CN113261158A - 电波吸收体 - Google Patents
电波吸收体 Download PDFInfo
- Publication number
- CN113261158A CN113261158A CN201980085933.6A CN201980085933A CN113261158A CN 113261158 A CN113261158 A CN 113261158A CN 201980085933 A CN201980085933 A CN 201980085933A CN 113261158 A CN113261158 A CN 113261158A
- Authority
- CN
- China
- Prior art keywords
- wave absorber
- radio wave
- layer
- dielectric layer
- resistive film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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Abstract
本发明所要解决的技术问题在于,提供一种电波吸收体,该电波吸收体对于斜入射、特别是对于在60GHz附近的电波的斜入射具有良好的电波吸收性,该技术问题由一种电波吸收体解决,该电波吸收体在45°入射的圆偏振波的测定中,其在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。
Description
技术领域
本发明涉及一种电波吸收体。
背景技术
近年,移动电话、智能手机等的便携通信机器的普及飞速进展,另外在车辆等中也搭载了大量的电子机器,它们产生的电波·噪声导致的电波干扰、其他的电子机器的故障等的问题多有发生。作为防止这样的电波干扰、故障等的对策,各种电波吸收体正在被研究。例如,专利文献1中公开了在60~90GHz的频带中,电磁波吸收量为20dB以上的频带的带宽为2GHz以上的电磁波吸收体。
现有技术文献
专利文献
专利文献1:特开第2018-098367号公报
发明内容
发明所要解决的技术问题
根据电波吸收体的用途,电波吸收体有时无法以使电波从法线方向入射的方式进行配置。此时,对斜入射的电波吸收性就很重要。本发明者着眼于这一点进行了研究,发现,以往的电波吸收体已经能够对应从法线方向入射的电波,但无法充分地吸收斜入射的电波。
因此,本发明以提供一种对于斜入射具有良好的电波吸收性的电波吸收体为课题。特别是,以提供一种对于60GHz附近的电波的斜入射具有良好的电波吸收性的电波吸收体为问题。
用于解决问题的技术方案
在进行研究的过程中,本发明人员发现了通过对45度入射时的特性进行最优化,能够对来自各个角度的入射发挥良好的电波吸收性。并且,基于上述发现,本发明人员进行了进一步锐意研究的结果,发现了一种电波吸收体能够解决上述技术问题,该电波吸收体在45°入射的圆偏振波的测定中,其在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。本发明人员基于上述发现继续进行研究,进而完成了本发明。
即,本发明包括下述实施方式。
第1项、一种电波吸收体,在45°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。
第2项、如第1项所述的电波吸收体,其具有电阻膜、电介质层、以及反射层。
第3项、如第2项所述的电波吸收体,其中,所述电阻膜的电阻值为250~520Ω/□。
第4项、如第2或3项所述的电波吸收体,其满足式(1):950≤d×√ε≤1500,
式中,d表示电介质层的厚度(μm),ε表示电介质层的相对介电常数。
第5项、如第2~4项中任一项所述的电波吸收体,其中,所述电介质层的相对介电常数为1~10。
第6项、如第2~5项中任一项所述的电波吸收体,其中,所述电阻膜包含阻隔层。
第7项、如第2~6项中任一项所述的电波吸收体,其中,所述电阻膜含有钼。
第8项、如第7项所述的电波吸收体,其中,所述电阻膜进一步含有镍和铬。
第9项、如第2~8项中任一项所述的电波吸收体,其中,所述反射层的电介质层一侧的表面的表面粗糙度(Rz)为1μm以上且10μm以下。
第10项、如第2~9项中任一项所述的电波吸收体,其进一步具有支撑体,其中,电波吸收体的支撑体一侧最表面的表面张力为35dyn/cm以上。
第11项、如第10项所述的电波吸收体,其中,所述支撑体的总光线透射率为30%以下。
第12项、一种λ/4型电波吸收体用部件,其具有电阻膜和电介质层,且在将厚度为10μm的铝板叠层至电介质层的另一个面上时,在45°入射的圆偏振波的测定中,该电波吸收体用部件在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。
发明的效果
根据本发明,可以提供一种电波吸收体,该电波吸收体对于斜入射、特别是对于在60GHz附近的电波的斜入射具有良好的电波吸收性。
附图说明
[图1]表示本发明的电波吸收体的一个例子的概要截面图。
[图2]上方的图是表示本发明的电波吸收体用部件的一个例子的概要截面图。下方是表示以与该部件相接的方式进行配置的、能够作为反射层发挥功能的被粘附体的一个例子的概要截面图。
[图3]表示本发明的电波吸收体的用途的一个例子(介由粘接剂而配置于壳体上的形态的一个例子)概要截面图。
具体实施方式
本说明书中,关于“含有”以及“包含”的表达,包含“含有”、“包含”、“实质上包含”以及“只包含”的概念。
本发明在一个实施方式中涉及一种电波吸收体(在本发明书中,有时称为“本发明的电波吸收体”),在45°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。以下将对此进行说明。
<1.特性>
本发明的电波吸收体具有以下特性(在本发明书中,有时也称为“本发明的特性”),即,在45°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。通过具备此特性,该电波吸收体能够对从各个角度的入射发挥出良好的电波吸收性。
所谓“在55~65GHz频带中吸收性能为15dB以上的吸收范围”是指,在55~65GHz频带中,显示出吸收性能为15dB以上(=反射衰减量为-15dB以下)的频带的宽度(单位GHz)。
可以通过以下方法测定上述吸收范围。
使用PNA微波网络分析仪N5227A(Keysight株式会社制造)、PNA-X系列2端口用毫米波控制仪N5261A(Keysight株式会社制造)、喇叭天线FSS-07(HVS株式会社制造)构成电波吸收测定装置。使用该电波吸收测定装置,基于JIS R1679测定电波吸收体的E波段(60~90GHz)、U波段(40~60GHz)处的电波吸收量。
需要说明的是,使电波以45°入射至测定样本的正面,相对于测定样本面中心的垂线,以相同角度安装喇叭天线。在入射波的电场垂直于入射面(TE波)的状态下进行测定,测定反射系数ГTE。
随后,以相同的方法,在入射波的电场与入射面平行(TM波)的状态下进行测定,测定反射系数ГTM。
将反射系数ГTE、ГTM的平均值设为圆偏振波的反射系数ГCP。
使用上述系数,通过-20log|ГCP|求出对于圆偏振波的反射衰减量。将反射衰减量的绝对值设为吸收性能。
上述吸收范围优选为5GHz以上,更优选为6GHz以上,进一步优选为8GHz以上,更进一步优选为9GHz以上,特别优选为9.5GHz以上。上述吸收范围由于是在55~65GHz频带中的范围,因此其上限为10GHz。
<2.构成>
本发明的电波吸收体的构成,只要具有所述本发明的特性就无特别限制,例如可以采用电波吸收体的公知的构成。在一个实施方式中,本发明的电波吸收体具备电阻膜、电介质层以及反射层这样的构成。也就是说,在一个实施方式中,本发明的电波吸收体是λ/4型电波吸收体。以下将对该实施方式进行说明。
<2-1.电阻膜>
电阻膜只要包含能够在电波吸收体中作为电阻层发挥功能的层,就无特别限制。
电阻膜的电阻值只要能够满足本发明的特性,则没有特殊的限制。通过调节电阻膜的电阻值,能够调节本发明的特性中的吸收范围。电阻膜的电阻值例如可以为200~600Ω/□。在该范围中,进一步优选为250Ω/□以上,更进一步优选为300Ω/□以上,特别优选为330Ω/□以上。在该范围中,进一步优选为520Ω/□以下,更进一步优选为450Ω/□以下,特别优选为390Ω/□以下。
电阻膜的电阻值可以使用表面电阻计(MITSUBISHI CHEMICALANALYTECH公司制,商品名“Loresta-EP”),通过四端法测定。
电阻膜的厚度只要是能满足本发明的特性的电阻值的厚度即可,无特别限制。电阻膜的厚度例如为1nm以上200nm以下,优选2nm以上100nm以下,更优选2nm以上50nm以下。
电阻膜的层构成无特别限制。电阻膜可以是由1种层单独构成,也可以是2种以上的多层组合而成。
<2-1-1.电阻层>
<2-1-1-1.含有ITO的电阻层>
作为电阻层,例如可以使用氧化铟锡(以下称为“ITO”)。其中,从非晶质结构极为稳定,即使在高温多湿的环境下也能抑制电阻层的薄层电阻的变动的观点出发,优选使用包含含有1~40重量%的SnO2的ITO的物质,更优选使用包含含有2~35重量%的SnO2的ITO的物质。所述ITO的含量在电阻层中,例如为50质量%以上,优选70质量%以上,更优选90质量%以上,进一步优选95质量%以上,通常不足100质量%。
<2-1-1-2.含有钼的电阻层>
作为电阻层,从易于进行耐久性、薄层电阻的调整的观点出发,优选使用含有钼的电阻层。钼的含量的下限无特别限定,从进一步提高耐久性的观点出发,优选为5重量%,更优选7重量%,进一步优选9重量%,更进一步优选11重量%,特别优选13重量%,非常优选15重量%,最优选16重量%。另外,所述钼的含量的上限,从表面电阻值的调整的容易化的观点出发,优选为70重量%,更优选30重量%,进一步优选25重量%,更进一步优选20重量%。
所述电阻层含有钼时,更优选进一步含有镍以及铬。通过使电阻层中除了钼外还含有镍以及铬,能够制得耐久性更优异的电波吸收体。作为含有镍、铬以及钼的合金,例如,可以举出哈氏合金B-2、B-3、C-4、C-2000、C-22、C-276、G-30、N、W、X等的各种牌号。
所述电阻层含有钼、镍以及铬时,优选钼的含量为5重量%以上、镍的含量为40重量%以上、铬的含量为1重量%以上。通过使钼、镍以及铬的含量在所述范围内,能够制得耐久性更优异的电波吸收体。所述钼、镍以及铬的含量进一步优选为,钼含量为7重量%以上、镍含量为45重量%以上、铬含量为3重量%以上。所述钼、镍以及铬的含量更优选为,钼含量为9重量%以上、镍含量为47重量%以上、铬含量为5重量%以上。所述钼、镍以及铬的含量更进一步优选为,钼含量为11重量%以上、镍含量为50重量%以上、铬含量为10重量%以上。所述钼、镍以及铬的含量特别优选为,钼含量为13重量%以上、镍含量为53重量%以上、铬含量为12重量%以上。所述钼、镍以及铬的含量非常优选为,钼含量为15重量%以上、镍含量为55重量%以上、铬含量为15重量%以上。所述钼、镍以及铬的含量最优选为,钼含量为16重量%以上、镍含量为57重量%以上、铬含量为16重量%以上。另外,所述镍的含量优选为80重量%以下,更优选70重量%以下,再更优选65重量%以下。所述铬含量的上限,优选为50重量%以下,更优选40重量%以下,再更优选35重量%以下。
所述电阻层可以含有所述钼、镍以及铬以外的金属。作为这样的金属,例如可以举出铁、钴、钨、锰、钛等。所述电阻层含有钼、镍以及铬时,所述钼、镍以及铬以外的金属的总含量的上限,从电阻层的耐久性的观点出发,优选为45重量%,更优选40重量%,进一步优选35重量%,更进一步优选30重量%,特别优选25重量%,非常优选23重量%。所述钼、镍以及铬以外的金属的总含量的下限,例如为1重量%以上。
所述电阻层含有铁时,从电阻层的耐久性的观点出发,含量的优选的上限为25重量%,进一步优选的上限为20重量%,更优选的上限为15重量%,优选的下限为1重量%。所述电阻层含有钴和/或锰时,从电阻层的耐久性的观点出发,分别独立地,含量的优选的上限为5重量%,进一步优选的上限为4重量%,更优选的上限为3重量%,优选的下限为0.1重量%。所述电阻层含有钨时,从电阻层的耐久性的观点出发,含量的优选的上限为8重量%,进一步优选的上限为6重量%,更优选的上限为4重量%,优选的下限为1重量%。
所述电阻层也可以含有硅和/或碳。电阻层含有硅和/或碳时,所述硅和/或碳的含量,分别独立地优选为1重量%以下,进一步优选0.5重量%以下。另外,电阻层含有硅和/或碳时,所述硅和/或碳的含量优选为0.01重量%以上。
电阻层的电阻值只要能满足本发明的特性就无特别限制。可通过调节电阻层的电阻值,来调节本发明的特性中的吸收范围。电阻层的电阻值例如可以为200~600Ω/□。在该范围中,进一步优选为250~520Ω/□,更进一步优选为300~450Ω/□,特别优选为330~390Ω/□。
电阻层的厚度只要是能满足本发明的特性电阻值的厚度就无特别限制。电阻层的厚度,例如为1nm以上200nm以下,优选2nm以上100nm以下,更优选2nm以上50nm以下。
电阻层的层构成无特别限制。电阻层可以是由1种电阻层单独构成,也可以是2种以上的电阻层多层组合而成。
<2-1-2.阻隔层>
从耐久性的观点出发,电阻膜优选包含阻隔层。阻隔层配置于电阻层的至少一者的表面上。关于阻隔层将在以下详述。
阻隔层只要是能够保护电阻层并抑制其劣化的层,就无特别限制。作为阻隔层的原材料,例如为金属化合物、准金属化合物,优选为金属或准金属的氧化物、氮化物、氮化氧化物等。阻隔层,只要不显著损害本发明的效果,也可以包含所述原材料以外的成分。此时,阻隔层中的所述原材料量,例如为80质量%以上,优选90质量%以上,更优选95质量%以上,进一步优选99质量%以上,通常不足100质量%。
作为阻隔层所包含的金属元素,例如可以举出钛、铝、铌、钴、镍等。作为阻隔层所包含的准金属元素,例如可以举出硅、锗、锑、铋等。
作为所述氧化物,例如可以举出以MOX[式中,X是满足式:n/100≤X≤n/2(n为金属或准金属的价数)的数,M为金属元素或准金属元素]表示的化合物。
作为所述氮化物,例如可以举出以MNy[式中,Y是满足式:n/100≤Y≤n/3(n是金属或准金属的价数)的数,M为金属元素或准金属元素]表示的化合物。
作为所述氮化氧化物,例如可以举出以MOXNy[式中,X和Y满足:n/100≤X,n/100≤Y,并且,X+Y≤n/2(n是金属或准金属的价数),M为金属元素或准金属元素]表示的化合物。
关于所述氧化物或氮化氧化物的氧化数X,例如可以通过对包含MOx或MOxNy的层的截面,以FE-TEM-EDX(例如,日本电子公司制“JEM-ARM200F”)进行元素分析,根据包含MOx或MOxNy的层的截面的单位面积的M和O的元素比算出X,从而算出氧原子的价数。
关于所述氮化物或氮化氧化物的氮化数Y,例如可以通过对包含MNy或MOxNy的层的截面,以FE-TEM-EDX(例如,日本电子公司制“JEM-ARM200F”)进行元素分析,根据包含MNy或MOxNy层的截面的单位面积的M和N的元素比算出Y,从而算出氮原子的价数。
作为阻隔层的原材料的具体例,可以举出SiO2、SiOx、Al2O3、MgAl2O4、CuO、CuN、TiO2、TiN、AZO(铝掺杂氧化锌)等。
阻隔层的厚度无特别限制。阻隔层的厚度,例如为1nm以上200nm以下,优选1nm以上100nm以下,更优选1nm以上20nm以下。
阻隔层的层构成无特别限制。阻隔层可以是由1种阻隔层单独构成,也可以是2种以上的阻隔层多层组合而成。
<2-2.电介质层>
电介质层只要对电波吸收体中目标波长能够作为电介质发挥功能,就无特别限制。作为电介质层,无特别限制,例如可以举出树脂片、粘接剂等。
树脂片只要是包含树脂作为原材料的片状物,就无特别限制。只要不显著损害本发明的效果,树脂片也可以包含树脂以外的成分。此时,树脂片中的树脂的总量,例如为50质量%以上,优选70质量%以上,更优选90质量%以上,进一步优选95质量%以上,通常不足100质量%。
作为树脂,无特别限制,例如优选将乙烯乙酸乙烯酯共聚物(EVA)、氯乙烯、氨基甲酸酯、丙烯酸、丙烯酸氨基甲酸酯、聚烯烃、聚乙烯、聚丙烯、聚硅氧烷、聚对苯二甲酸乙二醇酯、聚酯、聚苯乙烯、聚酰亚胺、聚碳酸酯、聚酰胺、聚砜、聚醚砜、环氧树脂等的合成树脂、聚异戊二烯橡胶、聚苯乙烯·丁二烯橡胶、聚丁二烯橡胶、氯丁二烯橡胶、丙烯腈·丁二烯橡胶、丁基橡胶、丙烯酸橡胶、乙烯·丙烯橡胶和聚硅氧烷橡胶等的合成橡胶材料作为树脂成分使用。它们可以单独使用1种,也可以组合使用2种以上。
电介质层也可以是泡沫、粘接剂。
电介质层可以是具备粘接性的物质。因此,在将不具有粘接性的电介质通过粘接剂层叠层至其他层上时,该电介质和粘接剂层合称为“电介质层”。从易于与相邻的层叠层的观点出发,电介质层优选包含粘接剂层。
电介质层的相对介电常数只要能满足本发明的特性就无特别限制。通过调节电介质层的相对介电常数(特别是通过调节后述的式(1)的值),能够调节本发明的特性中的吸收范围。电介质层的相对介电常数,例如为1~20,优选1~15,更优选1~10,进一步优选1~5。
电介质层的厚度只要能满足本发明的特性就无特别限制。通过调节电介质层的厚度(特别是通过由此调节后述的式(1)的值),能够调节本发明的特性中的吸收范围。电介质层的厚度例如可以为300~1500μm,优选为600~980μm,更优选为700~860μm。
就电介质层而言,作为调节本发明的特性中的吸收范围的一个方法,优选满足式(1):(式中,d表示电介质层的厚度(μm),ε表示电介质层的相对介电常数)。的优选的下限为1000,更优选的下限为1100,特别优选的下限为1150。的优选的上限1400,更优选的上限为1300,特别优选的上限为1250。
电介质层包含多个层时,通过分别得出各个层的值并计算总和而算出。例如,电介质层包含电介质层1以及电介质层2(例如粘接胶带等)时,通过计算“电介质层1的厚度×(电介质层1的相对介电常数)0.5”和“电介质层2的厚度×(电介质层2的相对介电常数)0.5”的总和而算出。
电介质层的厚度可以通过Nikon DIGIMICROSTANDMS-11C+Nikon DIGIMICRO MFC-101测定。
电介质层的相对介电常数可以通过使用网络分析仪、空腔共振器等,以空腔共振器摄动法测定10GHz中的相对介电常数。
电介质层的层构成无特别限制。电介质层可以是由1种电介质层单独构成,也可以是2种以上的电介质层多层组合而成。例如,可以举出包含不具有粘接性的电介质和其两面上配置的粘接剂层的3层结构的电介质层、包含具有粘接性的电介质的1层结构的电介质层等。
<2-3.反射层>
反射层只要能够在电波吸收体中作为电波的反射层而发挥功能就无特别限制。作为反射层,无特别限制,例如可以举出金属膜。
金属膜只要是包含金属作为原材料的层就无特别限制。只要不显著损害本发明的效果,金属膜也可以包含金属以外的成分。此时,金属膜中的金属的总量,例如为30质量%以上,优选50质量%以上,更优选75质量%以上,进一步优选80质量%以上,更进一步优选90质量%以上,特别优选95质量%以上,非常优选99质量%以上,通常不足100质量%。
作为金属,无特别限制,例如可以举出铝、铜、铁、银、金、铬、镍、钼、镓、锌、锡、铌、铟等。另外,金属化合物,例如ITO等,也可以作为金属膜的原材料使用。它们可以是单独的1种,也可以是2种以上的组合。
反射层的厚度无特别限制。反射层的厚度,例如为1μm以上500μm以下,优选2μm以上200μm以下,更优选5μm以上100μm以下。
在本发明的优选的一个方式中,反射层的电介质层侧的表面的表面粗糙度(Rz)优选为1μm以上10μm以下。通过在该范围内,能够发挥良好的电介质层和反射层的密合性,并且,能够发挥更良好的电波吸收性。该表面粗糙度(Rz)优选1μm以上8μm以下,更优选1μm以上5μm以下。
在本发明的优选的一个方式中,反射层的电介质层侧的相反侧的表面的表面粗糙度(Rz)为1μm以上。由此,能够发挥良好的与在反射层的电介质层侧的相反侧上叠层的层(例如,粘接剂层)的密合性,能够更容易地将本发明的电波吸收体装至其他的部件(例如,车辆内的装置等)上。该表面粗糙度(Rz)优选为30μm以下,更优选2μm以上15μm以下。
反射层的表面粗糙度(Rz)可以如下测定。可通过彩色3D激光显微镜(VK8710(Keyence公司制)或其同等品),进行反射层表面的凹凸的测定,来测量表面粗糙度(Rz)。具体而言,参照JIS B0601:2001,使用50倍物镜,测定反射层表面的任意5处的在10μm×10μm范围内的Rz,通过求出其平均值而得到。
反射层的表面粗糙度(Rz),可以依照或参照公知的调整表面粗糙度的调整方法而进行调节。例如,可以通过使用金属电镀技术的微细金属粒子的赋予或以物理·化学手法对表面进行切削的方法等进行调整。
反射层的层构成无特别限制。反射层可以是由1种反射层单独构成,也可以是2种以上的反射层多层组合而成。
<2-4.支撑体>
本发明的电波吸收体具有电阻膜时,优选进一步具有支撑体。由此,能够保护电阻膜,从而能够提高作为电波吸收体的耐久性。支撑体只要是片状的就无特别限制。作为支撑体,无特别限制,例如可以举出树脂基材。
树脂基材只要是包含树脂作为原材料的基材,且是片状的,就无特别限制。只要不显著损害本发明的效果,树脂基材也可以包含树脂以外的成分。例如,从调整相对介电常数观点出发,也可以包含氧化钛等。此时,树脂基材中的树脂的总量,例如为80质量%以上,优选90质量%以上,更优选95质量%以上,进一步优选99质量%以上,通常不足100质量%。
作为树脂,无特别限制,例如可以举出聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯、改性聚酯等的聚酯类树脂、聚乙烯(PE)树脂、聚丙烯(PP)树脂、聚苯乙烯树脂、环状烯烃类树脂等的聚烯烃类树脂、聚氯乙烯、聚偏二氯乙烯等的乙烯基类树脂、聚乙烯醇缩丁醛(PVB)等的聚乙烯醇缩醛树脂、聚醚醚酮(PEEK)树脂、聚砜(PSF)树脂、聚醚砜(PES)树脂、聚碳酸酯(PC)树脂、聚酰胺树脂、聚酰亚胺树脂、丙烯酸类树脂、三乙酰纤维素(TAC)树脂等。它们可以单独使用1种或组合使用2种以上。
其中,从生产性、强度的观点出发,优选聚酯类树脂,更优选举出聚对苯二甲酸乙二醇酯。
支撑体的相对介电常数无特别限制。支撑体的相对介电常数,例如为1~20,优选1~15,更优选1~10,进一步优选1~5。
支撑体的厚度无特别限制。支撑体的厚度,例如为5μm以上500μm以下,优选10μm以上300μm以下,更优选20μm以上300μm以下。
在本发明的优选的一个方式中,电波吸收体的支撑体侧的最表面(通常是支撑体的电阻膜侧的相反侧的表面)的表面张力优选为35dyn/cm以上。表面张力采取这样的值时,能够发挥优异的防污性。结果,在擦去污渍污后,电波吸收性也优异。该表面张力进一步优选为36dyn/cm以上。
该表面张力的上限无特别限制,从抑制制造时支撑体彼此的阻塞的观点出发,优选60dyn/cm以下,更优选57dyn/cm以下,进一步优选55dyn/cm以下。
表面张力,可以参照JIS K 6768“塑料-膜以及片润湿张力试验方法”,使用润湿张力试验用液(和光纯药制,润湿张力试验用混合液)进行测定。所述的表面张力可以通过支撑体的材料的选择、光反射剂、光吸收剂等的添加剂的混合而进行调整。
在本发明的优选的一个方式中,支撑体的总光线透射率优选为30%以下。支撑体的总光线透射率采取这样的值时,能够发挥优异的耐光性。该总光线透射率更优选的上限为20%,进一步优选的上限为16%。该总光线透射率的下限无特别限制,例如0.01%以上,优选0.05%以上,更优选0.1%以上。
总光线透射率可以使用雾度计(日本电饰公司制“NDH-4000”,或其同等品),基于JIS K7105进行测定。
所述的总光线透射率可以通过支撑体的材料的选择、光反射剂、光吸收剂等的添加剂的混合进行调整。
就支撑体而言,为了充分满足所述的表面张力以及总光线透射率的范围,优选包含光反射剂。光反射剂可以是与支撑体材料(所述树脂等)混合的状态,也可以包含在构成支撑体表面的涂覆层中。优选为光反射剂与支撑体材料(所述树脂等)混合的状态。
作为光反射剂,只要是能够对紫外线、可见光等(特别是紫外线)进行反射、散射等的物质,且即使被包含在支撑体中也不会显著降低本发明的电波吸收体的电波吸收特性,就无特别限制,例如,可以使用无机粉体。
无机粉体的平均粒径从满足上述表面张力和总光线透射率的范围的观点出发,优选为50~400nm,更优选为60~390nm,进一步优选为70~380nm。
作为无机粉体,例如可以列举二氧化钛、氧化锌等金属氧化物。其中,从由于折射率大且光的散射较大,故易于调整总光线透射率的观点出发,优选使用二氧化钛。
作为光反射剂而适用的氧化锌的平均粒径,从充分满足所述的表面张力以及总光线透射率的范围的观点出发,优选50~400nm,更优选60~390nm,进一步优选70~380nm。
作为光反射剂而适用的氧化锌的市售品的例子,可以举出:MZ-300(无表面处理剂,粒径30~40nm,TAYCA(株式会社)),MZ-303S(聚甲基硅氧烷处理,粒径30~40nm,TAYCA(株式会社)),MZ-303M(聚二甲基硅氧烷处理,粒径30~40nm,TAYCA(株式会社)),MZ-500(无表面处理剂,粒径20~30nm,TAYCA(株式会社)),MZ-505S(聚甲基硅氧烷处理,粒径20~30nm,TAYCA(株式会社)制),MZ-505M(聚二甲基硅氧烷处理,粒径20~30nm,TAYCA(株式会社)),MZ-700(无表面处理剂,粒径10~20nm,TAYCA(株式会社)),MZ-707S(聚甲基硅氧烷处理,粒径10~20nm,TAYCA(株式会社)),FINEX-25(无表面处理剂,粒径60nm,SakaiChemical(株式会社)制),FINEX-25LP(聚二甲基硅氧烷处理,粒径60nm,Sakai Chemical(株式会社)),FINEX-50(无表面处理剂,粒径20nm,Sakai Chemical(株式会社)),FINEX-50LP(聚二甲基硅氧烷处理,粒径20nm,Sakai Chemical(株式会社)),FINEX-75(无表面处理剂,粒径10nm,Sakai Chemical(株式会社)制)等。
作为光反射剂而适用的二氧化钛的平均粒径,从充分满足所述的表面张力以及总光线透射率的范围的观点出发,优选为50~400nm,更优选60~390nm,进一步优选70~380nm。
作为光反射剂而适用的二氧化钛的具体例,可以举出:TIPAQUE CR-50(氧化铝处理,粒径25nm,石原产业(株式会社)制),Bayer钛R-KB-1(氧化锌处理,氧化铝处理,二氧化硅处理,粒径30nm~40nm,Bayer公司制),TIPAQUE TTO-M-1(氧化锆,氧化铝处理,粒径10nm~25nm,石原产业(株式会社)制),TIPAQUE TTO-D-1(氧化锆处理,氧化铝处理,粒径20nm~30nm,石原产业(株式会社)制),SOLAVEIL CT-100、SOLAVEIL CT-200、SOLAVEIL CT-300、SOLAVEIL CT-434Croda Japan(株式会社)制),STR-100系列、STR-40(Sakai Chemical(株式会社)制)。但是,不限于这些例子。
作为调整上述的表面张力以及总光线透射率的方法,除了混合所述的光反射剂以外,例如可以举出以含有光吸收剂的涂料涂布支撑体表面等的方法。另外作为调整上述的表面张力的方法,可以举出:对对象面进行电晕放电处理、外线照射处理、臭氧处理以及等离子体处理等的处理的方法,涂布涂覆剂的方法等。
支撑体的层构成无特别限制。支撑体可以是由1种支撑体单独构成,也可以是2种以上的支撑体多层组合而成。
<2-5.层构成>
本发明的电波吸收体具有电阻膜、电介质层以及反射层时,各层以能够发挥电波吸收性能的顺序而进行配置。作为一个例子,电阻膜、电介质层以及反射层以该顺序配置。
进一步而言,本发明的电波吸收体具有支撑体时,作为一个例子,支撑体、电阻膜、电介质层以及反射层以该顺序配置。
在本发明的电波吸收体中,除了支撑体、电阻膜、电介质层以及反射层之外,也可以包含其他层。其他层可以配置在支撑体、电阻膜、电介质层以及反射层各个层的任一者的表面上。
<3.对斜入射的电波吸收性>
由于本发明的电波吸收体具备本发明的特性(在45度入射时的特定的特性),因此能够对于来自各种角度的入射(特别是,圆偏振波的入射)、特别是对60GHz附近(例如,55~65GHz)的电波的斜入射(特别是,圆偏振波的入射)表现出良好的电波吸收性。
本发明的电波吸收体的电波吸收性的具体例如下所述。
需要说明的是,可以根据以下方法测定以下具体例中的吸收范围。
使用PNA微波网络分析仪N5227A(Keysight株式会社制造)、PNA-X系列2端口用毫米波控制仪N5261A(Keysight株式会社制造)、喇叭天线FSS-07(HVS株式会社制造)构成电波吸收测定装置。使用该电波吸收测定装置,基于JIS R1679测定电波吸收体的E波段(60~90GHz)、U波段(40~60GHz)处的电波吸收量。使电波以20°、30°、或60°入射到测定样本的正面,相对于测定样本面心的垂线,以相同角度安装喇叭天线。在入射波的电场垂直于入射面(TE波)的状态下进行测定,测定反射系数ГTE。
随后,以相同的方法,在入射波的电场与入射面平行(TM波)的状态下进行测定,测定反射系数ГTM。
将反射系数ГTE、ГTM的平均值设为圆偏振波的反射系数ГCP。
使用上述系数,通过-20log|ГCP|求出对于圆偏振波的反射衰减量。将该反射衰减量的绝对值设为吸收性能。
本发明的电波吸收体优选发挥以下电波吸收性(电波吸收性1):在20°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为10dB以上(优选为15dB以上)的吸收范围为4GHz以上。电波吸收性1中的吸收范围优选为6GHz以上,更优选为8GHz以上,进一步优选为9GHz以上,更进一步优选为9.5GHz以上。
本发明的电波吸收体优选发挥以下电波吸收性(电波吸收性2):在30°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为10dB以上(优选为15dB以上)的吸收范围为4GHz以上。电波吸收性2中的吸收范围优选为6GHz以上,更优选为8GHz以上,进一步优选为9GHz以上,更进一步优选为9.5GHz以上。
本发明的电波吸收体优选发挥以下电波吸收性(电波吸收性3):在60°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为10dB以上(优选为15dB以上)的吸收范围为4GHz以上。电波吸收性3中的吸收范围优选为6GHz以上,更优选为8GHz以上,进一步优选为9GHz以上,更进一步优选为9.5GHz以上。
本发明的电波吸收体优选发挥选自电波吸收性1、电波吸收性2、以及电波吸收性3中的至少两种(优选为3种)电波吸收性。
上述吸收范围由于是在55~65GHz频带中的范围,因此其上限为10GHz。
<4.制造方法>
本发明的电波吸收体,根据其构成,能够依照或参照各种方法,例如公知的制造方法而获得。例如,本发明的电波吸收体具有电阻膜、电介质层以及反射层时,可以通过包含将电阻膜、电介质层以及反射层依次叠层在支撑体上的工序的方法而得到。
叠层方法无特别限制。
电阻膜,例如,可以通过溅射法、真空蒸镀法、离子镀法、化学蒸镀法、脉冲激光沉积法等而得到。其中,从膜厚控制性的观点出发,优选溅射法。作为溅射法,无特别限定,例如,可以举出直流磁控溅射、高频磁控溅射和离子束溅射等。另外,溅射装置可以是批次式也可以是卷对卷式。
电介质层、反射层,例如可以利用电介质层具有的粘接性进行叠层。
<5.λ/4型电波吸收体用部件>
本发明在其一个实施方式中,涉及一种λ/4型电波吸收体用部件,该部件具有电阻膜和电介质层,并且,在将厚度为10μm的铝板叠层至电介质层的另一个面上时,在45°入射的圆偏振波的测定中,该电波吸收体用部件在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。需要说明的是,就厚度为10μm的铝板而言,使用其与电介质层相接的表面的表面粗糙度(Rz)为4μm的铝板。
λ/4型电波吸收体用部件是依次具有电阻膜、电介质层并用于通过将电介质层以与能够作为金属等的反射层而发挥功能的被粘附体相接的方式进行配置而形成λ/4型电波吸收体的部件。λ/4型电波吸收体用部件可以进一步具有支撑体,此时,λ/4型电波吸收体用部件依次具有:支撑体、电阻膜、电介质层。关于支撑体、电阻膜、电介质层、本发明的特性、其它的构成,与本发明的电波吸收体相关的说明同样。
<6.用途>
本发明的电波吸收体由于具有吸收不必要的电波的性能,因此优选地用于例如光收发器、次世代移动通讯系统(5G)、短程无线传输技术等中的电波应对部件。同时,作为其他用途,还可以应用于在汽车、道路与人之间进行信息通信的智能交通系统(ITS)以及用于汽车防撞系统中的毫米波雷达中,以达到抑制电波干扰以及降低噪声的目的。
另外,本发明的电波吸收体,由于对于斜入射能够发挥良好的电波吸收性,因此能够适用于以相对于吸收对象的电波的入射方向进行倾斜(例如10~80度,20~60度、30~60度)配置的情况。
作为本发明的电波吸收体的对象的电波的频率优选为55~65GHz。
实施例
以下,基于实施例对本发明进行详细说明,但本发明不限于这些实施例。
(1)电波吸收体的制造
(实施例1)
作为支撑体,准备了厚度为125μm且混炼有氧化钛(平均粒径200μm)的聚对苯二甲酸乙二醇酯(PET)膜(相对介电常数3.4,TiO2;10重量%)。
在所述PET膜上,如下地形成了电阻值360Ω/□的电阻膜(阻隔层1/电阻层/阻隔层2):首先,通过DC脉冲溅射,导入将Ar和O2的比调整为1:1的气体,调整至0.2Pa,进行了SiO2层(阻隔层1:厚度10nm)的成膜。接下来,在阻隔层1上,通过DC脉冲溅射,形成了表面电阻值355Ω/□的电阻层。溅射如下进行:使用合金(组成:钼16.4重量%、镍55.2重量%、铬18.9重量%、铁5.5重量%、钨3.5重量%、二氧化硅0.5重量%)作为目标,以输出0.4kW、Ar气体流量100sccm的条件进行导入,将压力调整至0.12Pa。最后,以与阻隔层1同样的方式形成了阻隔层2(厚度5nm)。
接下来,在形成的阻隔层2上叠层由厚度780μm且相对介电常数为2.4的丙烯酸双面粘接胶带所构成的电介质,进一步在电介质上叠层由厚度10μm的铝(Rz=4.0μm)所构成的反射层而得到了电波吸收体。
(实施例2~5、7~12、比较例1~4)
除了将电阻膜的电阻值和/或电介质的厚度如表1和表2所示进行变更之外,以与实施例1同样的方式得到了电波吸收体。
(实施例6)
除了不形成阻隔层(电阻层=电阻膜)之外,以与实施例1同样的方式得到了电波吸收体。
(实施例13)
除了将反射层变更为厚度10μm的铜板(Rz=0.9μm)之外,以与实施例3同样的方式得到了电波吸收体。
(实施例14)
除了将反射层变更为厚度10μm的铜板(Rz=12μm)之外,以与实施例3同样的方式得到了电波吸收体。
(实施例15)
除了将支撑体变更为聚对苯二甲酸乙二醇酯(PET)膜(相对介电常数3.2,表面张力36dyn/cm)之外,以与实施例3同样的方式得到了电波吸收体。需要说明的是,通过向大气压等离子体装置(积水化学工业株式会社制,“AP/TO2”,直接电极型)中导入N2气体作为处理气体,以投入电力900W(140V-6.4A)而产生等离子体气体,以15m/分钟的速度输送,进行等离子体处理,以此对支撑体表面的表面张力进行了调整。需要说明的是,将进行等离子体处理的狭缝面积设为200mm2(膜的宽度方向上200mm且长度方向上1mm)。
(实施例16)
准备了混炼有氧化钛(平均粒径200μm)的、厚度125μm的聚对苯二甲酸乙二醇酯(PET)膜(TiO2;7重量%)。在支撑体的和与电阻层相接的面相反的面上,以绕线棒涂布器涂布液状的硬质涂层用材料,进一步使用烘箱将该涂布膜在100℃×1分钟的条件下加热干燥。接下来,通过对干燥后的涂布膜照射紫外线(照射量:300mJ/cm2),而在支撑体上配置了厚度2μm的硬质涂层。作为硬质涂层材料使用了向含有光聚合剂的丙烯酸类低聚物中,加入甲苯和甲基异丁基酮(MIBK)以5:5(重量比)的比例混合的混合溶剂而调制的液状的硬质涂层用材料(固体成分浓度:40重量%)。除了将制作的附有硬质涂层的PE T膜(相对介电常数3.4,表面张力32dyn/cm)作为支撑体使用之外,以与实施例3同样的方式得到了电波吸收体。
(2)特性的测定
在45°入射的圆偏振波的测定中,测定了在55~65GHz频带中吸收性能为15dB以上的吸收范围。具体而言,按照如下方式进行了测定。
使用PNA微波网络分析仪N5227A(Keysight株式会社制造)、PNA-X系列2端口用毫米波控制仪N5261A(Keysight株式会社制造)、喇叭天线FSS-07(HVS株式会社制造)构成电波吸收测定装置。使用该电波吸收测定装置,基于JIS R1679测定电波吸收体的E波段(60~90GHz)、U波段(40~60GHz)处的电波吸收量。使电波以45°入射到测定样本的正面,相对于测定样本面心的垂线,以相同角度安装喇叭天线。在入射波的电场垂直于入射面(TE波)的状态下进行测定,测定反射系数ГTE。
随后,按照相同的方法,在入射波的电场与入射面平行(TM波)的状态下进行测定,测定反射系数ГTM。
将反射系数ГTE、ГTM的平均值设为圆偏振波的反射系数ГCP。
使用上述系数,通过-20log|ГCP|求出对于圆偏振波的反射衰减量。将该反射衰减量的绝对值设为吸收性能。
其结果如表1和表2所示。
(3)对斜入射的电波吸收性的评价1
评价了对于斜入射的电波吸收性。就测量方法而言,除了分别更改了电波的入射角和喇叭天线的角度以外,以与45°入射的圆偏振波的测定相同的方法进行了测定。测定了在55~65GHz频带中,吸收性能为10dB以上的吸收范围。
其结果如表1和表2所示。
(4)对斜入射的电波吸收性的评价2
除了测定吸收性能为15dB以上的吸收范围以外,以与上述电波吸收性评价1相同的方法进行了评价。其结果,20度入射时的吸收范围为:实施例1为9GHz、实施例2为9GHz、实施例5为1GHz、实施例6为9GHz。30度入射时的吸收范围为:实施例1为10GHz、实施例2为6GHz、实施例5为1GHz、实施例6为10GHz。60度入射时的吸收范围为:实施例1为10GHz、实施例2为1GHz、实施例3为8GHz、实施例4为6GHz、实施例5为6GHz、实施例6为10GHz。
(5)粘接力(电介质层/反射层)的评价
将得到的实施例3、13以及14的电波吸收体裁剪为10mm宽度的短条状,以制作试验片,使电介质层的面向反射层的一侧的相反侧暴露。将暴露的面,通过双面粘接胶带(9708,3M公司制),固定于测定装置的台座。依照JI S Z0237对该试验样品的反射层,以剥离速度300mm/分钟进行180°方向的拉伸试验,测定了180°粘接力(N/10mm)。将电介质层/反射层间的粘接力在5N/10mm以上设为○,不足5N/10mm设为×。
(6)防污性评价(擦去油污后的电波吸收性)
用滴管在得到的实施例3、15以及16的电波吸收体的支撑体的与面向电阻膜的一侧相反的表面上滴下1滴色拉油后,以包含石油醚(Ligroin)的擦拭布(商品名:CleanWiper SF30C Kuraray公司制)进行了20次的往复擦拭。然后,以与特性的测定同样的方式进行了测定,将45°入射下的60GHz处的电波吸收量的变化量在5dB以内时设为○,其以上时设为×。
(7)耐光性的评价
对于得到的实施例3、15以及16的电波吸收体,使用阳光耐气候试验箱(S-80,SugaTest Instruments(株式会社)制),在阳光碳弧灯、相对湿度60%的条件下,进行了1000小时的曝光。然后,以与特性的测定同样的方式进行了测定,将45°入射下的60GHz处的电波吸收量的变化量在5dB以内时设为○,其以上时设为×。
其结果如表3和表4所示。
[表3]
[表4]
图示符号说明
1 支撑体
2 电阻膜
3 电介质层
4 反射层
5 粘接剂层
6 筐体
Claims (12)
1.一种电波吸收体,在45°入射的圆偏振波的测定中,该电波吸收体在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。
2.如权利要求1所述的电波吸收体,其具有电阻膜、电介质层、以及反射层。
3.如权利要求2所述的电波吸收体,其中,所述电阻膜的电阻值为250~520Ω/□。
5.如权利要求2~4中任一项所述的电波吸收体,其中,所述电介质层的相对介电常数为1~10。
6.如权利要求2~5中任一项所述的电波吸收体,其中,所述电阻膜包含阻隔层。
7.如权利要求2~6中任一项所述的电波吸收体,其中,所述电阻膜含有钼。
8.如权利要求7所述的电波吸收体,其中,所述电阻膜进一步含有镍和铬。
9.如权利要求2~8中任一项所述的电波吸收体,其中,所述反射层的电介质层一侧的表面的表面粗糙度(Rz)为1μm以上且10μm以下。
10.如权利要求2~9中任一项所述的电波吸收体,其进一步具有支撑体,其中,电波吸收体的支撑体一侧最表面的表面张力为35dyn/cm以上。
11.如权利要求10所述的电波吸收体,其中,所述支撑体的总光线透射率为30%以下。
12.一种λ/4型电波吸收体用部件,其具有电阻膜和电介质层,且在将厚度为10μm的铝板叠层至电介质层的另一个面上时,在45°入射的圆偏振波的测定中,该电波吸收体用部件在55~65GHz频带中吸收性能为15dB以上的吸收范围为4GHz以上。
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