WO2004032590A1

WO2004032590A1 - Electromagnetic shielding material provided with shielding layer

Info

Publication number: WO2004032590A1
Application number: PCT/JP2003/012293
Authority: WO
Inventors: Shigeki Miura
Original assignee: Fcm Co., Ltd.
Priority date: 2002-10-01
Filing date: 2003-09-25
Publication date: 2004-04-15
Also published as: JP2004128158A; AU2003266635A1; TW200417309A; TWI225768B

Abstract

An electro magnetic shielding material characterized in that a shielding layer (103) having a thickness of 1 to 8 μm and made of at lease one kind selected from the group consisting of Ni, Fe, Co, Ti, Zn, Cr, Sn, Cu and alloys containing at lease one of those metals is formed on a surface of a polymer film (101) in the form of a single layer or two or more layers by a sputtering method, a vapor deposition method or a plating method.

Description

Electromagnetic wave shielding material with shield layer

The present invention relates to an electromagnetic wave shielding material. More specifically, it can be attached to various communication devices, computers, home appliances, automobiles, electric vehicles, etc. to effectively shield electromagnetic waves such as noise generated from them from being emitted outside, etc. The present invention relates to an electromagnetic shielding material that effectively shields the electromagnetic wave emitted to the inside from the source of Background art

Conventionally, it is known that electromagnetic waves having various frequencies are generated as noise or the like from communication devices, computers, home appliances, automobiles, electric wires and the like. These electromagnetic waves are known to cause malfunction of other electronic products and to have an adverse effect on the human body. Therefore, various methods have been attempted to shield them. For example, rolled iron bands and ferrites have long been used as shielding measures for low frequency electromagnetic waves, but since these are heavy and bulky, they should be applied to various products that have become lighter and thinner in recent years. Was difficult. On the other hand, as a measure against shielding of high frequency electromagnetic waves, a synthetic resin film laminated with copper foil has been used, but this can be made thinner to some extent compared with the above-mentioned iron band etc. However, there is a limit in manufacturing copper foil thinly, and it is difficult to manufacture inexpensive copper foils with a thickness of 9 μπι or less. For this reason, in the case where it is used for applications that require flexibility, such as when used in recent light and thin, miniaturized products, further improvement of the performance has been desired. Furthermore, none of these conventional shielding measures can cope with both low frequency and high frequency simultaneously.

Japanese Patent Application Laid-Open No. 2000-215 discloses an electromagnetic wave shielding material in which a shielding layer made of metal is formed on a polymer film by a vacuum evaporation method. This is because the shield layer is formed by vacuum evaporation. It was difficult to form a thick shield layer, and a sufficient shield effect could not be achieved.

Further, Japanese Patent Application Laid-Open No. 20-1464 describes an electromagnetic wave shielding material in which an electrode film is formed on the outermost layer of a multilayer structure consisting of a conductive layer and a low conductive layer. However, this is because the electrode film of the outermost layer is formed only by sputtering or the like utilizing vacuum processing, so that it is difficult to form a thick shield layer, and achieving a sufficient serialode effect. I could not

Moreover, in JP-A-2001-2006, there is described an electromagnetic wave shielding material in which a first metal layer is formed by physical vapor deposition and a second metal layer is electroplated thereon. ing. However, this is because the first metal layer does not have a sufficient antioxidative effect, and the second metal layer may be deteriorated due to oxidation and peeled off, so that a sufficient shielding effect could not be achieved.

Further, JP-A-2002-6861 describes an electromagnetic wave shielding material in which a plating film is formed on the surface of a base material made of a resin or the like. However, since this is a direct plating film formed on the base material, the adhesion between the base material and the plating film is weak, and it is possible to achieve a sufficient shielding effect by peeling off or the like. I couldn't. Disclosure of the invention

The present invention has been made in view of the above-mentioned present conditions, and the purpose thereof is to make it flexible by making its thickness thin so as to be compatible with various products which are reduced in thickness and size. Another object of the present invention is to provide an electromagnetic wave shielding material having the following characteristics. Another object of the present invention is to provide an electromagnetic shielding material capable of shielding simultaneously both low frequency and high frequency electromagnetic waves as desired. The inventors of the present invention have conducted intensive studies to solve the above problems. It is difficult to solve the above problems by the conventional method of forming a shield layer, and it is necessary to form a shield layer by a completely new forming method. The present invention was finally accomplished by continuing the research based on this finding.

That is, in the electromagnetic wave shielding material of the present invention, the thickness is 1 to 8; um, and a shield selected from the group consisting of Ni, Fe, Co, Ti, Zn, Cr, Sn, Cu and an alloy containing at least one of these metals. The layer is characterized in that one or two or more layers are formed by any of sputtering, vapor deposition, and plating.

Moreover, the electromagnetic wave shielding material of the present invention has a thickness of 1 μπι or less between the surface of the polymer film and the shielding layer, and Ni, Co, Zn, Fe, Cu, Ti, Cr, The underlayer consisting of one selected from the group consisting of oxides, nitrides of these metals and alloys containing at least one of these metals is either a single layer or a double layer by either a sputtering method or an evaporation method. The above can be formed.

Moreover, the electromagnetic wave shielding material of the present invention has a thickness of 1 m or less between the surface of the polymer film and the shielding layer, and Ni, Co, Zn, Ti, Cr, and the metals thereof. An antioxidant, an oxide, a nitride and an alloy selected from at least one of these metals, which is selected from the group consisting of an oxide, a nitride, and an alloy containing at least one of these metals, which is formed by either sputtering or vapor deposition; A base layer having a thickness of 1 μm or less, and one selected from the group consisting of Ni, Co, Fe, Cu, and an alloy containing at least one of these metals Underlying layers that function as electrodes formed by either the sputtering method or the vapor deposition method may be formed in this order, respectively.

Further, in the electromagnetic wave shielding material of the present invention, the shielding layer can be made of one selected from the group consisting of Ni, Co, Fe, and an alloy containing at least one of these metals.

Further, in the electromagnetic wave shielding material of the present invention, the shielding layer may be made of Cu.

Further, in the electromagnetic wave shielding material of the present invention, the shielding layer is divided into two layers, one of which is made of Cu, and the other of which is Ni, Co, Fe and at least one of these metals. It can be made of one selected from the group consisting of alloys containing seeds.

Further, in the electromagnetic shielding material of the present invention, the shielding layer is divided into three layers and formed. A layer consisting of Cu is formed as an intermediate layer of the three layers, and a layer consisting of Ni, Co, Fe and an alloy containing at least one of these metals is formed on the upper and lower sides of the layer. It is possible to form one selected layer. Moreover, the electromagnetic wave shielding material of the present invention has a thickness of 1 μm or less on any one surface of the polymer film, and Ni, Co, Zn, Fe, Cu, Ti, Cr, and these. The underlayer consisting of at least one selected from the group consisting of oxides, nitrides and alloys containing at least one of these metals is one or two or more layers by a sputtering method or a vapor deposition method. A first shield layer formed of one selected from the group consisting of Ni, Co, Fe, and an alloy containing at least one of these metals is formed thereon; A second shield layer is formed, and the other surface of the polymer film has a thickness of 1 m or less, and Ni, Co, Zn, Fe, Cu, Ti, Cr, , These metals oxides, nitrides and these metals less One or two or more underlayers formed of one or more layers selected from the group consisting of one or more alloys are formed by sputtering or vapor deposition, and Ni, Co, and F are formed thereon. The third shield layer may be formed of one selected from the group consisting of e and an alloy containing at least one of these metals.

In addition, the electromagnetic wave shielding material of the present invention has a thickness of 1 or less on any one surface of the polymer film, and Ni, Co, Zn, Fe, Cu, Ti, Cr, and these. The underlayer consisting of at least one selected from the group consisting of oxides, nitrides and alloys containing at least one of these metals is one or two or more layers by a sputtering method or a vapor deposition method. A first shield layer formed of Cu and further comprising a first shield layer selected from the group consisting of Ni, Co, Fe and an alloy containing at least one of these metals. And a thickness of 1 μΐ or less and Ni, Co, Zn, Fe, Cu, Ti, Cr, on the other surface of the polymer film. Less of these metal oxides, nitrides and metals One or two or more underlayers formed of one or more layers selected from the group consisting of one or more alloys are formed by sputtering or vapor deposition, and Ni, Co, and F are formed thereon. e and these The third shield layer may be formed of one selected from the group consisting of an alloy containing at least one of the metals listed above.

Further, in the electromagnetic wave shielding material of the present invention, on the shield layer made of Cu, a discoloration prevention layer made of Sn, Ni, Co, Ti, Zn or Cr should be formed. Can. Brief description of the drawings

FIG. 1 is a schematic cross-sectional view of an electromagnetic wave shielding material in which a base layer is formed on the surface of a polymer film and a shield layer is formed thereon.

Fig. 2 shows a schematic cross section of an electromagnetic wave shielding material in which an undercoating layer having an antioxidative effect is formed on the surface of a polymer film, a second undercoating layer acting as an electrode is formed thereon, and a shield layer is formed thereon. FIG. '

In FIG. 3, an undercoat layer having an antioxidant effect is formed on the surface of the polymer film, a second undercoat layer acting as an electrode is formed thereon, a shield layer is formed thereon, and a color change is further formed thereon It is a schematic sectional drawing of the electromagnetic wave shielding material which formed the prevention layer. FIG. 4 is a schematic cross-sectional view of an electromagnetic wave shielding material in which an undercoat layer having an antioxidant effect is formed on the surface of a polymer film, and three shield layers are formed thereon.

FIG. 5 is a schematic cross-sectional view of an electromagnetic wave shielding material in which shield layers are formed on both sides of a polymer film. BEST MODE FOR CARRYING OUT THE INVENTION

The electromagnetic wave shielding material of the present invention basically has a configuration in which a shielding layer is formed on the surface of a polymer film. Each configuration will be described below.

As a polymer film used for this invention, a synthetic resin film, a thermoplastic elastomer 1 film, a rubber film etc. can be mentioned, for example. Examples of synthetic resin films include synthetics of PET, PEN, acrylic, nylon, polyethylene, polypropylene, polypropylene chloride, polyimide, liquid crystal polymer, epoxy, etc. The film which consists of synthetic resin can be mentioned. Examples of the thermoplastic elastomer film include films made of a thermoplastic elastomer such as styrene-based, polyvinyl chloride-based, lefenic-based, urethane-based, ester-based, and amide-based. Further, as the rubber film, for example, in addition to natural rubber, synthesis of butadiene rubber, isopropyl rubber, chloroprene rubber, styrene-butadiene rubber, etoril rubber, petryl rubber, ethylene-propylene rubber, atalinole rubber, urethane rubber, fluororubber, silicone rubber, etc. A film made of rubber can be mentioned. The types of synthetic resin, thermoplastic elastomer or rubber listed here are merely illustrative and are not limited thereto. Moreover, as a film as used in the field of this invention, what has a sheet-like shape with a thickness of 2 to 200 / im, preferably 4 to 30 μπι is included. If the thickness is less than 2 μπι, it will be difficult to function sufficiently as a substrate to support the shield layer described later, while if it exceeds 200 μm, it will lack flexibility and become lighter, thinner and smaller. It is not desirable either, as adaptation to other products is difficult. In the present invention, the type and thickness of the above-mentioned synthetic resin, thermoplastic elastomer or rubber can be selected according to the application. For example, in applications where heat resistance is required, it is preferable to select polyimide or liquid crystal polymer as a synthetic resin, and when heat resistance is not required, PET etc. should be selected in consideration of cost etc. In applications where elasticity is required, it is preferable to select a thermoplastic elastomer or rubber. In addition, various fillers such as glass fibers can be added to such a polymer film for the purpose of improving the strength and imparting a flame retardant effect and the like.

The polymer film used in the present invention is preferably subjected to a drying treatment so as to have a water content of less than approximately 0.01% before forming each layer described later. This is to improve the adhesion to the later-described layers, in particular, the cenote red layer. Is the said drying method can be performed according to a conventional method, for example, 40 to 200 ° C, preferably rather is 40 to 1 20 ° C vacuum (1 X 10 one ^3, which is heated to a temperature of ~ 1. can be mentioned a method of bombardment treatment with 5 X 10- ¹ P a). The conditions for the pompard treatment are: Ar gas: 60 to 300 cc / min, preferably 100 to 200 cc Z min, power: 0.5 to 2 kW, preferably 0.8 to 1.3 kW; This can be done by using a hooking device or the like.

Further, as the polymer film used in the present invention, it is preferable to use, as a pretreatment, one which has been irradiated with at least one type of ion using an ion gun which irradiates ions to an object. Examples of such ions include rare gas ions such as argon, oxygen ions or nitrogen ions, mixed ions of these, and the like.

Thus, when the polymer film is previously irradiated with ions, the adhesion of the below-described shield layer to the polymer film of the base layer is greatly enhanced. Although the mechanism has not been elucidated in detail yet, it is probably due to activation of the polymer film surface by ion irradiation, or roughening treatment (concave / convex process) in an extremely fine state. Conceivable.

Ion irradiation of such a polymer film is preferably carried out before the formation of the below-described seed layer or underlayer as a pretreatment.

Moreover, as conditions for ion irradiation by an ion gun, for example, in an apparatus equipped with an ion gun, a vacuum of ¹ × 10 ^{−3 to} 7 × 10 − [Pa, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ Pa] , Ion source gas 50 to 500 cc Z min, preferably 80 to 25 O cc / min, target current (power supply) 0.01 to 5 kW Zdm ² , preferably 0.1 to 3 kW / dm ² can do.

Dyseered layer>

The shield layer of the present invention has the function of shielding, that is, shielding, electromagnetic waves having various frequencies, and on the surface of the polymer film, or in the case where an underlayer described later is formed, It is formed. Such a shield layer has a thickness of 1 to 8 μπι and contains at least one of Ni, Fe, Co, Ti, Zn, Cr, Sn, Cu, and these metals. It consists of one kind selected from the group consisting of alloys, and is characterized in that it is formed to be divided into one or two or more layers by any method of sputtering method, vapor deposition method or plating method. . The thickness is limited to 1 to 8 μm ι 、電磁波性十分未満未満未満未満未満未満シールドシールドシールドシールドシールド一方一方一方一方一方一方一方一方一方一方一方一方 On the other hand, even if it exceeds 8 μm. On the contrary, flexibility will be impeded without much difference It is. In consideration of these points, the thickness is particularly preferably 2 to 5 μπμ. Further, the constituent component is limited to the above-mentioned metals if it is excellent in shielding property against electromagnetic waves, and it should be possible to adopt sputtering, vapor deposition or plating as a forming means. It is because it does not. In addition, sputtering, vapor deposition or plating is employed as the forming means because, as described above, these metals can not be used as metal foils, and in terms of their performance, polymer films This is because it is necessary to have sufficient adhesion with the like, and to freely set the thickness if desired.

In the shield layer of the present invention, it is preferable to select the kind of metal to be configured according to the frequency of the electromagnetic wave to be shielded. For example, for low frequency electromagnetic waves having a frequency of approximately 5000 Hz or less, it is preferable to select one selected from the group consisting of Ni, Co, Fe and alloys containing at least one of these metals. It is preferable to select Cu for high frequency electromagnetic waves having a frequency of approximately 5000 Hz or more. More specifically, when the shield layer is made of such Cu, an undercoat layer having the below-described antioxidant effect is formed on the surface of the polymer film, preferably on the surface thereof, After formation of the formation, the composition of the solution (copper sulfate 50 to 300 g / l, preferably 80 to: L 50 g / 1, sulfuric acid 50 to 300 g / l, preferably 90 to 160 g / l). L, chlorine 30 to L 00 ppm, preferably 50 to 70 ppm and others optionally mixed with a small amount of additives), current density 0.1 to 2 OA / dm ² , preferably 0.5 to 5 It can be formed as a thickness of 1 to 8 / m by electroforming under the conditions of 4 AZ dm ² and a solution temperature of 10 to 70 ° C., preferably 25 to 35 ° C. This makes it possible to form a shield layer that exhibits particularly excellent shieldability against high frequency electromagnetic waves.

Further, the shield layer of the present invention can be divided into two or more layers. For example, when the shield layer is divided into two layers by one selected from the group consisting of Ni, Co, Fe and an alloy containing at least one of these metals, and Cu, the low frequency and The shield layer can exhibit shielding properties against both high frequency electromagnetic waves, which is one of the particularly preferred embodiments of the present invention. More specifically, on the surface of the polymer film, preferably on the surface of the below-described underlayer formed on the surface Composition of plating solution (Nikkol sulfate 50 to 350 g / l, preferably 200 to 250 g / 1, nickel chloride 10 to: L 00 gZ 1, preferably 40 to 50 g / 1, boric acid 10 to 60 g / l , Preferably 30 to 50 g / l, and optionally a small amount of additives, and adjusted to pH 5 to 6.0, preferably pH 3.0 to 4.5), current density 1 to L It consists of Ni with a thickness of 1 to 8 m by electroplating under the conditions of 0 AZdm ² , preferably 2 to 4 AZ dm ² , solution temperature 30 to 70 ° C., preferably 45 to 55 ° C. A first shield layer can be formed, and a second shield layer made of Cu with a thickness of 1 to 8 μπι can be formed thereon under the same conditions as described above. The order of forming these two shield layers can, of course, be reversed as described above, and in this case also, both low frequency and high frequency electromagnetic waves can be shielded. When the shield layer is made of, for example, an alloy of Fe and Ni instead of the Ni described above, the composition of the plating solution (nickel sulfate 40 to 400 g / 1, preferably 80 to 320 g / l). l, dichloride nickel 20~: L 00 g / 1, preferably 4 0 to 80 g / 1, boric acid 10 to 70 g / l, preferably 35 to 50 g / l, ferrous 2 to 50 _§ sulfate / 1, preferably 5 to 20 g Z 1, and optionally a small amount of additive is added, pH 2-5, preferably pH 3 to 3.8), current density 1 to 15 A / dm ² preferably 4 to It can be formed by electroplating under the conditions of 6 AZdm ² , solution temperature 30 to 70 ° C., preferably 50 to 60 ° C. Furthermore, the shield layer of the present invention can be formed in three or more layers. For example, as described above, a first shield layer is formed of one selected from the group consisting of Ni, Co, Fe, and an alloy containing at least one of these metals, and Cu to Forming a second shield layer, and further forming thereon a third shield layer selected from the group consisting of Ni, Co, Fe, and an alloy containing at least one of these metals. Can be illustrated. If an electromagnetic wave shielding material of such a configuration is attached to an electric product, for example, the electromagnetic wave generated from the inside of the electric product can be shielded against low frequency electromagnetic waves, and some materials are intended to penetrate from the outside to the inside. It will be possible to shield effectively.

On the other hand, the shield layer of the present invention can be formed on both sides of the polymer film. For example, thickness force S l ^ m on either surface of a polymer film And selected from the group consisting of Ni, Co, Zn, Fe, Cu, Ti, Cr, oxides and nitrides of these metals, and alloys containing at least one of these metals. One or two or more underlayers (described later) consisting of Ni are formed by sputtering or evaporation, and Ni, Co, Fe and an alloy containing at least one of these metals are formed thereon. And a second shield layer of Cu is further formed thereon, and a thickness is formed on the other surface of the polymer film. and selected from the group consisting of Ni, Co, Zn, Fe, Cu, Ti, Cr, oxides, nitrides of these metals, and alloys containing at least one of these metals. The below-mentioned base layer which consists of Or one or more layers formed by any of vapor deposition methods, and one or more selected from the group consisting of Ni, Co, Fe, and an alloy containing at least one of these metals. An embodiment in which the third panoramic layer is formed can be mentioned. In another embodiment, for example, the thickness is less than or equal to μμπι on any one surface of the polymer film, and Ni, Co, Zn, Fe, Cu, Ti, Cr, or these The below-mentioned base layer which consists of 1 type chosen from the group which consists of a metal oxide, nitride, and an alloy which contains at least 1 sort of these metals forms one or two or more layers by the method of sputtering method or a vapor deposition method. And a first shield layer of Cu is formed thereon, and further, a second shield layer is selected from the group consisting of Ni, Co, Fe and an alloy containing at least one of these metals. And a thickness of 1 m or less on the other surface of the polymer film, and Ni, Co, Zn, Fe, Cu, Ti, Cr, and the like. , Oxides, nitrides of these metals and At least one underlayer selected from the group consisting of at least one alloy is formed of one or more layers by a sputtering method or a vapor deposition method, and Ni, Co, There can be mentioned an embodiment in which a third shield layer composed of one selected from the group consisting of Fe and an alloy containing at least one of these metals is formed.

The underlayer according to the present invention functions as a kind of electrode in forming the shield layer. It is particularly useful when the shield layer is formed by a plating method. In addition, the base layer has a function as an anti-oxidation layer that prevents oxidation of the layer formed above the layer, that is, the seed layer, the other base layer, and the like. It can also be done. The shield layer or the like is oxidized over time by the action of oxygen in the air or oxygen dissolved in water contained in the polymer film, and once these layers are oxidized in this way, adhesion with the polymer film is caused. The force is significantly reduced, and inconveniences such as peeling easily occur. In such a case, if an undercoating layer having an antioxidative effect is present between these layers and the polymer film, it effectively captures the oxygen diffused from the polymer film in the direction of these layers. The oxygen is effectively removed before reaching the layers. The underlayer having such an antioxidant effect is particularly effective when the shield layer or the other underlayer is composed of Fe or Cu, and is composed of other metals. There is no need to form it.

Such an underlayer is formed between the surface of the polymer film and the shield layer, has a thickness of 1 μπι or less, and N i, C o, Z n, F e, C u, T i , C r, oxides, nitrides of these metals, and alloys comprising at least one of these metals, and one selected from the group consisting of sputtering and vapor deposition. 1 'layer or two or more layers are formed. The thickness is limited to 1 μι or less because 1 μπι is sufficient to act as an electrode and / or an antioxidant layer, and it is not necessary to make it thicker. In addition, the reason that the constituent component is limited to the above-mentioned metals is that these metals exhibit excellent conductivity and antioxidative effect, and they are suitable for formation by sputtering or vapor deposition. It is from. Of these metals, mainly Fe and Cu have excellent action as electrodes, T i and C r have excellent effects as an antioxidant layer, and Ni, Co and Co and Z n is characterized by having both of these effects. On the other hand, the sputtering method or the vapor deposition method is adopted as the forming means, because it is not necessary to adopt a relatively thick plating method suitable for forming a layer, and the polymer film is treated in a dry state. Because you can do it. Also, such an underlayer can be formed in one or two or more layers as described above, and two or more layers can be formed. In the case of forming through layers, it is preferable to form an undercoat layer having an antioxidative effect mainly on the surface of the polymer film, and to form an undercoat layer acting as an electrode thereon.

Such undercoat layer, if formed, for example, a sputtering method is used, the conditions are as follows, the degree of vacuum ^{1 X 10- 4 ~1. 5 X} 1 O ^ P a, preferably 1 X 10_ ⁴ ~ 1. 5 X 10- ² P a, output 0.. 5 to 1 5 kW, preferably 0. 8~: L 0 kW, a r gas 100 to 400 cc Z component, it preferably to employ the 100 to 250 cc / min conditions Is preferred. Further, when formed by vapor deposition, as is the condition, the degree of vacuum ^{1 X 10 -5 ~: LX 1} 0- 2 P a, preferably ^{1 X 10- 4 ~: LX 10-} 3 P a, the output 10 It is preferred to adopt a condition of ~ 150 kW, preferably 40-90 kW. By adopting such conditions, the thickness can be set to 20Α-1 μπι, preferably 50 to 300 OA.

In addition, prior to forming the shield layer on such an underlayer, 0.5 to 50%, preferably 3 to 10%, of sulfuric acid is preferably added on the underlayer for 0.1 to 3 minutes. Preferably, it is activated by acid activation treatment for preferably 0.5 to 1.5 minutes. By performing such an acid activation treatment, even if the metal constituting the underlayer is oxidized (ie, when the metal is Cu, it is oxidized to form copper oxide). Also, it is possible to effectively reduce or dissolve and remove this, and to form a shield layer on the underlayer with high adhesion.

Discoloring prevention layer>

The anti-discoloring layer of the present invention is formed when the shield layer is formed of Cu (when the shield layer is formed of two or more, the uppermost layer is formed of Cu). It exhibits an effect of effectively preventing discoloration due to oxidation and the like. Therefore, it is formed immediately on the shield layer made of Cu. Such a color protection layer is formed of Sn, Ni, Co, Ti, Zn or Cr, and the formation method is not particularly limited, but it is usually formed by sputtering, vapor deposition or plating. it can. For example, when forming Sn by electroplating, the conditions are as follows: composition of plating solution (S nl O to 70 gZl, preferably 20 to 60 g Z 1, organic acid 70 to 200 g / l, Preferably 90 to: L 30 g / 1, In addition, if desired, a small amount of additives is blended), current density 0.5 to 10 dm ² , preferably 1 to ^{2 A} / dm ² , liquid temperature 10 to 70 ° C., preferably 20 to 30 ° C., etc. The condition of can be adopted. By adopting such conditions, the thickness can be made 0.01 to 2 μπι, preferably 0.1 to 1 μπι. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1

The present example relates to an electromagnetic wave shielding material in which an underlayer is formed on the surface of a polymer film, and a shield layer composed of an alloy composed of Ni and Fe is formed thereon. Hereinafter, description will be made with reference to FIG.

25 111 thick as a polymer film 101? After slitting the finorem into 25 Omm wide and 10 Om long, it is scraped into a stainless steel core and attached to the delivery shaft in the chamber of the sputtering device, and its tip is scraped off with polyimide tape with adhesive. Mounted on the take-off shaft. Then, after a vacuum of 4 X 10- ² P a in the chamber by the vacuum pump, the cooling device with the drive drum so that the polymer film is taken plated at a rate of 0.4 minutes, delivery shaft Oyo Pi The skimming shafts were each rotated. Thereafter, the temperature is adjusted to 110 ° C. by a heater, and the moisture content of the polymer film is 0.10% by performing bombardment processing under the conditions of Ar gas 120 cc / min and power of 0.9 kW in the bombarded portion. It was vacuum dried to be less than.

Subsequently, N 1 is attached to the first target and the second target 1 in the chamber, respectively, and the Ar gas is sputtered N i using a high magnetic wave magnet of 200 cc / min each and an output of 8 kW. As a result, an undercoat layer 102 having a thickness of 1800 A was formed on the surface of the vacuum-dried polymer film 101.

Thereafter, the polymer film on which the underlayer was thus formed was taken out from the sputtering apparatus and subsequently set in a continuous plating apparatus. The undercoat layer was acid-activated by continuously immersing the polymer film in a plating bath filled with 5% sulfuric acid at a moving speed of 1.0 mZ for 1 minute. Next, after repeated washing twice, a plating solution (nickel sulfate 240 g / 1, nickel chloride) was added to the plating bath of the above apparatus. The above polymer is charged with 50 g of KL, 40 g of boric acid, 20 g of ferrous sulfate and 1 70 g of ferroalloy FA (manufactured by Ebara Eugelite Co., Ltd.) and having a pH of 3.8. The film is continuously immersed at a moving speed of 1. O'm / min, and electroplated for 5 minutes under the conditions of a liquid temperature of 55 ° C and a current density of 4 A / dm ² , on the underlayer 102. A shield layer 103 composed of an alloy (N i: F e = 70:30) consisting of N i and F e with a thickness of 4.3 im was formed. Subsequently, the product was repeatedly washed with water three times, drained by a blower, and dried at 60 ° C. for 1 minute to obtain the electromagnetic shielding material of the present invention shown in FIG.

The electromagnetic wave shielding material thus obtained is measured with an oscilloscope while being irradiated with an electromagnetic wave of 100 to 200 Hz using a phase shift oscillator, and it is 100 to 200 hertz on the side not irradiated with the electromagnetic wave. No electromagnetic waves were detected. For this reason, the electromagnetic wave shielding material obtained above can be used for various applications as an electromagnetic wave shielding material for low frequency. Further, since the electromagnetic wave shielding material was also excellent in flexibility, it could be used in a wide range of various products which are light and thin and short.

Example 2>

In this example, an undercoat layer having an antioxidant effect is formed on the surface of a polymer film, a second undercoat layer acting as an electrode is formed thereon, and a shield layer made of Cu is formed thereon. It relates to a shield material. This will be described below with reference to FIG.

A PET film of 25 zm in thickness is slit to a width of 25 Omm and a length of 10 Om as a polymer film 201, and then it is scraped into a stainless steel core and attached to a delivery shaft in a chamber of a sputtering apparatus. Was attached to the take-off shaft with polyimide tape with adhesive. Then, after a vacuum of 4 X 10- ² P a in the chamber by the vacuum pump, the cooling device with the drive drum so that the polymer film is wound in a 0. 4 m / min, delivery shaft Oyo The take-off shafts were each rotated. Thereafter, the temperature is adjusted to 110 ° C. by a heater, the bombardment process is carried out under conditions of Ar gas 120 cc Z minutes and an output of 0.9 k W, and the moisture content of the polymer film is ○. Vacuum dried to less than 01%.

Subsequently, a first target in the chamber is attached with C r, and the vacuum-dried polymer film 201 is formed by sputtering C r under conditions of Ar gas for 100 c cZ and power of 2.2 kW. An underlayer 204 having an antioxidative effect with a thickness of 7 OA was formed on the surface.

Subsequently, Cu is attached to the second target in the chamber, and under conditions of an Ar gas of 200 ccZ and a power of 9 kW, sputtering is performed on Cu to form a thickness 210 on the underlayer 204 having the anti-oxidation effect. A second underlying layer 202 was formed to act as an OA electrode.

Thereafter, the polymer film on which the underlayer was thus formed was taken out from the sputtering apparatus and subsequently set in a continuous plating apparatus. The second undercoat layer 202 was acid-activated by continuously immersing the polymer film in a plating bath filled with 5% sulfuric acid at a moving speed of 1.0 m / min for 1 minute. Then, after repeating the water washing twice, plating solution (copper sulfate 90 gZl, sulfuric acid 150 g / 1, chlorine 50 ppm and Totupletina 380 H (Okuno Pharmaceutical Co., Ltd. product) 10 cc / l) was added to the plating bath of the above apparatus. 1), and the polymer film is immersed continuously at a moving speed of 1. OmZ minutes and electroplated for 4 minutes under the conditions of a liquid temperature of 29 ° C. and a current density of 4 A / dm ² Thus, the shield layer 203 made of Cu and having a thickness of 3.5 μπι was formed on the second underlayer 202. Subsequently, washing with water was repeated three times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute to obtain the electromagnetic shielding material of the present invention shown in FIG.

The electromagnetic wave shielding material thus obtained is measured with an oscilloscope while being irradiated with an electromagnetic wave of 1 to 2 GHz using a phase shift oscillator. Ruth's electromagnetic wave was not detected. Therefore, the electromagnetic wave shielding material obtained above can be used in various applications as an electromagnetic wave shielding material for high frequency. Further, since the electromagnetic wave shielding material was also excellent in flexibility, it could be widely used for various products which are reduced in size and size.

Example 3> In this example, an undercoat layer having an antioxidative effect is formed on the surface of a polymer film, a second undercoat layer acting as an electrode is formed thereon, and a shield layer of Cu is formed thereon. Furthermore, the present invention relates to an electromagnetic wave shielding material on which a discoloration prevention layer is formed. Hereinafter, this will be described with reference to FIG.

First, a polymer film 31 having a shield layer 303 formed was obtained in exactly the same manner as in Example 2 up to the point where the shield layer made of Cu was formed. Subsequently, in a plating bath of a continuous plating apparatus, a plating solution (Sn 5 5 g / 1, as an organic acid, Metaths AM (manufactured by Ruken Industrial Co., Ltd.) 120 g / 1 and SBS-R (Ruken Industrial (stock Made of) 60 cc / 1), the above polymer film is continuously immersed at a moving speed of 1. O m / min, liquid temperature is 30 ° C., current density is 2 A / dm By performing electric plating for 1 minute under the conditions of ^2, the anti-tarnish layer 305 consisting of Sn having a thickness of 0.6 μπι was formed on the shield layer 303. Subsequently, washing with water was repeated three times, and after being drained by a blower, it was dried at 60 for 1 minute to obtain the electromagnetic shielding material of the present invention shown in FIG.

The electromagnetic wave shielding material thus obtained is measured with an oscilloscope while being irradiated with an electromagnetic wave of 1 to 2 GHz using a phase shift oscillator. Ruth's electromagnetic waves were not detected. Therefore, the electromagnetic wave shielding material obtained above can be used in various applications as an electromagnetic wave shielding material for high frequency. Further, since the electromagnetic wave shielding material was also excellent in flexibility, it could be widely used for various products which are reduced in size and size.

Example 4>

The present example relates to an electromagnetic wave shielding material in which an undercoat layer having an antioxidative effect is formed on the surface of a polymer film, and three layers of a seinored layer are formed thereon. Hereinafter, description will be made with reference to FIG.

After slitting a PET film of 25 μπ 2 thickness to 25 O mm wide and 10 O m long as polymer fine norem 401, it is scraped into a stainless steel core and sent out in the chamber of the sputtering apparatus It was attached to the shaft, and its tip was attached to the take-off shaft with polyimide tape with adhesive. And by the vacuum pump After the chamber is evacuated to 4 × 10 ² Pa and the polymer film is removed at a speed of 0.4 m / min, the drive drum with cooling device, the delivery shaft and the winding shaft are Each was rotated. Thereafter, the temperature is adjusted to 110 ° C. by a heater, and the moisture content of the polymer film is 0.10 by performing a bombardment process under conditions of Ar gas 120 cCZ and an output of 0.9 kW in the bombarded portion. It vacuum-dried so that it was less than%.

Subsequently, N 1 is attached to the first target and the second target in the chamber, respectively, and N 2 is sputtered by using a high magnetic wave magnet with an output of 8 kW for 200 c cZ each for Ar gas. On the surface of the vacuum-dried polymer film 401 was formed an undercoat layer 404 having an antioxidation effect with a thickness of 180 OA.

Thereafter, the polymer film on which the underlayer having the antioxidative effect was formed was taken out from the sputtering apparatus and then set in a continuous plating apparatus. The plating bath was made up of plating solution (Nickel sulfate 240 _g Z 1, Eckel chloride 50 _g Zl, oxalic acid 40 _{g /} l, ferrous sulfate 20 _g Z 1 and Ferroalloy FA (manufactured by Ebara Eugelite Co., Ltd.) 70 cc / 1 , PH 3.8), the polymer film is continuously immersed at a moving speed of 1.0 m / min, and the liquid temperature is 55 ° C., the current density is 4 A / dm ² . By electroplating for 5 minutes, a first shield layer 403 a composed of an alloy of Ni and Fe having a thickness of 4.5 μπι was formed on the above-described underlayer 404 having an oxidation preventing effect. . Subsequently, washing with water was repeated 3 times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute.

Next, a plating bath (copper sulfate 90 g Zl, sulfuric acid 150 g / l, chlorine 50 ppm and Top Noretina 380 H (manufactured by Okuno Pharmaceutical Industry Co., Ltd.) 10 cc / 1) in the plating bath of the continuous plating apparatus By continuously immersing the above-mentioned polymer film at a moving speed of 1. OmZ, liquid plating at 29 ° C., current density 4 A, dm ² for 4 minutes, A second shield layer 403 b made of Cu with a thickness of 3.5 μπι was formed on the first shield layer 403 a. Subsequently, washing with water was repeated 3 times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute.

Furthermore, in the plating bath of the continuous plating apparatus, a plating solution (nickel sulfate 240 gZ 1, Nickel chloride 50 g / 1, boric acid 40 g / 1 _N ferrous sulfate 20 g / 1 and phaloy FA (described above) (having a pH of 3.8) The second shield layer 403 is formed by continuously immersing the film at a moving speed of 1. Om / min, and electroplating for 5 minutes under the conditions of a liquid temperature of 55 ° C. and a current density of 4 A / dm ^2. A third shield layer 403c composed of an alloy of Ni and Fe with a thickness of 4.4 μπι was formed on b. Subsequently, washing with water was repeated three times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute to obtain the electromagnetic shielding material of the present invention shown in FIG.

The electromagnetic wave shielding material thus obtained was measured with an oscilloscope while being irradiated with an electromagnetic wave of 1 to 200 Hz and 1 to 2 gigahertz using a phase shift oscillator. In the non-irradiated side, electromagnetic waves of 100 to 200 Hz and 1 to 2 gigahertz were not detected. For this reason, the electromagnetic wave shielding material obtained above can be used in various applications as an electromagnetic wave shielding material for both low frequency and high frequency. Further, since the electromagnetic wave shielding material was also excellent in flexibility, it could be used in a wide range of various products which are reduced in thickness and size.

Example 5>

The present example relates to an electromagnetic wave shielding material in which shield layers are formed on both sides of a polymer film. This will be described below with reference to FIG.

After slitting a 25 μm thick PET film as a polymer film 501 to a width of 25 Omm and a length of 10 Om, it is scraped into a stainless steel core and attached to a delivery shaft in a chamber of a sputtering apparatus. The tip was attached to the scraping shaft with polyimide tape with adhesive. Then, after a vacuum of 4 X 10- ² P a in the chamber by the vacuum pump, the cooling device with the drive drum so that the polymer film is taken seeded at 0. 4 m / min, delivery shaft Contact The winding shaft was rotated respectively. Thereafter, the temperature is adjusted to 110 ° C. by a heater, and the moisture content of the polymer film is 0. 0 by performing bombardment processing under the conditions of Ar gas 120 cc / min and power of 0.9 kW in the bombarded portion. Vacuum dried to less than 01%. Subsequently, N 1 is attached to the first target and the second target in the chamber, respectively, and N 2 is sputtered using a high magnetic wave magnet with an Ar gas output of 200 kW / min and an output of 8 kW each. On the surface of the vacuum-dried polymer film 501 was formed an undercoat layer 504 having an antioxidation effect with a thickness of 180 OA.

Thereafter, the polymer film on which the underlayer having the antioxidative effect was formed was taken out from the sputtering apparatus and then set in a continuous plating apparatus. The above-mentioned polymer film was continuously immersed in a plating bath filled with 5% sulfuric acid at a moving speed of 1. Om / min for 1 minute to acid-activate the undercoat layer having the above antioxidant effect. . Then, after repeating the water washing twice, plating solution (copper sulfate 90 g / 1, sulfuric acid 150 g / 1, chlorine 50 ppm and Totu Pluccia 380H (manufactured by Okuno Pharmaceutical Industries Co., Ltd.) in the plating bath of the above-mentioned apparatus) )) The above polymer film is continuously immersed at a moving speed of 1. Om / min under the conditions of a liquid temperature of 29 ° C. and a current density of 4 A / dm ² ). By electroplating for 4 minutes, a first shield layer 503 a made of 3.5 μm-thick Cu was formed on the underlayer 504 having the oxidation preventing effect. Subsequently, washing with water was repeated 3 times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute.

Next, the plating solution (nickel sulfate 240 g / 1, nickel chloride 50 g / 1, oxalic acid 40 g / 1, ferrous sulfate 20 g / 1, and ferroalloy FA (Evala) was added to the plating bath of the continuous plating apparatus. (Manufactured by Eugelite Co., Ltd.) 70 cc / 1 and filled with a polymer solution having a pH of 3.8), and continuously immersing the above polymer film at a moving speed of 1.0 mZ, and the solution temperature is 55 ° C. By electroplating for 5 minutes under the conditions of current density 4 A / dm ² , the first shield layer 503 a is made of an alloy comprising Ni and Fe having a thickness of 4.5 _i uπl. Two shield layers 503 b were formed. Subsequently, washing was repeated three times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute.

Furthermore, it was set again in the sputtering apparatus to treat the other side subsequently to the polymer film thus formed with the second shield layer. Then, N 1 is attached to the first target and the second target in the chamber of the sputtering apparatus, respectively, and 200 cc / min of Ar gas and 8 kW of high magnetic wave mag- nets of each output are provided. An undercoat layer 502 of thickness 180 OA was formed on the other surface of the polymer film 501 by sputtering Ni using a net.

Subsequently, the polymer film on which the underlayer was thus formed was taken out of the sputtering apparatus again, and then set in a continuous plating apparatus. The undercoat layer was acid activated by continuously immersing the polymer film in a plating bath filled with 5% sulfuric acid at a moving speed of 1.0 m / min for 1 minute. Then, after repeated washing with water twice, the plating solution (nickel sulfate 240 g / l, nickel chloride 50 g Zl, boric acid 40 g / 1, ferrous iron 20 g / 1 and ferrourea) was added to the plating bath of the above apparatus. B) Fill with 70 cc / l of FA (manufactured by Ebara Egylite Co., Ltd., pH 3.8), and continuously immerse the above polymer film at a transfer speed of 1. Om / min. By electroplating for 5 minutes under the conditions of a liquid temperature of 55 ° C. and a current density of 4 A / dm ² , an alloy consisting of Ni and Fe having a thickness of 4.3 μι on the underlayer 502 (Ni: A third shield layer 503 c composed of F e = 70: 30 was formed. Subsequently, washing with water was repeated three times, and after being drained by a blower, it was dried at 60 ° C. for 1 minute to obtain the electromagnetic shielding material of the present invention shown in FIG.

When the electromagnetic wave shielding material thus obtained is measured with a phase shift oscillator while being irradiated with an electromagnetic wave of 100 to 200 Hz and 1 to 2 gigahertz, respectively, the electromagnetic wave is not irradiated. In the other side, electromagnetic waves of 100 to 200 Hz and 1 to 2 gigahertz were not detected. For this reason, the electromagnetic wave shielding material obtained above can be used in various applications as an electromagnetic wave shielding material for both low frequency and high frequency. Further, since the electromagnetic wave shielding material was also excellent in flexibility, it could be used in a wide range of various products which are reduced in thickness and size.

Example 6>

In Examples 1, 2, 3, 4 and 5 above, all these are pretreated, except that the ion bombardment with the ion gun is performed as a pretreatment in place of the bombardment treatment performed on the polymer film. An electromagnetic wave shielding material was obtained in the same manner as in the above example.

Specifically, in each embodiment, the sputtering apparatus is The condition of argon gas 100 cc / min, power supply 0.5 k WZ dm ² , degree of vacuum 2 X 10- a by using a sputtering apparatus with an ion gun attached instead of the heater and bombardment processing Under this, pretreatment was performed by irradiating argon ions.

The electromagnetic wave shielding materials thus obtained have the same shielding effect as those of Examples 1, 2, 3, 4 and 5, but the adhesion between the polymer film and the underlayer and the shielding layer is further increased. It was improved. For this reason, the scope of application to various products could be further expanded. Industrial applicability

The electromagnetic wave shielding material of the present invention has a property rich in flexibility by reducing its thickness, so it can cope with various products which are reduced in thickness and size. In addition, the electromagnetic wave shielding material of the present invention can simultaneously shield both low frequency and high frequency electromagnetic waves, if desired.

Claims

The scope of the claims

1. a thickness of 1 to 8 im, and at least N i, F e, C o, T i, Z n, C r, S n, C u and at least one of these metals on the surface of the polymer finenerem It is characterized in that one or two or more layers of a shield layer consisting of one kind of alloy containing one kind are formed by any method of sputtering method, vapor deposition method or plating method. Electromagnetic shielding material.

2. The electromagnetic wave shielding material according to claim 1, wherein the polymer film is irradiated with ions by an ion gun as a pretreatment.

3. Between the surface of the polymer film (101) and the shield layer (103), the thickness is less and Ni, Co, Zn, Fe, Cu, Ti, Cr, of these metals Underlayer consisting of one selected from the group consisting of oxides, nitrides, and alloys containing at least one of these metals (102) Forced layer One or more layers are formed by either the sputtering method or the vapor deposition method The electromagnetic wave shielding material according to claim 1.

4. The electromagnetic shielding material according to claim 3, wherein the shield layer (103) is made of one selected from the group consisting of forces Ni, Co, Fe and alloys containing at least one of these metals.

5. A group in which the shield layer (103) is formed in two layers, one of which is made of Cu and the other of which is Ni, Co, Fe and an alloy containing at least one of these metals. The electromagnetic wave shielding material according to claim 3, wherein the electromagnetic shielding material is made of one selected from the group consisting of

6. shield layer made of C u, S n, N i , Co, T i, Σ 1 1 or 〇 1: electromagnetic wave shielding material according to claim 5, wherein the mosquito Ranaru tarnish layer is formed.

7. A seinoledo layer (403 a, 403 b, 403 c) is formed in three layers, and a layer consisting of Cu is formed as an intermediate layer of the three layers, and the upper and lower layers are sandwiched between the layers. N i, C o, F e and electromagnetic shea ^v Honoré Bokuzai according to claim 3, wherein a layer made of one selected from alloys or Ranaru group comprising at least one of these metals is formed on.

8. Between the surface of the polymer film (201) and the shield layer (203), the thickness is 1 m or less, and Ni, Co, Zn, Ti, Cr, oxides of these metals, An undercoat layer having an antioxidative effect, which is formed of one selected from the group consisting of a nitride and an alloy containing at least one of these metals, which is formed by either a sputtering method or a vapor deposition method. (204) and one selected from the group consisting of Ni, Co, Fe, Cu, and an alloy containing at least one of these metals, having a thickness of μμηα or less, which is a sputtering The electromagnetic wave shielding material according to claim 1, wherein the underlayer (202) acting as an electrode formed by any one of the method and the vapor deposition method is formed in this order.

9. The electromagnetic shield material according to claim 8, wherein the electromagnetic layer (203) is made of Cu.

10. The electromagnetic wave shield according to claim 9, wherein an anti-tarnish layer (305) comprising Sn, Ni, Co, Ti, Zn or Cr is formed on the Cu shield layer (303). Material.

1 1. The shield layer (203) is formed in two layers, one of which is made of Cu, and the other of which consists of Ni, Co, Fe and an alloy containing at least one of these metals. The electromagnetic wave shielding material according to claim 8, wherein the electromagnetic shielding material is made of one selected from the group consisting of

12. The electromagnetic wave shield according to claim 11, wherein an anti-tarnish layer (305) comprising Sn, Ni, Co, Ti, Zn or Cr is formed on the shield layer (303) comprising Cu. Material.

1 3. The shield layer is divided into three layers, and a layer consisting of Cu is formed as an intermediate layer of the three layers, and the layers are sandwiched to form Ni, Co and Fe on the upper and lower sides thereof. The electromagnetic wave shielding material according to claim 8, wherein a layer consisting of one selected from the group consisting of an alloy containing at least one of these metals is formed.

14. The polymer film (501) has a thickness of 1 μΐ or less and Ni, Co, Zn, Fe, Cu, Ti, Cr, an oxide of any of these metals, on one surface of the polymer film (501). It is selected from the group consisting of nitrides and alloys containing at least one of these metals One or more underlayers are formed by one or more layers by sputtering or vapor deposition, and Ni, Co, Fe and an alloy containing at least one of these metals are formed thereon. A first shield layer (503 a) consisting of one kind selected from the group, and a second shield layer (503 501) has a thickness of 1; zm or less, and Ni, Co, Zn, Fe, Cu, Ti, Cr, oxides, nitrides of these metals, and these. An underlayer (502) consisting of one selected from the group consisting of alloys containing at least one of the metals listed above is formed by one or two or more layers by either the sputtering method or the vapor deposition method, and Ni, Co, Fe and alloys containing at least one of these metals An electromagnetic shield material having a third shield layer (503 c) of one type selected from the group consisting of

The electromagnetic wave shielding material according to claim 14, wherein the polymer film is irradiated with ions by an ion gun as a pretreatment.

16. The electromagnetic wave shielding material according to claim 14, wherein an anti-tarnish layer comprising Sn, Ni, Co, Ti, Zn or Cr is formed on the shield layer comprising Cu.

1 7. The polymer film (501) has a thickness of 1 μπι or less, and Ni, Co, Zn, Fe, Cu, Ti, Cr, and oxides of these metals on one surface of the polymer film (501). An underlayer consisting of one selected from the group consisting of nitrides and alloys containing at least one of these metals is formed by one or more layers by sputtering or vapor deposition, and A first shield layer (503 a) composed of Cu is formed, and further composed of one selected from the group consisting of Ni, Co, Fe and an alloy containing at least one of these metals. A second shield layer (503 b) is formed, and the other surface of the polymer film (501) has a thickness of 1 μπι or less, and Ni, Co, Zn, Fe, Cu, T i, C r, oxides, nitrides of these metals and less of these metals An underlayer (502) of one or more selected from the group consisting of an alloy of one or more is formed by one or more layers by sputtering or vapor deposition, and Ni, Co, F are formed thereon. e and an alloy comprising at least one of these metals An electromagnetic wave shielding material in which a third shield layer (503 c) made of one type is formed.

18. The electromagnetic wave shielding material according to claim 17, wherein the polymer film is irradiated with ions by an ion gun as a pretreatment.