alumina has a boehmite structure or an amorphous form when analyzed by X-ray diffraction.

Such alumina may be used in a powder state of the above-described formula (1), or in some cases, a sol state in which these components are contained as particles may be used. Here, when using a pigment in a sol state, the particle size in the sol is preferably 20 to 200nm. At this time, if the size of the particles of the alumina is less than 20 nm, the ink absorbency is lowered, and if the size of the alumina exceeds 200 nm, there is a problem of lowering the transparency of the recording medium.

In addition, the content of alumina is preferably 50 to 95% by weight based on the total solids in the ink-receiving layer-forming composition. At this time, if the content of the alumina in the composition for forming an ink-receiving layer is too small or too much, the phenomenon of adhesion between films or a decrease in ink absorbency may occur as described above.

The composition for forming an ink-receiving layer may include other pigments other than alumina, such as calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, aluminum silicate, silicic acid, sodium silicate, magnesium silicate, Inorganic pigments such as calcium silicate and silica, organic pigments such as plastic pigments and urea resin pigments, and mixtures thereof can be mixed and used within a range that does not impair the effects of the present invention. Such additive pigments are preferably added in an amount of 20 parts by weight or less based on 100 parts by weight of alumina.

In the composition for forming an ink-receiving layer, the polyvinyl alcohol may be a general polyvinyl alcohol made by saponifying polyvinyl acetate, and a modified polyvinyl alcohol partially substituted with a cationic group and an anionic group. The polyvinyl alcohol is preferably a polymerization degree of 1000 or more, more preferably 1500 to 5000. The saponification degree is preferably 70 to 100 denier, more preferably 80 to 99.5.

The content of the polyvinyl alcohol in the ink-receiving layer-forming composition may be 5 to 30% by weight based on the total solids in the ink-receiving layer-forming composition, preferably 5 to 25% by weight. At this time, if the content of the polyvinyl alcohol is too small, it does not act as a binder, thereby weakening the adhesion to the base layer, and other components such as pigments are relatively increased, resulting in cracks in the ink receiving layer, and thus, poly If the content of the vinyl alcohol is too high, the ink receiving layer is almost made of a binder, so that there is a possibility that the ink absorbency and ink quick drying are also reduced.

On the other hand, in the composition for forming an ink-receiving layer, in addition to the polyvinyl alcohol used as the binder may be added to the hydrophilic polymer. For example, polyvinylpyrrolidone, methyl cellulose, hydroxypropylmethyl cellulose, gelatin, starch and polyethylene oxide and the like. The content of the hydrophilic polymer to be used is preferably used within 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol, more preferably has 0 to 20 parts by weight.

In the ink-receiving layer-forming composition, the styrene-maleimide copolymer may be a compound in which styrene and a maleimide having a tertiary amine group are copolymerized. More preferably, it may be one or more selected from copolymers of styrene-maleimide represented by the formula (2).

<Formula 2>

Where m + n = 1, 0.1 ≦ n ≦ 0.9.

Such copolymers of styrene-maleimide have tertiary amine groups and may be used in organic solvents or in water in the form of ammonium salts. Herein, the copolymer of styrene-maleimide preferably has a degree of polymerization of 1,000 or more, more preferably 2,000 to 20,000.

Here, the content of the copolymer of styrene-maleimide has 0.5 to 20% by weight in the total solids in the ink receiving layer formation composition. In this case, if the content of the copolymer of styrene-maleimide is too small, there is no use effect, and if the amount is too large, the ink absorption may be lowered, which may adversely affect the inkjet ink printing aptitude.

In the composition for forming an ink-receiving layer, the zirconium compound preferably contains a halogen element. Here, the zirconium compound may be water-soluble or water-insoluble if it can be present uniformly in the composition for forming an ink-receiving layer. For example, zirconium difluoride, zirconium trifluoride, zirconium tetrafluoride, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium oxychloride (zirconyl chloride), zirconium hydroxychloride, zirconium tribromide, zirconium tribromide, zirconium tribromide It may be one selected from the group consisting of zirconium bromide, zirconium trioxide and zirconium iodide.

Here, the content of the zirconium compound is preferably 0.05 to 20% by weight based on the total solids in the ink-receiving layer-forming composition. In this case, if the content of the zirconium compound in the composition for forming an ink-receiving layer is too small, there is no use effect, and if the amount is too large, the ink absorption may be lowered, which may adversely affect the inkjet ink printing aptitude.

As a result, by using a styrene-maleimide copolymer and a zirconium compound containing a halogen element at the same time, it is possible to supply a recording medium having excellent water resistance and ink fixability, less smearing of printed ink even under high temperature and high humidity, and very excellent moisture resistance.

In the ink receiving layer-forming composition, the solvent is not particularly limited, but water is mainly used in consideration of environmental problems and workability, and other ketones, glycol ethers, alcohol solvents or methyl cellosolve, ethyl cellosolve, dimethyl It may be at least one selected from the group consisting of formamide, dimethyl sulfoxide. Herein, specific examples of the ketones may be one selected from the group consisting of acetone and methyl ethyl ketone. Specific examples of the glycol ethers include diethylene glycol and diethylene glycol monobutyl ether, and specific examples of alcohol solvents include methanol and ethanol. It may be one selected from the group consisting of, butanol and isopropanol.

In addition, the content of the solvent is preferably diluted so that the solid content of the composition for forming an ink-receiving layer is 5 to 40% by weight. In this case, if the content of the solid is too small, not only the viscosity may be too low, but also difficult to dry during coating, and if too much, the viscosity may be too high, so that the coating surface may deteriorate.

Alcohols and other organic solvents other than water in the solvent are preferably 5 to 50% by weight of the total content of the solvent. In this case, when too small, the drying property tends to deteriorate, and when too small, there is a possibility that a solubility problem and a price increase factor of the composition may occur.

The ink receiving layer-forming composition may further include an additive to supplement physical properties. Here, the additive is at least one of the group consisting of a crosslinking agent, a fixing agent, a dye, a fluorescent dye, a light diffusing agent, a pH adjusting agent, an antioxidant, an antifoaming and defoamer, a leveling agent, a lubricant, an anti-curling agent, a surface control agent and a wettability improving agent Can be. The crosslinking agent crosslinks the binder component and the inorganic filler component. It serves to increase water resistance and surface strength. The amount of the crosslinking agent may be used in an amount of 0.015 to 8% by weight based on the total solids in the ink-receiving layer-forming composition. At this time, if the content of the cross-linking agent is too small, there is no effect of cross-linking, if too much cross-linking is so severe that the ink absorbency is to be taken into account. The crosslinking agent may be used oxazoline, isocyanate, epoxide, aziridine, melamine-formaldehyde, dialdehyde, boron compound or mixtures thereof. Here, specific examples of the isocyanate include tolylene diisocyanate (TDI) adduct, specific examples of the epoxide include epichlorohydrin, and specific examples of the dialdehyde include glyoxal, There is glutaric dialdehyde, and specific examples of the boron compound include boric acid and borax.

In addition, the fluorescent dye serves to increase the whiteness (apparent whiteness) felt by the eye. The total content of other additives other than the crosslinking agent in the ink-receiving layer-forming composition is preferably 0.015 to about 10% by weight based on the total solids in the ink-receiving layer-forming composition. At this time, if the content of the other additives is too small, the additive addition effect is insignificant, and if too large, the ink suitability and coating properties of the recording medium may be reduced.

Subsequently, the ink receiving layer coating agent is coated on the upper surface of the base layer 1, and then dried to form an ink receiving layer 2. Here, the drying is carried out at 50 to 130 ℃, in this step, if a crosslinking agent is added, the thermal crosslinking reaction by the crosslinking agent occurs. Therefore, if the drying temperature is lower than 50 ℃ cross-linking reactivity is lowered, if it exceeds 130 ℃ yellowing may occur.

Although the thickness of the ink receiving layer is not particularly limited, if the thickness of the ink receiving layer is too thin, the ink cannot be absorbed. If the ink receiving layer is too thick, it is difficult to increase the cost and to dry the coating, so that the ink receiving layer is formed to have a thickness of 8 to 80 μm. desirable.

Furthermore, an undercoat layer 3 may be further included to improve adhesion between the base layer 1 and the ink receiving layer 2.

Here, the undercoat layer 3 may be formed of a material selected from the group consisting of one-component primers such as polyols and polyisocyanates, one-component primers such as acrylic, urethane, acrylic-urethane, and vinyl, and the amount of the coating is 0.2 to 2 g / m ² , the coating thickness is preferably 0.2 to 2.0 μm, even more preferably about 1 μm.

In addition, a protective layer 4 may be further included on the ink receiving layer 2 to protect them. The protective layer is formed of a material selected from a compound consisting of a cellulose-based, polyethylene oxide-based and crosslinking agent having excellent surface strength due to excellent ink permeability and hardening to some extent, and its thickness is preferably about 0.5 to about 3 μm.

Furthermore, a rear coating layer 5 may be further included on the lower surface of the base layer to compensate for continuous feeding and culling.

The back coating layer 5 is polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, hydroxypropylmethyl cellulose, gelatin, polyethylene oxide, acrylic polymer, polyester, polyurethane and the crosslinking agents oxazoline, isocyanate , Epoxide, aziridine, melamine-formaldehyde, dialdehyde, boron compound is formed from a material, the thickness thereof is preferably 0.5 to 4㎛.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited only to the following examples.

Example 1

While providing a baryta paper having a basis weight of 200g / ㎡ as a base layer, while preparing an ink-receiving layer composition by coating a bar coater on the top of the base layer, and then drying for 3 minutes at a temperature of 110 ℃, A recording medium for an inkjet printer having an ink receiving layer of about 35 mu m thickness was formed. Here, the ink receiving layer composition is 87.5 g of alumina (manufactured by German Degussa, ALUMINIUMOXID C), 7.0 g of polyvinyl alcohol (Kuraray Co., Japan, PVA 224E), copolymer of styrene-maleimide (Sartomer, USA) 1000I) is 1.8 g, zirconium oxychloride (Japan quasi-seed) 2.1 g, leveling agent (German Tego, Flow 425) 1.0 g, fluorescent dye (Samsung Industrial Co., SW5274F) 0.5 g, boric acid (Samjeon Pure drug) has a composition of 0.1 g, and was formed by dissolving the ink aqueous layer composition at 400 g using a solvent in which distilled water, ethanol and dimethylformamide were mixed in a 75:10:15 weight ratio.

Example 2

A recording medium was manufactured in the same manner as in Experimental Example 1, except for the composition of the ink-receiving layer-forming composition.

Here, the composition for forming an ink receiving layer is 85.0 g of alumina sol (manufactured by US Cabot, PG 003), 10.0 g of polyvinyl alcohol (manufactured by Japan Kuraray, PVA 117), a copolymer of styrene-maleimide (manufactured by Sartomer USA, SMA 2000I). ) 1.3 g, zirconium oxychloride (Junsei, Japan) 1.5 g, glyoxal (Samjeon Pure Chemicals) 0.65 g, leveling agent (German Tego, Flow 425) 1.0 g, fluorescent dyes (Samwon Industrial, SW5274F) 0.5 g and borax (Samjeon Pure Chemicals Co., Ltd.), 0.05 g of a composition containing the ink-receiving layer-forming composition of distilled water, ethanol and dimethyl formamide in a weight ratio of 70:10:20 was formed by dissolving at 400 g.

Example 3

A recording medium for an inkjet printer was produced in the same manner as in Example 1 except for the composition of the ink receiving layer forming composition.

Here, the composition of the ink-receiving layer-forming composition is 76.9 g of alumina sol (manufacturer, SS 30), 8.5 g of alumina (ALUMINIUMOXID C) manufactured by Degussa, Germany, 8.0 g of polyvinyl alcohol (PVA P-17). 1.5 g of copolymers of styrene-maleimide (manufactured by Sartomer USA, SMA 3000I), 3.5 g of zirconyl hydroxychloride (manufactured by Aldrich, USA), 1.0 g of leveling agent (Teuge, Germany), fluorescent dye (Samwon Industries) SW5274F) 0.5 g, boric acid (Samjeon Pure Chemicals) 0.1 g, distilled water, ethanol, dimethyl formamide and dimethyl sulfoxide were dissolved in 400 g using a solvent mixed in a weight ratio of 70: 10: 15: 5 Formed.

Comparative Example 1

A recording medium for an inkjet printer was produced in the same manner as in Example 1 except for the composition of the ink receiving layer forming composition.

Here, the composition for forming an ink-receiving layer is 91.0 g of alumina (made by German Degussa, ALUMINIUMOXID C), 7.4 g of polyvinyl alcohol (made by Japan Kuraray, PVA 224E), 1.0 g of leveling agent (George Tego, Flow 425), 0.5 g of fluorescent dye (manufactured by Samwon Industrial Co., Ltd., SW5274F) and 0.1 g of boric acid (Samjeon Pure Chemicals Co., Ltd.), and the ink aqueous layer composition was prepared by using a solvent in which distilled water, ethanol and dimethylformamide were mixed at a 75:10 to 15:15 weight ratio. Formed by dissolving at 400 g.

Comparative Example 2

A recording medium for an inkjet printer was produced in the same manner as in Example 1 except for the composition of the ink receiving layer forming composition.

Here, the composition of the ink-receiving layer-forming composition is 85.0 g of alumina sol (manufactured by US Cabot, PG 003), 10.0 g polyvinyl alcohol (Kuraray Co., Japan, PVA 117), hydroxypropylmethyl cellulose (Shin-Etsu, Japan, 60SH-50) ) 1.3 g, zirconium oxychloride (Junsei, Japan) 1.5 g, glyoxal (Samjeon Pure Chemicals) 0.65 g, leveling agent (German Tego, Flow 425) 1.0 g, fluorescent dyes (Samwon Industrial, SW5274F) 0.5 g and borax (Samjeon Pure Chemicals Co., Ltd.) were formed by dissolving 400 g of a solvent having a composition of 0.05 g, distilled water and ethanol at a 80:20 weight ratio.                     

Comparative Example 3

A recording medium for an inkjet printer was produced in the same manner as in Example 1 except for the composition of the ink receiving layer forming composition.

Here, the composition of the ink-receiving layer-forming composition is 79.9 g of alumina sol (manufacturer, SS 30), 8.5 g of alumina (ALUMINIUMOXID C, made by Degussa, Germany) 8.5 g, polyvinyl alcohol (made by Dongyang Chemical, PVA P-17), 1.5 g of copolymers of styrene-maleimide (manufactured by Satomer, SMA 3000I), 1.0 g of leveling agent (Tego, German), 0.5 g of fluorescent dyes (from Samwon Industries, SW5274F), boric acid (Samjeon Pure Chemicals Co., Ltd.) It was formed by dissolving distilled water, ethanol, dimethyl formamide and dimethyl sulfoxide to 400 g using a solvent mixed in a weight ratio of 70: 10: 15: 5.

Image printing was performed on the inkjet recording media according to Examples 1 to 3 and Comparative Examples 1 to 3 using a color inkjet printer (MJC-1130i) manufactured by Samsung Electronics of Korea.

The inkjet recording media according to Examples 1 to 3 and Comparative Examples 1 to 3 on which the images were printed as described above were evaluated for ink absorption ability, clarity of color images (whether bleeding), short and long term water resistance and moisture resistance. The evaluation method for each item was as follows.

Assessment Methods

1) Ink absorption test

Immediately after taking a mixed black-based standard image (using MJC-1130i) on an A4 sized specimen, the white paper was piled up, a 5 kg iron ball was placed for 10 seconds, and the amount of ink on the white paper was checked.

2) Smearability test

After taking the mixed black-oriented standard line (using MJC-1130i) on the A4 size specimen, the degree of sharpness of the standard line was confirmed after 24 hours.

3) water resistance inspection

Place the specimen (2.5cm × 5.0cm) in a constant temperature bath at room temperature (25 ℃), and stir the constant temperature bath for 30 minutes for a short time and for 24 hours for a long time to check the degree of image deformation or ink receiving layer falling off It was.

4) Moisture resistance test

After taking a standard image of a color image (using MJC-1130i) on an A4 size specimen, the degree of bleeding of the image was confirmed after standing for 24 hours in a constant temperature and humidity chamber at 60 ° C and 95% relative humidity.

With respect to the inkjet recording medium according to Examples 1 to 3 and Comparative Examples 1 to 3, in which the images were printed in this way, for ink absorption power, clarity (whether bleeding) of color images, short and long term water resistance, moisture resistance, etc. The evaluation results are shown in Table 1.                     

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Ink Absorption Test ◎ ◎ ◎ ◎ ◎ ◎ Sharpness (smear check) ◎ ◎ ◎ △ ○ ○ Water resistance test short-term ◎ ◎ ◎ △ ○ ○ long time ◎ ◎ ◎ × △ × Moisture resistance ◎ ◎ ◎ × △ ×

          ◎: very good, ○: excellent, △: bad, ×: very bad

As shown in Table 1, the recording media for ink jet printers prepared in Examples 1 to 3 were incorporated into the ink receiving layer by introducing a zirconium compound containing a copolymer of styrene-maleimide and a halogen element into the ink receiving layer. Not only was improved but also excellent in water resistance and moisture resistance.

In addition, in the case of Comparative Example 1, which does not include a styrene-maleimide copolymer and a zirconium compound, short-term water resistance was not very good, and it was found that moisture resistance and long-term water resistance under high temperature and high humidity were very poor, and a zirconium compound containing a halogen element. In the case of Comparative Example 2 containing but not containing a copolymer of styrene-maleimide, the short-term water resistance was good, but it was found that the moisture resistance and the long-term water resistance under high temperature and high humidity were not good. In the case of Comparative Example 3, a copolymer of styrene-maleimide was included but did not contain a zirconium compound, and short-term water resistance was good but long-term water resistance and moisture resistance under high temperature and high humidity tended to be very poor.

As described above, the recording medium for an inkjet printer according to the present invention introduces a zirconium compound containing a copolymer of styrene-maleimide and a halogen element into an ink receiving layer, so that not only the absorbing power of the ink, but also long-term water resistance and moisture resistance under high temperature and high humidity, etc. Could improve.

Claims (26)

A base layer; And An ink receiving layer coated on one surface of the base layer, And the ink receiving layer is made of an inorganic filler, a hydrophilic resin, a styrene-maleimide copolymer, and a zirconium compound. The method of claim 1, The base layer may be a transparent or translucent film selected from polyester-based, polycarbonate-based, cellulose-acetate-based or polyethylene-based films, paper coated with single-sided or double-sided polyethylene or polypropylene, single-sided or double-sided art paper, cast coated paper, synthetic paper And a photo paper and a baryta paper. The method of claim 1, And the thickness of the base layer is 70 to 350 mu m. The method of claim 1, The inorganic filler is at least one selected from the group consisting of calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, aluminum silicate, silicate, sodium silicate, magnesium silicate, calcium silicate, silica and alumina A recording medium for an inkjet printer, characterized in that. The method of claim 1, The inorganic filler is a recording medium for an inkjet printer, characterized in that at least one selected from alumina represented by the formula (1), <Formula 1> _{Al 2 O 3-p (OH} ) 2p · qH 2 O         P is a natural number of 3 or less and q is a rational number of 10 or less. The method of claim 5, And the alumina has a boehmite structure or an amorphous form. The method of claim 5, And the alumina is used in the form of a powder or a sol having a particle size of 20 to 200 nm. The method of claim 1, And the inorganic filler has 50 to 95% by weight of the total solids in the ink-receiving layer-forming composition. The method of claim 1, The hydrophilic resin includes at least one recording medium selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, hydroxypropylmethyl, gelatin, starch and polyethylene oxide. . The method of claim 1, And said polyvinyl alcohol has a degree of polymerization of at least 1000 and a degree of saponification of from 70 to 100 parts. The method of claim 10, The polyvinyl alcohol has a degree of polymerization of 1500 to 5000 and a degree of saponification of 80 to 99.5 parts. The method of claim 1, And the hydrophilic resin has 5 to 30% by weight of the total solids in the ink-receiving layer-forming composition. The method of claim 12, And said hydrophilic resin has 5 to 25% by weight in the total solids in the ink-receiving layer-forming composition. The method of claim 1, And the zirconium compound contains a halogen element in a molecule thereof. The method of claim 14, The zirconium compound is zirconium difluoride, zirconium trifluoride, zirconium tetrafluoride, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium oxychloride (zirconyl chloride), zirconium hydroxy chloride, zirconium tribromide, zirconium tribromide A recording medium for an inkjet printer, characterized in that at least one selected from the group consisting of zirconium bromide, zirconium trioxide and zirconium iodide. The method of claim 1, And the zirconium compound has 0.05 to 20% by weight of the total solids in the ink-receiving layer-forming composition. The method of claim 1, And a copolymer of styrene-maleimide is a compound having a tertiary amine group. The method of claim 17, The copolymer of styrene-maleimide is at least one selected from a copolymer of styrene-maleimide represented by the formula (2). <Formula 2>

Where m + n = 1, 0.1 ≦ n ≦ 0.9. The method of claim 1, And the copolymer of styrene-maleimide has a degree of polymerization of 2000 to 20,000. The method of claim 1, And the copolymer of styrene-maleimide has 0.5 to 20% by weight of the total solids in the ink-receiving layer-forming composition. The method of claim 1, The ink receiving layer is at least one more from the group consisting of a crosslinking agent, a fixing agent, a dye, a fluorescent dye, a light diffusing agent, a pH adjusting agent, an antioxidant, an antifoaming and defoaming agent, a leveling agent, a lubricant, an anti-curling agent, a surface control agent and a wettability improving agent. And a recording medium for an ink jet printer. The method of claim 21, The crosslinking agent further comprises one or more from the group consisting of oxazoline, isocyanate, epoxide, aziridine, melamine-formaldehyde, dialdehyde and a boron compound. The method of claim 1, The recording medium for an ink jet printer, wherein the ink receiving layer has a thickness of 8 to 80 µm. The method of claim 1, And the undercoat layer is further included between the base layer and the ink receiving layer. The method of claim 1, And the protective layer is further included on the ink receiving layer. The method of claim 1, And the back coating layer further comprises a surface on which an ink receiving layer of the base layer is not formed.

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