JP2018159125A - Sn PLATED MATERIAL AND PRODUCTION METHOD THEREOF - Google Patents
Sn PLATED MATERIAL AND PRODUCTION METHOD THEREOF Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 169
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 229910017755 Cu-Sn Inorganic materials 0.000 claims abstract description 51
- 229910017927 Cu—Sn Inorganic materials 0.000 claims abstract description 51
- 239000010949 copper Substances 0.000 claims abstract description 51
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 10
- 238000007747 plating Methods 0.000 claims description 277
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000009713 electroplating Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000010410 layer Substances 0.000 abstract description 286
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 32
- 238000002788 crimping Methods 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 91
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 55
- 238000005452 bending Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
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- 229910052725 zinc Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229910052718 tin Inorganic materials 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- 238000005096 rolling process Methods 0.000 description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- 102100036409 Activated CDC42 kinase 1 Human genes 0.000 description 1
- 101710140250 Activated CDC42 kinase 1 Proteins 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910009038 Sn—P Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
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- Manufacturing Of Electrical Connectors (AREA)
Abstract
Description
本発明は、Ｓｎめっき材およびその製造方法に関し、特に、ワイヤーハーネスなどの電線に接続される端子などの材料として使用されるＳｎめっき材およびその製造方法に関する。 The present invention relates to an Sn plating material and a method for manufacturing the same, and more particularly to an Sn plating material used as a material for a terminal connected to an electric wire such as a wire harness and a method for manufacturing the same.
従来、車両用のワイヤーハーネスなどの電線として銅または銅合金からなる電線が使用され、その電線に接続される端子などの材料として、銅または銅合金にＳｎめっきを施したＳｎめっき材が使用されている。 Conventionally, an electric wire made of copper or a copper alloy is used as an electric wire for a wire harness for a vehicle, and an Sn plating material obtained by applying Sn plating to copper or a copper alloy is used as a material such as a terminal connected to the electric wire. ing.
近年、車両の軽量化による燃費効率の向上のため、車両用のワイヤーハーネスなどの電線として、銅または銅合金より比重の小さいアルミニウムまたはアルミニウム合金からなる電線が使用されている。 In recent years, electric wires made of aluminum or aluminum alloys having a specific gravity smaller than that of copper or copper alloys have been used as electric wires for vehicle wiring harnesses or the like in order to improve fuel efficiency by reducing vehicle weight.
しかし、アルミニウムまたはアルミニウム合金からなる電線にＳｎめっき材からなる端子を加締めなどの圧着加工により接続すると、電位差の大きい異種金属の接触によるガルバニック腐食（卑な金属が溶解する異種金属接触腐食）が生じる可能性がある。 However, if a terminal made of Sn plating material is connected to an electric wire made of aluminum or an aluminum alloy by crimping such as crimping, galvanic corrosion due to contact of a dissimilar metal with a large potential difference (dissimilar metal contact corrosion in which a base metal dissolves) occurs. It can happen.
そのため、接続部分に防食剤や樹脂を塗布して異種金属接触腐食を防止しているが、生産性が低下し、製造コストが高くなる。 For this reason, anticorrosives and resins are applied to the connecting portions to prevent contact with different metals, but productivity is lowered and manufacturing costs are increased.
また、異種金属接触腐食を防止する端子として、電線の一端に露出した第一の金属（アルミニウム系材料）からなる芯線を加締め接続する芯線バレル部を有する電線接続部を備え、第一の金属よりもイオン化傾向が小さい第二の金属（銅系材料）により形成された端子であって、芯線バレル部が芯線を加締める前に、イオン化傾向が第一の金属と第二の金属の間である第三の金属（亜鉛）で電線接触部がめっき処理され、芯線バレル部における接続面のめっき層が加締め時に破壊される端子が提案されている（例えば、特許文献１参照）。 In addition, the first metal has a wire connecting portion having a core wire barrel portion for caulking and connecting a core wire made of a first metal (aluminum-based material) exposed at one end of the wire as a terminal for preventing foreign metal contact corrosion. A terminal formed of a second metal (copper-based material) having a smaller ionization tendency than the first wire and the second metal before the core wire barrel portion crimps the core wire. There has been proposed a terminal in which a wire contact portion is plated with a third metal (zinc), and a plating layer on a connection surface in a core wire barrel portion is destroyed when caulking (for example, see Patent Document 1).
しかし、特許文献１の端子では、電線接触部が第三の金属（亜鉛）でめっき処理され、加締め時にめっき層が破壊されるように非常に薄いめっき層を形成する必要があるので、長期間にわたって異種金属接触腐食を防止することが困難である。また、端子の材料として一般的に使用されているＳｎめっき材の表面にＺｎめっきを施しても、Ｚｎめっき層の密着性が悪く、Ｓｎめっき材を端子の材料として使用した場合に、端子形状に加工する際にＺｎめっき層が剥離し易くなることがわかった。また、Ｓｎめっき材を端子の材料として使用する場合、曲げ加工性が良好であることが望ましい。 However, in the terminal of Patent Document 1, it is necessary to form a very thin plating layer so that the wire contact portion is plated with a third metal (zinc) and the plating layer is destroyed when caulking. It is difficult to prevent dissimilar metal contact corrosion over time. In addition, even if the surface of the Sn plating material generally used as a terminal material is subjected to Zn plating, the adhesion of the Zn plating layer is poor, and when the Sn plating material is used as the terminal material, the terminal shape It has been found that the Zn plating layer is easily peeled off during processing. Moreover, when using Sn plating material as a material of a terminal, it is desirable that bending workability is favorable.
したがって、本発明は、このような従来の問題点に鑑み、表面にＺｎめっき層が形成されたＳｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、圧着加工の際に接続部分の加工を施さなくても、耐食性が良好であり且つ表面に形成したＺｎめっき層の密着性が良好であるとともに、曲げ加工性が良好なＳｎめっき材およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention provides a terminal material for connecting a Sn plating material having a Zn plating layer formed on a surface thereof to an electric wire made of aluminum or an aluminum alloy by crimping or the like. When used, Sn plating with good corrosion resistance and good adhesion to the Zn plating layer formed on the surface and good bending workability, even if the connecting part is not processed during crimping An object is to provide a material and a method for producing the same.
本発明者らは、上記課題を解決するために鋭意研究した結果、銅または銅合金からなる基材の表面にＳｎ含有層が形成されたＳｎめっき材において、Ｓｎ含有層をＣｕ−Ｓｎ合金層とこのＣｕ−Ｓｎ合金層の表面に形成された厚さ５μｍ以下のＳｎからなるＳｎ層とから構成し、Ｓｎ含有層の表面にＮｉめっき層を形成し、このＮｉめっき層の表面に最表層としてビッカース硬さＨＶが８０以下のＺｎめっき層を形成することにより、表面にＺｎめっき層が形成されたＳｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、圧着加工の際に接続部分の加工を施さなくても、耐食性が良好であり且つ表面に形成したＺｎめっき層の密着性が良好であるとともに、曲げ加工性が良好なＳｎめっき材を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have determined that a Sn-containing layer is a Cu-Sn alloy layer in a Sn-plated material in which a Sn-containing layer is formed on the surface of a base material made of copper or a copper alloy. And a Sn layer made of Sn having a thickness of 5 μm or less formed on the surface of the Cu—Sn alloy layer, a Ni plating layer is formed on the surface of the Sn-containing layer, and the outermost layer is formed on the surface of the Ni plating layer By forming a Zn plating layer having a Vickers hardness HV of 80 or less, a Sn plating material having a Zn plating layer formed on the surface thereof is connected to an electric wire made of aluminum or an aluminum alloy by crimping such as crimping. When used as a material, the corrosion resistance is good and the adhesion of the Zn plating layer formed on the surface is good even if the connection part is not processed during the crimping process. , It found that it is possible to bend formability to produce a good Sn-plated material, thereby completing the present invention.
すなわち、本発明によるＳｎめっき材は、銅または銅合金からなる基材の表面にＳｎ含有層が形成されたＳｎめっき材において、Ｓｎ含有層がＣｕ−Ｓｎ合金層とこのＣｕ−Ｓｎ合金層の表面に形成された厚さ５μｍ以下のＳｎからなるＳｎ層とから構成され、Ｓｎ含有層の表面にＮｉめっき層が形成され、このＮｉめっき層の表面に最表層としてビッカース硬さＨＶが８０以下のＺｎめっき層が形成されていることを特徴とする。 That is, the Sn-plated material according to the present invention is an Sn-plated material in which a Sn-containing layer is formed on the surface of a substrate made of copper or a copper alloy, and the Sn-containing layer is composed of a Cu-Sn alloy layer and this Cu-Sn alloy layer. It is composed of a Sn layer made of Sn having a thickness of 5 μm or less formed on the surface, a Ni plating layer is formed on the surface of the Sn-containing layer, and a Vickers hardness HV is 80 or less as the outermost layer on the surface of this Ni plating layer A Zn plating layer is formed.
このＳｎめっき材において、Ｚｎめっき層の表面の算術平均粗さＲａが０．１〜３．０μｍであるのが好ましく、光沢度が１．２以下であるのが好ましい。また、Ｃｕ−Ｓｎ合金層の厚さが０．２〜２μｍであるのが好ましい。また、Ｎｉめっき層の厚さが０．０１〜５μｍであるのが好ましく、Ｚｎめっき層の厚さが１〜４０μｍであるのが好ましい。また、基材とＳｎ含有層との間に下地層を形成してもよい。この場合、下地層がＣｕおよびＮｉの少なくとも一方を含む層であるのが好ましい。また、基材の一方の表面のＳｎ含有層の表面のみにＮｉめっき層を介して最表層としてＺｎめっき層を形成し、基材の他方の面のＳｎ含有層を最表層として形成するのが好ましい。また、Ｎｉめっき層をＳｎ含有層の表面の一部に形成してもよい。 In this Sn plating material, the arithmetic average roughness Ra of the surface of the Zn plating layer is preferably 0.1 to 3.0 μm, and the glossiness is preferably 1.2 or less. Moreover, it is preferable that the thickness of a Cu-Sn alloy layer is 0.2-2 micrometers. Moreover, it is preferable that the thickness of Ni plating layer is 0.01-5 micrometers, and it is preferable that the thickness of Zn plating layer is 1-40 micrometers. Moreover, you may form a base layer between a base material and a Sn content layer. In this case, the underlayer is preferably a layer containing at least one of Cu and Ni. Further, the Zn plating layer is formed as the outermost layer only on the surface of the Sn-containing layer on one surface of the base material via the Ni plating layer, and the Sn-containing layer on the other surface of the base material is formed as the outermost layer. preferable. Moreover, you may form Ni plating layer in a part of surface of Sn content layer.
また、本発明によるＳｎめっき材の製造方法は、銅または銅合金からなる基材の表面にＳｎめっき層を形成した後、熱処理により、Ｃｕ−Ｓｎ合金層とこのＣｕ−Ｓｎ合金層の表面に形成されたＳｎからなるＳｎ層とから構成されたＳｎ含有層を形成してＳｎめっき材を製造する方法において、Ｓｎ層の厚さを５μｍ以下にし、Ｓｎ含有層の表面にＮｉめっき層を形成した後、硫酸浴中において電気めっきを行うことにより、Ｎｉめっき層の表面に最表層としてＺｎめっき層を形成することを特徴とする。 Moreover, the manufacturing method of the Sn plating material by this invention is, after forming a Sn plating layer on the surface of the base material which consists of copper or a copper alloy, it heat-processes on the surface of a Cu-Sn alloy layer and this Cu-Sn alloy layer. In a method for producing a Sn-plated material by forming a Sn-containing layer composed of a formed Sn layer made of Sn, the thickness of the Sn layer is made 5 μm or less, and a Ni-plated layer is formed on the surface of the Sn-containing layer Then, a Zn plating layer is formed as the outermost layer on the surface of the Ni plating layer by performing electroplating in a sulfuric acid bath.
このＳｎめっき材の製造方法において、熱処理により、Ｓｎ層の厚さを５μｍ以下にするのが好ましく、Ｃｕ−Ｓｎ合金層の厚さを０．２〜２μｍにするのが好ましい。また、Ｎｉめっき層の厚さを０．０１〜５μｍにするのが好ましく、Ｚｎめっき層の厚さを１〜４０μｍにするのが好ましい。また、Ｓｎめっき層を形成する前にＣｕめっき層を形成して、基材とＳｎ含有層との間にＣｕを含む下地層を形成してもよい。あるいは、Ｓｎめっき層を形成する前にＮｉめっき層とＣｕめっき層をこの順で形成して、熱処理により、基材とＳｎ含有層との間にＣｕおよびＮｉの少なくとも一方を含む下地層を形成してもよい。また、Ｎｉめっき層をＳｎ含有層の表面の一部に形成してもよい。 In this method for producing a Sn plating material, the thickness of the Sn layer is preferably 5 μm or less by heat treatment, and the thickness of the Cu—Sn alloy layer is preferably 0.2 to 2 μm. The thickness of the Ni plating layer is preferably 0.01 to 5 μm, and the thickness of the Zn plating layer is preferably 1 to 40 μm. In addition, a Cu plating layer may be formed before forming the Sn plating layer, and an underlayer containing Cu may be formed between the base material and the Sn-containing layer. Alternatively, before forming the Sn plating layer, the Ni plating layer and the Cu plating layer are formed in this order, and a base layer containing at least one of Cu and Ni is formed between the base material and the Sn-containing layer by heat treatment. May be. Moreover, you may form Ni plating layer in a part of surface of Sn content layer.
また、本発明による電線接続用端子は、銅または銅合金からなる基材の表面にＳｎ含有層が形成されたＳｎめっき材を材料として用いた接続端子であって、Ｓｎ含有層がＣｕ−Ｓｎ合金層とこのＣｕ−Ｓｎ合金層の表面に形成された厚さ５μｍ以下のＳｎからなるＳｎ層とから構成され、電線との接続部以外の部分においてＳｎ含有層の表面にＮｉめっき層が形成され、このＮｉめっき層の表面にビッカース硬さＨＶが８０以下のＺｎめっき層が形成されていることを特徴とする。 Moreover, the terminal for electric wire connection by this invention is a connection terminal using Sn plating material by which Sn containing layer was formed in the surface of the base material which consists of copper or a copper alloy, and Sn containing layer is Cu-Sn. It is composed of an alloy layer and a Sn layer made of Sn having a thickness of 5 μm or less formed on the surface of this Cu—Sn alloy layer, and a Ni plating layer is formed on the surface of the Sn-containing layer in a portion other than the connection portion with the electric wire A Zn plating layer having a Vickers hardness HV of 80 or less is formed on the surface of the Ni plating layer.
この電線接続用端子において、Ｚｎめっき層の表面の算術平均粗さＲａが０．１〜３．０μｍであるのが好ましく、光沢度が１．２以下であるのが好ましい。また、Ｃｕ−Ｓｎ合金層の厚さが０．２〜２μｍであるのが好ましい。また、Ｎｉめっき層の厚さが０．０１〜５μｍであるのが好ましく、Ｚｎめっき層の厚さが１〜４０μｍであるのが好ましい。また、基材とＳｎ含有層との間に下地層を形成してもよい。この場合、下地層がＣｕおよびＮｉの少なくとも一方を含む層であるのが好ましい。また、電線は、アルミニウムまたはアルミニウム合金からなるのが好ましく、単芯線または撚線であるのが好ましい。 In this wire connection terminal, the arithmetic average roughness Ra of the surface of the Zn plating layer is preferably 0.1 to 3.0 μm, and the glossiness is preferably 1.2 or less. Moreover, it is preferable that the thickness of a Cu-Sn alloy layer is 0.2-2 micrometers. Moreover, it is preferable that the thickness of Ni plating layer is 0.01-5 micrometers, and it is preferable that the thickness of Zn plating layer is 1-40 micrometers. Moreover, you may form a base layer between a base material and a Sn content layer. In this case, the underlayer is preferably a layer containing at least one of Cu and Ni. The electric wire is preferably made of aluminum or an aluminum alloy, and is preferably a single core wire or a stranded wire.
本発明によれば、表面にＺｎめっき層が形成されたＳｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、圧着加工の際に接続部分の加工を施さなくても、耐食性が良好であり且つ表面に形成したＺｎめっき層の密着性が良好であるとともに、曲げ加工性が良好なＳｎめっき材を製造することができる。 According to the present invention, when a Sn plating material having a Zn plating layer formed on the surface is used as a material for a terminal connected to a wire made of aluminum or an aluminum alloy by crimping or the like, the crimping process is performed. Even if the connection portion is not processed, it is possible to produce an Sn plating material that has good corrosion resistance and good adhesion of the Zn plating layer formed on the surface and good bending workability.
図１に示すように、本発明によるＳｎめっき材の実施の形態では、銅または銅合金からなる（板材や条材などの）基材１０の表面（図示した実施の形態では両面）にＳｎ含有層１２が形成されたＳｎめっき材において、Ｓｎ含有層１２がＣｕ−Ｓｎ合金層１２１とこのＣｕ−Ｓｎ合金層の表面に形成された厚さ５μｍ以下（好ましくは０〜２μｍ、さらに好ましくは０．１〜１．５μｍ）のＳｎからなるＳｎ層１２２とから構成され、Ｓｎ含有層１２の表面（図示した実施の形態では一方の面）にＮｉめっき層１４が形成され、このＮｉめっき層１４の表面に最表層としてビッカース硬さＨＶが８０以下のＺｎめっき層１６が形成されている。なお、Ｚｎめっき層１６は、Ｚｎ（または９０質量％以上のＺｎ含むＺｎ合金）からなり、最表層としてＺｎめっき層１６を形成することにより、Ｓｎめっき材の耐食性を大幅に向上させることができ、Ｓｎ含有層１２とＺｎめっき層１６との間にＮｉめっき層１４を形成することにより、（Ｓｎ含有層１２のＳｎとＺｎめっき層１６のＺｎなどの拡散を防止して、ＳｎやＺｎなどの拡散層の形成やその拡散によるボイドの発生を抑制して）Ｓｎ含有層１２とＺｎめっき層１６との密着性を大幅に向上させることができる。また、Ｚｎめっき層１６を軟らかく（ビッカース硬さＨＶを８０以下、好ましくは７０以下）にすることにより、Ｓｎめっき材の曲げ加工による基材１０の露出を抑制して、電位差の大きい異種金属の接触によるガルバニック腐食（卑な金属が溶解する異種金属接触腐食）を抑制することができ、Ｓｎめっき材の曲げ加工性を向上させることができる。
As shown in FIG. 1, in the embodiment of the Sn plating material according to the present invention, Sn is contained on the surface (both sides in the illustrated embodiment) of a base material 10 (such as a plate material or a strip material) made of copper or a copper alloy. In the Sn plating material in which the
このＳｎめっき材において、Ｚｎめっき層１６の表面の算術平均粗さＲａが０．１〜３．０μｍであるのが好ましい。また、光沢度は、１．２以下であるのが好ましく、０．５以下であるのがさらに好ましく、０．１〜０．２であるのが最も好ましい。
In this Sn plating material, the arithmetic average roughness Ra of the surface of the
また、Ｃｕ−Ｓｎ合金層１２１の厚さは、０．２〜２μｍであるのが好ましく、０．３〜１．５μｍであるのがさらに好ましい。Ｎｉめっき層１４の厚さは、０．０１〜５μｍであるのが好ましく、０．０２〜４μｍであるのがさらに好ましいが、２μｍ以下にしてもよい。Ｚｎめっき層１６の厚さは、１〜４０μｍであるのが好ましく、１〜３０μｍであるのがさらに好ましく、２〜１５μｍであるのがさらに好ましいが、１０μｍ以下にしてもよく、５μｍ以下にしてもよい。Ｚｎめっき層１６の厚さが厚過ぎると、Ｚｎめっき層１６を形成する際のめっき時間が長くなり過ぎて生産性が低下し、薄過ぎると、十分な耐食性を得ることができない。
In addition, the thickness of the Cu—
また、図２に示すように、基材１０とＳｎ含有層１２との間に下地層１８を形成してもよい。この場合、下地層がＣｕおよびＮｉの少なくとも一方を含む層（Ｎｉ層１８１とＣｕ層１８２の少なくとも一方の層）であるのが好ましい。Ｎｉ層１８１の厚さは、０．０５〜１．０μｍであるのが好ましく、Ｃｕ層１８２の厚さは、１．５μｍ以下であるのが好ましく、１．０μｍ以下であるのがさらに好ましい。なお、下地層としてＮｉ層１８１とＣｕ層１８２の両方の層を形成する場合には、基板１０の表面にＮｉ層１８１を形成し、その表面にＣｕ層１８２を形成するのが好ましい。
In addition, as shown in FIG. 2, a
なお、Ｚｎめっき層は、Ｓｎ含有層の表面の一部のみに形成してもよい。この場合、Ｚｎめっき層が形成されていないＳｎ含有層の表面の他の部分では、Ｓｎ含有層が最表層になり、この最表層のＳｎ含有層のＳｎ層の厚さは、５μｍ以下であるのが好ましく、０〜２μｍであるのが好ましく、０．１〜１．５μｍであるのが最も好ましい。また、この最表層のＳｎ含有層のＣｕ−Ｓｎ合金層の厚さは、０．２〜２μｍであるのが好ましく、０．３〜１．５μｍであるのがさらに好ましい。 Note that the Zn plating layer may be formed only on a part of the surface of the Sn-containing layer. In this case, in the other part of the surface of the Sn-containing layer where the Zn plating layer is not formed, the Sn-containing layer becomes the outermost layer, and the thickness of the Sn layer of the outermost Sn-containing layer is 5 μm or less. Is preferably 0 to 2 μm, and most preferably 0.1 to 1.5 μm. The thickness of the Cu-Sn alloy layer of the outermost Sn-containing layer is preferably 0.2 to 2 [mu] m, and more preferably 0.3 to 1.5 [mu] m.
上述したＳｎめっき材の実施の形態は、本発明によるＳｎめっき材の製造方法の実施の形態により製造することができる。 The embodiment of the Sn plating material described above can be manufactured by the embodiment of the method of manufacturing the Sn plating material according to the present invention.
本発明によるＳｎめっき材の製造方法の実施の形態では、銅または銅合金からなる基材の表面に（電気めっきなどにより、好ましくは厚さ０．１〜２μｍ、さらに好ましくは厚さ０．２〜１．５μｍの）Ｓｎめっき層を形成した後、（赤外線ヒーター、熱風循環、直火式などの熱処理装置により）熱処理（リフロー処理）により、Ｃｕ−Ｓｎ合金層とこのＣｕ−Ｓｎ合金層の表面に形成されたＳｎからなるＳｎ層とから構成されたＳｎ含有層を形成してＳｎめっき材を製造する方法において、Ｓｎ層の厚さを５μｍ以下（好ましくは０〜２μｍ、さらに好ましくは０．１〜１．５μｍ）にし、このＳｎ含有層の表面に（電気めっきなどにより）Ｎｉめっき層を形成した後、硫酸浴中において電気めっきを行うことにより、Ｎｉめっき層の表面に最表層としてＺｎめっき層を形成する。 In the embodiment of the method for producing a Sn-plated material according to the present invention, the surface of a base material made of copper or a copper alloy (by electroplating or the like, preferably 0.1 to 2 μm in thickness, more preferably 0.2 mm in thickness). After forming the Sn plating layer (˜1.5 μm), the Cu—Sn alloy layer and the Cu—Sn alloy layer were subjected to heat treatment (reflow treatment) (using a heat treatment device such as an infrared heater, hot air circulation, and direct flame type). In a method for producing a Sn-plated material by forming a Sn-containing layer composed of a Sn layer made of Sn formed on the surface, the thickness of the Sn layer is 5 μm or less (preferably 0 to 2 μm, more preferably 0 1 to 1.5 μm), and after forming a Ni plating layer (by electroplating or the like) on the surface of this Sn-containing layer, electroplating in a sulfuric acid bath is performed on the surface of the Ni plating layer. A Zn plating layer is formed as a surface layer.
このＳｎめっき材の製造方法において、熱処理により、Ｓｎ層の厚さを５μｍ以下（好ましくは０〜２μｍ、さらに好ましくは０．１〜１．５μｍ）にするとともに、Ｃｕ−Ｓｎ合金層の厚さを好ましくは０．２〜２μｍ（さらに好ましくは０．３〜１．５μｍ）にする。Ｎｉめっき層の厚さは、０．０１〜５μｍにするのが好ましく、０．０２〜４μｍにするのがさらに好ましいが、２μｍ以下にしてもよい。Ｚｎめっき層の厚さは、１〜４０μｍにするのが好ましく、１〜３０μｍにするのがさらに好ましく、２〜１５μｍであるのがさらに好ましいが、１０μｍ以下にしてもよく、５μｍ以下にしてもよい。また、Ｓｎめっき層を形成する前に（好ましくは厚さ０．１〜１．５μｍの）Ｃｕめっき層を形成して、基材とＳｎ含有層との間にＣｕを含む下地層を形成してもよい。あるいは、Ｓｎめっき層を形成する前に（好ましくは厚さ０．０５〜１．０μｍの）Ｎｉめっき層と（好ましくは厚さ０．１〜１．５μｍの）Ｃｕめっき層をこの順で形成して、基材とＳｎ含有層との間にＣｕおよびＮｉを含む下地層を形成してもよい。Ｃｕ−Ｓｎ合金層とＳｎ層の厚さは、電解式膜厚計などにより測定することができる。 In this method for producing a Sn plating material, the thickness of the Sn layer is reduced to 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm) by heat treatment, and the thickness of the Cu—Sn alloy layer. Is preferably 0.2 to 2 μm (more preferably 0.3 to 1.5 μm). The thickness of the Ni plating layer is preferably 0.01 to 5 μm, more preferably 0.02 to 4 μm, but may be 2 μm or less. The thickness of the Zn plating layer is preferably 1 to 40 μm, more preferably 1 to 30 μm, even more preferably 2 to 15 μm, but may be 10 μm or less, or 5 μm or less. Good. Further, before forming the Sn plating layer, a Cu plating layer (preferably having a thickness of 0.1 to 1.5 μm) is formed, and a base layer containing Cu is formed between the base material and the Sn-containing layer. May be. Alternatively, before forming the Sn plating layer, a Ni plating layer (preferably 0.05 to 1.0 μm thick) and a Cu plating layer (preferably 0.1 to 1.5 μm thick) are formed in this order. Then, an underlayer containing Cu and Ni may be formed between the base material and the Sn-containing layer. The thicknesses of the Cu—Sn alloy layer and the Sn layer can be measured with an electrolytic film thickness meter or the like.
なお、Ｎｉめっき層とＺｎめっき層は、（マスキングやめっき液面の高さの制御などにより）基材の一方の表面のＳｎ含有層の表面のみ（またはＳｎ含有層の表面の一部のみ）に形成してもよい。この場合、Ｚｎめっき層が形成されていないＳｎ含有層の表面の他の部分では、Ｓｎ含有層が最表層になり、この最表層のＳｎ含有層のＳｎ層の厚さは、５μｍ以下であるのが好ましく、０〜２μｍであるのが好ましい。 In addition, the Ni plating layer and the Zn plating layer are only the surface of the Sn-containing layer on one surface of the substrate (by masking or controlling the height of the plating solution surface) (or only a part of the surface of the Sn-containing layer). You may form in. In this case, in the other part of the surface of the Sn-containing layer where the Zn plating layer is not formed, the Sn-containing layer becomes the outermost layer, and the thickness of the Sn layer of the outermost Sn-containing layer is 5 μm or less. Is preferable, and it is preferable that it is 0-2 micrometers.
Ｚｎめっき層を形成するためのＺｎめっき浴として使用する硫酸浴は、硫酸亜鉛と硫酸アンモニウムを含む水溶液からなる硫酸浴であるのが好ましく、光沢剤などの添加剤を含まないのが好ましい。添加剤を含まないことにより、Ｚｎめっき浴のコストを低減することができる。また、Ｚｎめっき層を形成する際の電気めっきの電流密度は、１５〜６０Ａ／ｄｍ２の高電流密度であるのが好ましい。高電流密度にすることにより、生産性を向上させることができる。 The sulfuric acid bath used as the Zn plating bath for forming the Zn plating layer is preferably a sulfuric acid bath composed of an aqueous solution containing zinc sulfate and ammonium sulfate, and preferably does not contain additives such as brighteners. By not containing the additive, the cost of the Zn plating bath can be reduced. Moreover, it is preferable that the current density of electroplating when forming the Zn plating layer is a high current density of 15 to 60 A / dm 2 . Productivity can be improved by using a high current density.
上述したＳｎめっき材の実施の形態は、アルミニウムまたはアルミニウム合金からなる電線に接続される端子などの通電部材の材料として使用することができる。また、Ｎｉめっき層とＺｎめっき層をＳｎ含有層の表面の一部のみに形成する場合には、Ｚｎめっき層が形成されていないＳｎ含有層の表面の他の部分（Ｓｎ含有層が最表層になる部分）でアルミニウムまたはアルミニウム合金からなる電線に接続するのが好ましい。 The above-described embodiment of the Sn plating material can be used as a material for a current-carrying member such as a terminal connected to an electric wire made of aluminum or an aluminum alloy. Further, when the Ni plating layer and the Zn plating layer are formed only on a part of the surface of the Sn-containing layer, the other part of the surface of the Sn-containing layer where the Zn plating layer is not formed (the Sn-containing layer is the outermost layer) It is preferable to connect to an electric wire made of aluminum or an aluminum alloy.
以下、本発明によるＳｎめっき材およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the Sn plating material and the manufacturing method thereof according to the present invention will be described in detail.
［実施例１］
まず、５０ｍｍ×５０ｍｍ×０．２５ｍｍの大きさのＣｕ−Ｎｉ−Ｓｎ−Ｐ合金からなる平板状の導体基材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の基材）（ＤＯＷＡメタルテック株式会社製のＮＢ−１０９ＥＨ）を用意した。
[Example 1]
First, a flat conductor base material made of a Cu—Ni—Sn—P alloy having a size of 50 mm × 50 mm × 0.25 mm (1.0 mass% Ni, 0.9 mass% Sn and 0.05 mass) A copper alloy base material (NB-109EH manufactured by DOWA Metaltech Co., Ltd.) containing% P and the balance being Cu was prepared.
次に、前処理として、基材（被めっき材）をアルカリ電解脱脂液により１０秒間電解脱脂を行った後に水洗し、その後、１００ｇ／Ｌの硫酸に浸漬して酸洗した後に水洗した。 Next, as a pretreatment, the substrate (material to be plated) was electrolytically degreased with an alkaline electrolytic degreasing solution for 10 seconds, then washed with water, then immersed in 100 g / L sulfuric acid, pickled, and then washed with water.
次に、６０ｇ／Ｌの硫酸第一錫と７５ｇ／Ｌの硫酸と３０ｇ／Ｌのクレゾールスルホン酸と１ｇ／Ｌのβナフトールを含むＳｎめっき液中において、基材を陰極とし、Ｓｎ電極板を陽極として、電流密度５Ａ／ｄｍ２、液温２５℃で２０秒間電気めっきを行うことにより、基材の表面に厚さ１μｍのＳｎめっき層を形成してＳｎめっき材を得た。 Next, in a Sn plating solution containing 60 g / L stannous sulfate, 75 g / L sulfuric acid, 30 g / L cresol sulfonic acid, and 1 g / L β-naphthol, the substrate is used as the cathode, and the Sn electrode plate is As an anode, electroplating was performed at a current density of 5 A / dm 2 and a liquid temperature of 25 ° C. for 20 seconds to form a Sn plating layer having a thickness of 1 μm on the surface of the base material, thereby obtaining a Sn plating material.
次に、得られたＳｎめっき材を洗浄して乾燥した後、熱処理（リフロー処理）を行った。このリフロー処理では、２つの近赤外線ヒーター（株式会社ハイベック製のＨＹＰ−８Ｎ、定格電圧１００Ｖ、定格電力５６０Ｗ、平行照射タイプ）を２５ｍｍ離間して対向するように配置し、これらの近赤外線ヒーターの中央部にＳｎめっき材を配置して、設定電流値を１０．８Ａとして、大気雰囲気においてＳｎめっき材を１３秒間加熱してＳｎめっき層の表面を溶融させた直後に２５℃の水槽内に浸漬して冷却した。 Next, after the obtained Sn plating material was washed and dried, heat treatment (reflow treatment) was performed. In this reflow process, two near-infrared heaters (HYP-8N, manufactured by Hibeck Co., Ltd., rated voltage 100V, rated power 560W, parallel irradiation type) are arranged so as to face each other with a distance of 25 mm. Immediately after the Sn plating material is arranged at the center, the set current value is 10.8 A, the Sn plating material is heated in the air atmosphere for 13 seconds to melt the surface of the Sn plating layer, and then immersed in a 25 ° C. water bath. And cooled.
このリフロー処理後のＳｎめっき材を集束イオンビーム（ＦＩＢ）により切断して、Ｓｎめっき材の圧延方向に垂直な断面を露出させ、その断面を電界放射型オージェ電子分光分析装置（ＦＥ−ＡＥＳ）により分析した。その結果、Ｓｎめっき材の基材の表面にＣｕ−Ｓｎ合金からなるＣｕ−Ｓｎ合金層が形成され、このＣｕ−Ｓｎ合金層の表面にＳｎからなるＳｎ層が形成されていることが確認された。また、Ｃｕ−Ｓｎ合金層とＳｎ層の厚さを電解式膜厚計（株式会社中央製作所製のＴｈｉｃｋｎｅｓｓ Ｔｅｓｔｅｒ ＴＨ−１１）により測定したところ、Ｃｕ−Ｓｎ合金層の厚さは０．６μｍであり、Ｓｎ層の厚さは０．７μｍであった。 The Sn plating material after this reflow treatment is cut by a focused ion beam (FIB) to expose a cross section perpendicular to the rolling direction of the Sn plating material, and the cross section is exposed to a field emission Auger electron spectrometer (FE-AES). Was analyzed. As a result, it was confirmed that a Cu—Sn alloy layer made of a Cu—Sn alloy was formed on the surface of the Sn plating material substrate, and an Sn layer made of Sn was formed on the surface of this Cu—Sn alloy layer. It was. Moreover, when the thickness of a Cu-Sn alloy layer and Sn layer was measured with the electrolytic film thickness meter (Thickness Tester TH-11 by Chuo Seisakusho Co., Ltd.), the thickness of a Cu-Sn alloy layer was 0.6 micrometer. The thickness of the Sn layer was 0.7 μm.
次に、リフロー処理後のＳｎめっき材の一方の面の全面にテープを貼り付けてマスキングした後、そのＳｎめっき材を４０ｇ／Ｌの水酸化ナトリウム水溶液に浸漬して１０Ａ／ｄｍ２で３０秒間電解脱脂し、１００ｇ／Ｌの硫酸に１２０秒間浸漬して酸洗した後に水洗した。 Next, a tape is attached to the entire surface of one surface of the Sn-plated material after the reflow treatment and masked, and then the Sn-plated material is immersed in a 40 g / L sodium hydroxide aqueous solution at 10 A / dm 2 for 30 seconds. It was electrolytically degreased, dipped in 100 g / L sulfuric acid for 120 seconds, pickled, and then washed with water.
次に、８０ｇ／Ｌのスルファミン酸ニッケルと５０ｇ／Ｌのホウ酸を含むＮｉめっき浴（スルファミン酸浴）中において、（一方の面の全面にテープを貼り付けてマスキングした）Ｓｎめっき材を陰極とし、Ｎｉ電極板を陽極として、電流密度１０Ａ／ｄｍ２、液温５０℃で６秒間電気めっきを行うことにより、Ｓｎめっき材の他方の面にＮｉめっき層を形成した。このＮｉめっき層の厚さを蛍光Ｘ線膜厚計（セイコーインスツル株式会社製）により測定したところ、０．２μｍであった。 Next, in a Ni plating bath (sulfamic acid bath) containing 80 g / L nickel sulfamate and 50 g / L boric acid, a Sn plating material (masked with a tape attached to the entire surface of one surface) was used as a cathode. Then, using the Ni electrode plate as the anode, electroplating was performed at a current density of 10 A / dm 2 and a liquid temperature of 50 ° C. for 6 seconds to form a Ni plating layer on the other surface of the Sn plating material. It was 0.2 micrometer when the thickness of this Ni plating layer was measured with the fluorescent X ray film thickness meter (made by Seiko Instruments Inc.).
次に、２００ｇ／Ｌの硫酸亜鉛と３０ｇ／Ｌの硫酸アンモニウムを含む水溶液からなるＺｎめっき浴（硫酸浴）中において、（一方の面の全面にテープを貼り付けてマスキングした）Ｎｉめっき後のＳｎめっき材を陰極とし、Ｚｎ電極板を陽極として、電流密度２０Ａ／ｄｍ２、液温５０℃で３０秒間電気めっきを行うことにより、Ｓｎめっき材の他方の面に形成したＮｉめっき層の表面にＺｎめっき層を形成した。このＺｎめっき層の厚さを蛍光Ｘ線膜厚計（セイコーインスツル株式会社製）により測定したところ、３μｍであった。 Next, in a Zn plating bath (sulfuric acid bath) composed of an aqueous solution containing 200 g / L of zinc sulfate and 30 g / L of ammonium sulfate (tape is applied to the entire surface of one side and masked), Sn after Ni plating On the surface of the Ni plating layer formed on the other surface of the Sn plating material by performing electroplating at a current density of 20 A / dm 2 and a liquid temperature of 50 ° C. for 30 seconds with the plating material as the cathode and the Zn electrode plate as the anode. A Zn plating layer was formed. The thickness of the Zn plating layer was measured by a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.) and found to be 3 μm.
このようにしてＺｎめっき層を形成したＳｎめっき材を集束イオンビーム（ＦＩＢ）加工観察装置により切断して、Ｓｎめっき材の圧延方向に垂直な断面を露出させ、その断面を電界放射型オージェ電子分光分析装置（ＦＥ−ＡＥＳ）により分析した。その結果、Ｓｎめっき材の基材の表面にＣｕ−Ｓｎ合金からなるＣｕ−Ｓｎ合金層が形成され、このＣｕ−Ｓｎ合金層の表面にＳｎからなるＳｎ層が形成され、このＳｎ層の表面にＮｉめっき層が形成され、このＮｉめっき層の表面にＺｎめっき層が形成されていることが確認された。また、これらの層の厚さを走査イオン顕微鏡像（ＳＩＭ像）から測定したところ、Ｃｕ−Ｓｎ合金層の厚さは０．６μｍ、Ｓｎ層の厚さは０．７μｍ、Ｎｉめっき層の厚さは０．２μｍ、Ｚｎめっき層の厚さは３μｍであることが確認された。 The Sn plating material on which the Zn plating layer is formed in this manner is cut by a focused ion beam (FIB) processing observation device to expose a cross section perpendicular to the rolling direction of the Sn plating material, and the cross section is exposed to field emission Auger electrons. The analysis was performed using a spectroscopic analyzer (FE-AES). As a result, a Cu—Sn alloy layer made of Cu—Sn alloy is formed on the surface of the Sn plating material substrate, and an Sn layer made of Sn is formed on the surface of this Cu—Sn alloy layer. It was confirmed that a Ni plating layer was formed on the surface of the Ni plating layer, and a Zn plating layer was formed on the surface of the Ni plating layer. Moreover, when the thickness of these layers was measured from the scanning ion microscope image (SIM image), the thickness of the Cu—Sn alloy layer was 0.6 μm, the thickness of the Sn layer was 0.7 μm, and the thickness of the Ni plating layer. The thickness was confirmed to be 0.2 μm, and the thickness of the Zn plating layer was 3 μm.
また、Ｚｎめっき層を形成したＳｎめっき材から切り出した３０ｍｍ×１０ｍｍ×０．２５ｍｍの大きさの試験片に１０ｋＮの負荷を加えて、最小曲げ半径Ｒと板厚ｔの比Ｒ／ｔが１．０になるようにＪＩＳ Ｈ３１１０に準拠した９０°Ｗ曲げを行って、その試験片を樹脂に埋めた後、試験片の長手方向に平行な方向（９０°Ｗ曲げの曲げ軸に対して垂直方向）に切断して、その断面をレーザー顕微鏡（株式会社キーエンス製のＶＫ−Ｘ１００）で拡大して、金型で擦れた直線部と、谷折りの曲げ加工部と、山折りの曲げ加工部を観察し、Ｚｎめっき層の剥離の有無を目視によって評価した。その結果、いずれの部分でもＺｎめっき層の剥離はなく、密着性が良好であった。 Further, a load of 10 kN was applied to a test piece having a size of 30 mm × 10 mm × 0.25 mm cut out from the Sn plating material on which the Zn plating layer was formed, and the ratio R / t of the minimum bending radius R to the plate thickness t was 1. After performing 90 ° W bending according to JIS H3110 to be 0.0 and filling the test piece with resin, the direction parallel to the longitudinal direction of the test piece (perpendicular to the bending axis of 90 ° W bending) Direction) and a cross section thereof is enlarged with a laser microscope (VK-X100 manufactured by Keyence Corporation), and a linear portion rubbed with a mold, a valley fold bent portion, and a mountain fold bent portion And the presence or absence of peeling of the Zn plating layer was visually evaluated. As a result, there was no peeling of the Zn plating layer in any part, and the adhesion was good.
また、Ｚｎめっき層を形成したＳｎめっき材から切り出した５０ｍｍ×１０ｍｍ×０．２５ｍｍの大きさの試験片のＺｎめっき層を外側にして、このＳｎめっき材により直径０．８ｍｍ、長さ３０ｍｍの純アルミニウム単線（Ａ１０７０）を加締めた後、５質量％のＮａＣｌ水溶液中に浸漬し、ガルバニック腐食（卑な金属が溶解する異種金属接触腐食）によるガスの発生時間によって耐食性を評価した。その結果、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。 In addition, a test piece having a size of 50 mm × 10 mm × 0.25 mm cut out from the Sn plating material on which the Zn plating layer was formed was placed outside, and the Sn plating material had a diameter of 0.8 mm and a length of 30 mm. After caulking a pure aluminum single wire (A1070), it was immersed in a 5 mass% NaCl aqueous solution, and the corrosion resistance was evaluated by the gas generation time due to galvanic corrosion (dissimilar metal contact corrosion in which a base metal dissolves). As a result, the time until gas was generated was as long as 192 hours or more, and the corrosion resistance was good.
また、Ｚｎめっき層を形成したＳｎめっき材の表面のビッカース硬さＨＶを、マイクロビッカース硬度計（株式会社ミツトヨ製のＨＭ−２００）を使用して、測定荷重を０．００５ｋｇｆとして、ＪＩＳ Ｚ２２４４に準じて測定したところ、ＨＶ５５であった。 In addition, the Vickers hardness HV of the surface of the Sn plating material on which the Zn plating layer was formed was set to JIS Z2244 using a micro Vickers hardness meter (HM-200 manufactured by Mitutoyo Corporation) with a measurement load of 0.005 kgf. According to a similar measurement, it was HV55.
また、Ｚｎめっき層を形成したＳｎめっき材の表面粗さとして、接触式表面粗さ計（株式会社小坂研究所製のサーフコーダＳＥ４０００）により測定した結果から、ＪＩＳ Ｂ０６０１に基づいて表面粗さを示すパラメータである算術平均粗さＲａを算出したところ、Ｚｎめっき層を形成したＳｎめっき材の算術平均粗さＲａは０．１４μｍであった。 Further, as the surface roughness of the Sn plating material on which the Zn plating layer was formed, the surface roughness was measured based on JIS B0601 from the result of measurement with a contact surface roughness meter (Surfcoder SE4000 manufactured by Kosaka Laboratory Ltd.). When the arithmetic average roughness Ra which is a parameter to be calculated was calculated, the arithmetic average roughness Ra of the Sn plating material on which the Zn plating layer was formed was 0.14 μm.
また、Ｚｎめっき層を形成したＳｎめっき材の光沢度として、光沢度計（サカタインクス株式会社製のＲＤ９１８）を使用して視感反射濃度を測定したところ、光沢度は０．１５であった。 Moreover, when the luminous reflection density was measured using a gloss meter (RD918 manufactured by Sakata Inx Co., Ltd.) as the gloss level of the Sn plating material on which the Zn plating layer was formed, the gloss level was 0.15.
また、Ｚｎめっき層を形成したＳｎめっき材から切り出した３０ｍｍ×１０ｍｍ×０．２５ｍｍの大きさの試験片に１０ｋＮの負荷を加えて、最小曲げ半径Ｒと板厚ｔの比Ｒ／ｔが１．０になるようにＪＩＳ Ｈ３１１０に準拠した９０°Ｗ曲げを行って、山折りの曲げ加工部の表面をレーザー顕微鏡（株式会社キーエンス製のＶＫ−Ｘ１００）で拡大して観察した。その顕微鏡写真を図３に示す。図３に示すように、山折りの曲げ加工部の表面に深いしわの発生がないことが確認された。また、レーザー顕微鏡（株式会社キーエンス製のＶＫ−Ｘ１００）（カットオフ値０．０８ｍｍ）を使用して、山折りの曲げ加工部の表面の算術平均粗さＲａを算出したところ、０．７μｍであった。なお、この山折りの曲げ加工部の表面の算術平均粗さＲａは、１．７μｍ以下であるのが好ましく、１．５μｍ以下であるのが好ましい。 Further, a load of 10 kN was applied to a test piece having a size of 30 mm × 10 mm × 0.25 mm cut out from the Sn plating material on which the Zn plating layer was formed, and the ratio R / t of the minimum bending radius R to the plate thickness t was 1. The surface of the bent portion of the mountain fold was magnified and observed with a laser microscope (VK-X100, manufactured by Keyence Corporation). The micrograph is shown in FIG. As shown in FIG. 3, it was confirmed that there was no generation of deep wrinkles on the surface of the bent portion of the mountain fold. Moreover, when the arithmetic mean roughness Ra of the surface of the bending process part of a mountain fold was calculated using the laser microscope (VK-X100 by Keyence Corporation) (cut-off value 0.08mm), it was 0.7 micrometer. there were. The arithmetic average roughness Ra of the surface of the bent portion of the mountain fold is preferably 1.7 μm or less, and preferably 1.5 μm or less.
［実施例２］
電気めっき時間を４２０秒間としてとしてＺｎめっき層の厚さを４０μｍとした以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。
[Example 2]
An Sn plating material having a Zn plating layer formed thereon was produced in the same manner as in Example 1 except that the electroplating time was 420 seconds and the thickness of the Zn plating layer was 40 μm.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは５１、算術平均粗さＲａは１．２μｍ、光沢度は０．１２、山折りの曲げ加工部の表面の算術平均粗さＲａは１．２μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, the Vickers hardness HV, arithmetic average roughness Ra, glossiness, and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were determined, and the Vickers hardness HV was 51. The thickness Ra was 1.2 μm, the glossiness was 0.12, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 1.2 μm.
［実施例３］
電気めっき時間を１０秒間としてＺｎめっき層の厚さを１μｍとした以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。
[Example 3]
An Sn plating material having a Zn plating layer formed thereon was produced in the same manner as in Example 1 except that the electroplating time was 10 seconds and the thickness of the Zn plating layer was 1 μm.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１４４時間と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａ求めたところ、ビッカース硬さＨＶは６２．５、算術平均粗さＲａは０．１１μｍ、光沢度は０．１７、山折りの曲げ加工部の表面の算術平均粗さＲａは１．０μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 144 hours, and the corrosion resistance was good. Further, when the Vickers hardness HV, arithmetic average roughness Ra, glossiness, and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were obtained, the Vickers hardness HV was 62.5, the arithmetic average. The roughness Ra was 0.11 μm, the glossiness was 0.17, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 1.0 μm.
［実施例４］
電気めっき時間を９０秒間としてＳｎめっき材に厚さ３μｍのＮｉめっき層を形成した以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。
[Example 4]
An Sn plating material having a Zn plating layer formed thereon was produced in the same manner as in Example 1 except that the Ni plating layer having a thickness of 3 μm was formed on the Sn plating material with an electroplating time of 90 seconds.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは５５、算術平均粗さＲａは０．１４μｍ、光沢度は０．１５、山折りの曲げ加工部の表面の算術平均粗さＲａは０．７μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, when Vickers hardness HV, arithmetic average roughness Ra, glossiness and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were determined, the Vickers hardness HV was 55 and the arithmetic average roughness The thickness Ra was 0.14 μm, the glossiness was 0.15, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 0.7 μm.
［実施例５］
電気めっき時間を３秒間としてＳｎめっき材に厚さ０．１μｍのＮｉめっき層を形成した以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。
[Example 5]
An Sn plating material having a Zn plating layer formed thereon was produced in the same manner as in Example 1 except that a 0.1 μm thick Ni plating layer was formed on the Sn plating material with an electroplating time of 3 seconds.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは５５、算術平均粗さＲａは０．１４μｍ、光沢度は０．１５、山折りの曲げ加工部の表面の算術平均粗さＲａは０．７μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, when Vickers hardness HV, arithmetic average roughness Ra, glossiness and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were determined, the Vickers hardness HV was 55 and the arithmetic average roughness The thickness Ra was 0.14 μm, the glossiness was 0.15, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 0.7 μm.
［実施例６］
５０ｍｍ×５０ｍｍ×０．２５ｍｍの大きさのＣｕ−Ｚｎ合金からなる平板状の導体基材（３０質量％のＺｎを含み、残部がＣｕである銅合金Ｃ２６００の基材）を使用し、前処理の後、Ｓｎめっき層を形成する前に、基材上に厚さ０．６μｍのＣｕめっき層を形成した以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。なお、上記のＣｕめっき層は、１１０ｇ／Ｌの硫酸銅と１００ｇ／Ｌの硫酸を含むＣｕめっき液中において、基材を陰極とし、Ｃｕ電極板を陽極として、電流密度５Ａ／ｄｍ２、液温３０℃で４０秒間電気めっきを行うことにより形成した。
[Example 6]
Pre-treatment using a flat conductor base material (a copper alloy C2600 base material containing 30% by mass of Zn and the balance being Cu) made of a Cu—Zn alloy having a size of 50 mm × 50 mm × 0.25 mm After that, before forming the Sn plating layer, the Sn plating material on which the Zn plating layer was formed by the same method as in Example 1 except that the Cu plating layer having a thickness of 0.6 μm was formed on the substrate. Produced. In addition, said Cu plating layer has a current density of 5 A / dm 2 , a liquid in a Cu plating solution containing 110 g / L of copper sulfate and 100 g / L of sulfuric acid, with the base material as the cathode and the Cu electrode plate as the anode. It was formed by performing electroplating at a temperature of 30 ° C. for 40 seconds.
このリフロー処理後のＳｎめっき材を実施例１と同様の方法により分析したところ、Ｓｎめっき材の基材の表面にＣｕ層と（Ｃｕ−Ｓｎ合金からなる）Ｃｕ−Ｓｎ合金層が形成され、このＣｕ−Ｓｎ合金層の表面にＳｎからなるＳｎ層が形成されていることが確認された。また、Ｃｕ−Ｓｎ合金層とＳｎ層の厚さを実施例１と同様の方法により測定したところ、Ｃｕ−Ｓｎ合金層の厚さは０．６μｍであり、Ｓｎ層の厚さは０．７μｍであった。また、Ｃｕ層の厚さを電解式膜厚計（株式会社中央製作所製のＴｈｉｃｋｎｅｓｓ Ｔｅｓｔｅｒ ＴＨ−１１）により測定したところ、０μｍであった。 When the Sn plating material after this reflow treatment was analyzed by the same method as in Example 1, a Cu layer and a Cu—Sn alloy layer (made of a Cu—Sn alloy) were formed on the surface of the base material of the Sn plating material, It was confirmed that an Sn layer made of Sn was formed on the surface of the Cu—Sn alloy layer. Further, when the thicknesses of the Cu—Sn alloy layer and the Sn layer were measured by the same method as in Example 1, the thickness of the Cu—Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.7 μm. Met. Moreover, it was 0 micrometer when the thickness of Cu layer was measured with the electrolytic film thickness meter (Thickness Tester TH-11 by Chuo Seisakusho Co., Ltd.).
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは５５、算術平均粗さＲａは０．１４μｍ、光沢度は０．１５、山折りの曲げ加工部の表面の算術平均粗さＲａは０．７μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, when Vickers hardness HV, arithmetic average roughness Ra, glossiness and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were determined, the Vickers hardness HV was 55 and the arithmetic average roughness The thickness Ra was 0.14 μm, the glossiness was 0.15, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 0.7 μm.
［実施例７］
前処理の後、Ｓｎめっき層を形成する前に、基材上に厚さ０．３μｍのＮｉめっき層を形成し、その後、厚さ０．３μｍのＣｕめっき層を形成した後、電気めっき時間を１４秒間として厚さ０．７μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。なお、上記のＮｉめっき層は、８０ｇ／Ｌのスルファミン酸ニッケルと４５ｇ／Ｌのホウ酸を含むＮｉめっき液中において、前処理後の基材（被めっき材）を陰極とし、Ｎｉ電極板を陽極として、電流密度５Ａ／ｄｍ２、液温５０℃で１５秒間電気めっきを行うことにより形成し、Ｃｕめっき層は、１１０ｇ／Ｌの硫酸銅と１００ｇ／Ｌの硫酸を含むＣｕめっき液中において、Ｎｉめっき済の被めっき材を陰極とし、Ｃｕ電極板を陽極として、電流密度５Ａ／ｄｍ２、液温３０℃で１２秒間電気めっきを行うことにより形成した。
[Example 7]
After the pretreatment, before forming the Sn plating layer, an Ni plating layer having a thickness of 0.3 μm is formed on the substrate, and thereafter, a Cu plating layer having a thickness of 0.3 μm is formed. Was formed for 14 seconds by the same method as in Example 1 except that a 0.7 μm thick Sn plating layer was formed. The Ni plating layer described above is a Ni plating solution containing 80 g / L of nickel sulfamate and 45 g / L of boric acid. The anode is formed by electroplating for 15 seconds at a current density of 5 A / dm 2 and a liquid temperature of 50 ° C., and the Cu plating layer is formed in a Cu plating solution containing 110 g / L copper sulfate and 100 g / L sulfuric acid. The electrode was formed by performing electroplating for 12 seconds at a current density of 5 A / dm 2 and a liquid temperature of 30 ° C. using a Ni-plated material as a cathode and a Cu electrode plate as an anode.
このリフロー処理後のＳｎめっき材を実施例１と同様の方法により分析したところ、Ｓｎめっき材の基材の表面にＮｉ層と（Ｃｕ−Ｓｎ合金からなる）Ｃｕ−Ｓｎ合金層が形成され、このＣｕ−Ｓｎ合金層の表面にＳｎからなるＳｎ層が形成されていることが確認された。なお、Ｃｕめっき層のＣｕは、リフロー処理により拡散してＣｕ−Ｓｎ合金層になり、Ｃｕ層は観察されなかった。また、Ｃｕ−Ｓｎ合金層とＳｎ層の厚さを実施例１と同様の方法により測定したところ、Ｃｕ−Ｓｎ合金層の厚さは０．６μｍであり、Ｓｎ層の厚さは０．４μｍであった。また、Ｎｉ層の厚さを蛍光Ｘ線膜厚計（セイコーインスツル株式会社製）により測定したところ、０．３μｍであった。 When the Sn plating material after this reflow treatment was analyzed by the same method as in Example 1, a Ni layer and a Cu—Sn alloy layer (consisting of a Cu—Sn alloy) were formed on the surface of the base material of the Sn plating material, It was confirmed that an Sn layer made of Sn was formed on the surface of the Cu—Sn alloy layer. In addition, Cu of the Cu plating layer was diffused by the reflow process to become a Cu—Sn alloy layer, and the Cu layer was not observed. Further, when the thicknesses of the Cu—Sn alloy layer and the Sn layer were measured by the same method as in Example 1, the thickness of the Cu—Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.4 μm. Met. Moreover, it was 0.3 micrometer when the thickness of Ni layer was measured with the fluorescent X ray film thickness meter (made by Seiko Instruments Inc.).
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは５５、算術平均粗さＲａは０．１４μｍ、光沢度は０．１５、山折りの曲げ加工部の表面の算術平均粗さＲａは０．７μｍであった。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, when Vickers hardness HV, arithmetic average roughness Ra, glossiness and arithmetic average roughness Ra of the surface of the bent portion of the fold-folded portion were determined, the Vickers hardness HV was 55 and the arithmetic average roughness The thickness Ra was 0.14 μm, the glossiness was 0.15, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 0.7 μm.
［比較例１］
リフロー処理後のＳｎめっき材の電解脱脂と酸洗を行わず、Ｓｎめっき材の表面にＮｉめっき層およびＺｎめっき層を形成しなかった以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。
[Comparative Example 1]
The Sn plating material was subjected to the same method as in Example 1 except that the Sn plating material after reflow treatment was not electrolytically degreased and pickled, and the Ni plating layer and the Zn plating layer were not formed on the surface of the Sn plating material. Was made.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、耐食性の評価を行ったところ、ガスが発生するまでの時間は２４時間と非常に短く、耐食性が悪かった。 The Sn plating material thus produced was evaluated for corrosion resistance by the same method as in Example 1. As a result, the time until gas was generated was as short as 24 hours, and the corrosion resistance was poor.
［比較例２］
Ｓｎめっき材の表面にＮｉめっき層を形成しなかった以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。
[Comparative Example 2]
An Sn plating material was produced by the same method as in Example 1 except that the Ni plating layer was not formed on the surface of the Sn plating material.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性の評価を行ったところ、山折りの曲げ加工部ではＺｎめっき層の剥離はなかったが、金型で擦れた直線部と、谷折りの曲げ加工部でＺｎめっき層の剥離があり、密着性が良好でなかった。 The Sn plating material thus produced was evaluated for adhesion by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer in the bent portion of the mountain fold, but it was rubbed with the mold. There was peeling of the Zn plating layer at the straight line part and the bent part of the valley fold, and the adhesion was not good.
［比較例３］
電気めっき時間を２９０秒間としてＳｎめっき材に厚さ１０μｍのＮｉめっき層を形成した以外は、実施例１と同様の方法により、Ｚｎめっき層を形成したＳｎめっき材を作製した。
[Comparative Example 3]
An Sn plating material having a Zn plating layer formed thereon was produced in the same manner as in Example 1 except that the electroplating time was 290 seconds and a 10 μm thick Ni plating layer was formed on the Sn plating material.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性の評価を行ったところ、山折りの曲げ加工部ではＺｎめっき層の剥離はなかったが、金型で擦れた直線部と、谷折りの曲げ加工部でＺｎめっき層の剥離があり、密着性が良好でなかった。 The Sn plating material thus produced was evaluated for adhesion by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer in the bent portion of the mountain fold, but it was rubbed with the mold. There was peeling of the Zn plating layer at the straight line part and the bent part of the valley fold, and the adhesion was not good.
［比較例４］
Ｚｎめっき浴として、３５ｇ／Ｌの金属亜鉛と、２００ｇ／Ｌの塩化カリウムと、３０ｇ／Ｌのホウ酸と、３０ｍＬ／Ｌの光沢剤（奥野製薬工業株式会社製のジンクＡＣＫ−１）と、２ｍＬ／Ｌの光沢剤（奥野製薬工業株式会社製のジンクＡＣＫ−２）とを含む塩化カリウム浴からなるＺｎめっき浴を使用し、電流密度４Ａ／ｄｍ２、液温２５℃で１５８秒間電気めっきを行った以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。
[Comparative Example 4]
As a Zn plating bath, 35 g / L metallic zinc, 200 g / L potassium chloride, 30 g / L boric acid, and 30 mL / L brightener (Zinc ACK-1 manufactured by Okuno Pharmaceutical Co., Ltd.), Using a Zn plating bath consisting of a potassium chloride bath containing 2 mL / L brightener (Zinc ACK-2 manufactured by Okuno Pharmaceutical Co., Ltd.), electroplating for 158 seconds at a current density of 4 A / dm 2 and a liquid temperature of 25 ° C. An Sn plated material was produced in the same manner as in Example 1 except that the above was performed.
このようにして作製したＳｎめっき材について、実施例１と同様の方法により、密着性と耐食性の評価を行ったところ、Ｚｎめっき層の剥離はなく、密着性が良好であり、また、ガスが発生するまでの時間は１９２時間以上と長く、耐食性が良好であった。また、このＳｎめっき材のビッカース硬さＨＶ、算術平均粗さＲａ、光沢度および山折りの曲げ加工部の表面の算術平均粗さＲａを求めたところ、ビッカース硬さＨＶは８２．３、算術平均粗さＲａは０．０６μｍ、光沢度は１．８、山折りの曲げ加工部の表面の算術平均粗さＲａは１．９μｍであった。なお、山折りの曲げ加工部の表面の顕微鏡写真を図４に示す。図４に示すように、山折りの曲げ加工部の表面に深いしわの発生が確認された。 The Sn plating material thus produced was evaluated for adhesion and corrosion resistance by the same method as in Example 1. As a result, there was no peeling of the Zn plating layer, the adhesion was good, and the gas was removed. The generation time was as long as 192 hours or more, and the corrosion resistance was good. Further, when the Vickers hardness HV, arithmetic average roughness Ra, glossiness, and arithmetic average roughness Ra of the surface of the bent portion of the mountain fold were determined, the Vickers hardness HV was 82.3. The average roughness Ra was 0.06 μm, the glossiness was 1.8, and the arithmetic average roughness Ra of the surface of the bent portion of the mountain fold was 1.9 μm. In addition, the microscope picture of the surface of the bending process part of a mountain fold is shown in FIG. As shown in FIG. 4, generation | occurrence | production of the deep wrinkle was confirmed on the surface of the bending process part of a mountain fold.
これらの実施例および比較例のＳｎめっき材の製造条件および特性を表１〜表３に示す。なお、表３において、密着性が良好である場合を○、剥離があって密着性が良好でない場合を×で示している。 Tables 1 to 3 show the production conditions and characteristics of the Sn plating materials of these examples and comparative examples. In Table 3, the case where the adhesiveness is good is indicated by ◯, and the case where there is peeling and the adhesiveness is not good is indicated by ×.
１０ 基材
１２ Ｓｎ含有層
１４ Ｎｉめっき層
１６ Ｚｎめっき層
１８ 下地層
１２１ Ｃｕ−Ｓｎ合金層
１２２ Ｓｎ層
１８１ Ｎｉ層
１８２ Ｃｕ層
DESCRIPTION OF
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| JP2018090875A (en) * | 2016-12-06 | 2018-06-14 | Ｄｏｗａメタルテック株式会社 | Sn plated material and manufacturing method thereof |
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