JP2704586B2 - Thermal recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a physical device by heating which is used, for example, as a printout for a computer, a recording paper for facsimile reception, a ticket such as a ticket, a boarding pass, a label, a card, etc., particularly a prepaid card. The present invention relates to a heat-sensitive recording medium for performing recording such as printing by means of a target change.

[0002]

2. Description of the Related Art In general, a so-called thermal recording system in which an image display of characters or the like is obtained by utilizing a physical or chemical change of a substance by heat energy such as heating or the like, noise is generated at the time of recording. It is widely used not only for copying machines, but also for computer printouts, facsimile reception records, tickets, labels, and various types of cards. Have been. As a recording medium used in this thermal recording method, for example, a recording medium using a leuco body such as a fluoran dye as a coloring agent is widely used because of its excellent heat sensitivity. However, these have a problem in that they easily develop color even by pressure, an organic solvent such as alcohol, and also have a problem in light resistance, heat resistance, water resistance, and storage stability of print records.

For this reason, for example, a thermosensitive recording medium using a metal thin film layer has been put to practical use. This recording medium destroys the metal thin film layer based on a pattern of an image to be recorded by a heat source such as a thermal head, a laser beam, or a flash light, and exposes a colored layer provided below the metal thin film layer. Thus, an image is formed. Therefore, since the image display such as printing is formed by the contour of the metal thin film layer, its light resistance, heat resistance, water resistance and storage stability of the printed record are based on the thermosensitive recording medium using the above-described dye as a coloring agent. Excellent compared to.

[0004]

When a heat-sensitive recording medium using a metal thin-film layer is used for a prepaid card, a ticket, a label, etc., the metal thin-film layer is practically subjected to physical stimuli such as friction and scratching. It is necessary to provide a protective layer as an uppermost layer in order to protect against chemicals such as acid, alkali and alcohol. It is generally known that the protective layer contains a heat-resistant resin such as an acrylic resin or an epoxy resin and contains an appropriate amount of an inorganic or organic pigment and a lubricant such as wax or silicone. Further, JP-A-59-1992
No. 84, Japanese Patent Application Laid-Open No. 2-62287, and the like also disclose a technique in which the protective layer has a multi-layer structure, and the functions required for improving the above-mentioned required characteristics are separated by separating the functions of surface strength and adhesiveness with a medium.

[0005] However, even in a recording medium provided with such a protective layer, there is a problem that the protective layer is peeled off in a severe case where the card is erroneously washed, for example, when used as a prepaid card. Was. Further, in a field of application as a so-called magnetic card having a magnetic recording layer, there has been a problem that a protective layer is cut off by high-speed conveyance as seen in an automatic ticket gate and the like. Further, there has been a problem that the chemical resistance of the metal thin film layer is remarkably reduced due to peeling and scraping of the protective layer. The present invention has been made in view of the above circumstances, and has as its object to provide an excellent recording medium against physical stimuli such as friction and scratching and chemicals such as acids, alkalis, and alcohols.

[0006]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
In a heat-sensitive recording medium including a coloring layer (or a magnetic recording layer), a metal thin film layer, an adhesive layer, and a protective layer which are sequentially formed, the adhesive layer contains at least a modified silicone oil in a total solid content ratio in the adhesive layer. It is a thermosensitive recording medium characterized by containing 0.1 to 5% by weight. The present invention also provides a support having a magnetic recording layer on one surface, a colored layer (or a magnetic recording layer) formed sequentially, a metal thin film layer, an adhesive layer,
A heat-sensitive recording medium comprising a protective layer, wherein the adhesive layer contains at least 0.1 to 5% by weight of a modified silicone oil in a total solid content ratio in the adhesive layer. is there.

According to the present invention, since the protective layer is firmly fixed on the metal thin film layer by containing at least the modified silicone oil in the adhesive layer, peeling of the protective layer from strong physical impact is prevented. it can. Further, since the modified silicone oil has water repellency, it is possible to prevent chemicals such as saline, acid, alkali and the like from being mixed.

Hereinafter, the present invention will be described in detail with reference to the drawings. The thermosensitive recording medium of the present invention comprises a support 1, a colored layer 2,
It is composed of a combination of a metal thin film layer 3, an adhesive layer 4, a protective layer 5, an anchor layer 6, and a magnetic recording layer 7, and examples of the layer structure are shown in FIGS. That is, FIG. 1 shows a basic configuration including essential components constituting the thermal recording medium of the present invention,
The thermosensitive recording medium is obtained by sequentially laminating a colored layer 2, a metal thin film layer 3, an adhesive layer 4, and a protective layer 5 on one side of a support 1. In the thermal recording medium of the present invention, the laminated structure of the colored layer, the metal thin film layer, the adhesive layer and the protective layer in FIG. 1 may be provided on both sides of the support.

The thermosensitive recording medium shown in FIG. 2 has a structure in which an anchor layer 6 is provided between a colored layer 2 and a metal thin film layer 3. The thermosensitive recording medium of FIG. 3 has a configuration in which a magnetic recording layer 7 is provided instead of the colored layer 2 of FIG. In the thermal recording medium of the present invention, the laminated structure of the colored layer, the metal thin film layer, the adhesive layer and the protective layer in FIG. 3 may be provided on both sides of the support. Further, the thermosensitive recording medium of FIG. 4 has a configuration in which the anchor layer 6 of FIG. 3 is provided between the magnetic layer 7 and the metal thin film layer 3. The thermosensitive recording medium of FIG. 5 has a configuration in which a magnetic recording layer 7 and a protective layer (II) 8 are sequentially provided on the support 1 opposite to the metal thin film layer 3 of FIG. In the thermal recording medium of the present invention, the laminated structure of the colored layer, the metal thin film layer, the adhesive layer and the protective layer in FIG. 3 may be provided on both sides of the support. The thermosensitive recording medium of FIG. 6 has a configuration in which a magnetic recording layer 7 and a protective layer (II) 8 are sequentially provided on the support 1 opposite to the metal thin film layer 3 of FIG.

Each of the above-mentioned layers will be specifically described. As the support 1 used in the present invention, a conventionally known film, paper, glass, metal or the like can be used as it is. Specific examples thereof include various heat-resistant resin films such as polyethylene terephthalate (PET), polyimide, polyether, polycarbonate, polysulfone, cellophane, and aromatic polyamide, and condenser paper, sulfuric acid paper, art paper, name paper, and coated paper. , Laminated paper,
Paper base such as polyethylene synthetic paper, glass base such as quartz,
A metal substrate such as aluminum can be suitably used.

The coloring layer 2 is capable of displaying an image when it is optically exposed by heating the metal thin film layer 3 in accordance with the formation of an image pattern. After adding various organic and inorganic coloring pigments or coloring dyes, adding plasticizers, stabilizers, waxes, curing agents, and dispersants as necessary, kneading them sufficiently with a solvent or diluent. It is formed by a coating method or a printing method such as a so-called gravure method, a roll method, a knife edge method, and an offset method using the colored paint or ink thus obtained. As the binder, for example, ethyl cellulose, hydroxyethyl cellulose,
Cellulose acetate propionate, cellulose derivatives such as cellulose acetate, polystyrene, styrene resin or styrene copolymer resin such as poly-α-methylstyrene, acrylic resin or methacrylic resin such as polybutyl methacrylate homo- or copolymer resin, rosin , Rosin modified phenolic resin, rosin modified maleic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin,
Coumarone resin, vinyl toluene resin, vinyl chloride resin,
Resins such as polyester resin, polyurethane resin and butyral resin alone or copolymers of these resins are used.

As the colorant, pigments, dyes and the like can be used.
As specific examples of the color pigment, as the cyan pigment, diaseriton fast brilliant blue-R (manufactured by Mitsubishi Kasei Co., Ltd., trade name), Kayaron Polyester Bull-B-SF Conc (trade name, manufactured by Nippon Kayaku Co., Ltd.) As magenta color pigments, Diaseriton Fast Red R (manufactured by Mitsubishi Kasei Corporation,
Kayaron polyester light yellow 5GS (manufactured by Nippon Kayaku Co., Ltd., trade name) such as Kayaron Polyester Pink RCL-E (manufactured by Nippon Kayaku Co., Ltd.) Innerro-GRH (trade name, manufactured by Hodogaya Chemical Co., Ltd.) and the like can be mentioned. Further, as a cyan pigment, celerian bull-, phthalocyanine bull-and the like, magenta pigments such as brilliant carmine, alzaline lake, yellow pigments such as Hansa Yellow, bisazo yellow, etc., black pigments such as carbon black, graphite, Oil black and the like can be mentioned. Further, metals such as Fe, Ni and Al, Fe ₂
Metal oxides such as O ₃ and SnO ₂ can also be used. The coloring dye can be selected from disperse dyes, oil-soluble dyes, acid dyes, mordant dyes, vat dyes, basic dyes and the like, which are generally used in transfer printing of textiles and thermal transfer inks. Specific examples thereof include azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone, azomethine, coumarin, and condensed polycyclic dyes. Further, phosphorescent / fluorescent pigments and the like can also be used.

The metal thin film layer 3 is made of Te, Sn, Al, B
a metal such as i, Pb, Zn or an alloy thereof, or a compound of the above metal such as Te carbide,
It can be formed on the upper surface of the colored layer 2 provided on the support 1 by a sputtering method, a CVD method, a plating method, or the like.
In this case, the metal thin film layer 3 preferably has a low melting point so that it can be used as a heat-sensitive recording layer, and has a thickness of 100 ° to 1 μm, preferably 300 to 600 μm.
About Å.

The present invention is characterized in that the constituent material of the adhesive layer 4 contains at least a modified silicone oil. As the resin used for the adhesive layer 4,
It has the function of improving the mutual adhesion between the metal thin film layer 3 and the protective layer 5 and physically and scientifically protecting the metal thin film layer 3 together with the protective layer 5. A material having a function of promoting the destruction of the metal thin film layer 3 by thermal recording and improving the thermal energy sensitivity is selected. Specific examples include polyester resins, polyurethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, epoxy resins, cellulose resins, amino alkyd resins, and the like. These resins can be used alone or
Mixing of more than one species can be used.

As the modified silicone oil of the present invention, a silicone oil in which various organic groups are introduced into a part of the methyl group of dimethylpolysiloxane is preferably used. Specific examples of the modified silicone oil include olefin-modified silicone oil, methylstyrene-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, and carboxyl-modified silicone oil. And higher fatty acid-modified silicone oils, silicone diols and silicone diamines.

The formulas of these modified silicone oils are as follows.

Embedded image

Olefin-modified silicone oil: Formula I
In the above compound, R is a methyl group and A is an alkyl group having 2 to 30 carbon atoms. Methylstyrene-based silicone oil: In the formula I,
A compound wherein R is a methyl group and A is an α-methylphenylethyl group. Polyether-modified silicone oil: In formula I:
R is a methyl group, A is _{-CH 2 CH 2 O (C 2} H 4
_{O) a (C 3 H 6} O) b R 1 (a and b is 1 to 50 integer, R ¹ is a compound represented by an alkyl group).

Alcohol-modified silicone oil: Formula I
Wherein the one R and / or A is a hydroxyalkyl group having 1 to 30 carbon atoms, and the remainder is a methyl group. Silicone diol: In the formula I, R represents 1 to 1 carbon atoms.
A compound wherein the hydroxyalkyl group is 30 and A is a methyl group. Mercapto-modified silicone oil: In formula I, R
There is a methyl group, compounds wherein A is -CH ₂ CH ₂ CH ₂ SH.

Epoxy-modified silicone oil: In formula I, at least one of R and A is

Embedded image (A represents an integer of 1 to 30), and the remainder is a methyl group. Carboxyl-modified silicone oil: In Formula I:
R is a methyl group and A is -Cx HxaCOOH (x, a
Is an integer of 1 to 30). Higher fatty acid modified silicone oil: In formula I, A
There is methyl radical, R is -R ² OCOR ³ (R ² is C ₁
-C ₃₀ alkylene group, and R ³ represents a C ₁ -C ₃₀ alkyl group).

Silicone diamine: In formula I, A
Is a methyl group and R is an aminopropyl group. Amino-modified silicone oil: General formula

Embedded image (Where m and n are integers of 1 or more, R is a methyl group or a methoxy group, B is —CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH
Compounds represented by ₂ or an _{-CH 2 CH 2 CH 2 NH 2} ).

These modified silicone oils can be used alone or in combination of two or more. The modified silicone oil of the present invention is not particularly limited to the modified silicone oil shown in the above specific examples. It is necessary that the content of the modified silicone oil in the adhesive layer is in the range of 0.1 to 5% by weight based on the total solid content in the adhesive layer. More preferably, the range is 0.5 to 2% by weight. When the content of the modified silicone oil is less than 0.1% by weight, the adhesive strength with the metal thin film layer 3 is reduced, and the protective layer 5 is peeled off by physical impact. Where the protective layer 5 is peeled off, the metal thin film layer 3 is exposed on the surface portion, so that the chemical resistance deteriorates. In addition, chemical resistance is deteriorated because the water repellency is reduced. If the content is more than 5% by weight, the entire adhesive layer becomes considerably softer thermally,
Heat resistance and abrasion resistance deteriorate, and the ability to protect the metal thin film layer from physical impact, chemicals, and the like is significantly reduced. Further, this decrease in heat resistance also causes sticking and scum adhesion that shortens the life of the thermal head.

The thickness of the adhesive layer is desirably in the range of 0.1 to 5 μm. Preferably, the range is 1 to 2 μm. If the thickness is less than 0.1, chemical resistance and resistance to physical impact deteriorate. When the thickness is more than 5 μm, the printing energy attitude is deteriorated. Since unmodified silicone oil has water repellency and oil repellency, problems such as cissing occur when the protective layer 5 is provided by coating or the like. Also, the adhesive strength with the protective layer 5 is poor. The adhesive layer 4 includes the above-mentioned resin and the above-mentioned oils and fats as necessary, together with an organic / inorganic pigment (including the above-mentioned coloring pigment), a plasticizer, a stabilizer, a curing agent, a dispersant, and an organic solvent. Using a coating or ink prepared by sufficiently dispersing, dissolving and mixing with a stirrer, forming on the metal thin film layer 3 by a known coating method such as a gravure method, a roll method, a knife edge method, an offset method or a printing method. Is done.

Like the adhesive layer 4, the protective layer 5 must be designed to physically and chemically protect the metal thin film layer 3 and to prevent sticking and adhesion of scum during thermal recording. . According to the present invention, the protective layer 5 is configured to be composed of at least a heat-resistant resin and a lubricant.
Hereinafter, the material of the protective layer 5 will be specifically described. The heat-resistant resin is, for example, a polyester resin, a polyurethane resin, an epoxy resin, various cellulose resins, a polyimide resin, a polyamide resin, a polyarylate resin, a polycarbonate resin, a phenol resin, an alkyd resin, Melamine-based resin, styrene-based resin, silicone-based resin, fluorine-based resin, and thermoplastic resins composed of copolymers among these resins, thermosetting resins, UV-curable resins, and EB-curable resins , Whose glass transition point (Tg) is selected to be 30 ° C. or higher, preferably 50 ° C. or higher. here,
If the Tg is lower than 30 ° C., sticking may occur or the abrasion resistance may decrease during thermal recording.

The above lubricant has a function of preventing sticking with the thermal head, reducing the coefficient of friction and improving abrasion resistance, and includes waxes such as polyethylene wax, paraffin wax and microcrystalline wax. , Zinc stearate, higher fatty acid metal salts such as calcium stearate, stearamide,
Known materials such as oils and fats such as higher fatty acid amides such as behenic acid amide, silicone oil, fine powder of Teflon, and fine powder of boron nitride are used.If necessary, silica, calcium carbonate, magnesium hydroxide, zeolite, clay ,
Heat resistant inorganic pigments such as talc may also be used. The particle size of the pigment used is preferably in the range of 0.1 to 10 μm, particularly preferably 1 to 5 μm. The protective layer 5 is also formed on the adhesive layer by the same method as the adhesive layer 4. The thickness of the protective layer 5 is preferably in the range of 0.1 to 5, particularly 1 to 2 μm, for the same reason as for the adhesive layer 4.

The content ratios of the binder, lubricant and pigment are preferably 50 to 95% by weight and 2 to 30% by weight, respectively.
% By weight, 2 to 40% by weight. If the content of the lubricant is less than 2% by weight, the abrasion resistance is deteriorated.
Sticking occurs. If the content exceeds 30% by weight, the heat resistance of the protective layer is deteriorated, and scum adheres to the thermal head. When the content of the pigment is less than 2% by weight, the adhesion of scum to the thermal head increases. If it exceeds 40% by weight, the background density increases, the appearance deteriorates, and the thermal head becomes remarkable.

The anchor layer 6 includes the colored layer 2 and the metal thin film layer 3
These layers have a function of improving their mutual adhesiveness and promoting the destruction of the metal thin film layer 3 during thermal recording, thereby improving thermal energy sensitivity. Therefore, a resin having an appropriate thermoplasticity, specifically, for example, an acrylic resin such as polystyrene and polymethacryl methacrylate, a cellulose resin such as cellulose acetate propionate, a vinyl chloride-vinyl acetate copolymer, and a polyester resin , Polyurethane resin,
Epoxy resins, amino alkyd resins and copolymers of these resins can be used alone or as a mixture of two or more. In order to further control the thermoplasticity, a heat-fusible substance such as a plasticizer or wax may be added,
Further, a curing agent may be added to impart a certain solvent resistance to facilitate the formation of the next layer. Further, in order to control the glossiness of the metal thin film layer, a pigment which can be used in the above-described protective layer 5 may be added. The anchor layer 6 is also formed in the same manner as the adhesive layer 4 and the protective layer 5 described above.
The thickness of the anchor layer is not particularly limited. However, when the coloring layer is a magnetic recording layer, the characteristics of the magnetic recording layer are taken into consideration, because if the anchor layer is thick, reading and writing of magnetic recording will be hindered. And decide.

The magnetic recording layer 7 is formed by dispersing a magnetic material in a binder resin, and has a function of recording data or the like relating to image display or having an appropriate configuration. Data can be read and written by a magnetic card reading and writing device.
As the magnetic material, Fe ₂ O ₃ , barium ferrite and other ferrites, magnetite and the like, iron, nickel, manganese, metals such as chromium or alloys thereof, and any known materials can be used, Also,
As the binder resin, those exemplified for the colored layer can be similarly used. The thickness of the magnetic recording layer is usually 0.1
It is set in the range of ３０30 μm. The magnetic recording layer 7 according to the present invention may be a single layer or may be composed of a laminate of two layers having different magnetic properties. The magnetic recording layer 7 may be a solid coating layer on the entire surface, or a partial coating layer such as a stripe shape and a bar code shape. In the present invention, when the magnetic recording layer is provided between the support and the metal thin film layer, the colored layer does not necessarily have to be provided.

When a pigment having an average particle size of 1 to 5 μm is mixed into at least one of the anchor layer 6 and the coloring layer 2, the glare of the coating layer is reduced, This makes the recorded image display easy to see. When the average particle size of the pigment is less than 1 μm, the effect of preventing glare is not exhibited, and when the average particle size is 10 μm or less, the unevenness of the surface becomes large, so that the contact area with the heat-sensitive head becomes small, and printing is performed. Thermal recording, such as chipping and missing printing, will not be performed sufficiently. As the pigment, for example, silica, calcium carbonate aluminum hydroxide, clay, inorganic white pigments such as talc, crosslinked polystyrene, polyethylene beads, organic transparent or white pigments such as silicone beads, lead red, ultramarine, titanium yellow, Color pigments such as red-mouthed graphite and plastic-type fluorescent pigments can be used. The material of the protective layer 5 can be applied to the protective layer (II) 8 as it is.

The thermal recording medium of the present invention is configured as described above, and an image is reliably formed by a physical change due to the thermal energy of the thermal head. In addition, since the surface is covered with a protective layer, it has heat resistance, light resistance, and chemical resistance. Further, by forming a magnetic recording layer, for example, when used as a prepaid card, a discharge method is used. Since it is used for any of the thermal recording methods, a highly versatile prepaid card can be provided. Next, examples of the thermosensitive recording medium according to the present invention will be described.

[0030]

Example 1 A thermosensitive recording medium of the present invention was produced by sequentially laminating the surface of a support of a milky white polyethylene terephthalate film having a thickness of 188 μm by coating the following layers. 1. Colored layer: After being dried at a drying temperature of 110 ° C., the composition having the following composition was applied on a support so that the thickness and the surface smoothness were 3 μm and 500 seconds, respectively.・ 36 parts of linear polyester resin (manufactured by Toyobo: Byron 200) ・ 5 parts of carbon ・ 5 parts of fine powdered silica (manufactured by Tokuyama Soda: fine seal X70, average particle size 2.0 μm) ・ 2 parts of isocyanate-based curing agent ( Nippon Polyurethane Co .: Coronate L)-93 parts of methyl ethyl ketone-51 parts of toluene

2. Metal thin film layer: when the tin is measured by a film thickness measurement method using a quartz oscillator method by a vacuum evaporation method, 60
It vapor-deposited so that it might become 0 degree. 3. Adhesive layer: The composition having the following composition was applied at a drying temperature of 110 ° C. to a thickness of 1.0 μm after drying to form an adhesive layer of the present invention.・ Vinyl chloride-vinyl acetate copolymer (VACH: 67 parts) ・ Acrylic resin (acid value: 54, OH value: 36, Tg: 86 ° C.) 28 parts ・ Olefin modified silicone oil 2 parts (Shin-Etsu Chemical) Industrial Company: KF-413) ・ Methyl ethyl ketone 300 parts ・ Toluene 600 parts

4. Protective layer: The protective layer of the present invention was formed by applying a composition having the following composition so as to have a thickness of 1.0 μm after drying at a drying temperature of 110 ° C. 16 parts of epoxy resin (Yuika Shell Epoxy: Epicoat 1010 Tg85 ° C) 16 parts of polyester resin (Toyobo: Byron 290 Tg80 ° C) 16 parts Lubricant (Mitsui Chemicals: Mitsui High Wax 100P) 4 parts Pigment 4 parts Tetrafluoroethylene (KTL500F, manufactured by Kitamura Co.)-190 parts of toluene-190 parts of methyl ethyl ketone

Example 2 A thermosensitive recording medium of the present invention was prepared by sequentially laminating the following layers on the surface of a 188 μm-thick milk-white polyethylene terephthalate film support by coating or the like. 1. Colored layer (magnetic layer), magnetic resistance powder: Barium ferrite 100 parts _{BaO · 6 (Fe 2 O 3} ) ( coercive force 2750 Oe) Binder: vinyl chloride - vinyl acetate - vinyl alcohol copolymer 20 parts (UCC Co. , Brand name VAGH) Polyurethane resin 20 parts (Nippon Polyurethane Co., Nipporan N-2304)-Coating material: carbon black 3 parts-Dispersant: lecithin 1 part-Solvent: toluene 60 parts methyl ethyl ketone 60 parts methyl isobutyl ketone 60 Department

After dispersing the above mixture in a ball mill for 8 hours, a curing agent: polyisocyanate 75% ethyl acetate solution 12 parts (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate L) The above curing agent was added and further dispersed for 1 hour. , Thickness 188μ
m on a milky white polyethylene terephthalate film by a solvent coating method. The coating is subjected to an orientation treatment using a magnetic field orientation treatment device while the paint is in a dry state, dried at 100 ° C. for 5 minutes, thickness 15 μm, surface smoothness A magnetic recording layer was formed for 500 seconds.

2. Anchor layer: An anchor layer having the following composition was applied at a drying temperature of 110 ° C. so that the coating amount after drying was 1.8 g / m ² .・ Aqueous polyolefin resin 100 parts (Steel Chemical Co., Ltd .: Siixen AC 30% solid content) ・ Fine powder silica 5 parts (Tokuyama Soda Co., Ltd .: Fine Seal X70, average particle size 2.0 μm) ・ Trimethylolpropane-tri- β-aziridinyl propionate 1 part ・ Isopropio alcohol 15 parts ・ Water 25 parts

3. Metal thin film layer: when the tin is measured by a film thickness measurement method using a quartz oscillator method by a vacuum evaporation method, 60
It vapor-deposited so that it might become 0 degree. 4. Adhesive layer: The composition having the following composition was applied at a drying temperature of 110 ° C. so as to have a thickness of 0.75 μm after drying, thereby forming an adhesive layer of the present invention.・ Vinyl chloride-vinyl acetate copolymer (Sekisui Chemical Co., Ltd .: ESLEC M) 56 parts ・ Acrylic resin (acid value: 54, OH value: 36, Tg: 86 ° C.) 24 parts ・ Alcohol-modified silicone oil 1 part ( Toshiba Silicone Co., Ltd .: TSF4750) ・ Methyl ethyl ketone 30 parts ・ Toluene 60 parts

5. Protective layer: The protective layer of the present invention was formed by applying a composition having the following composition at a drying temperature of 100 ° C. so as to have a thickness of 0.75 μm after drying.・ Acrylic resin 15 parts (Syden Chemical Co .: Cybinol S-14 Tg80 ° C) ・ Polyurethane resin 15 parts (Mitsubishi Kasei Co., Ltd .: Mitec MX-4014 Tg70 ° C) ・ Lubricant 5 parts (Axel: Mold WIZ F -57 solid content 8%) ・ Pigment aluminum hydroxide 5 parts ・ Toluene 190 parts ・ Methyl ethyl ketone 114 parts ・ Cyclohexanone 76 parts

Example 3 A heat-sensitive recording medium of Example 3 was produced in the same manner as in Example 2 except that the oil component of the adhesive layer was omitted. Adhesive layer: The composition having the following composition was applied at a drying temperature of 110 ° C. to a thickness of 1.0 μm after drying to form an adhesive layer of the present invention.・ 45 parts of polyurethane resin (MX-4014 manufactured by Mitsubishi Kasei) ・ 45 parts of epoxy resin (acid value: 54, OH value: 36, Tg: 86 ° C.) ・ Higher fatty acid modified silicone oil (manufactured by Toshiba Silicone: TSF410) 1 part ・ Methyl ethyl ketone 30 parts ・ Toluene 60 parts

Comparative Example 1 A comparative thermosensitive recording medium was prepared in the same manner as in Example 2 except that the modified silicone oil component of the colored layer was omitted. Comparative Example 2 A heat-sensitive recording medium for comparison was produced in the same manner as in Example 2 except that the adhesive layer of Example 2 was changed as follows. Adhesive layer: The composition having the following composition was applied at a drying temperature of 110 ° C. to a thickness of 1.0 μm after drying to form an adhesive layer of the present invention. -Vinyl chloride-vinyl acetate copolymer 67 parts (Denka Vinyl 1000GKT, manufactured by Denki Kagaku Kogyo Co., Ltd.)-Acrylic resin 28 parts (acid value: 54, OH value: 36, Tg: 86 ° C)-Unmodified dimethylpolysiloxane type Silicone oil (KF96 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts ・ Methyl ethyl ketone 300 parts ・ Toluene 600 parts

Comparative Example 3 A comparative thermosensitive recording medium was prepared in the same manner as in Example 2 except that the adhesive layer of Example 2 was changed as follows. Adhesive layer: The composition having the following composition was applied at a drying temperature of 110 ° C. to a thickness of 1.0 μm after drying to form an adhesive layer of the present invention.・ Vinyl chloride-vinyl acetate copolymer 20 parts (Denka Vinyl 1000 GKT, manufactured by Denki Kagaku Kogyo Co., Ltd.) ・ Acrylic resin 20 parts (acid value: 54, OH value: 36, Tg: 86 ° C.) ・ Olefin-modified silicone oil (Shin-Etsu Chemical Industry Co .: KF-413) 20 parts ・ Methyl ethyl ketone 300 parts ・ Toluene 600 parts

With respect to the above-described Examples and Comparative Examples, when the following various characteristic evaluation tests were performed, the results shown in Table 1 below were obtained. (1) Recording Characteristics Printing was performed with a thermal printing apparatus equipped with a thin-film thermal head having a dot density of 6 dots / mm with a pulse width of 2.5 ms and an applied energy of 0.6 W. The recording density and the background density were measured using a Macbeth densitometer RD-914 (visual filter). (2) Head Matching Performance Printing was performed 10,000 times continuously under the above-mentioned recording conditions, and the state of stick and scum adhesion was examined. (3) Light fastness After exposure for 6 hours with a fade meter, the density of the recorded portion and the background were similarly measured with a Macbeth densitometer. (4) Water resistance Water resistance was examined by immersing in water at 20 ° C. for 3 days. (5) Alcohol resistance A 50% aqueous solution of ethanol was dropped and wiped out 2 minutes later, and the alcohol resistance was examined. (6) Acid resistance Acid resistance was examined by immersing in 5% acetic acid water for 24 hours. (7) Alkali resistance Alkali resistance was examined by immersing in a 1% aqueous solution of sodium carbonate for 24 hours.

(8) Saltwater resistance The saltwater was examined by immersing it in a 5% saline solution for 24 hours. (9) Oil resistance Cottonseed oil was applied and left at 20 ° C. for 24 hours to examine oil resistance. (10) Plasticizer Resistance A plastic eraser (dragonfly) was applied with a load of 100 g, and left at 20 ° C. for 24 hours to examine the plasticizer resistance. (11) Heat resistance After standing in a dryer at 100 ° C. for 10 minutes, the temperature was returned to normal temperature, and then the nail was scratched to examine the heat resistance. (12) Abrasion resistance Abrasion resistance was examined by passing the gate of an automatic ticket gate 2000 times in the same direction. (13) Adhesion A cellophane tape peeling test was performed to examine the adhesion at the interface between the adhesive layer and the protective layer. (14) Washing resistance About 30 mg of a neutral detergent is added to 30 cc of hot water at about 35 ° C., and the card is washed for 15 minutes. Table 1 shows the above evaluation results.
Are shown in three stages of ○ △ ×. Thus, Examples 1-3
Was superior to Comparative Examples 1 to 3 in all of the test items.

[0043]

[Table 1]

[0044]

As described above, since the heat-sensitive recording medium of the present invention contains at least the modified silicone oil in the adhesive layer, the metal thin film layer and the protective layer are firmly adhered to each other. Rubbing with a magnetic head for reading / writing data in the layer or a thermal head for printing makes it extremely difficult for the protective layer or the metal thin film layer to be peeled or scratched. Also, due to the water repellent effect of fats and oils, it is possible to prevent the mixing of chemicals such as acids, alkalis, alcohols,
Corrosion prevention of the metal thin film layer is significantly improved. As described above, according to the present invention, it is possible to provide an excellent thermosensitive recording medium against physical stimuli such as friction and scratching and chemicals such as acids, alkalis and alcohols.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a configuration of an embodiment of a recording medium according to the present invention.

FIG. 2 is a schematic sectional view showing the configuration of another embodiment of the recording medium according to the present invention.

FIG. 3 is a schematic sectional view showing the configuration of another embodiment of the recording medium according to the present invention.

FIG. 4 is a schematic sectional view showing the configuration of another embodiment of the recording medium according to the present invention.

FIG. 5 is a schematic sectional view showing the configuration of another embodiment of the recording medium according to the present invention.

FIG. 6 is a schematic sectional view showing the configuration of another embodiment of the recording medium according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 colored layer 3 metal thin film layer 4 adhesive layer 5 protective layer 6 anchor layer 7 magnetic recording layer 8 protective layer (II)

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-171220 (JP, A) JP-A-5-131786 (JP, A) JP-A-4-7192 (JP, A) JP-A-2- 175183 (JP, A)

Claims (4)

(57) [Claims] 1. A thermosensitive recording medium comprising a coloring layer, a metal thin film layer, an adhesive layer, and a protective layer which are sequentially formed on a support, wherein the adhesive layer contains at least a modified silicone oil in the entire adhesive layer. A heat-sensitive recording medium containing 0.1 to 5% by weight in terms of solid content. 2. A heat-sensitive recording medium comprising a magnetic recording layer, a metal thin film layer, an adhesive layer, and a protective layer sequentially formed on a support, wherein the adhesive layer contains at least a modified silicone oil in the adhesive layer. A heat-sensitive recording medium characterized by containing 0.1 to 5% by weight in total solids ratio. 3. A thermosensitive recording medium comprising a coloring layer, a metal thin film layer, an adhesive layer, and a protective layer sequentially formed on a support having at least one surface with a magnetic recording layer, wherein the adhesive layer is at least A heat-sensitive recording medium containing a modified silicone oil in an amount of 0.1 to 5% by weight based on the total solid content in the adhesive layer. 4. A magnetic recording layer, a metal thin-film layer, an adhesive layer,
A thermosensitive recording medium comprising a protective layer, wherein the adhesive layer contains at least 0.1 to 5% by weight of modified silicone oil in a total solid content ratio in the adhesive layer.