JPH0648032A - Thermoreversible recording material and thermoreversible recording medium and recording method using the same - Google Patents

Abstract

PURPOSE:To provide a themoreversible recording material which extends the temperature range for keeping a transparent state and strengthen the contrast in the transparent state or a turbid state and a recording method which can conduct printing on the same recording medium repeatedely in a visible condition with a heating means such as a thermal head. CONSTITUTION:A thermoreversible recording material uses polyvinyl acetal as a matrix material. A saturated 10-40 carbon number carboxylic acid or its derivative is mixed with the matrix material. The recording material can be controlled of its state to be transparent or turbid by the difference in the cooling rate between slow and rapid cooling and the heating temperature range of the material as indicated in Figure 1. The recording material mounted on a support is used as a thermoreversible recording medium. The recording medium can conduct printing using a thermoprinting device such as a thermal head and the printed record can be extinguished by thermal treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a thermoreversible recording material capable of reversibly recording or erasing visual information by thermal means and repeating this operation, and a thermoreversible recording material thereof. The present invention relates to a thermoreversible recording medium and a recording method using the thermoreversible recording medium.

[0002]

2. Description of the Related Art A thermoreversible recording material refers to a material having a characteristic that at least the transparency of the material to visible light changes due to thermal history. By applying a thermal means such as a thermal head to this thermoreversible recording material, the thermal history of a predetermined portion of the material is made different from that of other portions, and the transparency of both portions is made different. It is possible to display the information.

Conventionally, such a thermoreversible recording material has been described in, for example, JP-A-55-154198. The thermoreversible recording material disclosed in this publication was constituted by dispersing an organic low molecular compound such as behenic acid (docosanoic acid) in a matrix material composed of a polymer such as polyester or a resin.

FIG. 2 shows the structure of this conventional thermoreversible recording material.
FIG. 3 is a diagram showing a hysteresis curve of transparency change with respect to temperature, with the vertical axis representing transmittance and the horizontal axis representing temperature. Less than,
The characteristics of the conventional thermoreversible recording material will be described with reference to FIG. (A), (B), (C) in FIG.
(D) shows the transmittance at each temperature.
That is, (A) and (D) are the respective transmittances at room temperature (RT), (B) is the transmittance at temperature T ₁ , and (C).
Indicates the transmittance at temperature T ₂ or higher.

This conventional thermoreversible recording material has a room temperature (R
(A) in FIG. 2 in the vicinity of T) according to the past history.
Transmittance (white turbid state) or (D) transmittance (transparent state)
Had any of the characteristics of. Then, when this thermoreversible recording material is heated to a temperature T ₁ over the temperature T ₀ ,
The transmittance that was (A) or (D) changes to (B). Then, when this is cooled to room temperature, the transmittance which was (B) in any case is fixed to (D).

On the other hand, a thermoreversible recording material having a transmittance of (A) or (D) near room temperature (RT) is
When the temperature exceeds T ₀ and T ₁ and is heated to T ₂ or higher,
The transmittance of (A) or (D) changes to (C) after passing through the maximum transmittance (B). That is, the transparency is slightly lower than that in the transparent state (D). afterwards,
When this is cooled to room temperature, the transmittance which was (C) in any case becomes (A), and this thermoreversible recording material is fixed in the cloudy state (A).

As a specific example of this characteristic, the above publication discloses that
The following examples are described. The thermoreversible recording material containing a high molecular weight linear copolyester based on an aromatic dicarboxylic acid and an aliphatic diol and docosanoic acid showed stable transparency when heated to 72 ° C. and cooled. It could only be returned to a cloudy state by reheating to a temperature above 77 ° C.

A thermoreversible recording material containing a copolymer of vinylidene chloride and acrylonitrile, docosanoic acid, and a fluorad lubricant for improving fluidity has stable transparency when heated to 63 ° C. and cooled. showed that. It could only be returned to a cloudy state by reheating to a temperature above 74 ° C. The thermoreversible recording material containing a copolymer of vinyl chloride and vinyl acetate and docosanol showed stable transparency when heated to 68 ° C. and cooled. This is 70 ℃
It was possible to return to the cloudy state only by reheating to the above temperature.

The thermoreversible recording material containing polyester and docosanoic acid showed stable transparency when heated to 72 ° C. and cooled. It could only be returned to a cloudy state by reheating to a temperature above 77 ° C. Conventionally, an apparatus for recording by using a heat-generating recording element for image formation has a characteristic that the heat-generating recording element is low in price, the recording process is simple, and the apparatus price can be reduced, so that it is used as a recording apparatus. Widely applied. As the type, a heat-sensitive recording method in which writing is directly performed on heat-sensitive paper is known and is applied to a fax machine or a printer.

The recording paper used in this method is Japanese Patent Publication No.
As disclosed in Japanese Patent Laid-Open No. 5-14039, a color development reaction between a colorless dye (leuco dye) which is an electron donor and a color developer (phenolic acidic substance) which is an electron acceptor is used, and both of them and these are used. It was provided with a heat sensitive layer to assist the reaction. When heat energy from the heat-generating recording element of the recording device is applied to this recording paper, the colorless dye and the color developer dissolve and react,
Develops color. A density difference is generated between the colored portion and the non-colored portion, so that the portion is recorded as a character or an image and is visually recognized.

[0011]

However, in the conventional thermoreversible recording material, the temperature range for forming the transparent state is (77-72) = 5 ° C. in the above case.
In the above, the temperature was 11 ° C., in the above, 2 ° C., and in the above, 5 ° C., the maximum was only 11 ° C. and the temperature range was extremely narrow. .

By the way, in order to form a display device using a thermoreversible recording material and to display with good contrast, a colored plate is provided on the back surface of the display plate made of the thermoreversible recording material, By selectively making the print part of the display plate transparent using a thermal means such as a thermal head and leaving the background part cloudy, the color of the colored plate is transparent only in the print part. It is desirable to have a configuration in which the display is made visible.

However, in the conventional thermoreversible recording material, since the temperature range for forming the transparent state is narrow as described above, it is difficult to control the temperature of a thermal means such as a thermal head. It was difficult to obtain stable transparency when repeatedly creating images. Further, in the conventional thermoreversible recording material, the transmittance ratio (contrast) in each of the transparent state and the cloudy state is not so large, and further improvement has been desired.

Further, in the conventional thermoreversible recording material, the cloudy portion may become transparent in the temperature range (room temperature to 70 ° C.) used as a display device, and the visibility of the display portion deteriorates. there were. On the other hand, in a conventional recording apparatus, a recording medium such as a card or a sheet is visibly written, that is, printed and recorded, and the recorded portion is reproduced by erasing the recorded portion. There was no print record.

Therefore, once the heat-sensitive recording paper has been recorded, the information has to be discarded when the information is no longer needed, and in the information communication era of today, the amount of disposal is enormous, resulting in an increase in resource consumption. Moreover, although the use of recycled paper is encouraged and increased for the purpose of resource saving, resources are consumed when making recycled paper. By directly printing on a recording medium in a visible form, erasing and completely reproducing the recorded portion, and recording a new print on the reproduced portion, a recording medium and a printing device which can be repeatedly used can be provided. If development is possible, it will be resource saving and desirable.

Therefore, a first object of the present invention is that the temperature range in which the transparent state can be achieved is wider than that of the conventional one, and the contrast is larger than that of the conventional one.
An object of the present invention is to provide a thermoreversible recording material which is less likely to change its cloudiness. Further, a second object of the present invention is to print and record on a recording medium such as a card or a sheet in a visible form, to reproduce by erasing all the recorded and recorded portions, and to newly print and record on the reproduced portions. Be able to
That is, it is to provide a thermoreversible recording medium which can be directly and visually printed on the same recording medium.

A third object of the present invention is to provide a method for recording information on such a thermoreversible recording material. The fourth object of the present invention is to provide a recording method for a thermoreversible recording medium using such a thermoreversible recording material.

[0018]

In order to achieve the first object, the present invention provides a thermoreversible recording material containing a matrix material and an organic low molecular weight compound, the transparency of which changes depending on the heat history, and the matrix material is polyvinyl acetal. And a low-molecular organic compound is a saturated carboxylic acid having 10 to 40 carbon atoms and / or a derivative of the saturated carboxylic acid, which is a thermoreversible recording material.

The saturated carboxylic acid that can be used in the present invention is not limited to the following, but capric acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid,
Cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laxeric acid,
Tritriacontanoic acid, gedic acid, ceroplastic acid, hexatriacontanoic acid, heptatriacontanoic acid, nonatriacontanoic acid, tetracontanoic acid and the like are preferably used. These correspond to saturated carboxylic acids having 10 to 40 carbon atoms. Further, the derivative thereof is not limited to the following, but includes stearic acid amide, nonadecanoic acid amide, arachidic acid amide, heneicosanoic acid amide, behenic acid amide, tricosanoic acid amide, lignoceric acid amide, pentacosanoic acid amide, and serotic acid. Amides, heptacosanoic acid amides, montanic acid amides, nonacosanoic acid amides, melicinic acid amides, hentriacontanic acid amides,
Lacteric acid amide, tritriacontanoic acid amide, gedaic acid amide, ceroplastic acid amide, hexatriacontanoic acid amide, heptatriacontanoic acid amide, nonatriacontanoic acid amide, tetracontanic acid amide, etc., stearylamine, nonadecanoic acid Amine, amine arachinate, amine heneicosanoate, amine behenate, amine tricosanoate, amine lignocerate, amine pentacosanoate, amine serotonate, amine heptacosanoate, amine montanate, amine nonacosanoate, amine melicinate, hentriacontanoic acid Amine, amine laxerate, amine tritriacontanoate, amine gedate, amine ceroplastate, amine hexatriacontanoate, amine heptatriacontanoate, amine nonatriacontanoate, tet Amines such as underlying motive acid amine,
Palmitoanilide, stearylanilide, nonadecanoic acid anilide, arachidic acid anilide, heneicosanoic acid anilide, behenic acid anilide, tricosanoic acid anilide, lignoceric acid anilide, pentacosanoic acid anilide, serocinic acid anilide, montanic acid anilide, nonacocinic acid anilide, anilide melinide, anilide. Anilides such as triacontanic acid anilide, laccelic acid anilide, tritriacontanoic acid anilide, gedanoic acid anilide, celloplastic acid anilide, hexatriacontanoic acid anilide, heptatriacontanoic acid anilide, nonatriacontanoic acid anilide, tetracontanic acid anilide, etc., Cetyl alcohol, stearyl alcohol, nonadecanol, eicosanol, hene eicosanol, docosanol, tetracosanol, pentacosano Alcohols such as hexanol, hexanol, heptacosanol, octacosanol, nonacosanol, melisyl alcohol, gentriacontanol, lasenol, tritriacontanol, tetraacontanol, pentaacontanol, hexaacontanol, heptaacontanol, nonatriacontanol, tetraacontanol , Phenyl stearate, vinyl stearate, n-dodecyl stearate, methyl nonadecanoate, methyl arachiate, methyl heneicosanoate, methyl behenate, methyl tricosanoate, methyl lignocerate, methyl pentacosanoate, methyl serotonate, methyl heptakonoate, Methyl montanate, methyl nonacosanoate, methyl melicinate, methyl hentriacontanate, methyl laxerate, tritriacon Methyl phosphate,
Esters of methyl gedarate, methyl ceroplastate, methyl hexatriacontanoate, methyl heptatriacontanoate, methyl nonatriacontanoate, methyl tetracontanate, stearone, 19-heptatriacontanone, 20-nonatriacontanone, 21-Hentetracontanone, ketone such as 22-tritetracontanone, Ca stearate, Co stearate, C stearate
u, Fe stearate, K stearate, Li stearate, Mg stearate, Mn stearate, Ni stearate, Pb stearate, Sn stearate, Zn stearate, Zr stearate, Ca nonadecanoate,
Ca arachiate, Ca heneicoate, Ca behenate, Ca tricosanoate, Ca lignocerate, Ca pentacosanoate, Ca serotonate, Ca heptacosanoate, Ca montanate, Ca nonacosanoate, Ca mericinate, Ca hentriacontanoate, Lacteric acid Ca, tritriacontanoic acid Ca, gedic acid Ca, ceroplastic acid Ca, hexatriacontanoic acid Ca, heptatriacontanoic acid Ca,
A derivative of a saturated carboxylic acid selected from metal salts such as Ca nonatriacontanoate and Ca tetracontanoate, and imidazoles such as 2-heptadecylimidazole, 2-undecylimidazole and 2-stearylimidazole are preferable.

These saturated carboxylic acids and / or their derivatives such as amides, amines, anilides, alcohols, esters, ketones, metal salts and imidazoles may be used alone or in a mixture of two or more kinds. .
The mixing weight ratio of the saturated carboxylic acid and / or its derivative to the matrix material is preferably within the range of 1: 2 to 20: 1. The reason is that if the matrix material contains more than 1: 2 of saturated carboxylic acid and / or its derivative, it becomes difficult to form a film of the thermoreversible recording material.
This is because if it is less than 0: 1, the thermoreversibility becomes small.

The term "comprising a matrix material and an organic low molecular weight compound" in the present invention may be only these materials, or a material for improving the film quality of the thermoreversible recording material or a material for improving the lubricity in addition to these materials. It is also meant to include other substances such as. In the actual use of the thermoreversible recording material, when a coating solution of the thermoreversible recording material is prepared in order to apply the material to a support such as a substrate or a film made of a suitable material. There is. To prepare the coating solution of the thermoreversible recording material, the matrix material and the saturated carboxylic acid and / or its derivative are dissolved in a solvent to obtain a coating solution. As the solvent therefor, for example, one selected from tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, chloroform, carbon tetrachloride, ethanol, toluene, benzene, etc. may be used, or two or more thereof may be mixed and used. Is good. If necessary, the solvent may be heated before use when preparing the coating solution.

In order to achieve the second object, the present invention adopts the following structure. The present invention is
A support made of a material selected from plastic, paper or synthetic paper, a reflective layer or a light absorbing layer formed on the support, and a matrix formed on the reflective layer or the light absorbing layer. Characterized by comprising a thermoreversible recording / display layer made of a thermoreversible recording material containing a material and an organic low molecular weight compound, and a transparent protective layer formed on the thermoreversible recording / display layer. The recording medium is a thermoreversible recording medium.

The present invention also provides a support comprising a material selected from plastic, paper or synthetic paper, a reflection layer or a light absorption layer formed on the support, and the reflection layer or the light absorption layer. A heat-reversible recording material formed on the enhance layer having a function of enhancing the contrast between the transparent portion and the cloudy portion and the thermoreversible recording material formed on the enhance layer and containing the matrix material and the organic low-molecular compound. Reversible recording
A thermoreversible recording medium comprising a display layer and a transparent protective layer formed on the thermoreversible recording / display layer.

The present invention also provides a support selected from an inorganic fiber paper having a good thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and a support on the support. A thermoreversible recording / display layer formed of a thermoreversible recording material containing the above matrix material and an organic low molecular weight compound, and a transparent protective layer formed on the thermoreversible recording / display layer. A thermoreversible recording medium characterized by the above.

The present invention also provides a support selected from an inorganic fiber paper having a high thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder, etc. are dispersed, and a support on the support. A thermoreversible recording layer comprising a thermoreversible recording material formed on the enhance layer and having an action of increasing the contrast between the transparent portion and the cloudy portion and containing the matrix material and the organic low molecular weight compound. A heat-reversible recording medium comprising a heat-sensitive recording / display layer and a transparent protective layer formed on the heat-reversible recording / display layer.

The present invention also includes a support made of a material selected from plastic, paper or synthetic paper, a reflection layer or a light absorption layer formed on the support, and the reflection layer or the light absorption layer. A thermoreversible recording / display layer formed on the thermoreversible recording material comprising the above matrix material and an organic low molecular weight compound, and a transparent protective layer formed on the thermoreversible recording / display layer. And a recording layer formed under the support for recording coded information, and a protective layer formed under the recording layer. It is a thing.

The present invention also provides a support comprising a material selected from plastic, paper or synthetic paper, a reflection layer or a light absorption layer formed on the support, and a reflection layer or a light absorption layer. An enhance layer formed on the above and having a function of enhancing the contrast between the transparent portion and the cloudy portion, and a thermoreversible recording material formed on the enhance layer and containing the matrix material and the organic low molecular weight compound. A thermoreversible recording / display layer, a transparent protective layer formed on the thermoreversible recording / display layer, and a recording layer formed under the support for recording coded information. A thermoreversible recording medium comprising a protective layer formed under the recording layer.

The present invention also provides a support selected from an inorganic fiber paper, a ceramic sheet, a metal sheet or a plastic sheet having carbon powder or metal powder dispersed therein, which has good thermal conductivity, and a support on the support. A thermoreversible recording / display layer formed of a thermoreversible recording material containing the matrix material and an organic low molecular weight compound, and a transparent protective layer formed on the thermoreversible recording / display layer, Furthermore, a thermoreversible recording medium comprising a recording layer formed under the support for recording coded information, and a protective layer formed under the recording layer. Is.

The present invention also provides a support selected from an inorganic fiber paper having a good thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and a support on the support. A thermoreversible recording layer comprising a thermoreversible recording material formed on the enhance layer and having an action of increasing the contrast between the transparent portion and the cloudy portion and containing the matrix material and the organic low molecular weight compound. Functional recording / display layer, a transparent protective layer formed on the thermoreversible recording / display layer, and a recording layer formed under the support for recording coded information, A thermoreversible recording medium comprising a protective layer formed below the recording layer.

Further, the present invention is a thermoreversible recording comprising a transparent support made of a transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a transparent protective layer formed on the thermoreversible recording / display layer, and a reflective layer or a light absorbing layer formed under the transparent support. The recording medium is a thermoreversible recording medium.

Further, the present invention is a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a transparent protective layer formed on the thermoreversible recording / display layer, an adhesive layer formed on the periphery under the transparent support, a lower surface of the transparent support and a space. A space formed between the lower surface of the transparent support and the upper surface of the reflective layer or the light absorbing layer is provided with a reflective layer or a light absorbing layer that is adhered under the adhesive layer with a transparent portion and a cloudy portion. The thermoreversible recording medium is characterized in that it is an enhance layer having a function of enhancing the contrast with.

The present invention also provides a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a transparent protective layer formed on the thermoreversible recording / display layer, a reflection layer or a light absorption layer formed under the transparent support, and the reflection layer or the light absorption. A thermoreversible recording medium comprising a recording layer formed under a layer for recording coded information, and a protective layer formed under the recording layer.

The present invention also relates to a thermoreversible recording comprising a transparent support made of a transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a transparent protective layer formed on the thermoreversible recording / display layer, an adhesive layer formed under the transparent support and around the transparent support, a lower surface and a space of the transparent support. A reflective layer or a light absorbing layer adhered under the adhesive layer with a space between them, a recording layer formed under the reflective layer or the light absorbing layer for recording coded information, and a recording layer under the recording layer. An enhancement layer having a protective layer formed on the transparent support, and a space formed between the lower surface of the transparent support and the upper surface of the reflective layer or the light absorption layer having a function of enhancing the contrast between the transparent portion and the cloudy portion. Thermoreversible recording characterized by It is to the body.

The present invention also provides a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound. .A display layer, a reflection layer or a light absorption layer formed under the thermoreversible recording / display layer, and a protective layer formed under the reflection layer or the light absorption layer The recording medium is a thermoreversible recording medium.

The present invention also provides a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound.・ Display layer, an enhancement layer formed under the thermoreversible recording / display layer and having a function of enhancing the contrast between a transparent portion and a cloudy portion, and a reflection layer or a light absorption layer formed under the enhancement layer A thermoreversible recording medium comprising a layer and a protective layer formed under the reflection layer or the light absorption layer.

The present invention also provides a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a reflective layer or a light absorbing layer formed under the thermoreversible recording / display layer, and a recording layer formed under the reflective layer or the light absorbing layer for recording coded information. And a protective layer formed under the recording layer, which is a thermoreversible recording medium.

Further, the present invention is a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound.・ Display layer, an enhancement layer formed under the thermoreversible recording / display layer and having a function of enhancing the contrast between a transparent portion and a cloudy portion, and a reflection layer or a light absorption layer formed under the enhancement layer Layer, a recording layer formed under the reflection layer or the light absorption layer for recording coded information, and a protective layer formed under the recording layer. It is used as a recording medium.

Further, the present invention is a thermoreversible recording comprising a transparent support made of a transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound. A thermoreversible recording medium comprising a display layer and a transparent protective layer formed on the thermoreversible recording / display layer. The present invention also relates to a thermoreversible recording / display layer comprising a transparent support made of a transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound. And a transparent protective layer formed under the thermoreversible recording / display layer.

Further, the present invention is a thermoreversible recording medium comprising an edge light type planar light source and a thermoreversible recording material formed on the planar light source and containing the matrix material and the organic low molecular weight compound. A heat-reversible recording medium comprising a heat-sensitive recording / display layer and a transparent protective layer formed on the heat-reversible recording / display layer. Further, the present invention is
Thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed on the transparent support and containing the matrix material and the organic low molecular weight compound.
A display layer, a transparent protective layer formed on the thermoreversible recording / display layer, and a recording layer formed on a part of the lower surface of the transparent support for recording coded information; A thermoreversible recording medium comprising a protective layer formed below the layer.

The present invention also relates to a thermoreversible recording comprising a transparent support made of transparent plastic and a thermoreversible recording material formed under the transparent support and containing the matrix material and the organic low molecular weight compound. A display layer, a transparent protective layer formed under the thermoreversible recording / display layer, and a recording layer formed on a part of the lower surface of the transparent protective layer for recording coded information, A thermoreversible recording medium comprising a protective layer formed under the recording layer.

Further, the present invention is a thermoreversible recording medium comprising an edge-light type planar light source and a thermoreversible recording material formed on the planar light source and containing the matrix material and the organic low molecular weight compound. A recording / display layer, a transparent protective layer formed on the thermoreversible recording / display layer, and a recording layer formed on a part of the lower part of the planar light source body for recording coded information. A thermoreversible recording medium comprising a protective layer formed under the recording layer.

In the thermoreversible recording medium of the present invention, the upper surface of the thermoreversible recording / display layer is adhered to the upper layer via an adhesive layer, and the lower surface of the thermoreversible recording / display layer is It may be bonded to the layer below it via an adhesive layer. Further, the thermoreversible recording medium of the present invention may have a printing layer formed by printing characters or graphics with printing ink or the like on the upper surface or the lower surface of the adhesive layer.

The transparent protective layer, the transparent support or the planar light source which can be included in the thermoreversible recording medium of the present invention has characters or graphics printed on the upper or lower surface thereof with a printing ink or the like. A printed layer may be formed. By forming such a print layer at an appropriate location, information that does not need to be erased can be printed. The reflection layer or the light absorption layer that can be included in the thermoreversible recording medium of the present invention is a colored layer printed with black, red or blue having a large contrast with respect to white, or a contrast layer with a contrast against white. You may employ | adopt the coloring layer which printed the large several color. Further, the reflective layer or the light absorption layer,
A layer printed with a paint containing a fluorescent paint or a layer printed with a paint containing carbon powder or metal powder having good thermal conductivity may be adopted.

As the material of the support, polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin,
Plastics such as polyacrylonitrile, polyether sulfane, polybutadiene and polyimide, and paper and synthetic paper can be used. The thickness of the support may be such that the thermoreversible recording / display layer can be maintained, and is preferably 25 μm to 1 mm.

Materials for the transparent support include transparent plastics such as polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin,
Polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyacrylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane, polybutadiene and the like can be used.

The material of the reflection layer or the light absorption layer may contain a metal such as aluminum or copper, a pigment, a dye or the like. You may coat black, red, or blue ink on a support body with the usual film gravure printer. As for this color, it is desirable that the thermoreversible recording / display layer has a large contrast with respect to white when it is cloudy, but either green or yellow, or any color can be used. It is also possible to print a plurality of colors having a large contrast with respect to white. Further, it is possible to apply a paint including a fluorescent paint. When a coating material containing carbon powder or metal powder having good thermal conductivity is used, the thermal efficiency of the thermoreversible recording medium is improved.

Materials for the transparent protective layer include polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin,
Transparent plastics such as polyacrylonitrile, polyether sulfane, polybutadiene, polyimide, UV curable resin and transparent inorganic substances such as SiO ₂ can be used. The thickness of the transparent protective layer may be such that the heat-generating recording element transfers heat to the thermoreversible recording / display layer through the transparent protective layer, and is preferably 1 to 15 μm.

Materials for the protective layer include polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether. Plastic such as sulfane, polybutadiene, polyimide, UV resin, S
Inorganic substances such as iO ₂ , Al ₂ O ₃ and TiO ₂ can be used.

The material of the enhancement layer is polyester,
Polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane,
Transparent plastics such as polybutadiene and transparent inorganic substances such as SiO ₂ can be used. Further, the enhancement layer may be an air layer.

In order to achieve the third object of the present invention,
The present invention provides a transparent state by heating the thermoreversible recording material containing the matrix material and the organic low molecular weight compound by a thermal means, and then cooling the thermoreversible recording material while controlling the cooling rate. Alternatively, the recording method is characterized by forming a cloudy state. In order to achieve the fourth object of the present invention, the present invention is to heat a predetermined part of a thermoreversible recording medium containing a thermoreversible recording material containing the matrix material and an organic low molecular weight compound by a thermal means. Then, the recording method is characterized in that visual information is formed or erased by cooling the thermoreversible recording medium while controlling the cooling rate.

[0051]

FIG. 1 shows characteristics of light transmittance with respect to temperature of the thermoreversible recording material used in the present invention. Since the thermoreversible recording material of the present invention is a thermoreversible recording material composed of a matrix material made of polyvinyl acetal and an organic low molecular compound made of a saturated carboxylic acid and / or a derivative of the saturated carboxylic acid, When the thermoreversible recording material is heated to T ₁ or more and T ₂ or less in FIG. 1 and then cooled to room temperature (this time does not depend on the cooling rate), or it is heated to T ₂ or more and rapidly cooled (in this case, , 50 ° C./sec or more) shows the maximum transparency. On the other hand, when it is heated to T ₂ or more and then gradually cooled (in this case, 50 ° C./sec or less), the minimum transparency is exhibited. Therefore, the temperature range for forming the transparent state and the temperature range for forming the cloudy state are wider than those of the conventional thermoreversible recording material, and a novel heat capable of forming the transparent state and the cloudy state by controlling the cooling rate. A reversible recording material is obtained.

Further, since the thermoreversible recording medium of the present invention is constructed as described above, the thermoreversible recording / display layer is formed at a temperature of 82 ° C. to 20 ° C. by a thermal means such as a thermal head.
When heated to a temperature within the range of 0 ° C. (C in FIG. 1) and rapidly cooled to room temperature at a temperature decrease rate of 50 ° C./sec or more, the transparent state is fixed (D in FIG. 1). Then, for example, 82 ℃
When heated to a temperature in the range of up to 200 ° C. (C in FIG. 1) and gradually cooled to room temperature at a temperature decrease rate of 50 ° C./sec or less, the cloudy state is fixed (A in FIG. 1). By performing such an operation, visual information can be repeatedly recorded and erased.

Further, since the thermoreversible recording medium of the present invention has the same recording conditions as the thermosensitive recording paper, the printing apparatus used for the thermosensitive recording paper can be used as it is in the present invention. Furthermore, in the present invention, since visual information can be recognized from the transparent protective layer side or the transparent support side of the thermoreversible recording medium, a writing instrument such as an aqueous or oil-based felt-tip pen is provided on the transparent protective layer or the transparent support. It is possible to additionally write the information by this, and the additional information can be erased by a solvent such as alcohol or water.

Furthermore, since the thermoreversible recording medium of the present invention is provided with a recording layer for recording coded information, a portion recognized as visual information due to a difference in transparency and a portion containing code information are provided. Can have a
The coded information can be read by an appropriate device and displayed as visual information for multipurpose use as an information recording medium.

[0055]

EXAMPLE 1 An example of the thermoreversible recording material of the present invention will be described below with reference to the drawings. It should be understood that the materials and numerical conditions used in the examples are merely examples within the scope of the present invention, and therefore the present invention is not limited to these materials and numerical conditions. .

S-REC K as polyvinyl acetal
S-1 (trade name, manufactured by Sekisui Chemical Co., Ltd.) was prepared.
Further, as the saturated carboxylic acid and / or its derivative,
Behenic acid was prepared. And 5 parts by weight of ESLEK K
S-1 and 3 parts by weight of behenic acid were dissolved in 50 parts by weight of tetrahydrofuran (hereinafter abbreviated as THF) to prepare a coating solution of the thermoreversible recording material.

On the other hand, as Comparative Example 1, among the materials of the coating solution of the thermoreversible recording material of Example 1, behenic acid was used in the same manner as in Example 1, that is, 5% by weight. Part of ESLEK KS-1 with 50 parts by weight of TH
It was dissolved in F to prepare a coating solution of Comparative Example 1. Further, as Comparative Example 2, in the material of the coating solution of the thermoreversible recording material of Example 1, 5 parts by weight of vinyl chloride-vinyl acetate copolymer VYH was used instead of S-REC KS-1.
Comparative Example 2 in exactly the same manner as in Example 1 except that H (trade name, manufactured by Union Carbide Company (UCC)) was used.
Was prepared.

Next, the present Example 1,
The coating solutions of Comparative Example 1 and Comparative Example 2 were applied to a polyethylene terephthalate substrate with the same thickness. This drying time was set to the time when the solvent, THF, could be removed. With respect to the sample thus formed, the change in transparency with respect to temperature was measured, and the hysteresis curve shown in FIG. 1 was created.
This hysteresis curve is shown by plotting the transmittance on the vertical axis and the temperature on the horizontal axis. As can be understood from FIG. 1, the sample of the present Example 1 was heated to a temperature within the range of 60 to 82 ° C., or from 82 ° C. to 200 ° C. which is the softening point temperature of S-REC KS-1. When it is rapidly cooled (50 ° C./sec or more) after being heated to a temperature within the range up to T ₃ ), it is fixed in a transparent state. Also, after heating to a temperature in the range from 82 ° C. (T ₂ ) to 200 ° C. (T ₃ ) which is the softening point temperature of S-REC KS-1, gradual cooling (50 ° C./sec or less).
If it is done, it will be fixed in a cloudy state.

The contrast of the sample of Example 1 in terms of the transmittance ratio between the transparent state and the cloudy state (in this case, the transmittance ratio for light having a wavelength of 550 nm) was 10. on the other hand,
The sample of Comparative Example 1 was transparent after forming a coating film with the coating solution, and even when the temperature of this sample was changed to the range of 20 to 120 ° C. and then returned to room temperature, the sample did not become cloudy.

The hysteresis curve of the change in transparency with respect to temperature of the sample of Comparative Example 2 is similar to the conventional characteristic shown in FIG. 2, and the temperature range in which the transparent state is obtained is 8
It was as narrow as 0 to 82 ° C. The contrast was 4.0. The characteristics of the samples of Example 1, Comparative Example 1 and Comparative Example 2 are summarized in Table 1 below.

[0061]

[Table 1]

[0062]

[Embodiment 2] FIG. 3 is a sectional view showing the structure of a thermoreversible recording medium according to Embodiment 2 of the present invention. The second embodiment will be described with reference to FIG. The thermoreversible recording medium of Example 2 is
For example, it has a support 11 made of a plastic sheet having a film thickness of 100 μm, and a reflective layer or a light absorption layer 12 printed in black is formed on the surface of the support 11. Since the reflective layer or the light absorption layer 12 is black, it functions as a light absorption layer. A thermoreversible recording / display layer 13 having a film thickness of 20 μm is formed thereon. Further thereon, a transparent protective layer 14 made of a plastic sheet having a film thickness of 5 μm is formed.

As the material of the thermoreversible recording / display layer 13,
The thermoreversible recording material described in Example 1 will be described as an example. As polyvinyl acetal, 5 parts by weight of S-REC KS-1 (trade name, manufactured by Sekisui Chemical Co., Ltd.) was used, and saturated carboxylic acid and As a derivative thereof, 3 parts by weight of behenic acid is used, and both are dissolved in 50 parts by weight of THF to form a solution, and the solution is dried by a bar coat method so that the film thickness after drying becomes 20 μm. To form the thermoreversible recording / display layer 13.

Regarding the thickness of the transparent protective layer 14, the heat-generating recording element passes through the transparent protective layer 14 and the thermoreversible recording / display layer 1 is formed.
The thickness for transmitting heat to 3 is sufficient, and 1 to 15 μm is desirable.
If necessary, a character or a graphic can be printed at an arbitrary position on the transparent protective layer 14 by using a printing ink or the like. Thus, by performing normal printing separately from the thermal printing recording, it is possible to record information that does not need to be erased.

If necessary, an adhesive layer may be formed on the thermoreversible recording / display layer 13, and an adhesive layer may be formed below the thermoreversible recording / display layer 13. Further, a printing layer can be formed on the adhesive layer formed on the thermoreversible recording / display layer 13. For recording on the thermoreversible recording medium of Example 1, when heating is performed from the transparent protective layer 14 side using a thermal head, heat is efficiently transferred to the thermoreversible recording / display layer 13 for recording.

The visual information of the thermoreversible recording medium of Example 1 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0067]

[Embodiment 3] FIG. 4 is a cross-sectional view showing the structure of a thermoreversible recording medium according to another embodiment of the present invention. FIG. 4 shows the third embodiment.
It will be described based on. The structure of the thermoreversible recording medium of the third embodiment is the same as that of the thermoreversible recording medium of the second embodiment except that the reflective layer or the light absorbing layer 12 and the thermoreversible recording / display layer 1 are used.
3 and the enhancement layer 15 is formed between
The other layer structure is the same as that of the second embodiment. The enhancement layer 15 is provided to increase the contrast between the transparent portion and the cloudy portion.

In the recording on the thermoreversible recording medium of the third embodiment, when heat is applied from the transparent protective layer 14 side using a thermal head, the heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. Be seen. The visual information of the thermoreversible recording medium of Example 3 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0069]

[Embodiment 4] FIG. 5 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. Example 4
Will be described with reference to FIG. Reference numeral 21 is a support made of inorganic fiber paper having good thermal conductivity, or a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder, or the like is dispersed. A thermoreversible recording / display layer 13 of the same material as the material of the thermoreversible recording / display layer used in Example 2 was formed on the support 21, and the thermoreversible recording / display layer 13 was formed. The transparent protective layer 14 is formed on top.

Support 21 used in Example 4
Is composed of a material that causes reflection or light absorption, so that a reflection layer or a light absorption layer is not necessary. Recording on the thermoreversible recording medium of Example 4 is performed efficiently from the support 21 side using a thermal head, and the thermoreversible recording / display layer 13 is efficiently formed.
Heat is transmitted to and recording is performed.

The visual information of the thermoreversible recording medium of Example 4 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0072]

[Embodiment 5] FIG. 6 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. Example 5
Will be described with reference to FIG. The thermoreversible recording medium of Example 5 has the same structure as the thermoreversible recording medium of Example 4 except that an enhancement layer 15 is formed between the support 21 and the thermoreversible recording / display layer 13. The other layer structure is the same as that of the fourth embodiment. The enhance layer 15 is provided to increase the contrast between the transparent state and the cloudy state.

It is possible to write on the transparent protective layer 14 with a water-based or oil-based felt-tip pen or the like. Example 5
Recording on the thermoreversible recording medium is performed from the support 21 side using a thermal head, and heat is efficiently transmitted to the thermoreversible recording / display layer 13 to perform recording. In addition, the fifth embodiment
The visual information of the thermoreversible recording medium can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0074]

[Embodiment 6] FIG. 7 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. Example 6
Will be described with reference to FIG. The thermoreversible recording medium of Example 6 is capable of recording combined information of directly visible thermal recording and coded recording.

The construction of the thermoreversible recording medium of Example 6 is as follows.
A recording layer 16 for recording coded information is provided under the support 11 in the thermoreversible recording medium shown in Example 2 above.
Is formed, and the protective layer 17 is further formed thereunder. Other layer structure, that is, the reflection layer or the light absorption layer 1
2. The thermoreversible recording / display layer 13 and the transparent protective layer 14 are the same as in the second embodiment.

As the recording medium of the recording layer 16, a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, a thermomagnetic recording medium, etc. can be used. For recording on the thermoreversible recording medium of Example 6, when heating is performed from the transparent protective layer 14 side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. The thermoreversible recording medium of Example 6 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. So by combining the recording methods of each medium, in addition to visual information,
Code information can also be recorded.

Further, the visual information of the thermoreversible recording medium of Example 6 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0078]

[Embodiment 7] FIG. 8 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. Example 7
Will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 8 is the same as that of the thermoreversible recording medium of Example 6 except that an enhancement layer is provided between the reflective layer or the light absorbing layer 12 and the thermoreversible recording / display layer 13. 15 is formed, and the other layer structure, that is, the recording layer 16 and the protective layer 1 is formed.
7, the support 11 and the transparent protective layer 14 are the same as in the sixth embodiment.

In the recording on the thermoreversible recording medium of Example 7, when the transparent protective layer 14 side is heated by using a thermal head, the heat is efficiently transmitted to the thermoreversible recording / display layer 13 to perform recording. Be seen. The thermoreversible recording medium of Example 7 is
Since recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium are combined, it is possible to combine the recording methods of the respective media. In addition to visual information, code information can be recorded.

The visual information of the thermoreversible recording medium of Example 7 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0081]

[Embodiment 8] FIG. 9 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. Example 8
Will be described with reference to FIG. The thermoreversible recording medium of the present Example 8 is capable of recording composite information composed of a heat record and a coded record which are directly visible.

The structure of the thermoreversible recording medium of Example 8 is as follows.
A recording layer 16 for recording coded information under the support 21 in the thermoreversible recording medium shown in Example 4 above.
Is formed, and the protective layer 17 is further formed thereunder. Other layer structure, that is, thermoreversible recording / display layer 1
3. The transparent protective layer 14 is as described in Example 4 above.

The transparent protective layer 14 can be written with a water-based or oil-based felt-tip pen or the like. Recording on the thermoreversible recording medium of Example 8 is performed by performing thermal printing from the protective layer 17 side opposite to the transparent protective layer 14 using a thermal head. The thermoreversible recording medium of Example 8 was a magnetic recording medium, an optical recording medium,
Since recording means such as a thermal recording medium, an electric recording medium such as an IC card, an optical recording medium, and a thermomagnetic recording medium are combined,
By combining the recording methods of each medium,
In addition to visual information, code information can be recorded.

The visual information of the thermoreversible recording medium of Example 8 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0085]

[Embodiment 9] FIG. 10 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. The ninth embodiment will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 9 is the same as that of the thermoreversible recording medium shown in Example 8 except that the enhance layer 15 is provided between the support 21 and the thermoreversible recording / display layer 13. It is formed, and the other layer structure is the same as that of the eighth embodiment.

The type of recording medium for the recording layer 16 is as described in the sixth embodiment. It is possible to write on the transparent protective layer 14 with a water-based or oil-based felt-tip pen or the like, as in the case of the eighth embodiment. Recording on the thermoreversible recording medium of Example 9 is performed by performing thermal printing from the protective layer 17 side opposite to the transparent protective layer 14 using a thermal head.

The thermoreversible recording medium of Example 9 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium and a thermomagnetic recording medium. Therefore, code information can be recorded in addition to visual information by combining the recording methods of the respective media. Further, the visual information of the thermoreversible recording medium of Example 9 is as follows due to the incidence of light from the transparent protective layer 14 side.
It is obtained by visually observing the transparent protective layer 14.

[0088]

[Embodiment 10] FIG. 11 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The tenth embodiment will be described with reference to FIG. In the thermoreversible recording medium of Example 10, the thermoreversible recording / display layer 13 and the reflecting layer or the light absorbing layer 12 were formed in order to increase the contrast between the transparent portion and the cloudy portion of the thermoreversible recording / display layer 13. A transparent support 31 is provided between them.

In the constitution of the thermoreversible recording medium of Example 10, the thermoreversible recording / display layer 13 is formed on the transparent support 31, and the transparent protective layer 14 is further formed on the thermoreversible recording / display layer 13. The reflection layer or the light absorption layer 12 is formed under the support 31. The film thickness of the transparent support 31 is a thermoreversible recording.
A thickness that can maintain the display layer 13 is required, and is 25 μm to 1 m.
m is preferred.

In the recording on the thermoreversible recording medium of the tenth embodiment, when heat is applied from the transparent protective layer 14 side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. Be seen. The visual information of the thermoreversible recording medium of Example 10 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0091]

[Embodiment 11] FIG. 12 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. The eleventh embodiment will be described with reference to FIG. The thermoreversible recording medium of the eleventh embodiment reflected from the transparent support 31 of the thermoreversible recording medium of the tenth embodiment in order to enhance the contrast between the transparent portion and the cloudy portion of the thermoreversible recording / display layer 13. Layer or light-absorbing layer 12 and an enhancement layer 1 consisting of an air layer
5 is formed. The enhancement layer 15 composed of this air layer is formed by forming an adhesive layer 41 around the lower portion of the transparent support 31 and further adhering the reflective layer or the light absorbing layer 12 to the adhesive layer 41 to form a transparent support. A space is formed between 31 and the reflection layer or the light absorption layer 12.

In the recording on the thermoreversible recording medium of the eleventh embodiment, when heat is applied from the transparent protective layer 14 side using a thermal head, the heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. Be seen. The visual information of the thermoreversible recording medium of Example 11 can be obtained by visually observing the transparent protective layer 14 when light is incident from the transparent protective layer 14 side.

[0093]

[Embodiment 12] FIG. 13 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. The twelfth embodiment will be described with reference to FIG. The thermoreversible recording medium of the twelfth embodiment is capable of recording composite information consisting of directly visible thermal recording and coded recording.

The structure of the thermoreversible recording medium of Example 12 is such that the coded information is recorded under the reflecting layer or the light absorbing layer 12 of the thermoreversible recording medium shown in Example 10. The layer 16 is formed, and the protective layer 1 is formed thereunder.
7 is formed. The other layer structure is the same as that of the tenth embodiment. The type of recording medium for the recording layer 16 is as described in the sixth embodiment.

In the recording on the thermoreversible recording medium of this Example 12, when the transparent protective layer 14 side is heated by using a thermal head, the heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. Be seen. The thermoreversible recording medium of Example 12 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. By combining the recording methods of the respective media, code information can be recorded in addition to visual information.

Further, the visual information of the thermoreversible recording medium of the twelfth embodiment is obtained by the incidence of light from the transparent protective layer 14 side.
It is obtained by visually observing the transparent protective layer 14.

[0097]

[Embodiment 13] FIG. 14 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The thirteenth embodiment will be described with reference to FIG. The thermoreversible recording medium of the thirteenth embodiment has the same properties as the heat reversible recording medium of the twelfth embodiment in order to enhance the contrast between the transparent portion and the cloudy portion of the thermoreversible recording / display layer 13 of the thirteenth embodiment. The enhancement layer 15 formed of an air layer is formed between the transparent support 31 and the reflection layer or the light absorption layer 12 in the reversible recording medium. Enhance layer 15 consisting of this air layer
Forms an adhesive layer 41 around the bottom of the transparent support 31,
By further adhering the reflection layer or the light absorption layer 12 to the adhesive layer 41, a space is provided between the transparent support 31 and the reflection layer or the light absorption layer 12.

In the recording on the thermoreversible recording medium of Example 13, when the transparent protective layer 14 side is heated by using a thermal head, the heat is efficiently transferred to the thermoreversible recording / display layer 13 for recording. Be seen. The thermoreversible recording medium of Example 13 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. By combining the recording methods of the respective media, code information can be recorded in addition to visual information.

Further, the visual information of the thermoreversible recording medium of the thirteenth embodiment is obtained by the incidence of light from the transparent protective layer 14 side.
It is obtained by visually observing the transparent protective layer 14.

[0100]

[Embodiment 14] FIG. 15 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The fourteenth embodiment will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 14 is the same as that of the thermoreversible recording medium of Example 11 except that an adhesive layer 42 is formed on the upper surface of the thermoreversible recording / display layer 13 and An adhesive layer 43 is formed on the lower surface of the sex recording / display layer 13. The other layer structure is the same as that of the eleventh embodiment.

[0101]

[Embodiment 15] FIG. 16 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The fifteenth embodiment will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 15 is the same as that of the thermoreversible recording medium of Example 11 except that the printing layer 4 is provided under the transparent support 31.
4 is formed. Other configurations are the same as those of the first embodiment.
Same as 1. Characters and figures that do not need to be erased can be printed on the print layer 44.

[0102]

[Embodiment 16] FIG. 17 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The sixteenth embodiment will be described with reference to FIG. The thermoreversible recording medium of Example 16 has, for example, a transparent support 31 made of a plastic sheet having a thickness of 100 μm, and a thermoreversible recording / display layer having a thickness of 20 μm on the lower surface of the transparent support 31. 13 is formed. A reflection layer or a light absorption layer 12 printed in black is formed on the lower surface thereof. Since the reflective layer or the light absorption layer 12 is black, it functions as a light absorption layer. Further, a protective layer 17 made of a plastic sheet having a film thickness of 5 μm is formed on the lower surface thereof.

The film thickness of the transparent support 31 is such that the thermoreversible recording / display layer 13 can be held, and is preferably 25 μm to 1 mm. If necessary, characters or figures can be printed on the peripheral portion of the transparent support 31. In this way, by performing normal printing separately from the thermal printing record,
Information that does not need to be erased can be recorded.

The thickness of the protective layer 17 is such that the heat generating recording element passes through the protective layer 17 and the thermoreversible recording / display layer 13 passes through the protective layer 17.
The thickness is sufficient to transfer heat to, and 1 to 15 μm is desirable. Recording on the thermoreversible recording medium of Example 16 was performed using the protective layer 17
When heating is performed from the side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 and recording is performed.

The visual information of the thermoreversible recording medium of Example 16 was determined by the incidence of light from the transparent support 31 side.
It is obtained by visually observing the transparent support 31.

[0106]

[Embodiment 17] FIG. 18 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The seventeenth embodiment will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 17 is the same as that of the thermoreversible recording medium of Example 16 except that an enhancement layer is provided between the thermoreversible recording / display layer 13 and the reflective layer or the light absorbing layer 12. 15 is formed. Other layer configurations are the same as those in Example 16 described above.
Is the same as.

The enhancement layer 15 is provided for the purpose of enhancing the contrast between the transparent portion and the cloudy portion. In the recording on the thermoreversible recording medium of Example 17, heat is efficiently transmitted to the thermoreversible recording / display layer 13 by heating from the protective layer 17 side using a thermal head to perform recording.

The visual information of the thermoreversible recording medium of the seventeenth embodiment was determined by the incidence of light from the transparent support 31 side.
It is obtained by visually observing the transparent support 31.

[0109]

[Embodiment 18] FIG. 19 is a sectional view showing a structure of a thermoreversible recording medium according to still another embodiment of the present invention. The eighteenth embodiment will be described with reference to FIG. The thermoreversible recording medium of Example 18 is capable of recording combined information of directly visible thermal recording and coded recording.

The construction of the thermoreversible recording medium of Example 18 was coded between the reflective layer or the light absorbing layer 12 and the protective layer 17 in the thermoreversible recording medium shown in Example 16 above. The recording layer 16 for recording information is formed. The other layer structure is the same as that of the 16th embodiment.
The recording medium of the recording layer 16 is a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card,
A magneto-optical recording medium, a thermo-magnetic recording medium or the like can be used.

For recording on the thermoreversible recording medium of Example 18, when heating is performed from the protective layer 17 side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 for recording. . The thermoreversible recording medium of Example 18 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. Therefore, in addition to visual information, code information can be recorded by combining the recording methods of the respective media.

The visual information of the thermoreversible recording medium of the eighteenth embodiment is obtained by the incidence of light from the transparent support 31 side.
It is obtained by visually observing the transparent support 31.

[0113]

[Embodiment 19] FIG. 20 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The nineteenth embodiment will be described with reference to FIG. The thermoreversible recording medium of Example 19 is capable of recording combined information of directly visible thermal recording and coded recording.

The construction of the thermoreversible recording medium of Example 19 is the information coded between the reflection layer or light absorbing layer 12 and the protective layer 17 in the thermoreversible recording medium shown in Example 17. The recording layer 16 for recording is formed. The other layer structure is the same as that of the seventeenth embodiment.
The type of recording medium for the recording layer 16 is as shown in the eighteenth embodiment.

In recording on the thermoreversible recording medium of Example 19, when heating is performed from the protective layer 17 side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 to perform recording. . The thermoreversible recording medium of Example 19 combines recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. Therefore, in addition to visual information, code information can be recorded by combining the recording methods of the respective media.

Further, the visual information of the thermoreversible recording medium of the nineteenth embodiment is obtained by the incidence of light from the transparent support 31 side.
It is obtained by visually observing the transparent support 31.

[0117]

[Embodiment 20] FIG. 21 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The 20th embodiment will be described with reference to FIG. The thermoreversible recording medium of Example 20 has, for example, a transparent support 31 made of a polyester sheet having a film thickness of 100 μm, and the transparent support 31 has a thermoreversible recording / display layer 1 having a film thickness of 20 μm.
3 is formed. A transparent protective layer 14 made of a polyester sheet having a film thickness of 5 μm is formed thereon.

As a material for the transparent support 31, this Example 20 was used.
Then, polyester was used. The film thickness of the transparent support 31 is required to maintain the thermoreversible recording / display layer 13, and is preferably 25 μm to 1 mm. As the material of the thermoreversible recording / display layer 13, for example, S-REC KS-1 (trade name, manufactured by Sekisui Chemical Co., Ltd.) was used as polyvinyl acetal. Behenic acid was used as the saturated carboxylic acid and / or its derivative. Then, 5 parts by weight of S-REC KS-1 and 3 parts by weight of behenic acid were added to 50 parts by weight of THF.
To prepare a coating solution of the thermoreversible recording material. The film thickness of this solution after drying was adjusted to 20 μm by the bar coating method.

Regarding the thickness of the transparent protective layer 14, the heat-generating recording element passes through the transparent protective layer 14 and the thermoreversible recording / display layer 13 is formed.
The thickness is sufficient to transfer heat to, and 1 to 15 μm is desirable. In addition, if necessary, in the peripheral portion of the transparent protective layer 14,
That is, it is possible to print characters and figures on the peripheral portion of the transparent protective layer 14, which coincides with the peripheral portion of the thermoreversible recording / display layer 13 where printing is not normally performed.

In the recording on the thermoreversible recording medium of Example 20, when the transparent protective layer 14 side is heated by using a thermal head, the heat is efficiently transferred to the thermoreversible recording / display layer 13 for recording. . The visual information of the thermoreversible recording medium of Example 20 can be obtained by visually observing the transparent protective layer 14 side by the incidence of light from the transparent support 31 side.

[0121]

[Embodiment 21] FIG. 22 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The twenty-first embodiment will be described with reference to FIG. The thermoreversible recording medium according to the twenty-first embodiment has a constitution in which the vertical direction of the thermoreversible recording medium described in the twentieth embodiment is reversed. That is, in the constitution of the thermoreversible recording medium of Example 21, as shown in FIG. 22, the thermoreversible recording / display layer 13 is formed under the transparent support 31. This thermoreversible recording
A transparent protective layer 14 is further formed under the display layer 13. For the transparent support 31, the thermoreversible recording / display layer 13, and the transparent protective layer 14, the same materials as those shown in Example 20 can be used.

In the recording on the thermoreversible recording medium of Example 21, when the transparent protective layer 14 is heated by using a thermal head, heat is efficiently transferred to the thermoreversible recording / display layer 13 to perform recording. . The visual information of the thermoreversible recording medium of Example 21 can be obtained by visually observing the transparent support 31 side by the incidence of light from the transparent protective layer 14 side.

By additionally writing on the transparent support 31 with an aqueous or oil-based felt-tip pen or the like, this additionally written information can be erased with a solvent such as alcohol or water. In addition, if necessary, in the peripheral portion of the transparent support 31,
That is, it is possible to print characters and figures on the peripheral portion of the transparent protective layer 14, which coincides with the peripheral portion of the thermoreversible recording / display layer 13 where printing is not normally performed.

[0124]

[Embodiment 22] FIG. 23 is a sectional view showing the structure of a thermoreversible recording medium according to yet another embodiment of the present invention. The twenty-second embodiment will be described with reference to FIG. The structure of the thermoreversible recording medium of Example 22 is the same as that of the thermoreversible recording medium described in Example 20, except that the transparent support 31 is replaced by the planar light source 32, and other layers are used. The structure, that is, the thermoreversible recording / display layer 13 and the transparent protective layer 14 are the same as in Example 20.

As the planar light source 32, a so-called edge light type one in which light is incident from the end of the plate and emitted from one surface of the plate is used. The planar light source body 32 used in the twenty-second embodiment introduces ambient light from the edge, efficiently reflects and diffuses the ambient light, and emits the light from one surface perpendicular to the incident light path. For example, acrylic resin plate [Acrylite (trade name): Mitsubishi Rayon Co., Ltd.]
Was used as the edge light type planar light source body 32.

In the recording on the thermoreversible recording medium of Example 22, when heating is performed from the transparent protective layer 14 side using a thermal head, heat is efficiently transferred to the thermoreversible recording / display layer 13 for recording. . The visual information of the thermoreversible recording medium of Example 22 is that light is introduced from the edge of the planar light source 32 and is emitted from one surface facing the thermoreversible recording / display layer 13 to protect the transparency. It is obtained by visually observing the layer 14 side.

[0127]

Twenty-third Embodiment FIG. 24 is a sectional view showing the structure of a thermoreversible recording medium according to yet another embodiment of the present invention. The twenty-third embodiment will be described with reference to FIG. The construction of the thermoreversible recording medium of this Example 23 is such that the recording layer 16 for recording coded information is formed on a part of the lower part of the transparent support 31 in the thermoreversible recording medium described in the above Example 20. It is formed, and the protective layer 17 is further formed thereunder.
The other layer structure, that is, the transparent support 31, the thermoreversible recording / display layer 13, and the transparent protective layer 14 are the same as those in Example 20.

As the type of recording medium for the recording layer 16, those described in the sixth embodiment can be used. Example 23
In recording on the thermoreversible recording medium, when heat is applied from the transparent protective layer 14 side using a thermal head, heat is efficiently transmitted to the thermoreversible recording / display layer 13 to perform recording. The thermoreversible recording medium of Example 23 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. Therefore, in addition to visual information, code information can be recorded by combining the recording methods of the respective media.

Further, the visual information of the thermoreversible recording medium of the twenty-third embodiment was obtained by the incidence of light from the transparent support 31 side.
It is obtained by visually observing the transparent protective layer 14.

[0130]

[Embodiment 24] FIG. 25 is a sectional view showing the structure of a thermoreversible recording medium according to still another embodiment of the present invention. The twenty-fourth embodiment will be described with reference to FIG. The thermoreversible recording medium of the twenty-fourth embodiment is capable of recording information that is a combination of a directly visible thermal recording and a coded recording.

The constitution of the thermoreversible recording medium of the twenty-fourth embodiment is such that the coded information is recorded on a part of the lower part of the transparent protective layer 14 in the thermoreversible recording medium described in the twenty-first embodiment. The layer 16 is formed, and the protective layer 17 is further formed under the layer 16. Therefore, the transparent support 3
1, the thermoreversible recording / display layer 13, and the transparent protective layer 14 are the same as those in Example 21.

In the recording on the thermoreversible recording medium of Example 24, when the transparent protective layer 14 side is heated by using a thermal head, the heat is efficiently transmitted to the thermoreversible recording / display layer 13 to perform recording. Be seen. The thermoreversible recording medium of Example 24 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. So by combining the recording methods of each medium, in addition to visual information,
Code information can also be recorded.

Further, the visual information of the thermoreversible recording medium of the twenty-fourth embodiment is obtained by the incidence of light from the transparent protective layer 14 side.
It is obtained by visually observing the transparent support 31.

[0134]

Twenty-Fifth Embodiment FIG. 26 is a sectional view showing the structure of a thermoreversible recording medium according to a fifth embodiment of the present invention. The twenty-fifth embodiment will be described with reference to FIG. The thermoreversible recording medium of the twenty-fifth embodiment is capable of recording combined information of directly visible thermal recording and coded recording.

The construction of the thermoreversible recording medium of the twenty-fifth embodiment is such that coded information is recorded in a part of the lower part of the planar light source body 32 of the thermoreversible recording medium described in the twenty-second embodiment. The recording layer 16 is formed, and the protective layer 17 is further formed under the recording layer 16. Other layer configurations are the same as those in Example 2 described above.
Same as 2. In the recording on the thermoreversible recording medium of Example 25, when heat is applied from the transparent protective layer 14 side using a thermal head, the heat is efficiently transferred to the thermoreversible recording / display layer 13 for recording. The thermoreversible recording medium of Example 25 is a combination of recording means such as a magnetic recording medium, an optical recording medium, a thermal recording medium, an electric recording medium such as an IC card, a magneto-optical recording medium, and a thermomagnetic recording medium. Therefore, in addition to visual information, code information can be recorded by combining the recording methods of the respective media.

The visual information of the thermoreversible recording medium of Example 25 was obtained by introducing light from the edge of the planar light source 32.
It can be obtained by emitting light from one surface facing the thermoreversible recording / display layer 13 and visually observing the transparent protective layer 14 side.

[0137]

Twenty-sixth Embodiment A recording method of the thermoreversible recording medium having the above structure will be described with reference to FIGS. 27, 28 and 1. 27 and 28 are explanatory diagrams for explaining examples of use of the thermoreversible recording medium of the present invention, and FIG. 1 is a characteristic diagram of the transmittance of the thermoreversible recording material used in the present invention with respect to temperature. Is.

FIG. 3, FIG. 4, FIG. 5, FIG. 6, FIG.
2, FIG. 15, FIG. 16, FIG. 17, FIG. 18, FIG.
In using the thermoreversible recording medium shown in FIG. 23, a recording apparatus 200 for recording information on the thermoreversible recording medium 10 is prepared as shown in FIG. This recording device 200 is provided with information for recording (for example, “A” “I”)
"U", "E", "O") is stored in the host computer. Further, the recording device 200 includes a thermal head 202 for printing information and a heating roll 2 for erasing information.
A printing unit 201 including the printer 03 and the like is provided.

FIG. 5, FIG. 6, FIG. 9, FIG. 10, FIG.
8 and FIG. 22, when the thermoreversible recording medium 10 is used, the recording surface and the visual surface are opposite to each other, so that the normal "a""i""u""e"" It is necessary to adjust the host computer etc. so that "O" can be recognized. The procedure for using the thermoreversible recording medium 10 using this recording device 200 is as follows.

(1) The user inserts the thermoreversible recording medium 10 into the printing section 201 of the recording device 200. (2) The recording device 200 senses that the thermoreversible recording medium 10 has been inserted, and records information (for example, “A”) for recording.
"I""U""E""O") printing section 2
Send a command to 01. Printing unit 20 that received this command
The thermal head 202 is a thermal reversible recording / display layer 13 through a transparent protective layer 14, a protective layer 17, or a support 21 under the conditions of a printing power of 0.1 W / dot and a printing time of 1 msec. Start printing on.

(3) "A""I""U" printed on the thermoreversible recording / display layer 13 by the thermal head 202
When the “E” and “O” portions are heated to 82 ° C. to 200 ° C. and then rapidly cooled to room temperature at a cooling rate of 50 ° C./sec or more, the portions become transparent (state D in FIG. 1). ). (4) When the user takes out the thermoreversible recording medium 10 from the recording device 200 after printing is completed, the thermoreversible recording medium 1
In No. 0, the printed portions of "A", "I", "U", "E" and "O" are fixed transparently. In this case, the contrast represented by the transmittance ratio between the transparent state and the cloudy state is, for example, 10 (transmittance ratio for light with a wavelength of 550 nm), which allows the user to visually check the recorded information “A” “I” “ above"
This “O” can be recognized, and this recorded information can be retained until the next use. (5) When the user inserts the thermoreversible recording medium 10 into the recording device 200 again in order to erase the previous information and record other information on the thermoreversible recording medium 10, the printing unit 2
The heat-reversible recording medium 10 is heated in the range of 82 ° C. to 200 ° C. by the heating roll 203 of No. 01, and then gradually cooled to room temperature at a temperature lowering rate of 50 ° C./sec or less to obtain the thermo-reversible recording / display layer 13. Becomes a cloudy state (state A in FIG. 1), and the previously recorded information is erased. Thereafter, the thermal head 202 can be used to perform the same processing as the above (2) and (3) to print other information.

In the case where the previously recorded information is simply erased without recording other information, the thermoreversible recording medium 10 is heated in the range of 82 ° C. to 200 ° C., and then the temperature decreasing rate is set to 5
By gradually cooling to room temperature at 0 ° C./sec or less, the cloudy state is fixed (state A in FIG. 1), and the user holds the thermoreversible recording medium 10 in which previously recorded information is erased. can do.

FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG.
In order to use the thermoreversible recording medium having the recording layer 16 shown in FIG. 4, FIG. 19, FIG. 20, FIG. 24, FIG. 25, and FIG. The recording device 300 is prepared. This recording device 3
Reference numeral 00 indicates a thermoreversible recording medium 10 including a host computer or the like in which recording information (for example, numerical values) is stored.
Read head 302 for the coded information recorded on the recording layer 16 and the recording head 3 for recording the coded information
03, etc., and a printing section 211 having a thermal head 212 for printing visual information, a heating roll 213 for erasing visual information, and the like.

FIGS. 9, 10, 19, 20, and 25.
In using the thermoreversible recording medium shown in (1), the recording surface and the visual surface are reversed, so normal "a""i""u""e""o" can be recognized on the visual side. It is necessary to adjust the host computer and so on. The procedure for using the thermoreversible recording medium 10 using this recording device 300 is as follows.

(1) The user inserts the thermoreversible recording medium 10 into the recording section 301 of the recording apparatus 300. (2) The recording device 300 senses that the thermoreversible recording medium 10 is inserted, and reads the coded information recorded on the recording layer 16 of the thermoreversible recording medium 10 by the read head 302.

(3) If necessary, new coded information is recorded on the recording layer 16 by the recording head 303. (4) The thermoreversible recording medium 10 is heated in the range of 82 ° C. to 200 ° C. by the heating roll 213 of the printing unit 211, and is gradually cooled to room temperature at a temperature lowering rate of 50 ° C./sec or less, thereby being thermally reversible. The sex recording / display layer 13 becomes cloudy (state A in FIG. 1), and the previously recorded visual information is erased.

(5) The printing unit 21 prints the visual information (for example, the balance) corresponding to the new coded information.
The host computer sends a command to 1. (6) The printing unit 211 that has received this command uses the thermal head 212 to use the transparent protective layer 14 and / or the protective layer 17.
Printing is performed on the thermoreversible recording / display layer 13 via the, and visual information is recorded.

Although the respective embodiments of the present invention have been described in detail above, the materials used and the numerical conditions described in the above embodiments are merely examples within the scope of the present invention. It is to be understood that the materials used and the numerical conditions are not the only limitation.

[0149]

As described in detail above, the present invention is
A thermoreversible recording material in which a transparent state and a cloudy state are reversibly fixed due to a difference in cooling rate when heated and returned to room temperature,
The following effects can be expected by constructing the thermoreversible recording medium and the recording method thereof.

(1) Matrix material made of polyvinyl acetal, saturated carboxylic acid having 10 to 40 carbon atoms and /
Alternatively, since the thermoreversible recording material is composed of an organic low molecular weight compound composed of the derivative of the saturated carboxylic acid, the temperature range in which the thermoreversible recording material can be in a transparent state or a cloudy state is set to a conventional thermoreversible recording material. It was possible to make it wider, and the contrast could be improved.

(2) Since the recording and erasing of information can be repeated, the thermoreversible recording medium used for printing and recording can be reused and resource saving is excellent. (3) Information can be printed and recorded freely by a simple thermal means such as a thermal head. Therefore, a thermal head or the like which has been used for recording on conventional thermal recording paper can also be used.

(4) To erase the recorded information, for example, 8
Since it is necessary to heat the thermoreversible recording / display layer in the range of 2 ° C. to 200 ° C., it cannot be erased at ordinary room temperature. Therefore, the retention of the recorded data is excellent. (5) Visual information with high contrast can be recorded. (6) The thermoreversible recording medium of the present invention can be formed into a card shape and can be made highly portable.

(7) Since the thermoreversible recording medium of the present invention is provided with a recording layer for recording code information, it is possible to record code information together with visual information. Therefore, the information stored in the recording layer can be read and printed and displayed as visual information. (8) Since the thermoreversible recording medium of the present invention can print characters and figures on the upper surface or the lower surface of the transparent protective layer, the transparent support, the planar light source, and / or the adhesive layer with a printing ink or the like. You can display information that does not need to be erased.

[Brief description of drawings]

FIG. 1 is a characteristic diagram of light transmittance with respect to temperature of a thermoreversible recording material used in the present invention.

FIG. 2 is a characteristic diagram of light transmittance with respect to temperature of a conventional thermoreversible recording material.

FIG. 3 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 2.

FIG. 4 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 3.

FIG. 5 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 4.

FIG. 6 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 5.

FIG. 7 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 6.

FIG. 8 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 7.

FIG. 9 is a sectional view showing a configuration of a thermoreversible recording medium of Example 8.

FIG. 10 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 9.

FIG. 11 is a sectional view showing the structure of a thermoreversible recording medium of Example 10.

FIG. 12 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 11.

FIG. 13 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 12.

FIG. 14 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 13.

FIG. 15 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 14.

FIG. 16 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 15.

FIG. 17 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 16.

FIG. 18 is a cross-sectional view showing one configuration of a thermoreversible recording medium of Example 17.

FIG. 19 is a sectional view showing the structure of a thermoreversible recording medium of Example 18.

FIG. 20 is a sectional view showing the structure of a thermoreversible recording medium of Example 19.

FIG. 21 is a sectional view showing the structure of a thermoreversible recording medium of Example 20.

FIG. 22 is a sectional view showing the structure of a thermoreversible recording medium of Example 21.

FIG. 23 is a sectional view showing the structure of a thermoreversible recording medium of Example 22.

FIG. 24 is a sectional view showing the structure of a thermoreversible recording medium of Example 23.

FIG. 25 is a sectional view showing the structure of a thermoreversible recording medium of Example 24.

FIG. 26 is a sectional view showing the structure of a thermoreversible recording medium of Example 25.

FIG. 27 is a diagram for explaining an example of use of a thermoreversible recording medium having no recording layer such as a magnetic recording layer of the present invention.

FIG. 28 is a diagram for explaining another usage example of the thermoreversible recording medium having a recording layer such as a magnetic recording layer of the present invention together.

[Explanation of symbols]

 10 Thermoreversible Recording Medium 11, 21 Support 12 Reflective Layer or Light Absorption Layer 13 Thermoreversible Recording / Display Layer 14 Transparent Protective Layer 15 Enhance Layer 16 Recording Layer 17 Protective Layer 31 Transparent Support 32 Surface Light Source 41, 42, 43 Adhesive layer 44 Printing layer 200,300 Recording device 201, 211 Printing unit 202, 212 Thermal head 203, 213 Heating roll 301 Recording unit 302 Reading head 303 Recording head

[Procedure amendment]

[Submission date] September 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The saturated carboxylic acid that can be used in the present invention is not limited to the following, but capric acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid,
Cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laxeric acid,
Tritriacontanoic acid, gedic acid, ceroplastic acid, hexatriacontanoic acid, heptatriacontanoic acid, nonatriacontanoic acid, tetracontanoic acid and the like are preferably used. These correspond to saturated carboxylic acids having 10 to 40 carbon atoms. Further, the derivative thereof is not limited to the following, but includes stearic acid amide, nonadecanoic acid amide, arachidic acid amide, heneicosanoic acid amide, behenic acid amide, tricosanoic acid amide, lignoceric acid amide, pentacosanoic acid amide, and serotic acid. Amides, heptacosanoic acid amides, montanic acid amides, nonacosanoic acid amides, melicinic acid amides, hentriacontanic acid amides,
Laxeric acid amide, tritriacontanoic acid amide, gedamic acid amide, ceroplastic acid amide, hexatriacontanoic acid amide, heptatriacontanoic acid amide, nonatriacontanoic acid amide, tetracontanic acid amide, etc., dodecylamine, hexadecyl Amine, octade
Sylamine, stearylamine, amine nonadecanoate,
Araquinic acid amine, heneicosanoic acid amine, behenic acid amine, tricosanoic acid amine, lignoceric acid amine,
Amine pentacosanoate, amine serotonate, amine heptacosanoate, amine montanate, amine nonacosanoate,
Amine melicinate, Hentriacontanoic acid amine, Lacteric acid amine, Tritriacontanoic acid amine, Gedanoic acid amine, Ceroplastic acid amine, Hexatriacontanoic acid amine, Heptatriacontanoic acid amine, Nonatriacontanoic acid amine, Tetracontanoic acid Amines such as amines, palmitoanilide, stearylanilide, nonadecanoic acid anilide, arachidic acid anilide, heneicosanoic acid anilide, behenic acid anilide, tricosanoic acid anilide,
Lignoceric acid anilide, pentacosanoic acid anilide, serotinic acid anilide, montanic acid anilide, nonacosanoic acid anilide, melicinic acid anilide, hentriacontanoic acid anilide, laxellic acid anilide, tritriacontanoic acid anilide, gededic acid anilide, hexaplastinic acid anilide, hexa Anilides such as triacontanoic acid anilide, heptatriacontanoic acid anilide, nonatriacontanoic acid anilide, tetracontanoic acid anilide, cetyl alcohol, stearyl alcohol, nonadecanol, eicosanol, heneicosanol, docosanol, tetracosanol, pentacosanol, Hexanol, Heptacosanol, Octacosanol, Nonacosanol, Melisyl alcohol, Hentriacontanol, Lassenor, Tritriaconta Lumpur, tetra air conditioners ethanol,
Alcohols such as pentaacontanol, hexaacontanol, heptaacontanol, nonatriacontanol, tetraacontanol, etc., phenyl stearate, vinyl stearate, n-dodecyl stearate, methyl nonadecanoate, methyl arachiate, methyl heneicosanoate, behenic acid. Methyl, methyl tricosanoate, methyl lignocerate, methyl pentacosanoate, methyl serotinate, methyl heptacosanoate, methyl montanate, methyl nonacosanoate, methyl melicinate, methyl hentriacontanate, methyl laxelate, methyl tritriacontanate, Esters such as methyl gedate, methyl ceroplastate, methyl hexatriacontanoate, methyl heptatriacontanate, methyl nonatriacontanoate, and methyl tetracontanate, Ketones such as thearon, 19-heptatriacontanone, 20-nonatriacontanone, 21-hentetracontanone, 22-tritetracontanone, Ca stearate, Co stearate, Cu stearate, Fe stearate, stearic acid K, Li stearate, Mg stearate, Mn stearate, Ni stearate, Pb stearate, Sn stearate,
Zn stearate, Zr stearate, C nonadecanoate
a, Ca arachidate, Ca heneicoate, Behenate C
a, Ca tricosanoate, Ca lignocerate, Ca pentacosanoate, Ca serotonate, Ca heptacosanoate, Ca montanate, Ca nonacosanoate, Ca mericinate, Ca hentriacontanoate, Ca lactellate, Ca tritriacontaneate, Ca gedaate, Ca ceroplastate,
Hexatriacontanoic acid Ca, heptatriacontanoic acid Ca, nonatriacontanoic acid Ca, tetracontanoic acid C
A derivative of a saturated carboxylic acid selected from metal salts such as a and imidazoles such as 2-heptadecylimidazole, 2-undecylimidazole and 2-stearylimidazole is preferable.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C09K 9/02 C 7188-4H

Claims (38)

[Claims] 1. A thermoreversible recording material containing a matrix material and an organic low molecular weight compound, the transparency of which changes with heat history, wherein the matrix material is polyvinyl acetal, and the organic low molecular weight compound is a saturated carboxylic acid having 10 to 40 carbon atoms. And / or a derivative of the saturated carboxylic acid, a thermoreversible recording material. 2. A saturated carboxylic acid having 10 to 40 carbon atoms,
Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melicinic acid The heat-reversible recording according to claim 1, which is: hentriacontanoic acid, laxeric acid, tritriacontanoic acid, gedic acid, ceroplastic acid, hexatriacontanoic acid, heptatriacontanoic acid, nonatriacontanoic acid, tetracontanoic acid. material. 3. The saturated carboxylic acid derivative is an amide, amine, anilide, alcohol, ester, ketone, metal salt or imidazole of a saturated carboxylic acid.
Or the thermoreversible recording material according to item 2. 4. The thermoreversible recording material according to claim 1, wherein two or more kinds of organic low molecular weight compounds are simultaneously used as the organic low molecular weight compound. 5. The mixing weight ratio of the saturated carboxylic acid and / or its derivative to the matrix material is 1: 2 to 20: 1.
The thermoreversible recording material according to claim 1, which is in the range of 1. 6. (1) A support made of a material selected from plastic, paper or synthetic paper, (2) a reflection layer or a light absorption layer formed on the support, and (3) the reflection. A thermoreversible recording / display layer formed on the layer or the light absorbing layer, the thermoreversible recording / display layer comprising the thermoreversible recording material according to claim 1, (4) the thermoreversible recording / display A thermoreversible recording medium comprising a transparent protective layer formed on the layer. 7. (1) A support made of a material selected from plastic, paper or synthetic paper, (2) a reflection layer or a light absorption layer formed on the support, and (3) the reflection. An enhancement layer formed on the layer or the light absorption layer and having a function of enhancing the contrast between the transparent portion and the cloudy portion; (4) formed on the enhancement layer;
3. A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, and (5) a transparent protective layer formed on the thermoreversible recording / display layer. And a thermoreversible recording medium. 8. A support selected from (1) an inorganic fiber paper having a high thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and (2) the support. Formed on top of the above,
Or a thermoreversible recording comprising the thermoreversible recording material according to 5
A thermoreversible recording medium comprising a display layer and (3) a transparent protective layer formed on the thermoreversible recording / display layer. 9. A support selected from (1) an inorganic fiber paper having a high thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and (2) the support. An enhance layer formed on the transparent layer and having a function of enhancing the contrast between the transparent portion and the cloudy portion; and (3) formed on the enhance layer,
3. A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, and (4) a transparent protective layer formed on the thermoreversible recording / display layer. And a thermoreversible recording medium. 10. A support made of a material selected from plastic, paper or synthetic paper, (2) a reflection layer or a light absorption layer formed on the support, and (3) the reflection. A thermoreversible recording / display layer formed on the layer or the light absorbing layer, the thermoreversible recording / display layer comprising the thermoreversible recording material according to claim 1, (4) the thermoreversible recording / display A transparent protective layer formed on the layer; (5) a recording layer further formed under the support for recording coded information; and (6) a protective layer formed under the recording layer. A thermoreversible recording medium having a layer. 11. (1) A support made of a material selected from plastic, paper or synthetic paper, (2) a reflection layer or a light absorption layer formed on the support, and (3) the reflection. An enhancement layer formed on the layer or the light absorption layer and having a function of enhancing the contrast between the transparent portion and the cloudy portion; (4) formed on the enhancement layer;
A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, (5) a transparent protective layer formed on the thermoreversible recording / display layer, (6) A thermoreversible recording medium comprising: a recording layer formed under the support for recording coded information; and (7) a protective layer formed under the recording layer. 12. A support selected from (1) an inorganic fiber paper having a high thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and (2) the support. Formed on top of the above,
Or a thermoreversible recording comprising the thermoreversible recording material according to 5
A display layer, (3) a transparent protective layer formed on the thermoreversible recording / display layer, and (4) a recording layer which is formed under the support and records encoded information. And (5) a protective layer formed under the recording layer, which is a thermoreversible recording medium. 13. A support selected from (1) an inorganic fiber paper having a high thermal conductivity, a ceramic sheet, a metal sheet, or a plastic sheet in which carbon powder, metal powder or the like is dispersed, and (2) the support. An enhance layer formed on the transparent layer and having a function of enhancing the contrast between the transparent portion and the cloudy portion; and (3) formed on the enhance layer,
A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, (4) a transparent protective layer formed on the thermoreversible recording / display layer, (5) further A thermoreversible recording medium comprising: a recording layer formed under the support for recording coded information; and (6) a protective layer formed under the recording layer. 14. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed on the transparent support.
A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further A thermoreversible recording medium comprising a reflective layer or a light absorbing layer formed under the transparent support. 15. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed on the transparent support.
A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further An adhesive layer formed on the periphery under the transparent support, and (5) a reflective layer or a light absorption layer adhered under the adhesive layer with a space from the lower surface of the transparent support, ) The space formed between the lower surface of the transparent support and the upper surface of the reflection layer or the light absorption layer is an enhancement layer having a function of enhancing the contrast between the transparent portion and the cloudy portion. Thermoreversible recording medium. 16. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed on the transparent support.
A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further A reflective layer or a light absorbing layer formed under the transparent support, (5) a recording layer formed under the reflective layer or the light absorbing layer for recording coded information, (6) A thermoreversible recording medium comprising a protective layer formed below the recording layer. 17. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed on the transparent support.
A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further An adhesive layer formed around the bottom of the transparent support, (5) a reflective layer or a light absorption layer adhered under the adhesive layer with a space from the lower surface of the transparent support, (6) (7) a recording layer formed under the reflection layer or the light absorption layer for recording coded information; and (7) a protective layer formed under the recording layer, (8) of the transparent support. A thermoreversible recording medium, characterized in that the space formed between the lower surface and the upper surface of the reflection layer or the light absorption layer is an enhancement layer having a function of enhancing the contrast between the transparent portion and the cloudy portion. 18. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed under the transparent support.
(3) a thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, and (3) a reflective layer or a light absorbing layer formed under the thermoreversible recording / display layer, ) A protective layer formed under the reflective layer or the light absorbing layer,
A thermoreversible recording medium comprising: 19. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed under the transparent support.
A thermoreversible recording / display layer made of the thermoreversible recording material described in 3, 4, or 5; (3) formed under the thermoreversible recording / display layer to enhance the contrast between a transparent portion and a cloudy portion. An enhancing layer having a function; (4) a reflection layer or a light absorption layer formed under the enhancement layer; and (5) a protective layer formed under the reflection layer or the light absorption layer,
A thermoreversible recording medium comprising: 20. (1) A transparent support made of transparent plastic, (2) formed under the transparent support,
(3) a thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, and (3) a reflective layer or a light absorbing layer formed under the thermoreversible recording / display layer, ) A heat provided with a recording layer formed under the reflective layer or the light absorption layer for recording coded information, and (5) a protective layer formed under the recording layer. Reversible recording medium. 21. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed under the transparent support.
A thermoreversible recording / display layer made of the thermoreversible recording material described in 3, 4, or 5; (3) formed under the thermoreversible recording / display layer to enhance the contrast between a transparent portion and a cloudy portion. An enhancing layer having a function; (4) a reflective layer or a light absorbing layer formed under the enhancing layer; and (5) recording coded information formed under the reflecting layer or the light absorbing layer. And a protective layer formed under the recording layer, and a thermoreversible recording medium. 22. (1) A transparent support made of transparent plastic, and (2) a transparent support formed on the transparent support,
3. A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, and (3) a transparent protective layer formed on the thermoreversible recording / display layer. And a thermoreversible recording medium. 23. (1) A transparent support made of transparent plastic, (2) formed under the transparent support,
3. A thermoreversible recording / display layer comprising the thermoreversible recording material according to 3, 4 or 5, and (3) a transparent protective layer formed under the thermoreversible recording / display layer. And a thermoreversible recording medium. 24. An edge light type planar light source body, and (2) a flat light source body formed on the planar light source body.
3. A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, and (3) a transparent protective layer formed on the thermoreversible recording / display layer. And a thermoreversible recording medium. 25. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed on the transparent support.
A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further Formed on a part of the lower surface of the transparent support,
A thermoreversible recording medium comprising: a recording layer for recording coded information; and (5) a protective layer formed under the recording layer. 26. A transparent support comprising (1) a transparent plastic, and (2) a transparent support formed under the transparent support,
A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed under the thermoreversible recording / display layer, (4) the transparent Thermoreversible property, comprising: a recording layer for recording coded information formed on a part of the lower surface of the protective layer; and (5) a protective layer formed under the recording layer. recoding media. 27. (1) An edge light type planar light source body; and (2) formed on the planar light source body,
A thermoreversible recording / display layer made of the thermoreversible recording material according to 3, 4 or 5, (3) a transparent protective layer formed on the thermoreversible recording / display layer, (4) further Formed on a part of the lower surface of the planar light source,
A thermoreversible recording medium comprising: a recording layer for recording coded information; and (5) a protective layer formed under the recording layer. 28. An upper surface of the thermoreversible recording / display layer is adhered to an upper layer of the thermoreversible recording / display layer via an adhesive layer, and a lower surface of the thermoreversible recording / display layer is adhered to a lower side of the thermoreversible recording / display layer via an adhesive layer. 6. The adhesive layer of claim 6, 7, 8,
9, 10, 11, 12, 13, 14, 15, 16, 1
7, 18, 19, 20, 21, 22, 23, 24, 2
The thermoreversible recording medium according to 5, 26 or 27. 29. A printing layer having characters or graphics printed thereon is formed above or below the adhesive layer. 1
5, 16, 17, 18, 19, 20, 21, 22, 2
The thermoreversible recording medium according to 3, 24, 25, 26 or 27. 30. The printing layer having characters or graphics printed thereon is formed on the upper surface or the lower surface of the transparent protective layer.
14, 15, 16, 17, 22, 23, 24, 25, 2
The thermoreversible recording medium according to 6 or 27. 31. The printing layer on which characters or figures are printed is formed on the upper surface or the lower surface of the transparent support, according to claim 14, 15, 16, 17, 18, 19, and 2.
The thermoreversible recording medium according to 0, 21, 22, 23, 25, or 26. 32. The thermoreversible recording medium according to claim 24, wherein a printing layer on which characters or figures are printed is formed on the upper surface or the lower surface of the planar light source body. 33. The reflective layer or the light absorbing layer is a colored layer formed by printing black, red, blue or the like having a high contrast with respect to white.
0, 11, 14, 15, 16, 17, 18, 19, 20
Or the thermoreversible recording medium according to 21. 34. The reflective layer or the light absorbing layer is a colored layer formed by printing a plurality of colors having a high contrast with respect to white,
The thermoreversible recording medium according to 15, 16, 17, 18, 19, 20, or 21. 35. The reflection layer or the light absorption layer is a layer printed with a coating material containing a fluorescent coating material, 6, 7, 10, 11, 14, 15, 16, 17, 18. ,
The thermoreversible recording medium according to 19, 20 or 21. 36. The reflective layer or the light absorbing layer is a layer printed with a paint containing carbon powder or metal powder having good thermal conductivity.
The thermoreversible recording medium according to 4, 15, 16, 17, 18, 19, 20 or 21. 37. (1) The thermoreversible recording material according to claim 1, 2, 3, 4 or 5 is heated by a thermal means, and (2) the thermoreversible recording is then performed while controlling the cooling rate. A recording method, wherein a transparent state or a cloudy state is formed by cooling a material. 38. (1) Claims 6, 7, 8, 9, 10,
11, 12, 13, 14, 15, 16, 17, 18, 1
9, 20, 21, 22, 23, 24, 25, 26, 2
7, 28, 29, 30, 31, 32, 33, 34, 35
And (36) by heating a predetermined portion of the thermoreversible recording medium by a thermal means, and then cooling the thermoreversible recording medium while controlling the cooling rate, thereby forming or erasing visual information. Recording method characterized by making.