JPH0880681A - Thermal reversible recording material, production thereof, thermal reversible recording medium and recording apparatus using the same - Google Patents

Abstract

PURPOSE: To provide a thermal reversible recording material having a wide temp. range for forming a transparent state, easy in temp. control and capable obtaining stable transparency even when recording/erasing processing is repeated. CONSTITUTION: A thermal reversible recording medium has a heat historytransparency characteristic showing the max. transparency when the medium is quenched (e.g. 50 deg.C/sec or more) after heated to temp. T2 and showing the min. transparency when the medium is quenched (e.g. 50 deg.C/sec or more) after heated to the temp. range from T1 (T1<T2) to T2 or gradually cooled (e.g. below 50 deg.C/sec) after heated to T1 or higher. That is, the thermal reversible recording medium characterized by that a condition bringing a transparent state to a turbid state is gentle as compared with a conventional medium and the transparent and turbid states are stable up to high temp. can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoreversible recording material capable of reversibly repeatedly recording and erasing by a thermal means, a method for producing the same, a thermoreversible recording medium using the material and the medium. The present invention relates to a recording device used.

[0002]

2. Description of the Related Art Thermoreversible recording materials have the property that the transparency of the materials (herein, the transparency with respect to visible light will be discussed. The same applies hereinafter) changes depending on the thermal history. Therefore, for example, by a thermal means such as a thermal head or the like, it is possible to make a display or the like by making the thermal history of a predetermined portion of the material different from other portions and making the transparency of both portions different. Becomes

As a conventional example of such a thermoreversible recording material, for example, there is one disclosed in JP-A-55-154198. The thermoreversible recording material disclosed in this publication, a matrix material composed of a polymer such as polyester or a resin is dispersed with organic low-molecular compounds such as behenic acid (docosanoic acid).

As a specific example of the above characteristics, Japanese Patent Laid-Open No. 55-
Japanese Patent No. 154198 describes examples having the following configurations (A) to (D). (A) A thermoreversible recording material containing a high molecular weight linear copolyester based on an aromatic dicarboxylic acid and an aliphatic diol and docosanoic acid shows stable transparency when heated to 72 ° C. and cooled. It was It could only be returned to a cloudy state by reheating to a temperature above 77 ° C.

(B) A thermoreversible recording material containing a copolymer of vinylidene chloride and acrylonitrilo, docosanoic acid, and a fluorad lubricant for improving fluidity is 63 ° C.
When it was heated to and cooled, it showed stable transparency. It could only be returned to a cloudy state by reheating to a temperature above 74 ° C. The thermoreversible recording material containing (C) 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 (D) 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.

[0007]

However, as will be described in detail later with reference to a comparative example, in a conventional thermoreversible recording material, when recording and erasing are repeatedly performed, a transparent portion and a cloudy portion in an image are formed. There was a problem that the contrast with Further, in the conventional thermoreversible recording material, the temperature range for forming a transparent state is (A) above.
(77-72) = 5 ° C. for the above, (74-63) = 11 ° C. for the above (B), and (70-68) = for the above (C). In the case of 2 ° C. and (D) above, (77−72) = 5 ° C., which was 11 ° C. at the maximum.

In order to form a display device using a thermoreversible recording material and perform recording (display) with good contrast and the like, a colored plate is provided on the back surface of the display plate made of the thermoreversible recording material, A desired portion of the display plate is selectively made transparent by a thermal means such as a thermal head, and the background portion is kept in a cloudy state so that the color of the colored plate can be seen through only the transparent portion. A method of displaying in this way can be considered. In such a case, if the temperature range in which the transparent state of the thermoreversible recording material can be formed is narrow as described above,
(A) It is difficult to control the temperature of the thermal means. (B) Problems such as difficulty in obtaining stable transparency occur when images are repeatedly produced.

Further, in the conventional thermoreversible recording material, the formed image has a temperature of 60 ° C. [63 ° C. in the case of the above (2)].
When a certain temperature is applied and then this image is cooled, the cloudy portion in the image becomes transparent. That is, 70 that would occur in normal use
At a temperature of about ℃, the visibility of the image will be reduced.

The present invention eliminates the above problems and has a wide temperature range for forming a transparent state, temperature control is easy, and stable transparency can be obtained even when recording and erasing are repeated. An object of the present invention is to provide a reversible recording material, a manufacturing method thereof, a thermoreversible recording medium thereof, and a recording apparatus using the thermoreversible recording medium.

[0011]

In order to achieve the above-mentioned object, the present invention provides (1) a thermoreversible recording material of the present invention, which comprises a matrix material and an organic low molecule, and whose transparency changes with heat history. In the reversible recording material, polyvinyl acetal and an ultraviolet curable resin (provided that they are cured with a curing agent) are contained as a matrix material, and at least one selected from the group of saturated carboxylic acids and derivatives of the saturated carboxylic acids as an organic low molecule. (Hereinafter, also referred to as “predetermined carboxylic acid”). The thermoreversible recording material is assumed to include the thermoreversible recording material in which the UV curable resin before curing and the unreacted curing agent remain in the thermoreversible recording material.

(2) As a preferred method for producing the thermoreversible recording material of the present invention, at least one selected from the group of saturated carboxylic acids and derivatives of this saturated carboxylic acid, polyvinyl acetal, and ultraviolet rays. Cured resin [as a constituent, a polymerizable oligomer (monomer),
And containing a photopolymerization initiator], and irradiating the mixture with ultraviolet rays. In the production of this thermoreversible recording material, it is preferable to carry out the prescribed carboxylic acid, polyvinyl acetal and ultraviolet curable resin in a suitable solvent. Further, additives such as a leveling agent, a filler, a polymerization inhibitor, a thermosetting catalyst, an anaerobic catalyst and the like may be used depending on the purpose. In addition, here, the time and intensity of ultraviolet irradiation are determined according to the type of ultraviolet curable resin so that the desired curing can proceed.

The ultraviolet curable resin is composed of the following two components. That is, a polymerizable oligomer (monomer): a main component in an ultraviolet curable resin composition component, a photoreaction initiator: absorbs ultraviolet rays to start a polymerization reaction. The ultraviolet curable resin used here is not limited to this, but as the polymerizable oligomer (monomer), phenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol propylene oxide modified acrylate, 2-ethylhexyl carbitol Acrylate, ω
-Carboxy-polycaprolactone acrylate, ω-
Carboxacroyloxyethyl phthalate, acrylic acid dimer, monoacrylate such as 2-hydroxy-3-phenoxypropyl acrylate Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol Polyol polyacrylate such as hexaacrylate Modified propylene oxide triacrylate of trimethylol propane, ethylene oxide and lactone modification of isocyanuric acid, ethylene oxide modification of bisphenol A, etc. Modified polyol polyacrylate αω-diacryloyl- (bisethylene glycol)-
Polyester acrylates such as phthalate, αω-tetraacryloyl- (bistrimethylolpropane) -tetrahydrophthalate, αω-hexaacryloyl- (bispentaerythritol) -adipate Other epoxy acrylate, urethane acrylate, polyether acrylate, silicon acrylate, vinyl ether compound , And phosphazene compounds.

Further, commercially available UV curable resins are not limited to these, but include, for example, Aronix [trademark, polyester acrylate-based and urethane acrylate-based, Toa Gosei Chemical Industry Co., Ltd.], viscoat [trademark] , Polyester acrylate type, epoxy acrylate type and urethane acrylate type, Osaka Organic Chemical Industry Co., Ltd.], Ebecry1 (trademark, polyester acrylate type, epoxy acrylate type and urethane acrylate type, UCB chemical), lipoxy [trademark,
Epoxy acrylate type, Showa Polymer Co., Ltd.], NK ester [trademark, epoxy acrylate type and urethane acrylate type, Shin-Nakamura Chemical Co., Ltd.], Bremmer [trademark, epoxy methacrylate type, NOF Corporation], Kayarad [Trademark, Epoxy acrylate, Nippon Kayaku Co., Ltd.], Epoxy ester [Trademark, Epoxy acrylate and Epoxy Methacrylate, Kyoeisha Oil and Fat Chemical Co., Ltd.], Denacol [Trademark, Epoxy acrylate and Epoxy Methacrylate, Nagase Industrial Co., Ltd.], ART RANGE [Trademark, Urethane Acrylate-Based, Negami Kogyo Co., Ltd.], XP [Trademark, Urethane Acrylate-Based, Nippon Synthetic Chemical Industry Co., Ltd.], Chemlink (Trademark, Urethane Acrylate-Based, Sartome)
r), PPZ [trademark, phosphazene type, Idemitsu Petrochemical Co., Ltd.], Iupimer [trademark, polyester acrylate type and urethane acrylate type, Mitsubishi Yuka Co., Ltd.], Icatron [trademark, polyester acrylate type and epoxy acrylate type and Urethane acrylate type, Aika Industry Co., Ltd.], Fujihard [trademark, polyester acrylate type and epoxy acrylate type and urethane acrylate type, Fujikura Kasei Co., Ltd.], S-COAT U
V [trademark, Sekisui Chemical Co., Ltd.], and the like.

Examples of the photoreaction initiator include benzoin ether type 1-hydroxycyclohexylphenyl ketone such as isopropyl benzoin ether, isobutyl benzoin ether, isomethyl benzoin ether and isoethyl benzoin ether, and ketal type 2-hydroxy-type such as benzyl dimethyl ketal. 2-methyl-propiophenone, 4-
Acetophenone series such as isopropyl-2-hydroxy-2-methyl-propiophenone, benzophenone series such as methyl O-benzoylbenzoate, 2-methylthiooxanthone, thiooxanthone series such as 2-chlorothiooxanthone, etc. To be

Further, a reactive diluent is used in combination with a polymerizable oligomer (monomer) to lower the viscosity of the composition and improve the physical properties of a cured product, but the reactive diluent is not limited to this. It is not something that can be done. Examples of the reactive diluent include monofunctional groups such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-vinyl-2-pyrrolidone isobornyl acrylate and 2-hydroxyethyl acroyl phosphate 1,3-butane Difunctional groups such as diol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, thioglycol diacrylate, etc. Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipenta Examples include polyfunctional groups such as erythritol hexaacrylate and triallyl isocyanurate.

The saturated carboxylic acid which can be used here is
Specific examples of the monocarboxylic acid having at least 10 carbon atoms include, but are not limited to, capric acid, undecanoic acid, ularic acid, tridecanoic acid, myristic acid,
Pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid, hen Triacontanoic acid, dotriacontanoic acid, tritriacontanoic acid,
Tetratriacontanoic acid, pentatriacontanoic acid, hexatriacontanoic acid, heptatriacontanoic acid, nonatriacontanoic acid, tetracontanoic acid, hentetracontanoic acid, dotetracontanoic acid, tritetracontanoic acid,
Tetratetracontanoic acid, pentatetracontanoic acid, hexatetracontanoic acid, heptatetracontanoic acid, octatetracontanoic acid, nonatetracontanoic acid, pentacontanoic acid, hempentacontanoic acid, dopentacontanoic acid, tripentacontanoic acid, tetra Pentacontanoic acid,
Pentapentacontanoic acid, hexapentacontanoic acid, heptapentacontanoic acid, octapentacontanoic acid, nonapentacontanoic acid, hexacontanoic acid, dohexacontanoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecene Acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid,
Eicosenoic acid, heneicosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacosenoic acid, and dicarboxylic acids having at least 10 carbon atoms are not limited to the following. , Decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanoic acid, docosane Diacid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, tritoria Contanedioic acid, tetratriaco Tan diacid, pentatriacontanoic proximal diacid, hexatriacontane diacid, hepta triacontyl Tan diacid, nona triacontyl Tan diacid, Tetorakontan diacid, Heng tetra proximal diacid, Dotetorakontan diacid,
Tritetracontanedioic acid, tetratetracontanedioic acid,
Pentatetracontanedioic acid, hexatetracontanedioic acid, heptatetracontanedioic acid, octatetracontanedioic acid, nonatetracontanedioic acid, pentacontanedioic acid,
Hempentacontanedioic acid, dopentacontanedioic acid, tripentacontanedioic acid, tetrapentacontanedioic acid, pentapentacontanedioic acid, hexapentacontanedioic acid, heptapentacontanedioic acid, octapentacontanedioic acid,
Nonapentacontanedioic acid, hexacontanedioic acid, dohexacontanedioic acid, decenedioic acid, undecenedioic acid, dodecenedioic acid, tridecenedioic acid, tetradecenedioic acid, pentadecenedioic acid, hexadecenedioic acid, heptadecenedioic acid, octadecenedioic acid Diacid, nonadecenedioic acid, eicosendioic acid, heneicosendioic acid, docosenedioic acid, tricosenedioic acid, tetracosenedioic acid, pentacosenedioic acid, hensacosenedioic acid As derivatives of monocarboxylic acid having at least 10 carbon atoms, Decanoic acid amide,
Undecanoic acid amide, dodecanoic acid amide, tridecanoic acid amide, tetradecanoic acid amide, pentadecanoic acid amide, hexadecanoic acid amide, heptadecanoic acid amide, octadecanoic acid amide, nonadecanoic acid amide, eicosanoic acid amide, heneicosanoic acid amide, docosanoic acid amide, tricosanoic acid Amides, tetracosanoic acid amides, pentacosanoic acid amides, hexacosanoic acid amides, heptacosanoic acid amides, octacosanoic acid amides, nonacosanoic acid amides, triacontanic acid amides, hentriacontanoic acid amides, dotriacontanoic acid amides, tritriacontanoic acid amides, tetra Triacontanoic acid amide, pentatriacontanoic acid amide, hexatriacontanoic acid amide,
Heptatriacontanoic acid amide, Nonatriacontanoic acid amide, Tetracontanic acid amide, Hentetracontanic acid amide, Dotetracontanic acid amide, Tritetracontanic acid amide, Tetratetracontanic acid amide, Pentatetracontanic acid amide, Hexatetracontane Acid amide, heptatetracontanic acid amide, octatetracontanic acid amide, nonatetracontanic acid amide, pentacontanic acid amide, hempentacontanic acid amide, dopentacontanic acid amide, tripentacontanic acid amide, tetrapentacontanic acid amide, Pentapentacontanic acid amide, hexapentacontanic acid amide, heptapentacontanic acid amide, octapentacontanic acid amide, nonapentacontanic acid amide, hexacontanic acid amide,
Dohexacontanoic acid amide, decenoic acid amide, undecenoic acid amide, dodecenoic acid amide, tridecenoic acid amide,
Tetradecenoic acid amide, pentadecenoic acid amide, hexadecenoic acid amide, heptadecenoic acid amide, octadecenoic acid amide, nonadecenoic acid amide, eicosenoic acid amide,
Heneicosenoic acid amide, docosenoic acid amide, tricosenoic acid amide, tetracosenoic acid amide, pentacosenoic acid amide, hexacosenoic acid amide, heptacosenoic acid amide,
Amides such as octacocenoic acid amide and nonacocholic acid amide, amine decanoate, amine undecanoate, amine dodecanoate, amine tridecanoate, amine tetradecanoate,
Amine pentadecanoate, amine hexadecanoate, amine heptadecanoate, amine octadecanoate, amine nonadecanoate, amine eicosanoate, amine heneicosanoate, amine docosanoate, amine tricosanoate, amine tetracosanoate, amine pentacosanoate, amine hexacosanoate, heptacosanoic acid Amine, amine octacosanoate, amine nonacosanoate, amine triacontanate, amine hentriacontanoate, amine dotriacontanoate, amine tritriacontanoate, amine tetratriacontanoate, amine pentatriacontanoate, amine hexatriacontanoate , Amine, heptatriacontanoate, amine, nonatriacontanoate, amine tetracontanoate, amine henntetracontanoate, amine dotetracontanoate, tritetracone Amine acid, tetratetracontanate amine, pentatetracontanate amine, hexatetracontanate amine, heptatetracontanate amine, octatetracontanate amine, nonatetracontaneate amine, pentacontaneate amine, hempentacontaneate amine Amine, dopentacontanoic acid amine, tripentacontanoic acid amine, tetrapentacontanoic acid amine, pentapentacontanoic acid amine, hexapentacontanoic acid amine, heptapentacontanoic acid amine, octapentacontanoic acid amine, nonapentacontanoic acid amine, hexacone Amine tannate, amine dodecacontanate, amine decenoate, amine undecenoate, amine dodecenoate, amine tridecenoate, amine tetradecenoate,
Pentadecenoic acid amine, hexadecenoic acid amine, heptadecenoic acid amine, octadecenoic acid amine, nonadecenoic acid amine, eicosenoic acid amine, heneicosenoic acid amine, docosenoic acid amine, tricosenoic acid amine, tetracosenoic acid amine, pentacosenoic acid amine, hexacosenoic acid amine, heptacosenoic acid Amines, amines such as octacocenoic acid amine, nonacocholic acid amine, anilide decanoic acid anilide, undecanoic acid anilide, dodecanoic acid anilide, tridecanoic acid anilide, tetradecanoic acid anilide, pentadecanoic acid anilide, hexadecanoic acid anilide, heptadecanoic acid anilide, octadecanoic acid anilide, nonadecanoic acid Anilide, eicosanoic acid anilide, heneicosanoic acid anilide, docosanoic acid anilide, tricosanoic acid anilide, tetracosanoic acid anilide, Pentacosanoic acid anilide, Hexacosanoic acid anilide, Heptacosanoic acid anilide, Octacosanoic acid anilide, Nonacosanoic acid anilide, Triacontanic acid anilide, Hentriacontanic acid anilide, Dotriacontanic acid anilide, Tritriacontanic acid anilide, Tetratriacontanic acid anilide, Penta Tricontanic acid anilide, hexatriacontanoic acid anilide, heptatriacontanoic acid anilide,
Nonatoriacontanoic acid anilide, tetracontanoic acid anilide, hentetracontanoic acid anilide, dotetracontanoic acid anilide, tritetracontanoic acid anilide, tetratetracontanoic acid anilide, pentatetracontanoic acid anilide, hexatetracontanoic acid anilide, heptatetracontane Acid anilide, octatetracontanic acid anilide, nonatetracontanic acid anilide, pentacontanic acid anilide, hempentacontanic acid anilide, dopentacontanic acid anilide, tripentacontanic acid anilide, tetrapentacontanic acid anilide, pentapentacontanic acid anilide, Hexapentacontane anilide, heptapentacontane anilide, octapentacontane anilide, nonapentacontane anilide, hexacontane anilide, do Kisakontan acid anilide, decene acid anilide, undecenoic acid anilide, dodecene acid anilide, tridecene acid anilide, tetradecene acid anilide,
Pentadecenoic acid anilide, hexadecenoic acid anilide, heptadecenoic acid anilide, octadecenoic acid anilide, nonadecenoic acid anilide, eicosenoic acid anilide, heneicosenoic acid anilide, docosenoic acid anilide, tricosenoic acid anilide, tetracosenoic acid anilide, hexacosenoic acid anilide, hexacosenoic acid anilide, hexacosenoic acid anilide Anilides, anilides of octacosenoic acid, anilides of nonacosenoic acid, etc., decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentabecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, Docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, o Tacosanol, Nonacosanol, Triacontanol, Hentriacontanol, Dotriacontanol, Tritriacontanol, Tetratriacontanol, Pentatriacontanol, Hexatriacontanol, Heptatriacontanol, Octatriacontanol, Nonatriacontanol, Tetracontanol, hentetracontanol, dotetracontanol, tritetracontanol, tetratetracontanol, pentatetracontanol, hexatetracontanol, heptatetracontanol, octatetracontanol, nonatetracontanol, pentacontanol, pentacontanol, Hempentacontanol, dopentacontanol, tripentacontanol, tetrapentacontanol, pentapentacontanol, hex Pentacontanol, Heptapentacontanol, Octapentacontanol, Nonapentacontanol, Hexacontanol, Dohexacontanol, Decenol, Undecenol, Dodecenol, Tridecenol, Tetradecenol, Pentadecenol, Hexadecenol, Heptadecenol, Octadecenol, Nonadecenol, Eicosenol, Hencoenol , Tricocenol, tetracocenol, pentacocenol, hexacocenol, heptacocenol, octacocenol, nonacocenol and other alcohols, decyl octacosanoate,
Undecyl octacosanoate, dodecyl octacosanoate,
Tridecyl octacosanoate, tetradecyl octacosanoate, pentadecyl octacosanoate, hexadecyl octacosanoate, hepsadecyl octacosanoate, octadecyl octacosanoate, methyl decanoate, methyl undecanoate, methyl dodecanoate, methyl tridecanoate, methyl tetradecanoate, methyl pentadecanoate, hexadecanoate Methyl, methyl heptadecanoate, methyl octadecanoate, methyl nonadecanoate, methyl eicosanoate, methyl heneicosanoate, methyl docosanoate, methyl tricosanoate, methyl tetracosanoate, methyl pentacosanoate,
Methyl hexacosanoate, methyl heptacosanoate, methyl octacosanoate, methyl nonacosanoate, methyl triacontanate, methyl hentriacontanate, methyl dotriacontanate, methyl tritriacontanate, methyl tetratriacontanate, methyl pentatriacontanate , Methyl hexatriacontanate, methyl heptatriacontanate, methyl octatriacontanate, methyl nonatriacontanate, methyl tetracontanate, methyl hentetracontanate, methyl dotetracontanate,
Methyl tritetracontanate, Methyl tetratetracontanate, Methyl pentatetracontanate, Methyl hexatetracontanate, Methyl heptatetracontanate, Methyl octatetracontanate, Methyl nonatetracontanate, Methyl pentacontanate, Hempentacontane Methyl acid, methyl dopentacontanate, methyl tripentacontanate, methyl tetrapentacontanate, methyl pentapentacontanate, methyl hexapentacontanate, methyl heptapentacontanate, methyl octapentacontanate, methyl nonapentacontanate , Methyl hexacontanate, methyl dodecacontanate, methyl decenoate, methyl undecenoate, methyl dodecenoate, methyl tridecenoate, methyl tetradecenoate, methyl pentadecenoate, hexadecane Methyl phosphate, methyl heptadecenoic acid, methyl octadecenoic acid, methyl nonadecenoic acid, methyl eicosenoic acid, methyl heneicosene acid, methyl docosenoic acid, methyl tricosenoic acid, methyl tetracosenoic acid,
Methyl pentacosenoate, Methyl hexacosenoate, Methyl heptacosenoate, Methyl octacosenoate, Methyl nonacosenoate, Vinyl decanoate, Vinyl undecanoate, Vinyl dodecanoate, Vinyl tridecanoate, Vinyl tetradecanoate, Vinyl pentadecanoate, Vinyl hexadecanoate, Heptadecanoate Vinyl, vinyl octadecanoate, vinyl nonadecanoate, vinyl eicosate, vinyl heneicosate, vinyl docosanoate, vinyl tricosanoate, vinyl tetracosanoate, vinyl pentacosanoate, vinyl hexacosanoate, vinyl heptacosanoate, vinyl octacosanoate, vinyl nonacosanoate, Vinyl triacontanate, vinyl hentriacontanate, vinyl dotriacontanoate, vinyl tritriacontanate, vinyl tetratriacontanate, penta Vinyl reacontanate, vinyl hexatriacontanate, vinyl heptatriacontanate, vinyl octatriacontanate, vinyl nonatriacontanate, vinyl tetracontanate, vinyl henetetracontanate, vinyl detetracontanate, vinyl tritetracontanate , Vinyl tetratetracontanate, vinyl pentatetracontanate, vinyl hexatetracontanate, vinyl heptatetracontanate, vinyl octatetracontanate, vinyl nonatetracontanate, vinyl pentacontanate, vinyl hempentacontanate, dopentacon Vinyl tatanate, vinyl tripentacontanate, vinyl tetrapentacontanate, vinyl pentapentacontanate, vinyl hexapentacontanate, vinyl heptapentacontanate, octapentaco Vinyl Tan acid, nona penta proximal acid vinyl, vinyl Hekisakontan acid, vinyl Dohekisakontan acid, vinyl decenoic acid, vinyl undecenoic acid, vinyl dodecenoic acid, vinyl tridecenoic acid, vinyl tetradecenoic acid, vinyl pentadecenoic acid,
Vinyl hexadecenoate, vinyl heptadecenoate, vinyl octadecenoate, vinyl nonadecenoate, vinyl eicosenoate, vinyl heneicosenoate, vinyl docosenoate, vinyl tricosenoate, vinyl tetracosenoate, vinyl pentacosenoate, vinyl hexacosenoate, vinyl heptacenoate, octacosenoate. Vinyl, vinyl nonacosenoate, phenyl decanoate, phenyl undecanoate, phenyl dodecanoate, phenyl tridecanoate, phenyl tetradecanoate, phenyl pentadecanoate, phenyl hexadecanoate, phenyl heptadecanoate, phenyl octadecanoate, phenyl nonadecanoate, phenyl eicosanoate, Phenyl heicosanoate, phenyl docosanoate, phenyl tricosanoate, phenyl tetracosanoate, phenyl pentacosanoate, hexa Phenyl sanate, phenyl heptacosanoate, phenyl octacosanoate, phenyl nonacosanoate, phenyl triacontanoate, phenyl hentriacontanate, phenyl dotriacontanoate, phenyl tritriacontanoate, phenyl tetratriacontanoate, phenyl pentatriacontanoate , Phenyl hexatriacontanoate, phenyl heptatriacontanoate,
Phenyl octatriacontanoate, phenyl nonatriacontanoate, phenyl tetracontanoate, phenyl henetetracontanoate, phenyl dotetracontanoate, phenyl tritetracontanoate, phenyl tetratetracontanoate, phenyl pentatetracontanoate, hexatetracontane Phenyl acid, phenyl heptatetracontanoate, phenyl octatetracontanoate, phenyl nonatetracontanoate, phenyl pentacontanoate, phenyl hempentacontanoate, phenyl dopentacontanoate,
Phenyl tripentacontanate, phenyl tetrapentacontanate, phenyl pentapentacontanate, phenyl hexapentacontanate, phenyl heptapentacontanate, phenyl octapentacontanate, phenyl nonapentacontanoate, phenyl hexacontaconate, dohexacontane Phenyl acid, phenyl decenoate, phenyl undecenoate, phenyl dodecenoate, phenyl tridecenoate, phenyl tetradecenoate, phenyl pentadecenoate, phenyl hexadecenoate, phenyl heptadecenate, phenyl octadecenoate, phenyl nonadecenoate,
Phenyl eicosenoate, phenyl heicosenoate, phenyl docosenoate, phenyl tricosenoate, phenyl tetracosenoate, phenyl pentacosenoate, phenyl hexacosenoate, phenyl heptacosenoate, phenyl octacosenoate, phenyl nonacosenoate, laurone, stearone, 19-hepta Triacontanone, 20
-Nonatriacontanone, 21-hentetracontanone, ketone such as 22-tritetracontanone, Ca octadecanoate, Co octadecanoate, C octadecanoate
u, octadecanoic acid Fe, octadecanoic acid K, octadecanoic acid Li, octadecanoic acid Mg, octadecanoic acid M
n, octadecanoic acid Ni, octadecanoic acid Pb, octadecanoic acid Sn, octadecanoic acid Zn, octadecanoic acid Z
r, Ca decanoate, Ca undecanoate, C dodecanoate
a, Ca tridecanoate, Ca tetradecanoate, Ca pentadecanoate, Ca hexadecanoate, C heptadecanoate
a, Ca octadecanoate, Ca nonadecanoate, Ca eicosanoate, Ca heneicosanoate, Ca docosanoate, Ca tricosanoate, Ca tetracosanoate, Ca pentacosanoate, Ca hexacosanoate, Ca heptacosanoate, Ca octacosanoate, Ca nonacosanoate, Ca triacontanoate, Ca hentriacontanoate, Ca dotriacontanoate, Ca tritriacontanoate, Ca tetratriacontanoate, Ca pentatriacontanoate, Ca hexatriacontanoate, Ca heptatriacontanate, Octatriacontane Acid Ca, Ca nonatriacontanoic acid, Ca tetracontanoic acid, Ca hentetracontanoic acid, Ca dotetracontanoic acid, Ca tritetracontanoic acid, Ca tetratetracontanoic acid, Pentatetracontanoic acid C
a, Ca hexatetracontanate, Ca heptatetracontanate, Ca octatetracontaneate, Ca nonatetracontaneate, Ca pentacontaneate, Ca hempentacontaneate, Ca dopentacontaneate, Ca tripentacontaneate, Tetra Ca pentacontanate, Ca pentapentacontane, Ca hexapentacontane, Ca heptapentacontane, C octapentacontane
a, Ca nonapentacontanoate, C hexahexanoate
a, Ca dohexacontanoate, Ca decenoate, Ca undecenoate, Ca dodecenoate, Ca tridecenoate, Ca tetradecenoate, Ca pentadecenoate, C hexadecenoate
a, Ca heptadecenoate, Ca octadecenoate, Ca nonadecenoate, Ca eicosenoate, Hene eicosenoate C
a, Ca docosenoate, Ca tricosenoate, Ca tetracosenoate, Ca pentacosenoate, Ca hexacosenoate, Ca heptacosenoate, Ca octacosenoate, Ca nonacosenoate, metal salts such as decyl imidazole, undecyl imidazole, dodecyl imidazole, tridecyl Imidazole, tetradecyl imidazole, pentadecyl imidazole, hexadecyl imidazole, heptadecyl imidazole, octadecyl imidazole, nonadecyl imidazole, eicosyl imidazole, hene eicosyl imidazole, docosyl imidazole, tricosyl imidazole, tetra cosyl imidazole, Derivatives of monocarboxylic acids such as imidazole and imidazole such as hexacosylimidazole are preferred.

Derivatives of dicarboxylic acids having at least 10 carbon atoms include, but are not limited to, decanedioic acid amide, undecanedioic acid amide, dodecanedioic acid amide, tridecanedioic acid amide, and tetradecanedioic acid amide. ,
Pentadecanedioic acid amide, hexadecanedioic acid amide, heptadecanedioic acid amide, octadecanedioic acid amide, nonadecanedioic acid amide, eicosanedioic acid amide, heneicosanedioic acid amide, docosanedioic acid amide, tricosanedioic acid amide, tetracosanedioic acid amide, Pentacosane diacid amide, hexacosane diacid amide, heptacosane diacid amide, octacosane diacid amide, nonacosane diacid amide,
Triacontanedioic acid amide, Hentriacontanedioic acid amide, Dotriacontanedioic acid amide, Tritriacontanedioic acid amide, Tetratriacontanedioic acid amide, Pentatriacontanedioic acid amide, Hexatriacontanedioic acid amide, Heptatria Contanedioic acid amide, octatriacontanedioic acid amide, nonatriacontanedioic acid amide, tetracontanedioic acid amide, hentetracontanedioic acid amide, dotetracontanedioic acid amide, tritetracontanedioic acid amide, tetratetracontanedioic acid amide Acid amide,
Pentatetracontanedioic acid amide, Hexatetracontanedioic acid amide, Heptatetracontanedioic acid amide, Octatetracontanedioic acid amide, Nonatetracontanedioic acid amide, Pentacontanedioic acid amide, Hempentacontanedioic acid amide, Dopentacon Tandioic acid amide, tripentacontanedioic acid amide, tetrapentacontanedioic acid amide, pentapentacontanedioic acid amide, hexapentacontanedioic acid amide, heptapentacontanedioic acid amide,
Octapentacontanedioic acid amide, nonapentacontanedioic acid amide, hexacontanedioic acid amide, dohexacontanedioic acid amide, decenedioic acid amide, undecenedioic acid amide, dodecenedioic acid amide, tridecenedioic acid amide, tetradecenedioic acid Amide, pentadecenedioic acid amide, hexadecenedioic acid amide, heptadecenedioic acid amide, octadecenedioic acid amide, nonadecenedioic acid amide, eicosenedioic acid amide, heneicosenedioic acid amide, docosenedioic acid amide, tricosenedioic acid amide, tetracosenedioic acid Amides such as amides, pentacosenedioic acid amides, hexacosenedioic acid amides, heptacosenedioic acid amides, octacosenedioic acid amides, nonacosenedioic acid amides, decanedioic acid amines, undecanedioic acid amines, dodecanedioic acid amines, tridecanedioic acid amines, Te Radekan diacid amine, pentadecanedioic acid amine, hexadecanoic diacid amine, heptadecanedioic acid amine, octadecanedioic acid amine, nonadecanoic diacid amine, eicosanedioic acid amine, heneicosanoic diacid amine, docosanedioic acid amine, tricosanoic diacid amine,
Tetracosane diacid amine, pentacosane diacid amine, hexacosane diacid amine, heptacosane diacid amine, octacosane diacid amine, nonacosan diacid amine, triacontanedioic acid amine, hentriacontanedioic acid amine, dotriacontane diacid amine, Tritriacontanedioic acid amine, tetratriacontanedioic acid amine, pentatriacontanedioic acid amine, hexatriacontanedioic acid amine, heptatriacontanedioic acid amine, octatriacontanedioic acid amine, nonatriacontanedioic acid amine, tetra Contanedioic acid amine, hentetracontanedioic acid amine, dotetracontanedioic acid amine, tritetracontanedioic acid amine, tetratetracontanedioic acid amine, pentatetracontanedioic acid amine, hexatetracontanedioic acid amine, heptate Contanedioic acid amine, octatetracontanedioic acid amine, nonatetracontanedioic acid amine, pentacontanedioic acid amine, hempentacontanedioic acid amine, dopentacontanedioic acid amine, tripentacontanedioic acid amine, tetrapentacontanedioic acid amine Acid amines,
Pentapentacontanedioic acid amine, hexapentacontanedioic acid amine, heptapentacontanedioic acid amine, octapentacontanedioic acid amine, nonapentacontanedioic acid amine, hexacontanedioic acid amine, dohexacontanedioic acid amine, decene diamine Acid amine, undecenedioic acid amine, dodecenedioic acid amine, tridecenedioic acid amine, tetradecenedioic acid amine, pentadecenedioic acid amine, hexadecenedioic acid amine, heptadecenedioic acid amine, octadecenedioic acid amine, nonadecenedioic acid amine, eicosenedioic acid Acid amine, heneicosenedioic acid amine, docosenedioic acid amine, tricosenedioic acid amine, tetracosenedioic acid amine, pentacosenedioic acid amine, hexacosenedioic acid amine, heptacosenedioic acid amine, octacosenedioic acid amine, nonacosenedioic acid amine Amine, decanedioic acid anilide, undecanedioic acid anilide, dodecanedioic acid anilide, tridecanedioic acid anilide, tetradecanedioic acid anilide, pentadecanedioic acid anilide, hexadecanedioic acid anilide, heptadecanedioic acid anilide, octadecanedioic acid anilide, nonadecanedioic acid Acid anilide, eicosane diacid anilide, heneicosane diacid anilide, docosane diacid anilide, tricosane diacid anilide, tetracosane diacid anilide, pentacosane diacid anilide, hexacosane diacid anilide, heptacosane diacid anilide, octacosane diacid anilide, nonacosane di Acid anilide, triacontanedioic acid anilide, hentriacontanedioic acid anilide, dotriacontanedioic acid anilide, tritriacontanedioic acid anilide, tetratriacontanedioic acid anilide, Tatriacontanedioic acid anilide, hexatriacontanedioic acid anilide, heptatriacontanedioic acid anilide, octatriacontanedioic acid anilide, nonatriacontanedioic acid anilide, tetracontanedioic acid anilide, hentetracontanedioic acid anilide, dotetra Contanedioic acid anilide, tritetracontanedioic acid anilide, tetratetracontanedioic acid anilide, pentatetracontanedioic acid anilide, hexatetracontanedioic acid anilide, heptatetracontanedioic acid anilide, octatetracontanedioic acid anilide,
Nonatetracontanedioic acid anilide, pentacontanedioic acid anilide, hempentacontanedioic acid anilide, dopentacontanedioic acid anilide, tripentacontanedioic acid anilide, tetrapentacontanedioic acid anilide, pentapentacontanedioic acid anilide, hexapentaconone Tanidiic acid anilide, heptapentacontanedioic acid anilide, octapentacontanedioic acid anilide, nonapentacontanedioic acid anilide, hexacontanedioic acid anilide, dohexacontanedioic acid anilide, decenedioic acid anilide, undecenedioic acid anilide, dodecene Diacid anilide, tridecenedioic acid anilide, tetradecenedioic acid anilide, pentadecenedioic acid anilide, hexadecenedioic acid anilide, heptadecenedioic acid anilide, octadecenedioic acid anilide, nonadecenedioic acid anilide, eicose Diacid anilide, heneicosenedioic acid anilide, docosenedioic acid anilide, tricosenedioic acid anilide, tetracosenedioic acid anilide, pentacosenedioic acid anilide, hexacosenedioic acid anilide, heptacosenedioic acid anilide, octacosenedioic acid anilide, nonacocenedioic acid anilide, etc. Anilide, decanedioic acid alcohol, undecanedioic acid alcohol, dodecanedioic acid alcohol, tridecanedioic acid alcohol, tetradecanedioic acid alcohol, pentadecanedioic acid alcohol, hexadecanedioic acid alcohol, heptadecanedioic acid alcohol, octadecanedioic acid alcohol, nonadecane Diacid alcohol, eicosane diacid alcohol, heneicosane diacid alcohol, docosane diacid alcohol, tricosane diacid alcohol, tetracosane diacid alcohol, pentaco Alcohol, hexacosanedioic acid alcohol, heptacosanedioic acid alcohol, octacosanedioic acid alcohol, nonacosandioic acid alcohol, triacontanedioic acid alcohol, hentriacontanedioic acid alcohol, dotriacontanedioic acid alcohol, tritriacontanedioic acid Alcohol, tetratriacontanedioic acid alcohol, pentatriacontanedioic acid alcohol, hexatriacontanedioic acid alcohol, heptatriacontanedioic acid alcohol, octatriacontanedioic acid alcohol, nonatriacontanedioic acid alcohol, tetracontanedioic acid alcohol, Hen tetracontanedioic acid alcohol, dotetracontanedioic acid alcohol, tritetracontanedioic acid alcohol, tetratetracontanedioic acid alcohol, pentatetracontanedioic acid Cole, hexatetracontanedioic acid alcohol, heptatetracontanedioic acid alcohol, octatetracontanedioic acid alcohol, nonatetracontanedioic acid alcohol, pentacontanedioic acid alcohol, hempentacontanedioic acid alcohol, dopentacontanedioic acid alcohol,
Tripentacontanedioic acid alcohol, tetrapentacontanedioic acid alcohol, pentapentacontanedioic acid alcohol, hexapentacontanedioic acid alcohol, heptapentacontanedioic acid alcohol, octapentacontanedioic acid alcohol, nonapentacontanedioic acid alcohol, hexacon Tandioic acid alcohol, dohexacontandioic acid alcohol, decenedioic acid alcohol, undecenedioic acid alcohol, dodecenedioic acid alcohol, tridecenedioic acid alcohol, tetradecenedioic acid alcohol, pentadecenedioic acid alcohol, hexadecenedioic acid alcohol, heptadecenedioic acid Alcohol, octadecenedioic acid alcohol, nonadecenedioic acid alcohol, eicosenedioic acid alcohol,
Heneicosenedioic acid alcohol, docosenedioic acid alcohol, tricosenedioic acid alcohol, tetracosenedioic acid alcohol, pentacosenedioic acid alcohol, hexacosenedioic acid alcohol, heptacosenedioic acid alcohol, octacosenedioic acid alcohol, alcohols such as nonacosenedioic acid alcohol, octacosenedioic acid Decyl acid, undecyl octacosanedioate, dodecyl octacosanedioate, tridecyl octacosanedioate, tetradecyl octacosanedioate, pentadecyl octacosanedioate, hexadecyl octacosanedioate, heptadecyl octacosanedioate, octadecyl octacosanedioate, methyl decanedioate, undecanedioic acid Methyl acid, methyl dodecanedioate, methyl tridecanedioate, methyl tetradecanedioate, methyl pentadecanedioate, methyl hexadecanedioate , Methyl heptadecanedioate, Methyl octadecanedioate, Methyl nonadecanedioate, Methyl eicosanedioate, Methyl heneicosanedioate, Methyl docosanedioate, Methyl tricosanedioate, Methyl tetracosanedioate, Methyl pentacosanedioate, Methyl hexacosanedioate , Methyl heptacosanedioate, methyl octacosanedioate, methyl nonacosanedioate, methyl triacontanedioate, methyl hentriacontanedioate, methyl dotriacontanedioate, methyl tritriacontanedioate, methyl tetratriacontanedioate, Methyl pentatriacontanedioate, Methyl hexatriacontanedioate, Methyl heptatriacontanedioate, Methyl octatriacontanedioate, Methyl nonatriacontanedioate, Methyl tetracontanedioate, Methyl tetracontanedioate, Methyl tetracontanedioate, Methyl tritetracontanedioate, Methyl tetratetracontanedioate, Methyl pentatetracontanedioate, Methyl hexatetracontanedioate, Methyl heptatetracontanedioate, Methyl octatetracontanedioate, Nonatetra Methyl contanedioate, Methyl pentacontanedioate, Methyl hempentacontanedioate, Methyl dopentacontanedioate, Methyl tripentacontanedioate, Methyl tetrapentacontanedioate, Methyl pentapentacontanedioate, Hexapentacontanedioate Methyl acid,
Methyl heptapentacontanedioate, methyl octapentacontanedioate, methyl nonapentacontanedioate, methyl hexacontanedioate, methyl dodecacontanedioate, methyl decenedioate, methyl undecenedioate, methyl dodecenedioate, tridecene Methyl diacid, Methyl tetradecenedioate, Methyl pentadecenedioate, Methyl hexadecenedioate, Methyl heptadecenedioate, Methyl octadecenedioate, Methyl nonadecenedioate, Methyl eicosendioate, Methyl heneicosendioate, Methyl docosenedioate, Tricosene Methyl diacid, methyl tetracosenedioate, methyl pentacosenedioate, methyl hexacosenedioate, methyl heptacosenedioate, methyl octacosenedioate, methyl nonacosenedioate, vinyl decanedioate, vinyl undecanedioate, vinyl dodecanedioate, Decanedioate vinyl, tetradecane diacid vinyl, pentadecane diacid, vinyl hexadecane diacid, heptadecane diacid, vinyl octadecane diacid, nonadecane diacid vinyl, eicosane diacid vinyl, heneicosanoic diacid vinyl, docosane diacid vinyl,
Vinyl tricosane diate, vinyl tetracosane diate, vinyl pentacosane diate, vinyl hexacosane diate, vinyl heptacosane diate, vinyl octacosane diate, vinyl nonacosane diate, vinyl triacontane diate, vinyl hentriacontane diate, dotria Vinyl contanedioate, vinyl tritriacontanedioate, vinyl tetratriacontanedioate, vinyl pentatriacontanedioate, vinyl hexatriacontanedioate, vinyl heptatriacontanedioate, vinyl octatriacontanedioate, nonatriacontane Vinyl diacid, vinyl tetracontane diacid, vinyl hentetracontane diacid, vinyl detetracontane diacid, vinyl tritetracontane diacid, vinyl tetratetracontane diacid, vinyl pentatetracontane diacid, hexatetracontane Vinyl acid, hepta tetra proximal diacid vinyl, octa-tetra proximal diacid vinyl, nona tetra proximal diacid vinyl, pentacontanoic diacid vinyl,
Vinyl pentapentacontanedioate, vinyl dopentacontanedioic acid, vinyl tripentacontanedioic acid, vinyl tetrapentacontanedioic acid, vinyl pentapentacontanedioic acid, vinyl hexapentacontanetanedioate, vinyl heptapentacontanedioic acid, octane Vinyl pentacontanedionate,
Vinyl nonapentacontanedioate, vinyl hexacontanedioate, vinyl dohexacontanedioate, vinyl decenedioate, vinyl undecenedioate, vinyl dodecenedioate, vinyl tridecenedioate, vinyl tetradecenedioate, vinyl pentadecenedioate, Vinyl hexadecenedioate, vinyl heptadecenedioate, vinyl octadecenedioate, vinyl nonadecenedioate, vinyl eicosenedioate, vinyl henecosenedioate, vinyl docosenedioate, vinyl tricosenedioate,
Vinyl tetracosenedioate, vinyl pentacosenedioate, vinyl hexacosenedioate, vinyl heptacosenedioate, vinyl octacosenedioate, vinyl nonacosenedioate, phenyl decanedioate, phenyl undecanedioate, phenyl dodecanedioate, phenyl tridecanedioate, Phenyl tetradecanedioate, phenyl pentadecanedioate, phenyl hexadecanedioate, phenyl heptadecanedioate, phenyl octadecanedioate, phenyl nonadecanedioate, phenyl eicosanedioate, phenyl heneicosanedioate, phenyl docosanedioate, phenyl tricosanedioate, Phenyl tetracosane diate, phenyl pentacosane diate, phenyl hexacosane diate, phenyl heptacosane diate, phenyl octacosane diate, phenyl nonacosane diate, phenyl triacontane diate, Phenyl triacontanedioate, phenyl dotriacontanedioate, phenyl tritriacontanedioate, phenyl tetratriacontanedioate, phenyl pentatriacontanedioate, phenyl hexatriacontanedioate, phenyl heptatriacontanedioate, octa Phenyl triacontanedioate, phenyl nonatriacontanedioate, phenyl tetracontanedioate, phenyl henetetracontanedioate, phenyl dotetracontanedioate, phenyl tritetracontanedioate, phenyl tetratetracontanedioate, pentatetracontane Phenyl diacid, phenyl hexatetracontanedioate, phenyl heptatetracontanedioate, phenyl octatetracontanedioate, phenyl nonatetracontanedioic acid, phenyl pentacontanedioic acid, hempentacontane Phenyl acid, phenyl dopentacontanedioate, phenyl tripentacontanedioate, phenyl tetrapentacontanedioate, phenyl pentapentacontanedioate, phenyl hexapentacontanedioate, phenyl heptapentacontanedioate, octapentacontanedioate Phenyl, phenyl nonapentacontanedioate, phenyl hexacontanedioate, phenyl dohexacontanedioate, phenyl decenedioate, phenyl undecenedioate, phenyl dodecenedioate, phenyl tridecenedioate, phenyl tetradecenedioate, pentadecenedioic acid Phenyl, phenyl hexadecenedioate, phenyl heptadecenedioate, phenyl octadecenedioate, phenyl nonadecenedioate, phenyl eicosendioate, phenyl heneicosendioate, phenyl docosenedioate, tricosenedioic acid. Phenyl, phenyl tetracosenedioate, phenyl pentacosenedioate, phenyl hexacosenedioate, phenyl heptacosenedioate, phenyl octacosenedioate, phenyl nonacosenedioic acid, etc., laurone, stearone,
Ketones such as 19-heptatriacontanone, 20-nonatriacontanone, 21-hentetracontanone, 22-tritetracontanone, Ca octadecanedioate, Co octadecanedioate, Cu octadecanedioate, Fe octadecanedioate, Octadecanedioic acid K, Octadecanedioic acid L
i, Mg octadecanedioate, Mn octadecanedioate, Ni octadecanedioate, Pb octadecanedioate, Sn octadecanedioate, Zn octadecanedioate, Zr octadecanedioate, Ca decanedioate, Ca undecanedioate, Dodecanedioate Ca, Ca tridecanedioate, C tetradecanedioate
a, Ca pentadecanedioate, Ca hexadecanedioate, Ca heptadecanedioate, Ca octadecanedioate, Ca nonadecanedioate, Ca eicosanedioate, Ca heneicosanoate diacid, Ca docosanedioate, Ca tricosanedioate, Tetracosanedioate Ca, Ca pentacosanedioate, Ca hexacosanedioate, Ca heptacosanedioate, C octacosanedioate
a, Ca nonacosandioic acid, Ca triacontanedioic acid, Ca hentriacontanedioic acid, C dotriacontanedioic acid
a, Ca tritriacontanedioate, Ca tetratriacontanedioate, Ca pentatriacontanedioate, Ca hexatriacontanedioate, C heptatriacontanedioate
a, Ca octatriacontanedioate, Ca nonatriacontanedioate, Ca tetracontanedioate, Ca hentetracontanedioate, Ca dotetracontanedioate, Ca tritetracontanedioate, Ca tetratetracontanedioate, Pentatetracontanedioic acid Ca, hexatetracontanedioic acid Ca, heptatetracontanedioic acid Ca, octatetracontanedioic acid Ca, nonatetracontanedioic acid Ca, pentacontantanedioic acid Ca, hempentacontanedioic acid Ca, dopentacon Tannedioic acid Ca, tripentacontanedioic acid C
a, Ca tetrapentacontanedioate, Ca pentapentacontanedioate, Ca hexapentacontanedioate, Ca heptapentacontanedioate, C octapentacontanedioate
a, Ca nonapentacontanedioate, Ca hexacontanedioate, Ca dohexacontanedioate, Ca decenedioic acid, Ca undecenedioic acid, Ca dodecenedioic acid, Ca tridecenedioic acid, Ca tetradecenedioic acid, Pentadecenedioic acid Ca,
Hexadecenedioic acid Ca, heptadecenedioic acid Ca, octadecenedioic acid Ca, nonadecenedioic acid Ca, eicosenedioic acid Ca, heneicosenedioic acid Ca, docosenedioic acid Ca, tricosenedioic acid Ca, tetracosenedioic acid Ca, pentacosenedioic acid Ca, Ca Derivatives of dicarboxylic acids such as metal salts such as Ca hexacosendioate, Ca heptacosene diate, Ca octacosenedioate, and Ca nonacosendioate are preferred.

The reason why each of the above carboxylic acids has at least 10 carbon atoms is that the other ones are in a liquid state at room temperature and thus do not meet the purpose of the present invention. Further, if the mixing ratio of the above-mentioned matrix material to the saturated carboxylic acid and its derivative is more than 1: 2 by weight ratio of the saturated carboxylic acid and its derivative, it becomes difficult to form a film of the thermoreversible recording material. , Less than 20: 1, the thermoreversibility becomes small, so 1: 2 to 20: 1
It is suitable to be within the range.

Further, in the above (1), the mixing ratio of polyvinyl acetal and ultraviolet curable resin (cured) is as follows.
It has been confirmed that the effect of the above (1) is exhibited from the case where both are mixed in an amount of 1 part by weight of the ultraviolet curable resin before curing with respect to 0 part by weight.

Further, the upper limit of mixing the UV-curable resin is within a range in which the property of transparency of the thermoreversible recording material that changes due to heat history is not lost, but at least 2 parts by weight of polyvinyl acetal before curing. It has been confirmed that the thermoreversibility can be obtained even when the both are mixed at a ratio of 1 part by weight of the ultraviolet curable resin. From these, it is considered that the mixing ratio of the polyvinyl acetal and the ultraviolet curable resin before curing is, by weight, 600: 1 to 2: 1, more preferably about 60: 1 to 6: 1. .

In addition, in the above (1), a group of a saturated carboxylic acid and a derivative of this saturated carboxylic acid, which contains polyvinyl acetal and an ultraviolet curable resin (provided that it is cured with a curing agent) as a matrix material, and an organic low molecule. Not only in the case of containing only these, but also in the case of containing other substances such as a substance that improves the film quality of the thermoreversible recording material, a substance that improves the lubricity, etc. Also means.

In actual use of the thermoreversible recording material, a coating solution of the thermoreversible recording material is prepared so that the thermoreversible recording material can be applied to a support such as a substrate or a film made of a suitable material. There is a case. In that case, it is preferable to dissolve the matrix material and the saturated carboxylic acid and its derivative in a solvent to obtain a coating solution. And as this solvent, but not limited to, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone,
It is preferable to use one kind selected from chloroform, carbon tetrachloride, ethanol, toluene, benzene and the like, or to use a mixture of two or more kinds. Further, the solvent may be heated before use when preparing the coating solution.

(3) The thermoreversible recording medium of the present invention is a thermoplastic recording comprising the thermoreversible recording material described in (1) above or the thermoreversible recording material produced by the production method described in (2) above. The layer and a support for supporting the thermoreversible recording layer directly or via an intermediate layer. (4) In the thermoreversible recording medium according to the above (3), a protective layer is provided on the surface side of the thermoreversible recording layer opposite to the support, directly or via an intermediate layer, and the support and the protection are provided. At least one of the layers is composed of a material having transparency to visible light.

(5) In the thermoreversible recording medium according to (3) or (4) above, when the intermediate layer is used, the intermediate layer is at least among the reflection layer, the light absorption layer, the enhancement layer and the printing layer. To one or more layers selected according to the direction of light incidence on the thermoreversible recording medium and the direction of viewing the recording formed on this medium. (6) In the thermoreversible recording medium according to the above (3) or (4), the support is made of a material transparent to visible light, and the support is provided on the opposite side of the thermoreversible recording layer. The side is provided with a reflection layer or a light absorption layer.

(7) In the thermoreversible recording medium described in (3) or (4) above, the support has a property of changing the traveling direction of light incident on the support. (8) The thermoreversible recording medium according to any one of (3) to (7) above includes a recording layer in addition to the thermoreversible recording layer.

The thermoreversible recording medium referred to here is, specifically, a prepaid card such as a telephone card, an orange card, a highway card, a postpaid card, a point card, or a label used in various fields, Further, it includes a kanban of a kanban system, a word processor adopting a thermal recording system, a recording sheet for a facsimile, and a sheet of a projection image forming apparatus such as an overhead projector or a slide.

(9) The thermoreversible recording apparatus of the present invention is a thermoreversible recording apparatus comprising a thermoreversible recording medium and a device for recording information on this medium and erasing information on this medium. As the reversible recording medium, the thermoreversible recording medium described in any one of (3) to (8) above is used.

[0029]

According to the thermoreversible recording material of the present invention, as is clear from the experimental results described later, even when recording and erasing are repeated, the contrast between the transparent portion and the cloudy portion in the image is lowered. Less likely to occur than before. Since it contains polyvinyl acetal and a predetermined saturated carboxylic acid, this thermoreversible recording material, as shown in FIG.
After heating to a temperature of T ₂ or higher, rapid cooling (for example, 50 ° C. /
2 seconds or more) (in the case of the history indicated by 11 in FIG. 1)
It shows the maximum transparency, when it is heated to T ₁ (T ₁ <T ₂ ) or more and T ₂ or less and then rapidly cooled (for example, 50 ° C./sec or more), or when it is heated to T ₁ or more and gradually cooled (for example, , Less than 50 ° C./second) (in the case of the history shown by 13 in FIG. 1), the minimum transparency is shown.
It has a thermal history-transparency characteristic.

In FIG. 1, RT is room temperature (° C.)
Indicates. As one of the methods for the opaque state to a transparent state where, in the method that is heated in the range of T ₁ through T ₂ to rapid cooling, the width of the T ₁ through T ₂ is at least 30 a few degrees can do. Further, as another method for making the transparent state cloudy, a method of heating to T ₁ or higher and then gradually cooling (for example, showing less than 50 ° C./sec) can be adopted. The temperature T ₁ in these methods can be easily set to about 80 ° C. by selecting the carboxylic acid.

From these facts, the thermoreversible recording medium of the present invention has a milder condition under which the transparent state becomes a cloudy state, and the transparent state and the cloudy state are stable up to a higher temperature than before.

[0032]

Embodiments of the present invention will be described in detail below with reference to the drawings. It should be noted that the drawings used for the description are only schematically illustrated to the extent that the present invention can be understood.
Further, the materials used and the numerical conditions described in this embodiment are merely examples within the scope of the present invention. Therefore, it should be understood that the present invention is not limited to these materials used and numerical conditions.

(I) An example of the thermoreversible recording material of the present invention (first invention) and the method for producing the thermoreversible recording material (second invention) will be described together. (Example 1) First, in Example 1, as polyvinyl acetal, S-REC KS-1 manufactured by Sekisui Chemical Co., Ltd. was used.
(Trademark) is used as a polymerizable oligomer (monomer) of an ultraviolet curable resin, and benzophenone is prepared using Iupima-SA-1002 [trademark, polyester acrylate type, Mitsubishi Petrochemical Co., Ltd.] as a photoreaction initiator. Behenic acid is prepared as the saturated carboxylic acid and its derivative.

Then, 60 parts by weight of S-REC KS-1, 5 parts by weight of Iupima-SA-1002, 1 part by weight of benzophenone, and 35 parts by weight of behenic acid are added to 500 parts by weight of tetrahydrofuran (hereinafter abbreviated as THF). To prepare a coating solution of the thermoreversible recording material of the example.
In the liquid material thus obtained (which becomes the coating liquid of the thermoreversible recording material), ultraviolet rays (wavelength 100 to 100
(400 nm) is irradiated to generate radicals or cations, and the radicals or cations initiate and grow the polymerization of the polymerizable oligomer (monomer) and finally solidify. This reaction starts from the moment when the polymerizable oligomer (monomer) and the photoreaction initiator are mixed, and it takes a few hours to a few days under normal light (sunlight), and a few seconds to a few hours under a mercury lamp such as an ultraviolet curing device. Solidification ends at the minute level.

By the way, when the liquid substance itself is solidified, the thermoreversible recording material cannot be coated on the support, so that the layer of the desired thermoreversible recording material or the thermoreversible recording medium can be formed. Can no longer be formed. In the case of this Example 1, since it takes several days in ordinary light (sunlight) at room temperature until the liquid substance solidifies, it does not hinder the application, but In some of the examples, the solidification of the liquid material itself occurs relatively quickly, and therefore, care may be required.

Taking these points into consideration, when preparing a liquid material, a substance other than the ultraviolet curable resin (polyvinyl acetal, a predetermined carboxylic acid) is used as a solvent (here, TH).
It is placed in F) and the ultraviolet curable resin [polymerization oligomer (monomer), photoreaction initiator] is added last. Alternatively, it is desirable to apply a treatment such as winding a shield (black film or the like) so that the ultraviolet rays do not hit the liquid material.

Next, in this embodiment, as shown in FIG. 2, a polyethylene terephthalate substrate is prepared as the support 21 in this case. Then, the above coating solution is applied on the support 21 by a bar coating method to a predetermined thickness.
Next, this sample is heat-treated at a predetermined temperature for a predetermined time, for example, to obtain a layer 25 of a thermoreversible recording material (simply referred to as a thermoreversible recording layer).

The heat treatment here is performed under the condition that the THF used for preparing the coating solution can be removed. Here, heat treatment is performed at a temperature of 120 ° C. for a predetermined time in an air atmosphere. The thermoreversible recording layer 25 thus formed becomes cloudy over the entire surface. Here, as a coating method, other suitable methods such as a roll coating method, a gravure coating method, and a blade coating method may be used.

Next, the thermoreversible recording layer 25 is cured,
Irradiate with ultraviolet light to obtain the desired medium. Here, UV irradiation device [made by Eye Graphics Co., Ltd.]
Was irradiated for 2 minutes at 80 W / cm. here,
The discharge lamp method was used to irradiate with ultraviolet light, but the medium is also cured by irradiation with ultraviolet light from other flash methods, laser methods, and electrodeless lamp methods. Furthermore, since it cures in normal light (sunlight) within a few days, it can be left alone.

The structure comprising the support 21 and the thermoreversible recording layer 25 formed on the support 21 is
It can be said that the thermoreversible recording medium 26 has the most basic structure (the thermoreversible recording medium 26 of the first embodiment). In the thermoreversible recording medium 26, heat is applied to the thermoreversible recording layer 25.
In addition to the method of heating the thermoreversible recording layer 25 from the thermoreversible recording layer 25 side, if the support 21 has good thermal conductivity, heat is applied from the support 21 side via the support 21. A method of heating the reversible recording layer 25 can be adopted.

In FIG. 2, the arrow labeled "light" indicates the state of incidence of light on the thermoreversible recording medium 26, and the arrow labeled "eye" indicates the thermoreversible state. The direction in which a person looks at the image formed on the sexual recording medium 26 is shown, and the arrow with the word "heating" shows the direction in which heat is applied by the above two methods. (The same applies to the media in FIG. 3 and subsequent figures below). The example of this FIG.
This is an example of recognizing an image depending on the presence / absence of reflected light from the thermoreversible recording medium 26. Of course, in the configuration of FIG.
The light may be made incident on the thermoreversible recording medium 26 from the side of the support 21 and the image may be recognized by the presence or absence of transmitted light.

Next, the characteristics of the change in transparency with respect to the thermal history of the thermoreversible recording layer 25 are examined. As a result, as shown in FIG. 1, the thermoreversible recording layer 25 was heated to a temperature of T ₂ or higher and then rapidly cooled (for example, 50 ° C./sec or higher) (in the case of the history indicated by 11 in FIG. 1). ), Shows the maximum transparency, and is rapidly cooled (for example, 50 ° C./sec or more) after being heated to T ₁ (T ₁ <T ₂ ) or more and T ₂ or less, or T
After heating to an arbitrary temperature Tn of ₁ or more (however, the softening point of polyvinyl acetal (200 ° C for S-REC KS-1) is not exceeded), followed by slow cooling (for example, showing less than 50 ° C / sec) (Fig. In the case of the history indicated by 13 in 1, the minimum transparency (white turbid state) is shown.
It has a thermal history-transparency characteristic, and T ₁ =
It was found to show 80 ° C. and T ₂ = 120 ° C. That is, in the case of the thermoreversible recording material of Example 1, the temperature at which the transparent state can be formed may be in the range of 120 to 200 ° C., and the range is 80 ° C., and the temperature at which the cloudy state can be formed. Can be anywhere from 80 to 200 ° C, with a range of 120 ° C.

Further, the transmittance of light having a wavelength of 550 nm (visible light) in the transparent state and the cloudy state of the thermoreversible recording layer of Example 1 is obtained. The transmittance in the former state was 80%, and the transmittance in the latter state was 4%. The contrast obtained from the ratio of these transmittances is 2
It becomes 0. Further, the surface hardness of the thermoreversible recording layer of Example 1 determined by the pencil hardness test method (JIS K5401) was as hard as 2H and mechanically resistant to scratches.

The thermoreversible recording layer of Example 1 was heated to a temperature of 140 ° C. and then rapidly cooled to be transparent, and then heated again to a temperature of 140 ° C. and then gradually cooled. The recording / erasing process is repeated 100 times with one cycle of the process of making the liquid cloudy under certain conditions. And
After 100 cycles, the transmittance was measured again to calculate the contrast. It was found that the contrast at this time was 20 as well as the initial value.

As described above, the reason why the contrast is not likely to be deteriorated even when the recording / erasing process is repeated is that the matrix material also contains the ultraviolet curable resin, and therefore the dispersion state of the organic low molecular weight substance is S-REC KS- It is considered that this may be because there is no change even by the above-mentioned heat treatment at 140 ° C. exceeding the glass transition point (120 ° C.) of 1. Further, the curing of the ultraviolet curable resin may be performed only by irradiating the ultraviolet ray, and since the heat treatment is not required at the time of curing the medium, the dispersion state of the organic low molecular weight substance in the initial state of the medium formation does not change at the time of curing the medium. A recording medium is obtained.

(Examples 2 to 8) The same procedure as in Example 1 was carried out except that the polymerizable oligomer (monomer) in Example 1 was changed to the following. (Example 2) Iupima-AU-1100 [trademark, untan acrylate type, Mitsubishi Petrochemical Co., Ltd.] (Example 3) PPZ [trademark, phosphazene type, Idemitsu Petrochemical Co., Ltd.] (Example 4) Denacol DA -811 [trademark, epoxy acrylate type, Nagase & Co., Ltd.] (Example 5) Denacol DM-811 [trademark, epoxy methacrylate type, Nagase & Co., Ltd.] (Example 6) Viscoat 700 [trademark, polyester acrylate type] , Osaka Organic Chemical Industry Co., Ltd.] (Example 7) Kayarad R-167 [trademark epoxy acrylate type, Nippon Kayaku Co., Ltd.] (Example 8) Aikatron Z-661 [trademark, polyester acrylate type, Aika industry ( Ltd.] The drying conditions and UV irradiation conditions for curing in Examples 2 to 8 were the same as in Example 1. Further, it was found that the initial contrast and the contrast after 100 cycles of the clearing treatment and the clouding treatment were both 20.

Furthermore, the pencil hardness test method (JIS K540
The surface hardness obtained by 1) is
It was found to be 2H, 3H, H, H, 2H, H, 3H, respectively. Comparative Example (Comparative Example 1) Further, a copolymer of vinylidene chloride and acrylonitrile having 65 polymerized portions instead of S-REC KS-1 and the ultraviolet curable resin (Saran F31 manufactured by Dow Chemical Co., Ltd.)
0) was used to prepare a coating solution of Comparative Example 1 in exactly the same manner as in Example 1, to form a layer of this material on a support, and to measure the properties of this layer. Do each.

The transparency change characteristic with respect to the heat history of the thermoreversible recording material of Comparative Example 1 was the same as that of the material 3 described in the prior art, specifically, stable when heated to 63 ° C. and cooled. It had a characteristic of showing a transparent state, and when it was reheated to a temperature of 74 ° C. or higher (however, the softening point of Saran F310 was 160 ° C. or lower), a white turbid state was shown. That is, in the case of the thermoreversible recording material of Comparative Example 1, the temperature at which the transparent state can be formed is 63 to 74 ° C.
The range is only 11 ° C, and the temperature at which the cloudy state can be formed is 74 to 160 ° C, and the range is only 86 ° C.

Further, the wavelength of each of the thermoreversible recording layer of Comparative Example 1 in the transparent state and the cloudy state was 550 nm (visible light).
The respective light transmittances of are obtained. The transmittance in the former state was 60%, and the transmittance in the latter state was 10%. The contrast obtained from the ratio of these transmittances is 6. Further, regarding the thermoreversible recording layer of Comparative Example 1,
The recording / erasing process is repeated 100 times, with one cycle comprising a process of making transparent under the condition of heating to 70 ° C. and cooling, and then a process of turning cloudy under the condition of heating again at 140 ° C. and then cooling. Then, after 100 cycles, the above transmittance was measured again to calculate the contrast. At this time, the transmittance in the transparent state was 60%, and the transmittance in the cloudy state was 20%. Therefore, it was found that the contrast was 3, which was worse than the initial value of 6. In addition, the pencil hardness test method (JI
The surface hardness determined by SK5401) was 2B, which is worse than any of the present invention, and it was found that the medium is mechanically weak against scratches.

Comparative Example 2 Further, the coating solution of Comparative Example 2 was prepared in the same manner as in Example 1 except that the ultraviolet curable resin was removed, and a layer of this material was formed on the support. And measuring the properties of this layer.
The transparency change characteristic of the thermoreversible recording material of Comparative Example 2 with respect to the thermal history was the same as that of the material of Example 1. Also,
The contrast immediately after fabrication was the same as that of the material of Example 1.

The heat-reversible recording layer of Comparative Example 2 was heated to a temperature of 140 ° C. and then made to be transparent under a rapid cooling condition, and then heated again to a temperature of 140 ° C. and then gradually cooled. The recording / erasing process is repeated 100 times, with the process of clouding as one cycle under certain conditions. And 1
After the completion of 00 cycles, the transmittance was measured again to calculate the contrast. The transmittance of the transparent state at this time is 80%
And the transmittance in the cloudy state was 20%. Therefore, the contrast was 4, and it was found that the initial value was 20, whereas the contrast was deteriorated. Further, it was found that the surface hardness determined by the pencil hardness test method (JIS K5401) is worse than either F or the present invention, and the medium is mechanically weak against scratches.

(Effects of the Embodiments of the First and Second Inventions) As is clear from the above description, the thermoreversible recording materials of the embodiments of the present invention are comparative examples (especially, comparative examples). It can be seen that the temperature condition for forming a transparent state or a cloudy state is looser than that of 2). Furthermore, it can be seen that the transparent state or the cloudy state once formed is more stable than the conventional one at a higher temperature. Furthermore, it can be seen that the decrease in contrast when recording and erasing are repeated does not occur until at least 100 cycles, and thus it is more difficult to cause the decrease in contrast than in the past. In addition, the surface hardness is increased, and mechanical scratches are unlikely to occur.

Table 1 shows the temperature range in which the transparent state and the cloudy state can be formed and the initial contrast of each of the samples of Examples 1 to 8 and Comparative Examples 1 and 2, and the transmittance and the contrast after 100 cycles of the recording / erasing process. Is shown in Table 2, and the surface hardness obtained by the pencil hardness test method (JIS K5401) is shown in Table 3.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

(II) An example of the thermoreversible recording medium of the present invention (third invention) will be described. (First embodiment of the third invention) The most basic structural example (first embodiment) of this thermoreversible recording medium is the same as that described above with reference to FIG. That is, it has a structure in which the thermoreversible recording layer 25 and the support 21 for maintaining the thermoreversible recording layer 25 are laminated. Here, the support 21 can have any suitable shape, constituent material, and film thickness according to the design of the thermoreversible recording medium 26.
For example, any of those which are transparent to visible light, those which reflect part or all of visible light, and those which absorb part or all of visible light can be the support of the present invention.

In the case of the present invention, the transparent portion and the opaque portion can be selectively formed in the thermoreversible recording layer by selectively heating the thermoreversible recording layer from the thermoreversible recording layer side ( In addition, when the support is made of a material having good thermal conductivity, heating means is brought into contact with the support, and the thermoreversible recording layer is heated through the support. In addition, the transparent portion and the opaque portion can be selectively formed (display can be performed) from the support side (from the back side of the medium). When the thermoreversible recording medium is used as the display screen itself of the display device in the case where the display can be performed also from the support side, a desired display can be made without placing heating means on the side where the person views the medium. The advantage of being able to do is obtained. When the display can be performed from the side of the support (from the side of the back surface of the medium), in addition to the above advantages, other advantages can be obtained depending on the design (details will be described in a corresponding embodiment later). Examples of the material include, but are not limited to, polyethylene terephthalate, polyethylene terephthalate, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate,
Plastics such as polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane, polybutadiene, polyimide, paper, synthetic paper, inorganic fiber paper with good thermal conductivity, ceramic, metal, and carbon powder. Examples include plastics in which metal powder is dispersed.

Further, in order to expand the applications of the thermoreversible recording medium of the present invention and further improve the characteristics, in addition to the constitution of the first embodiment, to protect the thermoreversible recording medium as an intermediate layer. From the protective layer, the adhesive layer for improving the fixing strength between the components of the thermoreversible recording medium, the reflective layer or the light absorbing layer (details will be described later), and the enhance layer for improving the display contrast, One or more layers selected according to the design of the thermoreversible recording medium, and further a recording layer for recording bar code information or magnetic information that cannot be directly recognized by humans but can be read by an information reading device (book). A recording layer having a different meaning from the thermoreversible recording layer of the invention) may be optionally arranged to form a thermoreversible recording medium.

Specific examples of these will be described with reference to the following embodiments. (Second Embodiment of Third Invention) A thermoreversible recording medium according to a second embodiment of the present invention is provided with a support 21 and a support 21, as shown in the sectional view of FIG. It is composed of a reflective layer or a light absorbing layer 23 as a kind of intermediate layer and a thermoreversible recording material (thermoreversible recording layer 25) provided on the reflective layer or the light absorbing layer 23 of the present invention. . Further, in each of the cross-sectional views used in FIG. 3 and the following description, hatching showing the cross-section is attached only to the reflective layer or the light-absorbing layer 23 and the thermoreversible recording layer 25, and hatching to other layers is omitted. are doing.

The thermoreversible recording medium (also referred to as reversible thermosensitive recording medium) 27 of the second embodiment is manufactured as follows. The support 21 is made of a polyethylene terephthalate substrate having a predetermined thickness here. On this support 21, a vinyl chloride-vinyl acetate copolymer as a binder [VY manufactured by Union Carbide Company (UCC)]
HH] and cadmium red as a color pigment are applied in tetrahydrofuran to apply a coating solution. When the obtained coating film is dried, a layer that mainly reflects red light on the support 21 and absorbs or transmits other light (depending on the wavelength of interest, a reflective layer, a light absorbing layer, or a light transmitting layer). However, it is also a layer that can be called a colored layer from another perspective, and this layer will be referred to as a reflection layer or a light absorption layer.) 23 is formed. In addition, the first or second invention of the first invention is formed on the reflection layer or the light absorption layer 23 thus produced.
The thermoreversible recording layer 25 is formed by the procedure described in the example of the first invention by using each coating solution used in the examples to the eighth examples.

A heating means (for example, a thermal head) is brought into contact with the thermoreversible recording layer 25 of the thermoreversible recording medium 27, and the thermoreversible recording layer 25 is selectively heated to form a transparent portion (printing portion). When formed, it was possible to print in red letters. Further, repeated recording and erasing treatment experiments were conducted in the same manner as in the first aspect of the invention, and it was found that no print deterioration was observed. Of course, also in the case of the second embodiment,
As in the first embodiment, the support 21 may be made of a material having good thermal conductivity, and the thermoreversible recording layer 25 may be heated from the support side via the support.

The reflection layer or the light absorption layer 23 is not limited to the one including a layer containing a red pigment. The reflection layer or the light absorption layer 23 may be composed of a pigment other than red, a layer containing a pigment, or a layer containing metal powder such as copper powder or aluminum powder.
Further, the reflection layer or the light absorption layer 23 may be formed by coating the support 21 with ink or the like. Further, inks of a plurality of colors may be printed for the purpose of improving the display contrast. Further, when the reflection layer or the light absorption layer 23 is manufactured, pigments, dyes, and metal powders having good thermal conductivity may be used to improve the thermal response of the thermoreversible recording medium. .

(Third Embodiment of the Third Invention) The thermoreversible recording medium of the third embodiment is the second embodiment of the third invention as shown in the sectional view of FIG. In addition to the constitution of the thermoreversible recording medium, a first protective layer 29 which is transparent to visible light and protects the thermoreversible recording layer 25 is provided on the thermoreversible recording layer 25. Examples of the constituent material of the protective layer 29 include, but are not limited to, polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, and the like.
Examples include plastics such as polycarbonate, polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane, polybutadiene, and UV curing resin, and inorganic substances such as SiO ₂ , TiO ₂ , and Al ₂ O ₃ . The film thickness of the first protective layer 29 is such that heat from a means for heating the thermoreversible recording layer 25 (for example, a thermal head) is satisfactorily transferred to the thermoreversible recording layer 25, and the first protective layer 29 serves as a protective layer. The film thickness may be set to a suitable value within the range where the function is obtained.

On the surface of the first protective layer 29, a character or a graphic (for example, the application of this thermoreversible recording medium "○○○○" is provided on a portion which does not hit the display area of the thermoreversible recording layer.
Characters such as "card" may be printed. Also in the case of the third embodiment, the support can be made of a material having good heat conduction. In the case of this configuration, printing can be performed without disposing a heating means on the viewer side of the thermoreversible recording medium, and in addition, the characters or figures printed on the surface of the first protective layer 29 can be heated by the heating means. The advantage of being difficult to influence is obtained. This is considered to be useful in terms of protecting the written characters or figures when writing characters or figures on the surface of the first protective layer 29 with a water-based or oil-based magic ink or the like.

If necessary, as shown in FIG. 4B, between the first protective layer 29 and the thermoreversible recording layer 25 and / or the thermoreversible recording layer 25 and the reflective layer. Alternatively, an adhesive layer 31 for improving the adhesive strength between the two layers 25 and 23 may be provided as a kind of intermediate layer between the adhesive layer 31 and the light absorption layer 23.
Examples of the constituent material of the adhesive layer 31 include, but are not limited to, polyester resin, urethane resin, and epoxy resin. In addition, as another example of the intermediate layer, a layer dedicated for printing characters and graphics (printing layer)
33 can be provided at an appropriate place of the thermoreversible recording medium (not limited to that of the third embodiment).

FIG. 5A shows an example of a thermoreversible recording medium having a printing layer 33 between the adhesive layer 31 and the first protective layer 29, and FIG. 5B shows Examples of thermoreversible recording media having a printed layer 33 between the reflective or light absorbing layer 23 and the adhesive layer 31 are shown respectively. Of course, the provision of the adhesive layer and the printing layer is not limited to the third embodiment, but can be applied to each of the other embodiments.

(Fourth Embodiment of the Third Invention) The thermoreversible recording medium of the fourth embodiment is similar to that of the third embodiment as shown in the sectional view of FIG. 6 (A). In addition to the configuration of the thermoreversible recording medium shown in (A), an enhancement layer for improving display contrast is provided between the thermoreversible recording layer 25 and the reflection or light absorption layer 23 as a kind of intermediate layer. It is equipped with 35. The enhancement layer 35 enhances the contrast between the transparent portion and the cloudy portion formed on the thermoreversible recording layer 25 to improve the display contrast. Examples of the constituent material of the enhancement layer 35 include, but are not limited to, polyester, polyethylene,
Plastics such as polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane, polybutadiene, and SiO ₂ , TiO ₂ . ₂ , Al
Inorganic substances such as ₂ O ₃ can be mentioned.

As shown in FIG. 6B, the enhancement layer may be composed of the air layer 35a. This FIG. 6 (B)
In the above example, the adhesive layer 31 is provided in a part between the reflective layer or the light absorbing layer 23 and the thermoreversible recording layer 25, and the adhesive layer 31 is provided between the reflective layer or the light absorbing layer 23 and the thermoreversible recording layer 25. An air layer 35a is formed in a portion where the adhesive layer 31 is not provided, thereby forming an enhancement layer.

Also in the case of the fourth embodiment, the support 2
1 can be made of a material having good heat conduction. However, it is considered that the mode in which the enhancement layer 35 is composed of the air layer 35a is not so effective because the degree of heat transfer to the thermoreversible recording layer 25 is reduced by the air layer 35a. (Fifth embodiment of the third invention) The thermoreversible recording layer 25 provided in the thermoreversible recording medium of the third invention records visible characters and solids. However, if the thermoreversible recording medium of the third invention is capable of storing and rewriting coded information as well, it records composite information of directly visible thermal recording and coded recording, In addition, a thermoreversible recording medium that can be used is obtained, which is preferable. If the thermoreversible recording medium can be constructed in this way, it can be used to construct, for example, a prepaid card, and the recording layer can store code information indicating, for example, a balance. Furthermore, the balance information is read by an external reading device, a new balance is calculated from this information and the amount of money that has just been used by the external control device, the new balance is displayed on the thermoreversible recording layer, and the recording layer is displayed. This is preferable because the application of the thermoreversible recording medium is widened such that renewal recording becomes possible.

An example (fifth embodiment) of a thermoreversible recording medium having such a recording layer will be described below. Where the recording layer capable of storing and rewriting the code information is provided in the thermoreversible recording medium can be arbitrarily determined according to the design of the thermoreversible recording medium. In this embodiment, in the second embodiment, as shown in FIG.
Support 21 for thermoreversible recording medium described using (A)
As shown in FIG. 7A, a recording layer 37 is provided on the back surface of the recording layer 37, and a second protective layer 39 that covers the recording layer 37 is provided to protect the recording layer 37. Also, FIG.
As shown in (B), it is of course possible to provide an enhancement layer 35 between the thermoreversible recording layer 25 and the reflection layer or the light absorption layer 23.

The constituent material of the second protective layer 39 can be selected from various materials that can constitute the first protective layer 29, for example. In addition, as a recording format for the recording layer 37,
Although not limited to this, a magnetic recording method, an optical recording method,
One or more of an electrical recording method and a thermal recording method for recording invisible code information can be used. The recording layer 37 may be composed of, for example, the IC card itself.

Also in the case of the fifth embodiment, the support may be made of a material having good heat conduction. (Sixth Embodiment of Third Invention) As shown in a sectional view of FIG. 8A, a thermoreversible recording medium of a sixth embodiment is a support (transparent material) made of a material transparent to visible light. A thermoreversible recording layer 25 and a first protective layer 29 are provided on a support 41 in this order, and a reflective layer or a light absorption layer 23 is provided on the back surface of the transparent support 41.

In this structure, the transparent support 4 is used as the support.
1 is used and is disposed between the thermoreversible recording layer 25 and the reflection layer or the light absorption layer 23, the transparent support 41 itself acts like an enhancement layer. Of course, as shown in FIG. 8B, in addition to the structure of FIG. 8A, the original enhancement layer 35 (the air layer 35a is also acceptable) between the transparent support 41 and the reflection layer or the light absorption layer 23. May be provided.

As an example of the constituent material of the transparent support 41,
For example, transparent plastics such as polyester, polyethylene, polypropylene, cellophane, polyvinyl chloride, polyolefin, polyvinyl alcohol, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, polyarylate, polysulfone, fluororesin, polyacrylonitrile, polyether sulfane, polybutadiene. And so on.

Also in the case of the sixth embodiment, for example, as shown in FIG.
In the configuration of (A) or (B), the recording layer 37 and the second protective layer 39 as shown in FIG. 7 may be provided below the reflection layer or the light absorption layer 23. (Seventh embodiment of the third invention) In this seventh embodiment, as shown in FIG.
4A, the thermoreversible recording medium described with reference to FIG. 4A, the thermoreversible recording medium described with reference to FIG. 4B, and the thermoreversible recording medium described with reference to FIG. In each structure of the thermoreversible recording medium and the thermoreversible recording medium described with reference to FIG. 5B, the reflective layer or the light absorbing layer 23 is not provided, and the support itself is the transparent support 41. It consists of.

As one mode of this seventh embodiment, FIG.
An example in which the idea of the seventh embodiment is applied to the configuration of (A) is shown in FIG.
It shows in (A) and FIG. 9 (B). Here, FIG.
Heating is performed from the first protective layer 29 side to form the thermoreversible recording layer 2.
FIG. 9B shows an example in which the support 41 is made of a material having good thermal conductivity and a transparent material.
In this example, heating is performed from the first side to print on the thermoreversible recording layer 25. In both cases, an example is shown in which light is incident from the transparent support 41 of the thermoreversible recording medium. Of course, the first
The light may be incident from the side of the protective film 29.

As another aspect of the seventh embodiment,
As shown in FIG. 9C, the idea of the seventh embodiment is applied to the configuration including the recording layer 37. That is, in FIG. 9C, an example in which the recording layer 37 and the second protective layer 39 for protecting the recording layer 37 are provided in a portion of the back surface of the transparent support 41 which does not hinder the incidence of light. Is shown. Of course, also in the case of FIG. 9C, the transparent support 41 may be made of a material having good thermal conductivity, and the thermoreversible recording layer 25 may be heated via the transparent support 41.

(Eighth embodiment of the third invention) The above-mentioned first to first embodiments
In the thermoreversible recording medium of each of the seventh examples, the data printed on the medium was viewed mainly from the first protective film 29 side. However, as shown in FIG. 10, in this eighth embodiment, the support itself is composed of the transparent support 41, and the position where the reflection layer or the light absorption layer 23 is provided is the thermoreversible recording layer 25 and the first protection. By providing the layer 29 and the layer 29, the transparent support 4
The print data may be viewed from the first side. Some examples will be described below. However, in the case of the eighth embodiment, the first protective layer 29 may not have transparency.

First, FIG. 10A shows a transparent support 41.
In this example, the thermoreversible recording layer 25, the reflective layer or the light absorbing layer 23, and the first protective layer 29 are provided in this order on the top. exactly,
This corresponds to an example in which the medium of FIG. 4A is changed so that the display can be seen on the support side. Further, FIG. 10B shows an adhesive layer 31, a thermoreversible recording layer 25, an adhesive layer 31, a reflective layer or a light absorbing layer 23, and a first protective layer 29 on a transparent support 41.
Are provided in this order.

This corresponds to an example in which the medium of FIG. 4B is changed so that the display can be seen on the support side. FIG.
(C) is a printing layer 33 and an adhesive layer 3 on the transparent support 41.
1, a thermoreversible recording layer 25, an adhesive layer 31, a reflective layer or a light absorbing layer 23, and a first protective layer 29 are provided in this order. This corresponds to an example in which the medium in FIG. 5A is changed so that the display can be seen on the support side.

Further, FIG. 11A shows a transparent support 41.
This is an example in which an adhesive layer 31, a thermoreversible recording layer 25, an adhesive layer 31, a printing layer 33, a reflective layer or a light absorbing layer 23, and a first protective layer 29 are provided in this order on top. This corresponds to an example in which the medium of FIG. 5B is changed so that the display can be seen on the support side. Further, FIG. 11 (B) shows that on the transparent support 41,
This is an example in which the thermoreversible recording layer 25, the enhance 35, the reflecting layer or the light absorbing layer 23, and the first protective layer 29 are provided in this order.

This corresponds to an example in which the medium of FIG. 6A is changed so that the display can be seen on the support side. In addition, FIG.
(C) is the thermoreversible recording layer 2 on the transparent support 41.
5, an enhancement layer including the air layer 35a, a reflection layer or a light absorption layer 23, and a first protective layer 29 are provided in this order. This corresponds to an example in which the medium in FIG. 6B is changed so that the display can be seen on the support side.

Further, FIG. 12A shows a transparent support 41.
A thermoreversible recording layer 25, a reflective layer or a light absorbing layer 23,
This is an example in which the recording layer 37 and the second protective layer 39 are provided in this order. This corresponds to an example in which the medium of FIG. 7A is changed so that the display can be seen on the support side. In addition, FIG.
The thermoreversible recording layer 25, the enhancement layer 35 (which may be an air layer), the reflection layer or the light absorption layer 23, the recording layer 37, and the second protective layer 39 are provided in this order on the transparent support 41. It is an example. This corresponds to an example in which the medium of FIG. 7B is changed so that the display can be seen on the support side.

(Ninth embodiment of the third invention) The above-mentioned first to third embodiments
In each of the eighth embodiments, as a support used when light is incident from the support side, a structure having light entering the main surface of the support at a right angle was mainly considered. However, the support itself may have the property of changing the traveling direction of the light incident on the support. This is because, for example, restrictions on the design of the thermoreversible recording medium due to the positional relationship between the thermoreversible recording layer 25 and the light source can be reduced. The following example (9th Example) is the example.

FIG. 13 is a diagram showing one mode of this ninth embodiment. In this aspect, when light is incident from the end surface 51a of the plate-shaped body 51, the light is bent at a right angle in the plate-shaped body 51 and is emitted from the main surface of the plate-shaped body 51 (edge light system). Also referred to as an example, a plate-shaped body 51 having an optical path changing function is used as a support for a thermoreversible recording medium. Specific examples of such a plate-like body 51 include acrylite (trade name) provided by Mitsubishi Rayon Co., Ltd. using an acrylic resin. Of course, the structure to which the idea of the ninth embodiment can be applied is not limited to the structure shown in FIG. 13, and can be widely applied to the structures of the above-described first to eighth embodiments.

(Regarding Writing Information on Thermoreversible Recording Medium) Next, in order to deepen the understanding of the first and third inventions, a case of writing information on the thermoreversible recording medium of the third invention will be described. An example of the method will be described. FIG. 14 is a schematic configuration diagram of a recording device (fourth invention) using the thermoreversible recording medium of the present invention. An example of a device for writing information on the thermoreversible recording medium 100 of the third invention, FIG. 3 is a diagram showing a relationship with a thermoreversible recording medium 100.

In FIG. 14, reference numerals 200a to 200c denote recording devices having slightly different functions.
0 is information for recording (for example, "A""I""U""E")
"O") and stores the recording devices 200a to 200c
Is a control device for controlling. Here, the recording device 2
00a includes a thermal head 201 for printing information and a heating block (or heating roll) 202 for erasing information.

The recording device 200b includes, in addition to the configuration of the recording device 200a, an optical reading device 203 for reading the information of the recording layer 37 described in the third invention, particularly the information recorded by the optical recording method. Recording device 200c
In addition to the configuration of the recording device 200a, it comprises a read head 204 for reading the information of the recording layer 37, in particular coded information, and a recording head 205 for writing the coded information.

(1) In the case where the thermoreversible recording medium has, for example, the recording layer 37 of the third invention described above, the user uses the thermoreversible recording medium 100 in the recording device 200a. To insert. The control device 300 senses that the thermoreversible recording medium 100 is inserted, and prints the information for recording (for example, "A""I""U""E""O"). Send a command to. Receiving this command, the recording apparatus 200a uses the thermal head 201 for a predetermined time with a predetermined electric power and the thermoreversible recording medium 1
00 to the thermoreversible recording layer 25 directly or to the first protective layer 29.
Alternatively, it is selectively heated via the support 21.

When the thermoreversible recording medium 100 has the thermal history characteristics shown in FIG. 1, it is desired to print "A""I""U""E""O" of the thermoreversible recording medium 100. After heating the part to 120 to 200 ° C. and then rapidly cooling it to room temperature, the part becomes transparent and the other parts remain cloudy. The printing can be performed under the conditions that the printing power is 0.1 W / dot and the printing time is 1 msec. Of course, this printing condition is an example.

After the printing is completed, the user takes out the thermoreversible recording medium 100 from the recording device 200a. The thermoreversible recording medium 100 taken out is "a""i""u"
The printed parts of "E" and "O" were fixed in a transparent state. Furthermore, the contrast indicated by the transmittance ratio between the transparent portion and the cloudy portion is, for example, 20 (wavelength 550 nm
Is the transmittance for light. ).

As a result, the user can see the thermoreversible recording medium 1
Information recorded in 00 "A""I""U""E""O"
Can be visually recognized. In addition, this information "A""I"
"U", "E", and "O" are held until the next time the thermoreversible recording medium is used. In addition, the user can use the thermoreversible recording medium 1
To erase the previously recorded information of 00, the thermoreversible recording medium 100 is inserted into the recording device 200a. In the recording apparatus 200a, when the thermoreversible recording medium 100 has the thermal history characteristics shown in FIG. 1, the thermoreversible recording medium 100 is heated by the heating roll 202 at a temperature in the range of 90 to 200 ° C. Slowly cool. The thermoreversible recording medium 100 becomes opaque and the previous record is erased. Further, when new information is recorded on the thermoreversible recording medium that has been erased, it is processed by the above printing procedure.

(2) The thermoreversible recording medium is, for example, the third one described above.
In the case of the recording layer 37 of the invention described above, which has a recording layer for storing information by the optical recording method, the user inserts the thermoreversible recording medium 100 into the recording device 200b. To do. Then, the recording device 200b reads the optical information stored in the recording layer 37 by the optical reading device 203 and sends it to the control device 300.

This optical information is, for example, the thermal recording medium 100.
If it is the recognition information of the owner of the
By setting 0, it is possible to confirm whether the user of the thermoreversible recording medium 100 is correct or not. Writing of information in the thermoreversible recording layer and erasing of information in the thermoreversible recording layer can be performed by the same procedure as in the above (1). (3) The thermoreversible recording medium is, for example, the recording layer 37 of the third invention, and has a recording layer such as a magnetic recording layer capable of recording coded information and changing the coded information. In the case of the above, the user inserts the thermoreversible recording medium 100 into the recording device 200c. Then
The recording device 200c reads the coded information stored in the recording layer 37 of the thermoreversible recording medium 100 with the read head 204 and sends it to the control device 300.

Here, for example, the coded information can be, for example, balance information when the thermoreversible recording medium 100 is considered as a prepaid card. The control device 300 calculates a new balance from this balance information and the amount of money consumed by the user, and further records this new balance on the recording layer 37 of the thermoreversible recording medium 100, and the thermoreversible recording. The commands to be displayed on the layer 25 as a visual device are respectively sent to the recording device 200c. The recording device 200c uses the recording head 205 to transfer the new balance information to the recording layer 37.
And the thermal reversible recording layer 25 is formed by the thermal head 202.

The thermoreversible recording medium of the third invention is of a type in which the display is viewed from one side of the thermoreversible recording medium, and is heated from the other side of the thermoreversible recording medium. Printing type [for example, FIG. 9 (B) or FIG. 10 (B)]
In the medium shown in FIG. 2, it is necessary to adjust the print signal of the thermal head 201 in the control device 300 so that the character can be seen normally on the visual side.

Specific examples of the thermoreversible recording medium include prepaid cards such as telephone cards, orange cards, and highway cards, postpaid cards, point cards, labels used in various fields, and Examples thereof include a kanban of a kanban system, a word processor that employs a thermal recording method, a recording sheet for a facsimile, and a sheet of a projection image forming apparatus such as an overhead projector or a slide.

(III) An example of the thermoreversible recording apparatus (fourth invention) of the present invention will be described. (First Embodiment of Fourth Invention) FIG. 15 is a schematic diagram of the first embodiment of the thermoreversible recording apparatus (fourth invention) of the present invention. This thermoreversible recording device (hereinafter, simply referred to as a recording device) has a plate-like shape for erasing the entire surface of the frame 61 and the thermoreversible recording layer (see FIG. 2 etc.) of the thermoreversible recording medium provided in the frame 61. Whole eraser 6 composed of the heating element
3, the thermoreversible recording medium 100 provided so as to be in contact with the entire eraser 63, and the thermoreversible recording medium 100.
A writing tool 65 for forming a printing portion (image) on the sheet, a local erasing tool 67 for erasing a part of the image formed on the thermoreversible recording medium 100, and a temperature of the overall erasing tool 63 are controlled. And a temperature control unit 69 for controlling the temperature.

Here, the frame 61 can be made of a suitable material such as metal or resin according to the design of the recording apparatus. Further, the overall erasing tool 63 can be composed of, for example, a panel heater. The entire eraser 63 can apply a temperature according to the characteristics of the thermoreversible recording medium 100 (see FIG. 1, for example). The temperature control unit 69 that enables this can be configured by a conventionally known one. In addition, the thermoreversible recording medium 100
Uses the one described in the embodiment of the second invention.

Although not shown, the writing instrument 65 includes a cylindrical main body, a head provided at the tip thereof, and a heat generating portion for heating the head incorporated in the main body. , Power supply for heat generating part and ON as power switch
It has a / OFF switch. The head portion of the writing instrument 65 is preferably made of a material having a high thermal conductivity, such as a metal such as copper or a ceramic.

Further, the shape of the head portion is preferably tapered, but it is preferable to determine the thickness of the head portion in consideration of the size of characters to be drawn. Further, the heat generating portion can be composed of a resistance heating element such as a nichrome heater or a ceramics heater. The power source for the heat generating portion may be either a DC power source (including batteries) or an AC power source.

According to the recording apparatus of the first embodiment, when the full eraser 63 is operated according to the heat history condition 13 of FIG. 1, the recording layer of the thermoreversible recording medium 100 becomes cloudy. When the writing tool 65 in the on state is brought into contact with this cloudy screen, the recording layer becomes transparent at the portion of the cloudy screen that is in contact with the writing tool, and the color of the colored support becomes transparent, in this case red. The printing part of is obtained. As a result, an image composed of a white background portion and a red printing portion can be formed on the display body. When it is desired to erase only a part of the image, the image can be erased by bringing the local erasing tool 67 into contact with the part.

(Second Embodiment of Fourth Invention) FIG.
FIG. 7 is a schematic configuration diagram of a second embodiment of the thermoreversible recording device (fourth invention) of the present invention. The recording apparatus of the second embodiment is
It is an example of an apparatus in which the thermoreversible recording medium of the third invention is applied to the display surface of a display. More specifically, the thermoreversible recording medium according to the third aspect of the present invention is a loop-shaped thermoreversible recording medium 100a (hereinafter, also referred to as a loop-shaped medium) having a band shape and a closed loop shape. A first platen roll 206 and a second platen roll 207 for holding and orbiting the medium 100a when necessary, and a recording device 208 for recording information on the loop medium 100a and erasing information on the medium. , Traveling / stopping and traveling speed of the first and second platen rolls 206, 207,
This is a device including a control device 301 for controlling the recording and erasing of the information by the recording device 208. here,
The recording device 208 can be configured by, for example, the recording device 200a described with reference to FIG. Further, the control device can be configured by any suitable device using known print control technology and transport control technology.

In the recording apparatus of the second embodiment, when the display is performed while moving the loop-shaped thermoreversible recording medium 100a,
For example, it can be used as an electronic bulletin board. Further, if the loop medium 100a is stopped at a proper time, it can be used as a bulletin board for predetermined information. It should be noted that the present invention is not limited to the above-described embodiments, and various modifications can be made based on the spirit of the present invention, and they are not excluded from the scope of the present invention.

[0106]

As described above in detail, according to the present invention, (1) according to the invention of claim 1, the matrix material is polyvinyl acetal and an ultraviolet curable resin (however, a cured product), Since a predetermined saturated carboxylic acid and / or its derivative is used as the organic low molecular weight substance, the following effects can be obtained.

It is possible to obtain a medium in which the display contrast is less likely to decrease when recording and erasing are repeatedly performed as compared with the conventional medium. A medium wider than conventional can be obtained in both the temperature range in which the cloudy state can be formed and the temperature range in which the transparent state can be formed.
Therefore, it is possible to relax restrictions on temperature control of thermal means such as a thermal head as compared with the conventional case.

Since the white turbid state or the transparent state once formed is stable up to a higher temperature than before, it is used when the environment temperature is high (for example, in the summer, the vehicle interior temperature is 70 to 8).
It is also advantageous for use in automobiles that reach 0 ° C). A medium having a hard surface hardness can be obtained. A good medium is obtained because it is not heated during curing.

(2) According to the invention described in claim 2, at least one selected from the group of saturated carboxylic acids and derivatives of the saturated carboxylic acids, polyvinyl acetal and an ultraviolet curable resin are mixed, A thermoreversible recording material can be produced by irradiating the mixture with ultraviolet rays. The ultraviolet curable resin can be cured only by irradiating it with ultraviolet rays, and heat treatment is not required during medium curing. The state of dispersion of the organic low molecular weight substance in the state does not change when the medium is cured, and a good recording medium can be obtained.

(3) According to the invention described in claims 3 to 8,
A thermoreversible recording medium having the effect (1) above can be obtained. (4) According to the invention of claim 9, by using the thermoreversible recording medium, the temperature range for forming the transparent state is wide, the temperature control is easy, and the recording and erasing are repeated. However, it is possible to obtain a recording apparatus that can obtain stable transparency.

[Brief description of drawings]

FIG. 1 is a characteristic explanatory view of a thermoreversible recording material of the present invention.

FIG. 2 is an explanatory diagram of a thermoreversible recording medium of the first and third inventions.

FIG. 3 is an explanatory diagram of a second embodiment of the thermoreversible recording medium of the third invention.

FIG. 4 is an explanatory view (No. 1) of the third embodiment of the thermoreversible recording medium of the third invention.

FIG. 5 is an explanatory view (No. 2) of the third embodiment of the thermoreversible recording medium of the third invention.

FIG. 6 is an explanatory view of a fourth embodiment of the thermoreversible recording medium of the third invention.

FIG. 7 is an explanatory view of a fifth embodiment of the thermoreversible recording medium of the third invention.

FIG. 8 is an explanatory diagram of a sixth embodiment of the thermoreversible recording medium of the third invention.

FIG. 9 is an explanatory diagram of a seventh embodiment of the thermoreversible recording medium of the third invention.

FIG. 10 is an explanatory view (1) of the eighth embodiment of the thermoreversible recording medium of the third invention.

FIG. 11 is an explanatory view (No. 2) of the eighth embodiment of the thermoreversible recording medium of the third invention.

FIG. 12 is an explanatory view (No. 3) of the eighth embodiment of the thermoreversible recording medium of the third invention.

FIG. 13 is an explanatory diagram of a ninth embodiment of the thermoreversible recording medium of the third invention.

FIG. 14 is a schematic configuration diagram of a recording device (fourth invention) using the thermoreversible recording medium of the present invention.

FIG. 15 is a schematic configuration diagram of a first embodiment of a thermoreversible recording device (fourth invention) of the present invention.

FIG. 16 is a schematic configuration diagram of a second embodiment of a thermoreversible recording device (fourth invention) of the present invention.

[Explanation of symbols]

21 Support 25 Thermoreversible Recording Layer 26, 27, 100 Thermoreversible Recording Medium 23 Reflective Layer or Light Absorption Layer 29 First Protective Layer 31 Adhesive Layer 33 Printing Layer 35 Enhance Layer 35a Air Layer (Enhance Layer) 37 Recording Layer 39 Second protective layer 41 Support (transparent support) 51 Plate 51a End face 61 Frame 63 Whole erasing tool 65 Writing tool 69 Temperature control section 100a Loop thermoreversible recording medium 200a, 200b, 200c Recording apparatus 201 Information printing thermal head 202 Heating block (or heating roll) for erasing information 203 Optical reading device 204 Reading head 205 Recording head for writing coded information 206 First platen roll 207 Second platen roll 208 Recording Device 300, 301 Control device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G09F 9/00 356 D 7426-5H // B41M 5/26 C09K 9/02 C (72) Inventor Kenyuki Sekiya 1-7-12 Toranomon, Minato-ku, Tokyo Oki Electric Industry Co., Ltd.

Claims (9)

[Claims] 1. A thermoreversible recording material containing a matrix material and an organic low molecule, the transparency of which changes depending on heat history, comprising polyvinyl acetal and an ultraviolet curable resin (provided that it is cured with a curing agent) as the matrix material, and A thermoreversible recording material comprising at least one selected from the group of a saturated carboxylic acid and a derivative of the saturated carboxylic acid as a low molecule. 2. A mixture of at least one selected from the group consisting of a saturated carboxylic acid and a derivative of the saturated carboxylic acid, polyvinyl acetal, and an ultraviolet curable resin is mixed, and the mixture is irradiated with ultraviolet rays to be thermally reversible. A process for producing a thermoreversible recording material, which comprises producing a heat-sensitive recording material. 3. A thermoreversible recording layer composed of the thermoreversible recording material according to claim 1 or the thermoreversible recording material produced by the production method according to claim 2, and the thermoreversible recording layer directly or A thermoreversible recording medium comprising a support for supporting the intermediate layer. 4. The thermoreversible recording medium according to claim 3, further comprising a protective layer on the surface side of the thermoreversible recording layer opposite to the support, directly or via an intermediate layer. A thermoreversible recording medium, characterized in that at least one of the protective layers is made of a material having transparency to visible light. 5. The thermoreversible recording medium according to claim 3 or 4, wherein when the intermediate layer is used, the intermediate layer is thermoreversible at least among the reflective layer, the light absorption layer, the enhancement layer and the printing layer. A thermoreversible recording medium comprising one or more layers selected according to the direction of light incident on the recording medium and the direction of viewing the recording formed on the medium. 6. The thermoreversible recording medium according to claim 3 or 4, wherein the support is made of a material transparent to visible light, and the support is provided on the side opposite to the thermoreversible recording layer. A thermoreversible recording medium comprising a reflective layer or a light-absorbing layer. 7. The thermoreversible recording medium according to claim 3, wherein the support has a property of changing a traveling direction of light incident on the support. Thermoreversible recording medium. 8. The thermoreversible recording medium according to claim 3, wherein the thermoreversible recording layer is provided separately from the thermoreversible recording layer.
A thermoreversible recording medium comprising a recording layer. 9. A thermoreversible recording device comprising a thermoreversible recording medium and a device for recording information on the medium and erasing information on the medium, wherein the thermoreversible recording medium is a thermoreversible recording medium. A thermoreversible recording apparatus using the thermoreversible recording medium according to claim 1.