JPH06224590A - Laminate sheet having electromagnetic wave shielding property - Google Patents

Abstract

PURPOSE:To provide an amorphous metal thin film layer sheet excellent in an electromagnetic shielding property while having practically sufficient strength. CONSTITUTION:A laminate sheet having the electromagnetic wave shielding property having one or more of amorphous metal thin film layer 1 consisting of a parallel body of a plurality of amorphous metal ribbons, one or more of non-amorphous metal thin film layers 3 and one or more of porous reinforcing layers 5 laminated on at least one layer of these while consisting of flexible resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electromagnetic wave shielding laminated sheet. More specifically,
The present invention relates to a laminated sheet including an amorphous metal thin film, a non-amorphous metal thin film, and a flexible resin porous reinforcing layer, which has an excellent shielding effect against electromagnetic waves.

[0002]

2. Description of the Related Art In recent years, with the development and popularization of electronic devices, these devices, magnetic recording media, etc.
It is necessary to protect against the adverse effects of static electricity and electromagnetic waves, and as this protective material, sheet materials such as covering sheet materials and packaging sheet materials are in great demand.

In order to protect electronic equipment from the influence of static electricity, a conductive sheet containing a conductive material containing carbon powder, carbon fiber, metal foil or metal powder has been used. However, such a conventional conductive sheet cannot be said to be sufficiently effective for the purpose of protecting electronic equipment from the influence of electromagnetic waves. For example, in an MRI (Nuclear Magnetic Resonance Diagnostic Device) or the like, it is easily damaged by external electromagnetic waves, and therefore the MRI is shielded by an iron plate having a thickness of 2 cm. If such a thick shield material is used, the weight of the device becomes extremely large, and the manufacturing and processing thereof are difficult. Further, the most serious drawback of the iron plate shield is that the iron plate itself is easily magnetized.

The use of amorphous metal has been attempted in order to overcome the above-mentioned drawbacks of conventional electromagnetic wave shielding materials. Amorphous metal has an excellent shield effect against electromagnetic waves, and has an advantage that when the load is removed, it immediately returns to its original state and is not magnetized.

However, the amorphous metal has the following problems with respect to the conventional electromagnetic wave shielding material (for example, iron plate). (A) Generally, the thickness of the amorphous metal material is 100 μm.
m or less (most commercially available amorphous metal thin films are 50 μm
It is limited to have the following thickness), and it is difficult to obtain an amorphous metal material having a thickness greater than this.

(B) Generally, the amorphous metal material is 1
It is supplied with a width of 00 mm or less (most commonly 20 mm or less), and it is difficult to obtain one having a width wider than this. (C) Therefore, a wide width and a considerable thickness, for example, 1
It is difficult to obtain an amorphous metal material having a thickness greater than 00 μm. (D) Therefore, the amorphous metal material cannot be used as a wide sheet material.

[0007]

SUMMARY OF THE INVENTION The present invention uses an amorphous metal thin film having the above-mentioned problems, has a desired width and thickness, and has an electromagnetic wave shielding laminate sheet having sufficient strength for practical use. Is to provide.

[0008]

The electromagnetic wave shielding laminated sheet of the present invention comprises at least one amorphous metal thin film layer composed of a plurality of amorphous metal ribbons arranged in parallel with each other, and at least one layer laminated thereon.
A non-amorphous metal thin film layer, and at least one porous reinforcing layer made of a flexible resin material and laminated on at least one layer of the amorphous metal thin film and the non-amorphous metal thin film. It is characterized by that.

[0009]

[Function] Recently, based on the characteristics of amorphous metal,
Attempts have been made to use it in various applications. Generally, the amorphous metal thin film is supplied as a ribbon-shaped material having a width of 2.54 to 10.16 cm, and it is expected that a small width sheet having a width of 20.32 cm will be supplied in the near future with respect to the expansion of the width. It is only about. Further, the supplied amorphous metal thin film generally has a thickness of 5 to 50 μm, and very rarely has a thickness of about 100 μm.

Conventionally, the ribbon-shaped or small (narrow) width material as described above can be used only as a card case or as a packaging material for small articles, which is 100 to 300.
It was thought that it would be almost impossible to use it for a covering sheet that requires a wide width of cm. In the laminated sheet of the present invention, the amorphous metal thin film is used up to its supply width or, if necessary, bonded to a desired width.

In FIG. 1, the amorphous metal thin film layer 1 used in the laminated sheet of the present invention is composed of a plurality of amorphous metal ribbons 2 arranged in parallel with each other. In the thin film laminate used in the laminated sheet of the present invention shown in FIG. 2, a non-amorphous metal thin film layer 3 is laminated on an amorphous metal thin film layer 1 composed of a plurality of amorphous metal ribbons 2 to form a thin film laminate 4. Are formed.

In one embodiment of the laminated sheet of the present invention, as shown in FIG. 3, a thin film laminate 4 composed of an amorphous metal thin film layer 1 and a non-amorphous metal thin film layer 3 is further provided with a flexible resin material. Porous reinforcement layer 5
Are stacked.

Amorphous metal thin films useful in the present invention
The film generally contains iron as a main component, and boron,
Silicon, carbon, nickel, cobalt, and molybdenum
Amorph obtained by adding one or more selected from
It is preferable to be selected from As alloy. For example, Arai
Trademark of DO company: METGLAS No. 2605SC (F
e: 81%, B: 13.5%, Si: 3.5%, C: 2
% Amorphous alloy), No. 2605S-2 (Fe:
Amorphous mixture of 78%, B: 13%, Si: 9%
Gold), No. 2605-CO (Fe: 67 parts, B: 14
Part, Si: 1 part, Co: 18 parts amorphous alloy),
No. 2826-MB (Fe: 40%, Ni: 38%, M
o: 4%, B: 18% amorphous alloy)
You can In addition, the alloy system containing iron as the main component
In addition to alloys containing cobalt as a main component (for example, Co₉₀
Zr_Ten, Co₇₈Si_TenB₁₂, Co₅₆Cr₂₆C₁₈, Co₄₄
Mo₃₆C ₂₀, Co₃₄Cr₂₈Mo₂₀C₁₈), Mainly nickel
Alloy system as a component (eg Ni₉₀Zr_Ten, Ni₇₈Si_Ten
B₁₂, Ni₃₄Cr_{twenty four}Mo_{twenty four}C₁₈), And other metals
Alloys containing as a main component (for example, Pd₈₀Si₂₀, Cu₈₀Z
r₂₀, Nb₅₀Ni₅₀, Ti ₅₀Cu₅₀) Etc. can also be used.

The amorphous metal thin film may be a perforated thin film as long as it does not substantially affect the electromagnetic wave shielding property. Since these amorphous metal thin film materials are often supplied in the form of ribbons or narrow sheets as described above, when using them in the laminated sheet of the present invention, a plurality of ribbons may be added as necessary. -Shaped or narrow sheet amorphous metal thin film materials are arranged in parallel with each other to form a wide sheet-shaped body, or if necessary, their opposite side edges are bonded by a conductive adhesive or solder. To obtain a wide sheet body having a desired width. When forming a wide thin film from a plurality of ribbons, the ribbons may be arranged so as to extend parallel to the longitudinal axis direction of the obtained laminated sheet, or arranged so as to extend in a direction perpendicular to this. May be.

The amorphous metal thin film has an excellent shield effect against a magnetic field, but the shield effect against an electric field is not so high as the shield effect against a magnetic field.

In the laminated sheet of the present invention, a non-amorphous metal thin film is laminated and integrated on the amorphous metal thin film in order to solve the problems of the dimension of the amorphous metal thin film and the problems of the shield effect against an electric field.

Recently, it has been attempted to use a non-amorphous metal thin film (foil) for various applications based on its characteristics. Generally, a non-amorphous metal thin film is supplied as a narrow material having a width of 70 cm or less, generally 5 to 60 cm in width. Recently, rolled iron foil with a width of 96 cm and electrolytic iron foil with a width of 120 cm have been supplied. In addition, non-amorphous metal thin films (foil) that are generally on the market have a thickness of 0.
It is about 1 μm to 100 μm. Conventionally, a ribbon-shaped or small (narrow) width material as described above is used in the range of 100 to 300.
It was thought that it would be almost impossible to use it for a covering sheet that requires a wide width of cm. In the present invention, the non-amorphous metal thin film is used together with the amorphous metal thin film as a sheet having a desired width.

As the above-mentioned general commercially available non-amorphous metal thin film material, titanium, beryllium, copper, stainless steel, other materials having a width of about 6 cm and a thickness of 1.4 μm to 4.9 μm are used.
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, other general metal foil with a width of about 10 cm and a thickness of 5 to 100 μm, titanium, beryllium copper, nickel, gold, silver, platinum, palladium, aluminum, Red copper, silver alloy, other width 3-4 cm
, Ultra-thin foil with a thickness of 0.3-1.0 μm, titanium, copper and copper alloys (beryllium copper, brass, phosphor bronze, brass, inconel, constantan), nickel and nickel alloys, aluminum and aluminum alloys , Niobium, tantalum,
Iron, stainless steel, gold, silver, platinum, palladium,
A rare metal alloy, zinc, lead, tin, or another thin film having a width of about 5 cm and a thickness of 0.1 to 100 μm, particularly an ultrathin foil of 1.0 to 1.5 μm, and other at least one of the above metals. A metal thin film (foil) including a thin film of a metal compound as a main component can be selected and used. Also,
The metal thin film may be a perforated thin film within a range that does not substantially affect the electromagnetic wave shielding property.

Since these non-amorphous metal materials are often supplied in the form of ribbons or narrow sheets as described above, in order to use them in the laminated sheet of the present invention, a plurality of them may be used. Ribbon-shaped or narrow sheet-shaped non-amorphous metal materials are arranged in parallel with each other to form a wide sheet-shaped body, or if necessary, their opposite side edges are bonded with an adhesive or solder to form a desired sheet. A wide sheet having a width is used. Further, the non-amorphous metal sheet may be formed by using non-amorphous metal powder. Alternatively, it may be used as a non-amorphous metal sheet as a knitted woven fabric-like or non-woven fabric-like sheet made of fine wires made of non-amorphous metal.

Some of the non-amorphous metals as described above are magnetic substances and have an excellent shielding effect against a magnetic field, but particularly have an excellent shielding effect against an electric field.

In protecting the electronic equipment as described above, it is important that the electromagnetic wave energy is absorbed or reflected by the electromagnetic wave shield means so that the electronic equipment is not affected by the electromagnetic wave energy. . The degree of electromagnetic wave energy attenuation by the electromagnetic wave shield means is expressed in a unit decibel (dB), and as the electromagnetic wave shield material has a larger value, the attenuation effect is larger, which is preferable.

In the laminated sheet of the present invention, its electromagnetic wave shielding effect depends substantially 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, 60
It is more preferably at least dB, and even more preferably at least 90 dB.

In the laminated sheet of the present invention, at least one of the amorphous metal thin film and the non-amorphous metal thin film may have a plating layer made of a conductive metal material. As the conductive metal for plating, for example, copper, nickel, cobalt, iron, aluminum, gold, silver, tin, zinc, and an alloy of two or more selected from these can be used.

Thus, the amorphous metal thin film and / or
Alternatively, when a conductive metal is plated on at least one surface of a non-amorphous metal thin film, the obtained laminated sheet has an electromagnetic field shielding property of the amorphous metal thin film and the non-amorphous metal thin film, and an excellent electric field of the conductive metal plating layer. The shielding properties are added, and the laminated sheet as a whole can exhibit an excellent shielding effect against electromagnetic waves in a wide range from low frequencies to high frequencies. Further, the conductive metal plating layer also has an effect of improving the solder adhesiveness of the amorphous metal thin film and the non-amorphous metal thin film, and facilitating the formation of a wide thin film.

The conductive metal plating layer contained in the amorphous metal thin film and / or the non-amorphous metal thin film preferably has a thickness of 0.1 μm or more,
More preferably, it has a thickness of about 0.1 to 5 μm. Further, a thin protective film such as an anticorrosive agent may be formed on the surface of the amorphous metal thin film layer, the non-amorphous metal thin film layer, or the metal plating layer thereof.

In the laminated sheet of the present invention, at least one amorphous metal thin film layer and at least one non-amorphous metal thin film layer may be laminated and integrated in any order. In this case, an amorphous metal laminate may be formed by a plurality of amorphous metal thin film layers that are laminated and integrated, and a non-amorphous metal laminate may be formed by a plurality of non-amorphous metal thin film layers that are laminated and integrated. It may be formed.

As described above, the amorphous metal thin films each have a thickness of 5 to 100 μm, but the amorphous metal thin film laminate layer of the present invention has a total thickness of 50 μm.
It is preferable to have a thickness of m to 5,000 μm, and
More preferably, it has a thickness of 00 to 5,000 μm. Therefore, in the laminated sheet of the present invention, it is preferable that the amorphous metal laminated body is formed by laminating 2 to 200 amorphous metal thin film layers.

The amorphous metal thin film laminate layer in the laminated sheet of the present invention comprises at least one plated amorphous metal thin film layer and at least one amorphous metal thin film layer having no plated layer. Good.
Thus, by omitting the plating layer from a part of the amorphous metal thin film layer, it is possible to obtain the required electromagnetic wave shielding property while reducing the product cost.

In the laminated sheet of the present invention, the non-amorphous metal thin film generally has a thickness of 0.1 to 100 μm, and the non-amorphous metal laminate layer composed of a plurality of layers has a thickness of 50 to 5,000 μm. The thickness is preferably 50 to 3,000 μm, and more preferably 50 to 3,000 μm. When the thickness of the non-amorphous metal laminated body layer is more than 5,000 μm, the laminated body layer has excessive rigidity, is hard to be deformed, and has insufficient drapability.
A sharp cutting surface may be formed, which may be dangerous in operation.

In the laminated sheet of the present invention, an adhesive or a pressure-sensitive adhesive is used to join and integrate the amorphous metal thin film layer and the non-amorphous metal thin film layer with each other. When a large number of amorphous metal thin film layers and / or non-amorphous metal thin film layers are stacked and bonded to each other, the bonding areas of the adhesive or the pressure sensitive adhesive overlap each other, resulting in locally different thicknesses in the resulting laminate layer. It is preferred that the adhesive or cohesive bonding areas are distributed substantially evenly in the laminate layer so that no parts are formed, so that the adhesive or cohesive bonding areas do not overlap each other, thereby maintaining a uniform thickness, texture.

The adhesive or pressure-sensitive adhesive is preferably conductive or semi-conductive in order to electrically connect a plurality of laminated amorphous and / or non-amorphous metal thin films to each other. It may have rust resistance. There is no particular limitation on the type of such an adhesive or pressure-sensitive adhesive, and any of existing adhesives can be selected and used according to the purpose of use. For example, a material having high cold resistance or a material having high heat resistance may be selected and used according to the use environment.

In general, a plurality of amorphous or non-amorphous metal thin film layers in the laminate layer may be adhered or adhered to each other with an adhesive or a tackifier. In this adhesion or adhesion, an adhesive or a pressure-sensitive adhesive may be applied and fixed on the entire surfaces of the amorphous or non-amorphous metal thin film layers which are adjacent to each other and overlap each other. However, in this case, when the laminate layer is bent, the degree of freedom of mutual displacement between the amorphous metal thin film layers adhered or adhered to each other becomes insufficient. In order to solve such problems,
It is preferable that the plurality of amorphous or non-amorphous metal thin film layers are not adhered or adhered to each other, but this makes it difficult to integrate the plurality of amorphous or non-amorphous metal thin film layers.

In the laminate layer of the amorphous or non-amorphous metal thin film layer of the present invention, each amorphous or non-amorphous metal thin film layer is partially adhered or adhered to its adjacent and overlapping layers, except the adhered or adhered part. It is preferable that the portions can be displaced relative to each other. For this reason, each amorphous or non-amorphous metal thin film layer is provided with an adhesive or pressure-sensitive adhesive which is arranged only at its side edge portion or in at least one linear or dot shape with respect to the adjacent and overlapping layers. It is preferably adhered or tacked by layers. For example, in a laminate layer of a plurality of amorphous or non-amorphous metal thin film layers, the constituent amorphous metal thin film layers are adhesives distributed in at least one linear or dot shape or a mixture thereof. It is preferably adhered or tacked by a layer of agent or adhesive. The plurality of amorphous metal thin film layers are bonded and integrated with each other by the adhesion or the adhesion in this manner. However, the non-bonded parts of the amorphous or non-amorphous metal thin film layer can be mutually displaced in response to bending, which facilitates bending of the laminated layer and prevents breakage of the laminated layer due to bending. To be done.

The shape of the joints may be one or more straight lines, curves, or mixtures thereof, or may consist of one or more points, the sum of these joints being It is preferably 90% or less with respect to the bonding area of the amorphous or non-amorphous metal thin film layer.
More preferably, it is within the range of 90%.

The application area of the dot-like or linear adhesive or pressure-sensitive adhesive contained in the layered body layer of the amorphous or non-amorphous metal thin film layer does not cause local unevenness in the thickness of the layered body layer. In addition, it is preferable that the layers are distributed almost uniformly so as not to overlap each other, whereby a laminate layer having substantially uniform solidity can be obtained.

In the laminated sheet of the present invention, at least one flexible resin porous reinforcing layer is laminated on at least one layer of the amorphous metal thin film layer and the non-amorphous metal thin film layer.

For example, in the laminated sheet of the present invention, a thin film laminate composed of an amorphous metal thin film and a non-amorphous metal thin film is packed and integrated between two flexible resin porous reinforcing layers facing each other. Alternatively, a flexible resin porous reinforcing layer may be inserted and incorporated between a laminate of two or more amorphous metal thin films and a laminate of two or more non-amorphous metal thin films. The flexible resin porous reinforcing layer may be conductive or semi-conductive.

The flexible resin porous reinforcing layer can provide the laminated sheet of the present invention with desired flexibility, compression elasticity, shock absorbing property, shock absorbing property, rupture resistance and the like.
That is, when an external force such as bending acts on the laminated sheet, the flexible resin porous reinforcing layer absorbs the external force by being deformed, and the expansion and the compression of the amorphous metal thin film are reduced. It exerts a buffering effect of preventing the thin film from breaking and breaking and also preventing permanent deformation (crease formation). Such a laminated sheet is a sheet for covering electronic devices,
Alternatively, it is useful as a sheet for packing and storing.

Examples of the flexible resin material include natural rubber, neoprene rubber, chloroprene rubber, silicone rubber, synthetic rubber such as Hypalon, PVC resin, ethylene-vinyl acetate copolymer (EVA) resin, acrylic resin, silicone resin, polyurethane. Resins, polyethylene (PE) resins, polypropylene (PP) resins, polyester resins, fluororesins and other synthetic resins can be used. Such a material also has good waterproofness, and can impart desired waterproofness, flame retardancy, and mechanical strength to the resulting laminated sheet.

These flexible resin porous reinforcing layers use the above-mentioned rubber or resin film, solution, paste, straight or the like, and are known methods such as topping, calendering, coating and dipping. Can be formed on the surface of an amorphous or non-amorphous metal thin film. These rubbers or resins may contain a plasticizer, a stabilizer, a colorant, an ultraviolet absorber and the like, and other function-imparting agents such as a flameproofing agent and a flame retardant. A surface layer made of an antifouling / weather resistant synthetic resin can be formed on at least one surface of the laminated sheet of the present invention. A fluorine-containing resin and an acrylic resin can be used as the antifouling / weatherproof synthetic resin forming such a surface layer. That is, the antifouling / weather resistant resin surface layer is formed by sticking a film made of a fluorine-containing resin or an acrylic resin on one surface of the laminated sheet.

Fluorine-containing resins are generally flame-retardant and stain-proof.
Although it is weather resistant, it is extremely difficult to stick to the surface of the base layer as it is because it is not compatible with ordinary plastic adhesives. Therefore, by subjecting the surface of the fluorine-containing resin film to corona discharge or low-temperature plasma treatment and activating it as much as possible, compatibility with adhesives such as polyvinyl chloride, polyepoxy, polyacryl, and polyester resins is obtained. The sex is increasing. Usually, the surface treatment of the fluorine-containing resin film is activated by the above treatment. Therefore, for example, 100 to 200 V, 40 to 100 μF, short circuit current 1
Corona discharge treatment is performed under the condition of ~ 2A. By such an electric discharge treatment, a desired adhesive ability is given to the fluorine-containing resin film, but the surface treatment of the fluorine-containing resin film used in the present invention is not limited to this, and other surface treatments such as the same or more may be performed. Anything can be used as long as it has an effect.

As the resin constituting the fluorine-containing resin film, various polyfluoroethylenes synthesized from monomers in which one or more hydrogen atoms of ethylene are replaced with fluorine atoms, for example, polytetrafluoroethylene. , Or various polyfluorochloroethylene containing a part of chlorine, such as polytrifluorochloroethylene, etc., but also includes polyvinyl fluoride, polyvinylidene fluoride, polydichlorodifluoroethylene, and the like. The thickness of the film is generally 0.001 mm to 0.5 mm, preferably 5 to
Although it is about 50 μm, it can be made thicker or thinner as long as it achieves the objects of weather resistance, antifouling property and durability, and there is no particular limitation. Further, the fluorine-containing resin film may be mixed with other resins, for example, MMA or the like such as mixed or adhered, as long as it does not hinder the object of the present invention. Commercially available products containing fluorine-containing resin films include Chidra film (DuPont, trademark), Aflex film (Asahi Glass, trademark), KFC.
Films (Kureha Chemical, trademark) etc. are available.

In forming the fluorine-containing resin layer, it is preferable that a film-like fluorine-containing resin having a substantially smooth surface is attached to the upper surface of the laminated sheet, but a fluorine-containing resin solution or emulsion is applied. There is also a way to do it. The fluorine-containing resin film preferably has a tensile strength of 100 kg / cm ² or more.

The antifouling / weather resistant resin surface layer coated on the laminated sheet of the present invention may be formed of a polyacrylic resin. For this purpose, an acrylic resin film is generally used, but an acrylic resin solution or emulsion is used.
You may use the method of apply | coating on a laminated sheet and drying.

The above acrylic resin film is 100 kg /
It is preferable to have a tensile strength of cm ² or more, 1 to 50
g / m ^2, preferably a weight of 3 to 30 g / m ^2, or,
3 μm or more (usually 3 to 50 μm), more preferably 4
It is preferable to have a thickness of ˜30 μm.

The above acrylic resin film may be manufactured by any of the T-die method, the inflation method and the like. Further, although it may be a stretched film or an unstretched film, the elongation of the film is 100 to 300%.
Something is preferable. As described above, the thickness is usually about 3 μm to 50 μm, but it may be slightly thicker or thinner as long as sufficient weather resistance and antifouling property are achieved. The film material is a polyalkylmethacrylate-based film, for example, one mainly containing methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, or a homomonomer of acrylate, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, etc. Alternatively, a homopolymer or a copolymer which is a comonomer component is preferably molded into a film.
Such a film is adhered to the surface of the laminated sheet with an adhesive or is attached by other method. The antifouling / weather resistant resin surface layer formed on the laminated sheet is a laminate of a polyvinylidene fluoride resin layer and an acrylic resin layer in addition to the fluorine-containing resin and the acrylic resin as described above,
Alternatively, a polyvinylidene fluoride resin layer, an acrylic resin layer,
It may be composed of a laminate with a polyvinyl chloride resin layer. In these laminates, the polyvinylidene fluoride resin layer has a thickness of 2 to 3 μm, and the acrylic resin layer has a thickness of 2 μm.
~ 4 μm and the thickness of the polyvinyl chloride resin layer is 40 ~
It is preferably 45 μm.

The flexible resin porous reinforcing layer used in the laminated sheet of the present invention may be a rigid foam as long as it has desired flexibility, but a flexible foam is generally preferable.

The porosity of the flexible resin porous reinforcing layer is 50.
˜99% (foaming ratio: 2 to 100 times) is preferable, and 80 to 98% (foaming ratio: 5 to 50 times) is more preferable. Usually, a foaming ratio of 20 to 60 is used. Further, if the compression resistance of the foamed porous sheet material layer is 10 kg / cm ² or less at 25% compression, it is practically possible depending on the application, but generally 0.5 kg / cm.
Preferably ² or less, more preferably 0.1 kg / cm ² or less.

The thickness of the flexible resin porous reinforcing layer is not particularly limited and can be set arbitrarily according to the application of the laminated sheet, but generally it is within the range of 0.5 to 100 mm. It is preferable that it is, and it is more preferable that it is in the range of 1 to 50 mm.

The flexible resin porous reinforcing layer is bound in the laminated sheet of the present invention, but a foamed porous sheet is prepared in advance and is bound with an adhesive. Alternatively, the bonded surface portion of the foamed porous sheet may be heat-melted and fused. The flexible resin porous reinforcing layer may be formed by chemically foaming on an amorphous or non-amorphous metal thin film, or a polymer coating containing bubbles may be formed on the amorphous or non-amorphous metal thin film. You may form by what is called a mechanical foaming method of apply | coating and solidifying this.

The flexible resin porous reinforcing layer as described above is
It may be formed on both sides of the laminated sheet of the present invention, or may be formed on only one side thereof. In the latter case, the non-porous reinforcing layer made of the flexible resin material as described above may be bonded to the other surface.

[0052]

EXAMPLES The laminated sheet of the present invention will be further described below with reference to examples.

Example 1 Amorphous alloy thin film (Fe: 81%, B: 13.5)
%, Si: 3.5%, C: 2%, trademark: METGLAS
No. 2605SC, manufactured by Allied Co., Ltd., 13 ribbons made of 7.62 cm wide, 25 μm thick ribbon-shaped body are arranged in parallel, and a stainless steel metal film ribbon of 4.9 μm thick and 10 cm wide (tensile) Strength 12 ~ 20kg / 3c
m, average tensile strength 18 kg / 3 cm, breaking elongation 0.7%)
11 sheets are arranged side by side and these are made of synthetic rubber adhesive (trademark: S
C12N, manufactured by Sony Chemical Co., Ltd.) was adhered to obtain a thin film laminate. This thin film laminate exhibited an electromagnetic wave shielding effect of 45 dB.

A polyurethane foam having a foaming ratio of 40 times (porosity: 97.5%) and a thickness of 5 mm was attached to one surface of the obtained thin film laminate to prepare a laminated sheet for packaging material. When this laminated sheet was used to wrap a device having sharp corners, the polyurethane foam layer was compressed and deformed according to the shape of the device, and neither the amorphous metal nor the stainless steel thin film was stretched or broken.

Example 2 Amorphous alloy (Fe: 81%, B: 13.5%, S
i: 3.5%, C: 2%, trademark: METGLAS No.
2605SC, Allied, width 7.62 cm, thickness 25
The entire surface of the ribbon-like body having a thickness of 1 μm) was plated with copper having a thickness of 1 μm. Thirteen sheets of the amorphous metal ribbons were arranged in parallel and the side edges of the ribbons were joined by soldering to form a wide sheet having a width of about 1 m. Tensile strength of solder joint is 40-86
kg / 3 cm, average 68.6 kg / 3 cm, and the tensile strength of the solder joint was considerably low.

Further, the same surface as the stainless steel metal film ribbon of Example 1 having a thickness of 4.9 μm and a width of 10 cm was plated with copper having a thickness of 1 μm. 11 of this copper plated stainless steel metal film ribbon
The sheets were arranged in parallel with each other, and each side edge was overlapped by 1 cm, and formed into a wide sheet without adhering.

On both sides of this wide stainless steel sheet, the amorphous metal thin film wide sheet is superposed,
Synthetic rubber adhesive (Trademark: S
C12N, manufactured by Sony Chemicals Co., Ltd.) was applied to a circular spot having a diameter of 3 mm at a density of 2 pieces per cm ² , and these were integrally bonded. The area coverage of this adhesive is 14.13%
Met. The obtained laminated sheet exhibited a high electromagnetic shielding effect of 50 dB.

The above adhesive was applied to the entire surfaces of both sides of the above laminated sheet, and the same polyurethane foam as that described in Example 1 was attached thereto. The resulting laminate is good,
It had a shielding property against electromagnetic waves (50 dB), excellent waterproof property, antifouling property and weather resistance, and was capable of heat fusion bonding.

Example 3 The same operation as in Example 1 was performed. However, an acrylic resin adhesive was used instead of the adhesive. The obtained laminated sheet exhibited good flexibility and electromagnetic wave shielding properties similar to those of Example 1.

[0060]

The laminated sheet of the present invention comprises at least one amorphous metal thin film layer and at least one non-amorphous metal thin film layer, but has practically sufficient flexibility, flexibility, strength, and It has workability and, in addition to excellent electromagnetic wave shielding properties, also has an excellent electric field shielding effect. Therefore, in applications such as coating of electromagnetic wave shielding properties, packaging sheets, rugs, or wallpaper sheets,
A wide range of effects can be expected for magnetic field and electric field shields, and they are useful for these applications. Further, the laminated sheet of the present invention can be used in combination with any of the intermediate product and the finished product in the above-mentioned applications.

[Brief description of drawings]

FIG. 1 is a plan view showing an example of the configuration of an amorphous metal thin film layer used in a laminated sheet of the present invention.

FIG. 2 is an explanatory cross-sectional view of one embodiment of a thin film laminate including an amorphous metal thin film and a non-amorphous metal thin film of the laminated sheet of the present invention.

FIG. 3 is an explanatory cross-sectional view of one embodiment of the laminated sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Amorphous metal thin film layer 2 ... Amorphous metal ribbon 3 ... Non-amorphous metal thin film layer 4 ... Thin film laminated body 5 ... Flexible resin porous reinforcement layer

Claims (6)

[Claims] 1. At least one amorphous metal thin film layer comprising a plurality of amorphous metal ribbons arranged in parallel with each other, and at least one layer laminated thereon.
A non-amorphous metal thin film layer, and at least one porous reinforcing layer made of a flexible resin material and laminated on at least one layer of the amorphous metal thin film and the non-amorphous metal thin film. , Electromagnetic wave shielding laminated sheet. 2. The laminated sheet according to claim 1, wherein the amorphous metal laminate is formed by laminating and integrating a plurality of amorphous metal thin film layers. 3. The laminated sheet according to claim 1, wherein the non-amorphous metal layer is formed by laminating and integrating a plurality of non-amorphous metal thin film layers. 4. The laminated sheet according to claim 1, wherein at least one of the amorphous metal thin film and the non-amorphous metal thin film has a plating layer made of a conductive metal material. 5. The laminated sheet according to claim 1, wherein the flexible resin porous reinforcing layer forms at least one outermost surface layer of the laminated sheet. 6. The laminated sheet according to claim 1, wherein the flexible resin porous reinforcing layer is made of polyurethane foam.