JP2741469B2 - Thermal recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used, for example, as a printout of a computer, a recording paper for facsimile reception, a ticket such as a ticket, a boarding pass, or a label, a card, and the like, particularly a prepaid card. The present invention also relates to a thermosensitive recording medium capable of performing recording such as printing by physical change due to heating.

[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 has advantages such as not requiring development and fixing, so it can be used not only for copying machines, but also for computer printouts, facsimile reception records, tickets, labels, and print records on various cards. Widely used. 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 thermal sensitivity.

However, this recording medium has a problem in that it easily develops a color even by pressure, an organic solvent such as alcohol, and also has a light resistance, a heat resistance, a water resistance and a storage stability of a printed record.

For this reason, for example, a thermosensitive recording medium using a metal thin film layer has been put to practical use. This thermal recording medium, for example, destroys the metal thin film layer based on the pattern of the image to be recorded by a heat source such as a thermal head, laser beam, flash light, etc., and removes the coloring layer provided below the metal thin film layer. The image is formed by exposing.

Accordingly, since an image display such as a print is formed by the contour of the metal thin film layer, its light resistance, heat resistance, water resistance and storage stability of a printed record are determined by the heat sensitivity using the above-mentioned dye as a coloring agent. Superior to recording media.

A thermal recording medium using a metal thin film layer is used for a prepaid card, a ticket, a label, and the like.
In practice, it is necessary to provide a protective layer as the uppermost layer in order to protect the metal thin film layer from physical stimuli such as friction and scratching, and chemicals such as acids, alkalis and alcohols.

The protective layer is generally known to contain a heat-resistant resin such as an acrylic resin or an epoxy resin and contain an appropriate amount of an inorganic or organic pigment and a lubricant such as wax or silicone. . Further, Japanese Unexamined Patent Publication No.
JP-A-99-284 and JP-A-2-62287 also disclose a technique in which a protective layer is formed into a multilayer 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. .

[0008]

However, even in a recording medium provided with such a protective layer, under severe conditions such as when the card is washed by mistake, for example, when used as a prepaid card, etc. There was a problem that the protective layer was peeled off. Further, in a field of application as a so-called magnetic card having a magnetic recording layer, there is 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.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to withstand physical stimuli such as friction and scratching and to be stable against chemicals such as acids, alkalis and alcohols. To provide a heat-sensitive recording medium.

[0010]

According to one aspect of the present invention, there is provided a thermosensitive recording medium including a coloring layer, a metal thin film layer, an adhesive layer, and a protective layer which are sequentially formed on a support.
The content of the copolymer in the adhesive layer phosphoric acid ester Ri range near the 0.1 to 20.0 wt%, and the glass transition
Utsuriten temperature Ru der 30 ° C. or more vinyl chloride - vinyl acetate -
It is characterized by containing a phosphate ester copolymer.

Another one of the heat-sensitive recording media of the present invention is a heat-sensitive recording medium including a magnetic recording layer, a metal thin film layer, an adhesive layer and a protective layer which are sequentially formed on a support. The content of the acid ester in the copolymer is 0.1 to 2;
0.0 wt% of the range near is, and a glass transition temperature of
Ru der 30 ° C. or more vinyl chloride - are characterized in that they contain a phosphoric acid ester copolymer - vinyl acetate.

Another one of the heat-sensitive recording media of the present invention is a heat-sensitive recording medium including a coloring layer, a metal thin film layer, an adhesive layer and a protective layer formed sequentially on a support having a magnetic recording layer on at least one surface. In the medium, a phosphate ester is added to the adhesive layer.
Content in the copolymer is Ri <br/> Ah in the range of 0.1 to 20.0 wt%, and vinyl chloride glass transition temperature of Ru der 30 ° C. or higher - vinyl acetate - phosphate ester copolymers It is characterized by containing a polymer.

Still another heat-sensitive recording medium according to the present invention is such that a magnetic recording layer, a metal thin film layer, an adhesive layer, and a protective layer are sequentially formed on the other surface of a support having a magnetic recording layer on one surface. sensitive recording medium comprising, Ri range near content is 0.1 to 20.0% by weight of the copolymer of the phosphoric acid ester to the adhesive layer, and der glass transition temperature of 30 ° C. or higher < It is characterized by containing a vinyl chloride-vinyl acetate-phosphate ester copolymer.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 to FIG. 6 are schematic sectional views of the heat-sensitive recording medium of the present invention. In the figure, 1 is a support, 2 is a colored layer, 3 is a metal thin film layer, 4 is an adhesive layer, 5 is a protective layer, 6 is an anchor layer, 7 is a magnetic recording layer, and 8 is a protective layer.

The thermosensitive recording medium 10 shown in FIG. 1 has 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.
Have a layer configuration in which layers are sequentially laminated. The thermosensitive recording medium of the present invention may have a laminated structure including the colored layer, the metal thin film layer, the adhesive layer and the protective layer in FIG. 1 provided on both sides of the support.

The heat-sensitive recording medium 20 shown in FIG. 2 has the same basic structure as the heat-sensitive recording medium 10, but has a layer structure in which an anchor layer 6 is provided between the colored layer 2 and the metal thin film layer 3. .

The thermosensitive recording medium 30 shown in FIG. 3 has a layer structure in which a magnetic recording layer 7 is provided instead of the colored layer 2 in the thermosensitive recording medium shown in FIG. The thermosensitive recording medium of the present invention may have a laminated structure including the magnetic recording layer, the metal thin film layer, the adhesive layer, and the protective layer in FIG. 3 provided on both sides of the support.

The heat-sensitive recording medium 40 shown in FIG. 4 has the same basic structure as the heat-sensitive recording medium 30, but has a layer structure in which an anchor layer 6 is provided between the magnetic recording layer 7 and the metal thin film layer 3. doing.

The thermosensitive recording medium 50 shown in FIG. 5 has a colored layer 2, a metal thin film layer 3, an adhesive layer 4 and a protective layer 5 on one surface of a support 1.
Are sequentially laminated, and a magnetic recording layer 7 and a protective layer 8 are sequentially provided on the other surface of the support. In the thermal recording medium of the present invention, a metal thin film layer and an adhesive layer may be interposed between the magnetic recording layer 7 and the protective layer 8 in FIG.

The heat-sensitive recording medium 60 shown in FIG. 6 is similar to the heat-sensitive recording medium 40 shown in FIG.
And a protective layer 8 are sequentially provided.

Next, each of the above 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. Paper substrates such as paper, laminated paper, polyethylene synthetic paper, glass substrates such as quartz, and metal substrates such as aluminum can be suitably used.

The coloring layer 2 is capable of displaying an image when the metal thin film layer 3 is heated according to the formation of an image pattern and thus is optically exposed. Examples thereof include ethyl cellulose, hydroxyethyl cellulose, and cellulose. Acetate propionate, a cellulose derivative such as cellulose acetate, polystyrene, a styrene resin such as poly-α-methylstyrene or a styrene copolymer resin, an acrylic resin such as polybutyl methacrylate or a methacrylic resin alone or a copolymer resin, rosin, Rosin modified phenolic resin, rosin modified maleic resin, rosin ester resin such as polymerized rosin, vinyl acetate resin, cumarone resin, vinyl toluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, etc. Various inorganic or organic coloring pigments or coloring dyes are added to a binder resin such as a fat copolymer according to the color to be colored, and a plasticizer, a stabilizer, a wax, a curing agent, and a dispersant are added as necessary. After the addition, using a colored paint or ink prepared by sufficiently kneading with a solvent or a diluent, a so-called gravure method, a roll method, a knife edge method, a coating method such as an offset method or a printing method, is formed. You.

As the colorant, pigments, dyes and the like can be used. As specific examples of the color pigments, Cyan pigments such as Diaceriton Fast Brilliant-R (manufactured by Mitsubishi Kasei Corporation, trade name), Kaya Ron Polyester Bull-B
-Magenta color pigments such as SF Conc (product name, manufactured by Nippon Kayaku Co., Ltd.) include Diaceritone Fast Red R (product name, manufactured by Mitsubishi Kasei Co., Ltd.), Kayalon Polyester Pink RC
Examples of yellow color pigments such as LE (manufactured by Nippon Kayaku Co., Ltd.) include Kayalon polyester light yellow-5GS.
(Trade name, manufactured by Nippon Kayaku Co., Ltd.)
GRH (trade name, manufactured by Hodogaya Chemical Co., Ltd.) and the like.

Cyan color pigments such as celerian blue and phthalocyanine blue; magenta color pigments such as brilliant carmine and alizarin lake; yellow pigments such as Hanzayello and Bisazoyello.
Examples of black pigments include carbon black, graphite, and oil black.

Further, metals such as Fe, Ni and Al, Fe
Metal oxides such as ₂ 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 textile transfer printing 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 thickness of the colored layer is set in the range of 0.5 to 10 μm.

The metal thin film layer 3 is made of Te, Sn, Al, B
a metal such as i, Pb, Zn or an alloy thereof, and using these metals or a compound of these metals such as Te carbide, a vacuum evaporation method, a sputtering method, a CVD method, or the like.
It can be formed on the upper surface of the colored layer 2 provided on the support 1 by a 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 Å to 1 μm, preferably 300 to 600 μm.
Angstrom is selected.

The adhesive layer 4 is made of a phosphoric acid ester copolymer.
Content Ri range near the 0.1 to 20.0 wt%, and,
Vinyl chloride glass transition temperature of Ru der 30 ° C. or higher - is characterized by containing the phosphoric acid ester copolymer - vinyl acetate.

The content of the vinyl chloride-vinyl acetate-phosphate ester copolymer in the phosphate ester copolymer is as follows:
When the content is less than 0.1% by weight , the adhesion to the metal thin film layer 3 is reduced, and the content of the phosphate ester in the copolymer is 2 %.
0.0 If greater than the weight%, vinyl chloride - vinyl acetate -
Since the light stability and the heat stability of the phosphate ester copolymer are reduced, the content of the phosphate ester in the copolymer is 0.1% .
It is necessary to be 1-20.0% by weight .

The adhesive layer constituting the present invention may further include a polyester resin, a polyurethane resin, an acrylic resin, a vinyl chloride-vinyl acetate resin, an epoxy resin,
It is also possible to mix at least one resin selected from cellulose-based resins and aminoalkyd-based resins.
In that case, it is desired that the vinyl chloride-vinyl acetate-phosphate ester copolymer is in the range of 5% by weight or more, preferably 20% by weight or more in the total solid content ratio of the adhesive layer 4. That is, if the amount of the vinyl chloride-vinyl acetate-phosphate ester copolymer is less than 5% by weight, the adhesion to the metal thin film layer 3 is undesirably reduced. Further, the weight average molecular weight of the vinyl chloride-vinyl acetate-phosphate ester copolymer is preferably 300 or more. When the weight average molecular weight of the vinyl chloride-vinyl acetate-phosphate ester copolymer is less than 300, the chemical resistance and abrasion resistance of the adhesive layer are deteriorated, and the adhesion to the metal thin film layer is deteriorated. Absent. Further, in the present invention, the vinyl chloride-vinyl acetate-phosphate ester copolymer must have a glass transition temperature (DSC method) of 30 ° C. or higher.
It is . When the glass transition point temperature of the vinyl chloride-vinyl acetate-phosphate ester copolymer is lower than 30 ° C., the chemical resistance and abrasion resistance of the adhesive layer are deteriorated, and heat fusion to the thermal head occurs. Not preferred.

The adhesive layer 4 may be formed, if necessary, with a lubricant such as wax, an inorganic or organic 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 such as a three-roll or disperser, using a coating method such as a gravure method, a roll method, a knife edge method, or an offset method, or a printing method. It is formed on the metal thin film layer 3.

The thickness of the adhesive layer is desirably in the range of 0.1 to 5 μm. A particularly preferred range is 1-2 μm. When the thickness of the adhesive layer is smaller than 0.1 μm, the adhesive strength with another layer is reduced, and when the thickness is larger than 5 μm, the drying speed of the adhesive layer becomes slow, and peeling occurs inside the adhesive layer. .

The protective layer 5 comprises an adhesive layer 4 and a metal thin film layer 3
Must be physically and chemically protected and designed to prevent sticking and adhesion of scum during thermal recording. In the present invention, the protective layer 5 is configured to include at least a heat-resistant resin and a lubricant.

Examples of the heat-resistant resin include polyester resins, polyurethane resins, epoxy resins, various cellulose resins, polyimide resins, polyamide resins, polyarylate resins, polycarbonate resins, phenol resins, and alkyd resins. Thermoplastic resins, thermosetting resins, UV-curable resins, EB-curable resins made of resins, melamine-based resins, styrene-based resins, silicone-based resins, fluorine-based resins and copolymers of these resins Of which
The glass transition point (Tg) is selected to be 30 ° C. or higher, preferably 50 ° C. or higher.

Here, when Tg is lower than 30 ° C.,
During thermal recording, sticking occurs or abrasion resistance decreases.

The lubricant has a function of preventing sticking with the heat-sensitive head, reducing the coefficient of friction and improving abrasion resistance, and includes waxes such as polyethylene wax, paraffin wax, and microcrystalline wax. Known materials such as zinc stearate, higher fatty acid metal salts such as calcium stearate, fatty acids such as higher fatty acid amides such as stearamide and behenamide, silicone oil, fine powder of Teflon, and fine powder of boron nitride are used. If necessary, heat-resistant inorganic pigments such as silica, calcium carbonate, magnesium hydroxide, zeolite, clay, and talc may 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 content ratio of the binder, lubricant and pigment is preferably 50 to 95% by weight, respectively.
2 to 30% by weight, 2 to 40% by weight.

When the content of the lubricant is less than 2% by weight, the abrasion resistance is deteriorated, and sticking occurs during thermal recording. 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, 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 is significantly worn.

The protective layer 5 is also formed on the adhesive layer by a method similar to that for the adhesive layer 4. The thickness of the protective layer 5 is
For the same reason as above, 0.1-5 μm, especially 1-2
The range of μm is preferred.

The anchor layer 6 includes the coloring 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.

For this reason, resins having appropriate thermoplasticity, for example, acrylic resins such as polystyrene and polymethyl methacrylate, cellulose resins such as cellulose acetate propionate, vinyl chloride-vinyl acetate copolymer, Polyester resins, polyurethane resins, epoxy resins, amino alkyd resins and copolymers of these resins can be used alone or in combination of two or more.

In order to further control the thermoplasticity, a heat-fusible substance such as a plasticizer or a wax may be added. In order to impart a certain solvent resistance and facilitate the formation of the next layer. , A curing agent may be added.

Further, in order to control the glossiness of the metal thin film layer, a pigment which can be used in the above-mentioned 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 a magnetic recording layer is provided instead of the colored layer, if the thickness of the anchor layer is large, reading and writing of magnetic recording will be hindered. It is necessary to determine in consideration of the characteristics of the magnetic recording layer.

When a pigment having an average particle diameter of 1 to 10 μm is mixed in 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 easier 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 more, the unevenness of the surface becomes large, so that the contact area with the thermal head is small. Print blurring or missing printing
Thermal recording cannot be performed sufficiently.

Examples of the pigment include inorganic white pigments such as silica, calcium carbonate, aluminum hydroxide, clay and talc, cross-linked polystyrene, polyethylene beads,
Coloring pigments such as organic transparent or white pigments such as silicone beads, lead red, ultramarine blue, titanium yellow, red-mouthed graphite, and plastic-type fluorescent pigments can be used.

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 related to image display, and has an appropriate configuration. Data can be read and written by a magnetic card reading and writing device.

Examples of the magnetic material include Fe ₂ O ₃ , barium ferrite and other ferrites, magnetite and the like, iron,
Any known materials such as metals such as nickel, manganese, and chromium, and alloys thereof can be used. As the binder resin, those exemplified for the colored layer can be similarly used.

In the present invention, the magnetic recording layer may have a single-layer structure of one layer, or may have a layer structure of two or more layers having mutually different magnetic properties. You may. The thickness of the magnetic recording layer is usually set in the range of 0.1 to 30 μm.

In the present invention, the magnetic recording layer may be one in which a coating layer is formed over the entire surface of the support, or one in which a coating layer is partially formed in a stripe or bar code. Is also good.

In the present invention, when the magnetic recording layer is provided between the support and the metal thin film layer, the coloring layer is not necessarily provided.

The material of the protective layer 5 can be applied to the protective layer 8 as it is.

[0059]

Next, examples of the heat-sensitive recording medium according to the present invention will be described. All parts are parts by weight.

Example 1 A thermosensitive recording medium of the present invention was produced by sequentially laminating the following layers by coating on the surface of a 188 μm thick milky white polyethylene terephthalate film support.

1) Colored layer: A colored layer having the following composition was dried at a drying temperature of 110 ° C., and then 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 Co., Ltd., trade name: Byron 200)-5 parts of carbon-5 parts of fine powder silica (manufactured by Tokuyama Soda Co., Ltd., trade name: fine seal X70, average particle size 2.0 μm)・ Isocyanate curing agent 2 parts (Nippon Polyurethane Co., trade name; Coronate L) ・ Methyl ethyl ketone 93 parts ・ Toluene 51 parts

2) Metal thin film layer: When the thickness of tin is measured by a vacuum deposition method using a quartz crystal oscillator method, the thickness is 60%.
Vapor deposition was performed so as to be 0 Å.

3) Adhesive layer: An adhesive layer 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.

-Vinyl chloride-vinyl acetate-phosphate ester copolymer 67 parts (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka vinyl 1000P, glass transition point temperature 78 ° C ) ( content of phosphate ester in copolymer) 1 wt%) acrylic 28 parts of the resin (Saiden chemical Co., trade name: Saivinol X592-440S) (acid value: 54, OH number: 36, Tg: 86 ℃) · Methyl ethyl ketone 300 parts 600 parts toluene

4) Protective layer: The protective layer having the following composition was dried at a drying temperature of 110 ° C. and then applied to a thickness of 1.0 μm to form a protective layer.

-16 parts of epoxy resin (trade name, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 1010 Tg85 ° C)-16 parts of polyester resin (trade name, manufactured by Toyobo Co., Ltd .; Byron 290 Tg80 ° C)-Lubricant 4 parts of polyethylene wax (Mitsui Pigment tetrafluoroethylene 4 parts (product name; KTL500F, manufactured by Kitamura Co., Ltd.) 190 parts of toluene 190 parts of methyl ethyl ketone

Example 2 A thermosensitive recording medium of the present invention was produced by sequentially laminating the following layers by coating on the surface of a 188 μm thick milky white polyethylene terephthalate film support.

1) Magnetic recording layer • Magnetic powder: 100 parts of barium ferrite BaO · 6 (Fe ₂ O ₃ ) (coercive force 2750 Oersted) • Binder: 20 parts of vinyl chloride-vinyl acetate-vinyl alcohol copolymer (UCC) (Product name: VAGH) Polyurethane resin 20 parts (manufactured by Nippon Polyurethane Co., Ltd., product name: Nipporan N-2304) ・ Paint: carbon black 3 parts ・ Dispersant: lecithin 1 part ・ Solvent: toluene 60 parts Methyl ethyl ketone 60 parts Methyl isobutyl ketone 60 parts

After the above mixed solution was subjected to a dispersion treatment in a ball mill for 8 hours, the following curing agent was added. Hardening agent: Polyisocyanate 75% ethyl acetate solution 12 parts (Nippon Polyurethane Co., trade name; Coronate L)

After adding the above curing agent and dispersing for another hour,
It is applied on a milky white polyethylene terephthalate film having a thickness of 188 μm by a solvent coating method, orientation-treated by a magnetic field orientation treatment device while the paint is not dried, dried at 100 ° C. for 5 minutes, and dried at a thickness of 15 μm.
m, a magnetic recording layer having a surface smoothness of 500 seconds was formed.

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 18 g / m ² .

100 parts of an aqueous polyolefin-based resin (trade name; manufactured by Seiko Chemical Co., Ltd .; trade name: Siixen AC solid content: 30%) 5 parts of fine powdered silica (trade name; manufactured by Tokuyama Soda Co., Ltd .; trade name: Fine Seal X70, average particle size) 0 μm) ・ 1 part of trimethylolpropane-tri-β-aziridinylpropionate ・ 15 parts of isopropyl alcohol ・ 25 parts of water

3) Metal thin film layer: When the thickness of tin is measured by a vacuum deposition method and the thickness is measured by a quartz crystal oscillator method, the thickness is 60%.
Vapor deposition was performed so as to be 0 Å.

4) Adhesive layer: The adhesive having the following composition was dried at a drying temperature of 110 ° C., and then applied so as to have a thickness of 0.75 μm to form an adhesive layer.

-Vinyl chloride-vinyl acetate-phosphate ester copolymer 56 parts (trade name; Denka Vinyl 1000P, manufactured by Denki Kagaku Kogyo Co., Ltd., glass transition point temperature 78 ° C ) ( content of phosphate ester in copolymer) 1 wt%) acrylic 24 parts of the resin (Saiden chemical Co., trade name: Saivinol X592-440S) (acid value: 54, OH number: 36, Tg: 86 ℃) · Methyl ethyl ketone 30 parts 60 parts toluene

5) Protective layer: A protective layer was formed by applying a composition having the following composition at a drying temperature of 100 ° C. to a thickness of 0.75 μm after drying.

-Acrylic resin 15 parts (manufactured by Seiden Chemical Co., trade name; Cybinol S-14 Tg80 ° C)-Polyurethane resin 15 parts (manufactured by Mitsubishi Kasei Co., Ltd., Mytec MX-4014 Tg70 ° C)-Lubricant 5 Parts (manufactured by AXEL Co., Ltd., trade name; Mold Width F-57, solid content: 8%) ・ Pigment aluminum hydroxide 5 parts ・ Toluene 190 parts ・ Methyl ethyl ketone 114 parts ・ Cyclohexanone 76 parts

Comparative Example 1 A heat-sensitive recording medium for comparison was produced in the same manner as in Example 1 except that the adhesive layer of Example 1 was changed as follows.

Adhesive layer: A composition having the following composition was dried at a drying temperature of 11
After drying at 0 ° C., apply so that the thickness becomes 1.0 μm,
The adhesive layer of the present invention was formed.

-Vinyl chloride-vinyl acetate copolymer 56 parts (manufactured by UCC, trade name: VYHD)-Acrylic resin 24 parts (manufactured by Seiden Chemical Co., trade name: Cybinol X592-440S) (acid value: 54, (OH value: 36, Tg: 86 ° C)-30 parts of methyl ethyl ketone-60 parts of toluene

Comparative Example 2 A comparative thermosensitive recording medium 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 following composition having a drying temperature of 11
After drying at 0 ° C., apply so that the thickness becomes 1.0 μm,
The adhesive layer of the present invention was formed.

Polyester resin 56 parts (manufactured by Toyobo Co., trade name; Byron 200) Acrylic resin 24 parts (manufactured by Seiden Chemical Co., trade name: Cyvinol X592-440S) (acid value: 54, OH value: 36, (Tg: 86 ° C) ・ Methyl ethyl ketone 30 parts ・ Toluene 60 parts

Evaluation tests were carried out on the following examples with respect to the examples and comparative examples described above. The results shown in Table 1 below were obtained.

(1) Recording Characteristics Print recording was performed with a pulse width of 2.5 ms and an applied energy of 0.6 W using a thermal printing apparatus equipped with a thin-film thermal head having a dot density of 6 dots / mm. 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 sticking and residue was examined.

(3) Light Resistance After exposure for 6 hours with a fade meter, the densities of the recorded portion and the background were similarly measured with a Macbeth densitometer.

(4) Water Resistance Water resistance was examined by immersion in water at 20 ° C. for 3 days.

(5) Alcohol Resistance A 50% aqueous solution of ethanol was added dropwise and wiped off 2 minutes later to examine the alcohol resistance.

(6) Acid Resistance Acid resistance was examined by immersion in 5% acetic acid water for 24 hours.

(7) Alkali Resistance Alkali resistance was examined by immersion in a 1% aqueous sodium carbonate solution for 24 hours.

(8) Saltwater resistance The saltwater was immersed in a 5% saline solution for 24 hours to examine the saltwater resistance.

(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 drier at 100 ° C. for 10 minutes, the temperature was returned to room temperature, and the nail was scratched to examine the heat resistance.

(12) Abrasion Resistance The gate of the automatic ticket gate was passed 2,000 times in the same direction to check the abrasion resistance.

(13) Adhesiveness A cellophane tape peeling test was performed to examine the adhesiveness at the interface between the adhesive layer and the protective layer.

(14) Washing resistance To a hot water of about 35 ° C., 30 cc of hot water and 40 of a neutral detergent were added.
The card is washed for 15 minutes.

The above evaluation results are shown in Table 1 below.
Δ: Slightly poor, and ×: Poor in three stages.

[0101]

[Table 1]

As is clear from the results in Table 1, Example 1
It was clear that Nos. 2 were superior to Comparative Examples 1 and 2 in all items of the test.

[0103]

Thermosensitive recording medium of the present invention as described above, according to the present invention is in the range near content is 0.1 to 20.0 wt% in the copolymer of the phosphoric acid ester to the adhesive layer is, and, Glass roll
Utsuriten temperature Ru der 30 ° C. or more vinyl chloride - vinyl acetate -
Since the phosphoric acid ester copolymer is contained, the metal thin film layer and the protective layer are firmly adhered to each other, and are rubbed with, for example, a magnetic head for reading and writing data on the magnetic recording layer and a thermal head for printing. I'm also, the protective layer or a metal thin film layer on the peeling and scratches are less likely extremely month.

Further, since the protective layer is less likely to be peeled or damaged, corrosion of the metal thin film layer by chemicals such as acids, alkalis and alcohols is remarkably reduced.

As described above, according to the present invention, it is possible to provide an excellent thermosensitive recording medium which is stable 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 the configuration of an embodiment of a thermosensitive recording medium according to the present invention.

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

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

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

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

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

DESCRIPTION OF SYMBOLS 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 10, 20, 30, 40, 50, 60 ... thermosensitive recording medium

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-103493 (JP, A) JP-A-60-18388 (JP, A) JP-A-63-112675 (JP, A) JP-A 64-64 16686 (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 content of the adhesive layer in the copolymer of phosphate ester in the adhesive layer. /> is Ri range near the 0.1 to 20.0 wt%, and glasses
Transition temperature of Ru der 30 ° C. or more vinyl chloride - vinyl acetate - thermosensitive recording medium characterized by containing a phosphoric acid ester copolymer. 2. A magnetic recording layer sequentially formed on a support,
In a thermosensitive recording medium including a metal thin film layer, an adhesive layer, and a protective layer, the adhesive layer contains a phosphate ester copolymer.
Yuryou is Ri range near the 0.1 to 20.0 wt%, and, moth
Vinyl chloride glass transition point temperature Ru der 30 ° C. or higher - vinyl acetate - thermosensitive recording medium characterized by containing a phosphoric acid ester copolymer. 3. A thermosensitive recording medium comprising a coloring layer, a metal thin film layer, an adhesive layer, and a protective layer formed sequentially on a support having a magnetic recording layer on at least one surface, wherein the adhesive layer comprises a phosphate ester. Content of 0.1 to 20 in the copolymer .
0 wt% in the range near is, and a glass transition temperature of 30
Der Ru vinyl chloride or ° C. - vinyl acetate - thermosensitive recording medium characterized by containing a phosphoric acid ester copolymer. 4. A thermosensitive recording medium comprising a magnetic recording layer, a metal thin film layer, an adhesive layer and a protective layer formed on the other side of a support having a magnetic recording layer on one side. The content of the ester in the copolymer is 0.1 to 20.
0 wt% in the range near is, and a glass transition temperature of 30
Der Ru vinyl chloride or ° C. - vinyl acetate - thermosensitive recording medium characterized by containing a phosphoric acid ester copolymer.