JP2002056524A - Magnetic recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sticking type non-chlorine magnetic recording medium from which a passbook or the like is prepared so as not to generate dioxin when burnt since a chlorine-containing resin is not used as a binder resin of a magnetic layer and in which the dispersion of magnetic powder in the magnetic layer is equal to or more excellent than that of the conventional medium. SOLUTION: A non-chlorine copolymer having a radically polymerizable monomer component having a hydrophilic polar group, preferably containing hydroxyethyl (meth)acrylate, is used as the binder resin of the magnetic recording layer. It is preferable that the non-chlorine copolymer accounts for 20-70 wt.% of the whole binder resin. The passbook or the like is prepared by using the sticking type non-chlorine magnetic recording medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bonding magnetic recording medium having a chlorine-free magnetic recording layer, and
The present invention relates to a non-chlorine magnetic recording medium for lamination used for manufacturing a magnetic recording medium for passbooks used for postal savings passbooks and the like. The present invention also relates to a non-chlorine magnetic recording medium manufactured through a step of attaching a magnetic label, which is one of the magnetic recording media for lamination, and more particularly to a non-chlorine magnetic recording medium for passbooks.

[0002] The laminating magnetic recording medium of the present invention is
A medium in which a laminate including at least a magnetic recording layer is formed on a non-magnetic support serving as a bonding substrate, and an adhesive layer such as an adhesive layer is formed on the opposite side of the support with respect to the bonding substrate. A generic name for media used in the manufacture of magnetic recording media, such as passbooks with magnetic stripes, attached to other substrates.
There are various shapes such as sheets and tapes. Also,
These include magnetic label laminates and magnetic label tapes.

[0003] The magnetic recording medium for passbooks of the present invention is
Broadly includes media used as passbooks with magnetic stripes and media such as magnetic recording media for lamination used to make the media, but is used in particular in a narrow sense for passbooks, booklets This is a medium with a magnetic stripe in which a laminated body including a magnetic recording layer such as a stripe is formed on a non-magnetic support in the shape of a magnetic disk. It is a medium that can input and output magnetic data in addition to inputting character data. It is.

[0004]

2. Description of the Related Art Various magnetic recording media are manufactured from a magnetic recording medium for bonding through a process of bonding to a non-magnetic substrate. A bankbook and a bankbook for postal savings used for postal savings are one of them, but they are generally in the form of a booklet made of paper and have one or both sides of the front cover or back cover of the booklet. A magnetic recording layer is formed on part or the entire surface of the substrate.

Such a magnetic recording layer is a laminated magnetic recording medium having a magnetic recording layer on at least one surface and an adhesive layer on the other surface with a nonmagnetic support interposed therebetween. The magnetic recording medium for lamination having various shapes such as a raw material, a sheet, and a tape, for example, using a magnetic label laminate formed by cutting to a predetermined standard width and length, under pressure and under heating A magnetic recording region of a stripe shape or the like is formed on a passbook substrate by an attaching process.

In recent years, such magnetic recording media for passbooks have become finer and have higher coercive force in accordance with the demand for higher recording density of magnetic recording media and improvement of S / N ratio and C / N ratio. Therefore, it is more necessary to uniformly disperse the magnetic powder in the paint to obtain a smooth and highly filled magnetic recording layer. For this reason, the finely divided magnetic powder is uniformly dispersed,
The ability to disperse the binder resin was a very important factor.

On the other hand, vinyl chloride copolymers have generally been used for magnetic recording media for passbooks in view of high dispersibility of magnetic powder and cost. However, vinyl chloride-based copolymers tend to generate toxic chlorine-hydrogen gas at the time of landfill disposal, and when they are incinerated, generate harmful dioxins during low-temperature combustion, which tends to avoid them.

[0008] In most cases, the passbook substrate is paper, and the incineration process is easy and common. However, the use of a vinyl chloride copolymer in the magnetic stripe portion or the printing ink of the substrate is still important. Dioxin may be generated during incineration. Actually, there is a report that the chlorine amount at the time of incineration is not proportional to the amount of dioxin generated, and it has been pointed out that even a small amount of chlorine contained may generate a problem amount of dioxin at the time of incineration. Therefore, complete dechlorination of the magnetic recording medium for passbooks has been desired.

However, to date, there is no example in which the magnetic recording layer is completely non-vinyl chloride, the dispersibility of the magnetic powder equivalent to that of the vinyl chloride resin is realized, and the magnetic recording medium for passbooks is vinyl chloride-free.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a magnetic recording layer having a magnetic recording layer having a dispersion of magnetic powder equal to or greater than that of a conventional magnetic recording layer without using a chlorine-based resin as a binder resin. An object of the present invention is to provide a combined non-chlorine-based magnetic recording medium and a passbook-free non-chlorine-based magnetic recording medium manufactured using the same.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention.

That is, in a magnetic recording medium having a magnetic recording layer formed by a step of attaching a magnetic recording medium for pasting on a non-magnetic substrate for a passbook, the magnetic recording layer has a hydrophilic polar group as a binder resin. Non-chlorine-based copolymer containing a radical polymerizable monomer in the molecular chain (hereinafter, simply referred to as “copolymer having a polar group”) or “copolymer having a polar group” and no chlorine component By using a non-chlorine urethane resin, it is possible to obtain a non-chlorine magnetic recording medium for passbooks that excels in dispersibility and mechanical properties of magnetic powder and does not contain a chlorine component that causes toxic dioxin during waste combustion. I found that. Hereinafter, “non-chlorine” means “does not contain chlorine components”. Hereinafter, the present invention will be described in detail.

FIG. 1 is a schematic view of a passbook with a magnetic stripe according to an embodiment of the present invention. FIG. 2 is a diagram illustrating a magnetic label laminate as a bonding magnetic recording medium for forming a magnetic stripe for a passbook. FIG. 3 is a cross-sectional view of a body (with a nonmagnetic layer for concealment), and FIG.
FIG. 3 shows a cross-sectional view of a magnetic stripe portion of a passbook with a magnetic stripe (with a nonmagnetic layer for concealment). Hereinafter, each component will be described in detail with reference to these drawings.

As the base A of the passbook, for example, a cloth for magnetic passbook or the like, which is made of a cloth cloth as a base cloth and coated with a resin having good surface smoothness, is used.

Using this substrate A as the cover of a booklet, a magnetic stripe B, which is a laminate including a magnetic recording layer, is formed on one or both of the front cover and the back cover.

Next, the respective constituent materials of the magnetic stripe portion of the passbook with a magnetic stripe according to the present invention or the respective constituent materials of the magnetic recording medium for bonding used in the production of the passbook through the bonding step will be described in detail. I do.

As for the base 7 of the passbook, the use of the above-mentioned magnetic passbook cross paper is generally specified. However, the surface of the passbook is made of a resin coating that is suitable for attaching magnetic stripes and has good surface smoothness. A coated paper for magnetic passbooks or the like is used, and the surface roughness of the magnetic stripe attachment surface (cross paper) is preferably 20 μm or less in terms of the center line average surface roughness (however, the magnetic stripe attachment strength is low). 15 from the point
μm or less is more desirable).

On the other hand, as shown in FIG. 2, the structure of the magnetic label laminate used in the manufacture of a magnetic recording medium such as a passbook with a magnetic stripe in a sticking step (sticking step) is one of the magnetic label base 1. A magnetic recording layer 2 is formed on the surface, and a protective layer 4 (when there is no colored layer) is formed thereon. Further, an adhesive layer (adhesive layer) is provided on the other surface of the magnetic label substrate 1.
5 are provided. A release paper 6 or the like, which is a magnetic label substrate, is usually bonded on the adhesive layer.

Further, from the viewpoint of improving aesthetics and design,
Between the magnetic recording layer 2 and the protective layer 4, a colored layer 3 or a pattern layer for concealing the hue of the magnetic recording layer may be provided.

Usually, the laminated structure of such a magnetic recording medium for lamination such as a magnetic label laminated body is formed by coating the constituent layers on the raw material of the film-shaped magnetic label substrate.

Thereafter, the material is cut into a sheet,
Further, in some cases, the magnetic label laminate is cut into a desired size from a raw material or a sheet by a method such as slitting or punching before use. Further, a tape-shaped slit of a magnetic recording medium for bonding may be formed from the raw material or the above-mentioned sheet, and used as a magnetic label tape.
When affixing to the passbook substrate, the magnetic label laminate including the magnetic recording layer 2 is superimposed on the passbook substrate 7 via the adhesive layer 5, and pressure and heat are applied to the passbook substrate to apply the magnetic label laminate. The method for forming the magnetic recording layer is described below.

For the magnetic recording medium for lamination used in the production of a magnetic recording medium such as a passbook with a magnetic stripe in the laminating step, the binder resin for the magnetic paint used for this is generally a non-PVC-based binder resin. These can be widely used in paint resins.

In the present invention, as a binder resin for a magnetic recording layer, a non-chlorine-based copolymer containing a radically polymerizable monomer component having a hydrophilic polar group in a molecular chain (“a copolymer having a polar group”) Merging ”). The content of the non-chlorine copolymer is
The content is preferably 20 to 70% by mass based on the total binder resin of the magnetic recording layer, and more preferably 40 to 70% by mass.
６０60% by mass.

Examples of the radical polymerizable monomer having a hydrophilic polar group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, and a phosphate group-containing monomer. Is mentioned. Specifically, examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol polypropylene glycol mono (meth). A) acrylate, glycerol mono (meth) acrylate, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyethyl mono (meth) allyl ether, hydroxypropyl mono (meth) allyl ether, hydroxybutyl mono (meth) allyl ether, diethylene glycol Mono (meth) allyl ether, dipropylene glycol mono (meth) allyl ether, glycerin mono ( Data) allyl ether, vinyl alcohol, and (meth) allyl alcohol. In addition, (meth) allyl is a general term for allyl and methallyl.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid; unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; Half esters of acids and the like.

In the example of the sulfonic acid group-containing monomer,

[0027]

Embedded image

(Where M represents a hydrogen atom or an alkali metal, and R represents an alkyl group).

Examples of the phosphoric acid group-containing monomer include mono [(meth) acryloyloxyethyl] acid phosphate, mono [(meth) acryloyloxypropyl] acid phosphate, mono [(meth) acryloyloxybutyl] acid phosphate and mono [(meth) acryloyloxybutyl] acid phosphate. [(Meth) acryloyloxyethoxynoethyl] acid phosphate, mono [(meth) acryloyloxypolyoxyethylene glycol] acid phosphate, (meth) acryloyloxyethylmethyl acid phosphate,
(Meth) acryloyloxyethyl butyl acid phosphate, (meth) acryloyloxypropyl ethyl acid phosphate, (meth) acryloyloxyethyl methyl acid phosphate, (meth) acryloyloxy polyoxyethylene glycol butyl acid phosphate, vinyl acid phosphate and alkalis thereof Metal salts and the like.

The radical polymerizable monomer having a hydrophilic polar group may be used alone or in combination of two or more. If the amount is small, the dispersibility is reduced, and if the amount is too large, Has a high paint viscosity, so that it is difficult to obtain a good coating film. Therefore, the mixing ratio of the radical polymerizable monomer having a hydrophilic polar group during copolymerization is 1 to 1 of all monomers.
The content is 30% by mass, but preferably 1 to 10% by mass. When the radical polymerizable monomer contains hydroxyethyl (meth) acrylate, the effect of the present invention is more remarkable.

Examples of the monomer to be copolymerized with the above-mentioned radical polymerizable monomer having a hydrophilic polar group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, benzyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate And the like, and alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate.

If necessary, a radical polymerizable monomer other than the above acrylic monomer can be copolymerized. Examples of such monomers include vinyl acetate, vinyl propionate, styrene, ethylene, propylene, butylene, isobutylene, butadiene; and methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, Examples thereof include alkyl vinyl ethers such as n-octyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and stearyl vinyl ether. These monomers can be blended in an amount of 20% by mass or less based on the total amount of the monomers as long as the effects of the present invention are not impaired. The optimal blending amounts are the glass transition temperature and strength of the obtained copolymer, Young's modulus. , In consideration of physical properties such as interlayer adhesion at the time of multilayer coating. Since the object of the present invention is to provide a non-chlorine transfer laminate, it is, of course, an essential condition that all raw materials used do not contain a chlorine component.

The “copolymer having a polar group” composed of a combination of the above-described monomers has a low physical strength such as a brittle magnetic coating film if the molecular weight is too low, and the final form is This will reduce the durability of certain magnetic cards. On the other hand, if the molecular weight is too high, the viscosity of the magnetic paint increases, and the workability at the time of application deteriorates, making handling difficult. Therefore, the average molecular weight is preferably 5,000 to 100,000, more preferably 10,000 to 600,000.
00 range.

As the binder resin for the magnetic recording layer, a “copolymer having a polar group” and another resin containing no chlorine component in the molecular structure can be used in combination. Examples of the resin that can be used in combination include polyurethane resin, polyester resin, nitrocellulose, epoxy resin, phenol resin, cellulose derivative, alkyd resin, polyvinyl butyral resin, and the like. In the present invention, it is particularly preferable to use a chlorine-free polyurethane resin in combination. Polyurethane resin shows good mechanical properties such as surface hardness and adhesive strength of the magnetic recording layer, and when used in combination with a `` copolymer having a polar group '', the dispersibility and mechanical properties of the magnetic powder In both cases, an excellent magnetic recording layer can be obtained. The content of the non-chlorine polyurethane resin is 3 with respect to the total binder resin of the magnetic recording layer.
The amount is preferably from 0 to 80% by mass, more preferably from 40 to 60% by mass.

In preparing the coating material for the magnetic recording layer, the compounding ratio of the “copolymer having a polar group” varies depending on the compounding ratio of the polyurethane resin, but the preferable range is 20 to 70% by mass of the total binder resin. , More preferably 40 to
60% by mass.

The magnetic powder used in the present invention includes γ-Fe
_TwoO_Three, Co-coated γ-Fe_TwoO_Three, Fe _ThreeO_Four, Co-coated Fe
_ThreeO_Four, CrO_Two, Ba ferrite, Sr ferrite, P
Conventionally known magnetic powders such as b ferrite and Ca ferrite
Can be used

As the solvent used in the magnetic paint of the present invention, for example, acetone, methyl ethyl ketone (MEK),
Ketone solvents such as methyl isobutyl ketone (MIBK) and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; alcohol solvents such as methanol, ethanol and propanol; hydrocarbons such as hexane, benzene, toluene and xylene And ether solvents such as glycol dimethyl ether, glycol monoethyl ether, dioxane and tetrahydrofuran. These solvents can be used as a mixture of two or more kinds.

The coating solution for the magnetic recording layer can be obtained, for example, by kneading and dispersing the above-mentioned magnetic powder, binder resin, organic solvent and, if necessary, other components with a kneading / dispersing machine.

In kneading and dispersing for preparing the coating solution for the magnetic recording layer, various kneading and dispersing machines can be used. Examples of the kneading and dispersing machine include a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a Henschel mixer, a cobol mill, a tron mill, a sand mill,
Examples include a sand grinder, a segbar lighter, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a disper, a high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, and a pressure kneader.

The method of coating the magnetic recording layer is not particularly limited, and a known coating method may be used, and the magnetic recording layer is manufactured according to a method used for manufacturing a magnetic recording medium having a single layer or a plurality of layers. For example, 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, cast coater method, spray coater method, die method Etc. can be used.

As the orientation method, a known method, for example, a repulsion facing permanent magnet, a solenoid type electromagnet or the like can be used. The magnetic field strength is preferably in the range of 1000 to 6000G.

Next, a laminate such as a magnetic label laminate, which is one of the magnetic recording media for lamination used in the present invention, will be described.
Various constituent materials used other than the magnetic recording layer will be described in detail.

As the bonding substrate 1 that can be used for a magnetic recording medium for bonding such as a magnetic label laminate, any known bonding substrate can be used. Examples thereof include polyesters such as polyethylene terephthalate and polyethylene-2, 6-naphthalate, polyolefins such as polypropylene, cellulose derivatives such as cellulose triacetate and cellulose diacetate, and plastics such as polyamide and polycarbonate. Among them, polyethylene terephthalate, which has both tensile strength and heat resistance, is preferred.

The thickness of the bonding substrate 1 of the magnetic recording medium for bonding such as a magnetic label laminate is not particularly limited, but is usually 10 to 100 μm, preferably 20 to 80 μm.

Next, the coloring layer 3 may be applied to conceal the color of the magnetic recording layer 2 and to improve the decorativeness of the passbook itself. Further, a pattern layer may be applied in order to further improve the decorativeness of the passbook itself.

The colored layer 3 having an important concealing property is not limited to a single layer but may be a multilayer. Pigments used in the coloring layer include inorganic pigments such as alumina, titanium oxide, chromium oxide, iron oxide, zinc oxide, and barium sulfate; and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, and perylene pigments. , Anthraquinone pigments, thioindigo pigments, indanthrene pigments and the like, but are not particularly limited.

In order to form these colored layers 3, pigments may be used alone or as a mixture of two or more kinds in a binder resin, dispersed by a known method to prepare a coating solution for coloring, and applied by a known method.

The coloring layer 3 can be formed by, for example, applying and printing a printing ink containing a pigment, a resin binder and a solvent that dissolves the resin binder on the card substrate.

As the resin binder and the solvent, the above-mentioned non-chlorinated resin described in the section of the magnetic recording layer can be used.

For forming the colored layer 3, a known printing method such as gravure printing, flexographic printing, offset printing and screen printing can be used.

First, the magnetic recording layer of the present invention is formed on the above-mentioned substrate by the above-described method, and then the colored layer 3 is used to cover the magnetic color of the magnetic recording layer 2 and to improve the decorativeness of the passbook itself. Is applied to improve the

If the thickness of the pattern layer and the colored layer is too small, the magnetic color of the magnetic recording layer cannot be concealed. If the thickness is too large, the reproduction output decreases due to spacing loss. Therefore, it is usually used in the range of 0.5 to 20 μm.

Further, as a method of more effectively shielding the magnetic color of the magnetic recording layer, a metal vapor-deposited film can be provided between the magnetic recording layer 2 and the coloring layer 3, and aluminum, tin, gold,
A metal vapor deposition layer of silver, platinum, or the like can be used. By using this method, the magnetic color can be concealed with a thinner film thickness as compared with the formation of a coating film by applying a coloring paint, and deterioration of characteristics such as output and resolution can be prevented.

The range of the film thickness used as the metal deposition film is usually 0.05 to 0.1 μm.

Further, a magnetic recording layer 2 and a colored layer 3 are sequentially provided on the magnetic label substrate, and a protective layer 4 which also has a surface protection function as the outermost layer of each layer formed.
Can also be provided.

The material constituting the protective layer 4 is preferably a material which is durable and has heat resistance since it is subjected to heat and pressure when adhering to the passbook substrate 8, and examples thereof include a cellulose resin, a polyvinyl butyral resin, Epoxy resins, phenol resins, polyester resins, polyurethane resins, acrylic resins, polymethyl methacrylates and copolymers thereof, melamine resins and the like, and mixtures of these resins can be mentioned.

Further, soybean lecithin, phthalic acid plasticizer, microsilica, wax or the like can be added to the protective layer 4 as a film modifier, if necessary.

The protective layer 4 is formed, for example, by applying a coating obtained by dissolving or dispersing the above constituents in a solvent on the magnetic recording layer 2 or the colored layer by a known method.

On the other hand, when bonding a magnetic recording medium for lamination such as a magnetic label laminate which is a magnetic recording medium for lamination to a passbook, an adhesive layer provided on the opposite side of the magnetic recording layer on the magnetic label laminate is used. A certain pressure-sensitive adhesive layer 5 is first pressed at a predetermined temperature on a passbook substrate at a normal temperature, and then heated and pressed at a temperature of about 120 ° C. to further strengthen the adhesion. Therefore, it is desirable that the pressure-sensitive adhesive layer 5 provided on the surface of the magnetic label substrate opposite to the magnetic recording layer be a pressure-sensitive pressure-sensitive adhesive having excellent adhesive strength both at the time of normal pressure bonding and after heating and pressing. A release paper 6 is usually attached adjacent to the pressure-sensitive adhesive layer.

Examples of the pressure-sensitive adhesive resin used for the pressure-sensitive adhesive layer 5 for the magnetic label laminate, which is a magnetic recording medium for bonding, include alkyl acrylate and (meth) alkyl.
Vinyl chloride-based copolymers such as copolymers with acrylic acid, copolymers of alkyl acrylate with (meth) acrylic acid and vinyl acetate, or copolymers further added with vinyl alcohol, maleic anhydride or acrylic acid resin,
Examples include polyester resin, acrylic resin, polyimide resin, polyurethane resin, and phenol resin.

Further, by adding a cross-linking agent to the above resin composition, it is possible to control the adhesive strength at room temperature pressure bonding and the adhesive strength after heating. As the cross-linking agent, those conventionally used for pressure-sensitive adhesives can be used, and specific examples thereof include an isocyanate-based cross-linking agent, an amine-based cross-linking agent, and an epoxy-based cross-linking agent.

The coating for the pressure-sensitive adhesive layer that can be used for the pressure-sensitive adhesive layer 5 is prepared by dissolving a resin exhibiting pressure-sensitive adhesive in a solvent at 3 to 20% by mass of the resin relative to the solvent. Adjust by stirring. For the application of the pressure-sensitive adhesive layer 5, the known and commonly used application method described for the magnetic recording layer 2 can be used.

The range of the thickness of the pressure-sensitive adhesive layer is usually from 5 to
100 μm is used.

As a magnetic recording medium for bonding, an adhesive layer such as an adhesive layer is usually formed in advance on the surface of the bonding substrate opposite to the magnetic recording layer, but this adhesive layer is not formed.
An adhesive layer may be separately formed on the side of the base such as a passbook by application or the like, and the adhesive layers may be laminated using a magnetic recording medium for lamination such as a magnetic label laminate having no adhesive layer.

In order to prepare a passbook with a magnetic stripe through the attaching step using the magnetic label laminate formed as described above, the material or sheet of the magnetic recording medium for pasting must be once cut into a predetermined width. Create a magnetic label tape created by cutting into
Alternatively, a method is used in which a portion to be used for a magnetic stripe is directly punched from the material or sheet into an island shape and used as a label.

Thereafter, as described above, the pressure-sensitive adhesive layer 5 provided on the magnetic label laminate is first pressed at a predetermined temperature on the passbook substrate 7 at a normal temperature, and then heated at a temperature of about 100 to 120 ° C. And pressurized together to make the adhesion between the magnetic label laminate and the passbook substrate 7 stronger.

By using these techniques, a magnetic recording medium for a passbook magnetic stripe having a complicated pattern and excellent in design can be manufactured.

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention includes the following inventions. 1. In a magnetic recording medium for lamination having a magnetic recording layer on one surface of a nonmagnetic support and an adhesive layer on the opposite side of the nonmagnetic support from the magnetic recording layer, the magnetic recording layer is bonded. A non-chlorine-based magnetic recording medium for lamination, comprising a non-chlorine-based copolymer containing, as a resin, a radical polymerizable monomer component having a hydrophilic polar group in a molecular chain. 2. 2. The non-chlorine magnetic recording medium for lamination according to the above 1, wherein the content of the non-chlorine copolymer is 20 to 70% by mass based on the total binder resin of the magnetic recording layer. 3. The above-mentioned 1 or 2, wherein the content of the radical polymerizable monomer component having a hydrophilic polar group contained in the non-chlorine-based copolymer molecular chain is 1 to 30% by mass of all monomers. Non-chlorine magnetic recording media for bonding. 4. 4. The non-chlorine-based magnetic recording medium for lamination according to the above 1, 2, or 3, which contains hydroxyethyl (meth) acrylate as a radical polymerizable monomer having a hydrophilic polar group. 5. 5. The non-chlorine magnetic recording for lamination according to the above 1, 2, 3, or 4, wherein the magnetic recording layer contains 30 to 80% by mass of a non-chlorine-based polyurethane resin based on the whole binder resin. Medium. 6. 6. The non-chlorine magnetic recording medium for lamination according to the above 1, 2, 3, 4, or 5, wherein a non-magnetic layer for completely hiding the hue of the magnetic layer is laminated on the magnetic recording layer. 7. 7. A magnetic recording medium produced by laminating the non-chlorine magnetic recording medium for lamination according to the above 1, 2, 3, 4, 5, 6 on a non-magnetic substrate. 8. (7) the non-magnetic substrate is a booklet;
The magnetic recording medium according to the above. 9. 9. The magnetic recording medium according to the above items 7 and 8, wherein the magnetic recording medium is for a passbook.

[0069]

EXAMPLES Hereinafter, the magnetic label laminate for a passbook magnetic stripe of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to Examples. Hereinafter, "parts" represents parts by mass.

Example A polyethylene terephthalate film having a thickness of 38 μm was used as a support film as a substrate for a magnetic label, and each of the following compositions a, b and c was used on one side of the film, and a colored layer was formed to a thickness of 4 μm. Then, a protective layer was sequentially formed so as to have a thickness of 2 μm after drying. After that, an adhesive layer was formed on the surface of the film opposite to the surface where the above-mentioned constituent layer was applied by using the following composition d so as to have a thickness of 30 μm. Then, the magnetic label laminate was cut into a predetermined width to produce a magnetic label tape.

(A: Composition for Magnetic Recording Layer) Co-Containing γ-Fe ₂ O ₃ Iron Oxide 27 parts (Toda Kogyo Co., Ltd., “CTX-970”) Acrylic copolymer resin 3 parts (Nissin Chemical Co., Ltd.) 4-8 parts of polyurethane resin (manufactured by Dainippon Ink and Chemicals, Inc., "T-5206") 28 parts of MEK 28 parts of toluene 8 parts of cyclohexanone 2 parts of isocyanate compound

(B: Composition for Colored Layer) Aluminum powder 20 parts Cellulose derivative resin 7 parts (manufactured by Eastman Chemical Company, “CAB381-0.5”) Polyurethane resin 3 parts (manufactured by Dainippon Ink and Chemicals, Inc.) Pandex TR-01 ") MEK 35 parts Toluene 25 parts Ethyl acetate 10 parts

(C: Composition for protective layer) Acrylic resin 16 parts (“KU-273” manufactured by Dainippon Ink and Chemicals, Inc.) 8 parts of talc pigment (“# 5000 PJ” manufactured by Matsumura Sangyo Co., Ltd.) Isocyanate-based curing agent 2 (D-750 manufactured by Dainippon Ink and Chemicals, Inc.) MEK 37 parts Toluene 37 parts

(D: Composition for Pressure-Sensitive Adhesive Layer) Alkylphenol Resin 6 parts (Arakawa Chemical Industry Co., Ltd., “Tamanol 100S”) Acrylic ester / acrylic acid / vinyl acetate copolymer resin (Seiden Chemical Industry Co., Ltd.) , “Saiphenol SD-102”) 67 parts Toluene 26 parts Isocyanate-based curing agent 1 part (“Coronate L” manufactured by Nippon Polyurethane Co., Ltd.)

Next, the magnetic label tape was attached to a bankbook base (“Magnaprene 702”, manufactured by Dynic Corporation), and then heated and pressed at a temperature of 110 ° C. and a pressure of 0.1 MPa for 2 seconds. A passbook substrate with a magnetic stripe was prepared. Thereafter, the magnetic stripe portion was cut into a size of 7 mm × 14 mm to prepare a sample for measuring magnetic properties.

Comparative Example 1 A tape for a magnetic label was prepared in the same manner as in the example except that the composition of the coating composition for the magnetic recording layer was as follows, and then the present invention was performed in the same manner as in the example. A sample for measuring magnetic properties was prepared.

(F: Composition for Magnetic Recording Layer) 27 parts of Co-containing γ-Fe ₂ O ₃ iron oxide (“CTX-970” manufactured by Toda Kogyo Co., Ltd.) 4 parts of vinyl chloride resin (manufactured by Nippon Zeon Co., Ltd. MR-110 ") Polyurethane resin 4 parts (Dainippon Ink &Chemicals," T-5206 "Isocyanate curing agent 3 parts (Nippon Polyurethane Co., Ltd." Coronate L ") MEK 24 parts Toluene 24 parts Cyclohexanone 11 parts

Comparative Example 2 A tape for a magnetic label was prepared in the same manner as in the example except that the composition of the coating composition for the magnetic recording layer was as follows, and then the present invention was performed in the same manner as in the example. A sample for measuring magnetic properties was prepared.

(G: Composition for Magnetic Recording Layer) Co-Containing γ-Fe ₂ O ₃ Iron Oxide 27 parts (Toda Kogyo Co., Ltd., “CTX-970”) Acrylic copolymer resin 4 parts (Mitsubishi Rayon Co., Ltd.) , "BR-77" A radical polymerizable monomer component having a hydrophilic polar group is not included in the molecular chain.) 4 parts of polyurethane resin ("T-5206", isocyanate curing by Dainippon Ink and Chemicals, Inc.) Agent 3 parts ("Coronate L" manufactured by Nippon Polyurethanes) MEK 24 parts Toluene 24 parts Cyclohexanone 11 parts

(Test Items and Results) Magnetic properties (magnetic powder dispersibility) The magnetic static properties were measured (using an AC type BH tracer) with the obtained magnetic property measurement sample, and the value of φr / φm was expressed as the squareness ratio, and the magnetic powder was dispersed. Assess gender.

2. Presence / absence of chlorine in the layer structure Results of element mapping by SEM-EDS The results are shown in Table 1.

[Table 1]

As shown in the examples, according to the present invention, the magnetic recording medium for which vinyl chloride has been removed does not contain chlorine originating from the material, but also chlorine originating from impurities can be eliminated by the SEM-EDS. In the mapping method, chlorine was not detected from the layer structure. However, even when the magnetic recording medium having the configuration of the embodiment is used, since the squareness ratio is almost the same as that of the conventional PVC-based magnetic recording medium, the dispersibility of the magnetic powder is the same as the conventional vinyl chloride-based magnetic recording medium. It turns out that it is as good as a polymer.

The non-chlorine-based magnetic recording medium for lamination of the present invention has a non-chlorine-based magnetic recording medium containing a radical polymerizable monomer having a hydrophilic polar group in the molecular chain as a binder resin of the magnetic layer. It is formed using a polymer or a copolymer having a polar group and a chlorine-free urethane resin containing no chlorine component. For this reason, the magnetic recording medium for passbooks manufactured using the magnetic recording medium for lamination allows for the removal of vinyl chloride on the magnetic stripe for passbooks, which has not been realized in the past, and the magnetic recording with good dispersibility of the magnetic powder. This has a particularly remarkable effect in that a medium can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a passbook having a magnetic stripe.

FIG. 2 is a sectional structural view of a magnetic label laminate which is a magnetic recording medium for bonding.

FIG. 3 is a cross-sectional structural view of a passbook magnetic stripe portion when a magnetic stripe is formed on a passbook substrate by a sticking method using a magnetic label laminate having a magnetic recording layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS A Passbook base B Magnetic stripe 1 Magnetic label base 2 Magnetic recording layer 3 Colored layer 4 Protective layer 5 Adhesive layer 6 Release paper 7 Passbook base

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) G11B 5/702 G11B 5/702 5/72 5/72 5/74 5/74 F term (reference) 4J038 CG141 CH121 DG002 GA03 NA22 PB11 5D006 AA01 AA05 BA11 BA15 FA00

Claims (9)

[Claims] 1. A bonding magnetic recording medium having a magnetic recording layer on one surface of a non-magnetic support and an adhesive layer on the opposite side of the non-magnetic support from the magnetic recording layer. A non-chlorine-based magnetic recording medium for lamination, characterized in that the layer contains a non-chlorine-based copolymer containing a radical polymerizable monomer component having a hydrophilic polar group as a binder resin in a molecular chain. 2. The non-chlorine-based magnetic recording medium for lamination according to claim 1, wherein the content of the non-chlorine-based copolymer relative to the total binder resin of the magnetic recording layer is 20 to 70% by mass. 3. A non-chlorine-based copolymer molecular chain,
The non-chlorine-based magnetic recording medium for lamination according to claim 1 or 2, wherein the content of the radical polymerizable monomer component having a hydrophilic polar group is 1 to 30% by mass of all monomers. 4. The non-chlorine-based magnetic recording medium for lamination according to claim 1, which comprises hydroxyethyl (meth) acrylate as a radical polymerizable monomer having a hydrophilic polar group. 5. The magnetic recording layer has a thickness of 30% with respect to all binder resins.
5. The non-chlorine-based magnetic recording medium for lamination according to claim 1, wherein the non-chlorine-based magnetic recording medium contains about 80% by mass of a non-chlorine-based polyurethane resin. 6. The magnetic recording layer according to claim 1, wherein a non-magnetic layer for completely hiding the hue of the magnetic layer is laminated on the magnetic recording layer.
The non-chlorine magnetic recording medium for bonding according to the above. 7. A magnetic recording medium produced by laminating the non-chlorine magnetic recording medium for lamination according to claim 1, 2, 3, 4, 5, or 6 on a non-magnetic substrate. 8. The magnetic recording medium according to claim 7, wherein the non-magnetic substrate has a booklet shape. 9. The magnetic recording medium according to claim 7, wherein the magnetic recording medium is for a passbook.