JP5887283B2 - Metal foil for electromagnetic shielding and electromagnetic shielding material - Google Patents
Metal foil for electromagnetic shielding and electromagnetic shielding material Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims description 71
- 239000002184 metal Substances 0.000 title claims description 71
- 239000011888 foil Substances 0.000 title claims description 61
- 239000000463 material Substances 0.000 title claims description 40
- 229910045601 alloy Inorganic materials 0.000 claims description 109
- 239000000956 alloy Substances 0.000 claims description 109
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910002701 Ag-Co Inorganic materials 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 229910020900 Sn-Fe Inorganic materials 0.000 claims description 9
- 229910019314 Sn—Fe Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 162
- 238000007747 plating Methods 0.000 description 41
- 239000011135 tin Substances 0.000 description 35
- 238000005260 corrosion Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 239000010408 film Substances 0.000 description 19
- 239000011889 copper foil Substances 0.000 description 17
- 238000004544 sputter deposition Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 229910018100 Ni-Sn Inorganic materials 0.000 description 4
- 229910018532 Ni—Sn Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011104 metalized film Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 210000003491 skin Anatomy 0.000 description 3
- 229910020646 Co-Sn Inorganic materials 0.000 description 2
- 229910020709 Co—Sn Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910020938 Sn-Ni Inorganic materials 0.000 description 1
- 229910008937 Sn—Ni Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
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Description
本発明は、樹脂層又は樹脂フィルムを積層されて電磁波シールド材に用いられる金属箔、及び電磁波シールド材に関する。 The present invention relates to a metal foil used as an electromagnetic shielding material by laminating a resin layer or a resin film, and an electromagnetic shielding material.
Ｓｎめっき被膜は耐食性に優れ、かつ、はんだ付け性が良好で接触抵抗が低いと言う特徴を持っている。このため、例えば、車載電磁波シールド材の複合材料として、銅等の金属箔にＳｎめっきされて使用されている。
上記の複合材料としては、銅又は銅合金箔からなる基材の一方の面に樹脂層又はフィルムを積層し、他の面にＳｎめっき被膜を形成した構造が用いられている（特許文献１参照）。又、プラズマディスプレイ用の電磁波シールド体として、銅箔の回路を透明基材上に形成し、銅箔の表示画面側の面に錫とニッケルとモリブデンとからなる合金めっきを施すことで、反射率を低減した技術が報告されている（特許文献２参照）。
The Sn plating film is characterized by excellent corrosion resistance, good solderability and low contact resistance. For this reason, for example, Sn plating is used for metal foils, such as copper, as a composite material of a vehicle-mounted electromagnetic wave shielding material.
As said composite material, the structure which laminated | stacked the resin layer or the film on one surface of the base material which consists of copper or copper alloy foil, and formed the Sn plating film on the other surface is used (refer patent document 1). ). In addition, as an electromagnetic wave shield for plasma displays, a copper foil circuit is formed on a transparent substrate, and an alloy plating made of tin, nickel, and molybdenum is applied to the surface of the copper foil on the display screen side, thereby providing a reflectance. A technique for reducing the above has been reported (see Patent Document 2).
しかしながら、自動車用途をはじめとした屋外環境で使用される電磁波シールド材には厳しい耐食性が要求され、さらにＮＯＸやＳＯＸといった腐食ガスに対する耐性も必要である。
本発明は上記課題を解決するためになされたものであり、従来のＳｎめっきよりも耐食性に優れた電磁波シールド用金属箔および電磁波シールド材の提供を目的とする。
However, the demanding corrosion resistance in electromagnetic wave shielding material which is used at the beginning and outdoor environment automotive applications, is resistant needed for further corrosive gas such as NO X or SO X.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an electromagnetic shielding metal foil and an electromagnetic shielding material that are superior in corrosion resistance to conventional Sn plating.
本発明者らは種々検討した結果、金属箔の表面に所定の元素からなる合金層を形成することで、従来のＳｎめっきよりも耐食性を向上させることに成功した。 As a result of various studies, the inventors have succeeded in improving the corrosion resistance as compared with conventional Sn plating by forming an alloy layer made of a predetermined element on the surface of the metal foil.
上記の目的を達成するために、本発明の電磁波シールド用金属箔は、金属箔からなる基材の片面または両面に、Ｓｎ又はＡｇから選ばれる１種のＡ元素群と、Ｎｉ、Ｆｅ、及びＣｏの群から選ばれる１種以上のＢ元素群とからなる合金層が形成され（但し、Ｓｎ−Ｆｅ、Ａｇ−Ｆｅ及びＡｇ−Ｃｏを除く）、前記合金層の表面に前記Ａ元素群からなる金属層が存在せず、かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である。
又、本発明の電磁波シールド用金属箔は、金属箔からなる基材の片面または両面に、Ｓｎ又はＡｇから選ばれる１種のＡ元素群と、Ｎｉ、Ｆｅ、及びＣｏの群から選ばれる１種以上のＢ元素群とからなる合金層が形成され（但し、Ｓｎ−Ｆｅ、Ａｇ−Ｆｅ及びＡｇ−Ｃｏを除く）、かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、前記合金層の表面に、前記Ａ元素群からなる金属層から構成される第２層が形成され、前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である。
又、本発明の電磁波シールド用金属箔は、金属箔からなる基材の片面または両面に、Ｓｎ、Ａｇ及びＩｎの群から選ばれる１種以上のＡ元素群と、Ｎｉ、Ｆｅ、及びＣｏの群から選ばれる１種以上のＢ元素群とからなる合金層が形成され（但し、Ｓｎ−Ｆｅ、Ａｇ−Ｆｅ及びＡｇ−Ｃｏを除く）、前記合金層の表面に前記Ａ元素群からなる金属層が存在せず、かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、前記合金層と前記基材との間に、前記Ｂ元素群からなる金属層から構成される第１層が形成され、前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である。
又、本発明の電磁波シールド用金属箔は、金属箔からなる基材の片面または両面に、Ｓｎ、Ａｇ及びＩｎの群から選ばれる１種以上のＡ元素群と、Ｎｉ、Ｆｅ、及びＣｏの群から選ばれる１種以上のＢ元素群とからなる合金層が形成され（但し、Ｓｎ−Ｆｅ、Ａｇ−Ｆｅ及びＡｇ−Ｃｏを除く）、かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、前記合金層の表面に、前記Ａ元素群からなる金属層から構成される第２層が形成され、前記合金層と前記基材との間に、前記Ｂ元素群からなる金属層から構成される第１層が形成され、前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である。
In order to achieve the above-described object, the metal foil for electromagnetic wave shielding of the present invention comprises a group of A elements selected from Sn or Ag, Ni, Fe, and An alloy layer composed of one or more B element groups selected from the group of Co is formed (excluding Sn-Fe, Ag-Fe, and Ag-Co), and from the A element group on the surface of the alloy layer When the surface of the alloy layer is observed with an SEM, the average diameter represented by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion is 0.1 to It does not have a plurality of needle-like or columnar protrusions of 2.0 μm, the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more, and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
Further, the metal foil for electromagnetic wave shielding of the present invention is selected from one group of A elements selected from Sn or Ag and a group of Ni, Fe, and Co on one or both sides of a substrate made of metal foil. When an alloy layer composed of a group of B elements of at least species is formed (except for Sn-Fe, Ag-Fe, and Ag-Co) and the surface of the alloy layer is observed with an SEM, The surface of the alloy layer does not have a plurality of needle-like or columnar protrusions having an average diameter of 0.1 to 2.0 μm represented by the average value of the diameters of the smallest circles that can surround the convex portion. A second layer composed of a metal layer composed of an element group is formed, the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more, and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
In addition, the metal foil for electromagnetic wave shielding of the present invention comprises one or more A element groups selected from the group of Sn, Ag, and In, Ni, Fe, and Co on one side or both sides of a substrate made of metal foil. An alloy layer composed of one or more B element groups selected from the group is formed (excluding Sn—Fe, Ag—Fe, and Ag—Co), and a metal composed of the A element group on the surface of the alloy layer. When a layer is not present and the surface of the alloy layer is observed with an SEM, the average diameter expressed by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion is 0.1-2. A first layer composed of a metal layer made of the B element group is formed between the alloy layer and the base material without having a plurality of needle-like or columnar protrusions of 0 μm , the total deposition amount of the element a set of one side 10 .mu.mol / dm 2 or more, and the B element group The total coating weight is 40 [mu] mol / dm 2 or more.
In addition, the metal foil for electromagnetic wave shielding of the present invention comprises one or more A element groups selected from the group of Sn, Ag, and In, Ni, Fe, and Co on one side or both sides of a substrate made of metal foil. When an alloy layer composed of one or more B element groups selected from the group is formed (excluding Sn—Fe, Ag—Fe, and Ag—Co) and the surface of the alloy layer is observed with an SEM, It does not have a plurality of needle-like or columnar projections having an average diameter of 0.1 to 2.0 μm, which is expressed by an average value of the diameters of the smallest circles that can surround the convex portion of each projection, A second layer composed of a metal layer composed of the A element group is formed on the surface, and a first layer composed of a metal layer composed of the B element group is interposed between the alloy layer and the base material. is formed, the total deposition amount of the a element group of one surface of said substrate 10 .mu.mol / dm 2 On, and the total deposition amount of the B element group is 40 [mu] mol / dm 2 or more.
前記合金層がさらに、Ｐ、Ｗの群から選ばれる１種以上のＣ元素群を含み、前記合金層全体に対する前記Ｃ元素群の合計含有率が１〜４０質量％の範囲であることが好ましい。
請求項６に記載の電磁波シールド用金属箔において、前記第２層は、前記Ａ元素群と前記Ｃ元素群とからなることが好ましい。
請求項７に記載の電磁波シールド用金属箔において、前記第１層は、前記Ｂ元素群と前記Ｃ元素群とからなることが好ましい。
前記合金層又は前記第２層の表面に、クロム酸化物層が形成されていることが好ましい。
前記基材が金、銀、白金、ステンレス、鉄、ニッケル、亜鉛、銅、銅合金、アルミニウム、又はアルミニウム合金からなることが好ましい。
Wherein the alloy layer further, P, viewed contains one or more C element group selected from the group of W, that the total content of the C element group to the whole the alloy layer is in the range of 1 to 40 wt% preferable.
The metal foil for electromagnetic wave shielding of Claim 6 WHEREIN: It is preferable that a said 2nd layer consists of the said A element group and the said C element group.
The metal foil for electromagnetic wave shielding of Claim 7 WHEREIN: It is preferable that a said 1st layer consists of the said B element group and the said C element group.
It is preferable that a chromium oxide layer is formed on the surface of the alloy layer or the second layer.
The base material is preferably made of gold, silver, platinum, stainless steel, iron, nickel, zinc, copper, a copper alloy, aluminum, or an aluminum alloy.
本発明の電磁波シールド材は、前記電磁波シールド用金属箔の片面に、樹脂層が積層されている。
前記樹脂層は樹脂フィルムであることが好ましい。
In the electromagnetic wave shielding material of the present invention, a resin layer is laminated on one side of the metal foil for electromagnetic wave shielding.
The resin layer is preferably a resin film.
本発明によれば、従来のＳｎめっきよりも耐食性に優れた電磁波シールド用金属箔及び電磁波シールド材が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the metal foil for electromagnetic wave shielding and the electromagnetic wave shielding material which were excellent in corrosion resistance compared with the conventional Sn plating are obtained.
以下、本発明の実施の形態について説明する。なお、本発明において％とは、特に断らない限り、質量％を示すものとする。 Embodiments of the present invention will be described below. In the present invention, “%” means “% by mass” unless otherwise specified.
図１（ｂ）に示すように、本発明の第１の実施の形態に係る電磁波シールド用金属箔１０は、金属箔からなる基材１と、基材１の片面に形成された合金層２とを有する。
（基材）
基材１は、電磁波シールド効果を発揮する導電性の高い金属であればなんでもよい。基材１としては金、銀、白金、ステンレス、鉄、ニッケル、亜鉛、銅、銅合金、アルミニウム、又はアルミニウム合金などの箔が挙げられるが、銅又はアルミニウムの箔が一般的である。
基材１の形成方法は特に限定されず、例えば圧延して製造してもよく、電気めっきで箔を形成してもよい。また、後述する電磁波シールド材の樹脂層又は樹脂フィルムの表面に、乾式めっきして基材１を成膜してもよい。
基材１の厚みは、電磁波シールドの対象とする周波数と表皮効果を考慮して決定するのがよい。具体的には、基材１を構成する元素の導電率と、対象となる周波数を下式（１）に代入して得られる表皮深さ以上とするのが好ましい。例えば、基材１として銅箔を使用し、対象となる周波数が１００ＭＨｚの場合、表皮深さは６．６１μｍであるので、基材１の厚みを約７μｍ以上とするのがよい。基材１の厚みが厚くなると、柔軟性や加工性に劣り、原料コストも増加することから１００μｍ以下とするのがよい。
ｄ＝｛２／（２π×ｆ×σ×μ）｝１／２ （１）
ｄ：表皮深さ（μｍ）
ｆ：周波数（ＧＨｚ）
σ：導体の導電率（Ｓ／ｍ）
μ：導体の透磁率（Ｈ／ｍ）
As shown in FIG.1 (b), the electromagnetic shielding metal foil 10 which concerns on the 1st Embodiment of this invention is the base material 1 which consists of metal foil, and the alloy layer 2 formed in the single side | surface of the base material 1 And have.
(Base material)
The substrate 1 may be anything as long as it is a highly conductive metal that exhibits an electromagnetic wave shielding effect. Examples of the substrate 1 include a foil of gold, silver, platinum, stainless steel, iron, nickel, zinc, copper, copper alloy, aluminum, or aluminum alloy, but a copper or aluminum foil is common.
The formation method of the base material 1 is not specifically limited, For example, it may manufacture by rolling and you may form foil by electroplating. Further, the substrate 1 may be formed by dry plating on the surface of a resin layer or resin film of an electromagnetic wave shielding material described later.
The thickness of the substrate 1 is preferably determined in consideration of the frequency to be shielded by the electromagnetic wave and the skin effect. Specifically, it is preferable to set the skin depth to be equal to or greater than the skin depth obtained by substituting the conductivity of the elements constituting the substrate 1 and the target frequency into the following formula (1). For example, when copper foil is used as the base material 1 and the target frequency is 100 MHz, the skin depth is 6.61 μm, so the thickness of the base material 1 is preferably about 7 μm or more. When the thickness of the base material 1 is increased, the flexibility and workability are inferior, and the raw material cost is increased.
d = {2 / (2π × f × σ × μ)} 1/2 (1)
d: Epidermis depth (μm)
f: Frequency (GHz)
σ: Conductivity of conductor (S / m)
μ: Magnetic permeability of conductor (H / m)
基材１として銅箔を用いる場合、銅箔の種類に特に制限はないが、典型的には圧延銅箔や電解銅箔の形態で用いることができる。一般的には、電解銅箔は硫酸銅めっき浴やシアン化銅めっき浴からチタン又はステンレスのドラム上に銅を電解析出して製造され、圧延銅箔は圧延ロールによる塑性加工と熱処理を繰り返して製造される。
圧延銅箔としては、純度９９．９％以上の無酸素銅（ＪＩＳ-Ｈ３１００（Ｃ１０２０））又はタフピッチ銅（ＪＩＳ-Ｈ３１００（Ｃ１１００））を用いることができる。又、銅合金箔としては要求される強度や導電性に応じて公知の銅合金を用いることができる。公知の銅合金としては、例えば、０．０１〜０．３％の錫入り銅合金や０．０１〜０．０５％の銀入り銅合金が挙げられ、特に、導電性に優れたものとしてＣｕ-０．１２％Ｓｎ、Ｃｕ-０．０２％Ａｇがよく用いられる。例えば、圧延銅箔として導電率が５％以上のものを用いることができる。電解銅箔としては、公知のものを用いることができる。
又、アルミニウム箔としては、純度９９．０％以上のアルミニウム箔を用いることができる。又、アルミニウム合金箔としては、要求される強度や導電率に応じて公知のアルミニウム合金を用いることができる。公知のアルミニウム合金としては、例えば、０．０１〜０．１５％のＳｉと０．０１〜１．０％のＦｅ入りのアルミニウム合金、１．０〜１．５％のＭｎ入りアルミニウム合金が挙げられる。
When using copper foil as the base material 1, although there is no restriction | limiting in particular in the kind of copper foil, Typically, it can use with the form of rolled copper foil or electrolytic copper foil. In general, electrolytic copper foil is manufactured by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath or a copper cyanide plating bath, and the rolled copper foil is repeatedly subjected to plastic working and heat treatment by a rolling roll. Manufactured.
As the rolled copper foil, oxygen-free copper (JIS-H3100 (C1020)) or tough pitch copper (JIS-H3100 (C1100)) having a purity of 99.9% or more can be used. Moreover, as a copper alloy foil, a well-known copper alloy can be used according to the required intensity | strength and electroconductivity. Known copper alloys include, for example, 0.01-0.3% tin-containing copper alloys and 0.01-0.05% silver-containing copper alloys. -0.12% Sn and Cu-0.02% Ag are often used. For example, a rolled copper foil having a conductivity of 5% or more can be used. A well-known thing can be used as an electrolytic copper foil.
As the aluminum foil, an aluminum foil having a purity of 99.0% or more can be used. Moreover, as an aluminum alloy foil, a well-known aluminum alloy can be used according to the required intensity | strength and electrical conductivity. Examples of known aluminum alloys include aluminum alloys containing 0.01 to 0.15% Si and 0.01 to 1.0% Fe, and aluminum alloys containing 1.0 to 1.5% Mn. It is done.
（合金層）
合金層２は、Ｓｎ又はＡｇの群から選ばれる１種のＡ元素群と、Ｎｉ、Ｆｅ及びＣｏの群から選ばれる１種以上のＢ元素群とからなる（但し、Ｓｎ−Ｆｅ、Ａｇ−Ｆｅ及びＡｇ−Ｃｏを除く）。
Ｓｎめっき被膜は耐食性に優れるとされているが、ＮＯＸやＳＯＸといった腐食ガスに対する耐性が必ずしも高くない。
そこで、Ｓｎの代わりに、所定の元素からなる合金層を形成することで、Ｓｎの付着量を低減し又はＳｎを用いずに、なおかつ耐食性を向上させることができる。合金層２に含まれるＡ元素群とＢ元素群の質量比は、（Ａ元素群の合計量）/（Ｂ元素群の合計量）＝８/２〜１/９であるのが好ましい。
合金層２がさらに、Ｐ、Ｗの群から選ばれる１種以上のＣ元素群を含んでもよい。Ｃ元素群の元素が含まれることでさらに耐食性を向上させることができる。合金層２全体に対するＣ元素群の合計含有率は、ＳＴＥＭ（走査透過型電子顕微鏡）による線分析で、合金層２を構成する各元素を指定元素とし、指定元素の合計を１００％として１〜４０質量％の範囲であることが好ましく、５〜２０質量％の範囲であることがさらに好ましい。
(Alloy layer)
Alloy layer 2 is composed of a one A group of elements selected from the group consisting of Sn or Ag, Ni, and one or more B group of elements selected from the group consisting of Fe and Co (although, Sn-Fe, Ag- Except Fe and Ag-Co) .
Sn plating film is an excellent corrosion resistance, but resistance is not necessarily high for corrosive gases such as NO X or SO X.
Therefore, by forming an alloy layer made of a predetermined element instead of Sn, it is possible to reduce the adhesion amount of Sn or improve the corrosion resistance without using Sn. The mass ratio of the A element group and the B element group contained in the alloy layer 2 is preferably (total amount of A element group) / (total amount of B element group) = 8/2 to 1/9.
The alloy layer 2 may further include one or more C element groups selected from the group of P and W. Corrosion resistance can be further improved by including an element of the C element group. The total content of the C element group with respect to the entire alloy layer 2 is 1 to 1, with each element constituting the alloy layer 2 designated as a specified element and 100% as the total of the specified elements in a line analysis by STEM (scanning transmission electron microscope). The range is preferably 40% by mass, and more preferably 5 to 20% by mass .
（総付着量）
上記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上であることが好ましく、３０μｍｏｌ／ｄｍ２以上であることがより好ましい。
Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２未満であると、合金層２が十分に形成されず、合金層２の耐食性が低下する場合がある。上限は特に限定されるものではなく、厚いほど耐食性は向上するが、コストの観点から、例えば１０００μｍｏｌ／ｄｍ２以下とすることができる。
(Total adhesion amount)
Preferably has a total adhesion amount of the A element group is 10 .mu.mol / dm 2 or more, more preferably 30 [mu] mol / dm 2 or more.
If the total adhesion amount of the A element group is less than 10 μmol / dm 2 , the alloy layer 2 may not be sufficiently formed, and the corrosion resistance of the alloy layer 2 may be reduced. The upper limit is not particularly limited, and the corrosion resistance improves as the thickness increases. However, from the viewpoint of cost, it can be set to 1000 μmol / dm 2 or less, for example.
上記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上であることが好ましく、７５μｍｏｌ／ｄｍ２であることがより好ましい。
Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２未満であると、合金層２が十分に形成されず、合金層２の耐食性が低下する場合がある。Ｂ元素群は比較的安価な金属からなるため、その総付着量の上限は特に限定されないが、コスト等の観点から１０００μｍｏｌ／ｄｍ２以下とすることが好ましい。
The total adhesion amount of the B element group is preferably 40 μmol / dm 2 or more, and more preferably 75 μmol / dm 2 .
If the total adhesion amount of the B element group is less than 40 μmol / dm 2 , the alloy layer 2 may not be sufficiently formed, and the corrosion resistance of the alloy layer 2 may be reduced. Since the B element group is made of a relatively inexpensive metal, the upper limit of the total adhesion amount is not particularly limited, but is preferably 1000 μmol / dm 2 or less from the viewpoint of cost and the like.
総付着量とは、合金層２のみ形成されている場合は合金層２中の付着量であり、合金層２の他に、後述する第１層３及び／又は第２層５が形成されている場合は、これらのすべての層中の付着量である。従って、Ｂ元素群の総付着量は、合金層２に含まれるＢ元素群の量だけでなく、後述する第１層３のＢ元素群の量を加算した値である。同様に、Ａ元素群の総付着量は、合金層２に含まれるＡ元素群の量だけでなく、後述する第２層５のＡ元素群の量を加算した値である。
又、総付着量とは、合金層２等が基材１の両面に形成されている場合は、各面における、合金層２等の付着量の合計である。
The total adhesion amount is the adhesion amount in the alloy layer 2 when only the alloy layer 2 is formed. In addition to the alloy layer 2, the first layer 3 and / or the second layer 5 described later are formed. If so, it is the amount deposited in all these layers. Therefore, the total adhesion amount of the B element group is a value obtained by adding not only the amount of the B element group included in the alloy layer 2 but also the amount of the B element group of the first layer 3 described later. Similarly, the total adhesion amount of the A element group is a value obtained by adding not only the amount of the A element group included in the alloy layer 2 but also the amount of the A element group of the second layer 5 described later.
Further, the total coating weight, when the alloy layer 2 or the like is formed on both surfaces of the substrate 1, in each surface, the sum of the coating weight, such as the alloy layer 2.
（合金層の形成方法）
合金層２は、合金めっき（湿式めっき）、合金層を構成する合金のターゲットを用いたスパッタ、合金層を構成する成分を用いた蒸着等によって形成することができる。
又、図１（ａ）に示すように、例えば、基材１の片面にまずＢ元素群からなる第１めっき層２１を形成し、第１めっき層２１の表面にＡ元素群からなる第２めっき層２２を形成した後、熱処理して第１めっき層２１の元素を第２めっき層２２中に拡散させ、図１（ｂ）に示す合金層２を形成することもできる。熱処理の条件は特に限定されないが、例えば、１２０〜５００℃で２秒〜１０時間程度とすることができる。
又、図１（ａ）に示す方法で合金層２を形成する場合であって、第１めっき層２１又は第２めっき層２２が拡散しやすい元素であれば、熱処理せずに常温で合金化させることもできる。
(Method of forming alloy layer)
The alloy layer 2 can be formed by alloy plating (wet plating), sputtering using an alloy target constituting the alloy layer, vapor deposition using a component constituting the alloy layer, or the like.
Further, as shown in FIG. 1A, for example, a first plating layer 21 composed of a B element group is first formed on one surface of a substrate 1, and a second plating composed of an A element group is formed on the surface of the first plating layer 21. After forming the plating layer 22, the alloy layer 2 shown in FIG. 1B can be formed by heat treatment to diffuse the elements of the first plating layer 21 into the second plating layer 22. Although the heat treatment conditions are not particularly limited, for example, the heat treatment can be performed at 120 to 500 ° C. for about 2 seconds to 10 hours.
In addition, when the alloy layer 2 is formed by the method shown in FIG. 1A and the first plating layer 21 or the second plating layer 22 is an easily diffusing element, it is alloyed at room temperature without heat treatment. It can also be made.
次に、図２を参照し、本発明の第２の実施の形態に係る電磁波シールド用金属箔１１について説明する。電磁波シールド用金属箔１１は、第１の実施の形態に係る電磁波シールド用金属箔１０において、さらに基材１と合金層２との間に、第１層３が形成されていると共に、合金層２の表面にＡ元素群からなる第２層５が形成され、第２層５の表面にクロム酸化物層６が形成されている。
第１層３は、Ｂ元素群からなる金属層、又はＢ元素群とＣ元素群とからなる合金層から構成されている。第２層５は、Ａ元素群からなる金属層、又はＡ元素群とＣ元素群とからなる合金層から構成されている。
第１層３及び第２層５は、例えば図１（ａ）の第１めっき層２１及び第２めっき層２２の厚みを厚くし、熱処理後に第１めっき層２１及び第２めっき層２２の一部を合金層２とせずに残存させることで形成することができる。勿論、基材１の表面に、熱処理せずに直接第１層３、合金層２、及び第２層５をこの順でめっき等で形成してもよい。又、第１層３、合金層２、及び第２層５等は、湿式めっきの他、蒸着、ＰＶＤ、ＣＶＤ等によって形成することもできる。
なお、基材１と合金層２との間にＢ元素群からなる第１層３が形成されている構成や、合金層２の表面にＡ元素群からなる第２層５が形成されている構成も本発明に含まれる。又、本発明の電磁波シールド用金属箔の最表面（合金層又は第２層）にクロム酸化物層６が形成されている構成も本発明に含まれる。
Next, with reference to FIG. 2, the metal foil 11 for electromagnetic wave shielding which concerns on the 2nd Embodiment of this invention is demonstrated. In the electromagnetic shielding metal foil 10 according to the first embodiment, the electromagnetic shielding metal foil 11 further includes a first layer 3 formed between the base material 1 and the alloy layer 2, and an alloy layer. A second layer 5 made of an A element group is formed on the surface 2, and a chromium oxide layer 6 is formed on the surface of the second layer 5.
The first layer 3 is composed of a metal layer composed of a B element group or an alloy layer composed of a B element group and a C element group. The second layer 5 is composed of a metal layer composed of an A element group or an alloy layer composed of an A element group and a C element group.
The first layer 3 and the second layer 5 are formed by increasing the thicknesses of the first plating layer 21 and the second plating layer 22 in FIG. 1A, for example, and one of the first plating layer 21 and the second plating layer 22 after the heat treatment. It can be formed by leaving the part without the alloy layer 2. Of course, the first layer 3, the alloy layer 2, and the second layer 5 may be directly formed on the surface of the substrate 1 by plating or the like in this order without heat treatment. Further, the first layer 3, the alloy layer 2, the second layer 5 and the like can be formed by vapor deposition, PVD, CVD, or the like in addition to wet plating.
In addition, the structure in which the 1st layer 3 which consists of B element group is formed between the base material 1 and the alloy layer 2, and the 2nd layer 5 which consists of A element group is formed in the surface of the alloy layer 2 The configuration is also included in the present invention. Moreover, the structure by which the chromium oxide layer 6 is formed in the outermost surface (alloy layer or 2nd layer) of the metal foil for electromagnetic wave shielding of this invention is also contained in this invention.
次に、図３を参照し、本発明の実施の形態に係る電磁波シールド材１００について説明する。電磁波シールド材１００は電磁波シールド用金属箔１０と、この金属箔１０の片面に樹脂層又は樹脂フィルム４とを積層してなる。
樹脂層としては例えばポリイミド等の樹脂を用いることができ、樹脂フィルムとしては例えばＰＥＴ(ポリエチレンテレフタラート)、ＰＥＮ（ポリエチレンナフタレート）のフィルムを用いることができる。樹脂層や樹脂フィルムは、接着剤により金属箔に接着されてもよいが、接着剤を用いずに溶融樹脂を金属箔上にキャスティングしたり、フィルムを金属箔に熱圧着させてもよい。また、樹脂フィルムにＰＶＤやＣＶＤで直接銅やアルミニウムの層を基材として形成したフィルムや、樹脂フィルムにＰＶＤやＣＶＤで銅やアルミニウムの薄い層を導電層として形成した後、この導電層上に湿式めっきで金属層を厚く形成したメタライズドフィルムを用いてもよい。
樹脂層や樹脂フィルムとしては公知のものを用いることができる。樹脂層や樹脂フィルムの厚みは特に制限されないが、例えば１〜１００μｍ、より好ましくは３〜５０μｍのものを好適に用いることができる。又、接着剤を用いた場合、接着層の厚みは例えば１０μｍ以下とすることができる。
材料の軽薄化の観点から、電磁波シールド材１００の厚みは１．０ｍｍ以下、より好ましくは０．０１〜０．５ｍｍであることが好ましい。
Next, the electromagnetic shielding material 100 according to the embodiment of the present invention will be described with reference to FIG. The electromagnetic shielding material 100 is formed by laminating an electromagnetic shielding metal foil 10 and a resin layer or a resin film 4 on one surface of the metal foil 10.
For example, a resin such as polyimide can be used as the resin layer, and a film of PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) can be used as the resin film. The resin layer and the resin film may be bonded to the metal foil with an adhesive, but the molten resin may be cast on the metal foil without using the adhesive, or the film may be thermocompression bonded to the metal foil. In addition, a film in which a copper or aluminum layer is directly formed on a resin film by PVD or CVD, or a thin layer of copper or aluminum is formed on a resin film by PVD or CVD as a conductive layer. You may use the metallized film which formed the metal layer thickly by wet plating.
A well-known thing can be used as a resin layer or a resin film. Although the thickness of the resin layer or the resin film is not particularly limited, for example, a thickness of 1 to 100 μm, more preferably 3 to 50 μm can be suitably used. When an adhesive is used, the thickness of the adhesive layer can be set to 10 μm or less, for example.
From the viewpoint of lightening the material, the thickness of the electromagnetic shielding material 100 is preferably 1.0 mm or less, more preferably 0.01 to 0.5 mm.
次に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
（基材）
圧延銅箔としては、厚さ８μｍの圧延銅箔（ＪＸ日鉱日石金属製の型番Ｃ１１００）を用いた。
電解銅箔としては、厚さ８μｍの無粗化処理の電解銅箔（ＪＸ日鉱日石金属製の型番ＪＴＣ箔）を用いた。
Ｃｕメタライズドフィルムとしては、厚さ８μｍのメタライジングＣＣＬ（日鉱金属製の製品名「マキナス」）を用いた。
アルミニウム箔としては、厚さ１２μｍのアルミニウム箔（サン・アルミニウム工業社製）を用いた。
Ａｌメタライズドフィルムとしては、厚さ１２μｍのＰＥＴフィルム（東洋紡績社製）に真空蒸着でアルミニウムを２μｍ形成したものを用いた。
EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
(Base material)
As the rolled copper foil, a rolled copper foil having a thickness of 8 μm (model number C1100 made by JX Nippon Mining & Metals) was used.
As the electrolytic copper foil, a non-roughened electrolytic copper foil having a thickness of 8 μm (model number JTC foil made by JX Nippon Mining & Metals) was used.
As the Cu metallized film, a metalizing CCL having a thickness of 8 μm (product name “Makinas” manufactured by Nikko Metal) was used.
As the aluminum foil, an aluminum foil having a thickness of 12 μm (manufactured by Sun Aluminum Industry Co., Ltd.) was used.
As the Al metallized film, a 12 μm thick PET film (Toyobo Co., Ltd.) having 2 μm of aluminum formed by vacuum deposition was used.
(合金層)
合金層を、上記基材の片面に形成した。表１に、合金層の形成方法を示す。
表１において「めっき」とは、図１（ａ）に示す方法で第１めっき層２１、第２めっき層２２をこの順でめっきした後、表１に示す条件で熱処理したものである。表１において「合金めっき」は、合金めっきにより合金層を形成したものである。
なお、Ｎｉ、Ｓｎ、Ａｇ、Ｃｕ、Ｚｎ、Ｎｉ−Ｓｎ合金、Ｃｏ−Ｓｎ合金の各めっきは、以下の条件で形成した。
Ｎｉめっき：硫酸Ｎｉ浴（Ｎｉ濃度：２０ｇ／Ｌ、電流密度：２〜１０Ａ／ｄｍ２）
Ｓｎ：フェノールスルホン酸Ｓｎ浴（Ｓｎ濃度：４０ｇ／Ｌ、電流密度：２〜１０Ａ／ｄｍ２）
Ａｇめっき：シアン化Ａｇ浴（Ａｇ濃度：１０ｇ／Ｌ、電流密度：０．２〜４Ａ／ｄｍ２）
Ｃｕめっき：硫酸Ｃｕ浴（Ｃｕ濃度：２０ｇ／Ｌ、電流密度：２〜１０Ａ／ｄｍ２）
Ｚｎめっき：硫酸Ｚｎ浴（Ｚｎ濃度：２０ｇ／Ｌ、電流密度：１〜５Ａ／ｄｍ２）
Ｎｉ−Ｓｎ：ピロリン酸塩浴（Ｎｉ濃度１０ｇ／Ｌ、Ｓｎ濃度１０ｇ／Ｌ、電流密度：０．１〜２Ａ／ｄｍ２）
Ｃｏ−Ｓｎめっき：ピロリン酸塩浴（Ｃｏ濃度２０ｇ／Ｌ、Ｓｎ濃度２０ｇ／Ｌ、電流密度：０．２〜３Ａ／ｄｍ２）
Ｎｉ−Ｐ：硫酸浴（Ｎｉ濃度：２０ｇ／Ｌ、Ｐ濃度：２０ｇ／Ｌ、電流密度：２〜４Ａ／ｄｍ２）
Ｎｉ−Ｗ：硫酸浴（Ｎｉ濃度：２０ｇ／Ｌ、Ｗ濃度：２０ｇ／Ｌ、電流密度：０．１〜２Ａ／ｄｍ２）
Ｎｉ−Ｆｅ：硫酸浴（Ｎｉ濃度：２０ｇ／Ｌ、Ｆｅ濃度：１０ｇ／Ｌ、電流密度：０．１〜２Ａ／ｄｍ２）
Ｎｉ−Ｃｏ：硫酸浴（Ｎｉ濃度：２０ｇ／Ｌ、Ｃｏ濃度：１０ｇ／Ｌ、電流密度：０．１〜２Ａ／ｄｍ２）
(Alloy layer)
An alloy layer was formed on one side of the substrate. Table 1 shows a method for forming the alloy layer.
In Table 1, “plating” means that the first plating layer 21 and the second plating layer 22 are plated in this order by the method shown in FIG. 1A and then heat-treated under the conditions shown in Table 1. In Table 1, “alloy plating” is an alloy layer formed by alloy plating.
Each plating of Ni, Sn, Ag, Cu, Zn, Ni—Sn alloy, and Co—Sn alloy was formed under the following conditions.
Ni plating: sulfuric acid Ni bath (Ni concentration: 20 g / L, current density: 2 to 10 A / dm 2 )
Sn: phenolsulfonic acid Sn bath (Sn concentration: 40 g / L, current density: 2 to 10 A / dm 2 )
Ag plating: Cyanide Ag bath (Ag concentration: 10 g / L, current density: 0.2 to 4 A / dm 2 )
Cu plating: Cu sulfate bath (Cu concentration: 20 g / L, current density: 2 to 10 A / dm 2 )
Zn plating: Zn sulfate bath (Zn concentration: 20 g / L, current density: 1 to 5 A / dm 2 )
Ni-Sn: pyrophosphate bath (Ni concentration 10 g / L, Sn concentration 10 g / L, current density: 0.1 to 2 A / dm 2 )
Co—Sn plating: pyrophosphate bath (Co concentration 20 g / L, Sn concentration 20 g / L, current density: 0.2 to 3 A / dm 2 )
Ni-P: sulfuric acid bath (Ni concentration: 20 g / L, P concentration: 20 g / L, current density: 2-4 A / dm 2 )
Ni-W: sulfuric acid bath (Ni concentration: 20 g / L, W concentration: 20 g / L, current density: 0.1 to 2 A / dm 2 )
Ni-Fe: sulfuric acid bath (Ni concentration: 20 g / L, Fe concentration: 10 g / L, current density: 0.1 to 2 A / dm 2 )
Ni-Co: sulfuric acid bath (Ni concentration: 20 g / L, Co concentration: 10 g / L, current density: 0.1 to 2 A / dm 2 )
表１において「スパッタ」は、Ｎｉ，Ｓｎをこの順でスパッタした後、表１に示す条件で熱処理したものである。
表１において「合金スパッタ」は、対応する合金のターゲット材を用いてスパッタして合金層を形成したものである。なお、合金スパッタで成膜される層は合金層そのものの組成であるので、熱処理は行わなかった。
なお、スパッタ、合金スパッタは以下の条件で行った。
スパッタ装置：バッチ式スパッタリング装置（アルバック社、型式ＭＮＳ−６０００）
スパッタ条件：到達真空度１．０×１０-5Ｐａ、スパッタリング圧０．２Ｐａ、スパッタリング電力５０Ｗ
ターゲット：Ｎｉ（純度３Ｎ）、Ａｇ（純度３Ｎ）、Ｎｉ−Ｓｎ（Ｎｉ：Ｓｎ＝２０：８０ａｔ％）
In Table 1, “sputtering” refers to Ni and Sn sputtered in this order and then heat-treated under the conditions shown in Table 1.
In Table 1, “alloy sputtering” is an alloy layer formed by sputtering using a target material of a corresponding alloy. In addition, since the layer formed by alloy sputtering has the composition of the alloy layer itself, no heat treatment was performed.
Sputtering and alloy sputtering were performed under the following conditions.
Sputtering device: Batch type sputtering device (ULVAC, Model MNS-6000)
Sputtering conditions: ultimate vacuum 1.0 × 10 −5 Pa, sputtering pressure 0.2 Pa, sputtering power 50 W
Target: Ni (purity 3N), Ag (purity 3N), Ni—Sn (Ni: Sn = 20: 80 at%)
表１において「蒸着」は、以下の条件で行った。
蒸着装置：真空蒸着装置（アルバック社、型式ＭＢ０５−１００６）
蒸着条件：到達真空度５．０×１０-３Ｐａ、電子ビーム加速電圧６ｋＶ
蒸着源：Ｎｉ（純度３Ｎ）、Ｉｎ（純度３Ｎ）
In Table 1, “deposition” was performed under the following conditions.
Vapor deposition equipment: Vacuum vapor deposition equipment (ULVAC, model MB05-1006)
Deposition conditions: ultimate vacuum 5.0 × 10 −3 Pa, electron beam acceleration voltage 6 kV
Vapor deposition source: Ni (purity 3N), In (purity 3N)
（付着量の測定）
得られた電磁波シールド用金属箔を５０ｍｍ×５０ｍｍに切り出し、表面の皮膜をＨＮＯ3（２重量％）とＨＣｌ（５重量％）を混合した溶液に溶解した。そして、溶液中の金属濃度をＩＣＰ発光分光分析装置（エスアイアイ・ナノテクノロジー株式会社製、ＳＦＣ−３１００）にて定量し、単位面積当たりの金属重量から付着量（μｍｏｌ／ｄｍ2）を算出した。
（層構成の判定）
得られた電磁波シールド用金属箔について、ＳＴＥＭ（走査透過型電子顕微鏡、日本電子株式会社製ＪＥＭ−２１００Ｆ）による線分析を行い、層構成を判定した。分析した指定元素は、Ａ元素群、Ｂ元素群、Ｃ元素群、Ｃ、Ｓ及びＯである。また、上記した指定元素の合計を１００％として、各元素の濃度(質量％)を分析した（加速電圧：２００ｋＶ、測定間隔：２ｎｍ）。
Ａ元素群の元素の合計、及びＢ元素群の元素の合計を、それぞれ５質量％以上含む層を合金層２とした。例えば、Ａ元素群としてＳｎ，Ａｇの２元素を含む場合、ＳｎとＡｇの濃度の合計値を採用する。
合金層２よりも表層側に位置し、Ａ元素群の元素の合計を５質量％以上含むと共に、Ｂ元素群の元素の合計が５質量％未満の層を第２層５とした。
合金層２よりも下層側に位置し、Ｂ元素群の元素の合計を５質量％以上含むと共に、Ａ元素群の元素の合計が５質量％未満の層を第１層３とした。
又、図５に例示するチャートから、上記合金層として定義される深さ領域のＣ元素群の元素の面積と、他のすべての元素の合計の面積とをそれぞれ計算し、合金層中のＣ元素群の合計含有率を求めた。
(Measurement of adhesion amount)
The obtained metal foil for electromagnetic wave shielding was cut into 50 mm × 50 mm, and the surface film was dissolved in a mixed solution of HNO 3 (2 wt%) and HCl (5 wt%). Then, the metal concentration in the solution was quantified using an ICP emission spectroscopic analyzer (SFC-3100, manufactured by SII Nano Technology Co., Ltd.), and the adhesion amount (μmol / dm 2 ) was calculated from the metal weight per unit area. .
(Determination of layer structure)
About the obtained metal foil for electromagnetic shielding, the line analysis by STEM (scanning transmission electron microscope, JEM-2100F by JEOL Ltd.) was performed, and the layer structure was determined. The analyzed designated elements are the A element group, the B element group, the C element group, C, S, and O. Further, the concentration ( mass %) of each element was analyzed with the total of the specified elements described above being 100% (acceleration voltage: 200 kV, measurement interval: 2 nm).
A layer containing 5% by mass or more of the total of the elements of the A element group and the total of the elements of the B element group was used as the alloy layer 2. For example, when two elements of Sn and Ag are included as the A element group, the total value of the concentrations of Sn and Ag is adopted.
The second layer 5 is located on the surface layer side of the alloy layer 2 and contains 5% by mass or more of the total elements of the A element group and the total of the elements of the B element group is less than 5% by mass .
The first layer 3 is located on the lower layer side of the alloy layer 2 and contains 5% by mass or more of the total elements of the B element group and the total of the elements of the A element group is less than 5% by mass .
Further, from the chart illustrated in FIG. 5, the area of the element of the C element group in the depth region defined as the alloy layer and the total area of all other elements are respectively calculated, and the C in the alloy layer is calculated. The total content of the element group was determined.
又、得られた電磁波シールド用金属箔の合金層側の面について、それぞれ耐食性試験（塩水噴霧試験、及びガス腐食試験）を行ったのち、合金層側の最表面の接触抵抗を測定した。
接触抵抗の測定は山崎精機株式会社製の電気接点シミュレーターＣＲＳ−１を使用して四端子法で測定した。プローブ：金プローブ、接触荷重：２０ｇｆ、バイアス電流：１０ｍＡ、摺動距離：１ｍｍ
塩水噴霧試験は、ＪＩＳ−Ｚ２３７１（温度:３５℃、塩水成分：塩化ナトリウム、塩水濃度：５質量％、噴霧圧力：９８±１０ｋＰａ、噴霧時間：４８ｈ）に従った。
○：接触抵抗が１００ｍΩ以下
×：接触抵抗が１００ｍΩ以上
塩水噴霧試験の評価が○であれば実用上、問題はない。
ガス腐食試験は、ＩＥＣ６０５１２−１１−７の試験方法４（温度：２５℃、湿度：７５％、Ｈ２Ｓ濃度：１０ｐｐｂ、ＮＯ２濃度：２００ｐｐｂ、Ｃｌ２濃度：１０ｐｐｂ、ＳＯ２濃度：２００ｐｐｂ、試験時間：７日間または２１日間）に従った。
○：２１日間後も接触抵抗が１００ｍΩ以下
△：２１日間後は接触抵抗が１００ｍΩ以上であったが、７日間後は接触抵抗が１００ｍΩ以下
×：７日間後も接触抵抗が１００ｍΩ以上
ガス腐食試験の評価が○又は△であれば実用上、問題はない。
Further, the surface on the alloy layer side of the obtained metal foil for electromagnetic wave shielding was subjected to a corrosion resistance test (a salt spray test and a gas corrosion test), and then the contact resistance on the outermost surface on the alloy layer side was measured.
The contact resistance was measured by a four-terminal method using an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Co., Ltd. Probe: gold probe, contact load: 20 gf, bias current: 10 mA, sliding distance: 1 mm
The salt spray test was in accordance with JIS-Z2371 (temperature: 35 ° C., salt water component: sodium chloride, salt water concentration: 5 mass %, spray pressure: 98 ± 10 kPa, spray time: 48 h).
○: Contact resistance of 100 mΩ or less ×: Contact resistance of 100 mΩ or more If the evaluation of the salt spray test is ○, there is no practical problem.
The gas corrosion test is performed in accordance with IEC60512-11-7 test method 4 (temperature: 25 ° C., humidity: 75%, H2S concentration: 10 ppb, NO2 concentration: 200 ppb, Cl2 concentration: 10 ppb, SO2 concentration: 200 ppb, test time: 7 days. Or 21 days).
○: Contact resistance is 100 mΩ or less after 21 days. Δ: Contact resistance is 100 mΩ or more after 21 days, but contact resistance is 100 mΩ or less after 7 days. X: Gas corrosion test with contact resistance of 100 mΩ or more after 7 days. If the evaluation is ○ or △, there is no practical problem.
得られた結果を表１、及び図４〜図５に示す。 The obtained results are shown in Table 1 and FIGS.
表１から明らかなように、Ａ元素群とＢ元素群（さらに、必要に応じてＣ元素群）からなる合金層を有する各実施例の場合、耐食性に優れていた。
なお、実施例６は、熱処理を行っていないが、ＳｎとＮｉが拡散しやすい元素であるので、常温で合金層が形成された。又、実施例６は、熱処理を行っていないため、Ｓｎめっき層とＮｉめっき層のうち、合金層とならずにそれぞれＳｎとＮｉが残った第１及び第２層が形成された。実施例２〜５は、熱処理を行ったが、もとのＳｎ層及びＮｉ層の付着量を多くしたので、これら層の一部が合金化せずに残存し、第１又は第２層が形成された。他の実施例も同様である。
特に、Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつＢ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である実施例１〜２０の場合、Ａ元素群又はＢ元素群の総付着量が上記範囲未満である参考例２１、２２に比べて耐食性がさらに優れていた。
なお、図４、５は、それぞれ実施例４の試料のＳＴＥＭによる断面像、及びＳＴＥＭによる線分析の結果を示す。断面像におけるＸ層、Ｙ層は、線分析の結果から、それぞれＮｉ−Ｓｎ合金層、Ｎｉ層であることがわかる。
又、線分析の結果からわかるようにＹ層（合金層）のＳｎとＮｉの質量比が、Ｎｉ/Ｓｎ＝３／７程度となっており、この値と、Ｓｎ−Ｎｉ状態図より合金層がＮｉ３Ｓｎ４であると考えられる。なお、図５の横軸の距離0.00μｍが、銅箔基材の厚み方向の任意の位置であり、図５の右側が表層側である。
As is clear from Table 1, each example having an alloy layer composed of an A element group and a B element group (and a C element group as needed) was excellent in corrosion resistance.
In Example 6, heat treatment was not performed, but Sn and Ni are easily diffusing elements, so an alloy layer was formed at room temperature. In Example 6, since heat treatment was not performed, the first and second layers in which Sn and Ni remained were formed in the Sn plating layer and the Ni plating layer without being an alloy layer. In Examples 2 to 5, heat treatment was performed, but since the adhesion amount of the original Sn layer and Ni layer was increased, a part of these layers remained without being alloyed, and the first or second layer was Been formed. The same applies to the other embodiments.
In particular, the total deposition amount of the element A group 10 .mu.mol / dm 2 or more, and when the total adhesion amount of B element group of Example 20 is 40 [mu] mol / dm 2 or more, the total deposition of A group of elements or B element group Compared to Reference Examples 21 and 22 whose amount was less than the above range, the corrosion resistance was further excellent.
4 and 5 show a cross-sectional image of the sample of Example 4 by STEM and the result of line analysis by STEM, respectively. From the results of the line analysis, it can be seen that the X layer and the Y layer in the cross-sectional image are a Ni—Sn alloy layer and a Ni layer, respectively.
As can be seen from the results of the line analysis, the mass ratio of Sn and Ni in the Y layer (alloy layer) is about Ni / Sn = 3/7. From this value and the Sn-Ni phase diagram, the alloy layer Is considered to be Ni 3 Sn 4 . In addition, the distance of 0.00 micrometer of the horizontal axis of FIG. 5 is the arbitrary positions of the thickness direction of a copper foil base material, and the right side of FIG. 5 is a surface layer side.
一方、合金層を形成せず、Ｎｉ、又はＮｉＣｏ層を形成した比較例１、４、５の場合、塩水噴霧試験及びガス腐食試験の評価が劣り、耐食性が大幅に劣った。
Ｂ元素群としてＣｕを用いて合金層を形成した比較例２、６の場合、ガス腐食試験の評価が劣り、耐食性が劣った。これは、Ｃｕが合金層に耐食性を付与しないためと考えられる。
又、Ａ元素群としてＺｎを用いて合金層を形成した比較例３の場合も、ガス腐食試験の評価が劣り、耐食性が劣った。これは、Ｚｎが合金層に耐食性を付与しないためと考えられる。
On the other hand, in the case of Comparative Examples 1, 4, and 5 in which an alloy layer was not formed and an Ni or NiCo layer was formed, the evaluation of the salt spray test and the gas corrosion test was inferior, and the corrosion resistance was significantly inferior.
In Comparative Examples 2 and 6 in which an alloy layer was formed using Cu as the B element group, the evaluation of the gas corrosion test was inferior and the corrosion resistance was inferior. This is presumably because Cu does not impart corrosion resistance to the alloy layer.
Moreover, also in the case of the comparative example 3 which formed the alloy layer using Zn as A element group, evaluation of the gas corrosion test was inferior and corrosion resistance was inferior. This is presumably because Zn does not impart corrosion resistance to the alloy layer.
１ 金属箔
２ 合金層
３ 第１層
４ 樹脂層又は樹脂フィルム
５ 第２層
１０、１１ 電磁波シールド用金属箔
１００ 電磁波シールド材
DESCRIPTION OF SYMBOLS 1 Metal foil 2 Alloy layer 3 1st layer 4 Resin layer or resin film 5 2nd layer 10, 11 Metal foil for electromagnetic wave shielding 100 Electromagnetic wave shielding material
Claims (13)
前記合金層の表面に前記Ａ元素群からなる金属層が存在せず、
かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、
前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である電磁波シールド用金属箔。 On one side or both sides of a base material made of metal foil, there is an alloy layer composed of one kind of element A selected from Sn or Ag and one or more kinds of element B selected from the group of Ni, Fe, and Co. Formed (except for Sn-Fe, Ag-Fe and Ag-Co),
There is no metal layer composed of the A element group on the surface of the alloy layer,
When the surface of the alloy layer is observed with an SEM, a plurality of needles having an average diameter of 0.1 to 2.0 μm represented by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion. Or without columnar protrusions,
A metal foil for electromagnetic wave shielding , wherein the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、
前記合金層の表面に、前記Ａ元素群からなる金属層から構成される第２層が形成され、
前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である電磁波シールド用金属箔。 On one side or both sides of a base material made of metal foil, there is an alloy layer composed of one kind of element A selected from Sn or Ag and one or more kinds of element B selected from the group of Ni, Fe, and Co. Formed (except for Sn-Fe, Ag-Fe and Ag-Co),
When the surface of the alloy layer is observed with an SEM, a plurality of needles having an average diameter of 0.1 to 2.0 μm represented by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion. Or without columnar protrusions,
On the surface of the alloy layer, a second layer composed of a metal layer composed of the A element group is formed,
A metal foil for electromagnetic wave shielding , wherein the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
前記合金層の表面に前記Ａ元素群からなる金属層が存在せず、
かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、
前記合金層と前記基材との間に、前記Ｂ元素群からなる金属層から構成される第１層が形成され、
前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である電磁波シールド用金属箔。 On one side or both sides of a base material made of metal foil, there is an alloy layer composed of one kind of element A selected from Sn or Ag and one or more kinds of element B selected from the group of Ni, Fe, and Co. Formed (except for Sn-Fe, Ag-Fe and Ag-Co),
There is no metal layer composed of the A element group on the surface of the alloy layer,
When the surface of the alloy layer is observed with an SEM, a plurality of needles having an average diameter of 0.1 to 2.0 μm represented by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion. Or without columnar protrusions,
A first layer composed of a metal layer composed of the B element group is formed between the alloy layer and the base material,
A metal foil for electromagnetic wave shielding , wherein the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
かつ前記合金層をＳＥＭで表面観察したとき、一つ一つの突起の凸部を取り囲むことのできる最小円の直径の平均値で表される平均径０．１〜２．０μｍの複数の針状又は柱状の突起を有さず、
前記合金層の表面に、前記Ａ元素群からなる金属層から構成される第２層が形成され、
前記合金層と前記基材との間に、前記Ｂ元素群からなる金属層から構成される第１層が形成され、
前記基材の片面の前記Ａ元素群の総付着量が１０μｍｏｌ／ｄｍ２以上、かつ前記Ｂ元素群の総付着量が４０μｍｏｌ／ｄｍ２以上である電磁波シールド用金属箔。 On one side or both sides of a base material made of metal foil, there is an alloy layer composed of one kind of element A selected from Sn or Ag and one or more kinds of element B selected from the group of Ni, Fe, and Co. Formed (except for Sn-Fe, Ag-Fe and Ag-Co),
When the surface of the alloy layer is observed with an SEM, a plurality of needles having an average diameter of 0.1 to 2.0 μm represented by the average value of the diameters of the smallest circles that can surround the protrusions of each protrusion. Or without columnar protrusions,
On the surface of the alloy layer, a second layer composed of a metal layer composed of the A element group is formed,
A first layer composed of a metal layer composed of the B element group is formed between the alloy layer and the base material,
A metal foil for electromagnetic wave shielding , wherein the total adhesion amount of the A element group on one side of the substrate is 10 μmol / dm 2 or more and the total adhesion amount of the B element group is 40 μmol / dm 2 or more.
前記合金層全体に対する前記Ｃ元素群の合計含有率が１〜４０質量％の範囲である請求項１に記載の電磁波シールド用金属箔。 The alloy layer further includes one or more C element groups selected from the group of P and W,
The metal foil for electromagnetic wave shielding according to claim 1, wherein the total content of the C element group with respect to the entire alloy layer is in the range of 1 to 40% by mass.
前記合金層全体に対する前記Ｃ元素群の合計含有率が１〜４０質量％の範囲である請求項２又は４に記載の電磁波シールド用金属箔。 The alloy layer further includes one or more C element groups selected from the group of P and W,
The metal foil for electromagnetic wave shielding according to claim 2 or 4, wherein the total content of the C element group with respect to the entire alloy layer is in the range of 1 to 40% by mass.
前記合金層全体に対する前記Ｃ元素群の合計含有率が１〜４０質量％の範囲である請求項３又は４に記載の電磁波シールド用金属箔。 The alloy layer further includes one or more C element groups selected from the group of P and W,
The metal foil for electromagnetic wave shielding according to claim 3 or 4, wherein the total content of the C element group with respect to the entire alloy layer is in the range of 1 to 40% by mass.
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