JPH08324111A - Discharge breakdown recording medium - Google Patents

Abstract

PURPOSE: To obtain a discharge breakdown recording medium such as a ticket or a road pass having degradability as a whole, in the discharge breakdown recording medium obtained by successively laminating a color layer, a metal membrane layer, a protective layer and a printing layer on a support, by forming the support from a base material based on a degradable resin. CONSTITUTION: The base material 2 of the support having degradability of a discharge breakdown recording medium 1 is formed from a biodegradable resin composed of chemically synthesized polyester, a natural derivative resin or aliphatic polyester composed of a high-molecular material based on lactic acid. A color layer 3 exposed by discharge breakdown, a metal membrane layer 4 being a vapor deposition layer of a non-magnetic metal, a protective layer 5 formed by applying ink containing a polyester resin and a printing layer 6 are successively provided on the support. The support having degradability is composed of aliphatic polyester having a hydroxyalkanoate unit such as 3-hydroxyvalerate or 3-hydroxybutylate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medium used for a single-use type such as a ticket, a card for purchasing a ticket, a road ticket and a card in a transportation system such as a railroad. The present invention relates to a discharge breakdown recording medium having characteristics and having a decomposability as a whole medium structure.

[0002]

2. Description of the Related Art At present, recording media using a magnetic recording system are used in a wide variety of fields such as disks, tapes, cards, credit cards, stripes on cash cards and the like. In particular, a magnetic recording medium prepared by coating a paint consisting of a magnetic material such as iron oxide or barium ferrite and a binder resin on a plastic sheet is, as mentioned above, a ticket or a ticket for transportation such as railways because of its portability. , Commuter pass and prepaid card is generally used as a prepaid transportation medium. However, since this magnetic recording method magnetically records and reproduces information, there is a drawback that the information cannot be visually confirmed by the user in the past. A method has been used in which, for example, printing is provided with punches and the like 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 display an accurate amount of money.

Therefore, as a method for visually confirming the balance and the like, a printing method by thermal transfer, a thermal recording method for coloring a leuco dye, a method for thermally changing a metal vapor deposition film such as tin, and the like have been proposed and put into practical use. ing.

On the other hand, the base material that supports the recording medium has mechanical characteristics called gate characteristics so that it can be used in a machine for reading and writing the magnetic recording layer and the print recording layer provided on the base material. For example, durability, bending resistance, and rigidity are required. As a material that satisfies such conditions and is easy to manufacture, a plastic sheet such as a polyethylene terephthalate (PET) resin, that is, a resin satisfying only mechanical properties is generally used as a base material of a medium.

Further, polyvinyl chloride resin is used as a base material for general cards such as ID cards, membership cards, cash cards and credit cards. These are usually discarded after a card of this type is sold or rented to a user and then used by the user. And the plastic card made of the above materials is currently disposed of by incineration or landfill as waste after treatment.
According to the latter material, plastic waste has the problem of durability of the incinerator due to high combustion temperature due to incineration, and the pollution problem of combustion gas, etc. Even completely impossible to do. In the case of landfill as waste, it remains in its original form without being decomposed at the landfill site, and remains semi-permanently as waste, which has a problem of affecting the natural environment. In any case, there is a problem of disposal after use.

[0006] Further, conventionally, a card using paper as a medium base material has been made and used, and in particular, since paper is easy to dispose of such as incineration and landfill, and the manufacturing cost is low, it has been discussed in recent years. It is considered to be the best medium for resolving environmental problems such as dust.

Further, JP-A-57-150393, JP-A-59-220192 and JP-A-51-9.
As described in JP-A-3991, JP-A-63-260912, and JP-A-57-150393, plastics that can be decomposed in the natural environment such as light or underground have been developed, and particularly, disposable plastics. It is used in product packaging and is now partly commercialized. In the field of cards, JP-A-5-42786 and JP-A-5-8508
No. 8 describes the use of biodegradable or photodegradable plastic for the card substrate.

[0008]

However, when the above-mentioned paper is used as a card base material, durability, bending resistance, water resistance, chemical resistance, waterproofness, surface smoothness, glossiness,
Considering the suitability as a card such as processability, the function is inferior in all respects, so it is not possible to use paper alone as a pass ticket or an admission ticket.
It is not suitable for the above-mentioned prepaid card that is used for a certain period of time and is limited to temporary use such as a ticket.
In this case, polyethylene, polypropylene,
It is conceivable that an outer layer other than plastic, such as a synthetic resin such as polyvinyl chloride or polyethylene terephthalate, or an aluminum foil, may be laminated as a protective layer, but these have a drawback that they are not excellent in disposability and are not much different from plastic cards.

A card in which the card base material itself is made of degradable plastic is gradually disassembled after disposal due to the function of the plastic. However, this card is manufactured in consideration of the convenience of the card itself and problems in card manufacturing, and when a degradable plastic is simply used as the card base material, it has a mechanical strength such as bending resistance and rigidity. It can not be said that it has characteristics, and since it is necessary to have a certain thickness due to the strength and ease of use of the card, when it is integrally formed, warpage of the card surface occurs Since the plastics having the above properties are used, it takes a long time to disassemble the plastics, and the plastics having the decomposability are expensive.

On the other hand, as a method for visually displaying the balance and the like, there are a printing method by thermal transfer, a thermal recording method for coloring a leuco dye, and a method for thermally printing a metal vapor deposition film of tin or the like. Depending on the printing method,
There are problems such as maintenance of the recording apparatus and poor weather resistance and heat resistance. Therefore, the present invention, as a method for solving this problem, has an excellent feature that the heat resistance is high, the printing is clear, and the printing speed is fast, and the discharge breakdown recording method in which the entire medium structure is decomposable. Disclosed is a discharge breakdown recording medium.

[0011]

In order to achieve the above object, according to the present invention as set forth in claim 1, a colored layer, a metallic thin film layer, a protective layer and a printing layer are formed on a support constituting a medium. Is a discharge breakdown recording medium in which the support is composed of a base material containing a decomposable resin as a main component.

According to the invention described in claim 2, the support having decomposability according to claim 1 is 3-hydroxyvalerate, 3-hydroxybutyrate, 3-hydroxycaprolate, 3-hydroxycaprate. It is characterized by being an aliphatic polyester having a hydroxyalkanoate unit such as hydroxyheptanoate.

The invention according to claim 3 is characterized in that the support having decomposability according to claim 1 is a chemically synthesized polyester shown in "Chemical formula 1" or "Chemical formula 2".

The invention according to claim 4 is characterized in that the degradable support according to claim 1 is a composite resin of starch and polyvinyl alcohol.

In the invention described in claim 5, the degradable support according to claim 1 has an average molecular weight of 10,000 to 1,000,
It is characterized by being composed of decomposable polylactic acid obtained by stretching a thermoplastic resin whose main component is polylactic acid of 000 or a copolymer of lactic acid and oxycarboxylic acid.

According to a sixth aspect of the present invention, the decomposable support according to the first aspect is provided on at least one side of a card substrate made of a naturally decomposable material such as paper.
To 5 are laminated.

According to a seventh aspect of the present invention, in the discharge breakdown recording medium according to the first to sixth aspects, the coloring layer is colored with a magnetic material.

The invention according to claim 8 is characterized in that the resin in which the magnetic material according to claim 7 is dispersed is a biodegradable resin.

[0019]

According to the present invention, the base material of the medium is biaxially made of a microorganism-produced polyester, a chemically synthesized polyester, a natural product-derived resin, a polylactic acid or a thermoplastic resin whose main component is a copolymer of lactic acid and oxycarboxylic acid. By using a degradable resin formed by stretching, the mechanical properties such as durability, rigidity, forming processability, mechanical strength, hardness, impact strength, dimensional stability, and bending resistance of the medium base material are maintained. This makes it possible to improve the gate characteristics for reading / writing on a machine, and it can be sufficiently decomposed naturally even if it is left after being discarded. Further, by adopting the discharge destruction method as the printing method, a medium having excellent characteristics of high heat resistance, clear printing, and high printing speed can be obtained.

[0020]

Embodiments of the present invention will be described in detail with reference to the drawings. 1, 2, and 3 are cross-sectional views of a discharge breakdown recording medium of the present invention.

The medium 1 of the present invention shown in FIG. 1 is used as a base material 2 for a support having degradability, and is made of a microorganism-produced polyester, a chemically synthesized polyester, a natural product-derived resin, or a fat composed of a polymer material containing lactic acid as a main component. A resin having a biodegradable resin composed of a group polyester is used, and these have complete degradability. Further, like the medium 9 in FIG. 3, the above decomposable resin can be laminated on one side or both sides of a base material such as paper that naturally decomposes. Resins that can be used include polyesters produced by microorganisms such as copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, aliphatic polyesters such as polyglycolic acid, polylactic acid and polycaprolactone, polyvinyl alcohol (PVA), PVA modified resins, Starch-modified resins and the like can be used alone or in combination according to the required characteristics.

Particularly, lactic acid is a copolymer of D-lactic acid, L-lactic acid or a mixture thereof and D-lactic acid, L-lactic acid or a mixture thereof and glycolic acid or an oxycarboxylic acid represented by 6-hydroxycaproic acid. A thermoplastic degradable polymer whose main component is is used. This polymer preferably has a number average molecular weight of 10,000 to 1,000,000. Lactic acid includes D-lactic acid and L-lactic acid, and oxycarboxylic acid includes glycolic acid and 6-hydroxycaproic acid. However, since the thermoplastic polymer alone does not have sufficient rigidity, by further subjecting it to biaxial stretching processing, including rigidity, durability, forming processability, mechanical strength, hardness, impact strength, dimensional stability, In terms of mechanical properties such as bending resistance, surface smoothness, glossiness, water resistance, and water resistance, properties equivalent to conventional polyester materials and vinyl chloride materials can be obtained.

Further, if necessary, various additives such as 0.05 to 3 parts by weight of a coloring inhibitor and 0.05 to 0.05 parts of an antioxidant may be added to the above resin as long as the characteristics of the resin are not lost.
It is possible to add 3 parts by weight, a lubricant of 0.05 to 3 parts by weight, an organic pigment and an inorganic pigment. However, it is not preferable to add 50% or more of a non-decomposable substance, because the decomposability is remarkably lowered and a processing problem occurs.

In particular, as the filler, inorganic fillers such as calcium carbonate, mica, calcium silicate, white carbon, asbestos, porcelain clay (calcined), glass fiber, etc. are added, and the mixture is kneaded and biaxially stretched to obtain rigidity, Mechanical properties such as moldability, mechanical strength, hardness, impact strength, dimensional stability, and bending resistance can be further improved.

The production of the medium base material 2 of the present invention is carried out by forming the thermoplastic polymer obtained as described above into a sheet by a known extrusion method and further biaxially stretching it,
Calendar this sheet.

In addition to the single layer structure, the base member 2 may have a multi-layer structure in which sheets made of the same material or resins having different characteristics are stacked and adhered by a known thermocompression bonding method or heat laminating method.

The colored layer 3 is exposed by discharge breakdown and is not particularly limited as long as it is a process ink used for printing a prepaid card. The printing method is also a known printing method. A magnetic recording layer may be provided instead of the process ink. When the magnetic recording layer 7 is provided like the medium 8 of FIG. 2, for example, γ-F
e ₂ O ₃ , Co deposition γ-Fe ₂ O ₃ , Fe ₃ O ₄ , Cr
_{O 2, Fe, Fe-Cr} , Fe-Co, Co-Cr, C
A magnetic coating material composed of a dispersion of fine magnetic particles of o-Ni, MnAl, Ba ferrite, Sr ferrite or the like is applied. Generally, the holding force of a magnetic recording medium used for a magnetic recording medium such as a prepaid card is 300 to 3000 Oe, and the residual magnetic flux is
1.0 to 2.0 Maxwell / Cm.

The metal-based thin film layer 4 is a vapor-deposited layer of a non-magnetic metal, and examples of this type of metal include aluminum and tin. It is formed by a vacuum vapor 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 5 is, for example, a polyester resin,
Acrylic resin, urethane resin, nitrocellulose resin, styrene resin may be made into ink and coated. Further, a lubricant may be added for the purpose of improving suitability for discharge recording.

The print layer 6 can be printed with characters such as UV curable process ink used in prepaid cards by the offset printing method. However, when the return electrode (earth electrode) comes into contact with the printed layer during discharge breakdown recording, the conductivity of the return electrode side decreases, and discharge (earth return) occurs from the return electrode side. Therefore, in order to reduce the number of return electrodes (earth electrodes) on the printed layer, it is necessary to provide the characters of the printed layer by halftone printing or the like.

Hereinafter, one embodiment of the present invention will be described in detail.

<Example 1> L-having a number average molecular weight of 150,000
60% by weight of a 3: 2 copolymer of lactic acid and 6-hydroxycaproic acid, 35% by weight of mica (HAR160 manufactured by Shiraishi Industry Co., Ltd.), and 5% by weight of titanium oxide were kneaded in a vent-type extruder and then mixed with T-die. After extruding to a specified thickness at a processing temperature of 200 ° C. by a melt extruder, biaxial stretching processing and calendering processing were performed to obtain a sheet having a thickness of 188 μm and having improved surface smoothness. A gravure Sumi ink was provided on the base material by a gravure printing method to a thickness of about 1 μm, and aluminum was vapor-deposited thereon to a thickness of 0.1 μm by a vacuum vapor deposition method to form a metal vapor deposition layer. Next, a nitrocellulose resin was applied to a thickness of 1.0 μm to form a protective layer. A print layer was provided thereon by an offset printing method using UV process ink. The discharge breakdown recording medium having the biodegradable resin as a base material thus obtained was cut into a card shape.

A return electrode was placed on the printed layer of the discharge breakdown recording medium manufactured by the above process, and a voltage of -30 V was applied. As a result, the recording needle side is discharged, the metal vapor deposition layer is destroyed, and a colored layer hidden underneath appears,
It was possible to record clear discharge breakdown. Furthermore, when this card was embedded in field soil and the decomposition state was observed, it was found that the shape was not retained after 6 months.

<Example 2> L-having a number average molecular weight of 150,000
60% by weight of a 3: 2 copolymer of lactic acid and 6-hydroxycaproic acid, 35% by weight of mica (HAR160 manufactured by Shiraishi Industry Co., Ltd.), and 5% by weight of titanium oxide were kneaded in a vent-type extruder and then mixed with T-die. After extruding to a specified thickness at a processing temperature of 200 ° C. by a melt extruder, biaxial stretching processing and calendering processing were performed to obtain a sheet having a thickness of 188 μm and having improved surface smoothness. A magnetic coating material having the following composition was formed on this substrate by knife coating to form a black magnetic recording layer of about 10 μm, magnetic field orientation was applied in a horizontal magnetic field of about 3000 Gauss, and then dried with hot air at 100 ° C. for 3 minutes. Let・ Magnetic paint Magnetic powder (1750 / Oe: Barium ferrite) 100 parts by weight Vinyl chloride-vinyl acetate copolymer (VAGF: Union Carbide) 20 parts by weight Polyurethane resin (Nipporan 2304: Nippon Polyurethane Industry Co., Ltd.) 30 parts by weight Hexa Methylene diisocyanate (Coronate HX: Nippon Polyurethane Industry) 2 parts by weight Carbon black (# 3000: manufactured by Mitsubishi Kasei) 5 parts by weight Dispersant (Garfuck RE-610: manufactured by Toho Kagaku) 3 parts by weight Diluting solvent (toluene / MEK) / MIBK) 100 parts by weight Aluminum was vapor-deposited thereon to a thickness of 0.1 μm by a vacuum vapor deposition method to form a metal vapor deposition layer. Next, a nitrocellulose resin was applied to a thickness of 1.0 μm to form a protective layer. A print layer was provided thereon by an offset printing method using UV process ink. The discharge breakdown recording medium having the biodegradable resin as a base material thus obtained was cut into a card shape.

A return electrode was placed on the printed layer of the discharge breakdown recording medium manufactured by the above process, and a voltage of -30 V was applied. As a result, discharge was caused from the recording needle side, the metal vapor deposition layer was destroyed, and a black magnetic layer concealed underneath appeared, and clear discharge breakdown recording could be performed. Also,
2 for gate with magnetic read / write device for media
When passed at m / sec, no abnormality occurred.
Furthermore, when this card was embedded in field soil and the decomposition state was observed, after 6 months, the magnetic recording layer was left,
The shape was not retained.

[0036]

As described above, the discharge breakdown recording medium of the present invention is easily decomposed in the microbial active state of compost, field soil, etc., and even when scattered in the natural environment, the action of microorganisms in the environment Disassemble the card. Even if it is burnt and discarded, the heat of combustion is low and no toxic gas is generated. At the same time, the metal vapor deposition layer of the discharge breakdown recording system is provided, so the heat resistance is high and the printing is clear.
It also has the feature of high printing speed.

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of a discharge breakdown recording medium of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of the discharge breakdown recording medium of the present invention.

FIG. 3 is a sectional view showing another embodiment of the discharge breakdown recording medium of the present invention.

[Explanation of symbols]

 1, 8, 9 ... Discharge breakdown recording medium 2 ... Medium base material 3 ... Colored layer 4 ... Metal thin film layer 5 ... Protective layer 6 ... Printing layer 7 ... Magnetic recording layer 10 ... Paper base material

Claims (8)

[Claims] 1. A discharge breakdown recording medium in which a colored layer, a metal thin film layer, a protective layer, and a printing layer are sequentially laminated on a support constituting a medium, wherein the support contains a decomposable resin. A discharge breakdown recording medium comprising a base material as a main component. 2. An aliphatic polyester in which the degradable support has a hydroxyalkanoate unit such as 3-hydroxyvalerate, 3-hydroxybutyrate, 3-hydroxycaprolate, or 3-hydroxyheptanoate. The discharge breakdown recording medium according to claim 1, wherein 3. The degradable support is represented by the following formula: Embedded image The discharge breakdown recording medium according to claim 1, which is the chemically synthesized polyester shown in. 4. The discharge breakdown recording medium according to claim 1, wherein the degradable support is a composite resin of starch and polyvinyl alcohol. 5. The support having the degradability has an average molecular weight.
2. A discharge breakdown recording medium according to claim 1, which is composed of decomposable polylactic acid obtained by stretching a thermoplastic resin containing 10,000 to 1,000,000 polylactic acid or a copolymer of lactic acid and oxycarboxylic acid as a main component. . 6. The degradable support is formed by laminating the degradable resin according to any one of claims 1 to 5 on at least one surface of a card substrate made of a naturally degradable material such as paper. The discharge breakdown recording medium according to claim 1. 7. The discharge breakdown recording medium according to claim 1, wherein the colored layer is colored with a magnetic material. 8. The discharge breakdown recording medium according to claim 7, wherein the resin in which the magnetic material is dispersed is a biodegradable resin.