JPS6315657B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a magnetically laminated recording medium, and in particular to a magnetically laminated type recording medium that is capable of forming a magnetic recording layer that is provided with various colors different from the color of the magnetic material and has extremely small spacing loss and excellent input/output characteristics. Regarding the body. It is possible to form a magnetic recording layer on bankbooks, credit cards, computer input/output media, etc. using a magnetic bonding type recording material with a magnetic coating layer on the surface of the support and an adhesive layer on the back side. Recently, this practice has become widespread, but along with this, there has been a gradual increase in the desire to give the magnetic recording layer a color different from the black to brown colors characteristic of magnetic materials due to aesthetic needs. There is. Recently, in response to this, magnetic bonding type recording media used in bank passbooks and the like have been provided in which a colored coating layer is provided directly on the magnetic coating layer. In a laminated recording medium, the color of the laminated magnetic recording layer must be quite dirty due to the lack of hiding power of the colored coating layer, and the color of the laminated magnetic recording layer must be quite dirty. If the thickness of the coating is increased in order to increase the magnetic field, the input/output characteristics of the magnetic recording layer will deteriorate, resulting in a disadvantage that detection errors are likely to occur. The present invention has been made in view of these points,
Therefore, the object of the present invention is to provide a material with various colors different from those of the magnetic material, whose color does not change at all over a long period of time, and which is aesthetically excellent, and which has extremely small spacing loss and excellent input/output characteristics. An object of the present invention is to provide a magnetic bonding type recording material in which a magnetic recording layer can be formed. As a result of intensive research, the present inventors basically established a Sn vapor deposition layer on the magnetic coating layer, and then added Sn on top of this.
It has been found that the above object can be achieved by providing a colored protective coating layer that protects the deposited film layer. That is, although the Sn vapor-deposited coating layer is extremely thin, it has extremely high hiding power, so it is possible to completely hide the color of the magnetic coating layer, and therefore, When a colored protective coating layer is provided on top of this, the coloring is effective even if the coating thickness is made considerably thinner. Therefore, a magnetically laminated recording body having such a basic configuration can form a magnetic recording layer that is imparted with a desired color, has extremely small spacing loss, and has excellent input/output characteristics. In addition, a magnetic bonding type recording medium with a transparent protective coating layer instead of the colored protective coating layer described above allows the metallic color of the metal vaporized layer to appear as is, and has excellent input/output characteristics. It has also been found that interesting magnetic recording layers can be formed. The present invention has been completed based on such knowledge, and according to the present invention, a magnetic coating layer 2, a Sn vapor deposition layer 3 and a protective coating are provided on the surface of a seal-shaped or film-shaped support 1. A magnetic bonding type recording body is provided in which the layers 4 are sequentially laminated and an adhesive layer 5 is provided on the back surface of the support 1. As the support 1, a plastic sheet or film is used, and sheets or films of polyester, polycarbonate, etc. are particularly suitable. There is no particular limit to the thickness of the support 1, but it is usually
Those with a diameter of about 20 to 100 microns are generally used. A magnetic coating layer 2 is provided on the surface of the support 1, and in order to form the magnetic coating layer 2, magnetic fine particles such as γ-iron oxide, Co-doped iron oxide, chromium dioxide, ferrite, etc. are contained. The magnetic paint may be applied to the surface of the support 1 using a roll coater or the like. Further, the film thickness may be appropriately determined in consideration of storage capacity and the like, and is usually 5 to 20 microns. There are no particular restrictions on the magnetic paint; for example, the binder component may be cellulose resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, urethane resin, epoxy resin, polyester resin, styrene-butadiene rubber, etc., and it is preferable to use a binder component suitable for these resins. It is sufficient to use a magnetic coating material to which a curing agent and various auxiliary agents are added as necessary. A Sn evaporated film layer 3 is provided on the magnetic coating layer 2, but if we consider it only from the viewpoint of hiding the color of the magnetic coating layer without disturbing the magnetic properties of the magnetic coating layer 2, the Sn evaporation film is Mg.Al.Zn.Pt.Au.Ag instead of layer 3
It is also possible to use a vapor-deposited film layer according to et al. However, if the vapor-deposited film layer made of these metals is in contact with the magnetic coating layer, during long-term storage, the metals in the metal-deposited film layer and the γ-iron oxide and ferrite contained in the magnetic coating layer will be absorbed. Finger fat, etc. between magnetic particles such as
An electrochemical reaction occurs, which is thought to be caused by moisture, and as a result unsightly black spots often appear on the metallized film layer. However, when Sn is used as the vapor-deposited metal, no such spots are observed. A known metal vapor deposition machine may be used to form the Sn vapor deposition film layer 3. Further, the film thickness may be a minimum thickness sufficient to completely hide the magnetic coating layer 2, and may be, for example, 100 to 1000 A°. If the interlayer adhesion between the magnetic coating layer 2 and the Sn vapor deposition layer 3 is insufficient, in order to reinforce this, the magnetic coating layer 2 and the Sn vapor deposition layer 3 may be bonded together as necessary.
What is necessary is just to interpose the anchor agent layer 6 between them. As the anchor agent, commercially available anchor agents such as vinyl chloride-vinyl acetate copolymer, epoxy resin, and polyamide resin, and polyvinyl butyral-dichromate-carryphosphate wash primers can be used. In order to form the anchor agent layer 6, the above-mentioned anchor agent is coated on the magnetic coating layer 2 with a roll coater to form a film thickness.
The coating should be applied to a thickness of 0.01 to 1.0 microns. A protective coating layer 4 is provided on the Sn vapor deposition film layer 3, and the protective coating layer 4 protects the Sn vapor deposition film layer 3.
This is for coloring if necessary,
It does not matter whether it is transparent or opaque, colored or uncolored. That is, the protective coating layer 4 may be a single layer of either a transparent layer or a colored layer, or may be a composite layer thereof. To form the protective coating layer 4, the Sn vapor-deposited layer 3 is coated or printed with transparent or colored paint or ink using a roll coater, gravure printer, or the like. Examples of such transparent or colored paints or inks include cellulose acetate butyrate, cellulose resins such as nitrocellulose, acrylic resins, butyral resins, vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd resins, and urethane resins. Thermoplastic or Thermosetting paints or inks can be used. The thickness of the protective coating layer 4 is preferably as thin as possible from the viewpoint of input/output characteristics, but in consideration of balance with strength, durability, etc., it is preferably in the range of 0.1 to 5 microns. If the interlayer adhesion between the Sn vapor deposited film layer 3 and the protective coating layer 4 is insufficient, in order to reinforce this, the Sn vapor deposited film layer 3 and the protective coating film layer 4 may be
The anchor agent layer 7 may be interposed between the two, and the same anchor agent as described above may be used as the anchor agent. On the other hand, an adhesive layer 5 is provided on the back surface of the support 1, and the adhesive layer 5 may be either a heat-sensitive adhesive layer or a pressure-sensitive adhesive layer. To form the adhesive layer 5, for example, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, urethane resin, acrylonitrile butadiene resin, polyester resin, cellulose resin, vinyl chloride-vinylidene chloride copolymer, epoxy resin can be used. A heat-sensitive or pressure-sensitive adhesive made of natural rubber, rosin, etc. with addition of plasticizers, auxiliary agents, etc. as necessary is coated on the back surface of the support 1 with a roll coater or the like to a film thickness of 5 to 30 microns. Just apply it like this. In the magnetically bonded recording material of the present invention in which the adhesive layer 5 is a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is covered with a release paper, or the protective coating layer 4 is subjected to a release treatment in advance. Then, it can be used by winding it into a roll like a conventional adhesive tape. In the magnetically laminated recording material of the present invention, as described above, the transparent or colored protective coating layer is provided on the magnetic coating layer via the Sn vapor deposition layer, so the layer thickness is It is possible to apply any coloring that is not affected by the color of the magnetic coating layer, even if it is thin.Therefore, magnetic recording can be provided with various colors different from those of magnetic materials, and has extremely low spacing loss and excellent input/output characteristics. It can be used advantageously for bankbooks, credit cards, computer input/output media, etc. Next, the present invention will be specifically explained with reference to Examples, in which all "parts" mean "parts by weight". Example 1 [Magnetic paint - ()] (parts) 1 γ-Fe ₂ O ₃ 30.0 2 Lecithin 0.3 3 Epoxy resin ("Epicote 834", manufactured by Ciel Chemical Co., Ltd.) 3.0 4 PVC-vinyl acetate copolymer ("Vinyrite")
VAGH, manufactured by Union Carbide) 15.0 5 Low molecular weight polyethylene 0.3 6 Toluene 45.7 7 Methyl ethyl ketone 45.7 [Anchor agent - ()] (parts) 1 Polyvinyl butyral (Eslec
10 2 Phosphoric acid 1 3 Chromic anhydride 0.5 4 Isopropyl alcohol 78 5 Methyl ethyl ketone 10 6 Water 0.5 [Ink ()] (Parts) 1 Cyanine pigment 9 2 1/4 Nitrocellulose 4 3 Polyamide Resin (“Versamide 940”, 1st
General) 15 4 Low molecular weight polyethylene 1 5 Acetyl tributyl citrate 1 6 Toluene 40 7 Isopropyl alcohol 20 8 Ethyl acetate 10 [Heat-sensitive adhesive - ()' (parts) 1 Vinyl chloride - vinyl propionate copolymer (' 20 2 Acrylonitrile-butadiene rubber (``Hiker 1432'', manufactured by Nippon Zeon Co., Ltd.) 20 3 Methyl ethyl ketone 30 4 Toluene 30 A polyester film with a thickness of 38 microns is used as support 1, and the surface is Magnetic paint - () film thickness 14
A magnetic coating layer 2 was formed by applying the magnetic coating layer 2 to a thickness of 0.2 microns, and an anchoring agent layer 6 was formed by applying an anchor agent (2) to a thickness of 0.2 microns thereon. Next, Sn was vapor-deposited thereon to a thickness of 500 Å to form a Sn vapor-deposited film layer 3. Further, an anchor agent layer 7 was formed by applying an anchor agent () to a thickness of 0.2 microns, and then an ink layer () was applied to this layer to a thickness of 1.5 microns. A protective coating layer 4 was formed. On the other hand, a heat-sensitive adhesive layer 5 was formed by applying a heat-sensitive adhesive () to the back surface of the support 1 to a thickness of 7 microns, thus producing a magnetically laminated sheet. . This magnetic bonding type sheet is cut into 20mm wide and 50mm long sheets, stacked on bank passbook paper, and then passed through hot pressure rolls at 120℃ - 600Kg/m at a speed of 6m/min to bond under heat. In this way, a magnetic recording card having a magnetic recording layer with a clear blue color was produced. Table 1 shows the magnetic properties, reproduction output characteristics, and demagnetization rate of this magnetic recording card.

[Table] In addition, when the above-mentioned magnetically laminated sheets and magnetic recording cards were stored indoors for 6 months, changes in appearance such as spots were observed due to local electrochemical reactions between the Sn vapor-deposited film layer and the magnetic coating layer. We investigated whether or not this occurred, but no change was observed. Comparative Example 1 A polyester film with a thickness of 38 microns was used as a support, and magnetic paint () was applied to the surface of the support to a film thickness of 14 microns to form a magnetic coating film, and then ink was applied on top of this. () Film thickness 1.5
A protective coating layer was formed by applying the coating to a micron thickness. On the other hand, a heat-sensitive adhesive layer () was applied to the back side of the support to a thickness of 7 microns to form a heat-sensitive adhesive layer, thus producing a conventional magnetically laminated sheet. did. In addition, the thickness of the protective coating layer is
A conventional magnetic bonding type sheet was produced in the same manner as above except that the thickness was 3.0.6.0.9.0 microns. A magnetic recording card was produced in the same manner as in Example 1 using these magnetically bonded sheets. Table 2 shows the magnetic properties, colors, and reproduction output characteristics of these magnetic recording cards.

[Table] Comparative Example 2 In Example 1, Al.
A magnetic bonding type sheet and a magnetic recording card having a clear blue color were produced in the same manner as in the same Example except that Ag.Zn was used. Table 3 shows the magnetic properties and reproduction output characteristics of these magnetic recording cards. In addition, these magnetically bonded sheets and magnetic recording cards were stored indoors for 6 months and changes in appearance were observed. The results are shown in Table 4.

【table】

[Transparent paint-()]

Part 1 Self-curing silicone resin (Toshiba Silicon "YSR-3022", manufactured by Toshiba Silicon Co., Ltd.) 19 2 Curing accelerator (Toshiba Silicon "YC-6831",
(manufactured by the same company) 0.5 3 Curing accelerator (Toshiba Silicon "XC-6953",
(manufactured by the same company) 0.5 4 Rubber 50 5 Methyl ethyl ketone 20 6 Isopropyl alcohol 10 [Pressure sensitive adhesive - ()] Part 1 Acrylic resin (“KP-351”, manufactured by Nippon Carbide Co., Ltd.) 50 2 Methyl ethyl ketone 25 3 Toluene 25 Thickness A 38 micron polyester film is used as the support 1, and magnetic paint () is applied to the surface with a thickness of 14
A magnetic coating layer 2 was formed by applying the magnetic coating to a thickness of microns, and a metal vapor deposition layer 3 was formed by vapor-depositing Sn to a thickness of 500 Å on top of the magnetic coating layer 2. Next, an anchor agent layer 7 was formed by applying an anchor agent () to a film thickness of 0.2 microns, and then
Ink () was applied to a film thickness of 1.5 microns, and transparent paint () was further applied to a film thickness of 0.2 microns to form a protective coating layer 4 consisting of a colored layer and a transparent layer. . On the other hand, the support 1
A pressure-sensitive adhesive () was applied to the back side of the sheet to a thickness of 7 microns to form an adhesive layer 5, and the magnetically laminated sheet thus prepared was wound into a roll. This was cut into tape shapes. The magnetically bonded tape thus produced was bonded to magnetic ledger paper, and then they were applied under a pressure of 40°C.
A magnetic ledger was produced by passing it between pressure rolls of Kg/m at a speed of 5 m/min and pressing it. Table 5 shows the magnetic properties, reproduction output characteristics, and demagnetization rate of this magnetic ledger.

【table】 [Brief explanation of the drawing]

1 to 3 are partial cross-sectional views showing examples of the magnetic bonding type recording material of the present invention.

Claims (1)

[Claims] 1. A magnetic coating layer 2, a Sn vapor deposition layer 3, and a protective coating layer 4 are sequentially laminated on the surface of a sheet-like or film-like support 1, and are adhered to the back surface of the support 1. A magnetic bonding type recording body provided with an agent layer 5. 2. The magnetically bonded recording material according to claim 1, wherein the adhesive layer 5 is a heat-sensitive adhesive layer. 3. The magnetically bonded recording material according to claim 1, wherein the adhesive layer 5 is a pressure-sensitive adhesive layer. 4. Claim 2, in which the protective coating layer 4 is a transparent coating layer, a colored coating layer, or a composite coating layer thereof.
The magnetic bonding type recording material according to item 1 or 3.