JPH07285272A - Thermal transfer erasing ribbon, thermal transfer correcting ribbon, thermal transfer erasing method and thermal transfer correcting method using the same - Google Patents

Abstract

(57) [Summary] (Corrected) [Purpose] Thermal transfer decoloring ribbon and thermal transfer correction ribbon that can cleanly decolorize or correct any part of the printed matter that is color printed on thermosensitive coloring paper with a printing device. And a thermal transfer erasing method and a thermal transfer correcting method using the same. A thermal transfer ribbon formed by forming a thermal transfer layer on one surface of a substrate 1, wherein the surface of the thermal transfer layer is a thermal transfer erasing layer formed by an erasing agent layer 2 for erasing a color-developed portion of a thermosensitive color-developing paper. A color ribbon, a thermal transfer correction ribbon formed by two parts of a decoloring agent layer 2 and a heat-meltable ink layer 6 for correcting by decoloring / reprinting, and a thermal transfer decoloring method using the same , A thermal transfer correction method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer ink ribbon, and more particularly to a thermal transfer erasable ribbon capable of erasing a specific portion of a printed matter printed on a thermosensitive coloring paper by a thermosensitive coloring method for correcting erroneous characters. And a thermal transfer correction ribbon capable of erasing the specific portion and further printing, a thermal transfer erasing method and a thermal transfer correcting method using the same.

[0002]

2. Description of the Related Art Conventionally, there is a correction liquid which can be used not only for heat-sensitive color-developing paper but also for correcting a specific portion such as characters or figures printed on paper. This is a white ink in which a resin or the like serving as a binder is dissolved in a solvent and a white pigment having a hiding power such as titanium oxide is dispersed therein. Apply such a white ink on the characters or figures you want to erase with a brush,
Erase by air-drying.

[0003]

However, in the erasing method using such a correction liquid, since the color difference between the paper surface of the base material and the white pigment is large, the portion which is erased or corrected is conspicuous. Further, since the solvent is used, the printing portion to be erased is out of print, and there is a problem that the printing before erasing or correction can be discriminated from the back surface of the paper. In addition, the solvent of the correction fluid evaporates during use, increasing the viscosity,
There is also the inconvenience that it becomes thick when applied and it takes time to dry. Further, when these correction solutions are coated on a heat-sensitive color developing paper, the solvent in the correction solutions causes the surroundings of the coated parts to be colored or deteriorated, which impairs the external appearance and is not suitable for practical use.

The present invention has been made in view of the above circumstances, and in particular, it erases or erases a specific portion of a printed matter printed on a thermosensitive coloring paper by the thermosensitive coloring method.
A thermal transfer erasing ribbon and a rectifying ribbon that can be used for reprinting and rectification, and in which the erasing and erasing points are inconspicuous and the characters before erasing and the characters before erasing cannot be identified. It is an object to provide a decoloring method and a correcting method used.

[0005]

As a result of intensive research to solve the above problems, the following objects of the present invention have been achieved. That is, the invention of claim 1 is a thermal transfer ribbon comprising a thermal transfer layer formed on one surface of a substrate, wherein the thermal transfer layer contains an erasing agent for erasing the color-developed portion of the thermosensitive color-developing paper. It consists of a characteristic thermal transfer erasing ribbon. Further, according to the invention of claim 2, in a thermal transfer ribbon comprising a thermal transfer layer formed on one surface of a substrate, the surface of the thermal transfer layer contains an erasing agent for erasing the color-developed portion of the thermosensitive color paper. And a heat-meltable ink layer portion.

According to a third aspect of the present invention, the thermal transfer decoloring ribbon according to the first aspect is superposed on a specific portion of a printed matter printed on a thermosensitive coloring paper by the thermosensitive coloring system, and the rear surface of the erasing ribbon is removed. The thermal transfer erasing method is characterized by erasing by applying heat with a thermal head. Further, in the invention of claim 4, the thermal transfer correction ribbon according to claim 2 is superposed on a specific portion of a printed matter printed on a thermosensitive coloring paper by a thermosensitive coloring system, and first, the decoloring agent layer of the correction ribbon is formed. A thermal transfer correction method characterized in that heat is applied from the back of the portion with a thermal head to erase the color, and then heat is applied from the back of the portion of the heat-meltable ink layer of the correction ribbon with the thermal head to correct the print. It consists of

[0007]

According to the thermal transfer decoloring ribbon and the thermal transfer decoloring method of the present invention, an arbitrary portion such as a character thermally printed on the thermosensitive coloring paper can be removed by the action of the decoloring agent before or after the decoloring. It can be erased cleanly so that characters and the like cannot be distinguished.
Further, according to the thermal transfer correction ribbon and the thermal transfer correction method of the present invention, an arbitrary portion such as a character thermally printed on the thermosensitive coloring paper can be erased and a desired color by the action of the decoloring agent and the heat-meltable ink. It is possible to re-print with, and it is possible to make a clean correction so that the decolored portion and the character before decoloring cannot be discriminated.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail with reference to the preferred embodiments. 1A, 1B, and 1C are schematic cross-sectional views showing the configuration of an embodiment of the thermal transfer erasing ribbon of the present invention. The thermal transfer erasable ribbon of the present invention is shown in FIG.
As shown in FIG. 1B, the heat transferable decoloring agent layer 2 is provided on one surface of the substrate 1, and if necessary, as shown in FIG. A mat layer or a release layer 3 can be provided between the two, and a heat resistant slip layer 4 can be provided on the other surface of the substrate 1. Then, if further necessary, as shown in FIG. 1C, the adhesiveness between the matte layer or release layer 3 and the decoloring agent layer 2 may be adjusted, or the decoloring agent layer may be formed after transfer. It is also possible to provide an intermediate layer 5 for assisting the film property.

2A, 2B and 2C are schematic cross-sectional views showing the construction of an embodiment of the thermal transfer correction ribbon of the present invention. 2A shows the simplest structure, a thermal transfer layer is provided on one surface of the base material 1, and the surface of the thermal transfer layer is erased by a decoloring agent layer 2 for decoloring the colored portion of the thermosensitive coloring paper. And the portion of the heat-meltable ink layer 6. In addition, FIG. 2B is different from the configuration of FIG.
If necessary, a mat layer or a release layer 3 is provided between the substrate 1 and the decoloring agent layer 2 and the heat fusible ink layer 6, and a heat resistant slip layer 4 is further provided on the other surface of the substrate 1. It has a different structure. 2c is similar to the structure of FIG. 2b, in that the matting layer or peeling layer 3 and the decoloring agent layer 2 are bonded to each other in the same manner as in the case of the thermal transfer decoloring ribbon. The intermediate layer 5 is provided to adjust the properties and to assist the film forming property of the decoloring agent layer after transfer.

Further, a and b in FIG. 3 are respectively shown in FIG.
FIG. 6 is a schematic plan view showing an example of an arrangement pattern of a portion of a decoloring agent layer 2 and a portion of a heat-meltable ink layer 6 which constitute the surface of the thermal transfer correction ribbon shown in a, b, and c. In the thermal transfer correction ribbon of the present invention, the arrangement pattern of the portion of the decoloring agent layer 2 and the portion of the heat fusible ink layer 6 is not limited to these, and can be freely changed according to the printing device. be able to.

The layers of the thermal transfer decoloring ribbon and the thermal transfer correction ribbon of the present invention will be described below. The substrate used for the thermal transfer decoloring ribbon and the thermal transfer correction ribbon of the present invention may be the same as the substrate used for the conventional thermal transfer ink ribbon or thermal transfer sheet, and is not particularly limited. Specific examples include, for example, polyester, polypropylene, polycarbonate, cellulose acetate, polyethylene, polyvinyl chloride, polystyrene, nylon, polyimide, polyvinylidene chloride, polyvinyl alcohol, fluororesin, chlorinated rubber, plastic films such as ionomers, or glassine. In addition to paper such as paper, condenser paper and paraffin paper, cellophane, non-woven fabric and the like can be mentioned. Each of these may be used alone or in combination of two or more. The thickness of such a base material can be appropriately determined according to the material so that the required strength and thermal conductivity are appropriate, and is usually in the range of about 1 to 25 μm.

Directly on the base material 1 (FIG. 1a, FIG. 2a), or via the matte layer or release layer 3 (FIG. 1b, FIG. 2b), and if necessary. In case of intermediate layer 5
The decoloring agent layer 2 provided through (c in FIG. 1 and c in FIG. 2) is
When the decoloring agent is solid at room temperature, it can be formed by applying it alone or by mixing it with a thermoplastic resin such as styrene-butadiene rubber (hereinafter referred to as SBR) or a binder such as wax, but at room temperature. In the case of a liquid, it can be formed by applying a mixture of a heat-fusible material and a microcapsule mixed with a binder.

The decolorizer itself is a drug having a function of decoloring a leuco dye or the like formed on a thermosensitive color developing paper, and is different depending on the kind of the thermosensitive color developing agent. For example, thermoplastic polyether, polyethylene glycol, polypropylene. Glycols and their derivatives, alcohols such as stearyl alcohol, dicyclohexyl phthalate,
Plasticizers such as diethylhexyl phthalate and di2-ethylhexyl adipate, supercooling agents such as polycaprolactone,
Polyester, acetamide, stearamide, organic ammonium salt, organic amine, urea, thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholine Known decoloring agents such as compounds, piperidines, amidines, formazines, pyridines and olefin waxes can be used.

Of these, compounds having an ether bond in the molecule are effective in preventing color development of the thermosensitive color developing paper or decoloring the developed color paper. For example, polyethylene glycol and its derivatives, polypropylene. Examples thereof include glycol and its derivatives, polyglycerin and its derivatives, aliphatic ethers, aromatic ethers and cyclic ethers. The physical properties of such a decoloring agent are as follows:
It is preferably from 0 to 100 ° C, and the thermal transfer decolorizing ribbon or the modified ribbon using a decolorizing agent which is liquid at room temperature has poor storage stability, while the thermal transfer decoloring using a decoloring agent having a melting point of more than 100 ° C. Sufficient transferability and erasability cannot be obtained with the ribbon or the modified ribbon. However, even a decoloring agent that is liquid at room temperature can be used as a decoloring agent in the present invention by microencapsulating it with a capsule material such as a polymer material having an appropriate melting point. Moreover, these decolorizers are 1
The melt viscosity at 00 ° C is preferably 1,500 cps or less, and the melt viscosity at 100 ° C is 1,500 cps.
In the case of a material exceeding cps, the permeation of the decoloring agent into the printed portion of the thermosensitive color developing paper is lowered when the thermal transfer decoloring is performed, and the sufficient decoloring effect cannot be obtained.

Of the above decoloring agents, polyethylene glycol and its derivatives, polypropylene glycol and its derivatives are particularly preferable. Considering the melting point, melt viscosity, coagulation characteristics and the like suitable as a decoloring agent, the molecular weight thereof is preferably 7,000 or less in terms of weight average molecular weight.
More preferably, it is from 00 to 5000. Weight average molecular weight is 10
When it is less than 00, it becomes liquid and therefore needs to be microencapsulated. On the other hand, when the weight average molecular weight exceeds 7,000,
When thermal transfer bleaching is carried out as in the case of melt viscosity, the penetrability of the erasing agent into the printed portion of the thermosensitive color developing paper decreases, and a sufficient erasing effect cannot be obtained. In general, polyethylene glycol has a high affinity with water, which may cause problems with the storage stability of the thermal transfer decoloring ribbon or the modified ribbon obtained under high humidity conditions. At least one of the
Alternatively, it is preferable to use by etherifying or esterifying with an organic acid, a monomer, oligomer or polymer having a carboxyl group, and by doing so, the storage stability of the resulting thermal transfer decolorizable ribbon or modified ribbon is improved. .

Polyethylene glycols having appropriate melting points and melt viscosities can be used alone as a binder in the decoloring agent layer 2, but polyethylene glycols themselves have low fastnesses such as film strength. , Other binder, for example, SBR, acrylonitrile-butadiene copolymer resin, thermoplastic resin such as acrylic resin, ethylene resin, or wax is used together, or the film forming property of the decolorizer layer 2 is assisted. Therefore, it is preferable to provide the intermediate layer 5 between the decoloring agent layer 2 and the substrate 1. As the intermediate layer 5, the same thermoplastic resins and waxes as the binder of the decoloring agent layer 2 can be used. As described above, the decoloring agent can be used as a mixture with the binder. In that case, the mixing ratio of the binder and the decoloring agent is 10 to 100 parts by weight of the binder.
It can be added and mixed in the range of 500 parts by weight. The thickness of the decolorizing agent layer 2 is not particularly limited, but is, for example, about 0.
A thickness of 1 to 10 μm provides sufficient effect.

When forming the decoloring agent layer 2 as described above, a mat layer or a peeling layer 3 having a thickness of about 0.1 to 20 μm is formed on the surface of the base material 1 if necessary, and an intermediate layer 5 is further formed thereon. May be provided. Conventionally known materials can be used for the mat layer or the release layer 3. For example, in the case of the mat layer, an inorganic pigment such as silica or calcium carbonate dispersed in a resin dissolved in a solvent is applied. However, the surface of the substrate 1 may be mechanically matted to replace it. Such a matte layer can give a matt feeling to the decolored surface or the printed surface, and when the other surface is matte, it is difficult to distinguish the decolored portion or the corrected portion. The peeling layer is provided when the decoloring agent layer 2 and the heat-meltable ink layer 6 have insufficient peelability, and examples thereof include waxes, silicone wax, silicone resin, fluororesin, chlorinated polypropylene, and acrylic. It can be formed by applying a material having releasability such as resin. The formation method is as follows. A coating solution prepared by dissolving or dispersing the above-mentioned resins with necessary additives added thereto is dispersed or dispersed in an appropriate solvent and applied onto the substrate 1 by a known means such as gravure coating.・ Dry to form. The thickness of such a release layer is preferably about 0.1 to 5 μm.

The intermediate layer 5 assists the decoloring agent layer 2 when the film property is insufficient, or when the adhesion to the underlying mat layer (or peeling layer) is too weak, the adhesiveness is improved. It is provided as necessary in order to improve the temperature, and is formed by applying a material containing an adhesive resin as a main component such as an ethylene-vinyl acetate copolymer resin. Middle layer 5
Is usually a transparent layer, but may be a colored layer for the purpose of making it difficult to determine the corrected portion.

In the thermal transfer correction ribbon of the present invention, the surface of the thermal transfer layer is the decoloring agent layer 2 and the heat-meltable ink layer 6.
It consists of two parts. This heat-meltable ink layer 6
The same material as the heat-meltable ink layer used in the known thermal transfer ink ribbon can be used, which usually comprises a pigment and a binder, and various additives can be added if necessary. Of course, carbon black is preferable as the pigment for black monochromatic printing, but chromatic pigments such as yellow, magenta, and cyan can be used freely. It can also be used for multi-color printing, using chromatic color pigments such as yellow, magenta, and cyan. For example, a yellow ink layer, a magenta ink layer, and a cyan ink layer can be printed on the same substrate by a printing method. It can also be formed in a frame-sequential manner with a predetermined area. The amount of these pigments used is about 5 to 70% by weight in the ink layer.
The ratio occupying is preferable.

The binder contains wax as a main component, and in addition, a mixture of wax and a drying oil or a resin, a mineral oil, and a derivative of cellulose or rubber is used. Typical examples of waxes include microcrystalline wax, carnauba wax, and paraffin wax.
Furthermore, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, spermaceti wax, ivowa wax, wool wax, shellac wax, candelilla wax, petrolactam, polyester wax, partially modified wax, fatty acid ester, fatty acid amide, etc. Wax can be used. Further, a thermoplastic resin having a relatively low melting point can be mixed in the wax to improve the abrasion resistance of the ink and the adhesiveness to the transfer target. In this case, the thermoplastic resin is preferably used in a proportion of 5 to 300 parts by weight with respect to 100 parts by weight of the wax.

As a method of forming the heat-meltable ink layer 6, depending on the form of the heat-meltable ink to be applied, that is, the type of hot melt type, hot lacquer type, solution, dispersion, emulsion or the like, A known applicable method such as hot melt printing, hot lacquer printing, or normal gravure printing can be selected and used. The thickness of the heat-meltable ink layer 6 thus formed is 0.5.
The range of ˜20 μm is preferable.

On the other hand, the thermal transfer decoloring ribbon and the thermal transfer correction ribbon of the present invention are used for the base material 1 when the thermal transfer is performed on the surface of the thermosensitive coloring paper.
The image is transferred from the surface (rear surface) opposite to the surface provided with the decoloring agent layer 2 by a thermal head of the printer. For this reason, depending on the material of the base material 1, the base material 1 may be softened and adhered to make the movement of the thermal transfer ribbon worse. In such a case, the heat resistant slip layer 4 can be provided on the back surface of the base material 1 for the purpose of improving heat resistance, slip property, and releasability.

The heat resistant slip layer 4 is formed by applying a liquid obtained by adding other necessary additives to a solution of a binder resin to the back surface of the base material 1 and drying it. Examples of the resin that can be used for this binder include ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose resin such as nitrification cotton, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, acrylic resin,
Examples thereof include vinyl resins such as polyacrylamide and acrylonitrile-styrene copolymer, polyester resins, polyurethane resins, silicone-modified or fluorine-modified urethane resins, and the like.

Among these, it is preferable to use a resin having some reactive groups, for example, a hydroxyl group, and use a polyisocyanate or the like as a crosslinking agent to form a crosslinked resin layer. The thickness of the coating film may be thin, and a thickness of about 0.1 to 2 μm is sufficient. By providing such a heat-resistant slip layer 4, it becomes possible to use a resin film which is relatively weak against heat as the base material 1, but conversely, the base material 1 itself is
The heat resistant slip layer 4 is not necessary when it is excellent in heat resistance, releasability, slip property and the like.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples of thermal transfer decoloring ribbons and thermal transfer correction ribbons. [Example 1 (corresponding to thermal transfer decoloring ribbon)] A polyethylene terephthalate film [manufactured by Lumirror Toray Co., Ltd.] having a heat-resistant slip layer on the back surface and having a thickness of 6 μm was used as a base material,
A mat layer coating solution having the following composition was applied to the surface by a gravure coating method so that the coating amount was 0.3 g / m ² (solid content), and dried to form a mat layer. Then, a coating solution for decoloring agent layer having the following composition was applied on the matte layer by a gravure coating method so that the coating amount was 5 g / m ² (solid content) and dried to prepare a thermal transfer decoloring ribbon. did. Next, this heat transfer decoloring ribbon was used to thermally transfer to a color printed portion of a thermosensitive color developing paper to obtain a color erasing sample of Example 1. Composition of the coating liquid for the mat layer (releasing property) Binder Polyester resin (Elitel UE-3200 trade name) 40 parts by weight Filler carbon black 60 parts by weight Solvent (methyl ethyl ketone / toluene weight ratio 1: 1) 300 parts by weight (hereinafter methyl ethyl ketone) Is represented by MEK.) Composition of coating liquid for decoloring agent layer Decoloring agent Aliphatic amine 100 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight

[Example 2 (corresponding to thermal transfer decoloring ribbon)] A polyethylene terephthalate film having a heat-resistant slip layer provided on the back surface and having a thickness of 6 μm (manufactured by Lumirror Toray Co., Ltd.)
Was used as a base material, and a release layer coating solution having the following composition was applied to the surface of the base material by a gravure coating method so that the coating amount was 0.1 g / m ² (solid content) and dried to form a release layer. Subsequently, an intermediate layer coating solution having the following composition was applied onto the release layer by a gravure coating method so that the coating amount was 2 g / m ² (solid content), and dried to form an intermediate layer. A coating solution for the decolorizing agent layer having the following composition was applied thereon by a gravure coating method so that the coating amount was 5 g / m ² (solid content),
It was dried to obtain a heat transfer decoloring ribbon. Next, using this thermal transfer decoloring ribbon, thermal transfer was performed on the color printed portion of the thermosensitive color developing paper to prepare the decolorizing sample of Example 2. Composition of coating liquid for release layer Chlorinated polypropylene (molecular weight 80,000) 20 parts by weight Solvent (toluene / ethyl acetate weight ratio 1: 1) 80 parts by weight Composition of coating liquid for intermediate layer Ethylene-vinyl acetate copolymer resin [EVAFLEX # 420, manufactured by Mitsui Polychemical Co., Ltd.] 100 parts by weight Solvent (toluene) 900 parts by weight Composition of decolorizer layer coating solution Decolorizer Polyethylene glycol 4000 (molecular weight 4,000) 100 parts by weight Solvent (water / methyl) Alcohol weight ratio 1: 1) 100 parts by weight

[Example 3 (corresponding to thermal transfer decoloring ribbon)] In the structure of the thermal transfer decoloring ribbon of Example 2, only the composition of the coating liquid for the decoloring agent layer used for the decoloring agent layer was changed to the following composition. The thermal transfer decoloring ribbon of Example 3 and a decoloring sample using the same were prepared by the same processing as in Example 2 except that the coating was performed by the gravure coating method. Composition of coating liquid for decoloring agent layer Decoloring agent Polyethylene glycol 4000 (molecular weight 4,000) 100 parts by weight Binder SBR emulsion (solid content 40% by weight) 30 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 Parts by weight

Example 4 (Thermal Transfer Decoloring Ribbon) In the structure of the thermal transfer decoloring ribbon of Example 1, only the composition of the decoloring agent layer coating liquid used for the decoloring agent layer was changed to the following composition. The thermal transfer decoloring ribbon of Example 4 and a decoloring sample using the same were prepared by processing in the same manner as in Example 1 except that the ribbon was applied by the gravure coating method. Composition of coating liquid for decoloring agent layer Decoloring agent Stearyl alcohol 100 parts by weight (filling into heat-fusible microcapsules) Binder SBR emulsion (solid content 40% by weight) 30 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight

[Comparative Example 1 (Comparative Example Corresponding to Thermal Transfer Decoloring Ribbon)] A decoloring solution having the following composition was prepared, and a coating amount of 5 g / m ² was applied to the color-printed portion of the thermosensitive color-developing paper. Was applied to the sample to prepare a decolorized sample of Comparative Example 1. Composition of decoloring liquid White pigment Titanium oxide (fine powder) 100 parts by weight Binder Ethylcellulose 50 parts by weight Solvent (1-1-1 trichloroethane / methylcyclohexane / methylcellosolve weight ratio 3: 4: 3) 150 parts by weight

[Comparative Example 2 (Comparative Example Corresponding to Thermal Transfer Decoloring Ribbon)] 6 μm thick with a heat resistant slip layer provided on the back surface
Of polyethylene terephthalate film [manufactured by Lumirror Toray Co., Ltd.] as a base material, and a coating solution for the release layer having the following composition on its surface by a gravure coating method in an amount of 0.1 g.
/ M ² (solid content) was applied and dried to form a release layer. Subsequently, a coating liquid for a pigment decolorizing layer having the following composition was applied onto the release layer by a gravure coating method so that the coating amount was 5 g /
m ² (solid content) is coated and dried to form a pigment decoloring layer, and a coating solution for a heat-sensitive adhesive layer having the following composition is further applied thereon by a gravure coating method to give a coating amount of 1 g / m ² (solid content). Min.) And dried to prepare a thermal transfer decoloring ribbon. Next, this was used to thermally transfer to a color-printed portion of a thermosensitive color-developing paper to prepare an erasable sample of Comparative Example 2. Composition of coating liquid for release layer Chlorinated polypropylene (Molecular weight 80,000) 100 parts by weight Solvent (toluene / ethyl acetate weight ratio 1: 1) 400 parts by weight Composition of coating liquid for pigment decolorizing layer White pigment Titanium oxide (water dispersion Liquid Solid content 40% by weight 50 parts by weight Binder SBR emulsion (solids content 40% by weight) 50 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight Composition of coating liquid for heat-sensitive adhesive layer Ethylene-vinyl acetate Copolymer resin [EVAFLEX # 420, manufactured by Mitsui Polychemical Co., Ltd.] 100 parts by weight Solvent (toluene) 900 parts by weight

[Example 5 (corresponding to a thermal transfer correction ribbon)]
In the structure of the thermal transfer decoloring ribbon of Example 1, the decoloring agent layer provided on the matte layer was gravure-printed using a decoloring agent layer coating solution and a heat-meltable ink layer coating solution having the following composition. By the method, a two-part constitution of a decoloring agent layer and a heat-meltable ink layer of the type shown in FIG. 3B was applied and dried to prepare a thermal transfer correction ribbon of Example 5. The coating amount of the decoloring agent layer and the heat-meltable ink layer was 5 g / m ² (solid content), respectively.
And Next, using this heat transfer correction ribbon, the decolorant layer portion is first thermally transferred to the color printed portion of the heat sensitive color paper to decolor it, and then the decolored portion is printed with the heat fusible ink layer portion, A modified sample of Example 5 was obtained. Composition of coating liquid for decoloring agent layer Decoloring agent Aliphatic amine 100 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight Composition of coating liquid for heat-meltable ink layer Binder Carnauba wax emulsion (solid content 40% by weight) 80 parts by weight Coloring material Red pigment Lake red C aqueous dispersion (solid content 20% by weight) 20 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight

[Example 6 (corresponding to a thermal transfer correction ribbon)]
In the structure of the thermal transfer decoloring ribbon of Example 2, the laminated portion of the intermediate layer and the decoloring agent layer provided on the release layer was coated with the coating solution for the intermediate layer and the coating solution for the decoloring agent layer having the following compositions. A two-part structure consisting of a laminated portion of the intermediate layer / decolorant layer formed by sequential application and a heat-meltable ink layer portion formed by separately applying the coating liquid for the heat-meltable ink layer is provided. A thermal transfer correction ribbon of Example 6 was prepared by applying a pattern of the type shown in FIG. 3b by a printing method and drying it. Each layer of the coating amount, the intermediate layer is 2 g / m ² of the coating amount after drying, decolorizing agent layer 5 g / m ^2, hot-melt ink layer was 5 g / m ^2. Next, using this thermal transfer correction ribbon, the decolorant layer portion was first thermally transferred to the color printed portion of the thermosensitive color paper to erase the color,
Printing was performed on the decolored portion with the heat-meltable ink layer portion to obtain a corrected sample of Example 6. Composition of coating liquid for intermediate layer Ethylene-vinyl acetate copolymer resin [EVAFLEX # 420, manufactured by Mitsui Polychemical Co., Ltd.] 100 parts by weight Solvent (toluene) 900 parts by weight Composition of coating liquid for decolorizing agent layer Polyethylene Glycol 4000 (molecular weight 4,000) 100 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight Composition of coating liquid for hot-melt ink layer Binder Microcrystalline wax emulsion (solid content 30% by weight) 80 parts by weight Part Color material Black pigment Carbon black aqueous dispersion (solid content 20% by weight) 20 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight

[Example 7 (corresponding to a thermal transfer correction ribbon)]
In the structure of the thermal transfer correction ribbon of Example 6, a decoloring agent layer in which the laminated portion of the intermediate layer and the decoloring agent layer provided on the release layer is separately coated with the coating solution for the decoloring agent layer having the following composition. A thermal transfer correction ribbon and a correction sample of Example 7 were prepared in the same manner as in Example 6 except that the two-part structure was used. still,
The coating amount of this decolorizing agent layer is 5 g / m ² when dried.
Is. Composition of coating liquid for decoloring agent layer Decoloring agent Polyethylene glycol 4000 (molecular weight 4,000) 70 parts by weight Binder SBR emulsion (solid content 40% by weight) 30 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 Parts by weight

[Embodiment 8 (corresponding to a thermal transfer correction ribbon)]
In the construction of the thermal transfer correction ribbon of Example 5, all the operations were carried out except that the portion of the decoloring agent layer provided on the matte layer was changed to a coating liquid for the decoloring agent layer having the following composition and applied and formed. The thermal transfer correction ribbon of Example 8 and the correction sample were prepared in the same manner as in Example 5. The coating amount of this decolorizing agent layer is 5 g / m ² when dried. Composition of coating liquid for decoloring agent layer Decoloring agent Polyethylene glycol 400 (molecular weight 400) 70 parts by weight (filling into heat-fusible microcapsules) Binder SBR emulsion (solid content 40% by weight) 30 parts by weight Solvent (water / methyl) Alcohol weight ratio 1: 1) 100 parts by weight

Comparative Example 3 (Comparative Example Corresponding to Thermal Transfer Correction Ribbon) A white ink type correction liquid having the following composition was prepared and applied to a color-printed portion of a thermosensitive color paper at a coating amount of 5 g.
/ M ² (solid content), and then a black thermal transfer ink ribbon was used for printing on this portion to prepare a corrected sample of Comparative Example 3. Composition of correction fluid White pigment Titanium oxide (fine powder) 100 parts by weight Binder Ethylcellulose 50 parts by weight Solvent (1-1-1 trichloroethane / methylcyclohexane / methylcellosolve weight ratio 3: 4: 3) 150 parts by weight

[Comparative Example 4 (Comparative Example Corresponding to Thermal Transfer Correction Ribbon)] 6 μm thick with a heat-resistant slip layer provided on the back surface
Of polyethylene terephthalate film as a base material, and on its surface, a coating solution for a release layer, a coating solution for a pigment coloring layer, and a coating solution for a thermal adhesive layer, each having the following composition, are sequentially applied by a gravure coating method to form a release layer and a pigment. A colored layer and a heat-adhesive layer were formed to produce a decolorizing ribbon. Incidentally, each of the coating amount, the release layer is 0.1 g / m ² of the coating amount after drying, pigmented layer is 5 g / m ^2, the heat-bonding layer is 2 g / m ^2. Next, using this color erasing ribbon, the color was transferred to the color printed portion of the thermosensitive color paper to erase the color, and then the black portion of the color was used to make a correction printing, and the correction of Comparative Example 4 was performed. It was used as a sample. Composition of coating liquid for release layer Chlorinated polypropylene (Molecular weight 80,000) 20 parts by weight Solvent (toluene / ethyl acetate weight ratio 1: 1) 80 parts by weight Composition of coating liquid for pigmented layer Pigment titanium oxide (water dispersion solid 40% by weight) 50 parts by weight Binder SBR emulsion (solids 40% by weight) 50 parts by weight Solvent (water / methyl alcohol weight ratio 1: 1) 100 parts by weight Composition of coating liquid for heat-bonding layer Ethylene-vinyl acetate copolymer Resin [EVAFLEX # 420, manufactured by Mitsui Polychemicals Co., Ltd.] 100 parts by weight Solvent (toluene) 900 parts by weight

(Evaluation and Results) With respect to the decolorized samples of Examples 1 to 4 and Comparative Examples 1 and 2 and the modified samples of Examples 5 to 8 and Comparative Examples 3 and 4 prepared as described above, The following items were evaluated and the results are shown in Table 1. Description of evaluation items and evaluation symbols (1) Distinction of decolored or corrected parts ○: Indistinguishable items △: Distinguished items when viewed carefully ×: Determinable easily (2) Decolored or modified Whether or not the previous character can be discriminated ○: Indistinguishable item △: Distinguishable item when seen closely ×: Easily discernible item (3) Presence or absence of change in the erasing or modified area around the item ○: Unchangeable item △: Slightly changed ×: Slightly changed (hereinafter referred to as margin)

[0038]

[Table 1] Evaluation results

[0039]

As described above in detail, according to the thermal transfer erasing method according to the present invention, the thermal transfer erasing method according to the present invention can be used to produce the thermal printing on the thermosensitive coloring paper. It is possible to effectively erase the erased arbitrary portion without discoloring the periphery of the erased portion and to prevent the erased portion and characters before the erase from being discriminated. According to the thermal transfer correction method of the present invention, the thermal transfer correction ribbon of the present invention is used to change the color of an arbitrary portion thermally printed on the thermosensitive color developing paper around the decolored portion. In addition, there is an effect that the erased portion and characters before the erased can be clearly erased so that they cannot be discriminated, and reprinting can be performed to correct.

[Brief description of drawings]

1A, 1B, 1C are schematic cross-sectional views showing the configuration of an embodiment of a thermal transfer decoloring ribbon of the present invention of claim 1;

2A, 2B, and 2C are schematic cross-sectional views showing the configuration of an embodiment of the thermal transfer correction ribbon of the invention of Claim 2;

FIG. 3A and FIG. 3B respectively show an example of an arrangement pattern of a decoloring agent layer portion and a heat-meltable ink layer portion provided on the outermost surface of the thermal transfer correction ribbon of the present invention. It is a schematic plan view.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Decolorant layer 3 Matt layer or peeling layer 4 Heat-resistant slip layer 5 Intermediate layer 6 Heat-meltable ink layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location 9121-2H B41M 5/26 P

Claims (4)

[Claims] 1. A thermal transfer ribbon formed by forming a thermal transfer layer on one surface of a base material, wherein the thermal transfer layer contains a decoloring agent for decoloring a color-developed portion of a thermosensitive coloring paper. Color ribbon. 2. A thermal transfer ribbon comprising a thermal transfer layer formed on one surface of a substrate, wherein the surface of the thermal transfer layer contains an erasing agent for erasing the color-developed portion of the thermosensitive color paper. A thermal transfer correction ribbon, characterized in that the thermal transfer correction ribbon is composed of a portion of the heat-meltable ink layer and a portion of the heat-meltable ink layer. 3. The heat transfer decoloring ribbon according to claim 1 is superposed on a specific portion of a printed matter printed on a thermosensitive coloring paper by a thermosensitive coloring system, and heat is applied by a thermal head from the back of the erasing ribbon to erase the color. A thermal transfer erasing method characterized by coloring. 4. The thermal transfer correction ribbon according to claim 2 is superposed on a specific portion of a printed matter printed on a thermosensitive coloring paper by a thermosensitive coloring method, and first, a thermal head is applied from the back of the decoloring agent layer portion of the correction ribbon. A thermal transfer correction method, characterized in that heat is applied to erase the color, and then heat is applied from the back of the heat-meltable ink layer portion of the correction ribbon with a thermal head to correct the print.