JPH09226229A - Recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to record by a color ink jet printer by providing an ink receiving layer having specific ranges of ink absorbing velocity and soaking concentration retention rate at the time of specific amount of ink of water base ink containing water as main component and glycol and the like on a base material layer. SOLUTION: An ink receiving layer having an ink absorbing velocity of 360sec or less, soaking concentration retention rate of 30% or more and surface gloss of the layer of 55% or more at the time of the ink amount of 0.1 to 1.0ml/cm<2> of water base ink containing water as main component and glycol and the like and glycerin and the like is provided on a base material layer, and a recording medium having the resolving power of fine lines of 150μm or less is formed. The embodiments of the material layer include natural sheet, synthetic sheet, cloth, and nonwoven fabric. The embodiments of the resin for constituting the layer include polyvinyl alcohol, acrylic resin, and styrene- acryl polymer. The layer may be formed of one layer or two or more layers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium which absorbs ink rapidly, is hard to remove even if water is applied to the ink receiving layer after the ink is absorbed, has a high surface gloss, and has a good resolution. It is an object of the present invention to provide a medium capable of recording with a color ink jet printer, and capable of recording with high gloss and good appearance such as silver salt photographs.

[0002]

2. Description of the Related Art In recent years, with the spread of electronic still cameras or computers, hard copy technology for recording images on paper or the like has rapidly developed. The ultimate goal of these hard copies is silver halide photography. In particular, how to bring color reproducibility, image density, gloss, weather resistance, etc. close to silver halide photography has been a subject of development. As a method of recording a hard copy, various methods such as a sublimation heat transfer method, an ink jet method, and an electrostatic transfer method are known in addition to a method of directly photographing a display on which an image is displayed by a silver halide photograph. 2. Description of the Related Art Inkjet printers have been rapidly spreading in recent years due to their ease of full color printing and low printing noise. In the ink jet method, ink droplets are ejected from a nozzle toward a recording material at a high speed, and a large amount of solvent is contained in the ink. For this reason, a recording sheet for an ink jet printer is required to absorb ink quickly and have excellent color developing properties. These inkjet recordings were aimed at silver salt photography, but none of such printed matter had high quality, high quality, water resistance, and good absorbability regardless of the type of ink.

[0003]

SUMMARY OF THE INVENTION According to the present invention, the ink is quickly absorbed, and even if water is applied to the ink receiving layer after the ink is absorbed, the ink is difficult to remove and the surface glossiness is high.
It is an object of the present invention to provide a medium that can be recorded by a color inkjet printer and has high gloss and high quality and high-quality recording like silver salt photographs.

[0004]

The present invention relates to a recording medium having an ink receiving layer provided on a base material layer, which contains water as a main component, in which glycols, glycerins, alcohols and pyrrolidones are contained. Of the water-based ink containing at least one of the above, the ink absorption rate is 360 seconds or less and the water immersion concentration retention rate is 30% when the ink amount is 0.1 ml / cm ² or more and 1.0 ml / cm ² or less. With the above, the surface gloss of the ink receiving layer is 55% or more, and the resolution of fine lines is 15
The present invention relates to a recording medium having a thickness of 0 μm or less. In the present invention, the base material is not particularly limited, and includes, for example, natural paper, synthetic paper, cloth, non-woven fabric, wood, metal, plastic film, glass, artificial leather, natural leather and any two types thereof. The thing which stuck the above thing is mentioned.

In the present invention, an ink jet recording medium can be obtained by providing an ink receiving layer on such a substrate. As the receiving layer, any known resin having ink absorbability can be used, and examples thereof include polyvinyl alcohol, acrylic resin, styrene-acrylic polymer, ethylene-vinyl acetate polymer, starch, polyvinyl butyral, gelatin, and casein. , Ionomer,
One or more kinds of resins such as gum arabic, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylamide, polyester resin, and styrene-butadiene rubber can be used if desired. Preferably, it is polyvinyl alcohol. By containing a water-soluble melamine resin, such as an epoxy resin, a polyurethane resin, a polyether resin, or an isocyanate compound, as a curing agent in the receiving layer, the curing degree of the receiving layer is increased and the water resistance is improved. These are 0.5 with respect to the resin having ink absorbability.
It is preferable to add about 20% by weight. Also, silica,
Kaolinite, talc, calcium carbonate, zeolite,
Particles such as alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, organic white pigments, benzoguanamine particles, crosslinked polystyrene, crosslinked acrylic particles, and aluminum hydroxide may be added to the extent that the surface gloss is not lowered.

The receptive layer may be composed of one layer or two layers.
A configuration having more than two layers may be employed. By containing polyvinyl alcohol having a cation group or a dyeing agent having a cation group in the receiving layer, it is possible to further improve the ink absorbability.

By adding a surfactant to the receiving layer, it is possible to obtain high surface gloss while maintaining ink absorbability and water resistance. In particular, it is difficult to achieve both ink absorbability and water resistance depending on the drying conditions at the time of coating, in the case where a curing agent is added to the above water-soluble resin. That is, if the curing is sufficient, the ink absorbency becomes poor, and if the curing is stopped to such an extent that the ink is sufficiently absorbed, the water resistance becomes poor. Further, if particles or the like are added to the receiving layer so as to improve the ink absorbing ability, the water resistance can be improved, but the surface gloss is lowered, so that printing with good aesthetics becomes impossible. The surfactant may be any of a cationic type, an anionic type, a nonionic type and a nonionic type.

However, silicone-based or fluorine-based surfactants are preferred. Silicon-based surfactants include dimethyl silicon, amino silane, acrylic silane, vinyl benzyl silane, vinyl benzyl amino silane, glycid silane, mercapto silane, dimethyl silane, polydimethyl siloxane, polyalkoxy siloxane, hydrogen-modified siloxane, vinyl-modified siloxane, and vitroxy. Modified siloxane, amino-modified siloxane, carboxyl-modified siloxane, halogenated-modified siloxane, epoxy-modified siloxane, methacryloxy-modified siloxane, mercapto-modified siloxane, fluorine-modified siloxane, alkyl group-modified siloxane, phenyl-modified siloxane, alkylene oxide-modified siloxane, and the like. Examples of the fluorine-based surfactant include ethylene tetrafluoride, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonamide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfone Acid salt, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate, perfluoroalkylphosphate, perfluoroalkylalkyl compound, perfluoroalkylalkylbetaine, perfluoroalkylhalide, etc. Is mentioned.

The amount of these surfactants added is 0.5 to 20% by weight in the dried ink receiving layer, preferably 1 to 1
0% by weight. Less than 0.5% by weight or 20% by weight
If it exceeds, it is impossible to achieve both ink absorbency and water resistance. In addition, the method of adding the surfactant is to dissolve and disperse the surfactant in water and / or alcohols once, and then to add it, but preferably to once dissolve the surfactant in water and / or alcohols. In this method, PVA is dispersed in the dispersed solution, the temperature is raised to dissolve the PVA, the solution is returned to room temperature, and then another is added. Since this method can disperse the surfactant in the coat layer best,
It seems possible to prevent absorbency, water resistance, and bleeding in a wide variety of inks.

The ink receiving layer may contain particles. The particles are not limited, but preferably organic particles containing acrylic, styrene, nylon, ester or the like as a main component are preferable in that the surface gloss can be increased while the transportability in a printer is improved.

The method for providing the ink receiving layer is not particularly limited, but is a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method,
A commonly used method such as a reverse roll coating method or a bar coating method can be applied. Add a silicon-based or fluorine-based surfactant and dry under the conditions described below.
By thermosetting, it becomes possible to achieve both ink drying property and water resistance. The coating amount at this time is preferably 8 g / m ² or more and 50 g / m ² or less after drying. The drying condition of the coat layer is preferably set to the boiling point of the solvent of the coating liquid + 30 ° C. or less immediately after the start of drying, and thereafter higher than that temperature to obtain an ink receiving layer having both ink drying property and water resistance. be able to. Although no detailed study has been made on this phenomenon, it is expected that there is some relationship between the presence state of the surfactant in the ink receiving layer and the drying conditions.

By providing an anchor coat layer between the base material and the receiving layer, the adhesion between the base material and the receiving layer can be improved. As the compound constituting the anchor coat layer, a polyester resin is preferable, but other than this, compounds such as a polyurethane resin, a polyester urethane resin, and an acrylic resin can be applied. As a method for providing the coating layer, a commonly used method such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, and a reverse roll coating method can be applied.

The ink absorbency of the recording medium thus obtained has a drying time of 360 seconds or less, preferably 30 when the recording medium is printed by an ink jet printer.
Seconds or less, more preferably 15 seconds or less, still more preferably 5 seconds or less. This ink absorbency greatly changes depending on the components contained in the ink and the constitution of the ink receiving layer. In the present invention, the ink composition is an aqueous ink containing at least water as a main component and at least one kind selected from glycols, glycerins, alcohols, and pyrrolidones therein, and the ink amount is 0.1 ml. / Cm ²
If it is 1.0 ml / cm ² or less, the ink absorption rate must be 360 seconds or less in any case. If it exceeds 360 seconds, the lower printed ink will appear on the upper substrate when printing multiple sheets.

It is necessary that the rate of change in the concentration of water is 30% or less, preferably 40% or less. When it exceeds 30%, the water resistance becomes insufficient, and when the printed matter is splashed with water, the ink flows out or the ink receiving layer is peeled off from the substrate, and the original printed matter cannot be seen.

The surface gloss is 55% or more, preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If it is less than 55%, the glossiness similar to that of a silver circle photograph is high and a printed matter of high quality and high image quality cannot be obtained. The recording medium thus obtained absorbs the ink quickly, and the ink is difficult to remove even if water is applied after the ink has been absorbed by the ink receiving layer, the surface has a high glossiness, and recording with a color inkjet printer is possible, It has become possible to record high-quality, high-quality records with high gloss like silver salt photographs.

Examples Next, examples and comparative examples of the present invention will be shown. First, the measurement / evaluation methods used in the present invention are shown below. 1) Ink absorbency With an inkjet printer (DESKWRITER560J, manufactured by Hewlett-Packard Co.), width 3 mm,
Print 15 cm long lines in cyan and black. After the printing was completed, the line was rubbed with a finger, and the time when the line did not rub was obtained. The amount of ink at this time was about 0.2 ml / cm. The ink used at this time and the solvent composition thereof are as follows. Black Hewlett Packard HP51626A Main component, water, 2-pyrrolidinone Seiko Epson MIJI2 main component, water, diethylene glycol, tetraethylene glycol-butane cyan Hewlett Packard
HP51625A Main component, water, pentanediol, ethylene glycol manufactured by Seiko Epson MIJIC2 Main component, water, diethylene glycol, tetraethylene glycol-butane

2) Cyan, magenta, yellow (HP
51625A) and black ink (HP51626)
Print A) 5 × 5 cm, and soak the printed surface in running water for 3 minutes. The reflection density was measured with a Macbeth densitometer (TR-927) to determine the density of each color before and after the immersion in running water, and the water immersion density retention rate = density after water immersion / density before water immersion x 100
(%).

3) Resolution of fine lines 1) Printer for cyan, magenta, yellow (HP
51625A) and black ink (HP51626)
Print two 2 × 2 cm squares in A). At this time, the two gaps did not bleed, and the narrowest space where the white part could be discriminated as a white line was defined as the resolution.

4) Gloss Using VGS-1001DP from Nippon Denshoku Industries Co., Ltd., the reflectance at 60 ° of incident light and reflected light was determined.

Example 1 20 parts by weight of a silicone surfactant (Painted manufactured by Dow Corning) is dissolved in 80 parts by weight of methanol. This solution was diluted 5 times with water, 15 parts by weight of polyvinyl alcohol (GH-20 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dispersed, and dissolved at 70 ° C. Using this solution, 9.0% by weight of polyvinyl alcohol, 0.36% by weight of a surfactant, melamine resin (Sumimar made by Sumitomo Chemical Co., Ltd.)
0.7% by weight, cationic compound (Kayafix UR manufactured by Nippon Kayaku Co., Ltd.) 1.0% by weight, particles (Organazole 2002 manufactured by Nippon Rilsan Co., Ltd.) 0.04% by weight and water 8
A coating liquid was obtained by mixing 8.9% by weight. Then bar coat and dry at 120 ° C for 1 minute, then at 140 ° C for 2 minutes.
Minute drying was performed to obtain an inkjet recording film. At this time, the coating amount was 10 g / m ² (when dried).

Example 2 A final solution was prepared in the same manner as in Example 1 except that the surfactant was dispersed in 80 parts by weight of water, and the mixture was further diluted 5 times with water and then polyvinyl alcohol was dissolved. A film for inkjet recording was obtained.

Comparative Example 1 An ink jet recording film was obtained in the same manner as in Example 1 except that polyvinyl alcohol was dispersed and dissolved in water and then a surfactant was added.

Comparative Examples 2 and 3 An ink jet recording film was obtained in the same manner as in Example 1, except that the drying time was 120 ° C. for 4 minutes or 150 ° C. for 4 minutes.

Comparative Example 4 The same printing was performed using a special glossy film manufactured by Seiko Epson Corporation. Due to the low surface gloss, the quality was insufficient.

[0025]

[Table 1]

[0026]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to record with a color ink jet printer, which absorbs ink quickly and is difficult to remove even if water is splashed after the ink is absorbed in the ink receiving layer and the surface has a high glossiness. The objective is to provide a medium capable of high-quality, high-quality recording, such as silver halide photography, with high gloss.

Claims (7)

[Claims] 1. A recording medium in which an ink receiving layer is provided on a base material layer, which contains water as a main component and contains at least one or more of glycols, glycerins, alcohols, and pyrrolidones. When the amount of the contained aqueous ink is 0.1 ml / cm ² or more and 1.0 ml / cm ² or less, the ink absorption rate is 360 seconds or less, the water immersion concentration retention rate is 30% or more, and the surface of the ink receiving layer Gross 55
%, And the resolution of fine lines is 150 μm or less. 2. The recording medium according to claim 1, wherein the ink receiving layer is a layer containing an ink absorbing resin, a curing agent, and a surfactant. 3. The recording medium according to claim 1 or 2, wherein the ink receiving layer contains a compound having a cationic group. 4. The recording medium according to any one of claims 1 to 3, wherein the ink absorbing resin is polyvinyl alcohol. 5. The recording medium according to any one of claims 1 to 4, wherein the curing agent is a water-soluble melamine resin. 6. The recording medium according to claim 1, wherein the surfactant is fluorine-based and / or silicon-based. 7. The medium according to claim 1, wherein the recording medium is an inkjet recording medium.