JP5276034B2 - Magnetic film and magnetic card using the same - Google Patents

Description

The present invention relates to a magnetic film and a magnetic card using the magnetic film.
The magnetic film is a magnetic film having a displayable layer capable of opaque writing, printing, and printing, and can be viewed by magnetically attaching to a magnetic adherend such as a refrigerator, a steel shelf, or a whiteboard. There are hard magnetic (permanent magnet) films that can be used, and soft magnetic films that are used for the same applications but are magnetically attracted to the magnet surface. In other words, the present invention relates to a magnetic film that can be used for a sticker, a display, a printed picture, a trading card, a post card (picture postcard), and the like, and a magnetic card using the magnetic film.

There is a postcard as an application of a conventional sheet-like magnet (in this specification, the sheet-like means that the thickness is generally thicker than the film-like), and on the magnetized surface of the sheet-like magnet that is a permanent magnet A decorative postcard, characterized in that a weakly adhesive material is used to attach a free-writing coated paper, a postcard style is printed on the coated paper, and a decorative surface is provided on the other side of the sheet-like magnet. Has been proposed.
With this configuration, when the receiver peels and removes the coated paper, the air gap of the magnet (the distance between the magnet and the adherend via the nonmagnetic material) is eliminated, so that the necessary magnetic attractive force can be exhibited. There is something. (Patent Document 1)

  Further, it is a sheet for a postcard having an anisotropic thin magnetic layer that is magnetically oriented by coating on one side of a film-like substrate, and having a printable surface on the other side, A postcard sheet has been proposed in which a sheet having a printable surface is adhered to a magnet layer in a peelable manner. With this configuration, until the receiver peels and removes the sheet having the printable surface on the magnet layer, there is no inconvenience due to magnetic adsorption, and the receiver has the sheet having the printable surface on the magnet layer. By peeling and removing, some air gaps of the magnet are eliminated, so that the necessary magnetic attractive force can be exhibited. (Patent Document 2)

  Magnetic sheets and magnetic postcards using conventional sheet-like magnets can be written, printed and printed on the non-magnetized surface side of the magnets, or can be written, printed and printed. Since a magnet layer is formed by applying a magnetic material to a magnetized surface side of a magnet that has been magnetized, a writing, printing, printable paper, etc. is releasably adhered to the magnet. Each layer is different, such as writing, printing, printable paper, etc., stuck on the non-magnetized surface side, writing, printing, printable paper, etc. In addition, there is a disadvantage that the curling phenomenon may occur while being stored or magnetically adsorbed to the adherend because of the fact that the material has a difference in expansion and contraction due to changes in temperature and humidity. Can not be magnetically adsorbed If there is a.

  Prior art documents related to curling prevention of conventional magnetic films include paper (art paper, etc.) as a base material, and isotropic thin magnetic layer formed on one side by coating. A manufacturing method has been proposed in which a specific hydrophobic synthetic resin film is formed on the surface on which the product does not curl due to a change in humidity even when an aqueous coating solution is used to form the magnetic layer. (Patent Document 3)

Japanese Utility Model Publication No. 5-91869 JP 2003-80871 A Japanese Examined Patent Publication No. 56-15123

  The magnetic sheet according to Patent Document 3 is used for individual curl tests at low humidity (for example, 26 ° C., RH 35%) and high humidity (for example, 18 ° C., RH 95%) while being magnetically attracted to an iron plate. In this case, no curling occurs, but the occurrence of curling is observed when the magnetic film is tested by the curl test method of the present invention. That is, by placing a test sample on a non-magnetic material (such as a plastic plate), the magnetic adsorption force does not suppress curling as in the state of being magnetically adsorbed to an iron plate. The curl is then caused by a history of exposure to a low humidity atmosphere.

  Further, the above-mentioned Patent Document 3 and the magnetic sheet of the present invention differ in the cause of curling and the curling prevention measures. That is, Patent Document 3 discloses a method for producing a magnetic adhesive paper in which a coating paper prepared by mixing a powdered magnetic material with a binder such as an aqueous synthetic resin emulsion, synthetic rubber latex, or water-dispersed synthetic resin is directly applied to paper. This is a manufacturing method in which a magnetic layer is formed by applying the coating to the surface and drying the coated surface with hot air to form a magnetic layer. In this way, when hot air is applied to the coated surface and dried, the coated layer is cured and fixed before the paper is completely dried, so it was used by magnetically attaching it to a ferromagnetic material such as an iron plate. In this case, the humidity of the atmosphere decreases and the paper shrinks and shrinks, overcoming the adsorptive power of the magnet and the iron plate and curling, so there is a drawback of peeling or rolling up during use, and also during storage There is a disadvantage that it is curled remarkably due to changes in atmospheric humidity, making it unusable.

In order to prevent this defect, if the coating layer is dried from the paper side, the paper is excessively dried and easily breaks, and the workability is remarkably impaired.
In order to improve such a defect, the problem is solved by forming a hydrophobic layer having a specific property on the surface of paper and then forming a magnetic layer satisfying predetermined conditions on the surface.

  On the other hand, the cause of curling in the prior art documents 1 and 2 differs from the prior art document 3 in that the cross section is not symmetrical in the multilayer, and the expansion and contraction due to residual strain, temperature change and humidity change at the time of formation. It is caused by a force difference.

  Further, the magnetic sheet of the present invention is provided with displayable layers on both sides of a flexible magnetic film having a specific thickness, and is intended to be used for, for example, a post card. The cause of curling is the display on one side and the other side. This is caused by the difference in stretching force due to residual strain, temperature change, and humidity change during the formation of the displayable layer. As a preventive measure, we will try to solve it by adjusting the composition, formation conditions and thickness of the displayable layers on both sides. It is characterized in that the quality is determined by a specific test method.

  In the magnetic postcards of Prior Art Document 1 and Prior Art Document 2, the coated and writable coated paper that is pasted on the magnetized surface side for the magnetic attraction of the receiver is peeled off to remove the two postcards. Because it is necessary to divide into two, the relationship between the two may be lost at a later date. The present invention also solves the above disadvantages.

  As a result of repeated research aimed at solving the inconvenience caused by magnetic attraction between magnetic sheets and the curling properties of magnetic sheets, curling properties can be solved by specifying the material and configuration. As a result of research on the curl test method, the test piece is placed on a non-magnetic material (such as a plastic plate) and the atmosphere of low to high humidity and low humidity is maintained without relying on the anti-curl action of magnetic attraction. To find a short-term evaluation test method of test methods 1 to 3 to be described later, and to find out that the magnetic adsorption problem between magnetic sheets can be solved by specifying the magnetic pole direction of multipolar magnetization or between magnetic poles. The present invention has been accomplished.

(1) Opaque writing, printing, and printable display on both sides of a flexible magnetic film, which is a bonded magnet composed of hard magnetic material powder and organic polymer binder and multipolarized on one side It is assumed that the magnetic film is provided with a possible layer.

The hard magnetic material powder is ferrite magnetic material powder, the binder is polypropylene, the thickness of the flexible magnetic film is 80 μm to 350 μm, the thickness of the displayable layers on both sides is 15 μm to 60 μm, and multipolar magnetization The distance between the electrodes is 0.8 to 2.5 mm, and the vertical adsorption force is 0.5 g / cm. ² ~ 20g / cm ² As a result, the curl generated due to the difference in stretching force between one side of the displayable layer and the other side is 3.0 mm or less in each of the following (Test Method 1) to (Test Method 3). It is set as the magnetic film characterized by comprising.

(Test Method 1) A 60 mm × 60 mm test sample was placed on a flat, flat, non-magnetic flat plate and treated in a hot air circulating thermostat at 120 to 42 ° C. for 120 minutes. Measure the distance of the point where the lifting distance from the non-magnetic flat plate by the curl is the largest.
(Test Method 2) Using the test sample after the test of Test Method 1, from a non-magnetic flat plate by curling after treatment in a constant temperature and humidity apparatus of 23 to 27 ° C. and RH 90 to 96% × 180 minutes Measure the distance of the point where the lifting distance is the maximum.
(Test Method 3) Using the test sample after the test of Test Method 2, the lift distance from the flat plate made of non-magnetic material by curl after treatment for 120 minutes in a hot air circulating thermostat at 38 to 42 ° C. is the maximum Measure the distance of.

In the present invention, the flexible magnetic film is a film formed by heating and kneading a composition mainly composed of a magnetic powder and a plastic or rubber / elastomer as a binder (film-like). In the case of a magnet, it is then magnetized by applying a magnetic field), which means that it does not crack when bent along a round bar with a diameter of 15 mm. The product name of the present invention is called a magnetic film .

(2) The magnetic film as described in (1) above, wherein the displayable layer has the same composition, formation conditions, and thickness on both sides, and a thickness of 15 μm to 100 μm.

(3) The magnetic film according to (1) or (2), wherein the displayable layer is a layer formed by coating.

(4) The magnetic pole direction of multipolar magnetization is magnetized by providing an arbitrary inclination within a range of 10 ° to 80 ° or minus 10 ° to minus 80 ° with respect to the longitudinal direction. The magnetic film according to any one of (1) to (3) .

(5) The distance between the poles of the multipolar magnetization is a distance between the reference poles suitable for the thickness of the bonded magnet, and the distance between the reference poles x (4 to 6) is 1 unit. There are 4 to 6 magnetic poles in the range between the poles having the dimensions of 0.8, 0.9, 1.0, 1.1, and 1.2, and the order is continuous. The magnetic film according to any one of (1) to (3) , wherein the magnetic film is random within each unit.

(6) The distance between the poles of the multipolar magnetizing is a distance between the reference poles that is suitable for the thickness of the bonded magnet, and the distance between the reference poles x (4-6) is defined as one unit. There are 4 to 6 magnetic poles in the range between the poles having the dimensions of 0.8, 0.9, 1.0, 1.1, and 1.2, and the order is continuous. The magnetic pole direction is magnetized by providing an arbitrary inclination within a range of 10 ° to 80 ° or minus 10 ° to minus 80 ° with respect to the longitudinal direction. The magnetic film according to any one of items 1) to (3) .

(7) An opaque writable, printable and printable displayable layer was provided on both sides of a flexible magnetic bond magnetic film to be a magnetic adherend composed of a soft magnetic material powder and an organic polymer binder. A magnetic film, wherein the soft magnetic material powder is one selected from Sendust powder, triiron tetroxide powder, Mn-Zn ferrite powder, iron powder, or a mixture thereof, the binder is polypropylene, and the bond magnetic film By setting the thickness of the displayable layer to 50 μm to 350 μm and the thickness of the displayable layers on both sides to 15 μm to 60 μm, curling caused by the difference in stretching force between one side of the displayable layer and the other side is described below (Test Method 1 ) To (Test Method 3), each of which is configured to be 3.0 mm or less.

(Test Method 1) A 60 mm × 60 mm test sample was placed on a flat, flat, non-magnetic flat plate and treated in a hot air circulating thermostat at 120 to 42 ° C. for 120 minutes. Measure the distance of the point where the lifting distance from the non-magnetic flat plate by the curl is the largest.
(Test Method 2) Using a test sample after the test of Test Method 1 from a nonmagnetic plate made of curl after treatment for 180 minutes in a thermostatic chamber at 23 ° to 27 ° C. and RH 90 to 96% Measure the distance of the point where the lift distance is the maximum.
(Test Method 3) Using the test sample after the test of Test Method 2, the lift distance from the flat plate made of non-magnetic material by curl after treatment for 120 minutes in a hot air circulating thermostat at 38 to 42 ° C. is the maximum Measure the distance of.

(8) The magnetic film as described in (7) above, wherein the displayable layer has the same composition, formation conditions, and thickness on both sides, and a thickness of 15 μm to 100 μm.

(9) The magnetic film according to (7) or (8), wherein the displayable layer is a layer formed by coating.

(10) A magnetic card using the magnetic film according to any one of (1) to (9) . Thereby, the thing by said (1)- (6) item is obtained as a bonded magnet type magnetic card, and the thing by the item (7) - (9) is obtained a magnetic adherend type magnetic card.

(1) Hard magnetic film (bonded magnet type magnetic film) and magnetic card 1). A flexible magnetic film is provided with a displayable layer on both sides, and the displayable layer on both sides is coated, or the composition, formation conditions, and thickness of the displayable layer on both sides are the same. By providing a displayable layer having the same force and evaluating by a specific test method, the curl generation problem, which is a conventional defect, can be solved.
2). By specifying the magnetic pole direction of the multipolar magnetization of the bond magnet, the distance between the magnetic poles, and the distance between the magnetic pole direction and each magnetic pole, by magnetic adsorption between the magnetic films accompanying the means for solving the curl property Solved the inconvenience. Therefore, unlike the conventional magnetic postcard, there is no need to peel off the writable and printable coated paper that is pasted on the magnetized surface side so that the receiver can magnetically attract it. Therefore, the shortcoming that the relationship between the two would not be understood later was solved.
3). When the displayable layer is formed by coating, the thickness can be minimized, so the necessary magnetic attractive force can be obtained even if the thickness of the film-like magnet is reduced by reducing the air gap of the magnet. Therefore, the total thickness was reduced and the total weight was reduced.

(2) In the case of a magnetic card using a soft magnetic film (magnet adherend type) The same effect as a post card using a hard magnetic film (film-like bonded magnet type) (does not curl, reduces the total thickness, In addition to weight reduction, the effect of the invention of the magnetic film using the soft magnetic film is that the magnetic surface of the sheet-like magnet or the film-like magnet is faced to the front side and is attached or built in the magnetic field of the bulletin board or wall surface. Since the magnetic film alone is not attracted to the outside, the magnetic film does not generate magnetism to the outside, so there is no influence on the magnetic adsorption between the magnetic films and the magnetic recording medium, and the magnetizing process is unnecessary. Also, in the case of a magnetic card, there is an advantage that many sheets can be easily stacked with the ends aligned.

Sectional drawing of the magnetic film (bond magnet type) showing embodiment of this invention is shown. The top view (the space | interval is uniform) showing the multipolar magnetization of the conventional bond magnet sheet | seat is shown. It represents an example of the gradient magnetization of the magnetic film (bonded magnet type) of the present invention, (a) is a plan view seen from the magnetized surface side, (b) shows a plan view seen from the back side. . FIG. 2 is a schematic diagram for explaining a reduction in attractive force when a non-magnetized surface and a magnetized surface of a magnetic card subjected to tilt magnetization in the present invention are overlapped, (a) is a plan view, (b). Indicates an enlarged view of the smallest unit. FIG. 3 is a schematic diagram for explaining a reduction in the attractive force when the magnetized surfaces of the magnetic cards that are tilted and magnetized in the present invention are overlapped, where (a) is a plan view and (b) is an enlargement of the minimum unit. The figure is shown. Sectional drawing showing the multipolar magnetization of the conventional bond magnet sheet | seat is shown. Sectional drawing showing the schematic diagram when the conventional bonded magnet sheet | seat is magnetically adsorbed by a non-magnetized surface and a magnetized surface is shown. Sectional drawing showing the schematic diagram when it magnetically adsorbs on the non-magnetized surface and the magnetized surface of the magnetic film of the present invention (bonded magnet type with random magnetic poles between multipolar magnets) is shown. Sectional drawing showing the schematic diagram when magnetically attracting | sucking between the magnetized surfaces of the magnetic film of this invention (Band magnet type between the magnetic poles of multipolar magnetization) is shown. Sectional drawing showing the state which affixed the magnetic film (bond magnet type) of this invention on the to-be-adhered body is shown. Sectional drawing of the magnetic film (adhered body type of magnet) showing other embodiment of this invention is shown. Sectional drawing showing the state which stuck the other magnetic film (adhered body type of this invention) to the to-be-adhered body (magnet) of this invention is shown. Explanatory drawing showing the measuring method about a curl test is shown. An explanatory view showing a measuring method in the case of another deformation in the curl test is shown.

Hereinafter, embodiments of the present invention will be described with reference to FIGS.
(1). FIG. 1 is a sectional view showing an embodiment of the present invention, and P1 represents a magnetic film (bonded magnet type) of the present invention.
11 shows a flexible magnetic film (bonded magnet type). The flexible magnetic film (bonded magnet type) has a thickness of 80 μm after heating and kneading a composition mainly composed of hard magnetic material powder as a permanent magnet material and a small amount of plastic or rubber or elastomer as a binder. It is magnetized by applying a magnetic field after being formed into a film of ~ 400 μm, and the flexible magnetic film (bonded magnet type) does not crack when bent along a round bar with a diameter of 15 mm Say things.

  The hard magnetic material powder in the composition is used in an amount of about 50 to 65% by volume. If the thickness is less than 80 μm, the magnetic attractive force may be insufficient, and if it is thicker than 400 μm, the magnetic attractive force is insufficient. When it is used for a post card or the like, it is inconvenient because it is excessive for use and its own weight increases.

Reference numeral 12 denotes a displayable layer on the non-magnetized surface side, and reference numeral 13 denotes a displayable layer on the magnetized surface side.
Examples of 12 and 13 include a coating film coated with a coating containing inorganic powder and the like, and a plastic film containing synthetic paper inorganic powder and the like. Note that papers (quality paper, coated paper, etc.) are not preferable because they are greatly expanded and contracted by changes in humidity.

  Examples of synthetic paper include YUPO synthetic paper FEB, FGS, FPG, VJFP, VJF, etc. (manufactured by YUPO CORPORATION), Toyojet GP, MW, MT, YP, etc. (manufactured by Toyobo Co., Ltd.), Peach Coat SPY , MP, etc. (manufactured by Nisshinbo Co., Ltd.), and as a plastic film containing inorganic powder, semi-rigid vinyl chloride film-10P (manufactured by Riken Technos), etc., etc. Examples of the paint include polyester-based SS16-611 (manufactured by Toyo Ink Co., Ltd.), polyester-based PAL mat 8, polyester-based RAM, urethane acrylic-based ULA (manufactured by Seiko Advance Co., Ltd.).

  The lamination of the synthetic paper or the vinyl chloride film to the magnetic film can be performed by a known method using an adhesive and a laminator. Examples of the adhesive used in this case include polyester (two-component) AP-368A / B (manufactured by Chuo Rika Co., Ltd.), polyester (two-component) TM595 / CAT56 (manufactured by Toyo Morton Co., Ltd.), and the like. Can be mentioned.

  The coating of the paint on the magnetic film can be performed by a known method such as a blade coater, a bar coater, a comma coater, a gravure coater, a roll coater, or a reverse roll coater.

The displayable layer on the non-magnetized surface side and the displayable layer on the magnetized surface side should be comparable in terms of stretch force due to molding distortion, temperature, and humidity changes. And the possibility of causing a problem of curling at the time of sticking use increases.
In order to design the stretch force to be equal, it is necessary to examine the shrinkage rate, elastic modulus, temperature / humidity change and stretch rate, thickness, etc. of each material, and finally make a judgment by the curl test. good.

  As a result of the test, 3.0 mm or less is preferable, and if it exceeds 3.0 mm, there is a high possibility of causing a magnetic adsorption failure due to curling.

  Further, the thickness on the magnetized surface side indicated by 13 is preferably 15 μm to 100 μm, more preferably 15 μm to 60 μm. If the thickness is less than 15 μm, the hiding power of the flexible magnetic film with respect to the natural color becomes insufficient, resulting in a reduction in commercial value.

(2). In FIG. 1, 11 is a flexible magnetic film (bonded magnet type), 12 is a white displayable layer on the non-magnetized surface side, and 13 is a displayable layer on the magnetized surface side. . It is desirable that 12 and 13 have the same composition, formation conditions, and thickness. If they are not the same, the curling property due to the difference in stretching force between 12 and 13 increases, and the lifting distance is 3.0 mm in the curl test. The possibility of becoming above becomes large.

(3). In FIG. 1, when the displayable layers 12 and 13 are formed by coating, the minimum necessary coating is possible, and the influence of the air gap on the magnet is reduced, so the thickness of the magnetic film can be reduced. It leads to reducing weight. Further, since there is an advantage that almost no formation residual distortion occurs, it is very preferable when applied to a postcard.
In addition, in FIG. 1, when using commercially available synthetic paper as the displayable layers 12 and 13, by selecting a grade (ink receiving layer) suitable for the printing method, the processing of the ink receiving layer described later can be performed. This is preferable because it is not necessary to omit the process.

An ink receiving layer such as an ink jet may be applied to both surfaces of the displayable layer or the surface on the nonmagnetic adsorption surface side. Further, the case where the inkjet receiving layer, the thickness of the inkjet receiving layer 2μm~20μm is desirably thinner becomes accepting incompetence of ink from 2 [mu] m, which is uneconomical next thicker than necessary accepting capability than 20 [mu] m.

  The treating agent used for forming the ink receiving layer is not particularly limited and a commercially available one can be used. However, as the treating agent used for forming the ink jet receiving layer, for example, Pateracol IJ-150R (inorganic filler-containing urethane resin system) Dispersion) DIC Corporation, RSI-100 (inorganic filler-containing hybrid resin dispersion) DIC Corporation, MZ-477, MZ-480, (inorganic filler-containing acrylic resin dispersion) Takamatsu Oil The product made by Co., Ltd. is mentioned. A known coating device can be used, and examples include an air knife coater, a blade coater, a bar coater, a comma coater, a gravure coater, a roll coater, a reverse roll coater, and a curtain coater.

(4). Reference numeral 11 in FIG. 1 denotes a flexible magnetic film (bonded magnet type). As the hard magnetic material powder (magnet material powder) used for this, ferrite type (strontium ferrite, barium ferrite), rare earth type (Sm— Co, Nd—Fe—B, Sm—Fe—N) and the like.

  Examples of binders that are organic polymers include polyolefin resins (polypropylene, polyethylene), polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), polyamide resins (6 nylon, 12 nylon), acrylic resins (ethylene ethyl acrylate), and chlorine. Plastomers such as chlorinated polyethylene resins, chlorinated polyethylene elastomers, chlorosulfonated polyethylene elastomers, ethylene vinyl acetate copolymer elastomers, ethylene propylene elastomers, ethylene ethyl acrylate elastomers, polyamide elastomers, polyester elastomers, polyurethanes Based elastomers and the like.

  Among various hard magnetic materials, the ferrite system is a metal oxide, so that it does not cause oxidative deterioration and is not easily affected by bond magnet molding processing conditions, and is suitable for a flexible magnetic film because of its low cost. Among various binders, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyamide-6 are used in compositions that are highly filled with ferrite-based magnetic material powders because their heat melt viscosity is lower than that of rubber and elastomer. When forming a film, it is excellent in fluidity, has little load on the machine, and is suitable for extrusion / rolling molding. Among these, polypropylene is preferable in view of processability, physical properties and economy.

  When polypropylene is used as a binder, an appropriate amount of low density polyethylene can be used together for the purpose of adjusting the hardness. Also, for the purpose of imparting polarity to improve adhesion and improving wettability compatibility with magnetic materials, unsaturated carboxylic acid-modified α-olefins or copolymers, such as maleic anhydride-modified polypropylene, maleic anhydride Addition of acid-modified polyethylene, maleic anhydride-modified ethylene / polypropylene copolymer, and the like is preferable. In the combined use of polypropylene and polyethylene, addition of maleic anhydride-modified ethylene / polypropylene copolymer is preferable. Their added amount is preferably about 5 to 10 percent with respect to the total amount of the binder.

The specifications of the flexible magnetic film (bonded magnet type) used for trading cards, postcards (postcards), etc. are as follows. The thickness of the film is 80 μm to 350 μm, the thickness of the displayable layers on both sides is 15 μm to 60 μm, the distance between the poles of multipolar magnetization is 0.8 to 2.5 mm, and the vertical attractive force is 0.5 g / cm ^{2 to} 20 g. / Cm ² is desirable.

It is preferable from the viewpoint of processability, physical properties, and economy that the hard magnetic material is ferrite-based magnet material powder and the binder is polypropylene, and the thickness of the flexible magnetic film (bonded magnet type) is 80 μm to 350 μm. This is because if the thickness is less than 80 μm, the magnetic attractive force is insufficient, and if it is thicker than 350 μm, the attractive force becomes excessive and uneconomical. The thickness of the displayable layers on both sides is set to 15 μm to 60 μm because if it is thinner than 15 μm, the hiding power is insufficient, and if it is thicker than 60 μm, the influence on the air gap, self-weight and total thickness of the magnet becomes large, which is uneconomical. It is.

In addition, the gap between the poles of multipolar magnetization is set to 0.8 mm to 2.5 mm, and if it is narrower than 0.8 mm, it is difficult to produce a device that is magnetized between poles, which is uneconomical. If it is wider, it deviates from the range of the appropriate distance with respect to the thickness, so that the expression of the adsorption force decreases. Further, the perpendicular magnetic attraction ^force, for a 0.5g / cm ² ~20g / cm 2, there is a case made on the application adsorbed lack weaker than 0.5 g / cm ^2, from 20 g / cm ² This is because if it is strong, it is excessive in use and uneconomical.

(5). The end use of bonded magnet type magnetic film and magnetic card is to be magnetically adsorbed to a steel locker, steel desk, etc. as a single unit (single piece). It is handled in a stacked state.
FIG. 2 is a plan view showing multipolar magnetization of a conventional magnetic film (bonded magnet type).
This conventional magnetic film (bonded magnet type) 1001 is multipolarized with the magnetic pole direction aligned in a direction perpendicular to the width direction of the magnetic film (longitudinal direction), and the thickness of the magnetic film is extremely high. Unless it is extremely thick with respect to the gap, a magnetic pole having a different polarity on the back surface (non-magnetized surface) with respect to the multipolar magnetized surface, that is, an s pole is formed on the back surface of the N pole of the magnetized surface. Thus, n poles are generated on the back side of the S pole of the magnetized surface.
Therefore, when a magnetic card made using a magnetic film is stacked face up, the non-magnetized surface and the magnetized surface of another magnetic card overlap, so the N and s poles, and the S and n poles have a weak magnetic attractive force. It will overlap.
This weak attracting force is about 30% of the attracting force between the magnetized surfaces and does not cause a problem in practice, but it is not preferable in the work of stacking a plurality of magnetic cards with their upper, lower, left and right edges aligned.

  The present invention solves this undesirable magnetic adsorption problem associated with the means of solving the curl properties of the present invention. That is, this phenomenon occurs because the magnetic film of the present invention does not have a sufficient air gap layer that inhibits magnetic adsorption on the magnetized surface side as in the prior art, and can be solved by specifying the magnetizing method.

  The present invention uses a non-magnetized magnetic film cut to a regular size, and the magnetic pole direction of multipolar magnetization is within a range of 10 ° to 80 ° or minus 10 ° to minus 80 ° with respect to the longitudinal direction. It is to magnetize with an arbitrary inclination. That is, it is to randomize the supply angle to the magnetizer within a range of 10 ° to 80 ° or minus 10 ° to minus 80 ° for an unmagnetized magnetic film cut to a regular size. Can be achieved by manually feeding or supplying an automatic feeding apparatus without using a guide or a stopper for regulating the direction as in the prior art.

  Thus, although there is little possibility, when the crossing angle described later is not formed when the magnetic cards are overlapped, it can be solved by changing the overlapping order to form the overlapping where the crossing angle is formed. Further, when the magnetic pole direction of multipolar magnetization is smaller than 10 ° or minus 10 ° with respect to the longitudinal direction, and when the magnetic pole direction exceeds 80 ° or minus 80 ° and increases to 90 ° or minus 90 °, it will be described later. The possibility that the crossing angle between the magnetized surfaces of the magnetic card is reduced is not preferable.

Next, the adsorption force reducing action of the present invention will be described with reference to schematic views.
FIG. 3 shows an example of the gradient magnetization of the magnetic film (bonded magnet type) of the present invention, FIG. 3 (a) is a plan view seen from the magnetized surface side, and FIG. 3 (b) is the back side. The top view seen from is shown.
As shown in FIG. 3 (a), the magnetic poles S and N in this magnetic film (bonded magnet type) 101 are magnetized with an inclination of 30 ° counterclockwise with respect to the longitudinal direction. As in the conventional case, the non-magnetized surface on the back surface is magnetized with a 30 ° tilt in the clockwise direction, with the s pole on the back side of the N pole and the n pole on the back side of the S pole, as shown in FIG. It appears as it did.

FIG. 4 shows a reduction in the attractive force when a non-magnetized surface and a magnetized surface are overlapped using a magnetic card manufactured using a magnetic film (bonded magnet type) magnetically tilted as shown in FIG. FIGS. 4A and 4B are schematic views to be described. FIG. 4A is a plan view and FIG. 4B is an enlarged view of a minimum unit.
As shown in these figures, magnetic poles s and n having an inclination angle E are formed on the non-magnetized surface of the magnetic card 201, and the magnetic card is magnetized at different inclination angles F with respect to the surface. When 301 is placed, they overlap at the crossing angle represented by G.
Incidentally, in the current drawing, the inclination angle E is 30 °, the inclination angle F is 60 °, and the intersection angle G is 30 °.

Then, as shown in FIG. 4B, there are four magnetic attracting states in this state by crossing the pair of magnetic poles of gradient magnetization, that is, the N pole, the S pole, the n pole, and the s pole. Blocks “V (N, n same polarity repulsion), W (S, s same polarity repulsion), Y (N, s different polarity suction), Z (S, n different polarity suction)” having the same shape and area are formed. Since the two repelling blocks and the two blocks attracting different poles are used, the magnetic attraction force is substantially cancelled, and the magnetic cards have a large number of such relationships as shown in FIG. 4 (a). Similarly, the magnetic attractive force is substantially canceled (reduced magnetic attractive force).
This effect can be achieved as long as the crossing angle G is not 0 or very small. Therefore, as long as the conditions are within the range, the inclination angle E and the inclination angle F can be implemented by other than the above numerical values. Needless to say.

  Further, this phenomenon and the effect are produced in the same manner even when the magnetized surfaces are overlapped with each other, but will be described with reference to FIG.

That is, FIG. 5 explains the reduction in the attractive force when the magnetized surfaces are overlapped with each other using a magnetic card manufactured using a magnetic film (bonded magnet type) that is tilted and magnetized as shown in FIG. FIG. 5A is a schematic diagram, FIG. 5A is a plan view, and FIG. 5B is an enlarged view of the minimum unit.
As shown in these drawings, magnetic poles S and N having an inclination angle Ea are formed on the magnetized surface of the magnetic card 401, and the magnetic card 501 magnetized at different inclination angles Fa with respect to the surface. , It will overlap at the crossing angle represented by Ga.
Incidentally, in the current drawing, the inclination angle Ea is 30 °, the inclination angle Fa is 60 °, and the intersection angle Ga is 90 °.

And, as shown in FIG. 5B, there are four magnetic adsorption states in this state by crossing the pair of magnetic poles of gradient magnetization, that is, the N pole, the S pole, the N1 pole, and the S1 pole. Blocks “Va (N1, N homopolar repulsion), Wa (S1, S homopolar repulsion), Ya (S1, N heteropolar suction), Za (N1, S heteropolar suction)” having the same shape and area are formed. Since the two repelling blocks and the two blocks attracting different poles are used, the magnetic attraction force is substantially canceled out, and the magnetic cards have many relationships as shown in FIG. 5 (a). Similarly, the magnetic attractive force is substantially canceled (reduced magnetic attractive force).
In addition, since the effect in this case can be achieved as long as the crossing angle Ga is not 0 or very small, the inclination angle Ea and the inclination angle Fa can be implemented with values other than the above values within the range of the conditions. Needless to say.

  When the magnetized surfaces overlap each other, for example, when the picture on the postcard is printed by ink jet printing and the address and address are written on the back with a ballpoint pen, the ballpoint pen should not be contaminated by the ballpoint pen ink. In some cases, the entry surfaces, that is, the magnetized surfaces, may be stored in an overlapping manner, and according to the conventional method, the magnets are not subjected to inclined magnetization, so they are strongly magnetically attracted and organized later. However, the magnetic card subjected to the magnetization of the present invention is preferable because it hardly generates a magnetic attractive force.

(6). Next, another invention for solving the adsorption force problem will be described.
FIG. 6 is a cross-sectional view showing a schematic diagram of multipolar magnetization of a conventional magnetic sheet (bonded magnet type).
In this conventional magnetic sheet (bonded magnet type) 1001, n indicates the N pole of the non-magnetized surface, s indicates the S pole of the non-magnetized surface, N indicates the N pole of the magnetized surface, and S is The S poles of the magnetized surface are shown, but the distance between the magnet poles (d1, d2, d3, d4, d5, d6, d7, d8, d9) is uniform.

FIG. 7 shows that the conventional bonded magnets 1001 and 1001 are non-magnetized and magnetized surfaces, and the N-pole center line and the s-pole center line match, and the S-pole center line and the n-pole center line match. This shows the state of magnetic adsorption.
As described above, in the multipolar magnetization of the conventional bonded magnet, since the distance between the poles is uniform, the bonded magnets are not in contact with the non-magnetized surface or the magnetized surface and the magnetized surface. In such a case, magnetic adsorption is performed between Sn and Ns or between SN and NS due to different polar attraction, which is inconvenient in some cases.

In order to inhibit this phenomenon, if the distance between the poles is not uniform, the opposing NS position does not come on the center line of the pole, so that magnetic attraction can be inhibited.
FIG. 8 shows that the magnetic films (bonded magnet type) 91, 91 of the present invention are the non-magnetized surface and the magnetized surface, and the center line of the N pole and the center line of the s pole, the center line of the S pole and the center of the n pole It shows a state where the lines do not match.
In this state, the adsorptive power is remarkably reduced, so there is no fear of inconvenience. That is, the present invention randomly magnetizes the distance between the magnetic poles within a specific range.
Further, FIG. 9 shows that the magnetic films (bonded magnet type) 91, 91 of the present invention are magnetized surfaces with the N-pole center line and the S-pole center line, and the S-pole center line and the N-pole center line. It shows a state that does not match.
Even in this state, the attractive force is remarkably lowered, so there is no fear of inconvenience.

  The distance between the poles of the magnetic film of the present invention (bonded magnet type) is 1 to the dimension between the reference poles x (4 to 6) as one unit, with the gap between the poles suitable for the thickness of the bond magnet as the reference gap. Each unit in which 4 to 6 magnetic poles exist within the range between the reference poles x 0.8, 0.9, 1.0, 1.1, and 1.2 per unit and the order is continuous It is preferable to use multipolar magnetization that is random within the range, and more preferably, the dimension between the reference poles × 5 is 1 unit, and the reference gap between each unit is 0.8, 0.9, 1.0, The number of poles of 1.1 and 1.2 is one each, for a total of five, and multipole magnetization is random in each unit in which the order is continuous. For example, in the case of 2 mm between the reference electrodes, the unit size is 10 mm, and there is one each between 1.6 mm, 1.8 mm, 2.0 mm, 2.2 mm, and 2.4 mm, Multipolar magnetization in which the order is random and the order within each successive unit is random. For example, when one unit is represented by “”, “1.6 mm, 2.0 mm, 2.4 mm, 1.8 mm, 2.2 mm” “2.0 mm, 2.4 mm, 1.8 mm, 2 .2 mm "..., The order of the magnetic poles in each unit is random.

When one unit is between the reference poles x 4, there are four gaps between the reference poles x 0.8, 0.9, 1.1, and 1.2, for a total of 4 x reference gaps x 6 In the case of, there are a total of 6 between the reference poles × 0.8, 0.9, 1.1 and 1.2, one between each and the reference gap × 1.0 You can do it.
In addition, if one unit is smaller than the standard gap x 4 dimensions, the degree of freedom to make the gap between the poles is less, and if one unit is larger than the standard gap x 6, the gap between the same dimensions increases and the gap between This is not preferable because it causes a decrease in randomness.
In addition, it is preferable that the dimension between the magnetic poles is a reference inter-electrode interval × (0.8 to 1.2) because it does not deviate from the range between the inter-electrode electrodes suitable for the thickness.

  The random system between magnetic poles of the present invention can be implemented by specifying the distance between each pole in the form of a multi-pole magnetized roll using a conventionally known permanent magnet. There is an advantage that can be magnetized. Then, when cutting a magnetic card from a wide and long magnetized raw material, it is necessary to first cut into a strip shape in the longitudinal direction of the magnetic card in the horizontal direction of the original material, and then cut in the horizontal size of the magnetic card. . In this case, the magnetic pole pattern of the magnetic card manufactured from what was cut into each band shape is started by starting the discarding of the first end portion after randomly cutting it within a range of about 10 times the standard magnetic pole dimension. There is almost no coincidence with the magnetic pole pattern of other cards (a combination that does not produce an attractive force reduction effect).

  Taking this magnetic cutting method as an example, 20 sheets are produced by cutting a strip of 150 mm × 1020 mm in the lateral direction from a 1020 mm wide original. Next, one end of each belt-like magnetic film was cut off at random dimensions to avoid matching the dimensions within a range of 20 mm, and then cut every 100 mm to 200 magnetic postcards of 100 mm × 150 mm Get.

As described above, when the magnetized surfaces of the magnetic card of the present invention are overlapped, in principle, there is very little possibility that the magnetic pole patterns will coincide with each other, which is suitable for the storage and organization of the picture postcards.
In the event that there is a case in which magnetic adsorption is caused by superposition at the time of packaging, it can be solved by changing the superposition order.

(7). Next, another invention for solving the adsorption force problem will be described. With regard to the above-mentioned magnetization method that randomizes the distance between magnetic poles, if the non-magnetized surface and the magnetized surface are overlapped, the possibility is very low, but the effect of reducing the attractive force cannot be obtained when the pattern between the poles matches. In order to remedy the drawbacks, the magnetic card can be magnetized with a random distance between the magnetic poles and the magnetic pole direction inclined at random, so that the attractive force reduction effect cannot be obtained when the pattern between the poles matches. The sex was extremely low. The method of randomly inclining the magnetic pole direction can be implemented in the same manner as in the above (5).

  FIG. 10 is a cross-sectional view showing a state where the magnetic film (bonded magnet type) of the present invention is attached to an adherend, and B1 is a refrigerator and a steel shelf that are adherends of the magnetic film (bonded magnet type). And white board etc., P1 shows the magnetic film (bonded magnet type) of this invention.

Next, a magnetic film (magnet adherend type) using soft magnetic material powder will be described.
(8). FIG. 11 shows a cross-sectional view of the magnetic film (magnet adherend type) of the present invention.
PS1 is the magnetic film of the present invention (using a magnetic adherend), 11S is a flexible magnetic bond film (magnet adherend), and 12S is a non-magnetic attraction surface side display. Reference numeral 13S denotes a displayable layer on the magnetic adsorption surface side.

  The configuration and the manufacturing method of the present invention are obtained by replacing the hard magnetic material powder (magnet material powder) of the flexible magnetic film described in FIG. 1 with a soft magnetic material powder (magnet adherend material powder). Other structures and manufacturing methods are obtained in the same manner as in FIG. However, the thickness of the flexible magnetic film is preferably 50 μm to 350 μm. If the thickness is less than 50 μm, there is a possibility that the necessary adsorption force is insufficient, and if it is more than 350 μm, the necessary adsorption force is excessive, which is uneconomical.

(9). Soft magnetic material powders include iron powder, alloy powder with iron (Sendust, Permalloy, iron / silicon, iron / cobalt, iron / nickel / cobalt), iron trioxide powder, soft ferrite powder (Mn / Zn, Mn Ni) etc. are mentioned, and among these, Sendust powder, iron trioxide powder, iron powder, and soft ferrite powder (Mn / Zn-based) are preferable from the viewpoint of performance, workability, and economy.

  FIG. 12 is a sectional view showing a state in which another flexible magnetic film of the present invention (magnet adherend type) is magnetically attracted to an adherend (magnet), and B2 is a conventional bonded magnet. An adherend composed of a sheet is shown, and PS1 denotes the flexible magnetic film of the present invention.

Next, a magnetic card using a magnetic film will be described.
(10). Although illustration of the magnetic card using a magnetic film is abbreviate | omitted, FIG. 10 can be quoted in the case of a bonded magnet type about a magnetic sticking state, and FIG. 12 can be quoted in the case of the adherend type of a magnet.
The magnetic card is manufactured by appropriately printing the magnetic film described in any one of the items (1) to (11) in the “Means for Solving the Problems” and then cutting it into a predetermined card size. The bonded magnet type may be magnetized after the production of the magnetic film, or after the printing process.

(11). FIG. 13 is an explanatory diagram (cross-sectional view) showing a measurement method in the curl test, and FIG. 14 is an explanatory diagram (cross-sectional view) showing a measurement method in another deformation in the curl test. U, a flat plate made of a non-magnetic material used for the curl test, t1, t2, test samples, h1, h2, and measurement positions in the curl test.

Hereinafter, the present invention will be described using examples.
The examples are roughly classified into [1] bonded magnet type magnetic films and [2] magnet adherend type magnetic films. First, [1] bonded magnet type magnetic films are examples. 1 to 17 will be described.

(1) Creation (mixing) of flexible magnetic film (mixing No1)
・ Polypropylene (Prime Polypro, E-203GP) Prime Polymer Co., Ltd. [Resin] ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ 70 parts by weight ・ Low density polyethylene (Novatech LD, LF-440HB) manufactured by Nippon Polyethylene Co., Ltd. [Resin] ... 15 parts by weight Maleic anhydride modified polyolefin (Modic, F534A) manufactured by Mitsui Chemicals, Inc. [Resin] [Compatibilizer] ...・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 15 parts by weight ・ Calcium stearate (SC-100) manufactured by Sakai Chemical Co., Ltd. [Lubricant] ・ 0.2 parts by weight ・ 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyloxy) propioni Oxy] -1, -1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilyzer GA-80) manufactured by Tomo Chemical Co., Ltd. [Antioxidant)・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.15 parts by weight ・ Pentaerythritol tetrakis (3-laurylthiopropionate) (Sumilyzer TP-D) manufactured by Sumitomo Chemical Co., Ltd. [Antioxidant] ... 0.35 parts by weight Isotropic strontium ferrite powder (HM403) manufactured by Feeder Magnetics [Hard magnetic material] ... .... 730 parts by weight

Filling amount of magnetic material powder 87.9% by weight (56.0% by volume)

(Pellet creation)
The mixture stirred and mixed in the blender according to the above composition is kneaded at 240 ° C. to 270 ° C. with a KCK80 type kneading extruder and extruded into a string shape, and pulverized pellets are prepared with a hammer type pulverizer.
(Create flexible magnetic film)
-Using the pellets, a fishtail die (400 mm width) was attached to a φ65 mm single screw extruder (L / D18), and a film having a thickness of 300 μm was extruded at 240 ° C to 270 ° C. A flexible magnetic film having a thickness of 200 μm is prepared with this roll mill (surface temperature: 40 ° C. to 60 ° C.).

(2) Formation of displayable layer-After one side of the film is subjected to corona discharge treatment, polyester resin paint SS16-611 (manufactured by Toyo Ink Co., Ltd.) containing inorganic white powder or the like is used using a comma coater. Then, it is applied to a dry thickness of 30 μm and dried through a drying oven at 60 ° C. to 90 ° C. for 12 minutes. Next, the other surface is processed similarly.
(3) Magnetization: One side of the film is brought into contact with a known permanent magnet type magnetizing roll (2 mm pitch multipole between poles) to carry out continuous multipole magnetization. Thus, a bonded magnet type magnetic film is obtained.

(1) The flexible magnetic film is produced in the same manner as in Example 1.
(2) Formation of displayable layer: After forming a displayable layer having a thickness of 25 μm on one side of the film in the same manner as in Example 1, paint Pateracol for urethane resin ink jet receiving layer further containing inorganic powder and the like IJ-150R (manufactured by DIC Corporation) is applied using a comma coater so as to have a dry thickness of 15 μm and dried through a drying oven at 60 ° C. to 90 ° C. for 12 minutes. Next, the other surface is processed similarly.
(3) Magnetization: The same as in Example 1. Thus, a bonded magnet type magnetic film is obtained.

(1) The flexible magnetic film is produced in the same manner as in Example 1.
(2) Formation of displayable layer: A displayable layer having a thickness of 25 μm is formed on one side of the film in the same manner as in Example 1, and then a 15 μm thickness of ink jet receiving layer is formed in the same manner as in Example 2.
Next, a 40 μm-thick displayable layer is formed on the other side in the same manner as in Example 1.
(3) Magnetization Magnetization is performed in the same manner as in Example 1 with the displayable layer having a thickness of 40 μm as the magnetized surface side. Thus, a bonded magnet type magnetic film is obtained.

(1) The flexible magnetic film is produced in the same manner as in Example 1.
(2) Formation of displayable layer-A displayable layer having a thickness of 40 µm is formed on one side of the film in the same manner as in Example 1, and then a 15 µm thickness of ink jet receiving layer is formed in the same manner as in Example 2.
Next, a 40 μm-thick displayable layer is formed on the other side in the same manner as in Example 1.
(3) Magnetization Magnetization is performed in the same manner as in Example 1 with the displayable layer having a thickness of 40 μm as the magnetized surface side. Thus, a bonded magnet type magnetic film is obtained.

-The same as in Example 1 except for the formation of the displayable layer.
(Formation of displayable layer)
In the same manner as in Example 1, the non-magnetized surface side is set to 30 μm thickness, and the magnetized surface side is set to 25 μm thickness.

(1) The flexible magnetic film is produced in the same manner as in Example 1.
(2) Formation of white displayable layer ・ After corona discharge treatment was applied to one side of the flexible magnetic film, synthetic paper FPG (80 μm thick) manufactured by Yupoco-Poration Co., Ltd. was used as a polyester resin adhesive (2 liquids) Type) (AP-368A / B) (manufactured by Chuo Rika Co., Ltd.) and pasting with a laminator. Next, the synthetic paper FPG (80 μm thickness) is bonded to the other surface in the same manner.
(3) Magnetization: The same as in Example 1. Thus, a bonded magnet type magnetic film is obtained.

-It is the same as that of Example 6 except having changed the synthetic paper of Example 6 into the semi-rigid vinyl chloride film 10P (100 micrometers thickness) (made by Riken Technos Co., Ltd.).

(Comparative Example 1)
-The same as in Example 6 except for the formation of the displayable layer.
In the same manner as in Example 6, the synthetic paper on the non-magnetized surface side is 80 μm thick, and the synthetic paper on the magnetized surface side is 60 μm thick.

(Comparative Example 2)
-The same as in Example 6 except for the formation of the displayable layer.
-The same procedure as in Example 5 was conducted except that the synthetic paper of Example 6 was changed to coated paper (80 μm thick) (manufactured by Oji Paper Co., Ltd.).

(Comparative Example 3)
-It is the same as that of Example 6 except formation of a white displayable layer.
-The synthetic paper of Example 6 was changed to coated paper (manufactured by Oji Paper Co., Ltd.), except that the coated paper on the non-magnetized surface side was made 100 μm thick and the coated paper on the magnetized surface side was made 80 μm thick. In the same manner as in Example 6.

(1) Creation (mixing) of flexible magnetic film (mixing No. 2)
・ Polyethylene terephthalate (IP-120B), manufactured by Bell Polyester Products Co., Ltd. [Resin] ... 100 weight Part ・ Polyethylene glycol (PEG # 200) manufactured by NOF Corporation [Plasticizer] ・ ・ ・ 30 parts by weight ・ Mixed wax of ester compound of montanic acid and butylene glycol and calcium montanate (Licowax OP) Clariant Japan ( Co., Ltd. [Lubricant] ··· 1 part by weight · 2,2'6,6'-tetraisopropyldiphenylcarbimide (biscarboimide) line · Chemie Co. [hydrolysis inhibitor] ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2 parts by weight ・ 3,9-bis [2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyloxy) propionyloxy ] -1, -1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilyzer GA-80) manufactured by Sumitomo Chemical Co., Ltd. [Antioxidant]・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.13 parts by weight ・ Pentaerythritol tetrakis (3-laurylthiopropionate) (Sumilyzer TP-D) manufactured by Sumitomo Chemical Co., Ltd. [ Antioxidant] ... 0.37 parts by weightIsotropic strontium ferrite powder (HM403) manufactured by Feeder Magnetics [ Hard magnetic material] ... ... 673 parts by weight

Filling amount of magnetic material powder 83.7% by weight (56.0% by volume)

(Pellet creation)
・ The IP-120B pellets are stirred and dried in a hot air dryer at 140 ° C. for 4 hours. ・ The mixture obtained by stirring and mixing in a blender according to the above composition is kneaded at 260 ° C. to 290 ° C. with a KCK80 type kneading extruder. Then, it is extruded into a string shape, and pulverized pellets are prepared with a hammer type pulverizer.
(Create flexible magnetic film)
・ Using the pellets, a fishtail die (400 mm width) was attached to a φ65 mm single screw extruder (L / D18), a 300 μm thick film was extruded at 260 ° C. to 290 ° C., and immediately after that, φ12 inch 2 A flexible magnetic film having a thickness of 200 μm is prepared by this roll rolling machine (surface temperature 60 ° C. to 80 ° C.).

(2) Formation of displayable layer-After one side of the film is subjected to corona discharge treatment, polyester resin paint SS16-611 (manufactured by Toyo Ink Co., Ltd.) containing inorganic white powder or the like is used using a comma coater. Then, it is applied to a dry thickness of 30 μm and dried through a drying oven at 60 ° C. to 90 ° C. for 12 minutes. Next, the other surface is processed similarly.
(3) Magnetization: One side of the film is brought into contact with a known permanent magnet type magnetizing roll (2 mm pitch multipole between poles) to carry out continuous multipole magnetization. Thus, a bonded magnet type magnetic film is obtained.

(1) Preparation (mixing) of flexible magnetic film (mixing No. 3)
・ Glycol-modified polyethylene terephthalate (PET-G6763) manufactured by Eastman Chemical Co., Ltd. [Resin] ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by weight ・ Polyethylene glycol (PEG # 200) manufactured by NOF Corporation [Plasticizer] 30 parts by weight. Mixed wax of ester compound of montanic acid and butylene glycol and calcium montanate (Licowax OP) manufactured by Clariant Japan Co., Ltd. [ Lubricant] ... 1 part by weight, 2,2 ', 6,6'-tetraisopropyldiphenylcarbimide (biscarboimide) line, manufactured by Chemie [hydrolysis inhibitor] ...・ ・ ・ ・ ・ ・ ・ ・ ・ 2 parts by weight ・ 3,9-bis [2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyloxy) propionylo Si] -1, -1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilyzer GA-80) manufactured by Sumitomo Chemical Co., Ltd. [Antioxidant]・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・0.13 parts by weight ・ Pentaerythritol tetrakis (3-laurylthiopropionate) (Sumilyzer TP-D) manufactured by Sumitomo Chemical Co., Ltd. [ Antioxidant] ... 0.37 parts by weight-OP-56 (anisotropic and mechanically oriented strontium ferrite) manufactured by DOWA FTEC Co., Ltd. [Hard magnetic material] ... 700 parts by weight

Filling amount of magnetic material powder 84.2% by weight (56.0% by volume)

(Pellet creation)
-The pellet of PET-G6763 is dried with a hot air dryer at 140 ° C for 4 hours.
The mixture stirred and mixed in the blender according to the above composition is kneaded at 230 ° C. to 260 ° C. with a KCK80 type kneading extruder and extruded into a string shape, and pulverized pellets are prepared with a hammer type pulverizer.
(Create flexible magnetic film)
-Using the pellet, attach a fishtail die (400 mm width) to a φ65 mm single screw extruder (L / D18), extrude a 300 μm thick film at 230 ° C to 260 ° C, and immediately after that, φ12 inch 2 A flexible magnetic film having a thickness of 200 μm is prepared by this roll rolling machine (surface temperature 60 ° C. to 80 ° C.). At the time of rolling with this two-roll mill, strontium ferrite is of a mechanical orientation type, so that the easy magnetization axis (crystal C axis) is oriented in the thickness direction of the film.

(2) Formation of displayable layer: Performed in the same manner as in Example 1.
(3) Magnetization: The same as in Example 1.

(1) Preparation of flexible magnetic film The same procedure as in Example 9 is performed except that a film having a thickness of 150 μm is extruded and immediately thereafter a flexible magnetic film having a thickness of 100 μm is formed by a rolling mill.
(2) Formation of displayable layer The same as in Example 1 except that the non-magnetized surface side is 20 μm thick and the magnetized surface side is 20 μm thick.
(3) Magnetization: The same as in Example 1.

(1) Creation (mixing) of flexible magnetic film (mixing No. 4)
・ 6-Nylon resin (Nylon 1011FB) manufactured by Ube Industries, Ltd. [Resin] ・ 70 parts by weight ・ Ethylene methacrylate copolymer (Baymac G) manufactured by DuPont ・ 30 parts by weight [Elastomer]
・ Substituted diphenylamine (Naugard 445) manufactured by Uniroyal Corporation [Antioxidant] 1 part by weight ・ Calcium stearate (SC-100) Sakai Chemical Co., Ltd. [lubricant] ・ ・ ・ ・ 1 part by weight ・ Montanic acid and butylene glycol 1x parts by weight of isotropic strontium ferrite (HM403) manufactured by Feeder Magnetics Co., Ltd. [Lubricant] made by Clariant Japan Co., Ltd. Hard magnetic material] ... 612 parts by weight

Filling amount of magnetic material powder 85.6% by weight (56.0% by volume)

(Pellet creation)
・ Nylon 1011FB pellets are dried in a hot air dryer at 100 ° C. for 4 hours. ・ A mixture obtained by stirring and blending in a blender according to the above composition is kneaded at 230 ° C. to 260 ° C. with a KCK80 type kneading extruder. Extrude into a string and make pulverized pellets with a hammer-type pulverizer
(Create flexible magnetic film)
-Using the pellet, a fishtail die (400 mm width) was attached to a φ65 mm single screw extruder (L / D18), and a 400 μm thick film was extruded at 230 ° C to 260 ° C. A flexible magnetic film having a thickness of 200 μm is prepared with this roll mill (surface temperature: 40 ° C. to 60 ° C.).

(2) Formation of displayable layer-A polyester resin paint PAL mat 8 120 white (manufactured by Seiko Advance Co., Ltd.) containing inorganic powder or the like on one side of the film is dry 30 μm thick using a comma coater. And then dried through a drying oven at 60 ° C. to 90 ° C. for 12 minutes. Next, the other surface is processed in the same manner.
(3) Magnetization: The same as in Example 1.

(1) Creation (mixing) of flexible magnetic film (mixing No. 4)
・ Styrene ・ Ethylenebutylene ・ Styrene block copolymer) (Clayton G1657) Made by Kraton [Elastomer] ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 70 parts by weight ・ Ethylene / propylene copolymer Polymer (EPO7P) (manufactured by Nippon Synthetic Rubber Co., Ltd.) [Elastomer] ... 30 Part by weight • Ethylene / α-olefin copolymer oligomer (Lucanto), manufactured by Mitsui Chemicals Co., Ltd. • Mixed wax of ester compound of montanic acid and butylene glycol and calcium montanate (Licowax OP), manufactured by Clariant Japan Co., Ltd. [Lubricant] ... 1 part by weight 3,9-bis [2- [3- (3-tertiarybutyl-4-hydroxy-5-methylphenyloxy) propionyl XY] -1, -1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Sumilyzer GA-80) manufactured by Sumitomo Chemical Co., Ltd. [Antioxidant] ································································································· 0.15 parts by weight • Sumitizer TP-D (pentaerythritol tetrakis (3-laurylthiopropionate) manufactured by Sumitomo Chemical Co., Ltd. ] 0.35 parts by weight, isotropic strontium ferrite (HM403), manufactured by Feeder Magnetics [Hard Magnetic Material]・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 826 parts by weight

Filling amount of magnetic material powder 88.1% by weight (56.0% by volume)

(Pellet creation)
-According to the above composition, after kneading in a pressure kneader (40 L) at 140 ° C. for 15 minutes, cooling, and then preparing pulverized pellets with a hammer-type pulverizer.
(Create film)
-The above pellets are subjected to pellet rolling with a φ18 inch two-roll mill (surface temperature 90 ° C) to form a film having a thickness of 200 µm.

(2) Formation of white displayable layer-A white displayable layer having a dry thickness of 30 is formed on one side of the film in the same manner as in Example 11, and then the other side is treated in the same manner.
(3) Magnetization: Magnetization is performed in the same manner as in Example 1.

(1) Preparation (mixing) of flexible magnetic film (mixing No. 6)
・ Chlorinated polyethylene (elaslen 301A) manufactured by Showa Denko KK [elastomer]
100 parts by weight-epoxidized soybean oil (W100EL) made by DIC Corporation ... 5 parts by weight-calcium stearate (SC-100) made by Sakai Chemical Co., Ltd. -1.5 parts by weight-Dilauryl thiopropionate (Sumilyzer TPL-R) manufactured by Sumitomo Chemical Co., Ltd.
0.3 parts by weight, strontium ferrite, anisotropy, mechanical orientation (OP-56) DOWA FTEC Co., Ltd. [Hard magnetic material] ... .... 629 parts by weight

Filling amount of magnetic material powder 85.4% by weight (56.0% by volume)

(Pellet creation)
-After kneading at 120 ° C for 15 minutes with a pressure kneader (40 L) according to the above composition, the mixture is cooled and then pulverized pellets are prepared with a hammer type pulverizer.

(Create film)
-The above pellets are subjected to pellet rolling with a φ18 inch two-roll mill (surface temperature 75 ° C.) to form a 200 μm thick film.

(2) Formation of displayable layer A dry 30 μm-thick displayable layer is formed on one side of the film in the same manner as in Example 11, and then the other side is processed in the same manner.
(3) Magnetization: Magnetization is performed in the same manner as in Example 1.

(1) Preparation of flexible magnetic film The same as Example 13 except that the thickness of the flexible magnetic film is 330 μm.
(2) Formation of displayable layer / synthetic paper is the same as Example 7 except that FEB (thickness: 95 μm) manufactured by Yupoco-Poration is used.
(3) Magnetization: Magnetization is performed in the same manner as in Example 1.

(Comparative Example 4)
(1) The flexible magnetic film is produced in the same manner as in Example 13 except that the thickness is 400 μm.
(2) The displayable layer is formed in the same manner as in Example 13.
(3) Magnetization is performed in the same manner as in the first embodiment.

(Comparative Example 5)
(1) Preparation of flexible magnetic film-Blending of blending No. 6 magnetic material in Example 13 with isotropic strontium ferrite powder (HM403) made by Feder Magnetics [Hard magnetic material] (blending A film having a thickness of 180 μm was prepared in the same manner as in Example 13 except for No13).
(2) Formation of displayable layer
1. Created a magnetic film body with a displayable layer only on the non-magnetized surface.
-Coated paper (110 μm thick) with a laminator using a polyester (two-component) adhesive AP-368A / B (manufactured by Chuo Rika Co., Ltd.), and then magnetized in the same manner as in Example 1. .
2. Create a magnetic film with a coating layer on the magnetized surface .
・ 1. The high quality paper (150 μm thickness) is pasted on the magnetic film main body prepared in step 1 with a laminator using a non-support type acrylic fine adhesive (707 Teraoka Seisakusho).

(Comparative Example 6)
(1) Creation (composition) of magnetic film body (composition No. 14)
・ Vinyl chloride / vinyl acetate (VAGH) manufactured by Union Carbide [resin] 12.5 parts by weight ・ Polyurethane solution (solid content 25%) (Nipporan 3022 (manufactured by Nihon Polyurethane)) [resin]・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 35 parts by weight ・ Anisotropic strontium ferrite powder (FH801) (manufactured by Toda Kogyo Co., Ltd.) [Hard magnetic material] ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by weight ・ Methyl ethyl ketone (solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 60 parts by weightToluene [solvent] ... 60 parts by weight cyclohexane [solvent] ] ... 30 parts by weight Filling amount of magnetic material powder 82.5 wt. % (55.2% by volume)

(Creation of coating liquid)
-A ball paint is dispersed and mixed for 18 hours to obtain a magnetic paint.
(Formation of magnetic layer)
A white pet 50 μm-thick film (Lumirror E20) (manufactured by Toray Industries, Inc.) is applied to a dry coater with a dry film thickness of 60 μm using a reverse coater, followed by magnetic field orientation (in-plane orientation) and then dried in a hot air drying oven. (Magnetization)
-In-plane orientation (the C-axis of anisotropic strontium ferrite crystal is oriented in the plane direction), so that the direction perpendicular to the flow direction of the magnetic sheet is the magnetic pole direction of multipolar magnetization. Magnetization is performed in the same manner as in Example 1.
(Making a magnetic film with a coating layer on the magnetized surface side)
・ Synthetic paper (80 μm thick) (SEK-80) (made by Nisshinbo Co., Ltd.) on the magnetic layer surface of the magnetic film body using a non-support type acrylic slightly adhesive (707) (made by Teraoka Seisakusho) with a laminator Paste together.

-The same as in Example 1 except for magnetization.
(Magnetization)
(1) Examples / Examples In the first permanent magnet type magnetized roll (2 mm pitch multipole), the direction of each magnetic pole is shown in FIG. As described above, the magnetizing is performed with an inclination of about 30 ° with respect to the vertical direction. That is, conventionally known magnetization is regulated by providing a guide or the like in the direction of supply to the magnetizing roll so that it is magnetized parallel to the longitudinal end of the standard cut product. In order to randomize the magnetic pole direction, a standard-cut product is tilted approximately 30 ° freehand and magnetized.
(2) Preparation of a sample for measuring the attractive force between a non-magnetized surface and a magnetized surface-Create a sample that is magnetized by tilting to 30 ° and one that is magnetized by tilting to 60 °.
When the non-magnetized surface that is magnetized by tilting to 30 ° and the magnetized surface that is magnetized by tilting to 60 ° are overlapped, the crossing angle of the magnetic poles becomes 30 °.
(3) Preparation of samples for measuring the attractive force between the magnetized surfaces-Create a sample that is magnetized by tilting it at 30 ° and a sample that is magnetized by tilting it at 60 °.
If the magnetized surfaces are tilted at 30 ° and those magnetized at 60 °, the crossing angle of the magnetic poles becomes 90 °.

-The same as in Example 1 except for magnetization.
(Magnetization)
-Using the non-magnetized magnetic film in Example 1, it magnetizes using the permanent magnet type | mold magnetizing roll which makes each space | interval random which makes 2.0 mm of reference poles.
That is, the conventionally known permanent magnet type magnetizing roll makes the thickness of the incorporated permanent magnet uniform 2.0 mm, whereas the magnetizing roll implementing the present invention has a thickness of the incorporated permanent magnet of 1 unit. Is 10 mm, and there is one each between 1.6 mm, 1.8 mm, 2.0 mm, 2.2 mm, and 2.4 mm, and the order is random within each successive unit. Magnetization is performed using a magnetizing roll incorporated as described above.

-The same as in Example 1 except for magnetization.
(Magnetization)
(1) A permanent magnet type magnetizing roll with random poles used in Example 16, using the uncut magnetic cut film of Example 1 and Example 1, and the same as in Example 15. The magnet is magnetized by tilting the magnetic pole direction by approximately 30 °.
(2) Preparation of a sample for measuring the attractive force between a non-magnetized surface and a magnetized surface-Create a sample that is magnetized by tilting to 30 ° and one that is magnetized by tilting to 60 °.
When the non-magnetized surface that is magnetized by tilting to 30 ° and the magnetized surface that is magnetized by tilting to 60 ° are overlapped, the crossing angle of the magnetic poles becomes 30 °.
(3) Preparation of samples for measuring the attractive force between the magnetized surfaces-Create a sample that is magnetized by tilting it at 30 ° and a sample that is magnetized by tilting it at 60 °.
If the magnetized surfaces are tilted at 30 ° and those magnetized at 60 °, the crossing angle of the magnetic poles becomes 90 °.

  Next, [2] magnetic adherend type magnetic films will be described in Examples 18-24.

-The compound which replaced the strontium ferrite (HM403) which is a hard magnetic material in the compounding of Example 1 (compound No. 1) with iron trioxide (BL-10, manufactured by Titanium Industry Co., Ltd.) which is a soft magnetic material. (Formulation No. 7).
-Filling amount of magnetic material powder 87.9 wt% (56.0 vol%)
-The same as in Example 1 except for the blending. However, magnetization is not necessary.

A blend in which the hard magnetic material strontium ferrite (HM403) in the blend of Example 8 (blending No. 2) was replaced with a soft magnetic material, iron trioxide (BL-10, manufactured by Titanium Industry Co., Ltd.) (Formulation No. 8).
-Filling amount of magnetic material powder 83.7% by weight (56.0% by volume)
-The same as in Example 1 except for the blending. However, magnetization is not necessary.

The strontium ferrite (OP-56) in the blend of Example 9 (blend No. 3) was replaced with Sendust powder (SFR, manufactured by Nihon Atomize Co., Ltd.), which is a soft magnetic material ( Blend No. 9).
-Filling amount of magnetic material powder 83.6% by weight (51.0% by volume)
-The same as in Example 9 except for the blending. However, magnetization is not necessary.

-It is the same as that of Example 20 except the thickness of the flexible magnetic film of Example 20 being 60 micrometers.

-Blending (blending) in which the hard magnetic material strontium ferrite (HM403) in the blending of Example 11 (blending No. 4) was replaced with Mn-Zn ferrite (BSF547, manufactured by Toda Kogyo Co., Ltd.), which is a soft magnetic material. No10).
-Filling amount of magnetic material powder 85.6 wt% (56.0 vol%)
-The same as in Example 9 except for the blending. However, magnetization is not necessary.

-Compound (compound) in which the strontium ferrite (HM403), which is a hard magnetic material in the compound of Example 12 (compound No. 5), is replaced with iron powder (RDL-300A, manufactured by Powdertech Co., Ltd.), which is a soft magnetic material. No11).
-Filling amount of magnetic material powder 85.6 wt% (56.0 vol%)
-The same as in Example 12 except for the blending. However, magnetization is not necessary.

(1) Strontium ferrite (HM403), which is a hard magnetic material in the combination of Examples and Example 14 (Formulation No. 6), and iron powder (RDL-300A, manufactured by Powdertech Co., Ltd.), which is a soft magnetic material, It is set as the combination (composition No. 12) which used it as the combined use of triiron tetroxide (BL-10, Titanium Industry Co., Ltd.) and the volume ratio was set to 1: 2.
-Filling amount of magnetic material powder 86.9% by weight (55.0% by volume)
-The same as in Example 14 except for the blending. However, magnetization is not necessary.

(2) Formation of displayable layer, as in Example 6.
(3) Magnetization / magnetization is not required.

  Next, a performance evaluation test method and the like will be described.

1) Observe the processability of the flexible magnetic film, the load on the machine when the film is formed, the surface property of the molded film, the thickness distribution, the ear twisting, the middle looseness, etc.
◎: Particularly good, ○: good, △: slightly inferior, ×: bad

2) Flexibility of flexible magnetic film ・ Collecting strips of 20mm x 100mm test specimens from the longitudinal and lateral directions of the film left at room temperature of 21-25 ° C for more than 3 hours. The state when bent along a round bar having a diameter of 15 mm is observed.
○: No cracks are produced, Δ: Fine cracks are produced on the surface, and X: Fractures are evaluated.

3) Curling property of magnetic film The following (Test Method 1) to (Test Method 3) are performed, and the lifting distance h1 of the test sample t1 in the explanatory view showing the measurement method shown in FIG. 13 or another shown in FIG. The lift distance h2 of the test sample t2 shown in the explanatory diagram showing the measurement method in the case of deformation is measured.
Note that U in FIGS. 13 and 14 is a nonmagnetic flat plate.
Then, comprehensive evaluation is performed using the following symbols.
・: Excellent, ○: Good, Slightly bad: △, Bad: ×

(Test Method 1) A 60 mm × 60 mm test sample was placed on a flat, flat, non-magnetic flat plate and treated in a hot air circulating thermostat at 120 to 42 ° C. for 120 minutes. Measure the distance of the point where the lifting distance from the non-magnetic flat plate by the curl is the largest.

(Test Method 2) Using the test sample after the test of Test Method 1, from a non-magnetic flat plate by curling after treatment in a constant temperature and humidity apparatus of 23 to 27 ° C. and RH 90 to 96% × 180 minutes Measure the distance of the point where the lifting distance is the maximum.

(Test Method 3) Using the test sample after the test of Test Method 2, the lift distance from the flat plate made of non-magnetic material by curl after treatment for 120 minutes in a hot air circulating thermostat at 38 to 42 ° C. is the maximum Measure the distance of.

4) Adsorption power of magnetic film 4) -1. Standard adsorption force (Adsorption force with iron plate)
A square sample piece with a side of about 50 mm was attached to the surface of a smooth plastic plate with a non-magnetized surface of the sample piece using double-sided tape, and a hook was provided at the center of the back of the measurement surface 1 G / cm ² is calculated by magnetically attracting a square smooth iron plate (2 mm thick) with a side of 40 mm, and measuring the force required to pull it apart in the vertical direction by hooking a spring balance on the back of the iron plate.

4) -2. Adsorbing force between magnetized surfaces • Take two square sample pieces with a side of 40 mm, one side is aligned with the sample in the vertical direction, and the magnetized surfaces are overlapped with each other in the vertical direction. Adhesion with a double-sided tape on a smooth plastic plate, and other non-overlapping surfaces with a double-sided tape on a plastic plate (2mm thick) with a hook in the center of the back, and the force required to pull it apart vertically, G / cm ² is calculated by hooking a spring balance to the hook on the back of the plastic plate.

4) -3. Adsorption force between non-magnetized surface and magnetized surface ・ Same as 4) -2 except that the overlapping of the magnetized surfaces in 4) -2 is changed to the overlapping of the non-magnetized surface and the magnetized surface. To do.

4) -4. Adhesive force with the magnet surface. 0.4mm thick sheet-shaped magnet with 2.5mm pitch multipolar magnetization laminated with 0.12mm thick plastic film. A substrate having an adsorbing power of 15 g / cm ² is bonded to a smooth plastic plate with a square of about 50 mm on one side with a double-sided tape to form a standard adherend. In contrast, a square sample piece with a side of 40 mm is attached to a smooth plastic plate with a hook in the center of the back using double-sided tape, and the force required to pull it apart in the vertical direction is the pulling force on the back of the plastic plate. G / cm ² is calculated by hooking a spring balance to the hook.

Next, test results will be described.
Each test was carried out for each example and comparative example, and the results were summarized in a table.
Table 1 shows the ratio between the thickness of the non-magnetized surface side of the displayable layer and the thickness of the magnetized surface side when the flexible magnetic film is kept constant and the type / material of the displayable layer is changed. It is the result of having tested the curl property at the time of changing.
Those with the same thickness on the non-magnetized surface side and on the magnetized surface side have the same expansion and contraction force due to residual strain, temperature, and humidity changes during processing. There is little difference between PVC) and curl properties are excellent. However, as in Comparative Example 2, since the expansion and contraction of the paper is large due to the change in humidity, even if the thickness on the non-magnetized surface side and the thickness on the magnetized surface side are the same, the non-magnetized surface side (surface side) changes in humidity. Because it is easy to receive, the change in expansion and contraction is faster than other surfaces, resulting in a large curl.
Further, as in Example 5, since the coating film has little residual strain at the time of formation, it can be understood that a slight difference in thickness between the two surfaces has little influence on the curling property and causes no problem.
Further, it can be seen that curl is generated when there is a difference in thickness as in Comparative Example 1, and the curl is further increased when there is a difference in thickness between the two as in Comparative Example 3.

Further, it can be seen that the effect on the curling property is small and there is no problem if the ink jet receiving layer is provided as a part of the coating film as in Example 2 and Example 3. Further, it can be seen that even if the thickness of the ink jet receiving layer is not subtracted as in Example 4, the allowable range of the curl test is 3 mm or less. Thus, Examples 1 to 7 are excellent results with little curling property.

Table 2 shows the specifications similar to those of the prior patent document 1 (magnetic postcard), the specifications similar to the prior patent document 2 (magnetic postcard), and the specifications similar to the prior patent document 2. There is a possibility of causing practical problems.

Table 3 shows the results of testing the processability, curlability, and adsorption force when the binder of the flexible magnetic film is changed and when the thickness is changed.
PP, PET, PET-G, 6-nylon, and CPE are all good in binder type and processability, but in curling properties, the thickness of the non-magnetized surface side of the displayable layer, Since the thickness on the magnetized surface side is the same, the residual strain at the time of processing and the expansion / contraction force due to temperature / humidity change are both the same, so that the curl property is excellent.
Thus, Example 1, Example 8 to Example 13, and Comparative Example 4 exhibit excellent results with little curling property.

As for the magnetic attraction force, Example 8 and Example 9 are flexible because the magnetic material is anisotropic strontium ferrite, and therefore the magnetic force is superior to those using other isotropic strontium ferrites. The same attractive force is obtained even when the thickness of the magnetic film is thin. In Comparative Example 4, the thickness of the flexible magnetic film is 400 μm, which is thicker than the others, so that the adsorptive power is strong and excessive in use, which is uneconomical.

Table 4 shows test results showing the non-magnetized surface, the magnetized surface, and the effect of reducing the attractive force between the magnetized surfaces in the magnetized form of the present invention.
The magnetic attraction between the adherend and the magnetized surface is the same as the conventional one, and it is preferable that there is almost no magnetic attraction between the non-magnetized surface, the magnetized surface, and the magnetized surfaces. As you can see, a remarkable effect is observed.

  Table 5 tests the performance of the magnetic adherend type magnetic film. In terms of formulation, the magnetic material powder (hard magnetic material powder) in the compounding of the bonded magnet type magnetic film is replaced with the magnet adherent (soft magnetic material powder). The same results as those of the bonded magnet types in Tables 1 and 3 are exhibited.

Regarding the magnetic attractive force with the magnet, the magnetic attractive force with respect to the board or wall with the magnetized surface side of the magnet sheet, which has been widely used, facing the surface side, ie, (3) Test method, etc. 4) Adsorption power of magnetic film, 4) -3. The attractive force with the magnet surface sufficiently satisfies the value that is normally required.
It can be seen that the magnetic film of the present invention has excellent curling properties and magnetic attractive force.

  In addition to the above test results, the magnetic films of Examples 1 to 14, 18 to 24, and Comparative Examples 1 to 3, 5, and 6 were cut into postcard sizes, and Examples 1 to 14 and Comparative Examples 1 to 3 are magnetically attracted to a steel locker, and Examples 18 to 24 are the above (3) Test Method, etc., 4) Magnetic Film Adsorption Force, 4) -3. Magnetically attracted to a board with the same specifications as described in the attractive force with the magnet surface and left in the office building room in Kameido, Koto-ku, Tokyo from May 20, 2009 to November 20, 2009 And observed.

  The result is the same as the evaluation based on the curl test, the magnetic films of each example have no problem even under practical conditions, and the magnetic films of each comparative example have curling properties on days with high humidity or low humidity. It is not preferable because it is large and may cause problems in actual use.

  Widely used for stickers, postings, picture prints, trading cards, postcards (postcards), guides, etc., it can be easily attached or peeled off to a steel locker, steel desk, refrigerator, or magnetic bulletin board. When it is used for picture postcards and guidebooks, it can be attached after the recipient has finished reading, and can be easily peeled off after use.

11 Flexible magnetic film (bonded magnet type)
12 Displayable layer on non-magnetized surface side 13 Displayable layer on magnetized surface side 11S Flexible magnetic film (magnet adherend type)
12S Displayable layer on the non-magnetic attraction surface side 13S Displayable layer on the magnetic attraction surface side 91 Magnetic film (bonded magnet type) with multi-pole magnetization between the magnetic poles
101 Magnetic film (bonded magnet type) with multi-pole magnetized magnetic pole direction
201, 301, 401, 501 Magnetic card (bonded magnet type)
1001 Conventional magnet sheet (bonded magnet type with uniform spacing between multiple poles)
N, N1 N pole of magnetized surface of magnetic film (bonded magnet type) S, S1 S pole of magnetized surface of magnetic film (bonded magnet type) n N pole of non-magnetized surface of magnetic film (bonded magnet type) s S pole of non-magnetized surface of magnetic film (bonded magnet type) d1, d2, d3, d4, d5, d6, d7, d8, d9 Between magnet poles E, Ea, F, Fa Inclination angle G, Ga Crossing angle V, Va block (N pole homopolar repulsion)
W, Wa block (S pole homopolar repulsion)
Y, Ya block (different pole suction)
Z, Za block (different pole suction)
P1 Magnetic film of the present invention (bonded magnet type)
PS1 Magnetic film of the present invention (magnet adherend type)
B1 Adherence to magnetic film (bond magnet type) B2 Adherence to magnetic film (magnet adherence type) (bond magnet sheet)
U Flat plate made of non-magnetic material t1, t2 Test sample h1, h2 Lifting distance

Claims (10)

Opaque writing, printing, and printable displayable layers are provided on both sides of a flexible magnetic film, which is a bonded magnet made of hard magnetic material powder and organic polymer binder. Magnetic film,
The hard magnetic material powder is ferrite-based magnet material powder, the binder is polypropylene, the thickness of the flexible magnetic film is 80 μm to 350 μm, the thickness of the displayable layers on both sides is 15 μm to 60 μm, and between the poles of multipolar magnetization the 0.8～2.5Mm, by vertical suction force and ^{0.5g / cm 2 ~20g / cm 2} ,
In the following (Test Method 1) to (Test Method 3), the curl generated due to the difference in stretching force between one surface of the displayable layer and the other surface is configured to be 3.0 mm or less, respectively. Magnetic film.

(Test method 1) A test sample of 60 mm × 60 mm is placed on a flat, non-magnetic flat plate placed horizontally and treated in a hot air circulating thermostat at 120 to 42 ° C. for 120 minutes. Measure the distance of the point where the lifting distance from the non-magnetic flat plate by the curl is the largest.
(Test Method 2) Using a test sample after the test of Test Method 1, from a non-magnetic flat plate by curling after treatment in a constant temperature and humidity apparatus at 23 ° to 27 ° C. and RH 90 to 96% × 180 minutes Measure the distance of the point where the lift distance is the maximum.
(Test Method 3) Using the test sample after the test of Test Method 2, the maximum lifting distance from the flat plate made of non-magnetic material due to curling after treatment for 120 minutes in a hot air circulating thermostat at 38 to 42 ° C Measure the distance of.   2. The magnetic film according to claim 1, wherein the displayable layer has the same composition, formation conditions, and thickness on both sides, and a thickness of 15 μm to 100 μm.   The magnetic film according to claim 1, wherein the displayable layer is a layer formed by coating. The magnetic pole direction of multipolar magnetization is magnetized by providing an arbitrary inclination within a range of 10 ° to 80 ° or minus 10 ° to minus 80 ° with respect to the longitudinal direction . magnetic film according to any one of the three. The distance between the poles of multipolar magnetization is the distance between the poles suitable for the thickness of the bond magnet, and the distance between the reference poles × (4 to 6) is 1 unit. Within each unit where there are 4 to 6 magnetic poles within the range between the poles with dimensions of the reference poles x 0.8, 0.9, 1.0, 1.1, 1.2, the order of which is continuous The magnetic film according to claim 1 , wherein the magnetic film is random. The distance between the poles of multipolar magnetization is the distance between the poles suitable for the thickness of the bond magnet, and the distance between the reference poles × (4 to 6) is 1 unit. Within each unit where there are 4 to 6 magnetic poles within the range between the poles with dimensions of the reference poles x 0.8, 0.9, 1.0, 1.1, 1.2, the order of which is continuous in a random, and the magnetic pole direction 10 ° to 80 ° or to the longitudinal direction, claims 1 to 3, characterized in that the magnetized with an optional inclination in a range of minus 10 ° ~ minus 80 ° The magnetic film of any one of these. This is a magnetic film that has an opaque writable, printable, and printable displayable layer on both sides of a flexible magnetic bond magnetic film that is a magnetic adherend composed of a soft magnetic material powder and an organic polymer binder. And
The soft magnetic material powder is one selected from Sendust powder, triiron tetroxide powder, Mn-Zn ferrite powder, iron powder or a mixture thereof, the binder is polypropylene, and the thickness of the bond magnetic film is 50 μm to By setting the thickness of the displayable layers on both sides to 350 μm and 15 μm to 60 μm,
Said curling caused by such differences in one side consisting of a displayable layer and another side of stretching force, in the following (Test Method 1) to (Test Method 3) were constructed such that each becomes 3.0mm or less Magnetic film characterized by

(Test method 1) A test sample of 60 mm × 60 mm is placed on a flat, non-magnetic flat plate placed horizontally and treated in a hot air circulating thermostat at 120 to 42 ° C. for 120 minutes. Measure the distance of the point where the lifting distance from the non-magnetic flat plate by the curl is the largest.
(Test Method 2) Using a test sample after the test of Test Method 1, from a non-magnetic flat plate by curling after treatment in a constant temperature and humidity apparatus at 23 ° to 27 ° C. and RH 90 to 96% × 180 minutes Measure the distance of the point where the lift distance is the maximum.
(Test Method 3) Using the test sample after the test of Test Method 2, the maximum lifting distance from the flat plate made of non-magnetic material due to curling after treatment for 120 minutes in a hot air circulating thermostat at 38 to 42 ° C Measure the distance of . The magnetic film according to claim 7 , wherein the displayable layer has the same composition, formation conditions, and thickness on both sides, and a thickness of 15 μm to 100 μm. The magnetic film according to claim 7 or 8 , wherein the displayable layer is a layer formed by coating. A magnetic card using the magnetic film according to any one of claims 1 to 9 .

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