CN105309061B - 电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆 - Google Patents

电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆 Download PDF

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CN105309061B
CN105309061B CN201480035687.0A CN201480035687A CN105309061B CN 105309061 B CN105309061 B CN 105309061B CN 201480035687 A CN201480035687 A CN 201480035687A CN 105309061 B CN105309061 B CN 105309061B
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layer
alloy
electromagnetic wave
wave shielding
metal foil
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CN105309061A (zh
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田中幸一郎
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
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Abstract

[课题]提供耐腐蚀性比以往的镀Sn更优异的电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆。[解决手段]电磁波屏蔽用金属箔，在由厚度超过4μm的金属箔1构成的基材的单面或两面，形成包含A元素和B元素组的合金层2，所述A元素包含Sn或In，所述B元素组选自Ag、Ni、Fe、和Co中的1种以上，在合金层与基材之间形成有由B元素组构成的基底层3，所述A元素的附着量为10~300μmol/dm2、且B元素组的总附着量为40~900μmol/dm2。

Description

电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆
技术领域
本发明涉及层叠有树脂层或树脂膜且用于电磁波屏蔽材的金属箔、电磁波屏蔽材和屏蔽电缆。
背景技术
镀Sn覆膜具有耐腐蚀性优异且可焊性良好、接触电阻低这一特征。因此，例如作为车载电磁波屏蔽材的复合材料，对铜等的金属箔镀敷Sn来使用。
作为上述复合材料，使用了在由铜或铜合金箔构成的基材的一个面上层叠树脂层或膜，并在其它面上形成有镀Sn覆膜的结构（参照专利文献1）。
另外，作为等离子显示器用的电磁波屏蔽体，报告有如下技术：在透明基材上形成铜箔的电路，对铜箔的显示画面侧的表面实施由锡和镍和钼构成的合金镀敷，从而降低反射率（参照专利文献2）。
现有技术文献
专利文献
专利文献1：国际公开WO2009/144973号
专利文献2：日本特开2003-201597号公报。
发明内容
发明要解决的课题
然而，针对以汽车用途为首的室外环境中使用的电磁波屏蔽材要求严苛的耐腐蚀性，进而还需要耐受NOX、SOX之类的腐蚀性气体的耐性。另外，设想到发动机房等的高温环境中的使用，针对电磁波屏蔽材还要求耐热性。
本发明是为了解决上述课题而进行的，其目的在于，提供与以往的镀Sn相比耐腐蚀性、耐热性更优异的电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆。
用于解决问题的手段
本发明人等进行了各种研究，其结果，通过在金属箔的表面形成包含规定元素的合金层，与以往的镀Sn相比，成功地使耐腐蚀性、耐热性提高。
为了实现上述目的，本发明的电磁波屏蔽用金属箔在由厚度超过4μm的金属箔构成的基材的单面或两面形成包含A元素和B元素组的合金层，所述A元素包含Sn或In，所述B元素组选自Ag、Ni、Fe和Co中的1种以上，在前述合金层与前述基材之间形成有包含前述B元素组的基底层，前述A元素的附着量为10~300μmol/dm2、且前述B元素组的总附着量为40~900μmol/dm2。
前述合金层优选为金属间化合物。
前述合金层优选还包含选自P、W、Fe和Co中的1种以上的C元素组。
前述C元素组的总含有率相对于前述合金层总体优选为40wt%以下。
前述合金层中包含的Cu、Al和Zn的总含有率优选为10wt%以下。
前述合金层的表面优选形成有氧化物。
前述基材优选由金、银、铂、不锈钢、铁、镍、锌、铜、铜合金、铝或铝合金构成。
优选的是，前述基材为铝或铝合金，前述基材与前述基底层之间形成有Zn层。
本发明的电磁波屏蔽材中，在前述电磁波屏蔽用金属箔的单面层叠有树脂层。
前述树脂层优选为树脂膜。
本发明的屏蔽电缆被前述电磁波屏蔽材屏蔽。
发明的效果
根据本发明，能够获得与以往的镀Sn相比耐腐蚀性更优异的电磁波屏蔽用金属箔、电磁波屏蔽材和屏蔽电缆。
附图说明
图1是表示本发明的第一实施方式所述的电磁波屏蔽用金属箔的截面图。
图2是表示本发明的实施方式所述的电磁波屏蔽材的截面图。
图3是实施例4的试样的基于STEM的截面图像的示意图。
图4是实施例4的试样的基于STEM的线性分析的结果的示意图。
具体实施方式
以下，针对本发明的实施方式进行说明。需要说明的是，本发明中，%在没有特别限定的情况下表示质量%。
如图1的（b）所示那样，本发明的第1实施方式所述的电磁波屏蔽用金属箔10具备：由金属箔构成的基材1、在基材1单面上形成的合金层2、以及在基材1与合金层2之间形成的基底层3。
（基材）
基材1只要是发挥出电磁波屏蔽效果的高导电性金属即可。作为基材1，可列举出金、银、铂、不锈钢、铁、镍、锌、铜、铜合金、铝或铝合金等的箔，通常为铜或铝的箔。
基材1的形成方法没有特别限定，例如可以进行压延来制造，也可以通过电镀来形成箔。另外，还可以在后述电磁波屏蔽材的树脂层或树脂膜的表面进行干式镀敷来成膜为基材1。
基材1的厚度超过4μm。基材1的厚度为4μm以下时，屏蔽数十MHz的低频的性能差，且难以通过压延、电解来制造基材1，进而操作性差。基材1的厚度优选为5~100μm、更优选为6~50μm。基材1的厚度厚于100μm时，有时柔软性差、在后工序中难以加工，且原料成本也增加。
作为基材1而使用铜箔时，铜箔的种类没有特别限定，典型而言，可以以压延铜箔、电解铜箔的形态来使用。一般来说，电解铜箔通过由硫酸铜镀浴、氰化铜镀浴在钛或不锈钢的桶上电解析出铜来制造，压延铜箔通过重复进行利用压延辊的塑性加工和热处理来制造。
作为压延铜箔，可以使用纯度为99.9%以上的无氧铜（JIS-H3100（C1020））或韧铜（JIS-H3100（C1100））。另外，作为铜合金箔，可以根据要求强度、导电性来使用公知的铜合金。作为公知的铜合金，可列举出例如掺杂0.01~0.3%的锡的铜合金、掺杂0.01~0.05%的银的铜合金，尤其是，作为导电性优异的铜合金，常用Cu-0.12%Sn、Cu-0.02%Ag。例如，作为压延铜箔，可以使用导电率为5%以上者。作为电解铜箔，可以使用公知者。
另外，作为铝箔，可以使用纯度为99.0%以上的铝箔。另外，作为铝合金箔，可以根据要求强度、导电率来使用公知的铝合金。作为公知的铝合金，可列举出例如掺杂0.01~0.15%的Si和0.01~1.0%的Fe的铝合金、掺杂1.0~1.5%的Mn的铝合金。
（合金层）
合金层2含有：包含Sn或In的A元素和选自Ag、Ni、Fe和Co中的1种以上的B元素组。
镀Sn覆膜据称耐腐蚀性优异，但耐受NOX、SOX之类的腐蚀性气体的耐性未必高。
因而，通过形成包含Sn或In和规定元素的合金层2来代替纯Sn，能够提高耐腐蚀性、耐热性。
合金层2优选为金属间化合物。作为金属间化合物，可列举出例如Ag3Sn、Ni3Sn4、FeSn2、CoSn等。与非平衡合金层相比，金属间化合物的耐腐蚀性良好。
合金层2还可以包含选自P、W、Fe和Co中的1种以上的C元素组。合金层2包含C元素组时，合金层2的耐腐蚀性提高。合金层中的C元素组的总比例优选为1~40质量%、进一步优选为5~30质量%。
合金层2中包含的Cu、Al和Zn的总含有率为10wt%以下，优选为2wt%以下。合金层2中包含的Cu、Al和Zn的总含有率超过10wt%时，合金层2容易氧化、接触电阻增加。Cu、Al和Zn的总含有率是利用STEM（扫描透射型电子显微镜）进行线性分析，并将构成合金层2的各元素作为指定元素，且将指定元素的总和记作100%时的比例。
（基底层）
基底层3由B元素组构成。基底层3防止基材的构成元素从基材1向合金层2扩散，因此即使暴露于高温环境下，接触电阻也难以增加。例如基材使用铜箔时，Cu若向合金层2中扩散，则合金层2中的Cu被大气氧化，接触电阻增加。另外，基材使用铝箔时，想要在基材上镀敷合金层2时，需要在基材上首先置换镀敷Zn。因此，Zn从Zn镀层向合金层2扩散。此时，耐受盐水的耐腐蚀性降低。另外，合金层2中的Zn被大气氧化，接触电阻增加。因而，在Zn镀层与合金层2之间设置基底层3，防止Zn的扩散。
即，基材1包含Cu、Al、Zn时（例如基材1为铜箔时），通过形成基底层3，能够降低从基材1向合金层2扩散的Cu、Al、Zn的量。
基底层3可以由包含B元素组和C元素组的合金层构成。
（总附着量）
上述A元素的总附着量为10~300μmol/dm2，优选为20~200μmol/dm2，进一步优选为30~90μmol/dm2。
A元素的总附着量不足10μmol/dm2时，未充分形成合金层2，合金层2的耐腐蚀性降低。另一方面，A元素的总附着量超过300μmol/dm2时，电磁波屏蔽材例如用于汽车用电缆等时，在制造工序、安装于汽车时施加弯曲等变形而在合金层2表面产生裂纹、耐腐蚀性降低。另外，导致成本上升。
上述B元素组的总附着量为40~900μmol/dm2，优选为60~800μmol/dm2，更优选为75~700μmol/dm2。
B元素组的总附着量不足40μmol/dm2时，未充分形成合金层2，合金层2的耐腐蚀性降低。B元素组的总附着量超过900μmol/dm2时，施加弯曲等变形时，基底层3产生裂纹、耐腐蚀性降低。另外，导致成本上升。
另外，总附着量是指：合金层2等形成于基材1的两面时，两面的合金层2和基底层3的附着量的总和。
优选在合金层2的表面形成有A元素的氧化物。A元素的氧化物的耐腐蚀性高、合金层的表面存在氧化物时，合金层的耐腐蚀性进一步提高。
氧化物可以形成层，也可以不形成层，只要存在于合金层2的表面即可，为1~50nm、更优选为3~30nm、进一步优选为5~20nm的厚度即可。氧化物的接触电阻比合金层2高，因此层的厚度超过50nm时，接触电阻增加。
（合金层的形成方法）
合金层2可以通过合金镀敷（湿式镀敷）、使用构成合金层的合金的靶材进行的溅射、使用构成合金层的成分进行的蒸镀等来形成。
另外，如图1的（a）所示那样，例如，在基材1的单面首先形成由B元素组构成的第1镀层21，在第1镀层21的表面形成由A元素构成的第2镀层22后，进行热处理而使第1镀层21的元素扩散在第2镀层22中，从而也可以形成图1的（b）所示的合金层2。此时，增加第1镀层21的厚度，使第1镀层21的一部分在热处理后以基底层3的形式残留。另外，如图1的（a）所示那样，通过加热而形成合金层2时，在形成第2镀层22时通过自然氧化而在第2镀层22上形成氧化物，即使利用之后的加热来进行合金化，氧化物也会残留于合金层2表面。该氧化物具有提高耐腐蚀性之类的特性的效果。
但是，优选将热处理时的气氛的氧浓度设为2%以下，以便不会因热处理而在合金层2的表面过量地形成氧化物。氧浓度超过2%时，有时氧化物容易生长，氧化物的厚度达到50nm以上而导致初始的接触电阻增加。热处理温度没有特别限定，A元素为Sn时，优选为80~230℃，A元素为In时，优选为80~150℃。热处理温度超过A元素的熔点时，A元素熔融而成为液相，急剧地进行合金化，基底层3局部地消失，耐热性、耐腐蚀性降低。热处理时间没有特别限定，可以设为1~15小时左右。
热处理不充分时，无法形成金属间化合物，而是形成A元素与B元素的浓度沿着厚度方向阶梯性地变化的非平衡合金层。
另外，利用图1的（a）所示方法形成合金层2时，若第1镀层21或第2镀层22是容易扩散的元素，则不进行热处理也可以在常温下进行合金化。
自不用说，也可以在基材1的表面上直接通过镀敷等依次形成基底层3、合金层2而不进行热处理。另外，基底层3、合金层2除了利用湿式镀敷形成之外，还可以利用蒸镀、PVD、CVD等来形成。
需要说明的是，C元素组也可以在形成合金层2时包含在合金层2自身中。另外，使基底层3包含C元素组并在基底层3的表面形成合金层2后，也可以通过热处理而使C元素组扩散在合金层2中。
接着，参照图2，针对本发明的实施方式所述的电磁波屏蔽材100进行说明。电磁波屏蔽材100是将电磁波屏蔽用金属箔10和位于该金属箔10单面的树脂层或树脂膜4层叠而得到的。
作为树脂层，可以使用例如聚酰亚胺等树脂，作为树脂膜，可以使用例如PET(聚对苯二甲酸乙二醇酯)、PEN（聚萘二甲酸乙二醇酯）的膜。树脂层、树脂膜可以利用粘接剂粘接于金属箔，也可以不使用粘接剂地将熔融树脂浇铸在金属箔上，或者使膜热压接在金属箔上。另外，还可以使用：通过PVD、CVD直接将铜、铝的层以基材的形式形成于树脂膜而得到的膜；通过PVD、CVD将铜、铝的薄层以导电层的形式形成于树脂膜后，在该导电层上通过湿式镀敷厚厚地形成金属层而得到的镀金属膜。
作为树脂层、树脂膜，可以使用公知的树脂层、树脂膜。树脂层、树脂膜的厚度没有特别限定，可适合地使用例如1~100μm、更优选3~50μm的物质。另外，使用粘接剂时，粘接层的厚度例如可以为10μm以下。
从材料轻薄化的观点出发，电磁波屏蔽材100的厚度优选为1.0mm以下、更优选为0.01~0.5mm。
实施例
接着，列举出实施例更详细地说明本发明，但本发明不限定于这些实施例。
（基材）
作为压延铜箔，使用了调整至规定厚度的压延铜箔（JX日矿日石金属株式会社制的型号C1100）。
作为电解铜箔，使用了厚度为8μm的无粗化处理的电解铜箔（JX日矿日石金属株式会社制的型号JTC箔）。
作为Cu镀金属膜，使用了厚度为8μm的喷镀金属CCL（日矿金属株式会社制的制品名“マキナス”）。
作为铝箔，使用了厚度为12μm的铝箔（Sunalumi工业株式会社制）。
作为Al镀金属膜，使用了在厚度为12μm的PET膜（东洋纺绩株式会社制）上通过真空蒸镀形成有6μm铝的膜。
(合金层)
将合金层形成在上述基材的单面上。表1示出合金层的形成方法。
表1中，“镀敷”是指按照图1的（a）所示方法依次镀敷第1镀层21、第2镀层22后，按照表1所示的条件进行热处理而完成的镀敷。表1中，“合金镀敷”是指在基材上通过镀敷而形成基底层后，利用合金镀敷在基底层的表面上形成合金层而完成的合金镀敷。
需要说明的是，Ni、Sn、Ag、Co、Fe、Cu、Zn、各种Ni合金的各镀敷按照以下的条件来形成。
镀Ni：硫酸Ni浴（Ni浓度：20g/L、电流密度：2~10A/dm2）
镀Sn：苯酚磺酸Sn浴（Sn浓度：40g/L、电流密度：2~10A/dm2）
镀Ag：氰化Ag浴（Ag浓度：10g/L、电流密度：0.2~4A/dm2）
镀Co：氰化Ag浴（Co浓度：20g/L、电流密度：1~8A/dm2）
镀Fe：硫酸Fe浴（Fe浓度：20g/L、电流密度：2~10A/dm2）
镀Cu：硫酸Cu浴（Cu浓度：20g/L、电流密度：2~10A/dm2）
镀Zn：硫酸Zn浴（Zn浓度：20g/L、电流密度：1~5A/dm2）
镀Ni-Sn：焦磷酸盐浴（Ni浓度10g/L、Sn浓度10g/L、电流密度：0.1~2A/dm2）
镀Ni-P：硫酸浴（Ni浓度：20g/L、P浓度：20g/L、电流密度：2~4A/dm2）
镀Ni-W：硫酸浴（Ni浓度：20g/L、W浓度：20g/L、电流密度：0.1~2A/dm2）
镀Ni-Fe：硫酸浴（Ni浓度：20g/L、Fe浓度：10g/L、电流密度：0.1~2A/dm2）
镀Ni-Co：硫酸浴（Ni浓度：20g/L、Co浓度：10g/L、电流密度：0.1~2A/dm2）
表1中，“溅射”是依次溅射Ni、Sn后，按照表1所示条件进行了热处理。
表1中，“合金溅射”是在基材上溅射Ni而形成基底层后，使用相应的合金靶材进行溅射而形成合金层。需要说明的是，利用合金溅射而成膜的层是合金层自身的组成，因此未进行热处理。
需要说明的是，溅射、合金溅射按照以下的条件来进行。
溅射装置：间歇式溅射装置（ULVAC公司、型号MNS-6000）
溅射条件：极限真空1.0×10-5Pa、溅射压力0.2Pa、溅射电力：50W
靶材：Ni（纯度3N）、Sn（纯度3N）、Ni-Sn（Ni:Sn=30:70质量%）
表1中，“蒸镀”按照以下的条件来进行。
蒸镀装置：真空蒸镀装置（ULVAC公司、型号MB05-1006）
蒸镀条件：到达真空度5.0×10-3Pa、电子束加速电压6kV
蒸镀源：Ni（纯度3N）、In（纯度3N）、Sn（纯度3N）
（附着量的测定）
将所得电磁波屏蔽用金属箔切成50mm×50mm，将表面的覆膜溶于混合有HNO3（2重量%）和HCl（5重量%）的溶液。并且，利用ICP发光分光分析装置（エスアイアイ・ナノテクノロジー株式会社制、SFC-3100）对溶液中的金属浓度进行定量，由单位面积的金属重量算出附着量（μmol/dm2）。
（层构成的判定）
针对所得电磁波屏蔽用金属箔，利用STEM（扫描透射型电子显微镜、日本电子株式会社制JEM-2100F）进行线性分析，判定层构成。分析出的指定元素是A元素、B元素组、C元素组、C、S和O。另外，将上述指定元素的总和设为100%，分析各元素的浓度(wt%)（加速电压：200kV、测定间隔：2nm）。
将A元素的总量和B元素组的总量分别为5wt%以上的层作为合金层2。例如，B元素包含两种元素时，采用各元素的总值。
将与合金层2相比位于表层侧、包含A元素的总和为5wt%以上且O为5wt%以上的层作为氧化物，将与合金层2相比位于下层侧、包含B元素组的元素总和为5wt%以上且A元素的总和不足5wt%的层作为基底层3。
将基于上述定义的合金层2中的Cu、Al、Zn和C元素的比例的平均值作为Cu、Al、Zn和C元素的含有率。
接着，将所得电磁波屏蔽用金属箔的合金层侧表面作为外侧而卷绕于直径为2mm的管后，恢复至卷绕前的状态，评价以下的耐热性、耐腐蚀性、屏蔽效果。
（耐热性）
另外，针对所得电磁波屏蔽用金属箔的合金层侧的表面，分别在120℃下大气加热500小时后，测定合金层侧的最外表面的接触电阻。
接触电阻的测定中，使用山崎精机株式会社制的电接点模拟器CRS-1，利用四端子法进行测定。探针：金属探针、接触载重：20gf、偏压电流：10mA、滑动距离：1mm
◎：接触电阻不足20mΩ
○：接触电阻为20mΩ以上且不足100mΩ
×：接触电阻为100mΩ以上
大气加热后的接触电阻的评价若为◎或○，则可以说耐热性良好。
（耐腐蚀性）
另外，针对所得电磁波屏蔽用金属箔的合金层侧的表面，不进行大气加热地进行耐腐蚀性试验（盐水喷雾试验和气体腐蚀试验）后，测定合金层侧的最外表面的接触电阻。
接触电阻的测定与上述耐热性试验同样进行。
盐水喷雾试验基于JIS-Z2371（温度：35℃、盐水成分：氯化钠、盐水浓度：5wt%、喷雾压力：98±10kPa、喷雾时间：48h）。
◎：接触电阻不足20mΩ
○：接触电阻为20mΩ以上且不足100mΩ
×：接触电阻为100mΩ以上
气体腐蚀试验基于IEC60512-11-7的试验方法4（温度：25℃、湿度：75%、H2S浓度：10ppb、NO2浓度：200ppb、Cl2浓度：10ppb、SO2浓度：200ppb、试验时间：21天）。
◎：接触电阻不足20mΩ
○：接触电阻为20mΩ以上且不足100mΩ
×：接触电阻为100mΩ以上
盐水喷雾试验和气体腐蚀试验的评价若为◎或○，则可以说耐腐蚀性良好。
（电磁波屏蔽效果）
另外，在测定频率为50~1000MHz的范围内，利用KEC（关西电子工业振兴中心）法评价所得电磁波屏蔽用金属箔的电磁波屏蔽效果。KEC法是以装置内不存在试样的状态作为基准，通过分贝显示来评价在装置内插入试样时的衰减量（电磁波屏蔽效果）的方法，值越大则电磁波屏蔽效果越优异。
信号发生器：SIGNAL GENERATOR SML02（ROHDE＆SCHWARZ公司制）
频谱分析仪：R3132 SPECTRUM ANALYZER（ADVANTEST公司制）
针对各试样，按照上述KEC法分别测定3次，将其值进行平均化并按照以下基准进行判定。电磁波屏蔽效果的评价若为○或△，则在实用上没有问题。
○：衰减量超过80dB
△：衰减量超过40dB且为80dB以下
×：衰减量不足40dB
将所得结果示于表1、表2和图3~图4。
由表1、表2可明确：在基材的表面具有包含A元素和B元素组（以及根据需要的C元素组）的合金层、在合金层与基材之间形成有由B元素组（以及根据需要的C元素组）构成的基底层、A元素的总附着量为10~300μmol/dm2、且B元素组的总附着量为40~900μmol/dm2的各实施例的情况下，耐热性、耐腐蚀性、电磁波屏蔽效果优异。
尤其是，以A元素的熔点以下的温度进行热处理而形成了合金层的实施例1~5、7~15、18、20~23的情况下，与未进行热处理的实施例6、16、17、19和利用熔点以上的温度进行了热处理的实施例24相比，耐腐蚀性更优异。这是因为：如后所述，合金层为金属间化合物。
需要说明的是，图3、4分别表示实施例4的试样的基于STEM的截面图像和基于STEM的线性分析的结果。根据线性分析的结果可知，截面图像中的X层、Y层分别为Ni-Sn合金层、Ni层。
另外，通过TEM（日本电子株式会社制、JEM-2100F）分析各实施例和比较例的合金层的电子衍射图案，结果确认：实施例1~5、7~15、18、20~23、比较例1、3、5、9的合金层均为金属间化合物。
A元素的总附着量超过300μmol/dm2的比较例1、3的情况下，合金层产生裂纹，因此耐热性、耐腐蚀性差。
A元素的总附着量不足10μmol/dm2的比较例2的情况下，耐热性、耐腐蚀性差。
B元素组的附着量不足40μmol/dm2的比较例4的情况下，耐热性、耐腐蚀性差。
B元素组的附着量超过900μmol/dm2的比较例5的情况下，合金层产生裂纹，因此耐热性、耐腐蚀性差。
未形成基底层3的比较例6的情况下，通过镀敷后的热处理，基材的Cu扩散至合金层，合金层中的Cu浓度超过10%，因此耐热性、耐腐蚀性差。
利用超过A元素熔点的温度进行了热处理的比较例7的情况下，合金化局部地过度进行，因此原本成为基底层的图1的层21的一部分不会以基底层3的形式残留，合金层的一部分直接形成在基材上。因此，基材的Cu在热处理时扩散至合金层中，合金层中的Cu浓度超过10%，因此耐热性、耐腐蚀性差。
未形成基底层3的比较例8的情况下，基材的Cu在耐热试验后扩散至合金层，因此耐热性差。但是，比较例8的情况下，在形成合金层时未进行热处理，因此Cu不会扩散至合金层，合金层中的Cu浓度不足10%，因此耐腐蚀性良好。
基材的厚度为4μm以下的比较例9例的情况下，电磁波屏蔽效果差。
使用Cu来代替B元素组的比较例10的情况下，耐热性、耐腐蚀性差。
使用Zn来代替A元素的比较例11的情况下，耐热性、耐腐蚀性差。
附图标记说明
1 金属箔
2 合金层
3 基底层
4 树脂层或树脂膜
10 电磁波屏蔽用金属箔
100 电磁波屏蔽材。

Claims (11)

1.电磁波屏蔽用金属箔，其中，在由厚度超过4μm的金属箔构成的基材的单面或两面，形成包含A元素和B元素组的合金层，所述A元素包含Sn，所述B元素组选自Ag、Ni、Fe和Co中的1种以上，在所述合金层与所述基材之间形成有包含所述B元素组的基底层，所述A元素的附着量为10~300μmol/dm2，且所述B元素组的总附着量为40~900μmol/dm2，
在所述合金层的表面不存在由所述A元素构成的金属层。
2.根据权利要求1所述的电磁波屏蔽用金属箔，其中，所述合金层为金属间化合物。
3.根据权利要求1或2所述的电磁波屏蔽用金属箔，其中，所述合金层还包含选自P、W、Fe和Co中的1种以上的C元素组。
4.根据权利要求3所述的电磁波屏蔽用金属箔，其中，所述C元素组相对于所述合金层总体的总含有率为40wt%以下。
5.根据权利要求1或2所述的电磁波屏蔽用金属箔，其中，所述合金层中包含的Cu、Al和Zn的总含有率为10wt%以下。
6.根据权利要求1或2所述的电磁波屏蔽用金属箔，其中，在所述合金层的表面形成有氧化物。
7.根据权利要求1或2所述的电磁波屏蔽用金属箔，其中，所述基材由金、银、铂、不锈钢、铁、镍、锌、铜、铜合金、铝或铝合金构成。
8.根据权利要求1或2所述的电磁波屏蔽用金属箔，其中，所述基材为铝或铝合金，在所述基材与所述基底层之间形成有Zn层。
9.电磁波屏蔽材，其中，在权利要求1~8中任一项所述的电磁波屏蔽用金属箔的单面层叠有树脂层。
10.根据权利要求9所述的电磁波屏蔽材，其特征在于，所述树脂层为树脂膜。
11.屏蔽电缆，其被权利要求9或10所述的电磁波屏蔽材屏蔽。
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