JPH09188065A - INKJET PRINT RECORDING MEDIUM AND INKJET RECORDING METHOD - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording medium having the excellent preservability of water resistance, wear resistance and light resistance by sequentially laminating an undercoating layer containing fine particles of titanium oxide and/or zinc oxide, a non-porous layer having ink retentivity and light transmission properties and a porous layer having liquid permeability and light scatterability on a transparent base material. SOLUTION: The recording medium for ink jet printing used for the ink jet recording system is formed by sequentially laminating an undercoating layer containing the fine particles of titanium oxide and/or zinc oxide, a non-porous layer having ink retentivity and light transmission properties, and a porous layer having liquid permeability and light scatterability on a transparent base material. The particle size of the fine particles of the titanium oxide and/or zinc oxide is set to a range of 1 to 400nm, and the thickness of the undercoating layer is formed in a range of 0.05 to 5μm. The thickness of the base material is not particularly limited, but generally suitable in a range of 1 to 5000μm and preferably a range of 5 to 500μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a recording medium for inkjet printing and an inkjet recording method.

[0002]

2. Description of the Related Art Ink jet recording methods include various ink ejection methods, for example, an electrostatic suction method, a method in which a piezoelectric element is used to mechanically vibrate or displace the ink, the ink is heated to foam, and its pressure is adjusted. Depending on the method used,
Small ink droplets are generated and ejected, and some or all of them are attached to a recording medium such as paper or a plastic film coated with an ink receiving layer for recording, and noise is low, high-speed printing and It has been attracting attention as a method capable of multicolor printing.

In recent years, with the improvement in the performance of ink jet recording apparatuses in the speeding up of recording and multicolor printing, more advanced and broader characteristics have been required for recording media for ink jet printing. That is, (1) the ink absorption capacity is high (the ink absorption capacity is large, the absorption time is fast), (2) the optical density of the dots is high, the periphery of the dots is not blurred, and (3) the dot shape is true. It is close to a circle and its periphery is smooth (4) The image is stable and does not deteriorate even after long-term storage (especially under high temperature and high humidity environment), (5)
The change in characteristics due to the influence of temperature and humidity is small, curling does not occur, (6) blocking does not occur, and (7) printed matter posted for a long time,
It is required that the image does not fade (has light fastness) and that the characteristics such as the same are satisfied at the same time.

A recording medium applied to such an ink jet recording method is, for example, Japanese Patent Laid-Open No. 59-35977.
The dedicated coated paper described in Japanese Patent Publication can be used.

However, since the ink jet printing paper generally has a porous surface, (1) the surface of the paper has a light scattering property, so that a clear image with high optical density cannot be obtained. (2) paper Since the surface is porous, there is a problem that a translucent image having gloss is not obtained.

Further, since the image is observed from the recording surface,
(3) The recorded image is constantly exposed to air, and is affected by oxygen, water droplets, water vapor, etc. in the air, and the image has poor durability such as water resistance.

In order to solve these problems, a recording medium called a back print film having a recording surface and an observing surface has been devised (Japanese Patent Laid-Open No. 62-14087).
No. 8). In this recording medium, a non-porous layer and a porous surface layer are laminated on a transparent substrate, recording is performed from the surface side, and observation is performed from the substrate side. According to this method, the image is protected by the base material and is not affected by water droplets or water vapor, and the surface is smooth, so that the image has high glossiness and an image of higher density can be obtained. .

[0008]

However, as described above, when the image is observed from the base material side rather than the recording surface side, the adhesion between the base material and the non-porous layer is reduced. Unfortunately, if a slight space is formed between the two layers, there is a problem that diffuse reflection occurs on the image surface and a high-density image is damaged.

At present, since the ink used in the ink jet recording method is water-soluble, a water-soluble or hydrophilic resin is used as the non-porous layer, while the substrate is mainly hydrophobic. Film is used. Therefore, the wettability of the non-porous layer with respect to the substrate is poor, and a space may be formed during coating. Also, when printing,
When the non-porous layer absorbs moisture and swells, for example, when it is left in a high humidity environment, the non-porous layer peels off from the base material and causes dimples, which causes a reduction in image density.

Furthermore, since the durability such as water resistance is greatly improved by adopting the above-mentioned constitution, it is possible to display an image not only indoors but also outdoors, but in the ink jet recording system, various water-soluble inks are used as inks. In some cases, since the organic dye is used, the light resistance of the recorded image is more problematic than the pigment.

Therefore, an object of the present invention is to satisfy the above-mentioned various characteristics required for a recording medium for ink jet printing in a well-balanced manner, and at the same time, to obtain high image quality, high density, water resistance, abrasion resistance, light resistance, etc. An object of the present invention is to provide a recording medium for inkjet printing, which is capable of forming an image with excellent storage stability. Another object is to provide an ink jet recording method using this recording medium.

[0012]

Means for Solving the Problems The present inventors have conducted various studies to achieve the above object, and as a result, completed the present invention.

According to a first aspect of the present invention, a subbing layer containing fine particles of titanium oxide and / or zinc oxide, a non-porous layer having ink retaining property and light transmitting property is provided on a transparent substrate. The present invention relates to a recording medium for inkjet printing in which a porous layer having a liquid property and a light scattering property is sequentially laminated.

A second invention relates to the recording medium for ink jet printing according to the first invention, wherein the fine particles of titanium oxide and / or zinc oxide have a particle diameter of 1 to 400 nm.

A third invention is that the thickness of the undercoat layer is 0.05 to.
The recording medium for inkjet printing according to the first or second invention has a thickness of 5 μm.

A fourth invention relates to an ink jet recording method characterized by forming an image by applying ink droplets to the ink jet printing recording medium of the first, second or third invention.

The fifth invention relates to the ink jet recording method of the fourth invention, in which ink is applied from the porous layer side of the recording medium to form a mirror image of a desired image on the recording medium.

The sixth invention relates to the ink jet recording method of the fourth or fifth invention, in which a color image is formed by using inks of four colors of yellow, magenta, cyan and black.

The seventh invention relates to the ink jet recording method of the fourth, fifth or sixth invention, in which a color image is formed by using an ink containing a water-soluble dye.

An eighth aspect of the present invention relates to the ink jet recording method according to any one of the fourth to seventh aspects of the present invention, which uses a method in which thermal energy is applied to ink to eject droplets.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The fine particles of titanium oxide / zinc oxide used in the present invention have the role of improving the wettability of the substrate with respect to the non-porous layer and also serving as an ultraviolet ray blocking agent.

The particle size of the titanium oxide / zinc oxide used in the present invention is appropriately 1 to 400 nm, preferably 2 to 300 nm, and more preferably 5 to 200 nm. When the particle size is larger than 400 nm, the transparency is impaired due to light scattering.

The thickness of the undercoat layer is not particularly limited, but is preferably in the range of 0.05 to 5 μm, more preferably 0.1 to 2 μm, and further preferably 0.2 to 1 μm. . When the thickness is less than 0.05 μm, sufficient adhesion is not exhibited, and when it exceeds 5 μm, the transparency is impaired.

As the base material used in the present invention, conventionally known materials can be used, and specifically, polyester resin, diacetate resin, triacetate resin, polystyrene resin, polyethylene resin, polycarbonate resin, polymethacrylate resin, cellophane, Examples thereof include celluloid, plastic films such as polyvinyl chloride resin and polyimide resin, plastic plates, and glass plates.

As described above, according to the present invention, the recorded image is observed from the side opposite to the recording side. Therefore, the base material needs to have translucency, and therefore has translucency. If desired, the substrate may be subjected to any processing, for example, it is possible to give the substrate a desired pattern or luster (suitable gloss or silk pattern). Further, water resistance, abrasion resistance and blocking resistance may be imparted to the base material.

The thickness of the substrate is not particularly limited, but is generally in the range of 1 to 5000 μm, preferably 3 to 1000 μm, and more preferably 5 to 500 μm.

The porous layer constituting the recording medium of the present invention is
It is necessary to have liquid permeability. The liquid permeability as referred to in the present invention refers to the property of allowing the ink to quickly pass therethrough and substantially not allowing the recording agent in the ink to remain in the porous layer. A preferred embodiment of the porous layer for improving liquid permeability is one having a porous structure having cracks or communicating holes inside the porous layer.

Further, as described above, in the present invention, the porous layer needs to have a light scattering property in order to observe the recorded image from the side opposite to the recording surface.

For example, in the case of recording using a water-based ink, the following modes are available. (1) A mode in which a crack is formed inside, which is composed of resin fine particles and a binder. (2) A mode in which the inside of the layer is made porous by dispersing another material in the coating and treating with a solvent. (3) A mode in which a resin is dispersed in a mixed solvent and a solvent having a high boiling point serves as a poor solvent for the resin to make the inside of the layer porous. (4) A mode in which a foaming material is contained during film formation to make the inside of the layer porous.

It should be noted that all the materials used are those which are non-dyeing to the solvent and water in the ink.

The embodiment (1) comprising resin particles and a binder, which is one embodiment of the porous layer, will be described more specifically.

The resin particles used in the present invention include organic pigments such as thermoplastic resins and thermosetting resins which are non-adsorptive to recording agents, such as polystyrene, elastomers, ethylene-vinyl acetate copolymers, Styrene-acrylic copolymer, polyester, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyvinyl ether, polyamide, polyolefin, polyimide, guanamine,
At least one resin powder selected from SBR, NBR, MBS, polytetrafluoroethylene, urea-formalin resin, polyvinyl chloride, polyacrylamide, chlorobrene, etc., and an emulsion or suspension thereof are used as desired.

In order to increase the whiteness (light scattering property) of the porous layer, white inorganic pigments such as talc, calcium carbonate, calcium sulfate and magnesium hydroxide are used to the extent that the ink permeability of the porous layer is not hindered. , Basic magnesium carbonate, alumina, synthetic silica, calcium silicate, diatomaceous earth, aluminum hydroxide, clay, barium sulfate,
Titanium oxide, zinc oxide, zinc sulfide, satin white, silicon oxide, lithobon, etc. may be added.

The resin particles used in the present invention are not limited to the above resin particles, and any known material may be used as long as it is non-adsorptive to the recording agent.

The binder used in the present invention has a function of binding the above-mentioned resin particles to each other and / or the above-mentioned resin particles and the non-porous layer. On the other hand, it needs to be non-adsorptive.

As the material preferable as the binder, any conventionally known material can be used as long as it has the above-mentioned function, and examples thereof include polyvinyl alcohol, acrylic resin, styrene-acrylic copolymer, polyvinyl acetate and ethylene. -Vinyl acetate copolymer, starch, polyvinyl butyral,
Gelatin, casein, ionomer, gum arabic, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylamide, polyurethane, phenol, melamine, epoxy, styrene-butadiene rubber, urea, α
-One or more kinds of resins such as olefin, chlorobrene, nitrile rubber and the like can be used if desired.

When a heat-adhesive or pressure-adhesive material is used as the porous layer, after the image formation, the porous side is brought into close contact with the surface of a substrate such as metal or plastic to apply heat or pressure. Thus, an image can be easily formed on the substrate.

Further, in order to improve the above-mentioned function as the porous layer, various additives such as, for example,
A surfactant, a penetrating agent, a crosslinking agent, etc. may be added to the porous layer.

The mixing ratio (weight ratio) of the resin particles and the binder is preferably in the range of resin particles / binder = 1/2 to 50/1, and more preferably 3/1 to 20/1. Is the range.

If this mixing ratio is less than 1/2, cracks and communicating holes in the porous layer become small, and the effect of absorbing the recording liquid decreases. Further, when the mixing ratio exceeds 50/1, the adhesion between the resin particles or between the non-porous layer and the resin particles becomes insufficient, and the porous layer cannot be formed.

The thickness of the porous layer depends on the amount of ink applied, but is preferably 1 to 200 μm, and more preferably 3 to 50 μm.

The non-porous layer of the recording medium of the present invention has a stronger ink absorbing power than the porous layer in order to stably absorb and retain the ink temporarily absorbed in the porous layer. is necessary. Therefore, the non-porous layer must have a high affinity for the recording agent as well as for the ink medium. When the absorbency of the non-porous layer is weaker than that of the porous layer, the ink applied to the surface of the porous layer passes through the porous layer and the tip of the ink reaches the non-porous layer. At this time, the ink is retained in the porous layer, and the ink permeates and diffuses more than necessary at the interface between the porous layer and the non-porous layer. As a result, the resolution of the recorded image decreases, and it becomes impossible to form a high quality recorded image.

The non-porous layer satisfying the above requirements is preferably composed mainly of a light-transmitting resin which adsorbs a recording agent and has solubility and swellability in ink.

For example, when an aqueous ink containing an acidic dye or a direct dye is used as a recording agent, the non-porous layer is
It is desirable to be composed of a water-soluble or hydrophilic polymer having adsorptivity for these dyes and swelling for aqueous ink.

Examples of such water-soluble or hydrophilic polymers include albumin, gelatin, casein, starch, cationic starch, gum arabic, natural resin such as sodium alginate, carboxymethyl cellulose, hydroxyethyl cellulose, polyamide, polyacrylamide, polyethyleneimine. , Polyvinylpyrrolidone, quaternized polyvinylpyrrolidone, polovinylpyridylium halide, melamine, phenol, alkyd, polyurethane, acetal-modified polyvinyl alcohol, polyvinyl alcohol, ion-modified polyvinyl alcohol, polyester, polyacrylic acid and other synthetic resins. To be Preferred are a hydrophilic polymer obtained by crosslinking these polymers to make them water-insoluble, a hydrophilic and water-insoluble polymer complex composed of two or more polymers, a hydrophilic and water-insoluble polymer having a hydrophilic segment, and the like.

The thickness of the non-porous layer using the above material is preferably in the range of 1 to 30 μm, more preferably 3 to 10 μm.

As the method for forming the non-porous layer and the porous layer on the substrate, the known materials are prepared by dissolving or dispersing the above-mentioned suitable materials in a suitable solvent to prepare a coating solution. For example, the substrate surface is coated by a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a bar coater method, a size press method, a simsizer method, a spray coat method, a gravure coat method, a curtain coater method, or the like. . Further, in order to smooth the surface or increase the strength of the surface, a super calender treatment may be performed.

In the recording method of the present invention, since the recording surface and the observing surface are in a front-back relationship, when forming an image such as a character, a mirror image such as a mirror character for a desired image is formed unlike the conventional case. It is necessary to use such a device.

As the ink itself for carrying out ink jet recording on the recording medium of the present invention described above, known inks can be used without any problems. Further, as the ink, a direct dye, an acid dye, a basic dye, a reactive dye, a water-soluble dye typified by an edible pigment can be used, and as long as it is one for ordinary inkjet printing, it is not particularly limited. You can Among these, it is preferable to use an ink containing a direct dye and / or an acid dye.

Such a water-soluble dye is generally used in a conventional ink in a proportion of about 0.1 to 20% by weight, and the same may be applied to the present invention.

The solvent used in the aqueous ink used in the present invention is water or a mixed solvent of water and a water-soluble organic solvent,
Particularly preferred is a mixed solvent of water and a water-soluble organic solvent. As the water-soluble organic solvent, alcohols can be used, and among them, polyhydric alcohol having an effect of preventing ink drying is preferable.

Next, regarding the ink jet recording system,
This will be described below. The inkjet recording method can be applied to any conventionally known inkjet recording method in which a droplet of ink is ejected from a nozzle to perform recording by using various driving principles. As a typical example, in the method described in Japanese Patent Application Laid-Open No. 54-59936, the ink subjected to the action of thermal energy undergoes a rapid volume change, and the action force due to this state change ejects the ink from the nozzle. An inkjet method can be used.

An example of an inkjet recording apparatus suitable for the inkjet recording method of the present invention will be described below. 1 to 3 show examples of the print head configuration, which is the main part of the printing apparatus. 1 is an external perspective view of the recording head, FIG. 2 is a sectional view of the recording head taken along the line AA of FIG. 1, and FIG. 3 is a sectional view of the recording head taken along the line BB of FIG.

The recording head has an orifice (1) which is an ink ejection port, and a plate portion (2) (made of glass, ceramics, plastic or the like) having a groove (4) through which the ink passes, and dry heat recording. It is obtained by adhering the used heating head (3). The heating head (3) includes a protective film (5) made of silicon oxide or the like, an aluminum electrode (6a,
6b), a heating resistor layer (7) formed of nichrome or the like,
It comprises a heat storage layer (8) and a substrate (9) having a good heat dissipation property such as alumina.

The ink is distributed up to the orifice (1),
The pressure P forms a meniscus. When an electric signal is applied to the aluminum electrodes (6a, 6b), the area indicated by n of the heating head (3) rapidly generates heat and bubbles are generated in the ink in contact therewith. The pressure of the bubbles causes the meniscus to project, and the ink is ejected from the orifice (1). The ejected ink forms recording droplets from the orifice (1) and flies toward the recording sheet.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the above recording head. In FIG. 4, 4
Reference numeral 01 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade (401) is arranged at a position adjacent to the recording area by the recording head,
Further, in the case of this example, the recording head is held in a protruding form in the moving path of the recording head. Reference numeral 402 denotes a cap, which is arranged at a home position adjacent to the blade (401) and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head and comes into contact with the ejection port surface to perform capping. Further 40
Reference numeral 3 denotes a recovery absorber provided adjacent to the blade (401) and is held in a protruding form in the moving path of the recording head, like the blade (401). A discharge recovery section (404) is constituted by the blade (401), the cap (402) and the recovery absorbent body (403),
The blade (401) and the recovery absorber (403) remove water, dust and the like from the ink ejection port surface.

Reference numeral 405 denotes a recording head. This recording head (405) has ejection energy generating means, and the ejection port surface having the ejection ports is arranged at a position facing the recording sheet. Reference numeral 406 is a carriage for mounting the recording head (405) and moving the recording head. The carriage (406) slidably engages with the guide shaft (407), and a part of the carriage (406) is a motor (408).
Connected to belt (409) driven by (not shown)
doing. As a result, the carriage (406) can move along the guide shaft (407), and the recording head (4)
It is possible to move the recording area and the adjacent area according to 05).

Reference numeral 410 is a paper feed section for inserting a recording sheet, and 411 is a paper feed roller driven by a motor (not shown). With these configurations, the recording head (40
The recording sheet is provided at a position facing the discharge port surface of 5), and is discharged to a discharge unit (not shown) provided with a discharge roller (412) as the recording progresses.

In the above structure, the recording head (40
When the recording medium 5) returns to the home position after the recording is completed, the cap (402) of the ejection recovery unit (404) is moved to the recording head (4).
05), but the blade (40
1) is protruding in the moving route. As a result, the ejection port surface of the recording head (405) is wiped. When the cap (402) comes into contact with the ejection surface of the recording head (405) for capping, the cap (402) moves so as to project into the movement path of the recording head.

When the recording head (405) moves from the home position to the recording start position, the cap (402)
Also, the blade (401) is in the same position as the above-described wiping position. As a result, the ejection opening surface of the recording head (405) is wiped even during this movement.

The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at the home adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The position is moved, and the wiping is performed along with the movement.

When forming a color image, four recording heads containing black, cyan, magenta, and yellow inks are arranged in parallel on the carriage (406). Instead of arranging the recording heads in parallel, one recording head may be divided into four columns. further,
The ink is not 4 colors, but 3 colors of cyan, magenta, and yellow.
It may be a color.

Next, the function and effect of the present invention will be described.

In the recording medium of the present invention, the recording surface and the observation surface have a front-back relationship. That is, recording is performed from the porous layer side, which is the recording side, and the image is observed from the substrate side.

The porous layer in the recording medium of the present invention as described above has liquid permeability and has a function of promptly absorbing and transmitting the recording liquid adhering to the surface thereof. This porous layer has a high affinity for the liquid medium in the ink and at the same time,
On the contrary, it has a low affinity for recording agents (colorants such as dyes and pigments and materials having a coloring property).

In the present invention, in order to have such a function, the material of the porous layer has characteristics such as wetting / permeation / diffusion with respect to the ink liquid medium, and adsorption with respect to the recording material. A material having no reactivity is selected.

On the other hand, since the non-porous layer needs to absorb and retain the recording liquid which is apparently absorbed in the porous layer, the absorption capacity for the recording liquid should be stronger than that of the porous layer. The material is selected. Furthermore, the non-porous layer is configured to have a high affinity for the recording material as well as the ink liquid medium.

In the constitution of the recording medium of the present invention, since the image is observed from the side of the substrate, the non-porous layer holding the recording agent,
Also, the substrate needs to have translucency. At the interface between these two layers, it is necessary to maintain high adhesion so that there is no space or the like that causes diffuse reflection.

Therefore, in the present invention, the undercoat layer provided between the substrate and the non-porous layer has a role of enhancing the adhesiveness of these two layers. In the present invention, an undercoat layer containing fine particles of titanium oxide and / or zinc oxide is provided on the substrate. By providing such a layer containing fine particles on the surface of the base material, the surface area of the base material is increased, so that the wettability of the base material with respect to the non-porous layer is improved and the adhesion can be enhanced.

Although transparency is a required item for the undercoat layer in the present invention, a transparent layer can be provided by reducing the particle size of the fine particles.

Furthermore, the fine particles of titanium oxide and / or zinc oxide have a high refractive index and a high UV blocking effect due to irregular reflection. This action can also improve the light resistance.

[0073]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the text, “part” or “%” is based on weight unless otherwise specified.

Example 1 A polyethylene terephthalate film (manufactured by Toray) having a thickness of 100 μm was used as a translucent base material, and 100 parts of the composition A (titanium oxide dispersion paint, solid content 25%) was dried on the base material. It was applied by a bar coater method so as to have a film thickness of 0.2 μm, and dried in a drying oven at 120 ° C. for 5 minutes.

Next, the following composition B was applied thereon by a bar coater method so that the dry film thickness would be 8 μm.
Dried in a drying oven at 5 ° C for 5 minutes.

Composition B: Cation-modified polyvinyl alcohol (C-polymer, manufactured by Kuraray Co., Ltd., 10% aqueous solution)
100 parts, blocked polyisocyanate (Elastron BN-5, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 30%) 3
Section, organotin compounds (Elastron Catalyst 6
4, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 0.1 part.

Further, the following composition C was coated thereon by a bar coater method so as to have a dry film thickness of 25 μm.
It was dried in a drying oven at 0 ° C for 5 minutes.

Composition C: Urea-formalin resin (organic filler, manufactured by Nippon Kasei Co., Ltd., primary particle diameter 0.01 to 0.02 μ)
m) 100 parts, acetalized polyvinyl alcohol
(S-REC KX-1, manufactured by Sekisui Chemical Co., Ltd., nonvolatile content 8%) 500 parts, perfluoroalkyl betaine (Surflon S-131, manufactured by Seimi Chemical Co., Ltd., solid content 30%) 9 parts, organotin-based Compound (Elastron Catalyst 64, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 3 parts, blocked isocyanate (Elastron BN-5, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 50 parts, water / isopropyl alcohol mixed solution (4 / 6 weight ratio) 760 parts.

The recording medium obtained as described above was white and opaque.

Example 2 The polyethylene terephthalate film used in Example 1 was used as a translucent base material, and the following composition D was applied onto this base material.
100 parts of (zinc oxide dispersion paint (solid content 26%)) was applied by a bar coater method so as to have a dry film thickness of 1 μm,
It was dried in a drying oven at 120 ° C for 5 minutes.

Then, the following composition E was coated thereon by a bar coater method so that the dry film thickness would be 8 μm.
Dried in a drying oven at 5 ° C for 5 minutes.

Composition E: Cation-modified polyvinyl alcohol (C-polymer, manufactured by Kuraray Co., Ltd., 10% aqueous solution)
500 parts, isocyanate compound (Elastron E-
37, Daiichi Kogyo Seiyaku, 25% aqueous solution) 25 parts, catalyst (Elastron Catalyst 32, Daiichi Seiyaku Seiyaku)
Two copies.

Further, the following composition F was coated thereon by a bar coater method so as to have a dry film thickness of 15 μm.
It was dried in a drying oven at 0 ° C for 5 minutes.

Composition F: 100 parts of polymethacrylate resin (Microsphere M-100, Matsumoto Yushi Co., Ltd., average particle size 10 μm), acrylic resin (Boncoat 40
01, manufactured by Dainippon Ink and Chemicals, solid content 50%) 20
Part, sodium dioctyl sulfosuccinate (Perex OT-P Kao Co., Ltd., solid content 70%) 0.5
Part, 900 parts of water.

The recording medium obtained as described above was white and opaque.

Example 3 The polyethylene terephthalate film used in Example 1 was used as a translucent substrate, and the composition A used in Example 1 was applied onto this substrate to give a dry film thickness of 0.05 μm. It was applied by a bar coater method and dried in a drying oven at 120 ° C for 5 minutes.

Next, the following composition G was coated thereon by a bar coater method so that the dry film thickness would be 8 μm.
Dried in a drying oven at 5 ° C for 5 minutes.

Composition G: Polyvinylpyrrolidone (PVP
K-90, manufactured by GAF, 88 parts of 10% DMF solution, novolac-type phenol resin (Resitop PSK-232)
0, Gunei Chemical Co., Ltd., 10% DMF solution) 12 parts.

Further, the composition F used in Example 2 was applied thereon by a bar coater method so as to have a dry film thickness of 15 μm, and dried at 140 ° C. for 5 minutes in a drying oven.

The recording medium obtained as described above was white and opaque.

Example 4 The polyethylene terephthalate film used in Example 1 was used as a light-transmissive substrate, and the composition D used in Example 2 was coated on this substrate with a bar coater to a dry film thickness of 5 μm. And then dried in a drying oven at 120 ° C. for 5 minutes.

Then, the following composition H was applied thereon by a bar coater method so that the dry film thickness would be 8 μm.
Dried in a drying oven at 5 ° C for 5 minutes.

Composition H: Polyvinylpyrrolidone (PVP
K-90, manufactured by GAF, 10% DMF solution) 84 parts, styrene-acrylic acid copolymer (Oxylac SH-210
0, manufactured by Nippon Shokubai Kagaku) 16 parts.

Further, the composition C used in Example 1 was applied thereon by a bar coater method so as to have a dry film thickness of 15 μm, and dried at 140 ° C. for 5 minutes in a drying oven.

The recording medium obtained as described above was white and opaque.

Comparative Example 1 The procedure of Example 1 was repeated except that the coating of the composition A was omitted.
A white opaque recording medium was obtained.

Comparative Example 2 In the same manner as in Example 2 except that the coating of the composition D was omitted,
A white opaque recording medium was obtained.

Comparative Example 3 The procedure of Example 3 was repeated except that the coating of the composition A was omitted.
A white opaque recording medium was obtained.

Comparative Example 4 The procedure of Example 4 was repeated except that the coating of the composition D was omitted.
A white opaque recording medium was obtained.

Inkjet recording method A bubble jet color printer BT is used as the recording medium.
Color recording was performed using C-600J (manufactured by Canon Inc.).

Evaluation Method and Results The adhesion and light resistance of the non-porous layer were evaluated by the following methods. The results are shown in Table 1.

(1) Adhesion of non-porous layer A solid image having a density of 100% was formed with magenta (M) ink using the above apparatus, left for 12 hours, and then the recording surface was covered with a plastic eraser (Lion Office Machine). Rub 10 times.
The case where the magenta printed part was not peeled off, that is, the non-porous layer was not peeled off was marked with ◯, and the magenta printed part was peeled off, that is, the non-porous layer was peeled off was marked with x.

(2) Light resistance A solid image similar to that used in the evaluation (1) was formed with magenta ink, and this image was irradiated with a xenon lamp for 200 hours using an Atlas fade meter (Toyo Seiki),
The image density of the printed matter before and after the test was measured, and the ratio was determined and used as a measure of light resistance. The light resistance of 90% or more was evaluated as ◯, the light resistance of 80% or more and less than 90% was evaluated as Δ, and the light resistance of less than 80% was evaluated as x.

(3) Image Density A solid image similar to that used in the evaluation (1) is formed, and 1
Macbeth RD- reflection densitometer
Evaluation was performed using 918 (manufactured by Macbeth). A reflection density of 1.5 or more was evaluated as ◯, 1.3 or more and less than 1.5 was evaluated as Δ, and less than 1.3 was evaluated as x.

[0105]

[Table 1]

[0106]

As is apparent from the above description, according to the present invention, not only the water resistance and abrasion resistance of an image are improved, but also the adhesion between the base material and the non-porous layer is increased and the high density and high density are obtained. A high quality image can be obtained and at the same time, a recorded image having excellent light resistance can be formed.

[Brief description of the drawings]

FIG. 1 is an external perspective view of a recording head of an inkjet recording apparatus used in a method of the present invention.

FIG. 2 is a cross-sectional view of the recording head of the inkjet recording apparatus used in the method of the present invention taken along the line AA of FIG.

3 is a cross-sectional view of the recording head of the inkjet recording apparatus used in the method of the present invention, taken along line BB in FIG.

FIG. 4 is an explanatory diagram of an inkjet recording device used in the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Orifice 2 Plate part 3 Heating head 4 Groove 5 Protective film 6a, 6b Aluminum electrode 7 Heating resistor layer 8 Heat storage layer 9 Substrate 401 Blade 402 Cap 403 Recovery absorber 404 Discharge recovery part 405 Recording head 406 Carriage 407 Guide shaft 408 Motor 409 Belt 410 Paper feed unit 411 Paper feed roller 412 Paper ejection roller

Claims (8)

[Claims] 1. An undercoat layer containing fine particles of titanium oxide and / or zinc oxide, a non-porous layer having ink retention and light transmission, and liquid permeability and light on a light-transmissive substrate. A recording medium for inkjet printing, in which a porous layer having a scattering property is sequentially laminated. 2. The recording medium for inkjet printing according to claim 1, wherein the particle size of titanium oxide and / or zinc oxide particles is 1 to 400 nm. 3. The recording medium for inkjet printing according to claim 1, wherein the undercoat layer has a thickness of 0.05 to 5 μm. 4. An ink jet recording method, wherein an ink droplet is applied to the recording medium for ink jet printing according to claim 1, 2 or 3 to form an image. 5. The ink jet recording method according to claim 4, wherein ink is applied from the porous layer side of the recording medium to form a mirror image of a desired image on the recording medium. 6. The ink jet recording method according to claim 4, wherein a color image is formed by using inks of four colors of yellow, magenta, cyan and black. 7. The ink jet recording method according to claim 4, 5 or 6, wherein a color image is formed using an ink containing a water-soluble dye. 8. The ink jet recording method according to claim 4, wherein a method in which thermal energy is applied to the ink to eject droplets is used.