Electromagnetic shielding material

Abstract

Provided is an electromagnetic shielding material having improved electromagnetic shielding properties, light weight properties and formability. The present invention relates to an electromagnetic shielding material having a structure in which at least three metal foils are laminated via insulating layers, wherein all of combinations of the metal foils and the insulating layers making up the electromagnetic shielding material satisfy the equation: .sub.Md.sub.Md.sub.R310.sup.3, in which: the symbol .sub.M represents conductivity of each metal foil at 20 C. (S/m); the symbol d.sub.M represents the thickness of each metal foil (m); and the symbol d.sub.R represents the thickness of each insulating layer (m).

Claims

1. An electromagnetic shielding material having a structure in which at least three metal foils are laminated via insulating layers, the electromagnetic shielding material having a thickness of each insulating layer of 80 m or more and a total thickness of the metal foils of from 15 to 150 m, the total thickness of the electromagnetic shielding material being from 50 to 1051 m, wherein, in the case that the metal foils are aluminum, the thickness of each aluminum foil is 20 m or more, wherein every combination of the metal foils and the insulating layers making up the electromagnetic shielding material satisfy the equation: .sub.Md.sub.Md.sub.R310.sup.3, and wherein the minimum value among possible combinations of the metal foils and the insulating layers satisfies the equation: minimum .sub.Md.sub.Md.sub.R4.910.sup.1, in which: the symbol .sub.M represents conductivity of each metal foil at 20 C. (S/m); the symbol d.sub.M represents the thickness of each metal foil (m); and the symbol d.sub.R represents the thickness of each insulating layer (m).

2. The electromagnetic shielding material according to claim 1, wherein the conductivity of each metal foil at 20 C. is 1.010.sup.6 S/m or more.

3. The electromagnetic shielding material according to claim 1, wherein the thickness of each metal foil is from 4 to 100 m.

4. The electromagnetic shielding material according to claim 1, wherein each insulating layer has a relative dielectric constant at 20 C. of from 2.0 to 10.0.

5. The electromagnetic shielding material according to claim 1, wherein the thickness of each insulating layer is 100 m or more.

6. The electromagnetic shielding material according to claim 1, wherein the total thickness of the metal foils is from 15 to 100 m.

7. A covering material or a cladding material for electric and electronic devices, comprising the electromagnetic shielding material according to claim 1.

8. An electric or electronic device comprising the covering material or the cladding material according to claim 7.

9. The electromagnetic shielding material according to claim 1, wherein the thickness of each insulating layer is 500 m or less.

10. The electromagnetic shielding material according to claim 1, wherein each metal foil and each insulating layer are laminated without using an adhesive.

Description

DESCRIPTION OF EMBODIMENTS

(1) (Metal Foil)

(2) Materials of the metal foils for use in the electromagnetic shielding material according to the present invention are not particularly limited, but metal materials with high conductivity are preferred in terms of improving the shielding properties against an alternating magnetic field and an alternating electric field. Specifically, the metal foils may preferably be formed by a metal having conductivity of 1.010.sup.6 S/m (a value at 20 C.; the same will apply hereinafter) or more. The conductivity may preferably be 10.010.sup.6 S/m or more, and still more preferably 30.010.sup.6 S/m or more, and most preferably 50.010.sup.6 S/m or more. Examples of the metal include iron having conductivity of about 9.910.sup.6 S/m, nickel having conductivity of about 14.510.sup.6 S/m, aluminum having conductivity of about 39.610.sup.6 S/m, copper having conductivity of about 58.010.sup.6 S/m, and silver having conductivity of about 61.410.sup.6 S/m. In view of both electric resistivity and costs, aluminum or copper may preferably be used for practical use. All of the metal foils used in the electromagnetic shielding material according to the present invention may be the same metal, or different metals may be used for each layer. Further, alloys of the metals as stated above may be used. Various surface treated layers may be formed on the surface of the metal foil for the purpose of adhesion promotion, environmental resistance, heat resistance and rust prevention.

(3) The metal foils may be subjected to Au plating, Ag plating, Sn plating, Ni plating, Zn plating, Sn alloy plating (SnAg, SnNi, SnCu, and the like), a chromate treatment or like, for example in order to improve environmental resistance and heat resistance that will required when the metal surface is the outermost layer. These treatments may be combined. The Sn plating or the Sn alloy plating may be preferred in terms of costs.

(4) Further, the metal foils may be subjected to the chromate treatment, a roughening treatment, Ni plating or like in order to improve adhesion between the metal foil and the insulating layer. These treatments may be combined. The roughening treatment may be preferred because the adhesion is easily obtained.

(5) Further, it is possible to provide at least one additional metal layer having high relative magnetic permeability in order to improve the shielding effect against the direct current magnetic field. Examples of the additional metal layer having high relative magnetic permeability may include FeNi alloy plating, Ni plating, and the like.

(6) When using the copper foils, copper having higher purity may be preferred because it will improve the shielding performance. The purity may preferably be 99.5% by mass or more, and more preferably 99.8% by mass or more. Examples of the copper foil that can be used include rolled copper foils, electrolytic copper foils, metallized copper foils and the like. Among them, the rolled copper foils may be preferred because they have good flexibility and formability. When alloy elements are added to the copper foil to form a copper alloy foil, the total content of these elements and inevitable impurities may be less than 0.5% by mass. In particular, the copper foil may preferably contain one or more selected from the group consisting of Sn, Mn, Cr, Zn, Zr, Mg, Ni, Si, and Ag in the total amount of 200 to 2000 ppm by mass, in order to improve elongation as compared with a pure copper foil having the same thickness.

(7) The thickness of the metal foils used for the electromagnetic shielding material according to the present invention may preferably be 4 m or more per one foil. If the thickness is less than 4 m, the ductility of the metal foil may be remarkably lowered, leading to insufficient formability of the shielding material. Also, if the thickness of the foils per one foil is less than 4 m, the lamination of a large number of metal foils will be required for obtaining the improved electromagnetic shielding effect, thereby causing a problem of an increase in manufacturing costs. From this viewpoint, the thickness of the metal foils per one foil may preferably be 10 m or more, and more preferably 15 m or more, and still more preferably 20 m or more, and even more preferably 25 m or more, and still more preferably 30 m or more. On the other hand, if the thickness of the foils per one foil exceeds 100 m, the formability will be deteriorated. Therefore, the thickness of the foils may preferably be 100 m or less, and more preferably 50 m or less, and more preferably 45 m or less, and still more preferably 40 m or less.

(8) It is necessary that at least three metal foils are present in the electromagnetic shielding material in terms of ensuring the improved electromagnetic shielding properties while reducing the total thickness of the metal foils. One or two metal foil layers will lead to an increase in the total thickness of the metal foils needed for obtaining the magnetic field shielding property of 30 dB or more in a low frequency region of about 1 MHz frequency and also lead to an increase in the thickness of one metal foil, so that the formability will be adversely affected. Further, the lamination of three or more metal foils significantly improves the shielding effect as compared with the lamination of single metal foil layer or two metal foil layers, even if the total thickness of these metal foils is the same. However, although the lamination of more metal foils tends to improve the electromagnetic shielding properties, the increased number of the laminated metal foils increase the number of lamination steps, which will lead to an increase in manufacturing costs and will not provide further improvement of the shielding effect. Therefore, the number of the metal foils in the shielding material may preferably be 5 or less, and more preferably 4 or less.

(9) Therefore, in one embodiment of the electromagnetic shielding material according to the present invention, the total thickness of the metal foils may be from 15 to 150 m, or 100 m or less, or 80 m or less, or 60 m or less.

(10) (Insulating Layer)

(11) In the electromagnetic shielding material according to the present invention, significant improvement of the electromagnetic shielding effect by laminating a plurality of metal foils can be obtained by interposing the insulating layer between the metal foils. Although even if the metal foils directly overlap with each other, the shielding effect may be improved due to an increase in the total thickness of the metal foils, the significant improvement effect cannot be obtained. The reason would be that the presence of the insulating layer between the metal foils increases the number of reflections of electromagnetic waves to attenuate the electromagnetic waves.

(12) The insulating layer having a large difference in impedance from the metal layer may be preferred in order to obtain the improved electromagnetic shielding effect. To generate the large impedance difference, smaller relative dielectric constant of the insulating layer may be required. More specifically, the relative dielectric constant may preferably be 10 (a value at 20 C.; the same will apply hereinafter) or less, and more preferably 5.0 or less, and still more preferably 3.5 or less. In principle, the relative dielectric constant is never smaller than 1.0. In a generally available material, the relative dielectric constant is at least about 2.0. Even if the relative dielectric constant is lowered to be close to 1.0, the increase in the shielding effect is limited, whereas a special and expensive material must be used. In view of the balance between the cost and the effect, the relative dielectric constant may preferably be 2.0 or more, and more preferably 2.2 or more.

(13) Specific examples of the material making up the insulating layer may include glass, metal oxides, papers, natural resins, synthetic resins and the like. Among them, the synthetic resins may be preferred in terms of processability. The materials may contain fiber reinforcing materials such as carbon fibers, glass fibers and aramid fibers. In terms of availability and processability, the synthetic resins include olefin resins such as polyesters, polyethylene and polypropylene, including PET (polyethylene terephthalate), PEN (polyethylene naphthalate) and PBT (polybutylene terephthalate); polyamides, polyimides, liquid crystal polymers, polyacetals, fluororesins, polyurethanes, acryl resins, epoxy resins, silicone resins, phenol resins, melamine resins, ABS resin, polyvinyl alcohol, urea resins, polyvinyl chloride, polycarbonates, polystyrenes, styrene butadiene rubbers and the like. Among them, PET, PEN, polyamides, and polyimides may be preferred in terms of processability and costs. The synthetic resins may be elastomers such as urethane rubbers, chloroprene rubbers, silicone rubbers, fluororubbers, styrene-based elastomers, olefinic elastomers, vinyl chloride-based elastomers, urethane-based elastomers, amide-based elastomers and the like. Furthermore, the synthetic resin itself may play a role of an adhesive, in which case the metal foils will be laminated via the adhesive. Examples of the adhesive include, but not limited to, acrylic resin-based adhesives, epoxy resin-based adhesives, urethane-based adhesives, polyester-based adhesives, silicone resin-based adhesive, vinyl acetate-based adhesives, styrene butadiene rubber-based adhesives, nitrile rubber-based adhesives, phenol resin-based adhesives, cyanoacrylate-based adhesives, and the like. The urethane-based, polyester-based, and vinyl acetate-based adhesives may be preferred in terms of ease of manufacture and costs.

(14) The resin material can be laminated in the form of film or fiber. Although the resin layer may be formed by applying an uncured resin composition to the metal foil and then curing it, it is preferable to use a resin film that can be attached to the metal foil in terms of easy manufacturing. In particular, a PET film may be suitably used. More particularly, the use of a biaxially stretched film as the PET film can increase the strength of the shielding material.

(15) The thickness of the insulating layers is not particularly limited, but since the thickness of one insulating layer of less than 4 m tends to decrease a (elongation) breaking strain of the shielding material, the thickness of one insulating layer may preferably be 4 m or more, and more preferably 7 m or more, and more preferably 10 m or more, and still more preferably 20 m or more, and still more preferably 40 m or more, and even more preferably 80 m or more, and still more preferably 100 m or more. On the other hand, the thickness of one insulating layer more than 600 m also tends to decrease the (elongation) breaking strain of the shielding material. Therefore, the thickness of one insulating layer may preferably be 600 m or less, and more preferably 500 m or less.

(16) (Electromagnetic Shielding Material)

(17) The symbols used herein are defined as follows:

(18) .sub.M: conductivity of the metal foil at 20 C. (S/m);

(19) d.sub.M: thickness of the metal foil (m);

(20) Z.sub.R: impedance of the insulating layer ()=Z.sub.0(1/.sub.R);

(21) .sub.R: relative dielectric constant of the insulating layer at 20 C.;

(22) .sub.R: propagation constant=j2 (.sub.R/); j is the imaginary unit;

(23) : wavelength (m): 300 m at 1 MHz;

(24) d.sub.R: thickness of the insulating layer (m);

(25) Z.sub.o: impedance in vacuum=377.

(26) The electromagnetic shielding material according to the present invention can be manufactured by laminating the above-mentioned metal foils and the insulating layers. In this case, it is important to select the metal foils and the insulating layers such that all of combinations of the metal foils and the insulating layers making up the electromagnetic shielding material satisfy the equation: .sub.Md.sub.Md.sub.R310.sup.3, in terms of significantly improving the electromagnetic shielding effect.

(27) The shielding properties can be represented by the following relationship using the four-terminal matrix:

(28) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.1\right)\end{array}$

(29) in which E.sub.x.sup.i and H.sub.x.sup.i represent an electric field and a magnetic field of an incident wave, respectively; and E.sub.x.sup.t and H.sub.x.sup.t represent an electric field and a magnetic field of a transmitted wave.

(30) In this case, the shielding effect (SE) can be expressed by the following equation using the Schelkunov method:
SE=20 log|(a+b/Z.sub.0+cZ.sub.0+d)/2|(Eq. 2)

(31) When using the metal foil as the shielding material, a may be equal to 1, b may be equal to 0, c may be equal to .sub.Md.sub.M, and d may be equal to 1. Substituting these into the equation 1 yields the following equation:

(32) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}1& 0\\ {}_M{d}_M& 1\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.3\right)\end{array}$

(33) When using the insulating layer as the shielding material, a may be equal to 1, b may be equal to Z.sub.R.sub.Rd.sub.R, c may be equal to .sub.Rd.sub.R/Z.sub.R and d may be equal to 1. Substituting these into the equation 1 yields the following equation:

(34) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}1& Z_R{}_R{d}_R\\ {}_R{d}_R/Z_R& 1\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.4\right)\end{array}$

(35) Furthermore, the shielding properties when the shielding materials are laminated can be theoretically obtained from the product of the four-terminal matrices corresponding to respective layers. For example, when the shielding material is formed by a laminated structure of metal (M1)/resin (R1)/metal (M2), the incident and transmitted waves can be expressed by the following equation:

(36) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}1& 0\\ {}_{M1}{d}_{M1}& 1\end{array}\right)\left(\begin{array}{cc}1& Z_{R1}{}_{R1}{d}_{R1}\\ {}_{R1}{d}_{R1}/Z_{R1}& 1\end{array}\right)\left(\begin{array}{cc}1& 0\\ {}_{M2}{d}_{M2}& 1\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)=\left(\begin{array}{cc}1+Z_{R1}{}_{R1}{d}_{R1}{}_{M2}{d}_{M2}& Z_{R1}{}_{R1}{d}_{R1}\\ \begin{array}{c}{}_{M1}{d}_{M1}+\\ Z_{R1}{}_{R1}{d}_{R1}{}_{M1}{d}_{M1}{}_{M2}{d}_{M2}+\\ {}_{R1}{d}_{R1}/Z_{R1}+{}_{M2}{d}_{M2}\end{array}& 1+Z_{R1}{}_{R1}{d}_{R1}{}_{M1}{d}_{M1}\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.5\right)\end{array}$

(37) Further, when the shielding material is formed by a laminated structure of metal (M1)/resin (R1)/metal (M2)/resin (R2)/metal (M3), the incident and transmitted waves can be expressed by the following equation:

(38) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}1& 0\\ {}_{M1}{d}_{M1}& 1\end{array}\right)\left(\begin{array}{cc}1& Z_{R1}{}_{R1}{d}_{R1}\\ {}_{R1}{d}_{R1}/Z_{R1}& 1\end{array}\right)\left(\begin{array}{cc}1& 0\\ {}_{M2}{d}_{M2}& 1\end{array}\right)\left(\begin{array}{cc}1& Z_{R2}{}_{R2}{d}_{R2}\\ {}_{R2}{d}_{R2}/Z_{R2}& 1\end{array}\right)\left(\begin{array}{cc}1& 0\\ {}_{M3}{d}_{M3}& 1\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.6\right)\end{array}$

(39) When the formula is developed, the following equation is obtained:

(40) $\begin{array}{cc}\left(\begin{array}{c}{E}_x^t\\ H_x^t\end{array}\right)=\left(\begin{array}{cc}A& B\\ C& D\end{array}\right)\left(\begin{array}{c}{E}_x^i\\ H_x^i\end{array}\right)& \left(\mathrm{Eq}.7\right)\end{array}$

(41) in which A, B, C and D are as follows:
A=1+Z.sub.R1.sub.R1d.sub.R1.sub.M2d.sub.M2+Z.sub.R2.sub.R2d.sub.R2.sub.M3d.sub.M3+Z.sub.R1.sub.R1d.sub.R1.sub.M3d.sub.M3+Z.sub.R1.sub.R1d.sub.R1Z.sub.R2.sub.R2d.sub.R2.sub.M2d.sub.M2.sub.M3d.sub.M3;
B=Z.sub.R2.sub.R2d.sub.R2+Z.sub.R1.sub.R1d.sub.R1Z.sub.R2.sub.R2d.sub.R2.sub.M2d.sub.M2+Z.sub.R1.sub.R1d.sub.R1;
C=.sub.M1d.sub.M1+.sub.M2d.sub.M2+.sub.M3d.sub.M3+.sub.R1d.sub.R1/Z.sub.R1+.sub.R2d.sub.R2/Z.sub.R2+Z.sub.R1.sub.R1d.sub.R1.sub.M1d.sub.M1+Z.sub.R1.sub.R1d.sub.R1.sub.M1d.sub.M1.sub.M3d.sub.M3+Z.sub.R1.sub.R1d.sub.R1Z.sub.R2.sub.R2d.sub.R2.sub.M1d.sub.M1.sub.M2d.sub.M2.sub.M3d.sub.M3+Z.sub.R2.sub.R2d.sub.R2.sub.M2d.sub.M2.sub.M3d.sub.M3+Z.sub.R2.sub.R2d.sub.R2.sub.M3d.sub.M3.sub.R1d.sub.R1/Z.sub.R1;
D=Z.sub.R2.sub.R2d.sub.R2.sub.M1d.sub.M1+Z.sub.R2.sub.R2d.sub.R2.sub.M1d.sub.M1.sub.M2d.sub.M2+Z.sub.R2.sub.R2d.sub.R2.sub.M2d.sub.M2+Z.sub.R1.sub.R1d.sub.R1.sub.M1d.sub.M1+Z.sub.R2.sub.R2d.sub.R2.sub.R1d.sub.R1/Z.sub.R1.

(42) It is theoretically understood from the above examples that the shielding effect of the laminate of the metal foils and the insulating layers can be improved by increasing the .sub.Md.sub.MZ.sub.R.sub.Rd.sub.R for all combinations of the metal foils and the insulating layers to be used. However, as described, for example in Kenichi Hatakeyama at. al., (Electromagnetic Shielding Course for Biginner), Kagakujoho Shuppan Co., Ltd. (2013), p. 56, it was conventionally believed that the Z.sub.R.sub.Rd.sub.R was extremely small to be approximated to zero in the low frequency region. Therefore, according to this idea, the .sub.Md.sub.MZ.sub.R.sub.Rd.sub.R was also a parameter that was approximated to be zero. In contrast, the present inventors have found that the d.sub.R, .sub.M and d.sub.M are adjusted by combining suitable metal foils and suitable insulating layers, so that the .sub.Md.sub.MZ.sub.R.sub.Rd.sub.R becomes a large value in such an extent that it cannot be approximated to zero, which has a significant effect even in the low frequency region.

(43) The present inventors have repeated the experiments of the shielding effect of the laminates of the metal foils and the insulating layers, and found that the .sub.Md.sub.Md.sub.R has a significant effect even in the low frequency region of about 1 MHz, and that the shielding effect can be effectively improved by selecting the metal foils and the insulating layers such that all of the combinations of the metal foils and the insulating layers making up the electromagnetic shielding material satisfy the equation: .sub.Md.sub.Md.sub.R310.sup.3. All of the combinations of the metal foils and the insulating layers making up the electromagnetic shielding material may preferably satisfy .sub.Md.sub.Md.sub.R110.sup.2, and more preferably .sub.Md.sub.Md.sub.R410.sup.2, and more preferably .sub.Md.sub.Md.sub.R810.sup.2, and even more preferably .sub.Md.sub.Md.sub.R?0.110.sup.1.

(44) Although no particular upper limit is set to the .sub.Md.sub.Md.sub.R, all of the combinations of the metal foils and the insulating layers making up the electromagnetic shielding material may generally satisfy .sub.Md.sub.Md.sub.R10, and typically .sub.Md.sub.Md.sub.R1, in terms of the thickness or materials to be used.

(45) The laminate may be produced by using an adhesive between the insulating layer and the metal foil, or thermocompression-bonding the insulating layer to the metal foil without using the adhesive. Although the laminate may be formed by simply laminating the metal foils and the insulating layers without using the adhesive, at least end portions (for example, each side when the shielding material is in the form of quadrangle) may preferably be bonded by the adhesive or thermocompression bonding, in view of the integrity of the electromagnetic shielding material. However, from the viewpoint of not applying extra heat to the insulating layers, it may be preferable to use the adhesive. The same adhesives as described above may be used, including, but not limited to, acryl resin-based adhesives, epoxy resin-based adhesives, urethane-based adhesives, polyester-based adhesives, silicone resin-based adhesives, vinyl acetate-based adhesives, styrene butadiene rubber-based adhesives, nitrile rubber-based adhesives, phenol resin-based adhesives, cyanoacrylate-based adhesives and the like. Among them, the urethane-based adhesives, the polyester-based adhesives and the vinyl acetate-based adhesives may be preferred in terms of easy manufacturing and costs.

(46) The thickness of the adhesive layer may preferably be 6 m or less. If the thickness of the adhesive layer exceeds 6 m, only the metal foils tend to be broken after being laminated into the metal foil composite. However, when the adhesive layer also serves as the insulating layer, the thickness of the adhesive layer may not be limited thereto, and may be the thickness as described above in the section of the insulating layer.

(47) The electromagnetic shielding material according to the present invention should have a structure in which at least three metal foils are laminated via the insulating layers. Examples of the laminated structure having the requirement are as follows. It should be noted that the layer represented by the parenthesis means that the layer may be optionally added.

(48) (1) (insulating layer)/metal foil/insulating layer/metal foil/insulating layer/metal layer/(insulating layer);

(49) (2) (insulating layer)/metal foil/insulating layer/metal foil/insulating layer/metal foil/insulating layer/metal foil/(insulating layer).

(50) In the items (1) and (2), one metal foil can be formed by laminating a plurality of metal foils without interposing the insulating layer, and one insulating layer can also be formed by laminating a plurality of insulating layers without interposing the metal foil.

(51) Further, it is also possible to provide at least one layer other than the insulating layers and the metal foils.

(52) In one embodiment of the electromagnetic shielding material according to the present invention, the total thickness of the electromagnetic shielding material may be from 50 to 1500 m, or 1000 m or less, or 600 m or less, or 400 m or less, or 200 m or less.

(53) The electromagnetic shielding material according to the present invention can be used for various electromagnetic shielding applications such as covering materials or cladding materials, in particular for electric and electronic devices (for example, inverters, communication devices, resonators, electron tubes, discharge lamps, electric heating devices, electric motors, generators, electronic components, printed circuits, medical devices and the like), covering materials for harnesses and communication cables connected to the electric and electronic devices, electromagnetic shielding sheets, electromagnetic shielding panels, electromagnetic shielding bags, electromagnetic shielding boxes, electromagnetic shielding chambers, and the like.

(54) According to one embodiment of the electromagnetic shielding material according to the present invention, the electromagnetic shielding material may have a magnetic field shielding property (a degree of an attenuated signal on a receiving side) of 36 dB or more at 1 MHz, and preferably a magnetic field shielding property of 40 dB or more, and more preferably a magnetic field shielding property of 50 dB or more, and more preferably a magnetic field shielding property of 60 dB or more, and even more preferably a magnetic field shielding property of 70 dB or more, for example a magnetic field shielding property of 36 to 90 dB. In the present invention, the magnetic field shielding property is measured by a KEC method. The KEC method refers to an electromagnetic shielding property measurement method in KEC Electronic Industry Development Center.

EXAMPLE

(55) Examples of the present invention are described below together with comparative examples, which are provided for a better understanding of the present invention and its advantages, and are not intended to limit the invention.

(56) Each metal foil and each insulating film as shown in Table 1 were prepared and electromagnetic shielding materials of Examples and Comparative Examples were produced. Each symbol described in Table 1 has the following meaning:

(57) Cu: rolled copper foil (conductivity at 20 C.: 58.010.sup.6 S/m);

(58) Al: aluminum foil (conductivity at 20 C.: 39.610.sup.6 S/m);

(59) Electrolytic Cu: electrolytic copper foil (conductivity at 20 C.: 56.010.sup.6 S/m);

(60) Ni: nickel foil (conductivity at 20 C.: 14.510.sup.6 S/m);

(61) Fe: soft iron foil (conductivity at 20 C.: 9.910.sup.6 S/m);

(62) sus: stainless steel foil (conductivity at 20 C.: 1.410.sup.6 S/m);

(63) PI: polyimide film (relative dielectric constant at 20 C.: 3.5);

(64) PET: polyethylene terephthalate film (relative dielectric constant at 20 C.: 3.0);

(65) PTFE: polytetrafluoroethylene film (relative dielectric constant at 20 C.: 2.1);

(66) PA: polyamide film (relative dielectric constant at 20 C.: 6.0); and

(67) Void: space separated between metal foils by air (relative dielectric constant at 20 C.: 1.0).

Comparative Examples 1 and 2: Magnetic Field Shield Effect of One Metal Foil

(68) The magnetic field shielding effect of a single layer was examined for the rolled copper foil (thickness: 150 m) and the aluminum foil (thickness: 300 m). The prepared metal material was set to a magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.) and the magnetic field shielding effect was evaluated at a frequency of 1 MHz and at 20 C. according to the KEC method.

Comparative Example 3: Magnetic Field Shielding Effect when Three Metal Foils are Laminated

(69) Three rolled copper foils (each thickness of 33 m) were simply laminated without using an adhesive and set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Comparative Example 4: Magnetic Field Shielding Effect when Two Metal Foils are Laminated Via an Insulating Layer

(70) A polyethylene terephthalate (PET) film having a thickness of 250 m as the insulating layer and rolled copper foils each having a thickness of 7 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as shown in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.) and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Comparative Example 5: Magnetic Field Shielding Effect when Two Metal Foils are Laminated Via an Insulating Layer

(71) A polyethylene terephthalate (PET) film having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 8 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Comparative Example 6: Magnetic Field Shielding Effect when Two Metal Foils are Placed Via an Air Layer or Void

(72) Using air as the insulating layer and two aluminum foils having thicknesses of 6 m and 30 m, respectively, an electromagnetic shielding material having a laminated structure as described in Table 1 was prepared. In this example, the two aluminum foils were parallelly arranged at a space of 50 m in air by interposing a copper plate having a large square opening in the center between the two aluminum foils. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Comparative Example 7: Magnetic Field Shielding Effect when Three Metallic Foil are Laminated Via Insulating Layers: MdMdR<3103

(73) Polyimide (PI) films each having a thickness of 9 m as the insulating layer and aluminum foils each having a thickness of 6 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 1

(74) Polyimide (PI) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminating without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 2

(75) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and aluminum foils each having a thickness of 20 m as the metal foil were simply laminating without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 3

(76) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and electrolytic copper foils each having a thickness of 30 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 4

(77) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and nickel foils each having a thickness of 50 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 5

(78) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and soft iron foils each having a thickness of 50 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 6

(79) Polytetrafluoroethylene (PTFE) films each having a thickness of 500 m as the insulating layer and stainless steel foils each having a thickness of 50 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 7

(80) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 6 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 8

(81) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 9

(82) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and rolled copper foils having a thickness of 33 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 10

(83) Polyethylene terephthalate (PET) films each having a thickness of 9 m as the insulating layer and rolled copper foils having thicknesses of 7 m and 33 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 11

(84) Polyethylene terephthalate (PET) films each having a thickness of 500 m as the insulating layer and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 12

(85) Polytetrafluoroethylene (PTFE) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 13

(86) Polyamide (PA) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 14

(87) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer, and rolled copper foils each having a thickness of 33 m and a nickel foil having a thickness 30 m were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding, material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 15

(88) Polyethylene terephthalate (PET) films each having a thickness of 12 m as the insulating layer, and rolled copper foils each having a thickness of 12 m and rolled copper foils each having a thickness of 17 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 16

(89) Polyethylene terephthalate (PET) films each having a thickness of 100 m as the insulating layer and rolled copper foils each having a thickness of 12 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

Example 17

(90) Polyethylene terephthalate (PET) films each having a thickness of 9 m as the insulating layer and aluminum foils each having a thickness of 20 m as the metal foil were simply laminated without using an adhesive to prepare an electromagnetic shielding material having a laminated structure as described in Table 1. The electromagnetic shielding material was set to the magnetic field shielding effect evaluation apparatus (Model TSES-KEC available from Techno Science Japan Co., Ltd.), and the magnetic field shielding effect was evaluated by the same method as described in Comparative Example 1.

(91) In the above evaluation, the conductivity of the metal foil was measured by the double bridge method according to JIS C2525: 1999. The relative dielectric constant was measured by the B method according to JIS C2151: 2006.

(92) The results are shown in Table 1. The Minimum .sub.Md.sub.Md.sub.R in Table 1 represents a value for a combination of the metal foils and the insulating layers having the smallest .sub.Md.sub.Md.sub.R among all combinations of the metal foils and insulating layers used, in each experimental example. As can be seen from the results of Comparative Examples 1 and 2, the single metal foil only provides the shielding effect of about 31 to 33 dB, even if the thickness of the metal foil is more than 100 m. As can be seen from the results of Comparative Example 3, no significant improvement of the shielding effect is not observed if only the metal foils are laminated. As can be seen from the results of Comparative Examples 4 to 6, no significant improvement of the shielding effect is not observed if the two metal foils are laminated via the insulating layer. Also, as can be seen from the results of Comparative Example 7, even if the three metal foils are laminated via the insulating layers, the insufficient .sub.Md.sub.Md.sub.R only provides limited improvement of the shielding effect.

(93) However, as can be seen from the results of Examples 1 to 17 in which the three metal foils are laminated via the insulating layers and the .sub.Md.sub.Md.sub.R is 310.sup.3 or more for all of the combinations of the metal foils and the insulating layers, the shielding effect is significantly improved. For example, when comparing Example 1 with Comparative Example 1, the latter required the thickness of 150 m for the single copper foil to obtain the shielding effect of 31.1 dB, whereas the former increased the shielding effect by about 26 dB even if the thickness of the copper foil was about of that of Comparative Example 1. Further, when comparing Example 2 with Comparative Example 2, the latter required the thickness of 300 m for the single aluminum foil to obtain the shielding effect of 33.1 dB, whereas the former increased the shielding effect by about 19 dB even if the thickness of the aluminum foil was of that of Comparative Example 2.

(94) Further, it is understood that among Examples, the laminate having the higher minimum .sub.Md.sub.Md.sub.R value for the combination of the metal foils and the insulating layers can produce the higher shielding effect while reducing the total thickness of the metal foils. For example, it is understood that the total thickness of the copper foils for all Examples 10 to 13 is 51 m, but the shielding effects are significantly different depending on the values of the minimum .sub.Md.sub.Md.sub.R

(95) TABLE-US-00001 TABLE 1 1st 1st 2nd 2nd 3rd 3rd 4th Metal Insulat- Metal Insulat- Metal Insulat- Metal layer ing Layer layer ing Layer layer ing Layer layer Shielding Thick- Thick- Thick- Thick- Thick- Thick- Thick- Effect ness ness ness ness ness ness ness Minimum at 1 MHz Laminated Structure m m m m m m m .sub.Md.sub.Md.sub.R dB Example 1 Cu/PI/Cu/PI/Cu 17 100 17 100 17 9.9E02 57.6 Example 2 Al/PET/Al/PET/Al 20 100 20 100 20 7.9E02 52.1 Example 3 Electrolytic Cu/PET/Electrolytic 30 100 30 100 30 1.7E01 71.1 Cu/PET/Electrolytic Cu Example 4 Ni/PET/Ni/PET/Ni 50 100 50 100 50 7.3E02 50.0 Example 5 Fe/PET/Fe/PET/Fe 50 100 50 100 50 5.0E02 41.0 Example 6 sus/PTFE/sus/PTFE/sus 50 500 50 500 50 3.5E02 30.8 Example 7 Cu/PET/Cu/PET/Cu 6 100 6 100 6 3.5E02 33.5 Example 8 Cu/PET/Cu/PET/Cu 17 100 17 100 17 9.9E02 57.6 Example 9 Cu/PET/Cu/PET/Cu 33 100 33 100 33 1.9E01 74.4 Example 10 Cu/PET/Cu/PET/Cu 7 9 33 9 33 3.7E03 30.1 Example 11 Cu/PET/Cu/PET/Cu 17 500 17 500 17 4.9E01 85.1 Example 12 Cu/PTFE/Cu/PTFE/Cu 17 100 17 100 17 9.9E02 57.6 Example 13 Cu/PA/Cu/PA/Cu 17 100 17 100 17 9.9E02 57.6 Example 14 Cu/PET/Ni/PET/Cu 33 100 30 100 33 4.4E02 62.1 Example 15 Cu/PET/Cu/PET/Cu/PET/Cu 12 12 17 12 17 12 12 8.4E03 32.7 Example 16 Cu/PET/Cu/PET/Cu/PET/Cu 12 100 12 100 12 100 12 7.0E02 61.6 Example 17 Al/PET/Al/PET/Al/PET/Al 20 9 20 9 20 9 20 7.1E03 36.8 Comp. 1 Cu 150 31.1 Comp. 2 Al 300 33.1 Comp. 3 Cu/Cu/Cu 33 33 33 27.6 Comp. 4 Cu/PET/Cu 7 250 7 28.2 Comp. 5 Cu/PET/Cu 8 100 8 22.9 Comp. 6 Al/Void/Al 6 50 30 26.6 Comp. 7 Al/PI/Al/PI/Al 6 9 6 9 6 2.1E03 11.8