JPH0671821B2 - Recorded material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recorded matter obtained by a recording method using a recording liquid such as a felt pen, a fountain pen, a pen plotter, an ink jet recording device, etc., the absorptivity of the recording liquid and the color property of a recorded image. And a recorded matter having a high quality recorded image.

[0002]

2. Description of the Related Art Conventionally, a recording method using a recording liquid, for example, a fountain pen, a felt pen, a ballpoint pen, a pen plotter, and a paper used for recording by an ink jet recording apparatus include high-quality paper, bond paper, and writing paper. General paper, or coated paper such as art paper and cast coated paper.

However, in recent years, with the development of recording devices such as ink jet recording devices and pen plotters, the above-mentioned conventional recording material has not been able to obtain sufficient recording characteristics.

That is, since high-speed recording and multi-color recording, which are incomparable to those of the conventional recording medium, are performed, the conventional recording material absorbs the recording liquid and develops color when a plurality of recording liquids adhere to the same portion. The quality, color, etc. have not reached a satisfactory level.

In order to solve these problems, a coated paper having a porous ink absorption layer represented by an inkjet paper on the surface of a substrate has been devised.

For example, JP-A-60-214989 discloses a sheet having a porous ink absorbing resin layer provided on a substrate.

This ink absorbing layer is porous and contains pores and cracks inside, so that the ink absorbing speed is improved.

As described above, by providing the porous ink absorbing layer, it is possible to enhance the ink absorbing property to some extent, but since it is porous, it has a light diffusing property and has a clear optical density. High and glossy images cannot be obtained.

Further, since the image is observed from the recording surface of the ink, the recording agent is made to remain on the surface of the absorption layer as much as possible, which has a drawback that the durability of the image such as water resistance and the storage stability are poor. .

Recently, an ink jet recording apparatus,
As the recording speed using a pen plotter or the like has been increased and the quality has been improved, a material having a dramatic recording performance has been required for a recording material.

That is, the absorption of the recording liquid, the color development of the recording agent,
There has been a need for a recording material that is far superior to conventional recording materials in terms of recording performance such as image quality, resolution, chromaticity, recorded image density, and gloss.

[0012]

However, under the present circumstances, a recording material satisfying all of these recording characteristics at the same time has not yet been obtained. Therefore, it is an object of the present invention to provide a recorded material having a glossy surface using a recording material that solves the above conventional problems.

A further object of the present invention is to provide a recorded matter having excellent water resistance, abrasion resistance and storage stability.

Still another object of the present invention is to provide a recorded matter excellent in high quality and high optical density of a recorded image.

[0015]

The above object can be achieved by the present invention described below.

That is, according to the present invention, a non-porous layer having an ink retaining property and a light transmitting property and a porous layer having a liquid permeability and a light diffusing property are sequentially laminated on a translucent substrate to be recorded. An image to be recorded is formed on at least the non-porous layer of a material by a recording material.

[0017]

The present invention is mainly characterized by using a recording material having a recording surface and an observing surface in a front-back relation, unlike a conventional recording material having the same recording surface and observing surface.

That is, in the present invention, recording is performed from the porous layer side, which is the recording side, with the recording liquid, and the recorded image is observed from the substrate side, which is the observation side.

Therefore, the porous layer has liquid permeability and a function of promptly absorbing and permeating the recording liquid adhering to the surface thereof, while the non-porous layer has migrated from the porous layer. It has a function of absorbing and retaining a recording liquid or a recording agent.

In this case, the porous layer must have a high affinity for the liquid medium in the recording liquid, and at the same time, for the recording agent (colorant such as dye, pigment and material having coloring property). , On the contrary, must have a low affinity.

Therefore, the porous layer is made of a material which has characteristics such as wetting, permeation and diffusion with respect to the recording liquid medium and does not have characteristics such as adsorption, permeation and reaction with respect to the recording agent. Must be configured.

On the other hand, since the non-porous layer absorbs and captures the recording liquid temporarily absorbed by the porous layer, it must have a stronger absorbing power for the recording liquid than the porous layer. Absorption capacity here is a word that is compared with absorption speed,
It corresponds to the relationship between motor torque and rotation speed.

Therefore, the non-porous layer must have a high affinity for the recording liquid medium as well as for the recording liquid medium.

The present invention will be described in detail below based on embodiments.

The recorded matter of the present invention comprises a base material as a support, a non-porous layer formed on the support for substantially absorbing and capturing a recording liquid or a recording agent, and a non-porous layer on the non-porous layer. It can be obtained by using a recording material formed of a porous layer that directly receives the recording liquid and has liquid permeability and does not substantially leave the recording agent.

Regarding the above-mentioned recording material used for obtaining the recorded matter of the present invention, conventionally known base materials can be used, and specifically, polyester resin, diacetate resin, triacetate resin, Polystyrene resin,
Examples thereof include plastic films such as polyethylene resin, polycarbonate resin, polymethacrylate resin, cellophane, celluloid, polyvinyl chloride resin and polyimide resin, plates or glass plates.

As described above, according to the present invention, since the recorded image is observed from the side opposite to the recording side,
The base material needs to have translucency.

Further, the base material to be used may be subjected to any processing as long as it finally has translucency.
For example, it is possible to apply a desired pattern or luster (suitable gloss or silk pattern) to the base material.

Furthermore, by selecting a substrate having water resistance, abrasion resistance and blocking resistance as the substrate, it is possible to impart water resistance, abrasion resistance and blocking resistance to the image observation surface of the recorded matter. .

The porous layer constituting the recording material of the present invention is
It is necessary to have liquid permeability.

The liquid permeability as referred to in the present invention means the property that the recording liquid is allowed to pass through quickly and the recording agent in the recording liquid does not substantially remain in the porous layer.

Here, the porous layer is a layer having cracks and communicating holes inside the layer.

Further, as described above, in the present invention, it is necessary that the porous layer has a light diffusing property in order to observe the reflection recorded image from the side opposite to the recording surface.

The porous layer for satisfying the above characteristics is
It is mainly composed of resin particles and a binder.

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 polyethylene, polymethacrylate, elastomers, and ethylene-vinyl acetate. At least one selected from the group consisting of resin powders such as coalesced products, styrene-acrylic copolymers, polyesters, polyacrylics and polyvinyl ethers, and emulsions is optionally used.

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 has a function of binding the resin particles to each other and the non-porous layer, and like the resin particles, is non-adsorptive to the recording agent. is necessary.

As a preferable material for 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, ethylene-vinyl acetate copolymer. One or more kinds of resins such as polymers, starch, polyvinyl butyral, gelatin, casein, ionomer, gum arabic, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylamide, phenol, melanin, epoxy and styrene-butadiene rubber can be used if desired.

Further, in order to improve the above-mentioned function as the porous layer, various additives such as, for example,
A surfactant, a penetrant, 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, more preferably 3/1 to 20 /. The range is 1.

When the 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 is reduced. On the other hand, when the mixing ratio is 50/1 or more, the adhesion between the resin particles or the non-porous layer and the resin particles becomes insufficient, and the porous layer cannot be formed.

The thickness of the porous layer is preferably 1 to 200 μm, and more preferably 3 to 50 μm, though it depends on the amount of recording droplets.

Next, the non-porous layer that substantially traps the recording liquid or recording agent absorbs the recording liquid that has passed through the porous layer,
It is the one that is captured and held substantially permanently.

The non-porous layer is required to have a stronger absorbing power for the recording liquid than the porous layer.

This is because when the absorption capacity of the non-porous layer is weaker than that of the porous layer, the recording liquid applied to the surface of the porous layer passes through the porous layer and the recording liquid When the tip of the recording medium reaches the non-porous layer, the recording liquid stays in the porous layer, and the recording liquid permeates laterally in the porous layer at the interface between the porous layer and the non-porous layer. , Will spread. As a result, the resolving power of the recorded image is lowered, and it becomes impossible to form a high quality image.

Further, as described above, since the recorded image is observed from the side opposite to the recording surface, it is necessary that the non-porous layer be light transmissive.

The non-porous layer satisfying the above requirements is composed of at least one resin selected from a light-transmitting resin that adsorbs a recording agent and a light-transmitting resin that is soluble and swellable in a recording liquid. Preferably.

For example, when an aqueous recording system containing an acidic dye or a direct dye is used as the recording agent, the non-porous layer is
A cationic resin having adsorptivity for the dye, for example, at least one resin selected from quaternized polyamines and hydrophilic polymers having swelling properties for aqueous recording liquids.

The material constituting the non-porous layer is not particularly limited as long as it has a function of absorbing, capturing and holding the recording liquid.

The thickness of the non-porous layer may be sufficient to absorb and capture the recording liquid, and it varies depending on the recording droplet amount, but it is preferably 1 to 50 μm, and more preferably 3 to.
It is 20 μm.

As a method for forming the non-porous layer and the porous layer on the substrate, the coating solution is prepared by dissolving or dispersing the materials mentioned above in an appropriate solvent. For example,
A method of coating on a substrate by a known method such as a roll coating method, a rod bar coating method, a spray coating method, an air knife coating method, and then quickly drying is preferable, and the above material is a hot melt coating method or the above material. Alternatively, a method in which a single sheet is once formed and then the sheet is laminated on a substrate may be used.

However, when the non-porous layer is provided on the substrate,
It is necessary to strengthen the adhesion between the substrate and the non-porous layer and eliminate the space.

The presence of a space between the substrate and the non-porous layer is not preferable because the surface of the recorded image is diffusely reflected and the optical density of the image is substantially lowered.

As means for recording an image on a recording material forming the recorded matter of the present invention, a fountain pen, a ballpoint pen, a felt pen, a pen plotter, an ink mist, an ink jet, various kinds of printing, and the like containing a recording agent. A recording instrument and a recording device using a liquid can be mentioned.

From the viewpoint of high speed of image recording, an inkjet recording device and a pen plotter are suitable.

As the recording liquid used in the recording method for forming the recorded matter of the present invention, conventionally known water-based and oil-based recording liquids can be used, but they rapidly penetrate into the porous layer and are non-porous. The viscosity of the recording liquid needs to be 500 cps or less in order to be quickly absorbed and captured by the layer. The viscosity is preferably 100 cps or less, and preferably 50 cps or less.

In consideration of safety against fire and stain resistance to the environment, an aqueous recording liquid is preferable.

As the recording agent to be contained in the recording liquid, conventionally known coloring agents such as dyes and pigments and materials having a coloring property can be used. For example, as a recording agent used for ink jet recording, a water-soluble dye represented by a direct dye, an acid dye, a basic dye, a reactive dye, an edible dye and the like is preferable.

In the recording method for forming the recorded matter of the present invention, since the recording surface and the observing surface have a front and back relationship, when printing characters, a device capable of printing mirror characters unlike the conventional ones. Need to be used.

[0060]

EXAMPLES The present invention will be specifically described below based on examples.

Example 1 A polyethylene terephthalate film (thickness: 100 μm, manufactured by Toray Industries, Inc.) was used as a light-transmissive substrate, and the following composition A was coated on this substrate by a bar coater method so that a dry film thickness was 8 μm. And was dried in a drying oven at 120 ° C. for 5 minutes.

Composition A Polyvinylpyrrolidone (PVPK-90 GAF)
<10% DMF solution> 88 parts ・ Novolak type phenolic resin (resist top PSK-
2320 Gunei Chemical Co., Ltd.) <10% DMF solution> 12 parts

Further, the following composition B was applied by a bar coater method so as to have a dry film thickness of 15 μm.
C., and dried in a drying oven for 10 minutes.

Composition B Low-density polyethylene resin (Kemipearl M-200, Mitsui Petrochemical Industry Co., Ltd., solid content 40%, particle size 5 μm) 10
0 parts by weight ethylene-vinyl acetate copolymer resin (Chemipearl V-10
0 Mitsui Petrochemical Co., Ltd., solid content 40%, particle size 5 μm)
10 parts by weight Polyoxyethylene octyl phenyl ether (Emulken 810 manufactured by Kao Corporation) 0.2 parts by weight

The recording material thus obtained was white and opaque. For this recording material, the following 4
The ink-jet recording is performed by using a recording apparatus having an on-denmand type ink-jet recording head in which a bubble is generated by a heat-generating resistor by using one kind of ink and the recording liquid is ejected by the pressure. The thing was made. The compositions of the four recording liquids used are shown in Table-1. The recorded matter thus obtained was tested and evaluated according to the following method to determine whether or not the recorded matter was sufficiently suitable for the purpose of the present invention.

1) Ink absorptivity was measured by measuring the time required for ink to be recorded at room temperature after ink-jet recording and to be dried and fixed sufficiently without touching the recording area with a finger without the ink adhering to the finger. 2) Image optical density (OD) is Macbeth densitometer TR52
No. 4 was used to measure the black ink recording portion from the image observation surface side. 3) The image surface gloss is based on JIS Z 8741.
The 45 ° specular gloss of the surface of the observed image was measured. 4) As for operability, when the recorded image is formed, no complicated work is required, and the other is not.

A comprehensive evaluation was performed based on the above results. The results are shown in Table-2.

In the comprehensive evaluation, it is required that the absorption of the recording liquid is rapid, the ink jet recording suitability is excellent, and the glossiness of the image observation surface, the sharpness of the recorded image and the operability at the time of image formation are good. Good, one of the inkjet suitability, the gloss of the image observation surface, and the operability at the time of image formation was insufficient.

[0069]

[Table 1]

Example 2 The polyethylene terephthalate film used in Example 1 was used as a translucent substrate, and the following composition C was used on this substrate.
Was coated by a bar coater method so as to have a dry film thickness of 5 μm, and dried at 110 ° C. for 10 minutes in a drying furnace.

Composition C Polyvinylpyrrolidone (PVPK-90 GAF)
<10% DMF solution> 84 parts Styrenenoacrylic acid copolymer (Oxylac SH-
2100 Nippon Shokubai Chemical Co., Ltd.) <10% DMF solution> 16
Department

Further, the following composition D was further applied thereon to give a dry film thickness of 2
It is coated by the bar coater method so that it becomes 0 μm, and 80
C., and dried in a drying oven for 10 minutes.

Composition D Polymethacrylate resin (Ficrosphere M, Matsumoto Yushi Co., Ltd., average particle size: 10 μm) 100 parts by weight Ionomer resin (Kemipearl SA-100, Mitsui Petrochemical Co., Ltd., solid content: 35%) 30 Parts by weight Sodium octyl sulphate succinate (Perex O
TP Kao Co., Ltd. solid content 70%) 0.15 parts by weight water 20 parts by weight

The recording material thus obtained was white and opaque. Example 1 was applied to this recording material.
InkJet recording similar to that described above was carried out to produce a recorded matter of the present invention.

The recorded matter was evaluated according to the method of Example 1. The above results are shown in Table-2.

Example 3 The polyethylene terephthalate film used in Example 1 was used as a light-transmitting substrate, and the following composition E was prepared on this substrate.
Was coated by a bar coater method so as to have a dry film thickness of 10 μm, and dried at 100 ° C. for 12 minutes in a drying furnace.

Composition E ^** Comb type polymer (LHM-108, manufactured by Soken Kagaku) <2
5% Methocello solution> 60 parts Methyl vinyl ether / maleic anhydride monoethyl ester (manufactured by Gantrez ES-425GAF) <10
% Water / ethanol solution> 40 parts * Main chain (copolymer of 64 parts of 2-hydroxyethyl methacrylate and 16 parts of dimethylacrylamide) 80
Grafted with 20 parts of MMA macromer

Further, the following composition F was further added thereto to form a dry film thickness 1
Coated by the bar coater method so as to be 0 μm, and 70
C., and dried in a drying oven for 10 minutes.

Composition F Thermoplastic elastomer resin (Chemipearl A-100 Mitsui Petrochemical Industry Co., Ltd., solid content 40%, particle size 5 μm) 1
00 parts by weight Ionomer resin (Kemipearl SA-100 Mitsui Petrochemical Industry Co., Ltd., solid content 35%) 10 parts by weight Polyoxyethylene (Emulgen A-500 Kao Co., Ltd.)
Made) 0.2 parts by weight

The same ink-jet recording as in Example 1 was carried out on this recording material to prepare a recorded matter of the present invention. The recorded matter was evaluated according to the method of Example 1. The results are shown in Table-2.

Example 4 Composition E and composition F used in Example 3 were formed on a Teflon film in the same manner as in Example 3, and then the Teflon film was peeled off to obtain a white opaque recording material. The same ink-jet recording as in Example 1 was carried out on this recording material to prepare a recorded matter of the present invention.

The recorded matter was evaluated according to the method of Example 1.

The above results are shown in Table 2.

Comparative Example 1 The same ink jet recording as in Example 1 was carried out using a commercially available ink jet paper (IJ matte coated paper NM Mitsubishi Paper Mills Ltd.) as a recording material. Also, the recorded matter was evaluated according to the method of Example 1. The above results are shown in Table-2.

Comparative Example 2 The same inkjet recording as in Example 1 was performed using the inkjet paper used in Comparative Example 1 as a recording material, and then a laminator (MS Lampet L-230 Meiko Shokai Co., Ltd.) was used. Then, a laminating film (MS pouch film 100 μm manufactured by Meiko Shokai Co., Ltd.) was laminated on the image recording surface. This was evaluated according to the method of Example 1. The above results are shown in Table-2.

Comparative Example 3 The same ink jet recording as in Example 1 was carried out using a commercially available glossy paper (SA Kinto Super Art Kanzaki Paper Co., Ltd.) as a recording material. The recorded matter was evaluated according to the method of Example 1. Table above
Shown in 2.

[0087]

[Table 2]

[0088]

EFFECTS OF THE INVENTION In the recorded matter of the present invention having the above-described structure, it is not impossible to observe a recorded image from the surface recorded with a recording liquid like ordinary paper, but the recorded surface By observing the recorded image from the surface opposite to the side, that is, the base material side, it has an excellent effect that has not been obtained in the past. That is, since the non-porous layer has a light-transmitting property, diffuse reflection on the image observation surface side is reduced, which cannot be realized in a recorded matter recorded with a recording liquid on a porous sheet such as paper. Image optical density is obtained.

Further, since the porous layer serving as the recording surface has liquid permeability and light diffusibility, the absorption of the recording liquid and the resolution of the recording screen are improved, and a recording having a clear recorded image is obtained. You can provide things.

Further, since the light-transmissive base material is used as the support, in addition to the above-mentioned effect due to the light-transmissive property of the base material, the recorded image has gloss, water resistance, weather resistance and abrasion resistance. Sex is given.

The recorded matter of the present invention is remarkably excellent in the optical density of the recorded image and the operability in producing the recorded image, as compared with the conventional method of laminating a transparent film on the surface of the recorded image. is there.

As described above, the present invention has effects of excellent optical density, resolution, glossiness, water resistance, light resistance, abrasion resistance of recorded images and operability at the time of forming recorded images.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-89954 (JP, A) JP-A-58-136481 (JP, A) JP-A-58-134783 (JP, A) JP-A-59- 209189 (JP, A) JP 58-136480 (JP, A) JP 58-136478 (JP, A) JP 58-132585 (JP, A)

Claims (6)

[Claims] 1. At least a recording material in which a non-porous layer having an ink retaining property and a light transmitting property and a porous layer having a liquid permeability and a light diffusing property are sequentially laminated on a light transmitting substrate. An image recorded with a recording material is formed on the non-porous layer. 2. The recorded matter according to claim 1, wherein the non-porous layer is mainly composed of at least one resin selected from a cationic resin and a hydrophilic polymer. 3. The recorded matter according to claim 1, wherein the porous layer is mainly composed of a pigment and a binder. 4. The recorded matter according to claim 1, wherein the non-porous layer has a stronger ink absorption than the porous layer. 5. The porous layer has communicating holes.
Recorded matter described in. 6. The porous layer contains cracks therein.
Recorded matter described in.