JPH06305281A - Electric discharge recording medium - Google Patents

Abstract

PURPOSE:To provide an electric discharge recording medium in which information of high contrast can not only be recorded but also recording sensitivity is not reduced. CONSTITUTION:A heat-sensitive color developing layer 2, a metal thin film layer 3 are at least sequentially laminated on a base 1. Since the developing layer is normally white or pale, even it is a thin metal film layer, it can conceal the developing layer, and its recording sensitivity is excellent. In the case of electrosensitive recording, electric discharge occurs by a print head to destroy the thin film layer, and simultaneously the developing layer of the lower layer develops a color by heat generated in the case of the discharge, and hence information of high contrast can be recorded by electric discharge.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a card medium for tickets such as train tickets, commuter tickets, ticket purchasing cards, telecommunications cards, road traffic tickets and cards, merchandise trading cards, gift certificates, etc. Also relates to a discharge breakdown recording medium.

[0002]

2. Description of the Related Art Currently, prepaid card media called prepaid cards are widely used. These cards are issued at a certain fee, the usage fee is subtracted by the machine, and the card is used multiple times until the remaining amount runs out. However, since the information such as the usage fee and the remaining amount recorded on these cards is machine-readable information such as magnetic recording information, the information cannot be visually confirmed.

In order to solve this problem, there is used a method in which a standard such as a usage fee and a balance is provided by printing on a recording medium and punched holes are displayed according to the usage situation. However, in this case, the information that can be displayed is limited, and it is extremely difficult to accurately display the usage charge and the balance. In addition, as other methods, a print recording method by heat transfer, a heat recording method for coloring a leuco body, a heat destruction recording method for printing by thermally changing a thin metal film such as tin, have been proposed and put into practical use. Even with these printing methods, there are problems such as maintenance of the recording apparatus and poor weather resistance and heat resistance.

As a method of solving this problem, there is a discharge breakdown recording method. This recording system and recording medium have excellent characteristics such as high heat resistance and high printing speed. Explaining the discharge breakdown recording medium in detail, a colored layer formed by coating and forming an ink containing a pigment of a dark color such as carbon black on a substrate, and a metal thin film layer to be recorded and removed by discharge breakdown, A protective layer is provided if necessary.

When recording information, the metal thin film layer is destroyed by electric discharge to expose the colored layer. Then, the information becomes visible by the contrast between the color of the metal thin film layer and the color of the exposed colored layer.

By the way, the metal thin film layer in the above discharge breakdown recording medium must completely hide the colored layer formed by coating and forming the ink containing the pigment of the dark color in order to improve the contrast, and is a thick layer. I had to say. As a result, there has been a problem that the recording sensitivity is lowered.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention, of course, that high contrast information can be recorded, and to provide a discharge breakdown recording medium that does not reduce recording sensitivity.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and is characterized in that a thermosensitive coloring layer and a metal thin film layer are laminated at least sequentially on a substrate. It is a destructive recording medium.

[0009]

Since the thermosensitive coloring layer of the discharge breakdown recording medium according to the present invention is normally white or pale color, the thermosensitive coloring layer can be hidden even by a thin metal thin film layer. In addition, during recording by electric discharge, the print head discharges the metal thin film layer, and at the same time, the heat generated during the electric discharge causes the lower thermosensitive coloring layer to develop color, so high contrast information is discharged. It becomes possible to record destruction.

The present invention will be described below in detail with reference to the drawings. FIG. 1 is a sectional view of a discharge breakdown recording medium of the present invention, which comprises at least a thermosensitive coloring layer 2 and a metal thin film layer 3 on a substrate 1. Further, if necessary, a magnetic recording layer can be provided partially or entirely between the substrate 1 and the thermosensitive coloring layer 2. Further, the protective layer 4 may be provided on the metal thin film layer 3 for the purpose of protecting the metal thin film layer 3.

As the substrate 1, plastics such as polyvinyl chloride, polyester, polycarbonate, polymethylmethacrylate, polystyrene and the like, paper, synthetic paper and the like can be used alone or as a composite. The substrate 1 can be selected from the above-mentioned materials in consideration of physical properties required for the application of the recording medium such as a card and a sheet, for example, strength, rigidity, hiding power and light opacity. When the magnetic recording layer is provided, for example, γ-Fe ₂ O ₃ , Co-deposited γ-Fe ₂ O ₃ , Fe ₃ O ₄ , CrO ₂ , Fe, Fe-
Cr, Fe-Co, Co-Cr, Co-Ni, MnA
1, a magnetic paint composed of a magnetic fine particle dispersion liquid of Ba ferrite, Sr ferrite, or the like is applied. Generally, the coercive force of a magnetic recording layer used for a magnetic recording medium such as a prepaid card is 300 to 3000 (Oe), and the residual magnetic flux is 1.0.
~ 2.0 (Maxwell / cm).

The thermosensitive coloring layer 2 is composed mainly of a thermosensitive coloring material and a polymeric binder, and the polymeric binder is dissolved in a coating liquid prepared by dispersing the thermosensitive coloring material in water or a suitable solvent. The resulting dispersion is bar-coated, plaid-coated,
A solvent coating method such as air knife coating, gravure coating, or roll coating, or a known coating method such as screen printing is used for coating and drying. As the polymer binder, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, starch, styrene-maleic acid copolymer, polymethyl methacrylate,
A homo- or copolymer of a methacrylic resin such as polyethyl methacrylate, polystyrene, an acrylic-styrene copolymer, a polyester resin, a macron resin, an ABS resin, nitrocellulose or the like can be used.

As the thermosensitive coloring material, conventionally known materials can be used. They are roughly classified into two types, a metal compound coloring type and a dye coloring type.

Specific examples of the dye coloring type include ferric stearate, a combination of ferric myristate with tannic acid and gallic acid, and a combination of Ni, Co and Cu salts of stearic acid with SrS and BaS. , Silver behenate, silver stearate with hydroxine, spiroindane, ferric laurate, ferric pelargonate with thiosescicarbazites, lead caproate, lead behenate and thiourea derivatives , Ferric stearate, a combination of copper stearate and lead dibutylthiocarbamate, a combination of a molybdate of an organic amine and an aromatic polyhydroxy compound, and the like are used.

On the other hand, the dye-coloring type is a combination of a developer having a phenolic hydroxyl group and a colorless leuco dye, and 4,4'-isopropylidenephenol, benzyl-p-hydroxybenzoate, and 4 are used as the developers. ，
4′-dihydroxy-3,5′-diallyldiphenyl sulfone, methyl-bis (hydroxyphenyl) acetate, gallic acid ester, p-phenylphenol and the like can be mentioned. As leuco dyes, crystal violet lactone, 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 2- (2-fluorophenylamino) -6-diethylamino Fluoran, 2-
(2-Fluorophenylamino) -6-di-n-butylaminofluorane, 3-diethylamino-7-cyclohexylaminofluorane, 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino- 6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-butylanilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 2-anilino-3-methyl-6- (N-ethyl-p
-Toluidino) -fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-7-
Cyclohexylaminofluorane, 3-N-methylcyclohexylamino-6-methyl-7-anilinofluorane, 3-N-ethylpentylamino-6-methyl-7-
Anilino fluoran etc. can be mentioned. However, the present invention is not limited to the heat-sensitive color-developing materials in the above combinations, and any material that develops a dark color when heated is applied.

The metal thin film layer 3 is a layer formed by depositing a metal, and examples of this type of metal include aluminum and tin. It is formed by a vacuum deposition method, a sputtering method, an ion plating method or the like, and has a thickness of 0.03 to 0.
1 μm.

The protective layer 4 is, for example, a polyester resin,
Acrylic resins, urethane resins, nitrocellulose resins, styrene resins, vinyl chloride vinyl resins, methacrylic resins, nitrified cotton resins and the like are used.

Further, a lubricant may be added for the purpose of improving suitability for discharge recording. As the lubricant, silicone-based, metal stearate such as zinc stearate, and fluorine-based one can be used, but it is preferable to use a wax-based lubricant in consideration of abrasion resistance, coating film protection at heating, and sliding performance. , Paraffin wax having a melting point in the range of 30 to 150 ° C.,
Microcrystalline wax, carnauba wax, rice wax, montan wax, low molecular weight polyethylene wax, oxidized polyethylene wax, low molecular weight polypropylene wax, various fatty acids, various types of natural and synthetic waxes such as fatty acid, monoamide type, bisamide type, beef tallow type, etc., individually or as a mixture type. Add in. The coating material or ink made of these is provided in a film thickness of about 0.5 to 2 μm by various coating methods such as gravure coating, reverse roll coating, knife coating, blade coating and the like, and printing methods such as gravure printing and screen printing.

When a voltage is applied to the discharge breakdown recording medium thus manufactured, a discharge is generated, and as shown in FIG. 2, the metal thin film layer 3 is broken and the thermosensitive coloring layer 2 hidden under the metal thin film layer 3 is broken. At the same time that the exposed and printed portions 5 are formed, the coloring portions 6 are formed on the thermosensitive coloring layer 2.

[0020]

Example A white polyester substrate 1 having a thickness of 188 μm
A coating material for a thermosensitive coloring layer having the following composition (a) was applied on the above by a gravure coating method to form a thermosensitive coloring layer 2 having a thickness of about 5 μm. Next, aluminum was vapor-deposited to a thickness of 0.1 μm by a vacuum vapor deposition method to form a metal thin film layer 3. Further, a coating material for a protective layer having the following composition (b) was applied by a gravure coating method to form a protective layer 4 having a thickness of 1.0 μm.

(A) Paint for thermosensitive coloring layer Ferric myristylate 5 parts Tannic acid 1.5 parts Methacrylic resin 10 parts (BR-60 manufactured by Mitsubishi Rayon Co., Ltd.) Toluene 83.5 parts

(B) Coating for protective layer Zinc stearate 5 parts Methacrylic resin 30 parts (Rohm & Haas Company's Paraloid A-11) Isocyanate curing agent 3 parts (Nippon Polyurethane Co., Ltd. Coronate HL) Toluene 62 parts

The discharge breakdown recording medium thus obtained was cut into a card shape. This discharge breakdown recording medium was able to completely hide the thermosensitive coloring layer 2 by the metal thin film layer 3 and had a vivid metallic luster. Furthermore, when a voltage of -30 V was applied to this recording medium, discharge occurred,
The metal thin film layer 3 was destroyed, and the thermosensitive coloring layer 2 hidden under the metal thin film layer 3 was exposed in a colored state. When the printed portion was measured with a Macbeth reflection densitometer RD918S,
It had a reflection density of 1.4 to 1.6. Therefore, the contrast between the metal thin film layer 3 and the thermosensitive coloring layer 2 was very high.

Comparative Example 1 A colored layer coating material having the following composition (c) was applied on a white polyester substrate 1 having a thickness of 188 μm by a gravure coating method to form a colored layer having a thickness of about 5 μm. Next, aluminum was vapor-deposited to a thickness of 0.1 μm by a vacuum vapor deposition method to form a metal thin film layer. Further, a protective layer coating material having the composition (b) below was applied by a gravure coating method to form a protective layer having a thickness of 1.0 μm.

(C) Paint composition for colored layer Methacrylic resin 20 parts (Mitsubishi Rayon Co., Ltd. BR-60) Carbon black 5 parts (Colombian Carbon Japan Co., Ltd. RAVEN 450) Toluene 80 parts

The discharge breakdown recording medium thus obtained was cut into a card shape.

This discharge breakdown recording medium could not completely hide the colored layer by the metal thin film layer, and had a dull color. Furthermore, in this recording medium, -30
When a voltage of V was applied, electric discharge occurred, the metal thin film layer was destroyed, and the colored layer hidden under the metal thin film layer was exposed.
When the printed portion was measured with a reflection densitometer RD918S manufactured by Macbeth, the reflection density was 1.4 to 1.6. Therefore, the contrast between the metal thin film layer and the colored layer was lower than that of the example.

Comparative Example 2 The thickness of the metal thin film layer is 0.2 μm.
The same as Comparative Example 1 except that m was changed.

The discharge breakdown recording medium thus obtained was cut into a card shape.

This discharge breakdown recording medium was able to completely hide the colored layer by the metal thin film layer, and had a vivid metallic luster. Furthermore, in this recording medium, -5
When a voltage of 0 V was applied, electric discharge occurred, the metal thin film layer was destroyed, and the colored layer hidden under the metal layer was exposed. When the printed portion was measured with a reflection densitometer RD918S manufactured by Macbeth Co., it had a reflection density of 1.4 to 1.6. Therefore, the contrast between the metal thin film layer and the colored layer was about the same as that of the example.

[0031]

As described above, the discharge breakdown recording medium according to the present invention can have a thin metal thin film layer to be destroyed by discharge, and therefore has good recording sensitivity. In addition, since the lower thermosensitive coloring layer develops color due to the heat generated at the time of discharge breakdown, it is possible to record information with high contrast by discharge breakdown.

[0032]

[Brief description of drawings]

FIG. 1 is a sectional view showing the structure of a discharge breakdown recording medium according to the present invention.

FIG. 2 is a cross-sectional view showing a structure after information recording on a discharge breakdown recording medium according to the present invention.

[Explanation of symbols]

 1 Substrate 2 Thermosensitive coloring layer 3 Metal thin film layer 4 Protective layer 5 Printing part 6 Coloring part

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B41M 5/26 B42D 15/00 341 B 8604-2C G06K 19/10 8623-5L G06K 19/00 R (72) Inventor Toru Endo, 1-5-1 Taito, Taito-ku, Tokyo, Toppan Printing Co., Ltd.

Claims (1)

[Claims] 1. A discharge breakdown recording medium comprising a thermosensitive coloring layer and a metal thin film layer which are sequentially laminated on a substrate.