JPH0735118B2 - Image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a recording material suitable for recording using a recording liquid, and a novel image capable of easily forming an image on the surface layer of glass, metal, plastic or the like. It relates to a forming method.

[0002]

2. Description of the Related Art As a recording instrument and a recording device for recording using a recording medium (for example, ink) containing a recording material, a fountain pen, a felt-tip pen, a magic pen, a pen plotter, etc. or a hard copy device for information equipment. Various types of printers (wire dot system, thermal transfer system, inkjet system, etc.) are known.

For these recording methods, ordinary paper and special paper designed for exclusive use are usually used. However, since these papers are generally porous and have light diffusivity, high density is achieved. It was difficult to obtain a recorded image of No. 1, and an image having excellent optical density and sharpness could not be obtained.

Generally, when forming an image using the above-described recording apparatus and recording apparatus, some problems as recording materials will be listed below.

When a paper having a porous surface such as an inkjet paper is used, 1) the surface of the paper is light diffusive, so that a clear image with high optical density cannot be obtained. 2) Since the surface of the paper is porous, a translucent image having gloss on the surface cannot be obtained. 3) Since the porous surface serves as an observation surface, the recorded image is constantly exposed to air, which is affected by oxygen, water droplets, water vapor, etc. in the air, resulting in poor image durability and storage stability. There is a problem such as.

Further, as the recording material, members other than the above,
For example, when using general paper, glass, plastic, metal, etc., 4) Direct recording requires special processing on the above-mentioned members, or requires large-scale and special equipment such as printing. To do. There is a problem such as.

A recording system that solves these problems at the same time, that is, it is excellent in various ink recording characteristics, and forms an image recorded with ink without any special treatment on the surface of general paper, metal, glass, plastic, etc. At present, the enabled system has not yet been obtained.

[0008]

Therefore, an object of the present invention is to easily form an image on the surface of general paper, metal, glass, plastic, etc. without any special treatment. An object is to provide an image forming method.

A further object of the present invention is that the optical density is high,
An object of the present invention is to provide an image forming method capable of obtaining the image having excellent sharpness.

A further object of the present invention is to provide an image forming method which can obtain the above-mentioned image having gloss and excellent storage stability and durability.

[0011]

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

That is, according to the present invention, a recording material in which an ink holding layer and a surface layer having liquid permeability and heat or pressure-fusible property are sequentially laminated on a translucent substrate is recorded on the surface layer side. The image forming method is characterized in that a liquid is applied, an image is formed on the ink holding layer through the surface layer, the surface layer is melted by heat or pressure, and the surface layer side is fused to the substrate.

[0013]

The first feature of the present invention is to use a recording material in which the image recording surface and the observation surface have a front-back relationship, unlike the conventional recording material in which the image recording surface and the observation surface are the same. Secondly, the recording material can be fused to another member.

That is, according to the present invention, recording is performed with a recording liquid on the surface layer which is the recording side, and the recorded image is observed from the ink holding layer side which is the observation side.

Therefore, the surface layer has liquid permeability, and has a function of promptly absorbing and transmitting the recording liquid adhering to the surface thereof, while the ink holding layer has the recording liquid transferred from the surface layer or the recording liquid. It has a function of absorbing and retaining the agent.

At this time, the surface layer must have a high affinity for the liquid medium in the recording liquid, and at the same time, for the recording agent (coloring material such as dyes and pigments and material having coloring property), Conversely, it must have a low affinity.

Therefore, the surface layer is formed by selecting a material having properties such as wetting, permeation and diffusion with respect to the recording liquid medium and not having properties such as adsorption, permeation and reaction with respect to the recording agent. There must be.

Moreover, since the surface layer has a fusion property, a material satisfying the fusion property in addition to the above characteristics must be selected.

On the other hand, since the ink holding layer absorbs and captures the recording liquid temporarily absorbed in the surface layer, it must have a stronger absorbing power for the recording liquid than the surface layer.

The absorbing power mentioned here is a word to be compared with the absorbing speed, and corresponds exactly to the relationship between the motor torque and the rotational speed.

Therefore, the ink holding layer must have a high affinity for the recording agent as well as for the recording liquid medium.

[0022]

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

The recording material used in the present invention includes a base material as a support, an ink holding layer formed on the support for substantially absorbing and capturing a recording liquid or a recording agent, and an ink holding layer on the ink holding layer. It is composed of a surface layer having liquid permeability and fusability that directly receives the recording liquid but does not substantially leave the recording agent.

However, when the surface layer or the ink holding layer also has a function as a base material, the base material is not always necessary.

As the base material used for the recording material, any conventionally known base material can be used, and examples thereof include polyester resin, diacetate resin, triacetate resin, polystyrene resin, polyethylene resin, polycarbonate resin, polymethacrylate resin and cellophane. ,celluloid,
Examples thereof include plastic films such as polyvinyl chloride resin, polyimide resin and polysulfone resin, plates or glass plates.

As described above, since the present invention is observed from the side opposite to the recording surface, it is necessary that the base material has a light-transmitting property.

The base material used may be subjected to any processing as long as it finally has a light-transmitting property. For example, the base material may have a desired pattern or gloss (a suitable gloss). It is also possible to apply a silk pattern).

Further, by selecting a base material having water resistance, abrasion resistance and blocking resistance, it is possible to impart water resistance, abrasion resistance and blocking resistance to the image observation surface of the recording material. it can.

Next, the surface layer constituting the recording material used in the present invention is characterized by having liquid permeability and fusion property.

The liquid permeability as referred to in the present invention is a property that allows the recording liquid to pass through quickly and does not substantially leave the recording agent in the recording liquid in the surface layer.

A preferred embodiment for improving the liquid permeability is one having a porous structure including cracks and communicating holes (including those having a micro size) in the surface layer and inside thereof.

For example, in the case of recording using a water-based ink, the following modes are available. (1) A mode that is composed of non-porous particles and a binder and has a crack inside,
(2) A mode in which other materials are dispersed in the coating film and treated with a solvent to make the inside of the layer porous, (3) A resin is dispersed in a mixed solvent, and the solvent having a high boiling point is a poor resin. A mode in which the inside of the layer is made porous as a solvent, and (4) A mode in which a foamable material is contained during film formation to make the inside of the layer porous. The materials used are both non-swelling to water and the solvent in the ink and non-staining to the dye in the ink. Furthermore, the surface layer according to the present invention exhibits a fusion property in the post-treatment after forming the recorded image.

A preferred embodiment of the surface layer is one exhibiting heat fusion property and / or pressure fusion property.

When the surface layer shows a heat-fusible property, it is composed of, for example, a thermoplastic resin, and when the surface layer shows a pressure-fusible property, for example, it contains a resin and the resin or a plasticizer. It is composed of microcapsules.

Therefore, as an embodiment of the surface layer according to the present invention satisfying the above-mentioned properties, for example, non-porous particles which are non-dyeing to a recording agent and which have a heat-fusing property are bound. It is an aspect consisting of a material.

The non-porous particles satisfying the above properties include organic particles such as thermoplastic resin, for example, polyethylene, polymethacrylate, elastomer, ethylene-vinyl acetate polymer, styrene-acryl copolymer, polyester, poly. At least one of resin powders such as acrylic and polyvinyl ether and emulsions is used as desired.

Further, the binder used has a function of binding the resin particles to each other and / or the ink holding layer, and like the resin particles, is non-adsorptive to the recording agent. It is necessary.

As a preferable material for the binder, any conventionally known material having the above-mentioned function can be used. For example, polyvinyl alcohol, acrylic resin, styrene-acrylic copolymer, ethylene-vinyl acetate polymer. One or more of resins such as starch, polyvinyl butyral, gelatin, ionomer, gum arabic, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylamide, phenol, melanin, epoxy and styrene-butadiene rubber are optionally used.

The surface layer used in the present invention is composed of these non-porous particles and a binder. Among these materials, in particular,
The material must be selected so that the melting temperature of the surface layer is in the range of 70 to 150 ° C.

In order to improve the above-mentioned function as the surface layer, various additives such as a surfactant and a penetrant may be added to the surface layer, if necessary.

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.

When the mixing ratio is 1/2 or less, cracks and communicating holes in the surface layer become small, and the effect of absorbing the recording liquid decreases. Further, when the mixing ratio is 50/1 or more, the adhesion between the resin particles or the ink holding layer and the resin particles becomes insufficient, and the surface layer cannot be formed.

The thickness of the surface layer depends on the recording liquid droplet amount, but is preferably 1 to 200 μm, and more preferably 3
˜50 μm.

Next, the non-porous ink retaining layer that substantially captures the recording agent absorbs and captures the recording agent that has passed through the surface layer and substantially retains it permanently. The ink holding layer is required to have a stronger absorbing power for the recording liquid than the surface layer.

This is because, when the absorption power of the ink holding layer is weaker than that of the surface layer, the recording liquid applied to the surface of the surface layer passes through the inside of the surface layer, and the tip of the recording liquid is transferred to the ink holding layer. Upon arrival, the recording liquid stays in the surface layer, so that the recording liquid laterally permeates and diffuses in the surface layer at the interface between the surface layer and the ink holding layer.

As a result, the resolution 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, the ink holding layer needs to be light transmissive.

The ink holding layer satisfying the above requirements is preferably composed of a light-transmitting resin which adsorbs a recording agent and / or a light-transmitting resin which is soluble and swellable in a recording liquid.

For example, when an aqueous recording liquid containing an acidic dye or a direct dye is used as the recording agent, the ink holding layer contains a cationic resin (for example, quaternized polyamines) having adsorptivity for the dye. Etc.) and / or a hydrophilic polymer having a swelling property with respect to an aqueous recording liquid.

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

The thickness of the ink holding 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, more preferably 3 to 20 μm. Is.

As a method for forming the ink holding layer and the surface layer on the substrate, the coating solution is prepared by dissolving or dispersing it in the above-mentioned suitable solvent, and the coating solution is prepared, for example, by a roll coating method or a rod bar. By a known method such as a coating method, a spray coating method, an air knife coating method,
A method of coating on a substrate and then quickly drying is preferable, and a method of forming a single sheet from the above hot melt coating method or the above material and laminating the sheet on the substrate is also preferable. good.

However, when the ink holding layer is provided on the base material, it is necessary to strengthen the adhesion between the base material and the ink holding layer and eliminate the space.

The presence of a space between the substrate and the ink holding 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 a means for forming an image on a recording material used in the present invention, a fountain pen, a ballpoint pen, a felt pen, a pen plotter, an ink mist, an ink jet, various printing, and the like, a recording device using a recording liquid containing a recording agent is used. And a recording device.

Among these recording devices and recording devices, the inkjet recording device and the pen plotter are preferable from the viewpoint of high speed image recording.

The recording medium used in the recording method of the present invention is preferably a conventionally known water-based and / or oil-based recording medium, and in order to quickly permeate the surface layer and be quickly absorbed and captured by the ink holding layer. It is necessary that the viscosity of the recording liquid is 1000 cps or less. Viscosity is preferably 100 cp
s or less, and preferably 50 cps or less.

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

As the recording agent contained in the recording liquid, conventionally known coloring agents such as dyes and pigments and / or coloring agents can be used.

For example, a water-soluble dye represented by a direct dye, an acid dye, a basic dye, a reactive dye, an edible dye or the like is preferable as a recording agent used for ink jet recording.

Next, the image forming method of the present invention will be described in detail below.

An image is recorded with a recording liquid on the surface side of the recording material described above.

Since the recording surface and the observing surface of the recording material have a front and back surface relationship, when characters or the like are to be printed, it is necessary to print in mirror characters (reverse characters) unlike the conventional case.

Next, the surface side of the recording material on which an image is recorded is brought into close contact with a substrate such as metal or plastic,
It is possible to easily form a recorded image using the ink on the substrate by applying heat from the side of the substrate or pressing the two together.

By using the method of the present invention, conventional
In the recording method using the ink, it is possible to easily obtain a good quality ink with a high density on a substrate, such as metal or plastic that cannot form an image, which cannot be recorded unless a special treatment is applied to the surface. Image formation has become possible.

Reference Example 1 Polyethylene terephthalate film (thickness 100 μm: manufactured by Toray) as a transparent substrate
The following composition A is used on the base material, and the dry film thickness is 6 μm.
m by the bar coater method,
The ink holding layer was formed by drying in a drying oven at 5 ° C for 5 minutes. Composition A * Comb polymer (LHM 108, manufactured by Soken Kagaku) <25
% Methocello solution> 55 parts Methyl vinyl ether / monoethyl ether maleic anhydride <10% water / ethanol solution> 45 parts * To 80 parts of the main chain (copolymer of 64 parts of 2-hydroxyethyl methacrylate and 16 parts of dimethylacrylamide) 20 parts of MMA macromer graft-polymerized) Further, the following composition B was applied thereon by a bar coater method so that the dry film thickness was 15 μm, and dried in a drying oven at 75 ° C. for 10 minutes. The surface layer was formed. Composition B Low-density polyethylene resin (Kemipearl M-200 Mitsui Petrochemical Industry Co., Ltd. solid content 40%) 100 parts Ionomer resin (Cemipearl SA-100 Mitsui Petrochemical Industry Co., Ltd. solid content 35%) 7 parts Sodium dioctyl Sulfosuccinate (Perex OT-P Kao Co., Ltd., solid content 70%) 0.2 parts The recording material thus obtained was white and opaque.

Example 1 An on-demand type in which the recording material prepared in Reference Example 1 was used with the following four types to generate a valve (bubble) with a heating resistor and discharge the recording liquid at the pressure. Inkjet recording was performed.

The compositions of the four recording liquids used are shown in Table 1.

For the recorded matter thus obtained,
Polyethylene terephthalate film (thickness 1
00 μm: manufactured by Toray Co., Ltd., and fused by using a laminator (MS Lampet L-230: manufactured by Meiko Shokai).

[0070]

[Table 1]

For the recorded matter thus obtained,
It was tested and evaluated according to the following method whether or not it was sufficiently suitable for the purpose of the present invention.

1) The ink absorbency was measured by measuring the time until the ink was not adhered to the recording portion even if the recording material was left at room temperature after ink-jet recording and touched with a finger, and the ink was sufficiently dried and fixed.

2) The image optical density (OD) was measured by using a Macbeth densitometer TR-524 with respect to a black ink recording portion.
It was measured from the image observation surface.

3) The surface gloss of the image is JIS Z 874.
Based on 1, the 45 ° specular gloss of the observed image surface was measured.

From the above results, comprehensive evaluation was performed. The results are shown in Table 2. In the comprehensive evaluation, the absorption of the recording liquid is rapid, the inkjet recording suitability is excellent, the image observation surface is glossy, the image observation sheet is well prepared, and a clear image is obtained. The evaluation was performed by scoring one in which even one of the image observation surface gloss and the image optical density was insufficient.

Reference Example 2 The polyethylene terephthalate film used in Example 1 was used as a translucent substrate,
The following composition C was coated on the base material by a bar coater method so that the dry film thickness was 8 μm, and dried in a drying oven at 120 ° C. for 5 minutes to form an ink holding layer.

Composition C Polyvinylpyrrolidone (PVP K-90 GAF)
<10% DMF solution> 85 parts Novolac-type phenol resin (Resitop PSK-2
320 Gunei Chemical Co., Ltd.) <10% DMF solution> 15
Department

Further, the following composition D was applied thereon by a bar coater method so as to have a dry film thickness of 20 μm, and dried in a drying oven at 80 ° C. for 10 minutes to form a surface layer.

Composition D Ethylene-vinyl acetate copolymer resin (Flowback Q1
6079N, iron chemistry) 100 parts Carboxymethyl cellulose (Metroze 60SH Shin-Etsu Chemical, 4% solution) 25 parts Polyoxyethylenoctyl phenyl ether (Emulgen 810 manufactured by Kao) 0.3 parts The recording material thus obtained is It was white and opaque. (Example 2) The same ink jet recording as in Example 1 was performed on the recording material prepared in Reference Example 2.

After that, art paper (SA Kinto Super Art: Kanzaki Paper Co., Ltd., 157 g / m 2) was laid on the surface layer, and pressed from the art paper side with an iron (surface temperature 130 ° C.).

Further, according to the method of Example 1, the recording material was evaluated. The results are shown in Table 2.

Reference Example 3 The polyethylene terephthalate film used in Example 1 was used as the translucent substrate,
The following composition E was coated on the base material by a bar coater method so that the dry film thickness was 10 μm, and the temperature was 100 ° C.
The ink holding layer was formed by drying in a drying oven for a minute.

Composition E Polyvinylpyrrolidone (PVP K-90 GAF)
<10% DMF solution> 80 parts Styrene / acrylic acid copolymer (Oxylac SH-2
100 manufactured by Nippon Shokubai Kagaku) <10% DMF solution> 1
5 copies

Further, the following composition F was coated thereon by a bar coater method so that the dry film thickness was 10 μm,
It was dried in a drying oven at 70 ° C. for 10 minutes to form a surface layer.

Composition F Polyamide resin (Toin Thermotac SK-1, manufactured by Tokyo Ink, particle size 20 μm) 100 parts Styrene-butadiene rubber (ISR6619 Japan synthetic rubber solid content 50%) 15 parts Polyoxyethylene (Emulgen A-500) (Made by Kao)
0.2 parts The recording material thus obtained was white and opaque.

Example 3 The same ink jet recording as in Example 1 was performed on the recording material prepared in Reference Example 3.

Then, plate glass (thickness: 2 mm) was formed on the surface layer.
Were stacked and pressed from the substrate side with an iron (surface temperature: 140 ° C.).

Further, according to the method of Example 1, the recording material was evaluated. The results are shown in Table 2.

Reference Example 4 Compositions E and F used in Reference Example 3 were formed on a Teflon film in the same manner as in Reference Example 3, and then the Teflon film was peeled off to obtain a white opaque recording material. It was

Example 4 The same ink jet recording as in Example 1 was carried out on the recording material prepared in Reference Example 4.

Then, an aluminum foil was overlaid on the surface layer, and the aluminum foil was pressure-bonded with an iron (120 ° C.).

The recording material was evaluated according to the method of Example 1. The results are shown in Table 2.

[0093]

[Table 2]

[0094]

As described above, according to the image forming method of the present invention, the recording surface and the observing surface have a front-back relationship, that is, recording is performed from the surface layer side and observation is performed from the base material side (ink holding layer side). By using the recording material, it is possible to provide a clear recorded image having a very high optical density, which was impossible in the past when recording on a porous sheet such as paper.

Further, such a recording material is a completely new recording material which is not available in the past, because the above recorded image can be fused to another substrate.

Further, by using the method of the present invention, it becomes possible to easily form a recorded image excellent in high image density and sharpness, which has not been obtained by a recording liquid, on glass, plastic, cloth or the like. It was

Continuation of the front page (56) Reference JP-A-58-136481 (JP, A) JP-A-57-89954 (JP, A) JP-A-58-136478 (JP, A)

Claims (8)

[Claims] 1. A recording liquid is provided on the surface side of a recording material in which an ink holding layer and a surface layer having liquid permeability and heat or pressure-fusible property are sequentially laminated on a translucent substrate. Then, an image is formed on the ink holding layer via the surface layer, and then the surface layer is melted by heat or pressure, and the surface layer side is fused to the substrate. 2. The image forming method according to claim 1, wherein the surface layer of the recording material is porous. 3. The image forming method according to claim 1, wherein the surface layer of the recording material is mainly composed of non-porous particles and a binder. 4. The melting temperature of the surface layer of the recording material is 70 to
The image forming method according to claim 1, which is in a range of 150 ° C. 5. The image forming method according to claim 1, wherein the ink holding layer of the recording material is non-porous. 6. The image forming method according to claim 1, wherein the ink holding layer of the recording material is light transmissive. 7. The image forming method according to claim 1, wherein the ink holding layer of the recording material is mainly composed of at least one resin selected from a cationic resin and a hydrophilic polymer. 8. The image forming method according to claim 1, wherein the substrate is paper, plastic, metal, or glass.