JPH04226383A - Recorded material - Google Patents

Abstract

PURPOSE:To provide a recorded material which has luster on its surface, which is excellent in water resistance, wear resistance and shelf life, and is excellent in high image quality and high optical density. CONSTITUTION:A recording material is obtained wherein an image is formed by a recording agent on, at least, a non-porous layer of a material to be recorded in which the non-porous layer having an ink keeping property and a light transmitting property and a porous layer having a liquid transmitting property and light scattering property are successively laminated on a light transmitting base material.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to recorded matter obtained by a recording method using a recording liquid such as a felt pen, a fountain pen, a pen plotter, an inkjet recording device, etc. The present invention relates to a recorded material having excellent quality and high quality recorded images.

0002

[Prior Art] Conventionally, paper used for recording methods using recording liquid, such as writing with a fountain pen, felt pen, or ballpoint pen, or recording with a pen plotter or inkjet recording device, includes high-quality paper, bond paper, writing paper, etc. Examples include general paper, art paper, coated paper such as cast coated paper, etc.

However, in recent years, with the development of recording equipment such as inkjet recording devices and pen plotters, sufficient recording characteristics have not been obtained with the above-mentioned conventional recording materials.

In other words, since high-speed recording and multi-color recording are performed that are incomparable to conventional recording materials, conventional recording materials have poor absorbency of recording liquid and color development when multiple recording liquids adhere to the same location. Gender, color, etc. have not reached a satisfactory level.

[0005] In order to solve these problems, coated paper, such as inkjet paper, having a porous ink absorbing layer on the surface of the base material has been devised.

For example, Japanese Patent Application Laid-Open No. 60-214989 describes a sheet comprising a porous ink-absorbing resin layer provided on a substrate.

[0007] This ink absorbing layer is porous and contains pores and cracks inside, so that the ink absorption speed is improved.

As described above, by providing a porous ink absorption layer, it is possible to increase the ink absorption to some extent, but since it is porous, it has light diffusivity, and it is difficult to obtain clear images and optical density. High quality and glossy images cannot be obtained.

Furthermore, since the image is observed from the recording surface of the ink, the recording agent is left on the surface of the absorbent layer as much as possible, which has the drawback of poor durability such as water resistance and storage stability of the image. .

[0010] Also, recently, inkjet recording devices,
2. Description of the Related Art As the speed and quality of recording using pen plotters and the like progresses, there is a demand for recording materials with dramatic recording performance.

That is, the absorbency of the recording liquid, the coloring property of the recording agent,
There is now a need for a recording material that is significantly superior to conventional recording materials in all recording performances such as image quality, resolution, color properties, recorded image density, and gloss of recorded images.

0012

[Problems to be Solved by the Invention] However, at present, a recording material that simultaneously satisfies all of these recording characteristics has not yet been obtained. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a recorded material having a glossy surface using a recording material that solves the above-mentioned conventional problems.

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

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

[0015]

[Means for Solving the Problems] The above objects are achieved by the following present invention.

That is, the present invention provides a recording medium in which a non-porous layer having ink retention and light transmission properties and a porous layer having liquid permeability and light diffusion properties are sequentially laminated on a transparent substrate. The recorded object is characterized in that an image is formed using a recording agent on at least the non-porous layer of the material.

[0017]

[Operation] The main feature of the present invention is that, unlike conventional recording materials in which the recording surface and the viewing surface are the same, a recording material in which the recording surface and the viewing surface are front and back is used.

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

[0019] Therefore, the porous layer has liquid permeability and has the function of quickly absorbing and transmitting the recording liquid attached to its surface, while the non-porous layer has liquid permeability that has been transferred from the porous layer. It has the function of absorbing and retaining recording liquid or recording agent.

[0020] At this time, the porous layer must have high affinity for the liquid medium in the recording liquid, and at the same time must have a high affinity for the recording agent (colorants such as dyes and pigments and color-forming materials). , on the other hand, must have low affinity.

[0021] Therefore, the porous layer has properties such as wetting, permeation, and diffusion with respect to the recording liquid medium, and has properties such as wetting, permeation, and diffusion with respect to the recording medium.
It must be constructed by selecting a material that does not have properties such as adsorption, penetration, or reaction.

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

Therefore, the non-porous layer must have high affinity not only for the recording liquid medium but also for the recording agent.

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

The recorded matter of the present invention includes a base material as a support, a non-porous layer formed on the support material that absorbs and captures the recording liquid or recording agent, and a non-porous layer formed on the non-porous layer. This can be obtained by using a recording material formed of a porous layer that directly receives recording liquid, has liquid permeability, and leaves substantially no recording agent.

Regarding the recording material used to obtain the recorded matter of the present invention, conventionally known substrates can be used, and specifically, polyester resins, diacetate resins, triacetate resins, polystyrene resin,
Examples include plastic films, plates, and glass plates made of polyethylene resin, polycarbonate resin, polymethacrylate resin, cellophane, celluloid, polyvinyl chloride resin, polyimide resin, and the like.

[0027] As mentioned above, in the present invention, since the recorded image is observed from the side opposite to the recording side,
The base material needs to have translucency.

[0028] Further, the base material used may be subjected to any processing as long as it finally has translucency.
For example, it is possible to give the base material a desired pattern or gloss (moderate gloss or silk pattern).

Furthermore, by selecting a base material that has 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 recorded material. .

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

[0031] The term "liquid permeability" as used in the present invention refers to a property that allows the recording liquid to pass through the porous layer and substantially prevents the recording agent in the recording liquid from remaining inside the porous layer.

[0032] Here, the porous layer is a layer having cracks and communicating pores inside the layer.

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

[0034] The porous layer for satisfying the above characteristics is as follows:
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 that are non-adsorbent to the recording agent, such as polyethylene, polymethacrylate, elastomers, and ethylene-vinyl acetate polymers. At least one of resin powders and emulsions such as polymers, styrene-acrylic copolymers, polyesters, polyacrylics, and polyvinyl ethers may be used as desired.

It should be noted that the resin particles used in the present invention are not limited to the above-mentioned resin particles, and may be any known material as long as it is non-adsorbent to the recording material.

[0037] Furthermore, the binder used has the function of binding the above-mentioned resin particles to each other and the non-porous layer, and like the resin particles, is non-adsorbent to the recording material. is necessary.

[0038] Preferred materials for the binder include any conventionally known materials that have the above-mentioned functions, such as polyvinyl alcohol, acrylic resin, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, etc. One or more of resins such as polymers, starches, polyvinyl butyral, gelatin, casein, ionomers, gum arabic, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylamide, phenol, melanin, epoxy, and styrene-butadiene rubber can be used as desired.

Furthermore, in order to improve the above-mentioned function as a porous layer, various additives such as
Surfactants, penetrants, etc. may be added to the porous layer.

[0040] 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 20/1. The range is 1.

If this mixing ratio is less than 1/2, the cracks and communicating pores in the porous layer will become smaller and the recording liquid absorption effect will decrease. Furthermore, if the mixing ratio is 50/1 or more, the adhesion between the resin particles or between the non-porous layer and the resin particles becomes insufficient, making it impossible to form a porous layer.

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

Next, the non-porous layer that substantially captures the recording liquid or recording agent absorbs the recording liquid that has passed through the porous layer.
captured and retained substantially permanently.

[0044] The non-porous layer needs to have a stronger ability to absorb recording liquid than the porous layer.

This is because when the absorption power 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 reaches the non-porous layer, the recording liquid will stay in the porous layer, and the recording liquid will permeate laterally within the porous layer at the interface between the porous layer and the non-porous layer. , will continue to spread. As a result, the resolution of the recorded image decreases, making it impossible to form a high-quality image.

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

The non-porous layer that satisfies the above requirements is made 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 the recording liquid. It is preferable that

For example, when an aqueous recording system containing an acid dye or a direct dye is used as the recording material, the non-porous layer is
It is composed of at least one kind of resin selected from cationic resins that have adsorption properties for the above-mentioned dyes, such as quaternized polyamines and hydrophilic polymers that have swelling properties for aqueous recording liquids.

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

The thickness of the non-porous layer is sufficient as long as it is sufficient to absorb and capture the recording liquid, and although it varies depending on the amount of recording liquid droplets, it is preferably 1 to 50 μm, more preferably 3 to 50 μm.
It is 20 μm.

[0051] As a method for forming a non-porous layer and a porous layer on a substrate, a coating solution is prepared by dissolving or dispersing the materials preferably listed above in an appropriate solvent, and the coating solution is for example,
It is preferable to coat the 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, etc., and then dry it immediately. Alternatively, a method may be used in which a single sheet is first formed and then the sheet is laminated onto a substrate.

However, when providing a non-porous layer on the substrate,
It is necessary to strengthen the adhesion between the base material and the non-porous layer and eliminate spaces.

If a space exists between the base material and the non-porous layer, the surface of the recorded image will be subject to diffuse reflection, which will lower the substantial optical density of the image, which is not preferable.

Means for recording an image on the recording material forming the recorded matter of the present invention include recording materials containing a recording agent, such as fountain pens, ballpoint pens, felt-tip pens, pen plotters, ink mist, inkjet, and various types of printing. Examples include recording instruments and recording devices that use liquid.

From the viewpoint of high-speed image recording, an inkjet recording device or a pen plotter is suitable.

As the recording liquid used in the recording method for forming the recorded matter of the present invention, conventionally known aqueous and oil-based recording liquids can be used. In order to quickly absorb and trap the recording liquid in the layer, it is necessary that the viscosity of the recording liquid be 500 cps or less. Preferably, the viscosity is 100 cps or less, preferably 50 cps or less.

Furthermore, in consideration of safety against fire and resistance to environmental contamination, water-based recording liquids are preferred.

As the recording agent contained in the recording liquid, conventionally known coloring agents such as dyes and pigments and materials having color-forming properties can be used. For example, as the recording agent used in inkjet recording, water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes, and food colorings are preferred.

In the recording method for forming a recorded matter of the present invention, since the recording surface and the observation surface are in a front-back relationship, when printing characters, a device capable of printing mirror characters, unlike the conventional one, is used. It is necessary to use

[0060]

[Examples] The present invention will be specifically explained below based on Examples.

Example 1 A polyethylene terephthalate film (thickness: 100 μm, manufactured by Toray Industries, Inc.) was used as a light-transmitting base material, and the following composition A was coated on this base material using a bar coater method to a dry film thickness of 8 μm. The coating was coated using the following method and dried in a drying oven at 120°C for 5 minutes.

Composition A - Polyvinylpyrrolidone (PVPK-90 manufactured by GAF) <10% DMF solution> 88 parts - Novolak type phenol resin (Resitop PSK)
-2320 Gunei Chemical) <10% DMF solution>
12 parts

[0063] Furthermore, Composition B shown below was applied by a bar coater method to a dry film thickness of 15 μm, and dried in a drying oven at 80° C. for 10 minutes.

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

00
65 The recording material thus obtained was white and opaque. Using the following four types of ink on this recording material, generate bubbles with a heating resistor,
Inkjet recording was performed using a recording apparatus having an on-demand type inkjet recording head that ejects a recording liquid under the pressure to produce a recorded matter of the present invention. Table 1 shows the compositions of the four types of recording liquids used. The recorded material obtained in this way was tested in accordance with the following method to determine whether it was sufficiently suitable for the purpose of the present invention.
evaluated.

1) Ink absorption was measured by leaving the recorded matter at room temperature after inkjet recording, and measuring the time until the ink was sufficiently dried and fixed without adhering to the finger when the recorded area was touched with the finger. 2) Image optical density (O/D) is measured using Macbeth densitometer TR52.
Measurements were made from the image viewing surface side of the black ink recorded area using the following. 3) Image surface gloss was determined by measuring the 45° specular gloss of the observed image surface based on JIS Z 8741. 4) Regarding operability, when forming a recorded image, a case where no complicated work was required was rated ○, and a case where it was not required was rated x.

[0067] A comprehensive evaluation was made based on the above results. The results are shown in Table-2.

[0068] In the overall evaluation, the items that absorb the recording liquid quickly, have excellent suitability for inkjet recording, and have good gloss on the image viewing surface, clearness of the recorded image, and operability during image creation are selected. A score of "Poor" was given if at least one of the following was insufficient: ○, inkjet suitability, gloss of the image observation surface, and operability during image formation.

[0069]

[Table 1]

Example 2 The polyethylene terephthalate film used in Example 1 was used as a translucent base material, and the following composition C was applied on this base material.
was applied using a bar coater method to a dry film thickness of 5 μm, and dried in a drying oven at 110° C. for 10 minutes.

Composition C - Polyvinylpyrrolidone (PVPK-90 manufactured by GAF) <10% DMF solution> 84 parts - Styrene noacrylic acid copolymer (Oxilac SH-
2100 Nippon Shokubai Chemical) <10% DMF solution> 1
Part 6

Further, the following composition D was applied on top of it to a dry film thickness of 2.
Coating was performed using a bar coater method so that the thickness was 80 μm.
It was dried in a drying oven at ℃ for 10 minutes.

Composition D Polymethacrylate resin (Ficrosphere M manufactured by Matsumoto Yushi Co., Ltd., average particle size 10 μm) 100 parts by weight Ionomer resin (Chemipearl SA-100 manufactured by Mitsui Petrochemical Industries, Ltd., solid content 35%) 30 Part by weight Sodium octylsulfosuccinate (Perex OT-P
Manufactured by Kao Corporation (solid content 70%) 0.15 parts by weight Water 20 parts by weight

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

[0075] Furthermore, the above 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 translucent base material, and the following composition E was applied on this base material.
was coated by a bar coater method to a dry film thickness of 10 μm, and dried in a drying oven at 100° C. for 12 minutes.

Composition E *Comb-shaped 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
20 parts of MMA macromer was graft-polymerized to

Further, the following composition F was applied thereon to a dry film thickness of 1
Coating was performed using a bar coater method so that the thickness was 70 μm.
It was dried in a drying oven at ℃ for 10 minutes.

Composition F Thermoplastic elastomer resin (Chemipearl A-100 Mitsui Petrochemical Industries, Ltd., solid content 40%, particle size 5 μm)
100 parts by weight ionomer resin (Chemipearl SA-100 manufactured by Mitsui Petrochemical Industries, Ltd., solid content 35%) 10 parts by weight polyoxyethylene (Emulgen A-500 manufactured by Kao Corporation)
0.2 parts by weight

[0080] Inkjet recording similar to that in Example 1 was performed on this recording material to produce a recorded matter of the present invention. Further, this recorded material 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. Inkjet recording similar to that in Example 1 was performed on the octopus recording material to produce a recorded matter of the present invention.

[0082] Further, this recorded material was evaluated according to the method of Example 1.

The above results are shown in Table 2.

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

Comparative Example 2 After performing inkjet recording in the same manner as in Example 1 using the inkjet paper used in Comparative Example 1 as the recording material, a laminator (MS Lamipet L-230 manufactured by Meiko Shokai Co., Ltd.) was used. A laminating film (MS Pouch Film 100 μm, manufactured by Meiko Shokai Co., Ltd.) was laminated onto the image recording surface using the photosensitive resin. This product was evaluated according to the method of Example 1. The above results are shown in Table-2.

Comparative Example 3 Commercially available glossy paper (SA Kinto Super Art Kanzaki Paper Co., Ltd.)
) was used as the recording material, and inkjet recording was carried out in the same manner as in Example 1. Further, the recorded matter was evaluated according to the method of Example 1. The above results are shown in Table-2.

[0087]

[Table 2]

[0088]

Effects of the Invention In the recorded matter of the present invention constructed as described above, although it is not impossible to observe the recorded image from the side recorded with recording liquid like ordinary paper, By observing the recorded image from the opposite side, that is, from the substrate side, excellent effects not previously available can be obtained. In other words, since the non-porous layer has light-transmitting properties, diffuse reflection on the image viewing surface side is reduced, and a high level of light transmission that cannot be achieved with recorded materials recorded using a recording liquid on a porous sheet such as paper is achieved. Image optical density is obtained.

[0089] Furthermore, since the porous layer serving as the recording surface has liquid permeability and light diffusivity, the absorbency of the recording liquid and the resolution of the recording screen are improved, resulting in a record having a clear recorded image. can provide things.

Furthermore, since a light-transmitting base material is used as the support, in addition to the above-mentioned effects based on the light-transmitting nature of the base material, the recorded image has gloss, water resistance, weather resistance, and abrasion resistance. gender is given.

The recorded material of the present invention is significantly superior in terms of the optical density of the recorded image and the operability when creating the recorded image, compared to the conventional method of laminating a transparent film on the surface of the recorded image. be.

As described above, the present invention has excellent effects on the optical density, resolution, gloss, water resistance, light resistance, abrasion resistance, and operability of recorded images when creating recorded images.

Claims (6)

[Claims] Claim 1: A recording material comprising a transparent base material, and a non-porous layer having ink retention and light transmission properties, and a porous layer having liquid permeability and light diffusion properties, which are sequentially laminated on a transparent base material. A recorded matter characterized in that an image formed by a recording agent 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 cationic resins and hydrophilic polymers. 3. The recorded material 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 ability than the porous layer. 5. The recorded material according to claim 1, wherein the porous layer has communicating pores. 6. The recorded material according to claim 1, wherein the porous layer contains cracks.