WO2012159258A1 - 电磁屏蔽衬垫及其制备方法 - Google Patents

电磁屏蔽衬垫及其制备方法 Download PDF

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Publication number
WO2012159258A1
WO2012159258A1 PCT/CN2011/074517 CN2011074517W WO2012159258A1 WO 2012159258 A1 WO2012159258 A1 WO 2012159258A1 CN 2011074517 W CN2011074517 W CN 2011074517W WO 2012159258 A1 WO2012159258 A1 WO 2012159258A1
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Prior art keywords
electromagnetic shielding
shielding gasket
foam
foam substrate
gasket according
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PCT/CN2011/074517
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English (en)
French (fr)
Inventor
刘伟德
方敬
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to US14/116,932 priority Critical patent/US20140216807A1/en
Priority to CN201180070900.8A priority patent/CN103535123B/zh
Priority to KR1020137033606A priority patent/KR20140048134A/ko
Priority to PCT/CN2011/074517 priority patent/WO2012159258A1/zh
Priority to TW101118236A priority patent/TWI556720B/zh
Publication of WO2012159258A1 publication Critical patent/WO2012159258A1/zh
Anticipated expiration legal-status Critical
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0007Casings
    • H05K9/0015Gaskets or seals

Definitions

  • the present invention relates to the field of electromagnetic shielding, and more particularly to an electromagnetic shielding gasket for shielding electromagnetic interference (EMI) / radio frequency interference (RFI) and a method of fabricating the same.
  • EMI electromagnetic interference
  • RFID radio frequency interference
  • Electromagnetic interference is an unwanted electromagnetic component that is generated or radiated from an electronic/electrical device that interferes with the normal operation of the electronic/electrical device. In theory, such electromagnetic interference can occur in any frequency band of the electromagnetic spectrum. Radio Frequency Interference (RFI) often interacts with electromagnetic interference (EMI). In practice, Radio Frequency Interference (RFI) is limited to being generated in the RF portion of the electromagnetic spectrum, typically between 10 KHz and 100 GHz.
  • EMI electromagnetic interference
  • RFID radio frequency interference
  • a shield is placed between the electromagnetic interference / radio frequency interference source and the area to be protected. This shield is used to prevent electromagnetic energy from electromagnetic interference / radio frequency interference
  • the source is emitted; similarly, it can also be used to prevent external electromagnetic energy from entering the electromagnetic interference/radio frequency interference source.
  • the shield is in the form of a conductive enclosure which can be grounded, for example, via a grounding wire on the PCB.
  • the electrically conductive enclosure can be integrally formed from an electromagnetic shielding gasket material.
  • a slot may be formed in the conductive enclosure to form a gap on the shield.
  • a gap formed on the shield may be filled with a shielding gasket to prevent electromagnetic energy from being emitted from the electromagnetic interference/radio frequency interference source or external electromagnetic energy entering the electronic/electrical device.
  • the electronic module in the electronic/electrical device is externally provided with an absorbent pad material having a high impact and vibration absorbing function.
  • the absorbent pad material is typically constructed of a microporous material, such as a polyurethane foam, to provide a degree of elastic recovery.
  • the absorbent pad material in the above electronic/electrical device not only has a high impact and vibration absorbing function, but also needs to have a function of achieving a gapless seal in a narrow space in an electronic/electrical device, and an electron/ Electromagnetic interference (EMI) / radio frequency interference (RFI) generated inside and outside electrical equipment for shielding.
  • EMI Electromagnetic interference
  • RFID radio frequency interference
  • US 6,309,742 discloses a shielding liner made by depositing a layer of metallic material on an open cell foam. Since the deposited metal material penetrates the open-cell bubble body, the open-cell bubble body has good conductivity. Accordingly, the gasket material is die-cut into various shapes or formed into a shield and filled or covered around the electronic/electrical device, and its electrical conductivity can be utilized to cause electromagnetic interference (EMI) generated inside and outside the electronic/electrical device. ) / Radio Frequency Interference (RFI) for shielding.
  • EMI electromagnetic interference
  • RFID Radio Frequency Interference
  • the above-mentioned gasket material has a certain conductivity, so that it can have a relatively good shielding effect against static electricity, an electric field, etc., but it has a magnetic field generated inside and outside the electronic/electrical equipment. Especially, the shielding effect of the near-field magnetic field is not ideal.
  • An object of the present invention is to provide an electromagnetic shielding gasket capable of simultaneously realizing an electric field shielding function and a magnetic field shielding function.
  • an electromagnetic shielding gasket comprising a foam substrate and a metal layer deposited on the foam substrate, the metal layer comprising nickel and cobalt, wherein Co/(Co+Ni) The weight ratio is from 0.2% to 85%.
  • a method of making an electromagnetic shielding gasket comprising the steps of:
  • the pretreated foam substrate is subjected to metallization to obtain a metal layer containing Co and Ni.
  • the electromagnetic shielding gasket of the present invention can simultaneously realize an electric field shielding function and a magnetic field shielding function.
  • Figure 1 is a schematic view showing the structure of an electromagnetic shielding gasket according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural view of an electromagnetic shielding gasket according to another embodiment of the present invention.
  • Fig. 3 is a schematic view showing a magnetic property test method in the present invention.
  • 4 is a SEM photograph of an electromagnetic shielding gasket in accordance with one embodiment of the present invention.
  • FIG. 5 is an EDS spectrum of an electromagnetic shielding gasket in accordance with one embodiment of the present invention. detailed description
  • the foam substrate is an open-cell foam structure having openings distributed therein.
  • the material of the foam base is not limited as long as it has elasticity and has a predetermined recovery property under an external force.
  • the foam base of the electromagnetic shielding pad is an open-cell foam formed by a polymer elastic material and a thermoelastic body, and the polymer elastic material is, for example, polyurethane or polychlorinated.
  • the foam substrate of the electromagnetic shielding liner has a thickness of from 0.1 to 50 mm, preferably from 0.1 to 10 mm, more preferably from 0.5 to 5 mm, most preferably from 1.0 to 3.0 mm. If the thickness is less than 0.1 mm, the compression and rebound characteristics will not be achieved; if the thickness is greater than 50 mm, the conductivity in the vertical direction will decrease after depositing metal on the foam substrate.
  • the foam substrate of the electromagnetic shielding liner has a compressible deformation range of 50% or more, preferably 70% or more, more preferably 80% or more, and most preferably 90% or more. If the compressible deformation range is less than 50% of the initial thickness, the function of high shock and vibration absorption tends to be insufficient.
  • the compressible shape used herein becomes a value under the force of no more than 50 PSI.
  • the residual deformation (permanent deformation) of the foam substrate of the electromagnetic shielding liner is 50% or less, preferably 30% or less, more preferably 20% or less, and most preferably 10% or less. If the residual deformation (permanent deformation) of the foam substrate is more than 50%, the function of high impact and vibration absorption and gapless sealing tends to decrease after long-term use.
  • the foam substrate of the electromagnetic shielding liner has an open porosity of from 10 to 500 ppi, preferably from 50 to 300 ppi, more preferably from 50 to 200 ppi, most preferably from 80 to 150 ppi. If the open porosity of the matrix is less than 10 ppi, the deposition of the metal layer is difficult to achieve; if the open porosity is greater than 500 ppi, the mechanical strength of the foam substrate tends to be insufficient. In order to make the open-cell foam substrate have good electrical conductivity and magnetic permeability, the metal layer containing Co and Ni may be deposited into the open-cell foam by vacuum evaporation, electroplating or electroless plating. In the matrix.
  • an electromagnetic shielding gasket comprising a foam substrate and a metal layer deposited on the foam substrate, the metal layer comprising nickel and cobalt, wherein Co/(Co+ The Ni) weight ratio is from 0.2% to 85%, in a preferred embodiment from 2% to 70%, in a more preferred embodiment from 5% to 50%, and in a most preferred embodiment 5%. Up to 35%. Since the open-cell foam substrate has a plurality of minute openings, after the metal layer is deposited on the open-cell foam substrate, the open-cell foam substrate not only has surface conductivity but also vertically above and below the open-cell foam substrate. Free conductivity is also imparted in other directions, resulting in a three-dimensional foam structure with good continuous conductivity.
  • the metal layer contains Co, the ferromagnetic properties of the foam after plating are also improved.
  • the content of Co in the Co/Ni alloy is essential for achieving the object of the present invention, and when Co/Ni reaches a certain ratio, the magnetic permeability thereof is remarkably increased.
  • the present invention achieves this object by, for example, controlling the ratio of Co 2+ and Ni 2+ ions in the plating solution.
  • the Co/(Co+Ni) weight ratio is outside the range, it is difficult to achieve a relatively significant gain effect on magnetic properties while maintaining good conductivity.
  • the (Co+Ni)/foam weight ratio of the foam substrate on which nickel and cobalt are deposited is from 1% to 50%, preferably from 2% to 30%, more preferably from 3% to 20%, most preferably 5% to 10%.
  • the metal deposition layer has a thickness of 10 to 2000 nm, preferably 50 to 1800 nm, more preferably 100 to 1500 nm, and most preferably 200 to 1000 nm.
  • the electromagnetic shielding gasket can achieve a good electric field shielding function and a magnetic field shielding function, and has a suitable back resilience.
  • the (Co+Ni)/foam weight ratio or the thickness of the metal deposition layer increases, the rebound resilience of the electromagnetic shielding liner decreases.
  • the metal layer deposited on the foam substrate further comprises a metal selected from the group consisting of molybdenum, manganese, copper, chromium, and the like, and combinations thereof.
  • the foam base having a metal layer deposited has a total metal/foam weight ratio of from 1% to 50%, preferably from 2% to 40%, more preferably from 3% to 30%, most preferably from 5% to 20%.
  • the metal deposition layer has a thickness of 10 to 2000 nm, preferably 50 to 1800 nm, more preferably 100 to 1500 nm, and most preferably 200 to 1000 nm.
  • the electromagnetic shielding gasket can achieve a good electric field shielding function and a magnetic field shielding function, and has a suitable back resilience. As the metal total/foam weight ratio or the thickness of the metal deposition layer increases, the rebound resilience of the electromagnetic shielding gasket decreases.
  • a layer of polymer such as a layer of polyurethane polymer, is also applied over the metal layer deposited on the foam substrate.
  • the polymer layer can mainly function as an antioxidant and protect the metal plating.
  • the electromagnetic shielding liner has a tensile strength of from 0.1 to 100 N/inch, preferably from 0.3 to 80 N/inch, more preferably from 0.6 to 50 N/inch, and most preferably from 1 to 30 N/inch. If the tensile strength of the electromagnetic shielding gasket is less than 0.1 N/inch, the processing performance of the electromagnetic shielding gasket is poor.
  • the tensile strength test in the present invention was carried out in accordance with the method of ASTM D 1000 using a standard 1 inch width tensile strength test.
  • the electromagnetic shielding gasket has a surface resistance of from 1 to 2000 m Q /O, preferably from 5 to ⁇ ⁇ ⁇ / port, more preferably from 10 to 800 ⁇ ⁇ / mouth, most preferably from 20 to 500 m ⁇ / mouth. If the surface resistance of the electromagnetic shielding gasket is greater than 2000 ⁇ ⁇ / port, the electromagnetic shielding function of the electromagnetic shielding gasket will be insufficient.
  • the electromagnetically conductive liner has a standard ferromagnetic attraction distance of greater than 1.5 cm, preferably greater than 1.8 cm, more preferably greater than 2 cm, and most preferably greater than 2.5 cm. Since the present invention improves the overall magnetic permeability of the foam by depositing an optimized Co/Ni ferromagnetic coating on the foam substrate, the material is soft and compressible due to the foam substrate, and is not suitable for the conventional Test method for soft magnetic materials. However, since magnetic permeability is an important reference parameter for ferromagnetic evaluation of soft magnetic materials, the magnitude of magnetic permeability is characterized by the magnitude of the action under the same magnitude of magnetic field force, that is, the intensity of magnetic lines per unit area (density), usually density.
  • the present invention employs a standard permanent magnet as a constant external magnetic field that provides a constant magnetic field force to the metallized (magnetized) foam sample.
  • a constant weight foam is used to characterize the magnitude of the magnetic force. The load is judged by the distance at which the action occurs. It can be understood that if the weight of the foam is the same, in the case of the same external magnetic field strength (force), the greater the suction distance, the better the magnetic permeability of the foam sample and the stronger the magnetic properties.
  • the electromagnetic shielding gasket of the present invention has a large suction distance and exhibits good magnetic properties.
  • the compressive deformation of the electromagnetic shielding liner is greater than 30% of the initial thickness, preferably greater than 50% of the initial thickness, more preferably greater than 70% of the initial thickness, and most preferably greater than 80% of the initial thickness. If the compressible deformation range is less than 30% of the initial thickness, there is insufficient tendency for the absorption function of high impact and vibration.
  • the electromagnetic shield liner has a residual deformation (permanent deformation) of less than 50%, preferably less than 30%, more preferably less than 20%, and most preferably less than 10%. If the residual deformation (permanent deformation) of the electromagnetic shielding gasket is more than 50%, the absorption of high impact and vibration and the function of the gapless sealing tend to decrease after long-term use.
  • the electromagnetic shielding gasket of the present invention may further comprise other functional layers such as a conductive layer, release paper, and the like.
  • the other layers are joined to the foam by an adhesive.
  • the binder may be a conductive paste or a non-conductive paste. When non-conductive glue is used, it may have a certain influence on the electric field shielding effect of the electromagnetic shielding gasket. It is preferred to use a conductive paste as a binder.
  • the conductive paste can be made by adding an appropriate proportion of conductive particles to the acrylic glue.
  • the amount of the conductive particles is, for example, such that the [conductive particles / (conductive particles + glue)] weight ratio is between 3% and 60%.
  • the type of the conductive particles may be, for example, nickel powder, silver powder, silver coated glass, silver coated copper powder, graphite powder (carbon powder), composite conductive particles, and the like.
  • the conductive layer may be various metal foils including copper foil, or various metallized woven/nonwoven fabrics.
  • the present invention also provides a method of preparing an electromagnetic shielding gasket, the method comprising the steps of: pre-metallizing a foam substrate; and subjecting the pretreated foam substrate to metallization to obtain Co and Ni-containing Metal layer.
  • the pre-metallization process provides the necessary preparation for the subsequent metallization process, which deposits a thin layer of Ni metal on the foam substrate by a vacuum process, or other metals with similar potentials such as Pb, the metal layer is
  • the fibers of the foam are discontinuous, mainly acting as a sedimentary core in subsequent metallization treatments, such as depositing cores of Co 2+ and Ni 2+ in water plating, thereby ensuring effective Co 2+ and Ni 2+ deposition allows Co 2+ and Ni 2+ ions to migrate simultaneously onto the foam substrate, thereby forming a substantially uniform, dense and robust Co/Ni alloy coating.
  • the premetallization treatment can be performed by, for example, vacuum evaporation, chemical vapor deposition, plasma sputtering, and plasma chemical vapor deposition.
  • the metallization treatment can be performed by vacuum evaporation, electroplating or electroless plating, for example, by water plating.
  • the ratio of Co 2+ / (Co 2+ + Ni 2+ ) in the plating solution is, for example, 0.2% to 85%, preferably 2% to 70%, more preferably 5% to 50%, Most preferably it is 5% to 35%.
  • Figure 1 shows an embodiment of an electromagnetic shielding gasket of the present invention.
  • the electromagnetic shielding gasket comprises a cobalt/nickel-plated foam 1, on one side of which a copper foil 3 is bonded by a conductive paste 2, and a release paper 5 is bonded to the copper foil 3 via a conductive paste 4.
  • FIG. 2 shows another embodiment of the electromagnetic shielding gasket of the present invention.
  • the electromagnetic shielding gasket comprises a cobalt/nickel plated foam 1 having a conductive layer 6 bonded to one side thereof, and a copper foil 3 bonded to the other side of the foam by a conductive paste 2, and passed through The conductive paste 4 is bonded to the release paper 5 on the copper foil 3.
  • the preparation process for the Co/Ni metallization of the open-cell foam in the present invention includes:
  • Polyurethane (PU) foam was purchased from Inoue Co., Ltd. (INOAC), and its grades are summarized in Table 1. Table 1. PU foam properties
  • the chemicals such as nickel chloride, nickel sulfate, cobalt sulfate, and boric acid used in the examples were purchased from Sinopharm Group, an industrial grade.
  • a high-precision digital thickness gauge (543-392BS, available from Mitutoyo, Japan) was used, and the deformation holding jig with a stainless steel material and a nut fixed at four ends was used as follows.
  • a 2 inch ⁇ 2 inch foam sample was taken, 8 uniformly distributed points were taken, and the free thickness (no deformation thickness) was measured, and the average initial thickness T Q was calculated.
  • the screws at the four corners are tightened so that the upper and lower sides are completely closed, and the adhesion thickness of the jig is measured.
  • compress and fix the foam to the average initial thickness To 50%.
  • the clamp with the sample was placed in a constant temperature oven at an oven temperature of 70 ° C ⁇ 2 ° C for 22 hours.
  • Fig. 3 The method of magnetic property testing in the present invention is shown in Fig. 3, where 1 represents a NdFeB permanent magnet, 2 represents a Co/Ni electroplated foam sample, V represents a constant velocity, and D represents a distance from a magnetic field generated by a NdFeB permanent magnet. .
  • the content of the metal component and the thickness of the metal layer are tested using an energy dispersive diffraction method (EDS).
  • EDS energy dispersive diffraction method
  • the fiber diameter of the foam and the thickness of the metal layer can be clearly seen by a matching scanning electron microscope (SEM).
  • the instrument used was an OxFord JSM 6360LV SEM from Japan Electronics.
  • the observed area of the sample is 20 mm 2 .
  • the PU foam (MF-50P3) is pretreated by PVD vacuum plating under the following conditions: Vacuum degree: about 0.2 Pa;
  • PVD equipment external temperature room temperature
  • a nickel coating is obtained by web coating, and the coating is controlled to be a foam of 1.8 mm thickness, each The square gram of nickel is less than 5 grams.
  • the composition of the plating solution includes: nickel chloride, nickel sulfate, cobalt sulfate, boric acid, other electrolyte active additives and pure water.
  • the proportions are shown in Table 2.
  • the anode of the electrolytic cell used is a nickel plate, the cathode is a PVD pre-plated foam, the bath temperature is room temperature, the working voltage is ⁇ 12 V, and continuous plating is performed in a roll shape, and the linear velocity is 0.6 m to 1.5 m. /minute.
  • the air temperature is 60 ⁇ 80 degrees Celsius.
  • the winding speed is the same as the plating speed.
  • Example 2 This was carried out as described in Example 1, except that the plating solution shown in Table 2 was used.
  • the values of Co/(Co+Ni) obtained in Examples 2 and 3 by EDS were 22.4% and 19.9%, respectively.
  • 4 and 5 are SEM photographs and EDS spectra of Example 2, respectively. Comparative example 1
  • the present invention provides an electromagnetic shielding gasket which has good electrical conductivity and magnetic permeability, and can simultaneously realize an electric field shielding function and a magnetic field shielding function.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明提供一种电磁屏蔽衬垫及其制备方法,通过在开孔泡棉上电镀合适配比的Co/Ni合金层,获得了良好的导电性和导磁性,能够同时实现电场屏蔽功能和磁场屏蔽功能。

Description

电磁屏蔽衬垫及其制备方法
技术领域
本发明涉及电磁屏蔽领域, 更具体地, 本发明涉及一种用于屏蔽电磁干扰(EMI) /射频干扰 (RFI) 的电磁屏蔽衬垫及其制备方法。 背景技术
电磁干扰(EMI)是从电子 /电气设备中产生或辐射出来的不需要的电磁部分, 其 对电子 /电气设备的正常操作构成干扰。 理论上讲, 此种电磁干扰可能发生在电磁频谱 的任何频带上。 射频干扰 (RFI) 经常与电磁干扰 (EMI) 交互存在, 实践上, 射频干 扰(RFI)被限制为产生在电磁频谱的射频部分即通常为 10 KHz到 100 GHz之间的频 带部分上。
为了有效地防止电磁干扰 (EMI) /射频干扰 (RFD, 一般地, 在电磁干扰 /射频 干扰源和需要保护的区域之间放置屏蔽件。此屏蔽件用于防止电磁能量从电磁干扰 /射 频干扰源发射出来; 同样地, 其也可以用于防止外部电磁能量进入到电磁干扰 /射频干 扰源中。
一般地,屏蔽体采用导电封闭体的形式,该封闭体例如可通过 PCB板上的接地线 等接地。 在现有技术中, 此导电封闭体可以整体由电磁屏蔽衬垫材料形成。 另外, 在 实际工程中, 由于内部电路或者结构上的需要, 可能在导电封闭体上形成有开槽, 从 而在屏蔽体上形成间隙。 此时, 可以采用屏蔽衬垫将屏蔽体上形成的间隙予以填充, 以防止电磁能量从电磁干扰 /射频干扰源发射出来或外部电磁能量进入到电子 /电气设 备中。
近年来, 便携式移动电话、 PDA、 导航系统等电子 /电气设备越来越小型化, 而且 要求其具有自由移动性。 一方面, 为阻隔灰尘或湿气等进入到这些通信设备的核心部 件例如 LCD模块的内部, 并防止由个人携带或运送过程中的冲撞、掉落等引起的对模 块的冲击和振动, 需要在电子 /电气设备中的电子模块外部设置具有高冲击和振动吸收 功能的吸收衬垫材料。 该吸收衬垫材料一般由多微孔材料, 例如聚氨酯泡沫体构成, 以使其具有一定的弹性回复性。另一方面, 随着使用这些电子通信设备中的 LCD模块 的画面变大且影像、 文字通信、 数码照相机等功能的多样化, 使得电子 /电气设备中采 用的电路和电子模块对来自设备内部和外部的静电、 电磁波、 磁场等非常敏感, 易于 受到内、 外部电磁干扰 /射频干扰源的影响。
鉴于此,要求上述电子 /电气设备中的吸收衬垫材料不仅具有高冲击和振动吸收功 能, 还需要具备在电子 /电气设备中的窄小空间内实现无间隙地密封的功能, 以及对电 子 /电气设备中内、 外部产生的电磁干扰 (EMI) /射频干扰 (RFI) 进行屏蔽的功能。
US 6,309,742披露了一种屏蔽衬垫, 其通过在开孔泡沫体上沉积一层金属材料而 制成。 由于沉积的金属材料穿透开孔泡沬体, 从而使开孔泡沬体具有良好的导电性。 相应地, 将此衬垫材料冲切成各种形状或制成屏蔽体并且填充或覆盖在电子 /电气设备 周围, 可以利用其导电性对电子 /电气设备中内、 外部产生的电磁干扰(EMI) /射频干 扰(RFI)进行屏蔽。 但是, 上述现有技术具有下述缺点和问题: 上述衬垫材料具有一 定导电性, 从而可以对静电、 电场等具有比较好的屏蔽效果, 但是其对电子 /电气设备 中内、 外部产生的磁场, 特别是近地磁场的屏蔽效果不理想。
因此, 需要一种可以有效地同时对电场和磁场进行良好屏蔽的电磁屏蔽衬垫。 发明内容
本发明的目的在于提供一种电磁屏蔽衬垫, 其能够同时实现电场屏蔽功能和磁场 屏蔽功能。
根据本发明的一个方面, 提供一种电磁屏蔽衬垫, 其包括泡棉基体和沉积在所述 泡棉基体上的金属层,所述金属层包含镍和钴,其中 Co/(Co+Ni)重量比为 0.2%至 85%。
根据本发明的另一个方面, 提供一种制备电磁屏蔽衬垫的方法, 所述方法包括如 下步骤:
对泡棉基体进行预金属化处理; 和
对经预处理的泡棉基体进行金属化处理, 得到包含 Co和 Ni的金属层。
本发明的电磁屏蔽衬垫能够同时实现电场屏蔽功能和磁场屏蔽功能。 附图说明
图 1是根据本发明一个实施方案的电磁屏蔽衬垫的结构示意图。
图 2是根据本发明另一个实施方案的电磁屏蔽衬垫的结构示意图。
图 3是本发明中磁性能测试方法的示意图。 图 4是根据本发明一个实施例的电磁屏蔽衬垫的 SEM照片。
图 5是根据本发明一个实施例的电磁屏蔽衬垫的 EDS谱图。 具体实施方式
除非特别说明, 本发明中的百分比和比率均为按重量计。
在本发明的电磁屏蔽衬垫中,泡棉基体为具有分布于其中的开孔的开孔泡棉结构。 泡棉基体的材料不受限制, 只要其具有弹性并在外力作用下具有预定的回复性即可。
在本发明的一个实施方案中, 电磁屛蔽衬垫的泡棉基体为高分子弹性材料、 热弹 性体经发泡工艺形成的开孔泡棉, 所述高分子弹性材料为例如聚氨酯、 聚氯乙稀、 硅 树脂、 乙烯醋酸乙烯酯共聚物 (EVA)、 聚乙烯等。
在本发明的一个实施方案中, 电磁屏蔽衬垫的泡棉基体的厚度为 0.1至 50 mm, 优选 0.1至 10 mm,更优选 0.5至 5 mm,最优选 1.0至 3.0 mm。如果厚度小于 0.1 mm, 则会造成无法实现压缩和回弹特性; 如果厚度大于 50 mm, 则在泡棉基体上沉积金属 后在垂直方向的电导率会有下降的趋势。
一方面, 为了赋予泡棉基体冲击吸收性和振动阻断性, 同时, 为了保证在将电磁 屏蔽衬垫压合到预定间隙中的密合性, 需要泡棉基体在外力施加到其上时具有一定的 可压缩性。 在本发明的一个实施方案中, 电磁屏蔽衬垫的泡棉基体的可压縮形变范围 为初始厚度的 50%以上, 优选 70%以上, 更优选 80%以上, 最优选 90%以上。 如果可 压缩形变范围小于初始厚度的 50%, 则对高冲击和振动吸收的功能有不足的倾向。 本 文中所用的可压缩形变为在不超过 50 PSI的力作用下的值。
另一方面, 需要在外力从泡棉基体上去除时, 其具有一定的回复性。 在本发明的 一个实施方案中, 电磁屏蔽衬垫的泡棉基体的残余形变 (永久形变)为 50%以下, 优选 30%以下, 更优选 20%以下, 最优选 10%以下。 如果泡棉基体的残余形变 (永久形变) 大于 50%, 则在长期使用后, 对高冲击和振动吸收以及无间隙密封的功能会有下降的 倾向。
在本发明的一个实施方案中, 电磁屏蔽衬垫的泡棉基体的开孔隙度为 10 至 500 ppi, 优选 50至 300 ppi, 更优选 50至 200 ppi, 最优选 80至 150 ppi. 如果泡棉基体的 开孔隙度小于 10 ppi, 则会使金属层沉积难以实现; 如果开孔隙度大于 500 ppi, 则泡 棉基体的机械强度会有不足的倾向。为了使开孔泡棉基体具有良好的导电性和导磁性, 可以采用真空蒸镀、 电镀或化学镀层等方式将包含 Co、 Ni 的金属层沉积到开孔泡棉 基体中。
在本发明的一个实施方案中, 提供一种电磁屏蔽衬垫, 其包括泡棉基体和沉积在 所述泡棉基体上的金属层, 所述金属层包含镍和钴, 其中 Co/(Co+Ni)重量比为 0.2%至 85%,在一个优选实施方案中为 2%至 70%,在一个更优选的实施方案中为 5%至 50%, 在一个最优选的实施方案中为 5%至 35%。 由于开孔泡棉基体具有多个微小的开孔, 在将金属层沉积到开孔泡棉基体上之后, 开孔泡棉基体不仅具有表面导电性, 而且在 开孔泡棉基体的上下垂直方向和其它方向上也被赋予了自由导电性, 从而形成一种三 维的具有很好连续导电性的泡棉结构。 由于金属层中含有 Co, 电镀后泡棉的铁磁性能 也得到提高。 Co在 Co/Ni合金中的含量对于实现本发明的目的至关重要, 当 Co/Ni达 到一定比例后, 其导磁率会显著升高。 为了实现良好的导磁性, 必须保证 Co在 Co/Ni 合金中的含量在上述范围内, 本发明通过例如控制 Co2+和 Ni2+离子在电镀液中的比例 而实现了该目的。 当 Co/(Co+Ni)重量比在该范围以外时, 难以在保持良好导电性的同 时实现比较明显的对磁性能的增益效果。
在一个实施方案中,沉积有镍和钴的泡棉基体的 (Co+Ni)/泡棉重量比为 1%至 50%, 优选 2%至 30%, 更优选 3%至 20%, 最优选 5%至 10%。 金属沉积层的厚度为 10至 2000 nm,优选为 50至 1800 nm,更优选为 100至 1500 nm,最优选为 200至 1000 nm。 当 (Co+Ni)/泡棉重量比或金属沉积层的厚度在上述范围内时, 电磁屏蔽衬垫能够实现 良好的电场屏蔽功能和磁场屏蔽功能, 并且具有适宜的反回弹性。 随着 (Co+Ni)/泡棉 重量比或金属沉积层的厚度增加, 电磁屏蔽衬垫的反回弹性下降。
在本发明的一个实施方案中, 沉积在泡棉基体上的金属层中还包含选自钼、 锰、 铜、 铬等及其组合的金属。 沉积有金属层的泡棉基体的金属总量 /泡棉重量比为 1%至 50%, 优选 2%至 40%, 更优选 3%至 30%, 最优选 5%至 20%。 金属沉积层的厚度为 10至 2000 nm,优选为 50至 1800 nm,更优选为 100至 1500 nm,最优选为 200至 1000 nm。当金属总量 /泡棉重量比或金属沉积层的厚度在上述范围内时, 电磁屏蔽衬垫能够 实现良好的电场屏蔽功能和磁场屏蔽功能, 并且具有适宜的反回弹性。 随着金属总量 / 泡棉重量比或金属沉积层的厚度增加, 电磁屏蔽衬垫的反回弹性下降。
在本发明的另一个实施方案中, 在沉积于泡棉基体上的金属层上还涂覆有聚合物 层, 例如聚氨酯聚合物层。 聚合物层主要可以起到抗氧化、 保护金属镀层的作用。
在本发明的一个实施方案中, 电磁屏蔽衬垫的张力强度为 0.1 至 100 牛 /英寸 (N/inch), 优选 0.3至 80牛 /英寸, 更优选 0.6至 50牛 /英寸, 最优选 1至 30牛 /英寸。 如果电磁屏蔽衬垫的张力强度小于 0.1牛 /英寸, 则电磁屏蔽衬垫的加工性能较差。 本 发明中的张力强度测试按照 ASTM D 1000的方法,采用标准的 1英寸宽度的拉力断裂 强度测试进行。
在本发明的一个实施方案中, 电磁屏蔽衬垫的表面电阻为 1至 2000 m Q /O,优选 5至 ΙΟΟΟ ιη Ω /口, 更优选 10至 800 πι Ω /口, 最优选 20至 500 m Ω /口。 如果电磁屏蔽 衬垫的表面电阻大于 2000 ηι Ω /口, 则电磁屏蔽衬垫的电磁屏蔽功能会有不足的趋势。
在本发明的一个实施方案中, 电磁屏蔽衬垫的标准铁磁性吸引距离大于 1.5 cm, 优选大于 1.8 cm, 更优选大于 2 cm, 最优选大于 2.5 cm。 由于本发明是通过在泡棉基 材上沉积经过优化的 Co/Ni铁磁性镀层来提高泡棉的整体导磁性能, 这种材料因泡棉 基材柔软, 可压缩性大, 而不适用传统的软磁性材料的测试方法。 但由于磁导率是软 磁材料的铁磁性评估的一个重要参考参量, 磁导率的大小表征在同等大小的磁场力下 作用的大小, 即单位面积内的磁力线密集程度 (密度), 通常密度越大则软磁性能越好, 表现出的吸引作用力越大。 根据此理论, 本发明采用一个标准的永磁体作为恒定外磁 场, 其提供一个恒定的磁场力作用于金属化 (磁性化)的泡棉样品, 为了表征磁力的大 小, 利用恒定重量的泡棉作为载重, 通过发生作用的距离来判断其吸引力的大小。 可 以理解, 如果泡棉的重量一样, 在外磁场强度 (力)一样的情况下, 吸引距离越大表示 泡棉样品的磁导率越好, 磁性能越强。 本发明的电磁屏蔽衬垫具有较大的吸引距离, 显示出良好的磁性能。
在本发明的一个实施方案中, 电磁屏蔽衬垫的可压缩形变大于初始厚度的 30%, 优选大于初始厚度的 50%,更优选大于初始厚度的 70%,最优选大于初始厚度的 80%。 如果可压缩形变范围小于初始厚度的 30%, 则对高冲击和振动的吸收功能有不足的倾 向。
在本发明的一个实施方案中, 电磁屏蔽衬垫的残余形变 (永久形变)小于 50%, 优 选小于 30%, 更优选小于 20%, 最优选小于 10%。如果电磁屏蔽衬垫的残余形变 (永久 形变)大于 50%, 则在长期使用后, 对高冲击和振动的吸收以及无间隙密封的功能会有 下降的倾向。
除电镀金属的泡棉以外, 本发明的电磁屏蔽衬垫还可以包含其它功能层, 例如导 电层、 离型纸等。 所述的其它层通过粘结剂与泡棉连接。 粘结剂可以是导电胶, 也可 以是非导电胶。 当采用非导电胶时, 其可能对电磁屏蔽衬垫的电场屏蔽效果构成一定 的影响。 优选使用导电胶作为粘合剂。 导电胶可以通过在丙烯酸胶中添加适当比例的导电颗粒制成。 导电颗粒的量为, 例如, 使得 〔导电颗粒 /(导电颗粒 +胶)〕 重量比在 3%至 60%之间。 导电颗粒的类型可 以为, 例如镍粉、 银粉、 银包玻璃、 银包铜粉、 石墨粉 (碳粉)、 复合导电颗粒等。
导电层既可以是包括铜箔的各类金属箔, 也可以是各类金属化的编织物 /无纺织物 等。
本发明还提供一种制备电磁屏蔽衬垫的方法, 所述方法包括如下步骤: 对泡棉基 体进行预金属化处理; 和对经预处理的泡棉基体进行金属化处理, 得到含 Co和 Ni的 金属层。 其中, 预金属化处理为后续的金属化处理提供必要的准备, 其通过真空工艺 在泡棉基材上沉积薄薄的一层 Ni金属, 或其他电势位相近的金属如 Pb, 该金属层在 泡棉的纤维上是不连续的, 主要在随后的金属化处理中起到沉积核的作用, 例如在水 电镀中作为 Co2+和 Ni2+的沉积核, 从而保证有效的 Co2+和 Ni2+沉积, 使得 Co2+和 Ni2+ 离子同时迁移到泡棉基材上, 从而形成基本均匀、 致密并且牢靠的 Co/Ni合金镀层。 所述预金属化处理可以通过例如真空蒸镀、 化学气相沉积法、 等离子溅射法和等离子 化学气相沉积法完成。 所述金属化处理可以通过真空蒸镀、 电鍍或化学镀层等方式完 成, 例如通过水电镀完成。
为了使得电镀后的泡棉具有良好的铁磁性能, 需要控制 Co2+和 Ni2+离子在电镀液 中的比例, 从而保证在得到的金属层中, Co的含量在适宜范围内。 在本发明中, 电镀 液中的 Co2+/ ( Co2++Ni2+) 比率为, 例如, 0.2%至 85%, 优选为 2%至 70%, 更优选为 5%至 50%, 最优选为 5%至 35%。
图 1示出本发明电磁屏蔽衬垫的一个实施方案。 如图 1中所示, 电磁屏蔽衬垫包 括钴 /镍电镀的泡棉 1, 在其一侧通过导电胶 2结合铜箔 3, 并且通过导电胶 4在铜箔 3 上结合离型纸 5。
图 2示出本发明电磁屏蔽衬垫的另一个实施方案。 如图 2中所示, 电磁屏蔽衬垫 包括钴 /镍电镀的泡棉 1, 在其一侧结合有导电层 6, 在泡棉的另一侧上通过导电胶 2 结合铜箔 3 , 并且通过导电胶 4在铜箔 3上结合离型纸 5。
本发明中对开孔泡棉进行 Co/Ni金属化的制备工艺流程包括:
1 . 准备厚度、 宽度、 长度等符合要求的开孔泡棉;
2. 对开孔泡棉进行预金属化处理 (PVD工艺);
3. 对经预处理的开孔泡棉进行 Co/Ni水电镀金属化处理;
4. 烘干; 5. 收卷。 实施例
为了进一步说明本发明, 列举以下实施例, 但它并不限制各附加权利要求所定义 的发明范围。
I. 本发明中所使用的原料和来源概括如下。
聚氨酯 (PU)泡棉商购自日本井上株式会社 (INOAC ), 其牌号总结于表 1中。 表 1. PU泡棉性质
Figure imgf000008_0001
实施例中使用的氯化镍、 硫酸镍、 硫酸钴、 硼酸等化学品商购自国药集团, 工业 级。
II. 性质表征方法
1 . 残余形变测试
采用高精度数字式测厚仪 (543-392BS, 购自日本 Mitutoyo公司), 使用不锈钢材 质且四端采用螺母固定的形变保持夹具按照如下程序进行。
裁取一片 2英寸 χ2英寸的泡棉样品, 取 8个均匀分布的点, 测量其自由厚度 (无 形变厚度), 计算得到平均初始厚度 TQ。 在形变保持夹具不放置泡棉的情况下, 旋紧 四个角部的螺钉, 使其上下完全密合, 测量夹具的密合厚度 。 将泡棉样品置于形变 保持夹具的中心位置, 逐渐旋紧四个角部的螺钉, 使夹具的实测厚度 为 +0^/2), 艮卩,将泡棉压缩并固定在平均初始厚度 To的 50%。将夹有样品的夹具放到恒温烘箱中, 烘箱温度为 70°C±2°C , 保持 22小时。 取出夹具, 旋开螺钉, 取出泡棉, 在松弛状态 下冷却 10分钟后, 均匀取 8个点测量其自由厚度 (无形变厚度), 计算得到平均回弹 厚度 T3。 按照下式计算残余变形 X: X = ^ ~ ^ x lOOo/o 。
r
0
2. 表面电阻率测试
釆用 MIL-G-83528规定的标准测试夹具, 夹具的标准重量为 250克, 夹具电极采 用镀金处理, 单极与被测件的接触尺寸为: 25.4毫米 M.75毫米, 极间距是 25.4毫米。 将两个电极放置在电磁屏蔽衬垫的待测样品的一个表面上, 极间距是 25.4毫米, 读出 两个电极之间的电阻值即可。
3. 磁性能测试
本发明中磁性能测试的方法显示在图 3中,其中 1表示 NdFeB永磁体,2表示 Co/Ni 电镀泡棉样品, V表示恒定速度, D表示与由 NdFeB永磁体产生的磁场发生作用的距 离。 具体测试程序如下: 将 5.5~6.0 mg的泡棉放置在平坦木桌的表面上, 使 NdFeB永 磁体 (尺寸为 2.4 cmxl. l cmx0.3 cm, (BH)max=25 MGOe, 获自东北大学功能材料研究 所)以 l m/min的速度向下朝泡棉移动, 测量当泡棉与永磁体发生作用使得泡棉被吸引 上来时的距离。
4. 金属成分的含量和金属层厚度的测试
在本发明中, 金属成分的含量和金属层厚度使用能谱衍射方法 (EDS) 测试。 在能谱衍射试验中, 通过配套的扫描电镜 (SEM) 可以清楚地看到泡棉的纤维直 径尺寸及金属层的厚度。
所用仪器为获自日本电子的 OxFord JSM 6360LV SEM。 样品观测面积为 20 mm2
III. 实施例
实施例 1
首先对 PU泡棉 (MF-50P3 ) 在如下条件下进行 PVD真空电镀的预处理: 真空度: 约 0.2 Pa;
PVD设备外部温度: 室温;
靶材: 金属纯镍;
通过带状电镀 (web coating)得到镍镀层, 将镀层控制为对于 1.8毫米厚的泡棉, 每 平方米的镍克重小于 5克。
之后使用电镀液进行钴、 镍合金电镀。 电镀液的成分包括: 氯化镍、 硫酸镍、 硫 酸钴、 硼酸、 其他电解液活性添加剂及纯水, 配比见表 2。 所使用的电解槽的阳极为 镍板, 阴极为经过 PVD预电镀处理的泡棉, 槽液温度为室温, 工作电压为 <12 V, 采 用卷状的连续电镀, 线速度: 0.6米〜 1.5米 /分钟。
随后热鼓风烘干, 风温为 60~80摄氏度。
收卷速度与电镀速度相同。
使用在第 II部分中所述的方法对产品进行表征。 从 EDS得到 Co/(Co+Ni)的值为 31.0%。 - 实施例 2和 3
如实施例 1中所述进行, 不同之处在于使用表 2中所示配比的电镀液。 由 EDS得 到实施例 2禾 Π 3的 Co/(Co+Ni)的值分别为 22.4%和 19.9%。图 4和图 5分别为实施例 2 的 SEM照片和 EDS谱图。 比较例 1
使用不含硫酸钴的电镀液进行。 表 2. 电镀液的成分:
Figure imgf000010_0001
表 3中给出实施例 1至 3和比较例 1的可压缩性和导电性能测试结果。可以看到, 本发明实施例 1至 3的产品显示出更好的可压缩性和导电性能。 表 3. 产品的可压缩性和导电性能
Figure imgf000011_0001
表 4中给出实施例 1至 3和比较例 1根据 Π-3方法测量的磁性能数据。可以看到, 本发明实施例 1至 3的吸引距离远大于比较例 1的吸引距离, 如前文所述, 这证明本 发明的产品具有良好的导磁性。 表 4. 产品的磁性能
Figure imgf000011_0002
综上所述, 本发明提供了一种电磁屏蔽衬垫, 其具有良好的导电性和导磁性, 能 够同时实现电场屏蔽功能和磁场屏蔽功能。

Claims

权 利 要 求
1. 一种电磁屏蔽衬垫, 其包括- 泡棉基体; 和
沉积在所述泡棉基体上的金属层, 所述金属层包含镍和钴, 其中 Co/(Co+Ni)重量 比为 0.2%至 85%。
2. 根据权利要求 1所述的电磁屏蔽衬垫, 其中 Co/(Co+Ni)重量比为 2%至 70%, 优选为 5%至 50%, 更优选为 5%至 35%。
3. 根据权利要求 1所述的电磁屏蔽衬垫, 其中所述泡棉基体的可压縮形变为初始 厚度的 50%以上, 优选 70%以上, 更优选 80%以上, 最优选 90%以上。
4. 根据权利要求 1所述的电磁屏蔽衬垫,其中所述泡棉基体的残余形变为 50%以 下, 优选 30%以下, 更优选 20%以下, 最优选 10%以下。
5. 根据权利要求 1所述的电磁屏蔽衬垫, 其中所述泡棉基体的开孔隙度为 10至 500 ppi, 优选 50至 300 ppi, 更优选 50至 200 ppi, 最优选 80至 150 ppi。
6. 根据权利要求 1 所述的电磁屏蔽衬垫, 其中所述泡棉基体的厚度为 0.1 至 50 mm, 优选 0.1至 10 mm, 更优选 0.5至 5 mm, 最优选 1.0至 3.0 mm。
7. 根据权利要求 1所述的电磁屏蔽衬垫, 其中所述泡棉基体为高分子弹性材料或 热弹性体经发泡工艺形成的开孔泡棉。
8. 根据权利要求 7所述的电磁屏蔽衬垫, 其中所述高分子弹性材料包含聚氨酯、 聚氯乙稀、硅树脂、 乙烯醋酸乙烯酯共聚物(EVA)、聚乙烯或它们的混合物中的一种。
9. 根据权利要求 1所述的电磁屏蔽衬垫, 其中 (Co+Ni)/泡棉重量比为 1%至 50%, 优选 2%至 30%, 更优选 3%至 20%, 最优选 5%至 10%。
10. 根据权利要求 1所述的电磁屏蔽衬垫, 其中所述金属层的厚度为 10至 2000 nm, 优选为 50至 1800 nm, 更优选为 100至 1500 mn, 最优选为 200至 1000 nm。
11. 根据权利要求 1 所述的电磁屏蔽衬垫, 其中所述沉积在泡棉基体上的金属层 还包含选自钼、 锰、 铜、 铬及其组合的金属。
12. 根据权利要求 11所述的电磁屏蔽衬垫, 其中沉积有金属层的泡棉基体的金属 总量与泡棉重量比为 1%至 50%, 优选 2%至 40%, 更优选 3%至 30%, 最优选 5%至 20%。
13. 根据权利要求 1 所述的电磁屏蔽衬垫, 其还包含涂覆在沉积于泡棉基体上的 金属层上的聚合物层, 例如聚氨酯聚合物层。
14. 根据权利要求 1 所述的电磁屏蔽衬垫, 其还包含结合在所述泡棉基体上的其 它功能层。
15. 根据权利要求 14所述的电磁屏蔽衬垫, 其中所述其它功能层为导电层或离型 纸。
16. 根据权利要求 14所述的电磁屏蔽衬垫, 其中所述其它功能层通过粘结剂与所 述泡棉基体连接。
17. 根据权利要求 16所述的电磁屏蔽衬垫, 其中所述粘结剂是导电胶。
18. 根据权利要求 17所述的电磁屏蔽衬垫, 其中所述导电胶为添加了导电颗粒的 丙烯酸胶。
19. 根据权利要求 18所述的电磁屏蔽衬垫,其中所述导电颗粒存在的量为使得〔导 电颗粒 /(导电颗粒 +胶) ) 重量比在 3%至 60%之间。
20. 根据权利要求 18所述的电磁屏蔽衬垫, 其中所述导电颗粒为镍粉、 银粉、 银 包玻璃、 银包铜粉、 石墨粉 (碳粉)、 复合导电颗粒或它们的组合。
21. 根据权利要求 15所述的电磁屏蔽衬垫, 其中所述导电层是金属箔, 或金属化 的编织物或无纺织物。
22. 一种制备如权利要求 1所述的电磁屏蔽衬墊的方法, 所述方法包括如下步骤: 对泡棉基体进行预金属化处理以形成经预金属化的泡棉基体; 和
对经预金属化的泡棉基体进行金属化处理, 得到含 Co和 Ni的金属层。
23. 根据权利要求 22所述的方法, 其中所述预金属化处理包括真空工艺。
24. 根据权利要求 23所述的方法, 其中所述真空工艺包括真空蒸镀、 化学气相沉 积法、 等离子溅射法和等离子化学气相沉积法中的一种。
25. 根据权利要求 22所述的方法, 其中在所述预金属化处理中镀 Ni或 Pb。
26. 根据权利要求 22所述的方法, 其中所述金属化处理包括真空蒸镀、 电镀或化 学镀中的一种。
27. 根据权利要求 22所述的方法, 其中所述金属化处理包括水电镀。
28. 根据权利要求 27所述的方法,其中电镀液中的 C0 2+/ (Co2++Ni2+)比率为 0.2% 至 85%, 优选为 2%至 70%, 更优选为 5%至 50%, 最优选为 5%至 35%。
29. 根据权利要求 22所述的方法, 其中所述金属层还包含选自钼、 锰、 铜、 铬及 其组合的金属。
30. 根据权利要求 28所述的方法, 其中所述电镀液中还包含选自钼、 锰、 铜、 铬 的金属的离子或其组合。
PCT/CN2011/074517 2011-05-23 2011-05-23 电磁屏蔽衬垫及其制备方法 Ceased WO2012159258A1 (zh)

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