JPH08286579A - Recording material and regenerating method of image holding recording material - Google Patents

Abstract

PURPOSE: To provide such a recording material that at least the recording surface is a paper layer essentially comprising cellulose fiber, an image is formed on this recording material to produce an image holding and recording material, and that the image can be surely and enough peeled and removed by impregnating the recording material with a promoting liquid for removal of images containing water and then adhering an image peeling member to the image, and to provide a regenerating method of the image holding and recording material by which an image can be surely and sufficiently peeled and removed. CONSTITUTION: At least the recording surface of this recording material is a paper layer essentially comprising cellulose fiber. When a liquid having <40mN/m surface tension is dropped, the recording surface shows the contact angle θ satisfying -0.6<cosθ<0.8. The regenerating method includes the following process. After an image holding and recording material produced by forming an image on the recording material is impregnated with a promoting liquid for removal of images containing water, the image is adhered to an image peeling member by heat or pressure to peel and remove the image from the recording surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material having at least a recording surface made of a paper-like layer containing cellulose fibers as a main component, and more specifically, a heat-melting or heat-softening ink on the recording surface. From a recording material suitable for peeling and removing the image from the recording material on which the image has been formed and reproducing the recording material for reuse in image formation, and an image holding recording material on which the image is formed The present invention relates to a method for reproducing an image-holding recording material, in which an image is peeled and removed to reproduce the recording material.

[0002]

2. Description of the Related Art Due to the recent OA, a large amount of printer paper and copying paper have been used.
This has caused a problem of deteriorating the global environment due to deforestation. Conventionally, in order to solve such problems, a method in which used paper is disintegrated back into pulp, ink etc. adhering to the pulp is removed, and then paper is re-formed and recycled into paper called recycled paper or recycled paper. However, recently, there has been proposed a paper and a method for cleaning an image, in which an image such as a character on a paper that has been used once can be removed by a cleaning process and reused for copying or printing. . For example, such paper is disclosed in Japanese Patent Laid-Open No.
As described in JP-A-67043, the surface of a sheet-shaped recording material, particularly one surface, is subjected to a release treatment, and the release-treated recording material is marked to distinguish it from plain paper. There are things.

However, such copying paper has the following problems. This is a special paper whose surface is subjected to a release treatment, and cannot be applied to general copying paper and printing paper which are used in large quantities as at present, and thus it is difficult to apply. Therefore, it is difficult to copy or print by mixing with general copying paper. Further, from the viewpoint of resource reuse, it is important to perform double-sided copying, that is, it is possible to copy on both front and back sides of one copy sheet, and it is considered that copy sheets for both front and back sides will become mainstream in the future. Under such circumstances, there are difficulties in using a recording material having a release agent applied on one side. Further, JP-A-1-101576 and JP-A-1-10
In Japanese Patent No. 1577, the recording material on which the image is formed is immersed in an organic solvent that dissolves the toner resin of the image formed on the recording material, and the image is recorded from the recording material by ultrasonic treatment. Although a method for reproducing a recording material to be removed is disclosed, since this method uses an organic solvent, there are problems in use environment such as pollution, ignition property and toxicity.
There are difficulties in using it in ordinary offices and homes. on the other hand,
Japanese Patent Laid-Open No. 1-297294 discloses that a recording material is
An image formed on a recording material is heated by using a material formed of plastic, metal, paper having poor liquid permeability or ceramics, and heating the image formed on the recording material with a heat-meltable peeling body interposed. Although a cleaning method for peeling off from the paper is disclosed, a special paper (releasable paper) whose surface has been subjected to a release treatment must be used. Currently, general copying paper and printing paper used in large quantities. There is a difficulty that can not be applied to.

Therefore, as a method for solving the above-mentioned conventional problems, an image is formed on a recording material having a paper-like layer containing cellulose fibers as a main component at least on the recording surface by using a heat-melting or heat-softening ink. A method for reproducing an image-holding recording material, in which an image-removing promoting liquid containing water is held on the image-holding recording material on which the image is formed, and then the image is adhered to an image peeling member and peeled off from the recording material. This method is effective because it has no problem in use environment, can be applied to general copying paper, printing paper, etc., and can peel and remove the image without damaging the recording material. This is a method of reproducing an image-holding recording material, but it is not always possible to completely peel and remove the image from all recording materials, and there is a problem that the peeling and removal of the image is insufficient depending on the recording material. There is.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a recording material from which an image can be reliably and sufficiently peeled and removed, and a method of reproducing an image-bearing recording material that can reliably and sufficiently peel and remove an image. To do.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have noticed that the releasability of an image from an image-holding recording material varies depending on the difference of the recording material. We examined the difference in the characteristics of the recording material that is difficult to remove, and found that the wettability of the recording surface, which is composed of a paper-like layer composed mainly of cellulose fibers, in the recording material is related to the peelability of the image. The present invention has been achieved.

That is, the above object of the present invention is to provide a recording material in which at least the recording surface is composed of a paper-like layer containing cellulose fiber as a main component, and the surface tension of the recording surface is 40.
The contact angle cos θ when the liquid of mN / m is dropped is −0.
This is achieved by a recording material having a recording surface in the range of 6 or more and 0.8 or less.

BEST MODE FOR CARRYING OUT THE INVENTION

The contact angle here is a wetting index having a surface tension of 40 mN / m from a microsyringe attached to a contact angle meter CA-D manufactured by Kyowa Kagaku Co. under a temperature of 23 ° C. and a relative humidity of 50%. One drop of the standard liquid (manufactured by Wako Pure Chemical Industries, Ltd.) is dropped on the recording surface of the recording material, and the contact angle about 5 seconds after the dropping is measured by the same device.

Such a contact angle can be obtained by using a sizing agent in the papermaking process. As the sizing agent, various internally added sizing agents and surface sizing agents used in a general papermaking process can be used, but a liquid having a surface tension of 40 mN / m was dropped on a film obtained by drying the sizing agent. It is preferable to use a sizing agent having a contact angle cos θ of −0.6 to 0.8. Using a sizing agent outside this range, the cos of the contact angle on the recording surface
It is difficult to obtain a recording material having θ in the range of −0.6 to 0.8.

The contact angle is 23 ° C. and the relative humidity is 5
Under a 0% environment, one drop of a wetting index standard liquid (manufactured by Wako Pure Chemical Industries, Ltd.) having a surface tension of 40 mN / m was supplied from a microsyringe attached to a contact angle meter CA-D manufactured by Kyowa Scientific Co., Ltd.
The size is dropped on a film sample obtained by drying, and the contact angle about 5 seconds after the dropping is read by the same device and measured. The film obtained by drying the sizing agent was prepared by immersing a well-cleaned slide glass in an undiluted solution of the sizing agent, taking it out, and drying it at room temperature. It is created by leaving it for a minute.

As such a sizing agent, for example, an alkyl ketene dimer sizing agent is most effective and most suitable, but a styrene type or olefin type synthetic sizing agent can also be used. Specific examples of such a synthetic sizing agent include AK sizing agent manufactured by Misawa Ceramic Chemical Co., Ltd. and KN sizing agent manufactured by Harima Chemicals Co., Ltd. The sizing agent is internally added on the paper machine,
It is used for surface sizing with a size press, coating with a coating machine, impregnation, etc.
In order to obtain sθ, it is preferable that the sizing agent be present in a larger amount on the recording surface of the recording material, and it is preferable that the sizing is performed by a method such as surface sizing, coating or impregnation, rather than internal addition.

A typical example of the recording material of the recording material of the present invention in which at least the recording surface is composed of a paper material layer containing cellulose fibers as a main component is a paper containing cellulose fibers as a main component. Recording materials to be used include recording materials which are generally used as copy paper, printing paper, recording paper, and the like.

Further, the present invention relates to the above-mentioned recording material. Further, at least the recording surface of a recording material having a paper-like layer containing cellulose fibers as a main component has a heat-melting property. Alternatively, after the image-removing promoting liquid containing water is held on the image-holding recording material on which the image is formed by the heat-softening ink, the image is heat-bonded and / or pressure-bonded to the image peeling member. In a method of reproducing an image-holding recording material which is peeled off from a recording surface, the recording material is
An image-holding recording material having a recording surface having a contact angle cos θ of −0.6 to 0.8 when a liquid having a surface tension of 40 mN / m is dropped on the recording surface. It also includes the reproduction method of.

The image forming method of the image-holding recording material in the present invention includes, for example, a method of forming an image with a coloring agent by an electrophotographic method and a developer containing a thermosoftening resin as a main component, and a coloring agent by a thermal transfer method. And a method of forming an image with a thermal transfer ink layer containing a heat-melting polymer as a main component, a method of forming an image with a coloring agent by an inkjet method and a recording agent containing a heat-softening or heat-melting substance as a main component, Examples thereof include an image-bearing recording material on which an image is formed with a heat-softening ink as in an electrophotographic method, which is excellent in image releasability and is preferable. As the image removal promoting liquid in the present invention, it is preferable to use water, an aqueous solution containing a surfactant, an aqueous solution containing a water-soluble polymer, an aqueous solution containing a surfactant and a water-soluble polymer, or the like.

The surfactant can sufficiently and quickly permeate the image removal accelerating liquid containing water into the contact portion between the image on the recording surface of the recording material and the cellulose fiber, and the peeling of the image can be shortened. It is preferably used because it can be assured in time. Examples of the surfactant include anionic (carboxylic acid salt, sulfonic acid salt, sulfuric acid ester salt, phosphoric acid ester salt, phosphonic acid salt, etc.), cationic (amine salt, quaternary ammonium salt, benzalco salt). Aluminum salt, benzethonium chloride salt, pyridinium salt, imidazolinium salt, sulfonium salt, polyethylene polyamine, etc.), amphoteric system (amino acid, carboxybetaine, sulfobetaine, aminosulfate, aminocarboxylate,
(Imidazoline derivative, etc.), non-ionic type (ether type, ether ester type, ester type, nitrogen-containing type, polyhydric alcohol, amino alcohol, polyethylene glycol, etc.)
The usual surfactants, fluorine-based surfactants, etc. can be mentioned. The content in the aqueous solution is preferably 0.01% to 20%, particularly preferably 0.01% to 5%.

Further, as the water-soluble polymer, for example,
Starch quality (kansho starch, potato starch, tapioca starch, wheat starch, corn starch, etc.),
Mannan (konjac, etc.), seaweed (Funori, agar, sodium alginate, etc.), plant mucilage (troloois,
Gum tragacanth, gum arabic, etc.), mucilage by microorganisms (dextran, levan, etc.), protein (glue,
Gelatin, casein, collagen, etc., glue natural polymers and cellulosic (viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, etc.), starch-based (soluble starch, carboxymethylstarch, dialdecit starch) semi-synthetic polymers, A synthetic polymer etc. are mentioned. The content in the aqueous solution is preferably 0.01% to 20%, particularly preferably 0.01% to 5%.

Further, as the image peeling member in the present invention, various resins, organic polymer substances such as rubber, metals such as aluminum and nickel are directly formed into a sheet, a belt or a roller. Alternatively, it is possible to use a support obtained by supporting these on the surface of another support.

[0018]

EXAMPLES The present invention will be described in more detail with reference to examples. In the text,% is based on weight unless otherwise specified.

Example 1 LBKP beaten to 400 ml of freeness was added to a polyamide epichlorohydrin resin (WS-570 manufactured by Japan PMC Co., Ltd.) at a pulp ratio of 0.4% and a polyacrylamide resin at 6.0% (Arakawa Chemical Industry Co., Ltd.). Polystron 117) from each company was added internally, and 1 g / m ² of oxidized starch (MS from Nippon Shokuhin Kako Co., Ltd.) was further applied with a size press of a Fourdrinier paper machine.
# 3800), 0.7 g / m ² of polyvinyl alcohol (PVA 117 manufactured by Kuraray Co., Ltd.), 0.4 g / m ² of polyamide epichlorohydrin resin (WS-5 manufactured by Japan PMC Co., Ltd.)
25) and 0.9 g / m ² of alkyl ketene dimer sizing agent (AS-202 manufactured by Japan PMC Co., Ltd.) were surface-sized to fabricate the recording material of Example 1 having a basis weight of 74 g / m ² . Alkyl ketene dimer sizing agent A used here
S-202 was thinly spread on a slide glass, dried, and a liquid having a surface tension of 40 mN / m was dropped on the film to measure a contact angle cos θ of -0.5.
In addition, the contact angle cose of the surface of the recording material of Example 1 measured in the same manner was 0.0. A PPC copying machine (IMAGIO manufactured by Ricoh Co., Ltd. was used as the recording material of Example 1.
320 FPI) to form a solid black image and a character image. After the image-formed recording material was impregnated with an image removal accelerating solution of an aqueous solution containing 0.8% of anionic surfactant sodium dihexyl sulfosuccinate (MA-80 manufactured by Mitsui Cyanamid Co., Ltd.), the image peeling member was imaged. The image was adhered to the image peeling member and peeled off from the recording material when the image peeling member was separated from the recording material by passing it through the nip of two rubber loafs heated in close contact with the surface on which the . The density of the portion where the image was peeled off and removed and the density of the background portion where the image was not originally formed were measured with a Macbeth reflection densitometer, and the difference was taken as the density after peeling. The density of the recording material after peeling was 0.008, and it was not possible to visually read the formed characters after peeling the image.

Example 2 In surface sizing with a size press of a Fourdrinier paper machine, an olefinic sizing agent (AK-400 manufactured by Misawa Ceramics Chemical Co.) was used in place of the alkyl ketene dimer sizing agent AS-202, and polyamide epichlorohydride. A recording material of Example 2 was obtained in the same manner as in Example 1 except that glyoxal (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used instead of the phosphorus resin WS-525.

Example 3 Example 3 was repeated in the same manner as in Example 2 except that the sizing agent used in the size press liquid of the Fourdrinier paper machine was an acrylic sizing agent (KN-800 manufactured by Harima Chemicals). A recording material was obtained.

Example 4 LBKP beaten to a freeness of 400 ml was added to a polyamide epichlorohydrin resin (WS-570 manufactured by Japan PMC Co., Ltd.) at a pulp ratio of 0.4%, and a polyacrylamide resin at 1.0% (Arakawa Chemical Industry Co., Ltd.). Polystron 117),
0.5% alkyl ketene dimer sizing agent (Japan PM
C-manufactured AS-202) was added internally, and 1 g / m ² of oxidized starch (MS # 3800 manufactured by Nippon Shokuhin Kako Co., Ltd.), 0.7 g / m ² by a size press of a Fourdrinier paper machine.
Polyvinyl alcohol (PVA117 manufactured by Kuraray Co., Ltd.),
0.4 g / m ² of polyamide epichlorohydrin resin (WS-525 manufactured by Japan PMC), 0.5 g / m ² of alkyl ketene dimer sizing agent (AS- manufactured by Japan PMC)
202) was subjected to surface sizing to obtain a recording material of Example 4 having a basis weight of 74 g / m ² .

Comparative Example 1 The sizing agent used in the size press liquid of the Fourdrinier paper machine was a styrene-based sizing agent (Polymaron 36 manufactured by Arakawa Chemical Industry Co., Ltd.).
A recording material of Comparative Example 1 was obtained in the same manner as in Example 1 except for 0).

Comparative Example 2 The sizing agent used in the size press liquid of the Fourdrinier paper machine was a styrene-based sizing agent (S manufactured by Misawa Ceramics Chemical Co., Ltd.).
A recording material of Comparative Example 2 was obtained in the same manner as in Example 2 except for -810).

Comparative Example 3 Comparative Example 3 was carried out in the same manner as in Example 2 except that the sizing agent used in the size press liquid of the Fourdrinier paper machine was a styrene type sizing agent (KN-500 manufactured by Harima Kasei). A recording material was obtained.

Comparative Example 4 The sizing agent used in the size press liquid of the Fourdrinier paper machine was a styrene-based sizing agent (A manufactured by Misawa Ceramics Chemical Co., Ltd.).
A recording material of Comparative Example 4 was obtained in the same manner as in Example 2 except that the recording material was K-600).

For the recording materials of Examples 2 to 3 described above, an image was formed in the same manner as in Example 1, then the image was peeled and removed in the same manner as in Example 1, and the density after peeling was measured. did. Moreover, the readability of the characters after peeling was evaluated. The results obtained from these are shown in Table 1 together with the contact angle cos θ of the sizing film and the contact angle cos θ of the recording material surface measured in the same manner as in Example 1.

[0028]

[Table 1]

As shown in Table 1, it can be seen that the recording material according to the present invention is more surely and sufficiently peeled and removed from the recording material than the comparative example.

[0030]

According to the recording material of the present invention or the method of reproducing the image-holding recording material, the image formed on the recording material can be surely and sufficiently peeled and removed. The recording material can be reproduced from the recording medium to be repeatedly reused for forming images.

Claims (6)

[Claims] 1. A recording material having at least a recording surface composed of a paper-like layer containing cellulose fibers as a main component, and a contact angle cos θ when a liquid having a surface tension of 40 mN / m is dropped onto the recording surface. A recording material having a recording surface in a range of −0.6 to 0.8. 2. The cos of the contact angle when a liquid having a surface tension of 40 mN / m is dropped on a film obtained by drying a sizing agent.
2. The recording material according to claim 1, wherein the paper quality layer contains a sizing agent in which θ is in the range of −0.6 to 0.8. 3. The cos of the contact angle when a liquid having a surface tension of 40 mN / m is dropped on a film obtained by drying a sizing agent.
The recording material according to claim 1 or 2, wherein the recording surface has a sizing agent having θ in the range of -0.6 to 0.8. 4. The recording material, at least the recording surface of which is composed of a paper-like layer containing cellulose fibers as a main component, is a paper containing cellulose fibers as a main component. The recording material described. 5. An image bearing recording in which an image is formed by a heat-melting or thermosoftening ink on a recording surface of a recording material having at least a recording surface composed of a paper-like layer containing cellulose fibers as a main component. In a method for reproducing an image-holding recording material, which comprises holding an image removal promoting liquid containing water on the material, and peeling and removing the image from a recording surface by heat-bonding and / or pressure-bonding the image to an image-peeling member. , The recording material is
An image-holding recording material having a recording surface having a contact angle cos θ of −0.6 to 0.8 when a liquid having a surface tension of 40 mN / m is dropped on the recording surface. How to play. 6. The method for reproducing an image-holding recording material according to claim 5, wherein the recording material is a paper containing cellulose fibers as a main component.