JPH06135145A - Composite recording medium and production thereof - Google Patents

Abstract

PURPOSE:To provide a composite recording medium capable of performing both of recording due to transfer printing and thermal recording performed by changing a transparent state to an opaque state or the opaque state to the transparent state. CONSTITUTION:In a composite recording medium, a thermal recording layer is formed on a base material sheet and a transfer ink receiving layer having transparency is formed on the thermal recording layer and the recording to the thermal recording layer is performed by changing the layer from a transparent state to an opaque state or from the opaque state to the transparent state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a composite system in which ink recording by a heat-sensitive transfer ribbon and heat-sensitive recording consisting of changing a transparent state to an opaque state or changing an opaque state to a transparent state can be carried out in combination. The present invention relates to a recording medium and a manufacturing method thereof.

[0002]

2. Description of the Related Art A heat-sensitive recording medium for recording ink with a heat-sensitive transfer ribbon comprises a base sheet and a transfer ink receiving layer formed on the base sheet. Recording is accomplished by transferring the layer to a transfer ink receiving layer.

Further, a heat-sensitive recording medium in which recording is carried out by changing the heat-sensitive recording layer from a transparent state to an opaque state or from an opaque state to a transparent state is a base sheet and a base sheet. A heat-sensitive recording layer formed on the polymer layer, and as the heat-sensitive recording layer, for example, a resin layer in which fatty acid is dispersed in a polymer compound, a resin layer utilizing phase change of the polymer compound, and further a polymer compound A resin layer or the like in which liquid crystal is dispersed is used.

[0004]

SUMMARY OF THE INVENTION According to the present invention, variable information is recorded on a heat-sensitive recording layer interposed between an ink receiving layer and a substrate sheet, and fixed information is recorded on the ink receiving layer. Counterfeit by writing multiple types of recordings of different types, or by recording with an irreversible opaque portion on the heat-sensitive recording layer interposed between the ink receiving layer and the base sheet. Provided is a composite recording medium capable of achieving the purpose of measures such as prevention.

[0005]

The invention according to claim 1 has a substrate sheet, a heat-sensitive recording layer formed on the substrate sheet, and transparency formed on the heat-sensitive recording layer. A composite recording medium having a transfer ink receiving layer, wherein recording on the heat-sensitive recording layer is performed by changing the layer from a transparent state to an opaque state or from an opaque state to a transparent state.

According to a second aspect of the present invention, in the structure of the composite recording medium of the first aspect, the transparent recording ink receiving layer has a surface roughness of 0.1 μ to several μ.

According to a third aspect of the present invention, in the composite recording medium of the first or second aspect of the present invention, the transparent transfer ink receiving layer contains heat-resistant fine particles of 0.1 μm or less in the layer. Consists of a composite recording medium containing.

According to a fourth aspect of the present invention, in the composite recording medium of the first, second or third aspect of the present invention, a magnetic recording layer is formed on the front surface or the back surface of the base sheet. Consists of.

[0009] The invention of claim 5 is, claim 1, claim 2,
In the constitution of the composite recording medium of the invention of claim 3 or 4, the thermosensitive recording layer is formed of a composite recording medium formed between the base sheet and the reflective layer.

A sixth aspect of the present invention is the composite recording medium of the fifth aspect, wherein the reflective layer between the base sheet and the heat-sensitive recording layer is partially formed.

According to a seventh aspect of the present invention, there is provided a step of forming a heat-sensitive recording layer on a base material sheet for recording by changing from a transparent state to an opaque state or from an opaque state to a transparent state, and the heat-sensitive recording layer. A step of forming a coating layer containing an ultraviolet-curable oligomer containing a photopolymerization initiator on the entire upper surface, and a non-cured layer portion and a cured layer portion by partially irradiating the coating layer with ultraviolet rays To form a composite recording medium in which the non-cured layer portion serves as a protective layer for the transfer ink-receiving layer and the thermal recording layer, and the cured layer portion serves as a protective layer having transparency for the thermal recording layer. The manufacturing method of

The substrate sheet in the composite recording medium and the method for producing the same of the present invention having the above-mentioned structure is a sheet having rigidity required for the recording medium, for example, polyester film such as polyethylene terephthalate film and polybutylene terephthalate film, poly Acrylic resin films such as methyl methacrylate, polymethyl acrylate, polyethyl methacrylate, etc., as well as polystyrene films, acrylonitrile-butadiene-styrene copolymer films, cellulose triacetate films, polycarbonate films, polyvinyl chloride films, etc. A plastic film or high-quality paper having a thickness of about 10 to 500 μ is used.

A thermal recording layer is provided on the base sheet. This heat-sensitive recording layer may be formed directly on the base material sheet, or may be formed via a reflective layer.

The reflective layer, which is formed on the base sheet as required, is a transparent portion of the heat-sensitive recording layer on which recording is performed by changing from a transparent state to an opaque state or from an opaque state to a transparent state. It has the effect of giving reflexivity to.

The reflective layer is made of, for example, Cr, Ti, F.
e, Co, Ni, Cu, Ag, Au, Ge, Al, M
g, Sb, Pb, Pd, Cd, Bi, Sn, Se, I
Metals such as n, Ga and Rb, and oxides and nitrides thereof, or a combination of two or more, particularly,
It is preferably made of Al, Cr, Ni, Ag, Au, or the like, and is formed to have a thickness of about 200 to 2000 Å by, for example, a vacuum vapor deposition method, a sputtering method, a plating method, or the like. Also,
This reflective layer is formed of a cellulose derivative such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, or cellulose acetate, a styrene resin such as polyethylene or poly-α-methylstyrene, or a styrene copolymer resin, polymethyl methacrylate, polymethacrylic acid. Acrylic resin or methacrylic resin homo- or copolymer resin such as ethyl, ethyl polyacrylate, polybutyl acrylate, rosin, rosin-modified maleic acid resin, rosin-modified phenol resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, Various pigments are added to the binder such as coumarone resin, vinyltoluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin according to the color to be colored. Ordinary gravure method using a colored paint or ink prepared by adding agents, waxes, greases, desiccants, drying aids, curing agents, thickeners, dispersants, and then thoroughly kneading them with solvents or diluents. , Roll method,
It can also be formed as a colored layer by a coating method such as a knife edge method or an offset method or a printing method.

Further, the reflective layer may be partially formed, and a method for partially forming the reflective layer is as follows.
A conventionally known partial etching method, a masking method of forming a reflective layer through a mask, or a partial forming method of depositing oil on an unnecessary portion after forming the reflective layer on the entire surface can be used.

Since fixed information can be recorded on the reflecting layer made of a metal layer by partially melting and removing the reflecting layer, the layer can also be used as a fixed information recording layer. it can.

In the thermosensitive recording layer in which recording is performed by changing from the transparent state to the opaque state or from the opaque state to the transparent state, repetitive recording is performed due to the reversible change between the transparent state and the opaque state of the thermosensitive recording layer. In particular, a resin layer in which a fatty acid is dispersed in a polymer compound, a resin layer that utilizes the phase change of the polymer compound, and a liquid crystal is dispersed in the polymer compound. A resin layer or the like is used.

A thermosensitive recording layer comprising a resin layer in which a fatty acid is dispersed in a polymer compound, records and erases the record repeatedly by reversible change between transparent and opaque states of the thermosensitive recording layer. It is well known that it has the property of being capable of performing, and a matrix material made of at least one kind of resin, for example, vinyl chloride resin such as polyvinyl chloride / vinyl acetate copolymer, vinylidene chloride resin such as polyvinylidene chloride. , Ester resin, acrylic resin, methacrylic resin, urethane resin, phenol resin, silicon resin, melamine resin, epoxy resin, aryl resin, amide resin and their copolymers, modified products, Furthermore, a higher fatty acid comprising a mixture of these and at least one aliphatic monocarboxylic acid and / or aliphatic dicarboxylic acid For example, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid,
Saturated fatty acids such as heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heneicosanoic acid, heptacosanoic acid, montanic acid, melissic acid, laxeric acid, acrylic acid, crotonic acid, isocrotonic acid, hexadecene Acids, heptadecenoic acid, undecylenic acid, oleic acid, octadecenoic acid, elaidic acid, cetoleic acid, erucic acid, eleostearic acid, brassic acid, sorbic acid, propiolic acid, unsaturated fatty acids such as stearolic acid, oxalic acid, malon acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, mazelaic acid, sebacic acid, eicosane diacid,
Aliphatic dicarboxylic acids such as dodecane diacid, maleic acid, fumaric acid, and brassic acid are used.

For the purpose of widening the transparency temperature range of the thermosensitive recording layer comprising a resin layer in which fatty acid is dispersed in a polymer compound and increasing the contrast which is the ratio of the transparent state to the opaque state, the thermosensitive recording An organic low-molecular compound having a polyoxyethylene chain can be added to the layer. For example, polyoxyethylene fatty acid esters represented by [Chemical formula 1] and [Chemical formula 2], or represented by [Chemical formula 3] Polyoxyethylene alkyl ethers represented by [Chemical formula 4], polyoxyethylene alkyl phenyl ethers represented by [Chemical formula 5], polyoxyethylene sorbitan alkyl esters represented by [Chemical formula 5] Oxyethylene alkylamines and the like can be used.

[0021]

[Chemical 1]

[0022]

[Chemical 2]

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

When selecting the organic low molecular weight compound having the polyoxyethylene chain, a suitable one should be selected in combination with the aliphatic monocarboxylic acid and / or the aliphatic dicarboxylic acid used in combination. desirable.
For example, in a system of behenic acid / stearic acid, polyoxyethylene / alkyl phenyl ether and the like are preferable, and in a system of eicosane / 2. Acid / stearic acid, polyoxyethylene / sorbitan alkyl ester and the like are preferable. Of course, even if it is not such a specific combination, the transparency temperature range is wide by mixing the organic low molecular weight compound having the polyoxyethylene chain, and the transparency at the time of transparency and the opacity at the time of clouding A thermosensitive recording layer having a sufficient contrast, which is the ratio with the property, can be obtained.

The mixing amount of the organic low molecular weight compound having a polyoxyethylene chain is 50 to 500% by weight, preferably about 50 to 200% by weight, based on the total weight of the aliphatic monocarboxylic acid and the aliphatic dicarboxylic acid. Is. The organic low molecular weight compound having a polyoxyethylene chain is contained in the total amount of the aliphatic monocarboxylic acid and the aliphatic dicarboxylic acid is 50.
If it is less than wt%, the improvement effect of the addition by the organic low molecular weight compound cannot be measured, and the desired characteristics cannot be obtained. On the other hand, if it exceeds 500% by weight, reversibility of recording and erasing due to heating in the thermosensitive recording layer is impaired. Generally, the mixing amount of the organic low molecular weight compound having a polyoxyethylene chain is about the same as or more than the total weight of the aliphatic monocarboxylic acid and the aliphatic dicarboxylic acid. Is desirable.

The heat-sensitive recording layer comprising a resin layer utilizing the phase change of the polymer compound uses changes in optical properties such as the refractive index and the transmittance due to the reversible change of the crystalline / amorphous state of the polymer compound. are those recorded is obtained by, for example, _{"- {- S- (C 6 H} 4) -S-CH 2 -CH 2 -
_{(C 6 H 4) -CH 2} -CH 2} n - poly represented by "(1,4 benzenedithiol -CO-1,4-divinylbenzene) is transparent in the amorphous state (light transmittance 91 %
Above) has a high refractive index (1.81), becomes opaque (light transmittance of less than 1%) in a crystalline state, and has a thickness of 0.1 to 0.5.
When a μ thin film layer is used as a recording layer, it becomes transparent by heat recording at 170 ° C. for 1 to 2 seconds.
It becomes opaque again when heated for about 30 minutes, and recording and erasing of the recording on the thermosensitive recording layer can be reversibly repeated by utilizing such a mechanism.

The heat-sensitive recording layer composed of a resin layer in which liquid crystal is dispersed in a polymer compound is composed of a polymer material containing a polymer material having film-forming performance and a liquid crystal material-composite film layer. Then, it is usually formed as a composite film layer containing 10 to 500 parts by weight of a liquid crystal substance with respect to 100 parts by weight of a polymer substance having film forming performance.

A composite film layer composed of a polymer substance / liquid crystal substance containing a polymer substance having film forming performance and a liquid crystal substance,
A composite membrane layer in which a liquid crystal substance is dispersed substantially uniformly in a polymer substance having film-forming performance by a method such as a microencapsulation method, a solvent evaporation method, or a suspension polymerization method. The layer has recording properties and properties that allow the recorded information to be erased.

In the composite film layer composed of the polymer substance / liquid crystal substance, the polymer substance preferably has good film-forming ability and heat resistance. For example, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer Vinyl chloride resin such as coalesce, vinylidene chloride resin such as polyvinylidene chloride,
Polyester resins, polyamide resins, polyacrylates, polymethacrylates, acrylic resins such as acrylate / methacrylate copolymers, polyurethane resins, etc. are used. In addition, as the liquid crystal substance, a smectic liquid crystal polymer having a memory property, for example, BDH chemistry (BDH Chemi) of Pool, United Kingdom.
"Smectic A phase material S commercially available from Cal.
2 ”and Darmstadt (West Germany)
E.t. Merck Chemicals
K24, K30, K36, Z commercially available from
LI1840, CB15, etc. can be used.

In a composite film layer made of a polymer substance and a liquid crystal substance having film forming performance, if the liquid crystal substance is less than 10 parts by weight with respect to 100 parts by weight of the polymer substance, the printing sensitivity of the recording in the composite film layer. Is likely to be low, making it difficult to obtain clear recording. Further, when the amount of the liquid crystal material exceeds 500 parts by weight with respect to 100 parts by weight of the polymer material, the amount of liquid crystal leaching to the surface of the composite film layer increases, so that the surface of the composite film layer may be exposed. It tends to be difficult to form a protective resin layer. Therefore, in the composite film layer of the polymer substance / liquid crystal substance having film forming performance, the liquid crystal substances 10 to 5 are added to 100 parts by weight of the polymer substance having film forming performance.
It is preferable to use 100 parts by weight, more preferably 5 parts by weight.
About 0 to 200 parts by weight of liquid crystal material is used.

Further, in the composite film layer formed of the polymer substance and the liquid crystal substance, dichroic dye molecules matching the molecules of the liquid crystal substance in the composite film layer and having the same optical function as the liquid crystal substance are provided. By including it, the color of the recording portion can be made more clear. As this dichroic dye molecule, for example,
Indore Blue, Sudan Black B, Sudan 3, Sudan 2, and E.I. Merck Chemicals (E. Mer
D-3 commercially available from K Chemicals)
7, D-43, D-85 and the like can be used.

In the heat-sensitive recording layer comprising a composite film layer of a polymer substance and a liquid crystal substance containing a polymer substance having a film-forming property and a liquid crystal substance, the heat-sensitive recording layer is passed through an electric field by, for example, corona charging. And, since the liquid crystal molecules in the liquid crystal particles dispersed in the composite film layer of the polymer substance and the liquid crystal substance in the thermosensitive recording layer are aligned in the same direction, and the refractive index of the polymer substance and the liquid crystal substance are the same, The composite membrane layer appears transparent. When the heat-sensitive recording layer in such a state is heated, the alignment of liquid crystal molecules in the liquid crystal particles dispersed in the composite film layer of the polymer substance and the liquid crystal substance becomes random, and the refractive index of the polymer substance and the liquid crystal substance is changed. Therefore, only the heat-treated part is visually recognized as an opaque turbid state from the outside. Therefore, when the thermosensitive recording layer is again passed through the electric field, the molecular directions of the polymer substance and the liquid crystal substance in the composite film layer are aligned in the same direction. When the heat-sensitive recording layer coincides with a transparent state, recording on the heat-sensitive recording layer and erasing of the record can be repeated by reversible change between the transparent state and the opaque state of the heat-sensitive recording layer.

The transparent transfer ink receiving layer formed on the heat-sensitive recording layer is, for example, ethyl cellulose, cellulose nitrate, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose derivative such as cellulose acetate, polystyrene, Poly-α-
Styrene resins such as methyl styrene and styrene copolymer resins, homo- or copolymer resins of acrylic or methacrylic acid esters such as polymethyl methacrylate, polyethyl methacrylate, ethyl polyacrylate, polyacryl butyl, polyester resins, poly Vinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin and other vinyl polymers, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, polymerized rosin and other rosin ester resins, coumarone resin, vinyl Other resins such as toluene resin, polyurethane, polyamide resin, etc.
The thickness is about 10 μm.

As the UV-curable resin, a mixed resin composition containing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used. Specific examples of the prepolymer and oligomer are
In addition to unsaturated polyesters such as condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, melamine methacrylate, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate , Acrylates such as polyol acrylate, melamine acrylate and silicone modified acrylate are used. Further, specific examples of the monomer include styrene, a styrene-based monomer such as α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate,
Acrylic esters with butyl acrylate, methoxybutyl acrylate, phenyl acrylate, etc., Methacrylic acid esters with methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, etc. , 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, -2- (N, N-dibenzylamino) ethyl acrylate, methacrylic acid-2 Substituted amino alcohol esters of unsaturated acids with-(N, N-dimethylamino) methyl, 2- (N, N-diethylamino) propyl acrylate, etc., unsaturated carboxylic acid amides with acrylamide, methacrylamide, etc., ethylene glycol Diacrylate, B propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6
Hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate and other diacrylate compounds, dipropylene glycol diacrylate, ethylene glycol acrylate,
Polythiol having two or more thiol groups in the molecule such as propylene glycol dimethacrylate, polyfunctional compound such as diethylene glycol dimethacrylate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol, etc. A compound or the like is used.

In the case of forming a transfer ink receiving layer of an ultraviolet curable resin, in consideration of the coating suitability of the coating agent, usually 5 of the above-mentioned prepolymers or oligomers is used.
˜95% by weight, and 95 to 5% by weight of the monomer and / or polythiol compound, and / or ethyl cellulose, cellulose nitrate described above as the transfer ink receiving layer,
Cellulose derivatives such as ethyl hydroxyethyl cellulose, cellulose acetate propionate and cellulose acetate, polystyrene, styrene resins such as poly-α-methylstyrene and styrene copolymer resins, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate. , Homopolymer or copolymer resin of acrylic or methacrylic acid ester such as polyacrylbutyl, vinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl polymer such as polyvinyl butyral resin, rosin, rosin-modified maleic acid A mixed composition with an acid resin, a rosin-modified phenol resin, a rosin ester resin such as a polymerized rosin, a coumarone resin, a vinyltoluene resin, a polyurethane, a polyamide resin or the like and 0 to 50% by weight of another resin is used.

In addition, in the coating agent of the ultraviolet curable resin, for example, a photopolymerization initiator such as acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylmeuram monosulfide, thioxanthone, etc. And a photosensitizer optionally added, for example, a photosensitizer based on n-butylamine, triethylamine, tri-n-butylphosphine, or the like.

The coating agent for forming the ink receiving layer for transfer is, for example, roll coat, curtain flow coat, wire bar coat, reverse coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth. It is performed by a coat, comma coat, etc.

Further, the transfer ink-receiving layer made of the ultraviolet-curable resin may be partially cured by masking it during irradiation of ultraviolet rays. In this case, the layer is treated as a transfer ink-receiving layer and a protective layer. In addition, it is possible to divide in the plane direction. Curing of the ultraviolet curable resin layer is carried out by ultraviolet irradiation of a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp and a metal halide lamp.

The transfer ink receiving layer has transparency, and moreover, since the thermal recording tool is repeatedly contacted when the variable information is repeatedly recorded on the thermal recording layer, It must have higher durability than a normal transfer ink receiving layer, and must have excellent heat resistance, abrasion resistance, smoothness, and the like. For this reason, the transfer ink-receiving layer contains heat-resistant fine particles of 0.1 μ or less in the transfer ink-receiving layer, and more than 0.1 μ to several μm.
It is preferable to have a surface roughness of.

That is, the ink receiving layer for transfer containing heat-resistant fine particles of 0.1 μm or less has good absorption of ink in the transfer ribbon and has a surface roughness of 0.1 μm to several μm. The transfer ink receiving layer has good transferability and adhesiveness of the ink in the transfer ribbon. As the heat-resistant fine particles, fine particle powder having a melting point of 150 ° C. or higher, for example,
Micro silica, Teflon powder, etc. are used. Further, if the surface roughness of the transfer ink receiving layer exceeds several μ, the thermal recording tool may be used during thermal recording on the thermal recording layer existing between the transfer ink receiving layer and the substrate sheet. This is not preferable because the heat conduction to the heat-sensitive recording layer becomes poor.

The magnetic recording layer formed on the front surface or the back surface of the base material sheet as required enables the composite recording medium of the present invention to be used in combination with magnetic recording.
For example, Fe ₃ O ₄ , γ-Fe ₂ O ₃ , Co deposited γ-F
e ₂ O _3, oxides of Ba ferrite magnetic powder or Fe, F
It is formed as a black or colored coating layer by a coating agent in which magnetic metal powder such as e-Co alloy and an organic pigment such as carbon are uniformly dispersed in a synthetic resin binder, or, for example, Co, Co It is formed as a high coercive force metal thin film by Ni vapor deposition or a sputtered film.

Further, in the composite recording medium of the present invention, a protective layer may be formed after transfer printing is formed on the transfer ink-receiving layer, or a heat-sensitive recording layer not covered with the transfer ink-receiving layer. A protective layer may be formed on the surface of the.

The composite recording medium of the present invention having the above structure is used in the form of a transfer foil, a label, a sheet, a card or the like.

[0047]

In the composite recording medium of the present invention, a thermal printer,
Recording by a reversible state between a transparent state and an opaque state and erasing of the recording are performed on a thermal recording layer by a thermal head or the like, and ink recording is performed on a transfer ink receiving layer by a thermal transfer ribbon. .

Therefore, the variable information recorded by the former recording and the fixed information recorded by the latter can be recorded separately. Therefore, for example, when the composite recording medium of the present invention is used for a commuter pass of a transportation facility, the station name of the used section is recorded as fixed information in the transfer ink receiving layer and is recorded in the transfer ink receiving layer. If the station name of the commuter pass user's daily bid and the issue of the commuter pass is recorded as variable information in the area of the heat-sensitive recording layer that does not correspond to the area where the commuter pass is illegally used, a so-called check-up such as a boarding You can do it easily.

Further, recording on the heat-sensitive recording layer by extreme heating, that is, recording on which excessive heat is applied, can make the recording on the heat-sensitive recording layer immovable.
For example, by placing the same thermosensitive recording as the fixed information on the thermosensitive recording layer immediately below at least a part of the fixed information recorded on the transfer ink receiving layer by extreme heating,
It is possible to prevent falsification of fixed information recorded on the transfer ink receiving layer.

Further, in recording on the composite recording medium of the present invention, transfer recording on the ink receiving layer for transfer and thermal recording on the heat-sensitive recording layer can be carried out by the same thermal printer, so that the printing apparatus is compact. become.

Recording on the composite recording medium of the present invention is
By adjusting the sensitivity of the heat-sensitive recording layer or by adjusting the thickness of the transfer ink-receiving layer, it is possible to print with the same thermal printer and with the same energy. The sensitivity of the thermal recording layer can be adjusted by
For example, in the case of a heat-sensitive recording layer in which a low molecular weight organic compound is dispersed in a matrix composed of a high molecular weight compound, the phase transition temperature of the low molecular weight organic compound, the dispersed particle size, the addition amount, etc. may be adjusted. It

[0052]

EXAMPLES The specific structure of the composite recording medium of the present invention will be described below with reference to examples.

Example 1 After forming a reflective layer of a 400 Å-thick aluminum vapor-deposited layer on the surface of a base sheet made of a biaxially stretched polyethylene terephthalate film having a thickness of 188 μ by a vacuum vapor deposition method, and then on the reflective layer, A coating agent consisting of a mixed solution of 8 parts by weight of behenic acid, 20 parts by weight of vinyl chloride-vinyl acetate copolymer (VYHH manufactured by UCC Co., Ltd.) and 160 parts by weight of tetrahydrofuran was applied and dried to obtain a thermal recording having a thickness of about 10 μm. Layers were formed. The thermosensitive recording layer is composed of a resin layer in which a fatty acid is dispersed in a polymer compound, and recording and erasing of the thermosensitive recording layer are performed according to a transparent state and an opaque state of the thermosensitive recording layer. It has the property that it can be repeatedly performed by reversible changes between.

Then, on the heat-sensitive recording layer, a butyl acetate solution of a urethane acrylate-based UV-curable resin containing Teflon powder (Dainippon Ink and Chemicals Incorporated)
Co., Ltd .: Unidick 17-824-9) is applied with a wire bar, and after heating and drying, a stainless steel shielding plate is applied, and 80 w / c is applied only to predetermined openings.
The transparent transfer ink-receiving layer having a thickness of about 2 μm is formed by irradiating a UV lamp of m for 5 seconds.
A composite recording medium as an example product was obtained.

Example 2 A substrate having a thickness of 188 μ and a milk-white polyethylene terephthalate film was coated on the surface of the substrate sheet with a thickness of 40 by vacuum deposition.
After forming a 0Å aluminum layer, an etching resistant layer having a predetermined pattern was formed by a silk screen printing method. Next, this sheet is immersed in an alkaline etching solution for 30 seconds to dissolve the aluminum layer in the portion not covered with the etching resistant layer, and then the etching resistant layer is removed to form a partial reflection layer of the aluminum layer having a predetermined pattern. Formed.

Subsequently, the same step as the corresponding step in the manufacturing process of the composite recording medium of Example 1 is sequentially performed on the surface on which the partially reflective layer is formed, to form a composite of another Example of the present invention. A recording medium was obtained.

[Experiment] The composite recording medium obtained in Example 1 was heated to 100 ° C. to make the thermosensitive recording layer completely cloudy and opaque, and then 0.3 mJ / do by a thermal head.
When the energy of t was applied, the thermosensitive recording layer was changed to a transparent state, and the reflective layer laminated under the thermosensitive recording layer was visually recognized through the thermosensitive recording layer.

Subsequently, when energy of 0.6 mJ / dot was applied to the composite recording medium by the thermal head, the thermosensitive recording layer became completely cloudy and opaque, and the reflective layer was completely erased by the thermosensitive recording layer. Was hidden in.

On the surface of the obtained composite recording medium, that is, on the surface of the transfer ink receiving layer, thermal transfer was carried out using a transfer ink ribbon having a transfer layer composed of a colored wax layer, and predetermined fixed information was recorded.

Further, the composite recording medium obtained in Example 2 was subjected to the rewriting operation by the same thermal head as in the composite recording medium of Example 1, and the change between the transparent state and the opaque state was observed. Was perfect.

Further, when a transfer ink ribbon having a transfer layer composed of a colored wax layer was used to perform thermal transfer on the surface of the transfer ink receiving layer above the portion where the reflective layer is missing, a transfer ink receiving layer was formed. The printed image was visually recognized with the milky white color of the substrate sheet as the background color and could be read extremely clearly.

From the above facts, it was confirmed that the composite recording medium according to the embodiment example can be used as an area for recording variable information other than the fixed information area on the transfer ink receiving layer surface.

[0063]

[Effect] The composite recording medium of the present invention can be used in combination with ink recording by a heat-sensitive transfer ribbon and heat-sensitive recording consisting of changing from a transparent state to an opaque state or from an opaque state to a transparent state. Further, for example, it is possible to very effectively prevent illegal use or tampering of the commuter pass of the transportation means, and therefore, a great practical effect is achieved.

Claims (7)

[Claims] 1. A base sheet, a heat-sensitive recording layer formed on the base sheet, and a transparent transfer ink receiving layer formed on the heat-sensitive recording layer. Moreover, the composite recording medium is characterized in that the recording on the thermosensitive recording layer is performed by changing the layer from a transparent state to an opaque state or from an opaque state to a transparent state. 2. The composite recording medium according to claim 1, wherein the surface roughness of the transparent ink receiving layer for transfer is 0.1 μm to several μm. 3. The composite recording medium according to claim 1, wherein the transparent ink receiving layer for transfer contains heat-resistant fine particles of 0.1 μm or less in the layer. 4. The composite recording medium according to claim 1, which has a magnetic recording layer on the front surface or the back surface of the base material sheet. 5. The composite recording medium according to claim 1, wherein the heat-sensitive recording layer is formed between the heat-sensitive recording layer and the substrate sheet with a reflective layer interposed therebetween. 6. The composite recording medium according to claim 5, wherein the reflective layer is partially formed. 7. A thermosensitive recording layer on which recording is performed by changing from a transparent state to an opaque state or from an opaque state to a transparent state is formed on a substrate sheet, and then photopolymerized on the entire surface of the thermosensitive recording layer. Form a coating layer containing an ultraviolet curable oligomer containing an initiator, then,
The coating layer is partially irradiated with ultraviolet rays to form a non-cured layer portion and a cured layer portion, the non-cured layer portion serves as a protective layer for the transfer ink-receiving layer and the thermosensitive recording layer, and the cured layer portion A method for producing a composite recording medium, which is a protective layer having transparency to a heat-sensitive recording layer.