JPH0214800B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a non-amorphous metal laminate sheet. More specifically, the present invention relates to a non-amorphous metal laminate sheet that is strong, waterproof, has a shielding effect against electromagnetic waves, and has sufficient mechanical strength for practical use. Here, non-amorphous metals refer to metals having the above effects, excluding amorphous metals. [Prior art] Conventionally, a fiber sheet is used as a base fabric, and at least one
A waterproof sheet obtained by coating the surface with a flexible waterproof resin is known as an awning, a structural membrane, a floor sheet, or a covering sheet material. BACKGROUND ART In recent years, with the development and spread of electronic devices, there has been a need for sheet materials that can protect these devices from the negative effects of static electricity and/or electromagnetic waves and have sufficient mechanical strength for practical use. Conventionally, to protect electronic equipment from static electricity, carbon powder or fiber,
Alternatively, conductive sheets containing conductive materials containing metal foil or powder are used, but such conventional conductive sheets are not sufficiently effective to protect electronic equipment from electromagnetic waves. Moreover, the mechanical strength could not be said to be sufficient. [Problems to be Solved by the Invention] The present invention utilizes a non-amorphous metal thin film to have sufficient shielding and protection effects against both static electricity and electromagnetic waves, and has excellent resistance to damage. , aims to provide a laminated sheet material having practically sufficient mechanical strength by reinforcing a non-amorphous metal thin film. [Means and effects for solving the problems] The non-amorphous metal laminate sheet of the present invention can solve the above problems, and has a non-amorphous metal-containing core layer and an adhesive layer on both sides of the core layer. , and a reinforcing layer made of at least one fiber sheet, and a flexible/waterproof resin layer covering at least one layer of the fiber sheet reinforcing layer;
One of the fiber sheets is made of high-strength fibers having a tensile strength of 130 Kg/mm ² or more and a breaking elongation of 5% or less, and the other sheet is 130 Kg/mm ²
It is characterized in that it consists of high elongation fibers with lower tensile strength and elongation at break higher than 5%. Recently, attempts have been made to utilize non-amorphous metal thin films (foils) for various purposes based on their properties. Generally, a non-amorphous metal thin film is 70cm wide.
Most of them are supplied as narrow width materials of 5 to 60 cm. Recently, as an exception, width 96
cm-wide rolled iron foil and 120 cm-wide electrolytic iron foil are now available, but the supply is small. In addition, non-amorphous metal thin films (foils) generally available on the market
The thickness is approximately 50 μm to 20 μm. Conventionally, ribbon-like or small (thin)
It was considered almost impossible to use the wide material for covering sheets that require a wide width of 100 to 300 cm. In the present invention, a non-amorphous metal material is used in the form of a sheet having a desired width. In the laminated sheet of the present invention, the non-amorphous metal-containing core layer may be formed from a non-amorphous metal sheet alone, or may be formed from a non-amorphous metal sheet and a conductive layer covering at least one surface of the non-amorphous metal sheet. It may also consist of a metal plating layer. Examples of conductive metals include copper, nickel, cobalt, iron, aluminum,
Gold, silver, tin, zinc, and alloys of two or more selected from these can be used. Regarding the type of non-amorphous metal used in the present invention, it is known that it is free from static electricity and electromagnetic waves.
There is no particular limitation as long as it has the effect of protecting electronic equipment, and it can be selected from commercially available materials. What is the protective effect of the electronic equipment mentioned above?
This refers to the effect of absorbing or reflecting electromagnetic wave energy using electromagnetic wave shielding means to prevent the influence of electromagnetic wave energy from reaching electronic equipment. The degree of electromagnetic wave energy attenuation by this electromagnetic wave shielding means is expressed in units of denbels (dB), and the larger this value is, the greater the attenuation effect is, which is preferable for an electromagnetic wave shielding material. In the laminated sheet of the present invention, the electromagnetic shielding effect almost depends on the shielding effect of the metal thin film contained therein, and is generally preferably 10 dB or more, more preferably 30 dB or more, and 60 dB or more. It is even more preferable that
It is even more preferable that it is 90 dB or more. The general commercially available non-amorphous metal thin film materials mentioned above include titanium, beryllium, copper, stainless steel, and other materials with a width of about 6 cm and a thickness of 1.4 μm to 4.9 μm.
m ultra-thin metal foil, titanium, beryllium copper, copper alloy (phosphor bronze, brass, bronze), nickel silver, aluminum alloy, stainless steel, nickel, permalloy, nickel-chromium alloy, niobium, 42 alloy,
palladium, tantalum, tin, lead, zinc, iron, gold,
Silver, silver alloy, platinum, etc. Width about 10cm Thickness 5~
100μm general metal foil, titanium, beryllium copper,
Nickel, gold, silver, platinum, palladium, aluminum, red bronze, silver alloy, and other widths of about 3 to 4 cm,
Ultra-thin foil with a thickness of about 0.3 to 1.0 μm, titanium, copper and copper alloys (beryllium copper, red copper, phosphor bronze, brass, Inconel, constantan), nickel and nickel alloys, aluminum and aluminum alloys, niobium, tantalum, iron, stainless steel, gold,
Silver, platinum, palladium, rare metal alloys, zinc, lead,
It is possible to select and use tin, other ultra-thin foils with a width of about 5 cm and a thickness of 1.0 to 1.5 μm, and other metal thin films (foils). Further, the metal thin film may be a perforated thin film within a range that does not substantially affect its electromagnetic shielding properties. As mentioned above, these non-amorphous metal materials are often supplied in the form of ribbons or narrow sheets. Alternatively, narrow sheets of non-amorphous metal materials are arranged in parallel to form a wide sheet, or if necessary, opposing side edges are bonded with adhesive or solder to form a wide sheet with a desired width. Shall be a body. Additionally, the non-amorphous metal sheet may be formed using non-amorphous metal powder. Alternatively, a knitted or non-woven sheet made of thin wires made of non-amorphous metal may be used as the non-amorphous metal sheet. Some of the above-mentioned non-amorphous metals are magnetic and have an excellent shielding effect against magnetic fields. When a conductive metal is plated on at least one surface of a non-amorphous metal sheet, the resulting core layer has electric field shielding properties due to the plating layer in addition to the magnetic field shielding properties described above, and the core layer as a whole has a wide range of resistance from low frequencies to high frequencies. It can show excellent shielding effect against electromagnetic waves. The conductive metal plating layer also has the effect of improving the solder adhesion of the non-amorphous metal sheet. In the laminated sheet of the present invention, the non-amorphous metal-containing core layer preferably has a thickness of 200 μm or less, more preferably 1 to 100 μm, and even more preferably 5 to 100 μm. Preferably, it is even more preferred to have a thickness of 10 to 50 μm. Further, the conductive metal plating layer included in the non-amorphous metal-containing core layer preferably has a thickness of 0.1 μm or more, more preferably about 0.1 to 5 μm. The thickness of the non-amorphous metal-containing core layer is 200μm
If the core layer becomes larger, the rigidity of the core layer becomes excessively large, making it difficult to deform, resulting in insufficient drapability and forming a sharp cut surface, which may pose an operational hazard. Alternatively, a thin protective film such as a rust preventive agent may be formed on the surface of a non-amorphous metal or a metal-plated non-amorphous metal. When such a non-amorphous metal is used in the form of a thin sheet as described above, its tear strength is so low as to be almost zero, and it easily tears under low loads. Furthermore, such a thin sheet of non-amorphous metal has a relatively low tensile strength, and the strength varies widely. For example, the tensile strength of non-amorphous iron foil with a thickness of 25 μm is determined by JIS-L-1096.
(1979). According to 6.12 of "General Textile Testing Methods", tensile strength and elongation rate 6.12.1 (1) A method (strip method), width: 3 cm, grip interval: 20 cm, tension speed: 200 mm/min. When measured, the tensile strength is 65 to 125 kg/3 cm, with an average of 100 kg/3 cm, which is relatively weak, and the measured values vary widely. In addition, since non-amorphous metals are generally provided in a narrow state, if they are arranged in parallel to form a wide sheet, even if they are soldered at their opposing side edges, Alternatively, even if the sheet is bonded with an adhesive, there is a problem in that the tensile strength in the transverse direction of this sheet is insufficient and also has large variations. In order to solve the above problems, it is effective to bind reinforcing layers each consisting of one or more fiber sheets on both sides of the non-amorphous metal-containing core layer. This reinforcing layer can reinforce the tensile strength and tear strength of the metal sheet, thereby imparting practically desirable properties to the fiber sheet. The tensile strength of the reinforcing layer fiber sheet used for the above purpose is preferably higher than the tensile strength of the core layer. Such a reinforcing layer can reinforce the tensile strength of the core layer and reduce its variation. When a fiber sheet with a breaking elongation of 5% or less is used as the reinforcing layer, the difference in elongation between the core layer and the reinforcing layer becomes small, so that the S-S load curves of the two are approximated. Therefore, the resulting base layer consisting of the core layer and the reinforcing layer can exhibit relatively high tensile strength. In addition, when a fiber sheet with a breaking elongation equal to that of the non-amorphous metal of the core layer or 5% or less is combined with the core layer as a reinforcing layer, a ribbon-like or It is sufficient to simply arrange the narrow metal sheets in parallel, and adhesion of the ribbons by solder or adhesive is not necessarily required. A core layer containing such a non-amorphous metal sheet with no adhesive seams has a good appearance with no noticeable seams. The fibers constituting one of such fiber sheets have a tensile strength of 130 kg/mm ² or more and a breaking elongation of 5% or less. There are no particular limitations on the type of fibers having such performance, but the following are exemplified.

Table: These high-strength fibers are effective in achieving the above-mentioned reinforcing effect, but they have low elongation and low flexural strength. Therefore, when the fiber sheet is used for applications that require high bending resistance, it is recommended to use a sheet made of other fibers with high elongation and high bending strength in addition to the above-mentioned high-strength fiber sheet. It is valid. Although there is no particular limitation on the type of such high elongation fibers, examples thereof are as follows.

〔Example〕

The laminated sheet of the present invention will be further explained by examples. Example 1 and Comparative Example 1 In Example 1, a film with a thickness of 1 μm was applied to the entire surface of a stainless steel metal membrane ribbon with a thickness of 4.9 μm and a width of 10 cm.
Copper plating of m. The tensile strength and elongation of this rib were measured according to JIS-L-1096 (1979), 6.12.1(1) A method, and the tensile strength was 12 to 20 kg/
3 cm (average 18 kg/3 cm), and elongation at break was 0.7%. Eleven of these copper-plated stainless steel metal membrane ribbons were arranged in parallel with each other, their side edges overlapped by 1 cm, and formed into a wide sheet without bonding. A synthetic rubber adhesive (trademark: SC 12N, manufactured by Sony Chemical Co., Ltd.) is applied to both sides of this wide stainless steel sheet, and a glass fiber cloth for FRP (trademark: KS-2671, manufactured by Kanebo Glass Fiber Co., Ltd., thick Thickness 0.22mm, area weight 210g/m ² , plain weave diameter 19 pieces/
25.4mm, 19 wefts/25.4mm, fiber tensile strength 350
Kg/mm ^2Fiber elongation at break 3%, fabric tensile strength, both warp and weft directions: 111.6Kg/3cm, fabric break elongation, both warp and weft directions: 3.0%), and on the other side, a polyester filament with the following structure was attached. Plain weave canvas cloth: 500 denier x 500 denier / 7 pieces / 25.4 mm x 7 pieces / 25.4 mm was pasted to create a base sheet. This plain woven fabric has a thickness of 0.3 mm, a basis weight of 40 g/m ² , a tensile strength of both warp and weft of 25 kg/3 cm, and a fabric elongation at break:
15% in both warp and weft directions, fiber tensile strength 110Kg/
mm ² and fiber elongation at break was 13%. The base sheet was immersed in a flexible and waterproof resin coating solution having the following composition. Ingredients Polyvinyl chloride resin 80 parts by weight Butyl benzyl phthalate 68 parts by weight Epoxidized soybean oil 7 parts by weight Calcium carbonate 20 parts by weight Cadmium barium stabilizer 3 parts by weight Pigment 8 parts by weight Toluene (solvent) 130 parts by weight Above Squeeze the base sheet containing the coating liquid with a nip roller to adjust the amount of coating liquid attached to 100%,
It was dried in a dryer at 90°C for 1 minute. Next, this coating layer was heat treated at 180° C. for 1 minute to gel and fix the polyvinyl chloride. The thickness of the resulting flexible and waterproof resin base layer is 0.3
It was warm in mm. On one side of this laminated sheet is an anti-fouling and weather-resistant resin film (trademark: KFC sheet, manufactured by Kureha Chemical Industry Co., Ltd.,
The polyvinylidene fluoride resin layer (laminated sheet of polyvinylidene fluoride resin layer (2 to 3 μm)/polyacrylic resin layer (2 to 4 μm)/polyvinyl chloride resin layer (45 μm)) is heated and adhered to the other side. A polyacrylic resin film (manufactured by Mitsubishi Rayon Co., Ltd., 25 μm) was attached by heating. The obtained stainless steel metal film laminated sheet had good shielding properties against electromagnetic waves, excellent waterproofing properties, stainproofing properties, and weather resistance, and was also capable of being bonded by heat fusion. Such excellent heat-sealing properties make it possible to use stainless steel metal membranes in sheet materials (for example, sheets for large tents), which was previously unimaginable. It has become possible to perform suturing, simplify its use, and expand its field of use. When the tensile strength of this laminated sheet was measured, it was 113.8 kg/3cm (vertical) and 118.5 kg/3cm (horizontal), and the elongation at break was 3.3% (vertical) and 3.6% (horizontal), which is sufficient for practical use. The variation in tensile strength was about 3 kg/3 cm both vertically and horizontally, which was not much better than the performance of a single sheet made of stainless steel metal film, and the variation in strength was also small. In addition, in the laminate of this example, the stainless steel metal film ribbons arranged in parallel were not soldered together, but the metal film ribbons did not slip from their regular positions and did not cause any missing parts. It had a favorable appearance without the formation of unevenness due to overlapping of the side edges. In Comparative Example 1, a laminated sheet was created in the same manner as in Example 1 without using polyester cloth. The bending resistance of the laminated sheets of Example 1 and Comparative Example 1 was measured using JIS-K-6328 and Scott method, load: 1 kg, bending: 1000 times, and the strength retention rate after treatment was measured compared to before treatment. As a result, the percentage was 85% in the case of Example 1 in which the polyester cloth was used in combination, while it was 30% in the case in which it was not used in combination.
Laminated sheets containing polyester cloth are suitable for applications that involve repeated bending, while laminated sheets that do not contain polyester cloth are suitable for applications that do not involve bending, but are unsuitable for applications that involve bending. . The laminated sheets of Example 1 and Comparative Example 1 both had an electromagnetic shielding effect of 60 dB. Example 2 Eleven stainless steel metal membrane ribbons plated in the same manner as in Example 1 were placed in parallel, and the side edges of each ribbon were soldered to form a wide sheet with a width of about 1 m. Tensile strength of solder joint is 8~16Kg/3cm
The tensile strength of the soldered joint was quite low (average 13.2 kg/3 cm). This wide sheet was subjected to the same reinforcing layer adhesion operation as in Example 1. However, instead of fiberglass cloth,
A fabric made of highly elastic carbon fiber yarn with the same structure (tensile strength is 72.8Kg/3cm both vertically and horizontally,
It is 70.5Kg/3cm, and the elongation at break is 0.6% in warp and 0.5 in latitude.
%, fiber tensile strength 210Kg/ ^mm2 , elongation at break 0.6%)
was used. The obtained base layer sheet was immersed in a coating liquid containing a resin composition having the following composition. Ingredients Polyvinyl chloride resin paste 100 parts by weight DOP (plasticizer) 70 parts by weight Barium borate (smoke reducer) 20 parts by weight Aluminum hydroxide (flame retardant) 100 parts by weight Barium sulfate (flame retardant) 200 parts by weight Barium - Zinc stabilizer 2 parts by weight Ketin Black EC 30 parts by weight Squeeze the resin liquid impregnated sheet to a squeezing rate of 100% and hold it at 150°C.
The base sheet was dried for 2 minutes to remove the diluent, and then heat treated at 185° C. for 1 minute to coat and fix the resin composition on the base sheet at a weight of 70 g/m ² . Next, a film made of a resin composition having the same composition as above (however, polyvinyl chloride resin straight was used and the amount of Ketin Black EC used was 30 parts by weight) was placed on one side of the obtained laminated sheet. ,
The resin content coated on the base sheet by calendering was 200 g/m ² . The obtained laminated sheet showed good electromagnetic shielding effect of 70 dB and good waterproof property. Also,
The surface on which the resin film is attached and the opposite surface of the laminated sheet are 3.2 x 10 Ω-cm and 5.8 x 10 ⁸ Ω-cm, respectively.
The volume resistivity value in Ω-cm is shown. The tensile strength of this base sheet is vertical: 5.8Kg/
3cm, width: 4.5Kg/3cm, which sufficiently covered the weakness of the solder joint. Moreover, the variation in tensile strength was approximately 3 kg/3 cm, and very stable and desirable sheets were obtained. Place the resin film of the above laminated sheet on the adhesive surface,
When the same KFC film described in Example 1 was attached, the surface to which it was attached showed good stain resistance and weather resistance. Example 3 Eleven stainless steel metal film ribbons (without plating) identical to those described in Example 1 were arranged in parallel to form a wide sheet, and both sides of this sheet were coated with the following:
An adhesive (SC-12N) was applied to a fiber sheet and a resin film having the same fiber composition as those described in Example 2 (however, the content of Ketin Black EC was 15 parts by weight) with a thickness of 0.3 mm. one and 0.2
mm ones were attached to each side. Furthermore, the same KFC film as described in Example 1 was attached to the surface of the attached resin film with a thickness of 0.3 mm. Although the amorphous metal ribbons were not soldered and only partially overlapped, a laminated sheet having good tensile strength similar to that described in Example 2 was obtained. Example 4 Copper, copper alloy, aluminum, aluminum alloy, nickel, tin, lead, each having a thickness of about 5 μm
The same operation as in Example 2 was performed except that a thin film of zinc was used. Almost similar favorable results were obtained. Example 5 In each of Examples 1 to 4, the same procedure was carried out using a thin film having 3 holes with a diameter of 1 mm/ ^cm2 , but the shielding effect was almost the same, and it was preferable that the coating resin penetrate the thin film. A very preferable film body was obtained which adhered tightly. [Effects of the Invention] The non-amorphous metal laminate sheet of the present invention has a good electromagnetic shielding effect and also has good tensile strength in practical use, so it is advantageous for forming a simple shield room. In addition, the present invention is applicable to fields where non-amorphous metal films were previously considered unusable due to their high rigidity, low adaptability to other materials, and difficulty in sewing and joining, such as tents and sheets. Non-amorphous materials are used in outdoor membrane structures such as houses, flooring materials such as floor sheets for rooms equipped with electronic equipment, indoor interior materials such as wall materials and blinds, and packaging materials such as various covering sheets. This made it possible for metal laminated sheets to be widely used.

Claims (1)

[Scope of Claims] 1. A non-amorphous metal-containing core layer; reinforcing layers bonded on both sides of the core layer and each consisting of at least one fiber sheet; and at least one layer above the fiber sheet reinforcing layer. a flexible and waterproof resin layer covering the fiber sheet, and one of the fiber sheets is made of high-strength fibers having a tensile strength of 130 Kg/mm ² or more and a breaking elongation of 5% or less, A non-amorphous metal laminate sheet, characterized in that the other sheet is made of high elongation fibers having a tensile strength lower than 130 Kg/mm ² and a breaking elongation higher than 5%. 2. The laminated sheet according to claim 1, wherein the non-amorphous metal-containing core layer comprises a non-amorphous metal sheet and a conductive metal plating layer covering at least one surface of the non-amorphous metal sheet. 3. The laminated sheet according to claim 1, wherein the non-amorphous metal-containing core layer comprises a plurality of non-amorphous metal sheets arranged in parallel with each other. 4. The non-amorphous metal-containing core layer is a sheet-like body formed by soldering a plurality of non-amorphous metal sheets arranged in parallel to each other at their side edges. A laminated sheet according to scope 1. 5. The laminated sheet according to claim 1, wherein the fiber sheet reinforcing layer and the non-amorphous metal-containing core layer are bonded with an adhesive. 6. The flexible/waterproof resin coating layer includes a base layer made of a flexible/waterproof resin, and a surface layer formed on the base layer and made of an antifouling/weatherproof synthetic resin. The laminated sheet according to claim 1. 7. Claim 6, wherein the stain-proof/weather-resistant synthetic resin surface layer in the flexible/waterproof resin coating layer is formed of at least one selected from fluorine-containing synthetic resins and polyacrylic resins. Laminated sheet as described in section. 8. The laminated sheet according to claim 1, wherein the non-amorphous metal-containing layer has a thickness of 200 μm or less. 9. The laminated sheet according to claim 2, wherein the conductive metal plating layer in the non-amorphous metal-containing core layer has a thickness of 0.1 μm or more. 10 The flexible/waterproof resin coating layer is at least
The laminated sheet according to claim 1, having a thickness of 50 μm. 11. The laminated sheet according to claim 1, wherein the tensile strength of the fiber sheet reinforcing layer is higher than the tensile strength of the core layer. 12. The laminated sheet according to claim 1, wherein the fiber sheet reinforcing layer has a breaking elongation of 5% or less.