WO2009093555A1 - 磁気記録媒体の製造方法 - Google Patents
磁気記録媒体の製造方法 Download PDFInfo
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- WO2009093555A1 WO2009093555A1 PCT/JP2009/050716 JP2009050716W WO2009093555A1 WO 2009093555 A1 WO2009093555 A1 WO 2009093555A1 JP 2009050716 W JP2009050716 W JP 2009050716W WO 2009093555 A1 WO2009093555 A1 WO 2009093555A1
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- protective layer
- magnetic recording
- laminate
- particles
- recording medium
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
- G11B5/8408—Processes or apparatus specially adapted for manufacturing record carriers protecting the magnetic layer
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/72—Protective coatings, e.g. anti-static or antifriction
- G11B5/725—Protective coatings, e.g. anti-static or antifriction containing a lubricant, e.g. organic compounds
- G11B5/7253—Fluorocarbon lubricant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/90—Magnetic feature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to a method for producing a magnetic recording medium produced by forming a laminate having a magnetic recording layer and a protective layer on a nonmagnetic support as a substrate.
- a magnetic recording medium is produced by laminating a magnetic laminate having a magnetic recording layer, a protective layer and the like through a process such as coating, transferring, and laminating on a nonmagnetic support as a substrate. Except for the coating process, the magnetic recording medium formed in this way is often partially formed on a nonmagnetic support.
- hot pressing is performed on the magnetic laminate. And embedding the magnetic laminate in the substrate so that the surface of the protective layer, which is the outermost layer of the magnetic laminate, forms the same smooth plane as the surface of the substrate where the magnetic laminate is not formed.
- a method of forming a magnetic laminate on a substrate that is a non-magnetic support before hot-pressing a method of mainly forming a transfer laminate using a transfer laminate and a laminating laminate are used.
- a protective layer that is directly exposed to a hot press using a mirror-like metal press plate is required to have various characteristics.
- the main functions required of the protective layer of the laminate for thermal transfer and the laminate for lamination are anti-seizure properties that prevent seizure on the press plate when subjected to hot-pressing, and the outermost layer of the magnetic recording medium. In addition, it has scratch resistance that can be a protective layer for the magnetic layer.
- the protective layer uses a binder resin that has both peelability from the transfer support and interlaminar adhesion with the magnetic recording layer, ensuring easy peelability and improving scratch resistance.
- additives such as wax are used.
- the binder resin for the protective layer acrylic resins, butyral resins, cellulose resins (for example, Patent Document 1) and the like are known.
- additives for improving scratch resistance fatty acids and salts thereof
- Various waxes for example, Patent Document 2
- fluororesin particles for example, Patent Document 3 are known.
- a laminated body including a magnetic recording layer on a transfer support is thermally transferred to a substrate which is a nonmagnetic support, and then the transfer support is peeled off and a protective layer is formed.
- the laminated body including the magnetic recording layer transferred onto the substrate as the uppermost layer is subjected to hot pressing using a metal press plate polished to a mirror finish.
- the laminated body for bonding is arrange
- a polyethylene wax that is suitably used as a wax for improving the scratch resistance is the excellent abrasion resistance of polyethylene itself and the slipperiness of a low melting point wax component that melts by heat during hot press. It functions as a lubricant on the protective layer of a magnetic recording medium such as a magnetic card, reduces wear of the protective layer by a magnetic head for magnetic recording / reproducing, and imparts practically preferable durability as a magnetic recording medium.
- the adhesiveness with the binder resin is inferior, and the PTFE particles are separated from the binder resin during magnetic card production or normal handling such as magnetic recording / reproducing, resulting in practically preferable durability as a magnetic recording medium. It was difficult.
- it is effective to reduce the amount of polyethylene wax to be added or to use a polyethylene wax having a low migration property. Lubricity was lowered, and it was difficult to obtain practically preferable durability as a magnetic recording medium.
- JP 7-65356 A page 3
- JP 2001-351074 A page 3
- An object of the present invention is a manufacturing method for manufacturing a magnetic recording medium having a magnetic recording layer and a protective layer on a substrate which is a non-magnetic support, wherein the protective layer has good scratch resistance, magnetic While maintaining the adhesion to the recording layer, the metal press plate in the manufacturing process is suppressed in the manufacturing process by suppressing the transfer of the lubricant from the protective layer to the mirror-finished metal press plate surface in the hot press process during the production of the magnetic recording medium. It is an object of the present invention to provide a method of manufacturing a magnetic recording medium that does not contaminate and deform the surface and, in turn, the surface of the magnetic recording medium, and can realize excellent manufacturing efficiency.
- the present inventors aim to improve the protective layer of a thermal transfer laminate or a laminate for lamination used for laminating a magnetic laminate on a nonmagnetic support substrate.
- the scratch resistance is maintained while maintaining good recording / reproduction characteristics of the magnetic recording layer produced.
- additives such as wax can be prevented from adhering to the surface of a mirror-like metal press plate for hot press during production.
- the present invention has been completed as a result of considering the countermeasures in consideration of the further demand for good peelability of the protective layer itself.
- the present invention includes a step of forming a laminate having an adhesive layer, a magnetic recording layer, and a protective layer on a substrate that is a nonmagnetic support from the side close to the substrate, and hot pressing from above the protective layer.
- a method of manufacturing a magnetic recording medium comprising: embedding the laminate in the substrate, and forming a surface of the substrate that is the nonmagnetic support and the outermost surface of the laminate to form the same smooth plane.
- the protective layer contains particles made of a mixture containing polyethylene and polytetrafluoroethylene, and a binder resin, and provides a method for producing a magnetic recording medium.
- the present invention also provides the above-described method for producing a magnetic recording medium, wherein the formation of a laminate on a substrate that is a nonmagnetic support is performed in a transfer step using a laminate for thermal transfer. Furthermore, the present invention provides a thermal transfer laminate in which at least a protective layer, a magnetic recording layer and an adhesive layer are laminated in this order on a transfer support, wherein the protective layer comprises polyethylene and polytetrafluoroethylene. There is provided a laminate for thermal transfer, characterized in that it comprises particles comprising: a binder resin.
- the formation of the laminate on the substrate which is the nonmagnetic support has a magnetic recording layer and a protective layer on one side of the support from the side close to the support, and the other of the supports for bonding.
- the manufacturing method of the magnetic-recording medium formed through the bonding process of the laminated body for bonding which has an adhesive layer is provided.
- the present invention provides a laminated body having a magnetic recording layer and a protective layer on one side of the support from the side close to the support, wherein the protective layer is made of a mixture containing polyethylene and polytetrafluoroethylene.
- the laminated body for bonding characterized by having binder resin.
- the protective layer contains particles made of a mixture containing polyethylene and PTFE
- the magnetic recording layer and the protective layer are provided on the substrate that is a nonmagnetic support.
- the polyethylene as the lubricant in the protective layer is hot pressed. There is no transition to the mirror plate side. Since the laminate for thermal transfer and the laminate for bonding used in the production method of the present invention contain wax particles made of a mixture having polyethylene and PTFE in the protective layer, the laminate for thermal transfer and the laminate for bonding are included.
- the protective layer of the magnetic recording medium produced in the thermal transfer process and the bonding process using the body has good scratch resistance, and the presence of PTFE in the protective layer is the heat pressure in the manufacturing process of the magnetic recording medium. Suppresses the transfer of polyethylene wax to the metal press plate during pressing. For this reason, the surface of the magnetic recording medium produced is less likely to be contaminated or deformed due to the retransfer of polyethylene wax once attached to the metal press plate, and the design of characters and designs formed on the surface of the magnetic recording medium may be impaired. Absent.
- a laminate for thermal transfer containing wax particles made of a mixture having polyethylene and PTFE in the protective layer, and a lamination for bonding Since the magnetic recording layer and the protective layer are formed on the substrate in the thermal transfer process and the bonding process, the transfer of the wax to the metal press plate is suppressed when hot pressing is performed from the top of the protective layer. The frequency with which the metal press plate is cleaned is greatly reduced, which significantly improves the production efficiency.
- the reason why the laminated body for thermal transfer and the laminated body for bonding of the present invention, and further the magnetic recording medium produced from them exhibit the above-mentioned effects is considered from the mechanism that the lubricant added to the protective layer exerts its function. Then, it is considered as follows.
- the durability of magnetic recording media depends on the wear resistance of the protective layer of the thermal transfer laminate and the laminate for bonding, and the wear resistance of the protective layer is mainly due to the properties of the lubricant dispersed in the binder resin. It depends on you.
- Conventional thermal transfer laminates and laminating laminates produced by dispersing polyethylene wax particles having excellent lubricity in a protective layer are excellent in flexibility, abrasion resistance, and binder resin of polyethylene particles themselves.
- the surface of the protective layer is also subjected to heating and pressurization by a hot press process when forming the magnetic recording medium.
- the heating temperature and pressure applied in this process vary slightly depending on the configuration of the magnetic recording medium to be manufactured and the equipment used in the hot-pressing process, but in the normal manufacturing process, the heat pressure by a metal plate having a mirror surface is used.
- a pressing process is used, and a heating temperature of 120 to 180 ° C. and a pressure and pressure of 10 to 25 kgf / cm 2 are applied to the protective layer.
- This migrating lubricant component is a low molecular weight (or low melting point) component of polyethylene wax, and in this case, it is considered that this component mainly exerts a lubricity improving effect. Therefore, for example, this low molecular weight component can be greatly reduced, or instead, the medium to high molecular weight polyethylene particles that are difficult to migrate to the metal press plate surface can be added to the protective layer to improve wax migration. Can be planned.
- the low molecular weight component of the wax is significantly reduced, the slipperiness is weakened, the surface of the protective layer is easily scratched, and the polyethylene particles are easily removed from the coating film. Abrasion is reduced and the durability of the magnetic recording medium is insufficient.
- the reason why the polyethylene particles are easy to fall off is that the friction between the protective layer of the magnetic recording medium and the magnetic head becomes stronger due to the decrease in the slipperiness of the coating film due to the decrease in the low molecular weight component, which is highly effective in improving the lubricity. This is thought to be because the particle hardness increases with the molecular weight, and the action of releasing the magnetic head stress is weakened by the elasticity of the particles.
- PTFE particles have poor adhesion to the binder resin and can easily be granulated from the coating film by rubbing with a magnetic head, so that sufficient wear resistance cannot be obtained.
- the magnetic head rubs the surface of the protective layer while applying pressure with a predetermined force, the wax particles themselves in the protective layer themselves have moderate hardness (flexibility) to prevent degranulation and do not damage the magnetic head surface.
- polyethylene wax is excellent. Therefore, from a comprehensive point of view, the conventionally used polyethylene particles are considered to be suitable materials except for wax migration.
- the abrasion resistance of the protective layer of the laminate for thermal transfer is generally good with the abrasion resistance, flexibility, abrasion resistance of the particles such as wax dispersed in the protective layer and the binder resin. It is estimated that the excellent adhesion and the slipperiness of the particles themselves work comprehensively against the rubbing force of the magnetic head.
- the abrasion resistance of the protective layer of the laminate for thermal transfer and the laminate for bonding is the transfer of the wax component to the mirror plate for hot press. It seems that there is a trade-off relationship between ease.
- a polyethylene resin component suitable for the flexibility, wear resistance, and good adhesion to the binder resin of the wax particle itself is used as a main component, and PTFE is mixed with polyethylene wax at the particle production stage.
- PTFE is mixed with polyethylene wax at the particle production stage.
- the composite particles are formed as a plurality of non-spherical amorphous particles, and the PTFE particles are present on the surface of the polyethylene wax particles, and at least a part of the PTFE particles are embedded in the particles. Further, the adhesion between the composite particles containing PTFE particles and the binder resin is further improved, and the detachment from the coating film is more effectively suppressed. More preferably, a part of the PTFE particles is exposed on the surface of the wax particles, so that the contact pressure between the polyethylene wax and the metal press plate surface is reduced, the lubricity by the wax particles is further increased, and the wax migration property is increased. It is thought that an effect of further reducing the above is added. In this way, by using the wax particles made of a mixture having polyethylene and PTFE and complementing both properties, it is possible to adjust both the wear resistance and the lubricant migration suppression properties at the same time.
- a laminate having a magnetic recording layer and a protective layer is formed on a substrate which is a nonmagnetic support, and then the laminate is non-coated by performing hot-pressing from the protective layer. It has a step of embedding in a substrate which is a magnetic support, but the protective layer contains particles made of a mixture containing polyethylene and PTFE and a binder resin. Good seizure resistance in the process can be maintained, and the wax component transfer to the mirror-finished metal press plate of the hot press can be remarkably reduced.
- the laminate for thermal transfer used in the method for producing a magnetic recording medium of the present invention has excellent scratch resistance while the protective layer formed maintains good peelability in the transfer process and good adhesion to the magnetic recording layer.
- a lubricant such as wax does not migrate to the metal press plate. Therefore, the surface of the manufactured magnetic recording medium is not contaminated or deformed by the lubricant such as wax through the metal press plate.
- the frequency which cleans a metal press board for this reason can be reduced significantly, manufacturing efficiency improves remarkably. Further, these protective layers do not deteriorate the recording / reproducing characteristics of the formed magnetic recording medium.
- the laminate for bonding used in the method for producing a magnetic recording medium of the present invention has an excellent scratch resistance while the formed protective layer maintains good adhesion to the magnetic recording layer, and on the protective layer.
- a lubricant such as wax does not migrate to the metal press plate. Therefore, the surface of the manufactured magnetic recording medium is not contaminated or deformed by the lubricant such as wax through the metal press plate.
- the frequency which cleans a metal press board for this reason can be reduced significantly, manufacturing efficiency improves remarkably. Further, these protective layers do not deteriorate the recording / reproducing characteristics of the formed magnetic recording medium.
- the migration of the low molecular weight component of polyethylene wax to the metal press plate is reduced, and therefore the reduced surface lubricity is effectively compensated with PTFE particles.
- the wax particles contained in the protective layer of the laminate for thermal transfer or the laminate for bonding in the present invention are preferably polyethylene wax particles in which at least part of the PTFE particles are embedded in the particles, and the main component is polyethylene. It is preferable that the composite particles contain PTFE particles partially embedded in the particles and partially exposed on the particle surface.
- the composite particles made of a mixture containing polyethylene and PTFE are preferably non-spherical amorphous.
- the wax particles contained in the protective layer preferably have a volume average particle diameter of 6 ⁇ m or less.
- the protective layer binder resin of the thermal transfer laminate preferably contains a cellulose derivative resin as the main component of the binder resin, and the cellulose derivative resin is particularly preferably a cellulose acetate resin.
- the magnetic recording medium refers to magnetic disks such as magnetic disks and tapes, magnetic cards such as plastic credit cards and cash cards, synthetic paper magnetic passbooks such as banks, or paper tickets and pass tickets. Etc.
- a magnetic tape also referred to as a magnetic stripe
- a magnetic card provided in a magnetic card or a “heat transfer laminate” or “lamination laminate” itself described below is magnetic in a broad category. It is considered to be in the category of recording media.
- the thermal transfer laminate of the present invention is mainly used in the manufacture of magnetic cards and the like, and a magnetic sheet for transfer in which a magnetic recording layer and other functional layers are laminated (the one processed into a tape shape is called a transfer type magnetic tape). And a layer including a magnetic recording layer can be thermally transferred to a substrate for a magnetic recording medium.
- the thermal transfer laminate is a laminate structure in which at least three layers of a protective layer, a magnetic recording layer, and an adhesive layer, which are the uppermost layers in the final product, are formed in this order on a transfer support that is a nonmagnetic support. (See FIG. 1). Then, the adhesive layer is fixed in contact with the substrate for the magnetic recording medium, and the transfer support is peeled off from the interface with the protective layer after transfer. Then, the laminated body excluding the transfer support is subjected to a hot press from above the protective layer, and is embedded in the base for the magnetic recording medium.
- the specific wax used for the protective layer of the thermal transfer laminate of the present invention is wax particles made of a mixture having polyethylene and PTFE.
- a commercially available example of such wax particles is “Fluoroslip 731MG” which is a polyethylene / PTFE wax manufactured by Shamrock.
- PTFE has a melting point of 327 ° C, which is much higher than ordinary polyethylene, has excellent heat resistance and chemical resistance, is not affected by almost all organic solvents, acids and alkalis, and has water repellency, oil repellency and electrical properties. Excellent and coefficient of friction is small.
- PTFE is mixed with polyethylene as particulate PTFE obtained by radical polymerization of tetrafluoroethylene by suspension polymerization method or emulsion polymerization method, and has a volume average particle size of about 0.3 to 3 ⁇ m. It is considered that the particles are preferably taken into the polyethylene particles as PTFE particles having a polymerization degree suitable for mixing.
- the PTFE particles are preferably those that can be pulverized using a ball mill or other pulverizing apparatus and the particle diameter can be adjusted.
- wax particles comprising a mixture having polyethylene and PTFE
- the PTFE particles are dispersed in polyethylene or a monomer compound thereof, and are interposed during the production process.
- a wax similar to a normal method for producing polyethylene wax particles can be produced by containing PTFE particles and in a particle state at room temperature.
- Polyethylene wax can be widely used with a molecular weight conventionally used as a wax, but the low molecular weight component is reduced to such an extent that the surface hardness becomes too high and degranulation is not likely to occur. It is preferable that the sex component is small. Furthermore, other waxes that can be mixed in advance during the production of the wax particles, such as carnauba wax, can be added as necessary.
- PTFE is preferably 0.2 to 70% by mass of the total lubricant component, and more preferably 1 to 30% by mass with stable presence as composite particles.
- the volume average particle diameter of the wax particles that are the composite particles is preferably 6 ⁇ m or less from the viewpoint of the balance with the film thickness of the protective layer and the uniformity of the distribution of the wax particles, and 3 ⁇ m or less. Is more desirable.
- the protective layer of the present invention is a thermal transfer protective layer for protecting the pattern layer and the magnetic recording layer against hot press during the production of the magnetic recording medium. Even if the particle diameter is somewhat larger than 5 to 3 ⁇ m, it does not protrude onto the protective layer of the magnetic recording medium after thermal transfer.
- the added wax particles are partially exposed on the surface of the protective layer of the magnetic recording medium depending on the addition amount and the particle size, and a part of the wax component is transferred from the exposed portion to a mirror plate used for hot press. .
- the larger the wax particle diameter the stronger the tendency of the transition.
- the exposed area on the surface of the protective layer is reduced by setting the average particle diameter to be equal to or smaller than the above-described average particle diameter, and the elution of the wax component through the exposed portion of the wax particles during the hot press is suppressed. Migration to the metal press plate surface can be suppressed.
- the PTFE component of the wax particles non-spherical indefinite, it is difficult for the particles to fall off from the binder particles, and an excellent lubricity imparting effect can be obtained.
- composite particles in which at least a part of PTFE particles are embedded in particles having polyethylene as a main component are preferable. By using such composite particles, the PTFE particles can be prevented from falling off.
- a plurality of PTFE particles are present on the particle surface containing polyethylene as a main component, a part of the PTFE particle is embedded in the particle, and a part of the PTFE particle is exposed on the particle surface. More preferably.
- the transition component eluted from the polyethylene component inside the composite particle at the time of hot press is added to the effect of making it difficult to transfer to the surface of the mirror-finished metal press plate for hot press.
- the addition amount of the wax is preferably 1 to 10% by mass, more preferably 2 to 5% by mass with respect to the binder resin of the protective layer.
- the amount added is less than 1% by mass, sufficient surface slipperiness of the protective layer cannot be obtained, and when it is more than 10% by mass, the coating of the protective layer becomes brittle and has practically preferable durability as a magnetic recording medium. It becomes difficult to obtain.
- the binder resin contained in the protective layer of the laminate for thermal transfer of the present invention when a coating film is formed, the film / film-forming property is high and the elastic modulus is relatively high, and at the interface with the transfer support. It is preferable that it has good peelability and has good heat resistance when it becomes the outermost layer after transfer. If it has such a characteristic, the binder resin conventionally used for the protective layer can be widely used. For example, fiber resins such as nitrocellulose and synthetic resins such as acrylic resins can be used alone or in combination. In the present invention, a composition in which a cellulose derivative resin having a relatively hard, good film property, and excellent releasability as a main component and an isocyanate compound is added and crosslinked is preferable.
- the weight average molecular weight of the cellulose derivative resin suitable for the protective layer of the present invention is 10,000 to 70,000.
- the molecular weight is too small, good characteristics relating to the production process such as easy peelability and aging peel stability will not be exhibited.
- the molecular weight is too large, the viscosity of the coating becomes high and thin film coating becomes difficult.
- the cellulose derivative resin include, for example, cellulose acetate, cellulose acetate butyrate, cellulose acetate nitrate, cellulose acetate propionate and the like, which are excellent in releasability from PET film, and in particular, cellulose acetate.
- Cellulose acetate resin is particularly preferred. They can be used alone or in combination.
- the hydroxyl group content in the cellulose derivative resin is preferably in the range of 1 to 7%.
- the heat resistance and mechanical strength characteristics tend to decrease, which may cause seizure during hot press processing and damage to the protective layer during recording head running.
- the hydroxyl group content is high, it tends to be difficult to form a paint because it is hardly soluble in organic solvents, and the paint tends to thicken with the addition of a crosslinking accelerator (curing agent). There is a possibility of causing problems in the coating process.
- the crosslinking accelerator is an isocyanate compound or the like added to improve the mechanical properties of the protective layer, such as scratch resistance, and causes a crosslinking reaction to accelerate curing.
- the amount of the isocyanate compound used is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.
- the protective layer coating used in the present invention is prepared by adjusting the wax particles comprising the above-mentioned mixture containing polyethylene and polytetrafluoroethylene, the above-mentioned binder resin, and, if necessary, known and commonly used dispersion stabilizers, surfactants, and anti-blocking agents.
- the agent is mixed and stirred with a stirrer such as a disper in a mixed solvent such as acetone, ethyl acetate, cyclohexanone, toluene, etc., and uniformly dispersed.
- a stirrer such as a disper in a mixed solvent such as acetone, ethyl acetate, cyclohexanone, toluene, etc., and uniformly dispersed.
- the solid content ratio of the paint at that time is preferably 5 to 35%.
- the magnetic recording layer of the thermal transfer laminate of the present invention can be widely used with known materials and configurations, but the method of using a coating process for the magnetic recording layer is used.
- the degree of freedom of material selection is wide, and it is preferable from the viewpoint of being able to easily cope with various shapes, film thicknesses, and the like and at low cost.
- the magnetic material used when the magnetic recording layer of the thermal transfer laminate of the present invention is produced using the magnetic recording layer coating material known and commonly used materials such as ⁇ -iron oxide, magnetite, cobalt-coated iron oxide, Magnetic powders such as chromium dioxide, iron-based metal magnetic powder, strontium ferrite, and barium ferrite can be used.
- the binder resin used in the magnetic recording layer coating known and commonly used, for example, polyvinyl chloride resin, acrylic resin, acrylic urethane resin, nitrocellulose resin, polyurethane, polyester, etc., alone or in combination, Can be used.
- the coating material for the magnetic recording layer is prepared by adding the above magnetic powder and 20 to 30% by mass of the above binder resin, and, if necessary, known and commonly used dispersion stabilizers, surfactants, resin fillers and the like. , Dissolved and dispersed in a mixed solvent such as methyl ethyl ketone, toluene and cyclohexanone.
- the solid content concentration of the paint at that time is preferably 25 to 60% by mass.
- a known and commonly used dispersing machine such as a ball mill or a sand grind mill can be used.
- the adhesive layer of the thermal transfer laminate of the present invention can be formed through an application process of a known adhesive layer coating material containing a binder resin for an adhesive.
- the binder resin for the adhesive layer may be any thermoplastic binder resin that is tack-free at room temperature but develops adhesiveness when heated, such as a commonly used, for example, polyvinyl chloride resin, A polyurethane resin or the like can be used.
- the coating material for the adhesive layer is prepared by, for example, dissolving in a mixed solvent such as methyl ethyl ketone and toluene so that the binder resin is 3 to 70% by mass.
- antiblocking agents such as a silica, can also be added as needed.
- the transfer support that can be used in the thermal transfer laminate of the present invention is generally a synthetic resin film or a synthetic paper called a release paper, and can be selected without any limitation as long as it matches the use conditions. It is.
- a synthetic resin film is suitable, and in particular, a PET (polyethylene terephthalate) film having a thickness of 12 to 50 ⁇ m is more suitable from the viewpoint of heat resistance and tensile strength.
- the method for producing a thermal transfer laminate of the present invention can be formed by laminating at least a protective layer, a magnetic recording layer, and an adhesive layer in this order on the transfer support.
- Each layer can be formed by using a forming paint for each layer and simultaneously or sequentially by a coating process.
- the dry thickness of the protective layer is preferably 0.3 to 3 ⁇ m.
- coating system A well-known and usual system can be used, It can manufacture by employ
- gravure method reverse method
- air doctor coater method blade coater method
- air knife coater method squeeze coater method
- impregnation coater method transfer roll coater method
- kiss coater method kiss coater method
- cast coater method cast coater method
- spray coater method die The method etc.
- the magnetic recording layer is formed by adding an isocyanate compound as a curing agent to the above-described coating material for the magnetic recording layer, applying the dried coating thickness on the above-described protective layer to 2 to 30 ⁇ m, and then performing a heat curing treatment.
- an isocyanate compound as a curing agent
- coating of a protective layer can be used.
- the formation of the adhesive layer is performed by applying the adhesive layer coating material on the magnetic recording layer so that the dry coating thickness is 0.3 to 10 ⁇ m.
- coating system There is no restriction
- a method of forming a laminate on a transfer support it is generally produced by a coating process in which paints for each layer are sequentially used.
- a thermal transfer laminate is used for forming each layer. It can also be produced by a transfer process.
- the thermal transfer laminate is a colored layer (hiding layer) on the magnetic recording layer when transferred to a substrate for a magnetic recording medium.
- the coloring layer and the pattern layer may be formed in this order, and the protective layer may be formed thereon.
- the protective layer is formed on the transfer support, the colored layer or pattern layer and the colored layer are formed in this order, and then the magnetic recording layer and the adhesive layer are laminated.
- a known manufacturing method can be used for the colored layer (hiding layer) and the pattern layer.
- a thermal transfer laminate using a known transfer technique on a conventionally known magnetic card substrate in order to produce a magnetic card using the thermal transfer laminate (see FIG. 1) produced by the above method, a thermal transfer laminate using a known transfer technique on a conventionally known magnetic card substrate. It can be performed by passing through a transfer step for transferring the upper laminate and a hot pressing step for further applying heat as necessary.
- the adhesive layer side of the thermal transfer laminate having a protective layer, a magnetic recording layer and an adhesive layer on the transfer support is brought into close contact with the surface of the magnetic recording medium substrate which is a non-magnetic support.
- an adhesive layer on a magnetic recording medium substrate such as a magnetic card After fixing by applying pressure from the support side, or heating and pressurization, and peeling the support for transfer from the interface with the protective layer, an adhesive layer on a magnetic recording medium substrate such as a magnetic card, A laminate having a magnetic recording layer and a protective layer can be formed.
- the laminated body for thermal transfer is slit in advance to the width of the laminated body formed in the transfer step to form a transfer type magnetic tape, which is thermally transferred onto a substrate such as a magnetic card.
- the substrate for the magnetic recording medium to which the thermal transfer laminate is thermally transferred has various materials depending on the application as long as it has mechanical strength, chemical resistance, solvent resistance, and heat resistance that can withstand repeated use. Is applicable.
- paper such as fine paper, OCR paper, carbonless paper, art paper, and various plastic films can be applied.
- plastic film materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, Examples thereof include acrylic resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate, and polycarbonate.
- the base film may be a copolymer resin mainly composed of these resins, or a mixture or a laminate composed of a plurality of layers.
- a polyester film such as polyethylene terephthalate and polyethylene naphthalate and a vinyl film such as polyvinyl chloride are preferably used.
- the base film may be subjected to an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, an ozone treatment, a primer application treatment for applying an easy adhesive, or the like to the coated surface prior to the application.
- an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, an ozone treatment, a primer application treatment for applying an easy adhesive, or the like to the coated surface prior to the application.
- additives such as a filler, a plasticizer, a coloring agent, and an antistatic agent, to this resin film as needed.
- the filler extender pigments such as silica and calcium carbonate can be applied.
- a base material containing a pigment such as titanium oxide and colored white is used.
- the thickness of the substrate is not particularly limited as long as the overall rigidity is appropriately maintained, and a thickness of 100 to 800 ⁇ m is usually applicable. If the thickness exceeds 800 ⁇ m, it is too rigid and inconvenient to carry, etc., heavy and expensive. If the thickness is less than 100 ⁇ m, wrinkles and creases may occur due to external force during repeated use or carrying. As a result, magnetic reading failure occurs and durability is poor.
- a single layer may be used, but a plurality of substrates having a total thickness falling within the above range may be used.
- a magnetic recording layer or the like is formed on a transparent base material and laminated with an opaque base material on which a pattern layer is separately formed, high designability can be imparted and the production process can be rationalized.
- a similar technique can be applied to the back side of the magnetic card. For this reason, when manufacturing a magnetic recording medium for cards, a magnetic recording layer or the like is formed on at least one of the two opaque base materials called a core sheet having a pattern or the like as necessary.
- a magnetic card is formed including a step of laminating two transparent oversheets.
- the laminate formed on the magnetic recording medium substrate in this way is further subjected to hot-pressing from the protective layer side so that the entire laminate is embedded in the magnetic recording medium substrate, and the laminate is formed on the outermost surface of the laminate.
- a hot pressing process is performed so that the surface of a certain protective layer and the surface of a substrate for a magnetic recording medium such as a magnetic card as a nonmagnetic support form the same smooth plane.
- the hot pressing step is performed simultaneously with the step of hot pressing the plurality of bases to integrate them. You can go.
- the magnetic card substrate having undergone the above-mentioned transfer process is used as one overlay sheet, and two core sheets are sandwiched between the other overlay sheet and the four sheets are thermocompression-bonded to obtain the card thickness.
- the step of forming the integrated sheet can be performed simultaneously with the hot-pressing step.
- the laminate for bonding of the present invention is mainly used for the production of magnetic cards and the like, and is typified by a magnetic tape processed into a tape shape after laminating a magnetic recording layer and other functional layers, It has a laminated structure in which at least two layers of a magnetic recording layer and a protective layer, which are substantially functional layers for magnetic recording and reproduction, are formed in this order on a bonding support that is a nonmagnetic support.
- an adhesive is coated on the support for bonding on the opposite side of the magnetic recording layer and then applied to the substrate for the magnetic recording medium. Overlap, and then hot press.
- the adhesive may be applied in advance on a bonding support to form an adhesive layer.
- an adhesive layer is provided in advance on a substrate for a magnetic recording medium, and the bonding support surface on the side opposite to the magnetic recording layer of the laminate for bonding is aligned with that portion, and hot pressing is performed.
- Manufactures magnetic recording media such as cards.
- the substrate for the magnetic recording medium is plastic, it is desirable to previously provide an adhesive layer on the side opposite to the magnetic recording layer on the bonding support. For this reason, all layers including the support for bonding of the laminated body for bonding are configured to be embedded in the base for the magnetic recording medium (see FIGS. 4, 5, and 7).
- the same wax as that used for the laminate for thermal transfer can be used.
- binder resin contained in the protective layer of the laminate for bonding according to the present invention when a coating film is formed, the film / film-forming property is high, the film has good adhesion to the magnetic recording layer, and is difficult to curl. And it is preferable that it has favorable heat resistance. If it has such a characteristic, binder resin suitable for a well-known protective layer can be widely used. For example, synthetic resins such as butyral resin, polyester resin, acrylic resin, and polyvinyl chloride resin are used singly or in combination. In the present invention, a cross-linking composition using an isocyanate compound or the like is preferable in consideration of solvent resistance.
- Adjustment of the coating for the protective layer is carried out by using wax particles made of a mixture containing the above polyethylene and polytetrafluoroethylene, a binder resin, and, if necessary, known and commonly used dispersion stabilizers, surfactants, antiblocking agents, etc., acetone, This is carried out by mixing and stirring uniformly in a mixed solvent such as ethyl acetate, cyclohexanone, and toluene with a stirrer such as a disper.
- the solid content ratio of the paint at that time is preferably 5 to 35%.
- the same material as the magnetic recording layer of the thermal transfer laminate can be used, and a magnetic recording layer can be produced by a similar method.
- the laminate for bonding used in the present invention preferably has an adhesive layer in advance on the side opposite to the side on which the magnetic recording layer and the protective layer of the support for lamination are laminated (FIG. 4, (See FIG. 5).
- the adhesive layer for adhering the laminate for bonding of the present invention and the substrate for the magnetic recording medium is formed through an application process of a coating material for an adhesive layer containing a binder resin for a known adhesive. Can do.
- the binder resin for the adhesive layer may be any thermoplastic binder resin that is tack-free at room temperature but develops adhesiveness when heated, such as a commonly used, for example, polyvinyl chloride resin, A polyurethane resin or the like can be used.
- the coating material for the adhesive layer is prepared by, for example, dissolving in a mixed solvent such as methyl ethyl ketone and toluene so that the binder resin is 3 to 70% by mass. Moreover, when forming an adhesive bond layer in advance in the laminate for bonding, an anti-blocking agent such as silica can be added as necessary.
- the bonding support that can be used in the bonding laminate of the present invention is a synthetic resin film, synthetic paper, or the like, and can be selected without particular limitation as long as it matches the use conditions.
- a synthetic resin film is suitable, and among these, a PET (polyethylene terephthalate) film having a thickness of 9 to 25 ⁇ m is more preferred from the viewpoint of heat resistance and tensile strength. Since the support is used by being embedded in a magnetic recording medium (see FIG. 7), a thickness of 9 to 16 ⁇ m is particularly preferable. Further, if necessary, an easy adhesion treatment in which a corona treatment or an easy adhesion layer is formed on one surface or both surfaces of the resin support may be performed.
- the method for producing a laminate for bonding according to the present invention can be formed by laminating at least a magnetic recording layer and a protective layer in this order on a support for bonding.
- Each layer can be formed by using a forming coating material for each layer by simultaneous application or sequential application by an application process.
- an isocyanate compound is added as a curing agent to the above-described coating material for the magnetic recording layer, and is applied on the support so that the dry coating thickness is 2 to 30 ⁇ m, followed by heat curing treatment.
- coating system A well-known and usual system can be used, It can manufacture by employ
- gravure method reverse method
- air doctor coater method blade coater method
- air knife coater method squeeze coater method
- impregnation coater method transfer roll coater method
- kiss coater method kiss coater method
- cast coater method cast coater method
- spray coater method die The method etc.
- the dry coating thickness of the protective layer is preferably 0.3 to 3 ⁇ m.
- coating system The method similar to having been used for application
- the adhesive layer is formed by coating the adhesive layer coating material on the opposite surface of the bonding support on which the magnetic recording layer is formed or on the substrate so that the dry coating thickness is 0.3 to 10 ⁇ m.
- coating system There is no restriction
- the laminate for bonding is a colored layer (hiding) on the magnetic recording layer when bonded to a substrate for a magnetic recording medium.
- Layer or a colored layer and a patterned layer may be formed in this order, and a protective layer may be formed thereon.
- the protective layer is laminated, and if necessary, the support for bonding
- An adhesive layer is formed on the opposite side of the body from the magnetic recording layer.
- a known manufacturing method can be used for the colored layer (hiding layer) and the pattern layer.
- the same material and shape as those used for the thermal transfer laminate can be used.
- it can be carried out by subjecting a conventionally known magnetic card substrate to a known hot pressing process.
- a laminated body in which an adhesive layer is provided in advance on the opposite side of the magnetic recording layer see FIG. 5
- the adhesive layer is brought into close contact with the substrate surface for the magnetic recording medium and heated and pressed.
- a laminate having an adhesive layer, a magnetic recording layer, and a protective layer can be formed on a substrate for a magnetic recording medium.
- a hot pressing process is performed in which the entire laminate for bonding is embedded in the substrate so that the surface of the protective layer, which is the outermost surface of the laminate, and the surface of the substrate for magnetic recording medium form the same smooth plane.
- the substrate is plastic
- the hot-pressing step is performed simultaneously with the step of hot-pressing and integrating the plurality of substrates.
- a bonding laminate in which an adhesive layer is provided in advance on the opposite surface of the magnetic recording layer of the bonding support is temporarily bonded to the substrate by weakening the heat and pressure conditions to form one overlay sheet.
- a magnetic recording medium in which the card thickness is integrated can be manufactured by sandwiching two core sheets together with the overlay sheet and thermocompressing these four sheets.
- the type (and addition amount) of the lubricant was changed as follows to prepare each protective layer coating material.
- a protective layer coating (b) was prepared in the same manner as the protective layer coating (a) except that the polyethylene / PTFE wax of the protective layer coating (a) was 0.48 part.
- ⁇ Coating for protective layer (c)> The protective layer coating material (a) is the same as the protective layer coating material (a) except that the polyethylene / PTFE wax used in the protective layer coating material (a) is pulverized with a ball mill to give a volume average particle size of about 2 ⁇ m as a lubricant.
- a protective layer coating material (c) was prepared.
- the protective layer coating material (a) is the same as the protective layer coating material (a) except that the polyethylene / PTFE wax used in the protective layer coating material (a) is pulverized with a ball mill to give a volume average particle size of about 1 ⁇ m as a lubricant. Similarly, a protective layer coating (d) was prepared.
- a protective layer coating material (j) was prepared in the same manner as the protective layer coating material (a) except that 0.48 part of silica particles (“Silicia 350” manufactured by Fuji Silysia Chemical Co., Ltd.) (average particle size of about 4 ⁇ m) was used.
- ⁇ Coating for protective layer (k)> In place of the lubricant for the protective layer paint (a), Stearic acid (“NAA-180” manufactured by NOF Corporation) 0.48 parts A protective layer coating material (k) was prepared in the same manner as the protective layer coating material (a), except that ⁇ Coating for protective layer (l)> A protective layer paint (l) was prepared in the same manner as the protective layer paint (a) except that the lubricant for the protective layer paint (a) was not added.
- ⁇ Magnetic recording layer coating (a)> 40 parts of Ba ferrite magnetic powder ("MC-127” manufactured by Toda Kogyo Co., Ltd.) 6 parts of vinyl chloride resin ("MR-110” manufactured by Zeon Corporation) 4 parts of polyurethane resin ("T-5206” manufactured by Dainippon Ink & Chemicals, Inc.) 20 parts of methyl ethyl ketone 20 parts of toluene 8 parts of cyclohexanone Isocyanate compound 2 parts ("Hardener No. 50" manufactured by Dainippon Ink & Chemicals, Inc.) The above components were kneaded and dispersed with a kneading and dispersing machine to prepare a magnetic recording layer coating material.
- Example 1 The protective layer coating material (a) was applied on a transfer support (24 ⁇ m thick, PET film) with a reverse coating system coating machine so that the dry coating thickness was 1.2 ⁇ m. Then, after drying in a nitrogen atmosphere, a thermosetting treatment was performed in air at 105 ° C. for 30 seconds to form a protective layer. On the protective layer, the above magnetic recording layer coating material is applied with a reverse coating method coating machine so that the dry coating thickness is 8 ⁇ m, dried in a nitrogen atmosphere, and then thermally cured at 105 ° C. for 30 seconds. The magnetic recording layer was formed by processing.
- Example 2 the above adhesive layer coating material was applied with a reverse coating system coating machine so that the dry coating thickness was 1.5 ⁇ m, and dried in a nitrogen atmosphere to form an adhesive layer. It formed and the laminated body for thermal transfer was obtained. This thermal transfer laminate was cut into a predetermined width to produce a transfer type magnetic tape.
- Examples 2 to 4 In the same manner as in Example 1, except that the protective layer paints (b), (c) and (d) were used instead of the protective layer paint (a). The transfer type magnetic tapes of Examples 2, 3, and 4 were produced.
- Comparative Examples 1 to 8 Comparative Example 1 to Comparative Example 1 were carried out in the same manner as in Example 1 except that the protective layer paints (e) to (l) were used in place of the protective layer paint (a). A transfer type magnetic tape of Comparative Example 8 was produced.
- test magnetic cards were produced.
- Thermal transfer conditions Using a heat sealer (manufactured by Tester Sangyo Co., Ltd.), a transfer type magnetic tape having a tape width of 13 mm is placed at a predetermined position of a 100 ⁇ m-thick polyvinyl chloride overlay sheet at 120 ° C. and 4 kgf / cm 2 for 5 seconds. After that, the transfer support film was peeled off to obtain an overlay sheet with a magnetic tape.
- Hot pressing conditions The overlay sheet with the magnetic tape is in contact with the two 280 ⁇ m-thick polyvinyl chloride core sheets, and another 100 ⁇ m polyvinyl chloride overlay sheet is stacked on the opposite side. Then, sandwiched between mirror-finished metal press plates (SUS430 buff finish made by Nikkin Steel) and using a card making machine (LX-EM-4 made by Interline) at a temperature of 148 ° C. and a pressure of 10 krf / cm 2. A pressure press was performed. The obtained card base material was punched into a predetermined size to obtain a test magnetic card (see FIGS. 2 and 3).
- mirror-finished metal press plates SUS430 buff finish made by Nikkin Steel
- LX-EM-4 made by Interline
- ⁇ Peelability test> The peelability between the transfer support (PET film) and the protective layer, that is, the peel strength is measured. When the peel strength value was in the range of 10 to 80 mN, it was judged as easy peelability, and “good”, and the others were “poor”.
- the laminated body for thermal transfer obtained in Examples 1 to 4 and Comparative Examples 1 to 8 was cut into a width of 10 mm to produce a transfer type magnetic tape, and the thickness of the magnetic card substrate made of polyvinyl chloride 100 ⁇ m.
- a peel test sample before peeling of the transfer support was obtained by heat transfer to the overlay sheet.
- the thermal transfer apparatus and thermal transfer conditions are as follows.
- the test magnetic card was repeatedly read 20,000 times with a card reader / writer (manufactured by OMRON). The number of repetitions was set to about 20,000 times in the five years of the card expiration date when used twice a magnetic card, and about 20,000 times considering environmental errors such as handling five times.
- a magnetic card that can be read after 20,000 repetitions and that can be used without a partial loss of the magnetic recording layer on the surface of the magnetic tape portion on the magnetic card is considered to have good durability. did.
- the magnetic recording layer is worn by friction with the magnetic head on the surface of the magnetic tape portion on the magnetic card by repeated reading of 20,000 to 5,000 times, and the magnetic recording layer is lost partially or entirely. The magnetic recording layer wears due to friction with the magnetic head on the surface of the magnetic tape on the magnetic card after repeated reading less than 5,000 times.
- a magnetic card in which the magnetic recording layer has been partially or wholly lost is indicated as x as a poor durability.
- the gloss value of the surface in contact with the magnetic tape portion of the mirror-finished metal press plate in contact with the magnetic tape surface before hot pressing is measured on a gloss meter (measurement angle 20 °, manufactured by Big Gardner). To measure. Hot-pressing is performed so that the magnetic tape is in contact with the measured part. Using the same mirror-finished metal press plate, repeat the hot press process 4 times so that the magnetic tape is in contact with the same position, the gloss value of the part measured before the hot press process and the same location after the 4 repeats The gloss values are compared, and the change in gloss value (the degree of decrease in gloss value) is evaluated according to the following criteria.
- Comparative Example 2 when only PTFE particles are used, in Comparative Example 2 which is used alone, the shift to the metal press plate is reduced, but the durability deteriorates. Further, in Comparative Example 4 in which PTFE particles and polyethylene wax particles are used in combination, the shift to the metal press plate is increased as compared with the case of only PTFE particles, while the durability is not improved. In Comparative Example 6 using only silica particles, the transition to the metal press plate is small, but the durability is not improved. In the case of Comparative Example 7 using stearic acid, which is generally used as a lubricant, the durability is not improved, and the shift to the metal press plate is much more than when only silica particles or PTFE particles are used. It has become. Further, in Comparative Example 8 in which no lubricant was added, it can be seen that the transferability is ⁇ , but the durability is ⁇ .
- the type of lubricant (and the amount added) was changed as follows to prepare each protective layer paint.
- a protective layer paint (b) was prepared in the same manner as the protective layer paint (a) except that the polyethylene / PTFE wax of the protective layer paint (m) was 1 part.
- a protective layer coating material (c) was prepared.
- S-REC BM-1 manufactured by Sekisui Chemical Co., Ltd.
- Soybean lecithin 2.4 parts Methyl ethyl ketone 200 parts 48 parts of cyclohexanone Toluene 200 parts
- ⁇ Coating for protective layer (q)> The protective layer coating (m) is protected in the same manner as the protective layer coating (m) except that 0.6 part of silica particles ("Silysia 350" manufactured by Fuji Silysia Chemical Ltd.) (average particle size of about 4 ⁇ m) is added.
- a layer coating material (q) was prepared.
- ⁇ Coating for protective layer (r)> The protective layer coating (r) was prepared in the same manner as the protective layer coating (p), except that 2.5 parts of silica particles ("Silicia 350" manufactured by Fuji Silysia Chemical Co., Ltd.) were added to the protective layer coating (p). Produced.
- a protective layer coating material (t) was prepared in the same manner as the protective layer coating material (m) except that 0.6 part was used.
- ⁇ Coating for protective layer (u)> instead of the lubricant for the protective layer paint (m), Polyethylene powder (“FB LE-1080” manufactured by Sumitomo Seika Co., Ltd.) (average particle size of about 6 ⁇ m) A protective layer coating material (u) was produced in the same manner as the protective layer coating material (m) except that 0.6 part was used ⁇ Protective layer coating material (v)> In place of the lubricant for the protective layer paint (p), A protective layer coating material (v) was prepared in the same manner as the protective layer coating material (p) except that 1.5 parts of silica particles (“Silicia 350” manufactured by Fuji Silysia Chemical Co., Ltd.) (average particle size of about 4 ⁇ m) were used.
- ⁇ Coating for protective layer (w)> A protective layer paint (w) was prepared in the same manner as the protective layer paint (m) except that the lubricant for the protective layer paint (m) was not added.
- ⁇ Coating for protective layer (x)> A protective layer coating (x) was prepared in the same manner as the protective layer coating (p) except that the lubricant for the protective layer coating (p) was not added.
- Example 5 On the resinous support (12 ⁇ m thickness, PET film) of the laminate for bonding, the above magnetic recording layer coating material was applied with a reverse coating system coating machine so that the dry coating thickness was 8 ⁇ m. After coating and drying in a nitrogen atmosphere, a magnetic recording layer was formed by thermal curing at 105 ° C. for 30 seconds. On the magnetic recording layer, the protective layer coating material (m) is applied with a reverse coating system coating machine so that the thickness of the dry coating film becomes 2 ⁇ m, dried in a nitrogen atmosphere, and then in air. A protective layer was formed by heat curing at 30 ° C. for 30 seconds.
- Example 6 On the opposite support on which the magnetic recording layer and the protective layer are formed, apply the above adhesive layer coating with a reverse coating system coating machine so that the dry coating thickness is 2 ⁇ m, and dry in a nitrogen atmosphere. Thus, an adhesive layer was formed to obtain a laminate for bonding. This laminate was cut into a predetermined width to produce a magnetic tape for the bonding process.
- Examples 6 to 9 Example 5 to 9 were carried out in the same manner as Example 5 except that the protective layer paints (n) to (q) were used in place of the protective layer paint (m). Magnetic tapes for the bonding process of 6 to Example 9 were produced.
- Example 10 On the support (12 ⁇ m thickness, PET film) of the laminate for bonding, the magnetic recording layer coating material was applied with a reverse coating system coating machine so that the dry coating thickness was 8 ⁇ m. After drying in a nitrogen atmosphere, the film was thermally cured at 105 ° C. for 30 seconds to form a magnetic recording layer. On the magnetic recording layer, the above coating for protective layer (r) is applied with a reverse coating system coating machine so that the dry coating thickness is 2.5 ⁇ m, dried in a nitrogen atmosphere, and then in the air. The laminate for bonding was obtained by forming a protective layer by thermal curing at 105 ° C. for 30 seconds. The laminated body was cut into a predetermined width to produce a magnetic tape for the bonding process of Example 10.
- Magnetic tapes for testing were produced using the magnetic tapes for bonding steps obtained in Examples 5 to 10 and Comparative Examples 9 to 14 under the following conditions.
- Lamination conditions Using a heat sealer (manufactured by Tester Sangyo Co., Ltd.), heat bonding was performed at 120 ° C. and 4 kgf / cm 2 for 5 seconds to obtain an overlay sheet with a magnetic tape.
- Hot-pressing condition Core sheet 2 made of polyvinyl chloride having a thickness of 280 ⁇ m in contact with an overlay sheet in which a magnetic tape having a tape width of 13 mm is arranged at a predetermined position of the overlay sheet made of polyvinyl chloride having a thickness of 100 ⁇ m Overlapping the sheets, another 100 ⁇ m polyvinyl chloride overlay sheet is stacked on the opposite side, and sandwiched between mirror-finished metal press plates (SUS430 buff finish made by Nikkin Steel Co., Ltd.), card making machine (LX made by Interline) -EM-4) was used and hot pressing was performed at 148 ° C.
- mirror-finished metal press plates SUS430 buff finish made by Nikkin Steel Co., Ltd.
- card making machine LX made by Interline
- the magnetic tape of Example 6 was formed in advance on the support opposite to the magnetic recording layer before spraying an adhesive layer having a thickness of 2.5 ⁇ m with an overlay sheet by hot-pressing.
- the obtained card base was punched into a predetermined size to obtain a test magnetic card (see FIGS. 6 and 7).
- the test magnetic card was repeatedly read 20,000 times with a card reader / writer (manufactured by OMRON). The number of repetitions was set to about 20,000 times in the five years of the card expiration date when used twice a magnetic card, and about 20,000 times considering environmental errors such as handling five times.
- a magnetic card that can be read after 20,000 repetitions and that can be used without a partial loss of the magnetic recording layer on the surface of the magnetic tape portion on the magnetic card is considered to have good durability. did.
- the magnetic recording layer is worn by friction with the magnetic head on the surface of the magnetic tape portion on the magnetic card by repeated reading of 20,000 to 5,000 times, and the magnetic recording layer is lost partially or entirely. The magnetic recording layer wears due to friction with the magnetic head on the surface of the magnetic tape on the magnetic card after repeated reading less than 5,000 times.
- a magnetic card in which the magnetic recording layer has been partially or wholly lost is indicated as x as a poor durability.
- the magnetic recording / reproduction characteristics of the magnetic card evaluated in the durability test are evaluated using a magnetic stripe analyzer “MAGTESTER 2000” manufactured by Burns Co., Ltd., and satisfy the standards described in “ISO / IEC7811-6, Section 7.3 Table 1”. The recording / reproducing characteristics were used.
- the gloss value of the surface in contact with the magnetic tape portion of the mirror-finished metal press plate in contact with the magnetic tape surface before hot pressing is measured on a gloss meter (measurement angle 20 °, manufactured by Big Gardner). To measure. Hot-pressing is performed so that the magnetic tape is in contact with the measured part. Using the same mirror-finished metal press plate, repeat the hot press process 4 times so that the magnetic tape is in contact with the same position, the gloss value of the part measured before the hot press process and the same location after the 4 repeats The gloss values are compared, and the change in gloss value (the degree of decrease in gloss value) is evaluated according to the following criteria.
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Abstract
Description
そして、熱圧プレス前の非磁性支持体である基体上に磁性積層体を形成する手法としては、主に転写用積層体を用いて転写工程で形成する方法と、貼合用積層体を用いてラミネート工程で形成する方法が用いられており、鏡面状の金属プレス板による熱圧プレスに直接晒される保護層には種々の特性が要求されている。
熱転写用積層体や貼合用積層体の保護層に求められる主な機能としては、熱圧プレスを受けたときにプレス板に焼き付くことを防止する焼き付き防止性、磁気記録媒体の最表層となった後に磁気層の保護層となりうる耐擦傷性がある。また熱転写用積層体の保護層の場合には、磁気記録媒体用の基体に熱転写する際に転写用支持体から容易に剥離する易剥離性が必要とされる。これらの機能を満たすために、保護層には転写用支持体からの剥離性と磁気記録層との層間密着性を兼ね備えたバインダー樹脂が使用されて易剥離性が確保され、耐擦傷性を向上させるためにはワックス等の添加剤が使用されている。保護層用バインダー樹脂としては、アクリル系樹脂、ブチラール系樹脂、セルロース系樹脂(例えば、特許文献1)などが知られており、耐擦傷性を向上させるための添加剤としては、脂肪酸およびその塩、各種ワックス類(例えば、特許文献2)、フッ素樹脂粒子(例えば、特許文献3)などが知られている。
従来、耐擦傷性を向上させるためのワックスとして好適に使用されているポリエチレンワックスは、ポリエチレン自身の優れた耐摩耗性と、熱圧プレス時の熱によって溶融する低融点ワックス成分の滑性によって、磁気カード等の磁気記録媒体の保護層上の滑剤として機能し、磁気記録・再生のための磁気ヘッドによる保護層の摩耗を減少させ、磁気記録媒体としての実用上好ましい耐久性を付与してきた。
また従来より耐擦傷性を向上させる添加剤として知られているフッ素樹脂粒子のうち、ポリテトラフルオロエチレン(以後、PTFEとの略称を併用する)粒子を滑剤として添加した場合は、それ自身の融点が高いために熱圧プレス時に鏡面調の表面を有する金属プレス板には移行せず、良好な滑性付与効果が得られる。しかしながら、バインダー樹脂との密着性に劣り、PTFE粒子が磁気カード製造時や、磁気記録再生等の通常の取り扱い時にバインダー樹脂から脱粒してしまい、結果として磁気記録媒体として実用上好ましい耐久性を得ることが困難であった。
上述した金属プレス板へのポリエチレンワックス成分の移行を減らすには、添加するポリエチレンワックス量を減らす、或いは移行性の低いポリエチレンワックスを使用する事が有効であるが、何れの場合も保護層の表面滑性が低下し、磁気記録媒体として実用上好ましい耐久性を得ることが困難であった。
また本発明は、非磁性支持体である基体上への積層体の形成が、熱転写用積層体を用いた転写工程で行われる上記の磁気記録媒体の製造方法を提供する。
さらに本発明は、転写用支持体上に、少なくとも保護層、磁気記録層および接着剤層がこの順に積層された熱転写用積層体であって、前記保護層がポリエチレンおよびポリテトラフルオロエチレンを有する混合物からなる粒子と、バインダー樹脂とを有することを特徴とする熱転写用積層体を提供する。
また本発明は、前記非磁性支持体である基体上への積層体の形成は、支持体の一方に支持体に近い側から磁気記録層と保護層を有し、貼合用支持体の他方に接着剤層を有する貼合用積層体の貼合工程を経て形成される磁気記録媒体の製造方法を提供する。
さらにまた本発明は、支持体の一方に支持体に近い側から磁気記録層と保護層を有する貼合用積層体であって、前記保護層がポリエチレンおよびポリテトラフルオロエチレンを有する混合物からなる粒子と、バインダー樹脂とを有することを特徴とする貼合用積層体を提供する。
本発明の製造方法に用いる熱転写用積層体や、貼合用積層体は、保護層中にポリエチレン及びPTFEを有する混合物からなるワックス粒子を含有するため、該熱転写用積層体や該貼合用積層体を用いて、熱転写工程や貼合工程で作製された磁気記録媒体の保護層は、良好な耐擦傷性を有すると共に、保護層中のPTFEの存在が、磁気記録媒体の製造工程の熱圧プレス時における金属プレス板へのポリエチレンワックスの移行を抑制する。このため作製された磁気記録媒体の表面には、金属プレス板に一度付着したポリエチレンワックスの再移行による汚れや変形が生じ難く、磁気記録媒体表面に形成された文字や図柄による意匠を損なうことがない。
また上記の熱転写工程や貼合工程を用いる本発明の磁気記録媒体の製造方法によれば、保護層にポリエチレン及びPTFEを有する混合物からなるワックス粒子を含有した熱転写用積層体や、貼合用積層体を用いるので、磁気記録層及び保護層を熱転写工程や貼合工程で基体上に形成後、保護層の上から熱圧プレス加工したときに、金属プレス板へのワックスの移行が抑えられるため、金属プレス板を清掃する頻度が大幅に減少する、このため製造効率が著しく向上する。
磁気記録媒体の耐久性は、熱転写用積層体や貼合用積層体の保護層の耐摩耗性に依存しており、保護層の耐摩耗性は主にバインダー樹脂に分散された滑剤の特性に左右されている。
滑性に優れたポリエチレンワックス粒子を保護層中に分散して製造された従来の熱転写用積層体や貼合用積層体は、ポリエチレン粒子自身の柔軟性、耐摩耗性およびバインダー樹脂との良好な密着性とワックス効果による滑性によって、磁気記録・再生時の磁気ヘッドによる擦過の影響を緩和している。
しかし、保護層表面はまた磁気記録媒体を形成するときに、熱圧プレス工程による加熱、加圧を受ける。本工程で加えられる加熱温度、加圧圧力については、製造する磁気記録媒体の構成や、熱圧プレス工程における使用装置によって若干異なるが、通常製造工程では鏡面状態の表面を有する金属板による熱圧プレス工程が用いられ、加熱温度120~180℃、加圧圧力10~25kgf/cm2の温度、圧力が保護層に加えられる。
このため、磁気記録媒体に必要な耐久性をポリエチレンワックス粒子のみで実現しようとした場合、磁気記録媒体の熱圧プレス加工で軟化(または溶融)したポリエチレンワックスの一部が鏡面調に研磨した金属プレス板表面に移行して、これを汚染してしまう。この移行する滑剤成分は、ポリエチレンワックスの低分子量(あるいは低融点)成分であって、この場合は同成分が滑性向上効果を主に発揮していると考えられる。それ故、例えばこの低分子量成分を大幅に低減させるか、あるいはこれに換えて金属プレス板表面に移行しにくい、中~高分子量ポリエチレン粒子を保護層中に添加することでワックスの移行性の改善が図ることができる。しかし、ワックスの低分子量成分が大幅に減少させると滑性が弱くなり、保護層表面の擦過傷が付きやすくなると共に、ポリエチレン粒子が塗膜から脱粒しやすくなって熱転写用積層体の保護層の耐摩耗性が低下し、磁気記録媒体の耐久性が不足する。ポリエチレン粒子が脱粒しやすくなる原因は、滑性向上効果の高い低分子量成分減少による塗膜滑性の低下によって、磁気記録媒体の保護層と磁気ヘッドとの摩擦が強くなると共に、ポリエチレン粒子の高分子量化によって粒子硬度も上がり、粒子の弾性によって磁気ヘッド応力を逃がす作用が弱くなるためと考えられる。
一方、滑性が高くてかつ移行性の成分がない滑剤と考えられるPTFE粒子を保護層中に分散させた場合は、未添加の場合に比べて熱転写用積層体の保護層の耐摩耗性は向上する傾向にあり、しかも金属プレス板表面への移行は発生しない。しかし、PTFE粒子はバインダー樹脂との密着性に乏しく、磁気ヘッドによる擦過によって容易に塗膜中から脱粒するため、十分な耐摩耗性を得ることができない。
また一方、磁気ヘッドは所定の力で加圧しながら保護層表面を擦るために、保護層中のワックス粒子自身にも適度な堅さ(柔軟性)が脱粒防止と、磁気ヘッド表面を傷つけないためにも必要であり、この点においては、ポリエチレンワックスが優れている。したがって、総合的に考えて、従来用いられてきたポリエチレン粒子はワックス移行性の点を除けば好適な材料と考えられる。
本発明の磁気記録媒体の製造方法に用いる貼合用積層体は、形成される保護層が磁気記録層との良好な接着性を維持しつつ優れた耐擦傷性を実現し、かつ保護層上から熱圧プレスをかけて磁気記録媒体を製造するときに、金属プレス板にワックス等の滑剤が移行することがない。したがって、製造された磁気記録媒体の表面に金属プレス板を介してワックス等の滑剤による汚れや変形が発生することがない。また、このために金属プレス板の清掃を行う頻度を大幅に低下させることが出来るので、製造効率が著しく向上する。さらにこれら保護層は形成された磁気記録媒体の記録再生特性を低下させることがない。
保護層に含有されるワックス粒子の体積平均粒子径は6μm以下であることが好ましい。
また熱転写用積層体の保護層用バインダー樹脂としては、セルロース誘導体樹脂をバインダー樹脂の主成分として含有することが好ましく、セルロース誘導体樹脂としては特に酢酸セルロース樹脂が好ましい。
本発明において磁気記録媒体とは、磁気ディスクやテープ類、プラスティック製クレジットカード、キャッシュカードなどの磁気カード類、銀行などの合成紙製磁気通帳類、あるいは紙製乗車券・通行券等の磁気切符類などである。また本発明においては磁気記録媒体には数えないが、磁気カードに具備された磁気テープ(磁気ストライプとも呼ぶ)あるいは後述する「熱転写用積層体」「貼合用積層体」そのものも広い分類では磁気記録媒体のカテゴリーに入るものであると考えられる。
本発明の熱転写用積層体とは、主に磁気カードなどの製造に用いられ、磁気記録層およびその他の機能層を積層した転写用磁気シート(テープ形状に加工したものは転写型磁気テープと呼ぶ)であって、磁気記録層を含む層を磁気記録媒体用の基体に熱転写できる構成としたものである。熱転写用積層体は、非磁性支持体である転写用支持体上に、最終製品において最上層となる保護層、磁気記録層および接着剤層の、少なくとも3層をこの順に形成してなる積層構造を有している(図1参照)。そして磁気記録媒体用の基体に接着剤層を接して固定され、転写後に転写用支持体が保護層との界面から剥離される。そして保護層上より熱圧プレスを受けて、転写用支持体を除いた積層体が、磁気記録媒体用の基体中に埋め込まれる。
ポリエチレン及びPTFEを有する混合物からなるワックス粒子を作製するには、公知のポリエチレンワックス粒子の製造方法において、前記PTFE粒子をポリエチレン、あるいはその単量体化合物中に分散させて、製造工程時に介在させ、その存在下でポリエチレンワックス粒子の通常の製造方法と同様の手順を行うことにより、PTFE粒子を含有し常温で粒子状態のワックスを作製することができる。
さらに、該ワックス粒子の製造過程で予め混合可能な他のワックス類、例えばカルナバワックス等を必要に応じて添加することも可能である。
PTFEとポリエチレンワックスの混合比率としては、最も重視するべき特性が耐摩耗性であるか滑剤の移行抑制であるかによって調整の方向が異なる、また磁気記録媒体の製造工程条件、使用条件に応じて適宜調整することができるが、PTFEが全滑剤成分の0.2~70質量%が好ましく、複合粒子としての存在が安定している1~30質量%がより好ましい。
また、該ポリエチレンを主成分とする粒子内に少なくともPTFE粒子の一部が埋設された複合粒子であることが好ましい。このような複合粒子を用いることによりPTFE粒子の脱落が防止できる。またポリエチレンを主成分とする粒子表面には複数のPTFE粒子が存在し、該粒子内にPTFE粒子の一部が埋設され、また該粒子表面上にPTFE粒子の一部が露出した状態となっていることがさらに好ましく。このような状態をとることによって、熱圧プレス時に複合粒子内部のポリエチレン成分から溶出してくる移行成分が、熱圧プレス用の鏡面調金属プレス板表面に移行しにくくする効果を付加していると考えられる。
ワックスの添加量は、保護層のバインダー樹脂に対して1~10質量%が好ましく、2~5質量%がより好ましい。添加量が1質量%よりも少ない場合は保護層の表面滑性が十分得られず、10質量%よりも多い場合は保護層の塗膜が脆くなり、磁気記録媒体として実用上好ましい耐久性を得ることが困難となる。
本発明で使用する保護層用塗料の調整は、上記ポリエチレン及びポリテトラフルオロエチレンを有する混合物からなるワックス粒子と、上記バインダー樹脂、必要に応じて公知慣用の分散安定剤、界面活性剤、ブロッキング防止剤等を、アセトン、酢酸エチル、シクロヘキサノン、トルエン等の混合溶剤中にディスパー等の攪拌機で混合撹拌し均一に分散させて行う。そのときの塗料の固形分比は5~35%が好ましい。
本発明の貼合用積層体とは、主に磁気カードなどの製造に用いられ、磁気記録層およびその他の機能層を積層した後にテープ形状に加工した磁気テープに代表されるものであって、非磁性支持体である貼合用支持体上に磁気記録再生の実質的機能層である磁気記録層および保護層の少なくとも2層をこの順に形成してなる積層構造を有している。
5~35%が好ましい。
また、以上の方法で作製した貼合用積層体を用いて例えば磁気カードを作製するためには、従来公知の磁気カード用基体に、公知の熱圧工程を経ることによって行うことができる。例えば接着剤層を予め磁気記録層の反対面に設けた貼合用積層体であれば(図5参照)、接着剤層を磁気記録媒体用の基体表面に密着させ、加熱および加圧を行って固着させることにより、磁気記録媒体用の基体上に接着剤層、磁気記録層及び保護層を有する積層体を形成することができる。
その後、貼合用積層体全体を基体中に埋め込んで、積層体の最表面である保護層の表面と磁気記録媒体用基体の表面とが同一平滑平面を形成するようにする熱圧プレス工程を行う。基体がプラスティックの場合、基体を複数枚積層して磁気カード等の磁気記録媒体を作製するときは、該熱圧プレス工程はこれら複数の基体を熱圧プレスして一体化する工程と同時に行っても良い。例えば接着剤層を予め貼合用支持体の磁気記録層の反対面に設けた貼合用積層体を基体に、熱圧条件を弱めて仮接着して一方のオーバーレイシートとし、もう1枚のオーバーレイシートとともに2枚のコアシートを間に挟んで、これら4枚のシートを熱圧着することによってカード厚さを一体化した磁気記録媒体が製造できる。
酢酸セルロース(ダイセル化学社製『L-AC L-20』) 7.6部
セルロースアセテートプロピオネート
(イーストマンケミカル社製『CAP504-0.2』) 1.9部
大豆レシチン 0.1部
アセトン 40部
酢酸エチル 40部
シクロヘキサノン 30部
トルエン 30部
ポリエチレン/PTFEワックス(滑剤) 0.29部
(シャムロック社製『Fluoroslip 731MG』)(体積平均粒径約5μm)
イソシアネート化合物 4部
(大日本インキ化学工業社製『ハードナーNo.50』)
以上の各成分をディスパーにて混合撹拌・均一分散して保護層用塗料(a)を作製した。
<保護層用塗料(b)>
保護層用塗料(a)のポリエチレン/PTFEワックスを0.48部にする他は保護層用塗料(a)と同様にして保護層用塗料(b)を作製した。
<保護層用塗料(c)>
保護層用塗料(a)で用いたポリエチレン/PTFEワックスをボールミルにて粉砕し、体積平均粒径約2μmとしたものを、滑剤として0.29部用いる他は、保護層用塗料(a)と同様にして保護層用塗料(c)を作製した。
<保護層用塗料(d)>
保護層用塗料(a)で用いたポリエチレン/PTFEワックスをボールミルにて粉砕し、体積平均粒径約1μmとしたものを、滑剤として0.29部用いる他は、保護層用塗料(a)と同様にして保護層用塗料(d)を作製した。
<保護層用塗料(e)>
保護層用塗料(a)の滑剤に換えて、
低分子量ポリエチレンワックス(三井化学社製『ハイワックス200PF』)(粉砕処理後の平均粒径約6μm)0.29部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(e)を作製した。
<保護層用塗料(f))>
保護層用塗料(a)の滑剤に換えて、
PTFE粒子 (シャムロック社製『Fluoro A』)(平均粒径約1μm) 0.29部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(f)を作製した。
<保護層用塗料(g)>
保護層用塗料(a)の滑剤に換えて、
ポリエチレンパウダー(住友精化社製『FB LE-1080』)(平均粒径約6μm)
0.29部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(g)を作製した
<保護層用塗料(h)>
保護層用塗料(a)の滑剤に換えて、
ポリエチレンパウダー(住友精化社製『FB LE-1080』)(平均粒径約6μm)
0.15部及び
PTFE粒子(シャムロック社製『Fluoro A』)(体積平均粒径約1μm)
0.14部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(h)を作製した
<保護層用塗料(i)>
保護層用塗料(a)の滑剤に換えて、
高分子量ポリエチレン(三井化学社製『ミペロンPM-200』)(平均粒径約10μm) 0.29部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(i)を作製した。
<保護層用塗料(j)>
保護層用塗料(a)の滑剤に換えて、
シリカ粒子 (富士シリシア化学社製『サイリシア350』)(平均粒径約4μm)0.48部を用いる他は保護層用塗料(a)と同様にして保護層用塗料(j)を作製した。
<保護層用塗料(k)>
保護層用塗料(a)の滑剤に換えて、
ステアリン酸 (日本油脂社製『NAA-180』) 0.48部
を用いる他は保護層用塗料(a)と同様にして保護層用塗料(k)を作製した。
<保護層用塗料(l)>
保護層用塗料(a)の滑剤を添加しないことの他は保護層用塗料(a)と同様にして保護層用塗料(l)を作製した。
Baフェライト磁性粉 (戸田工業社製『MC-127』) 40部
塩化ビニル系樹脂 (日本ゼオン社製『MR-110』) 6部
ポリウレタン樹脂 (大日本インキ化学工業社製『T-5206』) 4部
メチルエチルケトン 20部
トルエン 20部
シクロヘキサノン 8部
イソシアネート化合物 2部
(大日本インキ化学工業社製『ハードナーNo.50』)
上記各成分を混練分散機により混練分散して磁気記録層用塗料を作製した。
塩化ビニル-酢酸ビニル共重合体樹脂 3.5部
(電気化学社製『1000LT3』)
ポリウレタン樹脂 1.5部
(大日本インキ化学工業社製『TS-03』)
メチルエチルケトン 45部
トルエン 50部
上記各成分をディスパーにて混合・完全溶解して接着剤層用塗料を作製した。
(実施例2~実施例4)実施例1において、保護層用塗料(a)に替えて保護層用塗料(b)(c)、(d)を用いた以外は実施例1と同様にして実施例2、3、4の転写型磁気テープを作製した。
以下の条件で実施例1~4、比較例1~8により得られた転写型磁気テープを使用し、試験用磁気カードを作製した。
熱転写条件:ヒートシーラー(テスター産業社製)を用いて、厚さ100μmのポリ塩化ビニル製のオーバーレイシートの所定の位置にテープ幅13mmの転写型磁気テープを120℃、4kgf/cm2で5秒間の熱融着を行い、その後に転写用支持体フィルムを剥離させて磁気テープ付きのオーバーレイシートを得た。
熱圧プレス条件:この磁気テープ付きのオーバーレイシートをこれに接して厚さ280μmのポリ塩化ビニル製のコアシート2枚を重ね、更に反対面に100μmのポリ塩化ビニル製のオーバーレイシートを1枚重ねて、鏡面調金属プレス板(日金スチール社製SUS430バフ仕上げ)に挟み、カード作製機(インターライン社製LX-EM-4)を用い、温度148℃、圧力10krf/cm2の設定で熱圧プレスを行った。
得られたカード基材を所定の大きさに打ち抜く事によって試験用磁気カードを得た(図2、図3参照)。
転写用支持体(PETフィルム)と保護層との剥離性、すなわち、剥離強度を測定する。剥離強度値が10~80mNの範囲にあれば、易剥離性と判定して○とし、それ以外を×とした。試験は、実施例1~4、比較例1~8で得た熱転写用積層体を10mm幅に裁断して転写型磁気テープを作製し、磁気カード用基体であるポリ塩化ビニル製の厚さ100μmのオーバーレイシートに熱転写して転写用支持体剥離前の剥離試験サンプルを得た。熱転写装置および熱転写条件は次の通りである。
装置:ヒートシーラー(テスター産業社製)
熱転写条件:120℃ 0.4kgf/cm2 9.9秒
次に、ここで得た剥離試験サンプルを剥離試験機にかけ、保護層からPETフィルムを引き剥がす力を以下の装置条件にて測定した。
装置:高速剥離試験機(テスター産業社製)
測定条件:剥離速度20m/分、180°剥離で測定
得られたチャートからピーク強度を読み取って剥離強度とした。
テープ幅を13mmとした上記試験用磁気カードを用いて、保護層と磁気記録層との接着性をJIS K5600-5-6記載のクロスカット法に準じて評価し、全てのマス目が剥がれなければ○、それ以外を×とした。
上記試験用磁気カードをカードリーダーライター(オムロン社製)にて20,000回の繰り返し読み取りを行った。繰り返し回数は、磁気カードとして毎日2回使用したとしてカード有効期限の5年間で約4000回、取り扱い等の環境誤差を5倍に考慮して約20,000回とした。
20,000回の繰り返し後にも磁気記録の読み取りが可能であり、且つ磁気カード上の磁気テープ部分の表面に磁気記録層が部分的に欠けずに使用可能な磁気カードを耐久性良好として○とした。20,000回~5,000回の繰り返し読み取りで磁気カード上の磁気テープ部分の表面に磁気ヘッドとの摩擦によって磁気記録層が摩耗し、部分的あるいは全体的に磁気記録層が失われてしまった磁気カードを実使用上耐久性不足となる可能性がある△とし、5,000回未満の繰り返し読み取りで磁気カード上の磁気テープ部分の表面に磁気ヘッドとの摩擦によって磁気記録層が摩耗し、部分的あるいは全体的に磁気記録層が失われてしまった磁気カードを耐久性不良として×とした。
実施例および比較例で得られた転写型磁気テープを使用し、カード作製機(インターライン社製)により、ポリ塩化ビニル製のカード基材に熱転写させた後に支持体フィルムを除去し、鏡面調金属プレス板にてプレス加工をした際、プレス板表面に磁気テープから移行する滑剤によるテープ跡(曇り)がどの程度確認できるかを以下の試験方法により判定した。
上記試験用磁気カードを作製する際、熱圧プレス加工前の磁気テープ面に接する鏡面調金属プレス板の磁気テープ部分に接する表面の光沢値を光沢計(測定角20°ビックガードナー社製)にて測定する。測定した部分に磁気テープが接触するような配置で熱圧プレス加工を行う。同じ鏡面調金属プレス板を用い、同じ位置に磁気テープが接するように熱圧プレス加工を4回繰り返して行い、熱圧プレス加工前に測定した部位の光沢値と4回繰り返し後の同じ場所の光沢値を比較し、光沢値の変化(光沢値の低下度合い)を以下の基準で評価する。
4回プレス加工後の光沢値が95%以上・・・・・・・・・・◎
95%未満~93%以上・・・・○
93%未満~90%以上・・・・△
90%未満・・・・・・・・・・×
尚、評価結果は、4回プレス後の光沢値が100%に近い程(金属プレス板表面の光沢低下度合いが小さい程)、金属プレス板への移行が少なく、移行する滑剤による金属プレス板表面のテープ跡(曇り)が弱い事を表している。
また、実施例および比較例で作成した磁気カードの磁気記録再生特性は、バーンズ社製磁気ストライプ・アナライザー「MAGTESTER2000」を用いて「ISO/IEC7811-6 7.3項 Table1」に記載の規格を満足するものを磁気特性○として表1に併記した。
上記試験結果を、以下の表1に示した。
一方、ポリエチレンワックス粒子のみを使用した場合、比較例1では耐久性は良好であるが、金属プレス板へのワックス成分の移行が著しい。比較例3や比較例5で使用したポリエチレンは、金属プレス板へのワックス成分の移行が少ないものの、このために逆に耐久性が悪化しており、ポリエチレンワックスのみで耐久性と金属プレス板への移行抑制を両立することは困難であることがわかる。
一方PTFE粒子のみを使用した場合、単独使用の比較例2では金属プレス板への移行は低減されるが耐久性が悪化する。またPTFE粒子とポリエチレンワックス粒子と併用した比較例4ではPTFE粒子のみの場合よりも金属プレス板への移行が増え、一方耐久性は改善されないままである。
シリカ粒子のみを使用した比較例6の場合も、金属プレス板への移行は少ないが、耐久性が改善されない。一般的に滑剤として使用されているステアリン酸を用いた比較例7の場合は、耐久性は改善されないままで、金属プレス板への移行がシリカ粒子やPTFE粒子のみを用いた場合に比べて多くなっている。
また、滑剤を添加しなかった比較例8では、移行性は○であるが耐久性は×となる事が判る。
ブチラール樹脂 (積水化学社製『エスレックKS-1』) 20部
大豆レシチン 1部
アセトン 90部
酢酸エチル 90部
シクロヘキサノン 70部
トルエン 70部
ポリエチレン/PTFEワックス(滑剤) 0.6部
(シャムロック社製『Fluoroslip 731MG』)(体積平均粒径約5μm)
イソシアネート化合物 8.5部
(大日本インキ化学工業社製『ハードナーNo.50』)
以上の各成分をディスパーにて混合撹拌・均一分散して保護層用塗料(m)を作製した。
<保護層用塗料(n)>
保護層用塗料(m)のポリエチレン/PTFEワックスを1部にする他は保護層用塗料(a)と同様にして保護層用塗料(b)を作製した。
<保護層用塗料(o)>
保護層用塗料(m)で用いたポリエチレン/PTFEワックスをボールミルにて粉砕し、体積平均粒径約1μmとしたものを、滑剤として0.6部用いる他は、保護層用塗料(m)と同様にして保護層用塗料(c)を作製した。
<保護層用塗料(p)>
ブチラール樹脂 (積水化学社製『エスレックBM-1』) 48部
大豆レシチン 2.4部
メチルエチルケトン 200部
シクロヘキサノン 48部
トルエン 200部
ポリエチレン/PTFEワックス(滑剤) 1.5部
(シャムロック社製『Fluoroslip 731MG』)(体積平均粒径約5μm)
イソシアネート化合物 18.5部
(大日本インキ化学工業社製『ハードナーNo.50』)
以上の各成分をディスパーにて混合撹拌・均一分散して保護層用塗料(p)を作製した。
<保護層用塗料(q)>
保護層用塗料(m)にシリカ粒子(富士シリシア化学社製『サイリシア350』)(平均粒径約4μm)を0.6部添加した他は、保護層用塗料(m)と同様にして保護層用塗料(q)を作製した。
<保護層用塗料(r)>
保護層用塗料(p)にシリカ粒子(富士シリシア化学社製『サイリシア350』)を2.5部添加した他は、保護層用塗料(p)と同様にして保護層用塗料(r)を作製した。
<保護層用塗料(s)>
保護層用塗料(m)の滑剤に換えて、
低分子量ポリエチレンワックス(三井化学社製『ハイワックス200PF』)(粉砕処理後の平均粒径約6μm)0.6部を用いる他は保護層用塗料(m)と同様にして保護層用塗料(s)を作製した。
<保護層用塗料(t))>
保護層用塗料(m)の滑剤に換えて、
PTFE粒子 (シャムロック社製『Fluoro A』)(平均粒径約1μm) 0.6部を用いる他は保護層用塗料(m)と同様にして保護層用塗料(t)を作製した。
<保護層用塗料(u)>
保護層用塗料(m)の滑剤に換えて、
ポリエチレンパウダー(住友精化社製『FB LE-1080』)(平均粒径約6μm)
0.6部を用いる他は保護層用塗料(m)と同様にして保護層用塗料(u)を作製した
<保護層用塗料(v)>
保護層用塗料(p)の滑剤に換えて、
シリカ粒子 (富士シリシア化学社製『サイリシア350』)(平均粒径約4μm)1.5部を用いる他は保護層用塗料(p)と同様にして保護層用塗料(v)を作製した。
<保護層用塗料(w)>
保護層用塗料(m)の滑剤を添加しないことの他は保護層用塗料(m)と同様にして保護層用塗料(w)を作製した。
<保護層用塗料(x)>
保護層用塗料(p)の滑剤を添加しないことの他は保護層用塗料(p)と同様にして保護層用塗料(x)を作製した。
磁性粉 (戸田工業社製『QX-440』) 150部
塩化ビニル系樹脂 (日信化学工業社製『ソルバイン-TAO』) 20部
ポリウレタン樹脂 (大日本インキ化学工業社製『T-5206L』) 13部
ポリウレタン樹脂 32部
(大日本インキ化学工業社製『TS-03』)
大豆レシチン 3部
メチルエチルケトン 125部
トルエン 170部
シクロヘキサノン 50部
イソシアネート化合物 25部
(大日本インキ化学工業社製『ハードナーNo.50』)
上記各成分を混練分散機により混練分散して磁気記録層用塗料(b)を作製した。
塩化ビニル-酢酸ビニル共重合体樹脂 3.5部
(電気化学社製『1000LT3』)
ポリウレタン樹脂 1.5部
(大日本インキ化学工業社製『TS-03』)
メチルエチルケトン 45部
トルエン 50部
上記各成分をディスパーにて混合・完全溶解して接着剤層用塗料を作製した。
(実施例6~実施例9)実施例5において、保護層用塗料(m)に替えて保護層用塗料(n)~(q)をそれぞれ用いた以外は実施例5と同様にして実施例6~実施例9の貼合工程用の磁気テープを作製した。
以下の条件で実施例5~10、比較例9~14により得られた貼合工程用の磁気テープを使用し、試験用磁気カードを作製した。
ラミネート条件:ヒートシーラー(テスター産業社製)を用いて、120℃、4kgf/cm2で5秒間の熱融着を行い磁気テープ付きのオーバーレイシートを得た。
熱圧プレス条件:厚さ100μmのポリ塩化ビニル製のオーバーレイシートの所定の位置にテープ幅13mmの磁気テープを配置したオーバーレイシートを、これに接して厚さ280μmのポリ塩化ビニル製のコアシート2枚を重ね、更に反対面に100μmのポリ塩化ビニル製のオーバーレイシートを1枚重ねて、鏡面調金属プレス板(日金スチール社製SUS430バフ仕上げ)に挟み、カード作製機(インターライン社製LX-EM-4)を用い、148℃設定で熱圧プレスを行った。尚、実施例6の磁気テープは、磁気記録層と反対の支持体上にスプレーコートにて厚さ2.5μmの接着剤層をオーバーレイシートと熱圧プレスする前に予め形成した。得られたカード基体を所定の大きさに打ち抜く事によって試験用磁気カードを得た(図6、図7参照)。
上記試験用磁気カードをカードリーダーライター(オムロン社製)にて20,000回の繰り返し読み取りを行った。繰り返し回数は、磁気カードとして毎日2回使用したとしてカード有効期限の5年間で約4000回、取り扱い等の環境誤差を5倍に考慮して約20,000回とした。
20,000回の繰り返し後にも磁気記録の読み取りが可能であり、且つ磁気カード上の磁気テープ部分の表面に磁気記録層が部分的に欠けずに使用可能な磁気カードを耐久性良好として○とした。20,000回~5,000回の繰り返し読み取りで磁気カード上の磁気テープ部分の表面に磁気ヘッドとの摩擦によって磁気記録層が摩耗し、部分的あるいは全体的に磁気記録層が失われてしまった磁気カードを実使用上耐久性不足となる可能性がある△とし、5,000回未満の繰り返し読み取りで磁気カード上の磁気テープ部分の表面に磁気ヘッドとの摩擦によって磁気記録層が摩耗し、部分的あるいは全体的に磁気記録層が失われてしまった磁気カードを耐久性不良として×とした。
耐久性試験で評価した磁気カードの磁気記録再生特性は、バーンズ社製磁気ストライプ・アナライザー「MAGTESTER2000」を用いて評価を行い「ISO/IEC7811-6 7.3項 Table1」に記載の規格を満足するものを記録再生特性○とした。
実施例および比較例で得られた磁気テープを使用し、カード作製機(インターライン社製)により、鏡面調金属プレス板にて熱圧プレス加工をした際、プレス板表面に磁気テープから移行する滑剤によるテープ跡(曇り)がどの程度確認できるかを以下の試験方法により判定した。
上記試験用磁気カードを作製する際、熱圧プレス加工前の磁気テープ面に接する鏡面調金属プレス板の磁気テープ部分に接する表面の光沢値を光沢計(測定角20°ビックガードナー社製)にて測定する。測定した部分に磁気テープが接触するような配置で熱圧プレス加工を行う。同じ鏡面調金属プレス板を用い、同じ位置に磁気テープが接するように熱圧プレス加工を4回繰り返して行い、熱圧プレス加工前に測定した部位の光沢値と4回繰り返し後の同じ場所の光沢値を比較し、光沢値の変化(光沢値の低下度合い)を以下の基準で評価する。
4回プレス加工後の光沢値が95%以上・・・・・・・・・・◎
95%未満~93%以上・・・・○
93%未満~90%以上・・・・△
90%未満・・・・・・・・・・×
尚、評価結果は、4回プレス後の光沢値が100%に近い程(金属プレス板表面の光沢低下度合いが小さい程)、金属プレス板への移行が少なく、移行する滑剤による金属プレス板表面のテープ跡(曇り)が弱い事を表している。
上記試験結果を、以下の表2に示した。
一方、ポリエチレンワックス粒子のみを使用した場合、比較例9では耐久性は良好であるが、金属プレス板へのワックス成分の移行が著しい。比較例11で使用したポリエチレンは、金属プレス板へのワックス成分の移行が少ないものの、このために逆に耐久性が悪化しており、ポリエチレンワックスのみで耐久性と金属プレス板への移行抑制を両立することは困難であることがわかる。
一方PTFE粒子のみを使用した場合、単独使用の比較例10では金属プレス板への移行は低減されるが耐久性が悪化する。シリカ粒子のみを使用した比較例12の場合も、金属プレス板への移行は少ないが、耐久性が改善されない。また、滑剤を添加しなかった比較例13や比較例14では、移行性は良好となるが耐久性は著しく低下する。
2 保護層
3 磁気記録層
4 接着剤層
5 転写工程を経て作製された磁気カード
6 転写用積層体
7 貼合用支持体
8 磁気記録層
9 保護層
10 接着剤層
11 貼合工程を経て作製された磁気カード
12 貼合用積層体を用いて形成された磁気ストライプ
13 貼合用積層体
14 磁気記録媒体用の基体(カード用基体)
15 転写用積層体を用いて形成された磁気ストライプ
Claims (14)
- 非磁性支持体である基体上に、該基体に近い側から接着剤層、磁気記録層、保護層を有する積層体を形成する工程、保護層上より熱圧プレスを行って前記積層体を前記基体中に埋めこみ、前記基体表面と前記積層体の最表面が同一平滑平面を形成するようにする工程、を有する磁気記録媒体の製造方法であって、前記保護層はポリエチレン及びポリテトラフルオロエチレンを有する混合物からなる粒子とバインダー樹脂とを含有することを特徴とする磁気記録媒体の製造方法。
- 前記粒子は、ポリエチレンを主成分とする粒子内に、少なくともポリテトラフルオロエチレン粒子の一部が埋設された複合粒子である請求項1に記載の磁気記録媒体の製造方法。
- 前記粒子が不定形である請求項1に記載の磁気記録媒体の製造方法。
- 前記粒子の体積平均粒子径が6μm以下であることを特徴とする請求項2または3のいずれか1項に記載の磁気記録媒体の製造方法。
- 前記基体上への積層体の形成は、熱転写用積層体を用いた転写工程を経て行われる請求項1に記載の磁気記録媒体の製造方法。
- 転写用支持体上に、少なくとも保護層、磁気記録層および接着剤層がこの順に積層された熱転写用積層体であって、前記保護層がポリエチレンおよびポリテトラフルオロエチレンを有する混合物からなる粒子と、バインダー樹脂とを有することを特徴とする熱転写用積層体。
- 前記粒子は、ポリエチレンを主成分とする粒子内に、少なくともポリテトラフルオロエチレン粒子の一部が埋設された複合粒子である請求項6に記載の熱転写用積層体。
- 前記粒子が不定形である請求項6に記載の熱転写用積層体。
- 前記粒子の体積平均粒子径が6μm以下であることを特徴とする請求項7または8のいずれか1項に記載の熱転写用積層体。
- 前記基体上への積層体の形成は、支持体の一方に支持体に近い側から磁気記録層と保護層を有する貼合用積層体の、貼合工程を経て形成される請求項1に記載の磁気記録媒体の製造方法。
- 支持体の一方に支持体に近い側から磁気記録層と保護層を有する貼合用積層体であって、前記保護層がポリエチレンおよびポリテトラフルオロエチレンを有する混合物からなる粒子と、バインダー樹脂とを有することを特徴とする貼合用積層体。
- 前記粒子は、ポリエチレンを主成分とする粒子内に、少なくともポリテトラフルオロエチレン粒子の一部が埋設された複合粒子である請求項11に記載の貼合用積層体。
- 前記粒子が非真球状の不定形である請求項11に記載の貼合用積層体。
- 前記ワックス粒子の体積平均粒子径が6μm以下であることを特徴とする請求項12または13のいずれか1項に記載の貼合用積層体。
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KR1020107015033A KR101258886B1 (ko) | 2008-01-21 | 2009-01-20 | 자기 기록 매체의 제조 방법 |
AU2009207079A AU2009207079B2 (en) | 2008-01-21 | 2009-01-20 | Process for producing magnetic recording medium |
CN2009801027032A CN101925954B (zh) | 2008-01-21 | 2009-01-20 | 磁记录介质的制造方法 |
US12/863,366 US8563148B2 (en) | 2008-01-21 | 2009-01-20 | Process for producing magnetic recording medium |
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JP2008010361A JP4539723B2 (ja) | 2008-01-21 | 2008-01-21 | 熱転写用積層体およびこれを用いた磁気記録媒体の製造方法 |
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US (1) | US8563148B2 (ja) |
JP (1) | JP4539723B2 (ja) |
KR (1) | KR101258886B1 (ja) |
CN (1) | CN101925954B (ja) |
AU (1) | AU2009207079B2 (ja) |
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WO2013044133A1 (en) * | 2011-09-23 | 2013-03-28 | Carnegie Mellon University | Thin-film media structures for perpendicular magnetic recording and storage devices made therewith |
CN102501681B (zh) * | 2011-11-15 | 2014-07-16 | 保定乐凯新材料股份有限公司 | 一种存折用转移型磁条 |
TWI480295B (zh) * | 2012-08-31 | 2015-04-11 | Tai Yuen Textile Co Ltd | 表面具有熱融膠的透氣防水薄膜與其形成方法 |
JP2014110065A (ja) * | 2012-12-03 | 2014-06-12 | Panasonic Corp | 磁気シートの製造方法、磁気シートの使用方法および磁気シート |
JP6163925B2 (ja) * | 2013-07-12 | 2017-07-19 | 凸版印刷株式会社 | マット調転写フィルム、及びそれを用いた成形品 |
JP6638725B2 (ja) * | 2015-03-31 | 2020-01-29 | ソニー株式会社 | 磁気記録媒体 |
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JP2001351074A (ja) * | 2000-06-08 | 2001-12-21 | Dainippon Ink & Chem Inc | 熱転写用積層体および磁気記録媒体 |
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FR2639647B1 (fr) * | 1988-10-18 | 1990-09-21 | Kodak Pathe | Milieu d'enregistrement magnetique |
FR2638000B1 (fr) * | 1988-10-18 | 1990-12-14 | Kodak Pathe | Carte a memoire magnetique a grande capacite et procede de fabrication |
FR2638001B1 (fr) * | 1988-10-18 | 1990-12-07 | Kodak Pathe | Carte magnetique a haute densite dont l'une des faces est susceptible de recevoir une image thermographique |
JPH06286364A (ja) * | 1993-02-02 | 1994-10-11 | Dainippon Printing Co Ltd | 磁気記録媒体 |
JPH0765356A (ja) | 1993-08-30 | 1995-03-10 | Dainippon Ink & Chem Inc | 転写型磁気記録シート |
JP2001202614A (ja) * | 2000-01-18 | 2001-07-27 | Toray Ind Inc | 磁気記録媒体 |
JP4366811B2 (ja) | 2000-02-17 | 2009-11-18 | 凸版印刷株式会社 | 転写媒体およびこれを使用した磁気記録媒体 |
JP2004249610A (ja) * | 2003-02-20 | 2004-09-09 | Fuji Photo Film Co Ltd | 情報媒体 |
JP4424015B2 (ja) * | 2004-03-09 | 2010-03-03 | 富士電機デバイステクノロジー株式会社 | 磁気記録媒体の製造方法 |
JP2007066390A (ja) * | 2005-08-30 | 2007-03-15 | Konica Minolta Opto Inc | 磁気記録媒体用基板、及び磁気記録媒体用基板の製造方法 |
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AU2009207079A2 (en) | 2010-12-09 |
JP4539723B2 (ja) | 2010-09-08 |
KR20100103560A (ko) | 2010-09-27 |
TWI447722B (zh) | 2014-08-01 |
AU2009207079B2 (en) | 2013-08-15 |
CN101925954B (zh) | 2012-07-04 |
US20110045319A1 (en) | 2011-02-24 |
US8563148B2 (en) | 2013-10-22 |
TW200937402A (en) | 2009-09-01 |
KR101258886B1 (ko) | 2013-04-29 |
CN101925954A (zh) | 2010-12-22 |
JP2009170067A (ja) | 2009-07-30 |
AU2009207079A1 (en) | 2009-07-30 |
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