TW201825284A - Tin-plated product and method for producing same - Google Patents

Tin-plated product and method for producing same Download PDF

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Publication number
TW201825284A
TW201825284A TW106141000A TW106141000A TW201825284A TW 201825284 A TW201825284 A TW 201825284A TW 106141000 A TW106141000 A TW 106141000A TW 106141000 A TW106141000 A TW 106141000A TW 201825284 A TW201825284 A TW 201825284A
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layer
plating
thickness
plating layer
alloy
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TW106141000A
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Chinese (zh)
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TWI719270B (en
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成枝宏人
園田悠太
土井龍大
富谷隆夫
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日商同和金屬技術有限公司
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Priority claimed from JP2016236780A external-priority patent/JP6734185B2/en
Priority claimed from JP2017221415A external-priority patent/JP6940380B2/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component

Abstract

There is provided a tin-plated product having good corrosion resistance and good adhesion to a zinc plating layer formed on the surface thereof, even if the processing of a connecting portion is not carried out during compression bonding, if the tin-plated product having the zinc plating layer on the surface thereof is used as the material of a terminal to be connected to an electric wire of aluminum or an aluminum alloy by compression bonding such as swage, and a method for producing the same. In a tin-plated product wherein a tin containing layer 12 is formed on the surface of a substrate 10 of copper or a copper alloy, the tin containing layer 12 is composed of a copper-tin alloy layer 121 and a tin layer 122 of tin which is formed on the copper-tin alloy layer 121 and which has a thickness of 5 [mu]m or less, and a zinc plating layer 16 serving as the outermost layer is formed on the surface of a nickel plating layer 14 formed on the surface of the tin containing layer 12.

Description

Sn鍍敷材及其製造方法Sn plating material and manufacturing method thereof

本發明有關一種Sn鍍敷材及其製造方法，尤其關於一種供用作連接線束(Wire Harness)等電線之端子等材料的Sn鍍敷材及其製造方法。The present invention relates to a Sn plating material and a method of manufacturing the same, and, in particular, to a Sn plating material for use as a material for connecting a wire such as a wire harness (Wire Harness), and a method of manufacturing the same.

背景技術 迄今，使用由銅或銅合金構成之電線來作為車輛用之線束等電線，且連接該電線之端子等的材料則使用對銅或銅合金施加Sn鍍敷而成之Sn鍍敷材。Background Art Conventionally, an electric wire made of copper or a copper alloy is used as an electric wire such as a wire harness for a vehicle, and a material for connecting a terminal of the electric wire or the like is a Sn plating material obtained by applying Sn plating to copper or a copper alloy.

近年來，為了透過車輛之輕量化來提升燃油效率，車輛用之線束等電線使用了較銅或銅合金密度更小之鋁或鋁合金所構成之電線。In recent years, in order to improve fuel efficiency by reducing the weight of vehicles, wires such as wire harnesses for vehicles use wires made of aluminum or aluminum alloy having a lower density than copper or copper alloy.

然而，若利用歛縫等壓接加工將Sn鍍敷材構成之端子連接到鋁或鋁合金構成之電線，會有發生電位差較大之異種金屬接觸所引起之電蝕(卑金屬發生熔解之異種金屬接觸腐蝕)的可能性。However, if the terminal formed of the Sn plating material is connected to the wire composed of aluminum or aluminum alloy by crimping or the like, there is a metal corrosion caused by the contact of a different metal having a large potential difference. The possibility of metal contact corrosion).

因此，雖於連接部分塗佈防蝕劑或樹脂來防止異種金屬接觸腐蝕，但生產性降低且製造成本提高。Therefore, although an anticorrosive agent or a resin is applied to the joint portion to prevent contact corrosion of the dissimilar metal, the productivity is lowered and the manufacturing cost is increased.

此外，就防止異種金屬接觸腐蝕之端子而言，已提出一種端子，其具備具芯線樽部之電線連接部，該芯線樽部係將露出電線一端且由第一金屬(鋁系材料)構成之芯線予以歛縫並連接者，該端子係由離子化傾向較第一金屬更小之第二金屬(銅系材料)所形成，並且，芯線樽部將芯線歛縫前，電線接觸部已由離子化傾向落在第一金屬與第二金屬間之第三金屬(鋅)作電鍍處理，芯線樽部中連接面之鍍層會於歛縫時受到破壞(參照如專利文獻1)。 先行技術文獻 專利文獻Further, in terms of a terminal for preventing contact corrosion of dissimilar metals, a terminal having a wire connecting portion having a core portion which exposes one end of the wire and is composed of a first metal (aluminum-based material) has been proposed. The core wire is caulked and connected, and the terminal is formed by a second metal (copper-based material) having a smaller ionization tendency than the first metal, and the wire contact portion has been ionized before the core wire is crimped by the core wire. The third metal (zinc) which falls between the first metal and the second metal is subjected to electroplating treatment, and the plating layer on the joint surface in the core portion is damaged at the time of caulking (refer to Patent Document 1). Advanced technical literature

[專利文獻1]日本特開2013-134891號公報(段落編號0008、0022)[Patent Document 1] Japanese Laid-Open Patent Publication No. 2013-134891 (paragraph No. 0008, 0022)

發明概要 發明欲解決之課題 然而，專利文獻1之端子中，電線接觸部經第三金屬(鋅)鍍敷處理，且須以歛縫時鍍層會受到破壞的方式來形非常薄之鍍層，因此難以長期防止異種金屬接觸腐蝕。此外，已知即使於一般用作端子材料之Sn鍍敷材表面施行Zn鍍敷，Zn鍍層之密著性仍不良，將Sn鍍敷材用作端子材料時，於加工成端子形狀之際，Zn鍍層容易發生剝離。SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, in the terminal of Patent Document 1, the wire contact portion is subjected to a third metal (zinc) plating treatment, and a very thin plating layer is required to be damaged in a manner that the plating layer is broken during caulking. It is difficult to prevent contact corrosion of dissimilar metals for a long time. Further, it is known that even when Zn plating is applied to the surface of a Sn plating material which is generally used as a terminal material, the adhesion of the Zn plating layer is poor, and when the Sn plating material is used as a terminal material, when it is processed into a terminal shape, The Zn plating layer is easily peeled off.

因此，本發明鑒於此種習知之問題點，目的即在於提供一種Sn鍍敷材及其製造方法，其於將表面形成有Zn鍍層之Sn鍍敷材用作端子(其係可透過歛縫等壓接加工而連接到鋁或鋁合金構成之電線者)的材料時，即使不在壓接加工時施行連接部分之加工，耐蝕性仍良好且形成於表面之Zn鍍層的密著性良好。 用以解決課題之手段Accordingly, the present invention has been made in view of such conventional problems, and an object thereof is to provide a Sn plating material and a method for producing the same, which are used as a terminal for a Sn plating material having a Zn plating layer formed on a surface thereof (the system can be used for caulking, etc.) In the case of a material which is bonded to a wire composed of aluminum or an aluminum alloy by crimping, the corrosion resistance is good and the adhesion of the Zn plating layer formed on the surface is good even if the joining portion is not processed during the press working. Means to solve the problem

本案發明人等為了解決上述課題而精心研究，結果發現，於銅或銅合金所構成之基材表面形成有含Sn層之Sn鍍敷材中，使含Sn層由Cu-Sn合金層與Sn層(其係由形成在Cu-Sn合金層表面之Sn構成且厚度5μm以下者)構成，且於含Sn層之表面形成Ni鍍層，再於該Ni鍍層之表面形成Zn鍍層來作為最表層，藉此，可製出如下述之Sn鍍敷材，進而完成本發明：將表面形成有Zn鍍層之Sn鍍敷材用作端子(其係可透過歛縫等壓接加工而連接到鋁或鋁合金構成之電線者)的材料時，即使於壓接加工時不對連接部分施行加工，耐蝕性良好且形成於表面之Zn鍍層之密著性良好。In order to solve the above problems, the inventors of the present invention have intensively studied and found that a Sn-containing plating layer is formed on a surface of a substrate made of copper or a copper alloy, and the Sn-containing layer is made of a Cu-Sn alloy layer and Sn. a layer (which is composed of Sn formed on the surface of the Cu-Sn alloy layer and having a thickness of 5 μm or less), and a Ni plating layer is formed on the surface of the Sn-containing layer, and a Zn plating layer is formed on the surface of the Ni plating layer as the outermost layer. Thereby, the Sn plating material as described below can be produced, and the present invention can be completed: a Sn plating material having a Zn plating layer formed on its surface is used as a terminal (which can be bonded to aluminum or aluminum by crimping or the like by crimping or the like) In the case of the material of the alloy wire, even if the joint portion is not subjected to the press working, the corrosion resistance is good and the adhesion of the Zn plating layer formed on the surface is good.

亦即，本發明之Sn鍍敷材係一於銅或銅合金所構成之基材表面形成有含Sn層之Sn鍍敷材，其特徵在於：含Sn層係由Cu-Sn合金層與Sn層構成，該Sn層係由形成在該Cu-Sn合金層表面之Sn構成且厚度5μm以下，含Sn層之表面形成有Ni鍍層，且該Ni鍍層表面形成有Zn鍍層作為最表層。That is, the Sn plating material of the present invention is a Sn plating material containing a Sn layer formed on the surface of a substrate composed of copper or a copper alloy, characterized in that the Sn-containing layer is composed of a Cu-Sn alloy layer and Sn. In the layer structure, the Sn layer is composed of Sn formed on the surface of the Cu-Sn alloy layer and has a thickness of 5 μm or less, a Ni plating layer is formed on the surface of the Sn-containing layer, and a Zn plating layer is formed on the surface of the Ni plating layer as the outermost layer.

於該Sn鍍敷材中，Cu-Sn合金層之厚度宜為0.2~2μm。此外，Ni鍍層之厚度宜為0.01~5μm，Zn鍍層之厚度宜為0.5~40μm。又，可於基材與含Sn層之間形成基底層。此時，基底層宜為含Cu及Ni中至少一者之層。此外，宜僅在基材一側表面之含Sn層表面隔著Ni鍍層形成Zn鍍層作為最表層，並將基材另一側面之含Sn層形成為最表層。In the Sn plating material, the thickness of the Cu-Sn alloy layer is preferably 0.2 to 2 μm. Further, the thickness of the Ni plating layer is preferably 0.01 to 5 μm, and the thickness of the Zn plating layer is preferably 0.5 to 40 μm. Further, a base layer may be formed between the substrate and the Sn-containing layer. At this time, the underlayer is preferably a layer containing at least one of Cu and Ni. Further, it is preferable to form the Zn plating layer as the outermost layer only on the surface of the Sn-containing layer on the surface of the substrate side via the Ni plating layer, and to form the Sn-containing layer on the other side surface of the substrate as the outermost layer.

上述Sn鍍敷材中，Zn鍍層之維氏硬度HV宜為80以下。此時，Zn鍍層表面之算術平均粗度Ra宜為0.1~3.0μm，Zn鍍層表面之光澤度宜為1.2以下。此外，亦可將Ni鍍層形成於含Sn層之部分表面上。In the above Sn plating material, the Vickers hardness HV of the Zn plating layer is preferably 80 or less. At this time, the arithmetic mean roughness Ra of the surface of the Zn plating layer is preferably 0.1 to 3.0 μm, and the gloss of the surface of the Zn plating layer is preferably 1.2 or less. Further, a Ni plating layer may be formed on a part of the surface of the Sn-containing layer.

此外，本發明之Sn鍍敷材之製造方法特徵在於：於銅或銅合金所構成之基材表面形成Sn鍍層後，藉由熱處理形成含Sn層來製造Sn鍍敷材，該含Sn層係由Cu-Sn合金層與Sn層購成，該Sn層係形成在該Cu-Sn合金層表面之Sn構成；並且，該製造方法係令Sn層之厚度在5μm以下，且於含Sn層表面形成Ni鍍層後，於該Ni鍍層表面形成Zn鍍層來作為最表層。Further, the method for producing a Sn plating material according to the present invention is characterized in that after a Sn plating layer is formed on a surface of a substrate made of copper or a copper alloy, a Sn-containing layer is formed by heat treatment to produce a Sn plating layer. The Cu-Sn alloy layer and the Sn layer are formed, and the Sn layer is formed of Sn on the surface of the Cu-Sn alloy layer; and the manufacturing method is such that the thickness of the Sn layer is 5 μm or less and the surface of the Sn-containing layer is After the Ni plating layer is formed, a Zn plating layer is formed on the surface of the Ni plating layer as the outermost layer.

該Sn鍍敷材之製造方法中，宜利用熱處理使Sn層之厚度在5μm以下，且宜使Cu-Sn合金層之厚度為0.2~2μm。此外，宜使Ni鍍層之厚度為0.01~5μm，宜使Zn鍍層之厚度為0.5~40μm。又，亦可在形成Sn鍍層前形成Cu鍍層，在基材與含Sn層之間形成含Cu之基底層。或者，也可在形成Sn鍍層前依序形成Ni鍍層與Cu鍍層，再利用熱處理，於基材與含Sn層之間形成含有Cu及Ni中至少一者之基底層。In the 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. Further, it is preferable that the thickness of the Ni plating layer is 0.01 to 5 μm, and the thickness of the Zn plating layer is preferably 0.5 to 40 μm. Further, a Cu plating layer may be formed before the formation of the Sn plating layer, and a Cu-containing underlying layer may be formed between the substrate and the Sn-containing layer. Alternatively, the Ni plating layer and the Cu plating layer may be sequentially formed before the formation of the Sn plating layer, and a base layer containing at least one of Cu and Ni may be formed between the substrate and the Sn-containing layer by heat treatment.

上述Sn鍍敷材之製造方法中，宜於硫酸浴中施行電鍍來形成Zn鍍層。此時，亦可將Ni鍍層形成於含Sn層之部分表面上。In the method for producing the Sn plating material, it is preferred to perform electroplating in a sulfuric acid bath to form a Zn plating layer. At this time, a Ni plating layer may be formed on a part of the surface of the Sn-containing layer.

此外，本發明之電線連接用端子特徵在於：其係一將Sn鍍敷材用作材料之連接端子，該Sn鍍敷材係於銅或銅合金所構成之基材表面形成有含Sn層者，含Sn層係由Cu-Sn合金層與Sn層構成，該Sn層係由形成在該Cu-Sn合金層表面之Sn構成且厚度在5μm以下，並且，該端子係於其與電線之連接部以外的部分，在含Sn層表面形成有Ni鍍層，該Ni鍍層表面則形成有Zn鍍層。Further, the terminal for electric wire connection according to the present invention is characterized in that a Sn plating material is used as a connection terminal of a material, and the Sn plating material is formed on a surface of a substrate composed of copper or a copper alloy to form a Sn-containing layer. The Sn-containing layer is composed of a Cu-Sn alloy layer and a Sn layer composed of Sn formed on the surface of the Cu-Sn alloy layer and having a thickness of 5 μm or less, and the terminal is connected to the wire. A portion other than the portion is formed with a Ni plating layer on the surface of the Sn-containing layer, and a Zn plating layer is formed on the surface of the Ni plating layer.

該電線連接用端子中，Cu-Sn合金層之厚度宜為0.2~2μm。此外，Ni鍍層之厚度宜為0.01~5μm，Zn鍍層之厚度宜為0.5~40μm。又，亦可於基材與含Sn層之間形成基底層。此時，基底層宜為一含Cu及Ni中至少一者之層。此外，電線宜由鋁或鋁合金構成，且宜為單芯線或鉸合線。In the terminal for wire connection, the thickness of the Cu-Sn alloy layer is preferably 0.2 to 2 μm. Further, the thickness of the Ni plating layer is preferably 0.01 to 5 μm, and the thickness of the Zn plating layer is preferably 0.5 to 40 μm. Further, a base layer may be formed between the substrate and the Sn-containing layer. At this time, the underlayer is preferably a layer containing at least one of Cu and Ni. Further, the electric wire is preferably made of aluminum or an aluminum alloy, and is preferably a single core wire or a hinge wire.

上述電線連接用端子中，Zn鍍層之維氏硬度HV宜為80以下。此時，Zn鍍層表面之算術平均粗度Ra宜為0.1~3.0μm，Zn鍍層表面之光澤度宜為1.2以下。 發明效果In the above-mentioned terminal for electric wire connection, the Vickers hardness HV of the Zn plating layer is preferably 80 or less. At this time, the arithmetic mean roughness Ra of the surface of the Zn plating layer is preferably 0.1 to 3.0 μm, and the gloss of the surface of the Zn plating layer is preferably 1.2 or less. Effect of the invention

若依本發明，可製出一種如下述之Sn鍍敷材：將表面形成有Zn鍍層之Sn鍍敷材用作端子(其係可透過歛縫等壓接加工而連接到鋁或鋁合金構成之電線者)的材料時，即使在壓接加工時不對連接部分施行加工，耐食性仍良好且形成於表面之Zn鍍層之密著性良好。According to the present invention, a Sn plating material can be produced by using a Sn plating material having a Zn plating layer formed thereon as a terminal (which can be joined to aluminum or an aluminum alloy by crimping or the like by crimping or the like). In the case of the material of the wire, even if the joint portion is not processed during the crimping process, the food resistance is good and the adhesion of the Zn plating layer formed on the surface is good.

用以實施發明之形態 [第1實施形態] 如圖1所示，以本發明之Sn鍍敷材之第1實施形態而言，於銅或銅合金所構成之(板材或條狀材等之)基材10表面(圖示之實施形態係於兩面)上形成有含Sn層12之Sn鍍敷材中，含Sn層12係由Cu-Sn合金層121與Sn層122構成，該Sn層122係由形成在該Cu-Sn合金層表面之Sn構成且厚度5μm以下(宜0~2μm，更宜0.1~1.5μm)，含Sn層12之表面(圖示之實施形態係於一側之面)上形成有Ni鍍層14，且該Ni鍍層14之表面形成有Zn鍍層16作為最表層。另，Zn鍍層16係由Zn(或含90質量%以上之Zn的Zn合金)構成，藉由形成Zn鍍層16作為最表層，可大幅提升Sn鍍敷材之耐蝕性，且藉由在含Sn層12與Zn鍍層16之間形成Ni鍍層14，可(防止含Sn層12之Sn與Zn鍍層16之Zn等發生擴散，進而抑制Sn或Zn等擴散層之形成或因該擴散所致空孔)大幅提升含Sn層12與Zn鍍層16間之密著性。[First Embodiment] As shown in Fig. 1, in the first embodiment of the Sn plating material of the present invention, it is composed of copper or a copper alloy (such as a plate material or a strip material). In the Sn plating material in which the Sn layer 12 is formed on the surface of the substrate 10 (the embodiment shown on both sides), the Sn-containing layer 12 is composed of a Cu-Sn alloy layer 121 and a Sn layer 122, and the Sn layer is formed. 122 is composed of Sn formed on the surface of the Cu-Sn alloy layer and has a thickness of 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm), and the surface of the Sn-containing layer 12 is provided (the embodiment shown in the figure is on one side) A Ni plating layer 14 is formed on the surface, and a surface of the Ni plating layer 14 is formed with a Zn plating layer 16 as the outermost layer. Further, the Zn plating layer 16 is composed of Zn (or a Zn alloy containing 90% by mass or more of Zn), and by forming the Zn plating layer 16 as the outermost layer, the corrosion resistance of the Sn plating material can be greatly improved, and by including Sn The Ni plating layer 14 is formed between the layer 12 and the Zn plating layer 16 to prevent diffusion of Sn containing the Sn layer 12 and Zn of the Zn plating layer 16, thereby suppressing formation of a diffusion layer such as Sn or Zn or voids due to the diffusion. The adhesion between the Sn-containing layer 12 and the Zn plating layer 16 is greatly improved.

該Sn鍍敷材中，Cu-Sn合金層121之厚度宜為0.2~2μm，更宜為0.3~1.5μm。Ni鍍層14之厚度宜為0.01~5μm，更宜為0.02~4μm，但亦可設在2μm以下。Zn鍍層16之厚度宜為0.5~40μm，較宜為1~30μm且更宜為2~15μm，但可設在10μm以下，亦可設在5μm以下。Zn鍍層16之厚度若過厚，則形成Zn鍍層16時之鍍敷時間將變得過長而使生產性降低。In the Sn plating material, the thickness of the Cu-Sn alloy layer 121 is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm. The thickness of the Ni plating layer 14 is preferably 0.01 to 5 μm, more preferably 0.02 to 4 μm, but may be set to 2 μm or less. The thickness of the Zn plating layer 16 is preferably 0.5 to 40 μm, more preferably 1 to 30 μm and more preferably 2 to 15 μm, but may be set to 10 μm or less, or may be set to 5 μm or less. When the thickness of the Zn plating layer 16 is too thick, the plating time when the Zn plating layer 16 is formed becomes too long, and the productivity is lowered.

又，如圖2所示，也可於基材10與含Sn層12之間形成基底層18。此時，基底層宜為含有Cu及Ni中至少一者之層(Ni層181與Cu層182中至少一者之層)。Ni層181之厚度宜為0.05~1.0μm，Cu層182之厚度宜為1.5μm以下，更宜為1.0μm以下。另，形成Ni層181與Cu層182之二層來作為基底層時，宜在基板10表面形成Ni層181，並在其表面形成Cu層182。Further, as shown in FIG. 2, the underlayer 18 may be formed between the substrate 10 and the Sn-containing layer 12. In this case, the underlayer is preferably a layer containing at least one of Cu and Ni (a layer of at least one of the Ni layer 181 and the Cu layer 182). The thickness of the Ni layer 181 is preferably 0.05 to 1.0 μm, and the thickness of the Cu layer 182 is preferably 1.5 μm or less, more preferably 1.0 μm or less. Further, when two layers of the Ni layer 181 and the Cu layer 182 are formed as the underlayer, it is preferable to form the Ni layer 181 on the surface of the substrate 10 and form the Cu layer 182 on the surface thereof.

另，Zn鍍層可僅形成於含Sn層之部分表面上。此時，在未形成Zn鍍層之含Sn層表面之其他部分，含Sn層會成為最表層，且該最表層之含Sn層之Sn層厚度宜為5μm以下，更宜為0~2μm，最宜為0.1~1.5μm。又，該最表層之含Sn層之Cu-Sn合金層厚度宜為0.2~2μm，更宜為0.3~1.5μm。Alternatively, the Zn plating layer may be formed only on a part of the surface of the Sn-containing layer. At this time, in the other portion 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 containing the Sn layer in the outermost layer is preferably 5 μm or less, more preferably 0 to 2 μm, most It should be 0.1~1.5μm. Further, the thickness of the Cu-Sn alloy layer containing the Sn layer in the outermost layer is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm.

上述Sn鍍敷材之第1實施形態可藉由本發明之Sn鍍敷材製造方法之第1實施形態來製造。若依該Sn鍍敷材製造方法之第1實施形態，可製出如下述之Sn鍍敷材，即：將表面形成有Zn鍍層之Sn鍍敷材用作端子(其係可透過歛縫等壓接加工而連接到鋁或鋁合金所構成之電線者)的材料時，即使於壓接加工時不對連接部分施行加工，耐蝕食性仍良好且形成於表面之Zn鍍層之密著性良好。The first embodiment of the Sn plating material can be produced by the first embodiment of the method for producing a Sn plating material of the present invention. According to the first embodiment of the method for producing a Sn plating material, a Sn plating material obtained by using a Sn plating material having a Zn plating layer on its surface as a terminal (which can be used for caulking or the like) can be produced. When the material of the wire formed by aluminum or aluminum alloy is bonded by crimping, the joint portion is not processed during the crimping process, the corrosion resistance is good, and the adhesion of the Zn plating layer formed on the surface is good.

就本發明之Sn鍍敷材製造方法之第1實施形態而言，於銅或銅合金所構成之基材表面形成(利用電鍍等方式，宜厚度0.1~2μm，更宜厚度0.2~1.5μm之)Sn鍍層後，藉由(利用紅外線加熱器、熱風循環、直火式等熱處理裝置)熱處理(迴流處理)形成含Sn層以製造Sn鍍敷材之方法中，該含Sn層係由Cu-Sn合金層與Sn層構成，且該Sn層係由形成在該Cu-Sn合金層表面之Sn構成，該方法係令Sn層厚度為5μm以下(宜0~2μm，更宜0.1~1.5μm)，且在該含Sn層表面(利用電鍍等方式)形成Ni鍍層後，在該Ni鍍層表面形成Zn鍍層(利用電鍍等方式)來作為最表層。In the first embodiment of the method for producing a Sn plating material according to the present invention, the surface of the substrate formed of copper or a copper alloy is formed (by plating or the like, the thickness is preferably 0.1 to 2 μm, more preferably 0.2 to 1.5 μm). After the Sn plating, the Sn-containing layer is formed by a heat treatment (heat treatment by an infrared heater, a hot air circulation, a direct heat treatment, or the like) to form a Sn-containing layer to produce a Sn plating material. The Sn alloy layer is composed of a Sn layer, and the Sn layer is composed of Sn formed on the surface of the Cu-Sn alloy layer. The method is such that the thickness of the Sn layer is 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm). After the Ni plating layer is formed on the surface of the Sn-containing layer (by plating or the like), a Zn plating layer (by plating or the like) is formed on the surface of the Ni plating layer as the outermost layer.

於該Sn鍍敷材之製造方法中，在藉由熱處理將Sn層之厚度製成5μm以下(宜0~2μm，更宜0.1~1.5μm)之同時，將Cu-Sn合金層之厚度製成0.2~2μm(更宜0.3~1.5μm)。宜將Ni鍍層之厚度設成0.01~5μm，更宜設成0.02~4μm，但也可設在2μm以下。Zn鍍層之厚度宜設成0.5~40μm，且較宜設成1~30μm，更宜設成2~15μm，但可設在10μm以下，也可設在5μm以下。此外，可於形成Sn鍍層前形成(宜厚度0.1~1.5μm之)Cu鍍層，也可在基材與含Sn層之間形成含Cu之基底層。或者，可在形成Sn鍍層前依序形成(宜厚度0.05~1.0μm之)Ni鍍層與(宜厚度0.1~1.5μm之)Cu鍍層，並於基材與含Sn層之間形成含Cu及Ni之基底層。Cu-Sn合金層與Sn層之厚度可藉電解式膜厚計等來測定。In the method for producing the Sn plating material, the thickness of the Cu-Sn alloy layer is made while the thickness of the Sn layer is 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm) by heat treatment. 0.2~2μm (more preferably 0.3~1.5μm). The thickness of the Ni plating layer should be set to 0.01 to 5 μm, more preferably 0.02 to 4 μm, but it may be set to 2 μm or less. The thickness of the Zn plating layer is preferably set to 0.5 to 40 μm, and is preferably set to 1 to 30 μm, more preferably 2 to 15 μm, but may be set to 10 μm or less, or may be set to 5 μm or less. Further, a Cu plating layer (preferably having a thickness of 0.1 to 1.5 μm) may be formed before the Sn plating layer is formed, or a Cu-containing underlayer may be formed between the substrate and the Sn-containing layer. Alternatively, a Ni plating layer (preferably having a thickness of 0.05 to 1.0 μm) and a Cu plating layer (having a thickness of 0.1 to 1.5 μm) may be sequentially formed before the formation of the Sn plating layer, and a Cu-containing and Ni-containing layer may be formed between the substrate and the Sn-containing layer. The base layer. The thickness of the Cu-Sn alloy layer and the Sn layer can be measured by an electrolytic film thickness meter or the like.

另，Ni鍍層與Zn鍍層可(藉由遮蔽或控制液面高度等而)僅形成於基材一側表面之含Sn層表面(或含Sn層之部分表面)。此時，在未形成Zn鍍層之含Sn層表面之其他部分，含Sn層會成為最表層，該最表層之含Sn層之Sn層厚度宜在5μm以下，更宜為0~2μm。Further, the Ni plating layer and the Zn plating layer may be formed only on the surface of the Sn-containing layer (or a portion of the surface containing the Sn layer) on the surface of one side of the substrate (by masking or controlling the liquid level or the like). At this time, in the other portion 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 containing the Sn layer in the outermost layer is preferably 5 μm or less, more preferably 0 to 2 μm.

上述Sn鍍敷材之第1實施形態可作為連接鋁或鋁合金所構成之電線的端子等通電構件之材料來使用。此外，將Ni鍍層與Zn鍍層僅形成於含Sn層之部分表面時，宜在未形成Zn鍍層之含Sn層表面之其他部分(含Sn層會成為最表層之部分)連接鋁或鋁合金構成之電線。The first embodiment of the Sn plating material can be used as a material for connecting an electric current member such as a terminal of an electric wire composed of aluminum or aluminum alloy. In addition, when the Ni plating layer and the Zn plating layer are formed only on a portion of the surface of the Sn-containing layer, it is preferable to connect the aluminum or aluminum alloy to other portions of the surface of the Sn-containing layer on which the Zn plating layer is not formed (the portion in which the Sn-containing layer becomes the outermost layer). Wire.

[第2實施形態] 如圖1所示，以本發明之Sn鍍敷材之第2實施形態而言，於銅或銅合金所構成之(板材或條狀材等之)基材10表面(圖示之實施形態係於兩面)上形成有含Sn層12之Sn鍍敷材中，含Sn層12係由Cu-Sn合金層121與Sn層122構成，該Sn層122係由形成在該Cu-Sn合金層表面之Sn構成且厚度5μm以下(宜0~2μm，更宜0.1~1.5μm)，含Sn層12之表面(圖示之實施形態係於一側之面)上形成有Ni鍍層14，且該Ni鍍層14之表面形成有維氏硬度HV於80以下之Zn鍍層16作為最表層。另，Zn鍍層16係由Zn(或含90質量%以上之Zn的Zn合金)構成，藉由形成Zn鍍層16作為最表層，可大幅提升Sn鍍敷材之耐蝕性，且藉由在含Sn層12與Zn鍍層16之間形成Ni鍍層14，可(防止含Sn層12之Sn與Zn鍍層16之Zn等發生擴散，進而抑制Sn或Zn等擴散層之形成或因該擴散所致空孔)大幅提升含Sn層12與Zn鍍層16間之密著性。此外，藉由令Zn鍍層16較軟(維氏硬度HV在80以下，且宜70以下)，可抑制因Sn鍍敷材彎曲加工而引發之基材10露出，而可抑制因電位差較大之異種金屬接觸所導致之電蝕(卑金屬會發生溶解之異種金屬接觸腐蝕)，進而可提升Sn鍍敷材之彎曲加工性。[Second Embodiment] As shown in Fig. 1, in the second embodiment of the Sn plating material of the present invention, the surface of the substrate 10 (such as a plate material or a strip material) composed of copper or a copper alloy ( In the embodiment shown in the figure, in the Sn plating material in which the Sn layer 12 is formed on both sides, the Sn-containing layer 12 is composed of a Cu-Sn alloy layer 121 and an Sn layer 122, and the Sn layer 122 is formed by The surface of the Cu-Sn alloy layer is composed of Sn and has a thickness of 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm), and the surface of the Sn-containing layer 12 (the embodiment shown in the figure is on one side) is formed with Ni. The plating layer 14 and the surface of the Ni plating layer 14 are formed with a Zn plating layer 16 having a Vickers hardness HV of 80 or less as the outermost layer. Further, the Zn plating layer 16 is composed of Zn (or a Zn alloy containing 90% by mass or more of Zn), and by forming the Zn plating layer 16 as the outermost layer, the corrosion resistance of the Sn plating material can be greatly improved, and by including Sn The Ni plating layer 14 is formed between the layer 12 and the Zn plating layer 16 to prevent diffusion of Sn containing the Sn layer 12 and Zn of the Zn plating layer 16, thereby suppressing formation of a diffusion layer such as Sn or Zn or voids due to the diffusion. The adhesion between the Sn-containing layer 12 and the Zn plating layer 16 is greatly improved. Further, by making the Zn plating layer 16 softer (Vickers hardness HV is 80 or less, and preferably 70 or less), it is possible to suppress the exposure of the substrate 10 caused by the bending of the Sn plating material, and it is possible to suppress a large potential difference. The electric corrosion caused by the contact of dissimilar metals (the contact metal corrosion of the dissolving metal may occur), thereby improving the bending workability of the Sn plating material.

於該Sn鍍敷材中，Zn鍍層16之表面算術平均粗度Ra宜為0.1~3.0μm。此外，光澤度宜在1.2以下，更宜為0.5以下，最宜為0.1~0.2。In the Sn plating material, the arithmetic mean roughness Ra of the surface of the Zn plating layer 16 is preferably 0.1 to 3.0 μm. Further, the gloss is preferably 1.2 or less, more preferably 0.5 or less, and most preferably 0.1 to 0.2.

此外，Cu-Sn合金層121之厚度宜為0.2~2μm，更宜為0.3~1.5μm。Ni鍍層14之厚度宜為0.01~5μm，更宜為0.02~4μm，但亦可設在2μm以下。Zn鍍層16之厚度宜為1~40μm，較宜為1~30μm且更宜為2~15μm，但可設在10μm以下，亦可設在5μm以下。Zn鍍層16之厚度若過厚，則形成Zn鍍層16時之鍍敷時間將變得過長而使生產性降低，但若過薄則無法獲得充分耐蝕性。Further, the thickness of the Cu-Sn alloy layer 121 is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm. The thickness of the Ni plating layer 14 is preferably 0.01 to 5 μm, more preferably 0.02 to 4 μm, but may be set to 2 μm or less. The thickness of the Zn plating layer 16 is preferably 1 to 40 μm, more preferably 1 to 30 μm and more preferably 2 to 15 μm, but may be set to 10 μm or less, or may be set to 5 μm or less. When the thickness of the Zn plating layer 16 is too large, the plating time when the Zn plating layer 16 is formed becomes too long and the productivity is lowered. However, if it is too thin, sufficient corrosion resistance cannot be obtained.

又，如圖2所示，也可於基材10與含Sn層12之間形成基底層18。此時，基底層宜為含有Cu及Ni中至少一者之層(Ni層181與Cu層182中至少一者之層)。Ni層181之厚度宜為0.05~1.0μm，Cu層182之厚度宜為1.5μm以下，更宜為1.0μm以下。另，形成Ni層181與Cu層182之二層來作為基底層時，宜在基板20表面形成Ni層181，並在其表面形成Cu層182。Further, as shown in FIG. 2, the underlayer 18 may be formed between the substrate 10 and the Sn-containing layer 12. In this case, the underlayer is preferably a layer containing at least one of Cu and Ni (a layer of at least one of the Ni layer 181 and the Cu layer 182). The thickness of the Ni layer 181 is preferably 0.05 to 1.0 μm, and the thickness of the Cu layer 182 is preferably 1.5 μm or less, more preferably 1.0 μm or less. Further, when two layers of the Ni layer 181 and the Cu layer 182 are formed as the underlayer, it is preferable to form the Ni layer 181 on the surface of the substrate 20 and form the Cu layer 182 on the surface thereof.

另，Zn鍍層可僅形成於含Sn層之部分表面上。此時，在未形成Zn鍍層之含Sn層表面之其他部分，含Sn層會成為最表層，該最表層之含Sn層之Sn層厚度宜為5μm以下，更宜為0~2μm，最宜為0.1~1.5μm。又，該最表層之含Sn層之Cu-Sn合金層厚度宜為0.2~2μm，更宜為0.3~1.5μm。Alternatively, the Zn plating layer may be formed only on a part of the surface of the Sn-containing layer. At this time, in the other portion 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 containing the Sn layer in the outermost layer is preferably 5 μm or less, more preferably 0 to 2 μm, and is most suitable. It is 0.1~1.5μm. Further, the thickness of the Cu-Sn alloy layer containing the Sn layer in the outermost layer is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm.

上述Sn鍍敷材之第2實施形態可藉由本發明之Sn鍍敷材製造方法之第2實施形態來製造。若依該Sn鍍敷材製造方法之第2實施形態，可製出如下述之Sn鍍敷材，即：將表面形成有Zn鍍層之Sn鍍敷材用作端子(其係可透過歛縫等壓接加工而連接到鋁或鋁合金所構成之電線者)的材料時，即使於壓接加工時不對連接部分施行加工，耐蝕食性仍良好且形成於表面之Zn鍍層之密著性良好，同時彎曲加工性良好。The second embodiment of the Sn plating material can be produced by the second embodiment of the method for producing a Sn plating material of the present invention. According to the second embodiment of the method for producing a Sn plating material, a Sn plating material obtained by using a Sn plating material having a Zn plating layer on its surface as a terminal (which can be used for caulking, etc.) can be produced. When the material is bonded to a wire composed of aluminum or aluminum alloy, the joint portion is not processed during the crimping process, the corrosion resistance is good, and the adhesion of the Zn plating layer formed on the surface is good, and at the same time Good bending workability.

就本發明之Sn鍍敷材製造方法之第2實施形態而言，於銅或銅合金所構成之基材表面形成(利用電鍍等方式，宜厚度0.1~2μm，更宜厚度0.2~1.5μm之)Sn鍍層後，藉由(利用紅外線加熱器、熱風循環、直火式等熱處理裝置)熱處理(迴流處理)形成含Sn層以製造Sn鍍敷材之方法中，該含Sn層係由Cu-Sn合金層與Sn層構成，且該Sn層係由形成在該Cu-Sn合金層表面之Sn構成，該方法係令Sn層厚度為5μm以下(宜0~2μm，更宜0.1~1.5μm)，且在該含Sn層表面(利用電鍍等方式)形成Ni鍍層後，在硫酸浴中進行電鍍，藉此在該Ni鍍層表面形成Zn鍍層來作為最表層。In the second embodiment of the method for producing a Sn plating material according to the present invention, it is formed on the surface of a substrate made of copper or a copper alloy (by plating or the like, preferably 0.1 to 2 μm in thickness, more preferably 0.2 to 1.5 μm in thickness). After the Sn plating, the Sn-containing layer is formed by a heat treatment (heat treatment by an infrared heater, a hot air circulation, a direct heat treatment, or the like) to form a Sn-containing layer to produce a Sn plating material. The Sn alloy layer is composed of a Sn layer, and the Sn layer is composed of Sn formed on the surface of the Cu-Sn alloy layer. The method is such that the thickness of the Sn layer is 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm). After the Ni plating layer is formed on the surface of the Sn-containing layer (by plating or the like), electroplating is performed in a sulfuric acid bath, whereby a Zn plating layer is formed on the surface of the Ni plating layer as the outermost layer.

於該Sn鍍敷材之製造方法中，在藉由熱處理將Sn層之厚度製成5μm以下(宜0~2μm，更宜0.1~1.5μm)之同時，將Cu-Sn合金層之厚度製成0.2~2μm(更宜0.3~1.5μm)。宜將Ni鍍層之厚度設成0.01~5μm，更宜設成0.02~4μm，但也可設在2μm以下。Zn鍍層之厚度宜設成1~40μm，且較宜設成1~30μm，更宜設成2~15μm，但可設在10μm以下，也可設在5μm以下。此外，可於形成Sn鍍層前形成(宜厚度0.1~1.5μm之)Cu鍍層，也可在基材與含Sn層之間形成含Cu之基底層。或者，可在形成Sn鍍層前依序形成(宜厚度0.05~1.0μm之)Ni鍍層與(宜厚度0.1~1.5μm之)Cu鍍層，並於基材與含Sn層之間形成含Cu及Ni之基底層。Cu-Sn合金層與Sn層之厚度可藉電解式膜厚計等來測定。In the method for producing the Sn plating material, the thickness of the Cu-Sn alloy layer is made while the thickness of the Sn layer is 5 μm or less (preferably 0 to 2 μm, more preferably 0.1 to 1.5 μm) by heat treatment. 0.2~2μm (more preferably 0.3~1.5μm). The thickness of the Ni plating layer should be set to 0.01 to 5 μm, more preferably 0.02 to 4 μm, but it may be set to 2 μm or less. The thickness of the Zn plating layer is preferably set to 1 to 40 μm, and is preferably set to 1 to 30 μm, more preferably 2 to 15 μm, but may be set to 10 μm or less, or may be set to 5 μm or less. Further, a Cu plating layer (preferably having a thickness of 0.1 to 1.5 μm) may be formed before the Sn plating layer is formed, or a Cu-containing underlayer may be formed between the substrate and the Sn-containing layer. Alternatively, a Ni plating layer (preferably having a thickness of 0.05 to 1.0 μm) and a Cu plating layer (having a thickness of 0.1 to 1.5 μm) may be sequentially formed before the formation of the Sn plating layer, and a Cu-containing and Ni-containing layer may be formed between the substrate and the Sn-containing layer. The base layer. The thickness of the Cu-Sn alloy layer and the Sn layer can be measured by an electrolytic film thickness meter or the like.

另，Ni鍍層與Zn鍍層可(藉由遮蔽或控制液面高度等而)僅形成於基材一側表面之含Sn層表面(或含Sn層之部分表面)。此時，在未形成Zn鍍層之含Sn層表面之其他部分，含Sn層會成為最表層，該最表層之含Sn層之Sn層厚度宜在5μm以下，更宜為0~2μm。Further, the Ni plating layer and the Zn plating layer may be formed only on the surface of the Sn-containing layer (or a portion of the surface containing the Sn layer) on the surface of one side of the substrate (by masking or controlling the liquid level or the like). At this time, in the other portion 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 containing the Sn layer in the outermost layer is preferably 5 μm or less, more preferably 0 to 2 μm.

用作用以形成Zn鍍層之Zn渡浴的硫酸浴宜為由含硫酸鋅與硫酸銨之水溶液所構成的硫酸浴，且宜不含光澤劑等添加劑。可藉由不含添加劑來減低Zn鍍浴之成本。又，形成Zn鍍層時，電鍍之電流密度宜為15~60A/dm2 之高電流密度。可藉由設成高電流密度來提升生產性。The sulfuric acid bath used as the Zn bypass 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 contains no additives such as a glossing agent. The cost of the Zn plating bath can be reduced by not containing additives. Further, when the Zn plating layer is formed, the current density of the plating is preferably a high current density of 15 to 60 A/dm 2 . Productivity can be improved by setting a high current density.

上述Sn鍍敷材之第2實施形態可作為連接鋁或鋁合金所構成之電線的端子等通電構件之材料來使用。此外，僅將Ni鍍層與Zn鍍層形成於含Sn層之部分表面時，宜在未形成Zn鍍層之含Sn層表面之其他部分(含Sn層會成為最表層之部分)連接鋁或鋁合金構成之電線。 實施例The second embodiment of the Sn plating material can be used as a material for connecting an electric current member such as a terminal of an electric wire composed of aluminum or aluminum alloy. In addition, when only the Ni plating layer and the Zn plating layer are formed on a portion of the surface of the Sn-containing layer, it is preferable to connect the aluminum or aluminum alloy to other portions of the Sn-containing layer surface (the portion where the Sn layer is the outermost layer). Wire. Example

茲就本發明之Sn鍍敷材及其製造方法之實施例詳細說明如下。The embodiments of the Sn plating material of the present invention and the method for producing the same are described in detail below.

[實施例1] 首先，準備50mm×50mm×0.25mm大小且由Cu-Ni-Sn-P合金構成之平板狀導體基材(含1.0質量%之Ni、0.9質量%之Sn與0.05質量%之P且殘餘部分為Cu之銅合金基材)(DOWA METALTECH Co.,Ltd.製NB-109EH)。[Example 1] First, a flat conductor substrate composed of a Cu-Ni-Sn-P alloy having a size of 50 mm × 50 mm × 0.25 mm (containing 1.0% by mass of Ni, 0.9% by mass of Sn and 0.05% by mass) was prepared. P and the residual portion is a copper alloy substrate of Cu) (NB-109EH manufactured by DOWA METALTECH Co., Ltd.).

接著，就前置處理而言，將基材(被鍍敷材)以鹼性電解脫脂液進行10秒電解脫脂後水洗，之後，浸漬於100g/L硫酸中酸洗後進行水洗。Next, in the pretreatment, the substrate (plated material) was electrolytically degreased in an alkaline electrolytic degreasing liquid for 10 seconds, and then washed with water, and then immersed in 100 g/L of sulfuric acid for pickling and then washed with water.

接著，於含有60g/L之硫酸錫(II)、75g/L之硫酸、30g/L之甲酚磺酸與1g/L之β萘酚的Sn鍍液中，以基材為陰極且以Sn電極板為陽極，於電流密度5A/dm2 、液溫25℃下進行20秒電鍍，藉此於基材表面形成厚度1μm之Sn鍍層而獲得Sn鍍敷材。Next, in a Sn plating solution containing 60 g/L of tin (II) sulfate, 75 g/L of sulfuric acid, 30 g/L of cresolsulfonic acid and 1 g/L of β-naphthol, the substrate is used as a cathode and Sn is used. The electrode plate was an anode, and electroplating was carried out for 20 seconds at a current density of 5 A/dm 2 and a liquid temperature of 25 ° C to form a Sn plating layer having a thickness of 1 μm on the surface of the substrate to obtain a Sn plating material.

其次，將所得Sn鍍敷材洗淨並乾燥後，進行熱處理(迴流處理)。該迴流處理係將2個近紅外線加熱器(HYBEC CORPORATION.製HYP-8N，額定電壓100V，額定功率560W，平行照射型)以間隔25mm對向配置，並於該等近紅外線加熱器之中央部位配置Sn鍍敷材，令設定電流值為10.8A，於大氣環境下將Sn鍍敷材加熱13秒使Sn鍍層表面熔融後，立刻浸漬於25℃水槽內冷卻。Next, the obtained Sn plating material was washed and dried, and then subjected to heat treatment (reflow treatment). In the reflow treatment, two near-infrared heaters (HYP-8N manufactured by HYBEC CORPORATION, rated voltage of 100 V, rated power of 560 W, parallel illumination type) are disposed at an interval of 25 mm, and are disposed at the center of the near-infrared heaters. The Sn plating material was placed so that the set current value was 10.8 A, and the Sn plating material was heated in an atmosphere for 13 seconds to melt the surface of the Sn plating layer, and immediately immersed in a 25 ° C water tank for cooling.

以聚焦離子束(FIB)切斷該迴流處理後之Sn鍍敷材，使與Sn鍍敷材之軋延方向呈垂直之截面露出，並以電場放射型歐傑電子能譜分析裝置(FE-AES)分析該截面。結果，確認了Sn鍍敷材之基材表面形成有Cu-Sn合金所構成之Cu-Sn合金層，且該Cu-Sn合金層表面形成有由Sn構成之Sn層。此外，以電解式膜厚計(中央製作所股份有限公司製Thickness Tester TH-11)測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm。The Sn plating material after the reflow treatment is cut by a focused ion beam (FIB), and a cross section perpendicular to the rolling direction of the Sn plating material is exposed, and an electric field emission type Auger electron spectroscopy analyzer (FE- AES) analyzes the section. As a result, it was confirmed that a Cu-Sn alloy layer composed of a Cu-Sn alloy was formed on the surface of the substrate of the Sn plating material, and a Sn layer made of Sn was formed on the surface of the Cu-Sn alloy layer. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured by an electrolytic film thickness meter (Thickness Tester TH-11 manufactured by Konica Minolta Co., Ltd.), and as a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.7 μm.

接著，將膠帶貼附於迴流處理後之Sn鍍敷材之一側面的全面上予以遮蔽後，將該Sn鍍敷材浸漬於40g/L之氫氧化鈉水溶液並以10A/dm2 進行30秒電解脫脂，再浸漬於100g/L硫酸30秒酸洗後進行水洗。Next, after the tape was attached to the side surface of one of the Sn plating materials after the reflow treatment, the Sn plating material was immersed in a 40 g/L sodium hydroxide aqueous solution and subjected to 10 A/dm 2 for 30 seconds. Electrolytic degreasing, immersed in 100 g / L sulfuric acid for 30 seconds, pickling, and then washing with water.

接著，於含有80g/L之胺磺酸鎳及50g/L之硼酸的Ni鍍浴(胺磺酸浴)中，以(已於一面之全面上貼附膠帶遮蔽之)Sn鍍敷材為陰極，並以Ni電極板為陽極，於電流密度10A/dm2 、液溫50℃下進行電鍍6秒，藉此，於Sn鍍敷材之另一面上形成Ni鍍層。以螢光X射線膜厚計(Seiko Instruments Inc.製)測定該Ni鍍層之厚度，結果為0.2μm。Next, in a Ni plating bath (amine sulfonic acid bath) containing 80 g/L of nickel sulfamate and 50 g/L of boric acid, the Sn plating material (which has been covered with a tape on one side) is used as a cathode. The Ni electrode plate was used as an anode, and plating was performed at a current density of 10 A/dm 2 and a liquid temperature of 50 ° C for 6 seconds, whereby a Ni plating layer was formed on the other surface of the Sn plating material. The thickness of the Ni plating layer was measured by a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.) and found to be 0.2 μm.

其次，於含有35g/L之金屬鋅、200g/L之氯化鉀、30g/L之硼、30mL/L之光澤劑(奥野製藥工業股份有限公司製Zinc ACK-1)與2mL/L之光澤剤(奥野製薬工業株式会社製Zinc ACK-2)之Zn鍍浴中，以(於一面之全面上貼附膠帶遮蔽之)鍍Ni後之Sn鍍敷材為陰極，以Zn電極板為陽極，於電流密度16A/dm2 、液溫25℃下進行45秒電鍍，藉此於已形成在Sn鍍敷材另一面之Ni鍍層的表面形成Zn鍍層。以螢光X射線膜厚計(Seiko Instruments Inc.製)測定該Zn鍍層之厚度，結果為3μm。Next, it is a 35 g/L metal zinc, 200 g/L potassium chloride, 30 g/L boron, 30 mL/L gloss (Zinc ACK-1 manufactured by Okuno Pharmaceutical Co., Ltd.) and a gloss of 2 mL/L. In the Zn plating bath of 剤 (Zinc ACK-2 manufactured by Okuno Kasei Co., Ltd.), the Sn plating material after Ni plating (masked on one side of the entire surface) is used as a cathode, and the Zn electrode plate is used as an anode. Plating was performed for 45 seconds at a current density of 16 A/dm 2 and a liquid temperature of 25 ° C to form a Zn plating layer on the surface of the Ni plating layer formed on the other side of the Sn plating material. 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.

以聚焦離子束(FIB)加工觀察裝置將已如前述般形成Zn鍍層之Sn鍍敷材切斷，使Sn鍍敷材之與軋延方向垂直之截面露出，再以電界放射型歐傑電子能譜分析裝置(FE-AES)分析該截面。結果，確定了Sn鍍敷材之基材表面形成有Cu-Sn合金構成之Cu-Sn合金層，且該Cu-Sn合金層表面形成有Sn構成之Sn層，該Sn層表面形成有Ni鍍層，該Ni鍍層表面則形成有Zn鍍層。此外，從掃描離子顯微鏡像(SIM像)測定該等層之厚度，確認了Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm，Ni鍍層之厚度為0.2μm，Zn鍍層之厚度為3μm。The Sn plating material which has formed the Zn plating layer as described above is cut by a focused ion beam (FIB) processing observation apparatus, and the cross section perpendicular to the rolling direction of the Sn plating material is exposed, and then the electric radiation type Auger electron energy is used. The cross section was analyzed by a spectral analysis device (FE-AES). As a result, it was confirmed that a Cu-Sn alloy layer composed of a Cu-Sn alloy was formed on the surface of the substrate of the Sn plating material, and a Sn layer composed of Sn was formed on the surface of the Cu-Sn alloy layer, and a Ni plating layer was formed on the surface of the Sn layer. A Zn plating layer is formed on the surface of the Ni plating layer. Further, the thickness of the layers was measured from a scanning ion microscope image (SIM image), and it was confirmed that 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 was 0.2 μm, and the thickness of the Zn plating layer was The thickness is 3 μm.

此外，對截取自形成有Zn鍍層之Sn鍍敷材且50mm×10mm×0.25mm大小之試驗片施加10kN之荷重，以最小彎曲半徑R與板厚t之比R/t會成為1.0之方式施行90°W彎曲，將該試驗片埋入樹脂後，朝對試驗片之長向呈平行之方向(相對於90°W彎曲之彎曲軸呈垂直方向)切斷，並以雷射顯微鏡放大該截面，觀察經模具刮擦之直線部、谷摺彎曲加工部與山摺彎曲加工部，並以目測評價Zn鍍層有無剝離。結果，任一部分皆無Zn鍍層剝離，密著性(初期密著性)良好。另，分別將90°W彎曲後之直線部與谷摺彎曲加工部之顯微鏡照片顯示於圖3A及圖3B。Further, a load of 10 kN was applied to a test piece of a size of 50 mm × 10 mm × 0.25 mm taken from a Sn plating material on which a Zn plating layer was formed, and the ratio R/t of the minimum bending radius R to the thickness t was 1.0. After bending at 90°W, the test piece was embedded in the resin, and was cut in a direction parallel to the longitudinal direction of the test piece (vertical direction with respect to a bending axis bent at 90° W), and the section was enlarged by a laser microscope. The straight portion, the valley bending portion, and the mountain bending portion processed by the mold were observed, and the presence or absence of peeling of the Zn plating layer was visually evaluated. As a result, no part of the Zn plating layer was peeled off, and the adhesion (initial adhesion) was good. Further, a microscope photograph of a linear portion bent at 90° W and a valley bending portion is shown in FIGS. 3A and 3B.

此外，於120℃下將截取自已形成Zn鍍層之Sn鍍敷材且50mm×10mm×0.25mm大小之試驗片保持120小時後，進行與上述相同之密著性(耐熱試驗後之密著性)評價，結果無論任一部分皆無Zn鍍層剝離，密著性良好。Further, the test piece having a size of 50 mm × 10 mm × 0.25 mm which was cut out from the Sn plating material on which the Zn plating layer was formed was held at 120 ° C for 120 hours, and the same adhesion as described above (adhesiveness after the heat resistance test) was performed. As a result, no Zn plating was peeled off in any part, and the adhesion was good.

又，以截取自已形成Zn鍍層之Sn鍍敷材且50mm×10mm×0.25mm大小之試驗片的Zn鍍層為外側，並以該Sn鍍敷材將直徑0.8mm、長度30mm之純鋁單線(A1070)歛縫後，浸漬於5質量%之NaCl水溶液中，並以電蝕(卑金屬會發生溶解之異種金屬接觸腐蝕)所引起之氣體發生時間來評價耐蝕性。結果，至發生氣體為止之時間長達192時間以上，耐食性良好。Further, a Zn plating layer of a test piece of a size of 50 mm × 10 mm × 0.25 mm which was cut out from a Sn plating material having a Zn plating layer was taken out, and a pure aluminum single wire having a diameter of 0.8 mm and a length of 30 mm was used as the Sn plating material (A1070). After the caulking, the corrosion resistance was evaluated by immersing in a 5 mass% NaCl aqueous solution and gas generation time caused by electrolytic etching (contact metal corrosion in which the metal was dissolved). As a result, the time until the gas generation was as long as 192 times or longer, and the food resistance was good.

[實施例2] 迴流處理後之Sn鍍敷材不進行酸洗，於含有200g/L之氯化鎳與100g/L之鹽酸的Ni鍍浴(伍德浴(Wood’s bath))中，以(已於一側面之全面上貼附膠帶遮蔽之)Sn鍍敷材為陰極並以Ni電極板為陽極，於電流密度10A/dm2 、液溫60℃下進行6秒電鍍，除此之外，利用與實施例1相同方法製作出形成有Zn鍍層之Sn鍍敷材。[Example 2] The Sn plating material after the reflow treatment was not subjected to pickling, and was used in a Ni plating bath (Wood's bath) containing 200 g/L of nickel chloride and 100 g/L of hydrochloric acid. The Sn plating material is shielded on the one side and the Sn plating material is used as the cathode, and the Ni electrode plate is used as the anode. The current density is 10 A/dm 2 and the liquid temperature is 60 ° C for 6 seconds, and the use is performed. In the same manner as in Example 1, a Sn plating material in which a Zn plating layer was formed was produced.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，初期與耐熱試驗後無論任一者皆無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。In the same manner as in Example 1, the Sn plating material produced in this manner was evaluated for the adhesion and the corrosion resistance. As a result, no Zn plating layer was peeled off after the initial heat resistance test, and the adhesion was good. The time until gas generation is as long as 192 hours or more, and the corrosion resistance is good.

[實施例3] 將電鍍時間設成90秒，並於Sn鍍敷材上形成厚度3μm之Ni鍍層，除此之外，以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 3] A Sn plating having a Zn plating layer was formed in the same manner as in Example 1 except that the plating time was set to 90 seconds, and a Ni plating layer having a thickness of 3 μm was formed on the Sn plating material. material.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，初期與耐熱試驗後無論任一者皆無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。In the same manner as in Example 1, the Sn plating material produced in this manner was evaluated for the adhesion and the corrosion resistance. As a result, no Zn plating layer was peeled off after the initial heat resistance test, and the adhesion was good. The time until gas generation is as long as 192 hours or more, and the corrosion resistance is good.

[實施例4] 將電鍍時間設成2秒，並於Sn鍍敷材上形成厚度0.05μm之Ni鍍層，除此之外，以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 4] A Sn plating plated with a Zn plating layer was produced in the same manner as in Example 1 except that the plating time was set to 2 seconds, and a Ni plating layer having a thickness of 0.05 μm was formed on the Sn plating material. Dressing.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，初期與耐熱試驗後無論任一者皆無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。In the same manner as in Example 1, the Sn plating material produced in this manner was evaluated for the adhesion and the corrosion resistance. As a result, no Zn plating layer was peeled off after the initial heat resistance test, and the adhesion was good. The time until gas generation is as long as 192 hours or more, and the corrosion resistance is good.

[實施例5] 將電鍍時間設成620秒，並令Zn鍍層之厚度為40µm以上，除此之外，以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 5] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 1 except that the plating time was 620 seconds and the thickness of the Zn plating layer was 40 μm or more.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 1. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long. 192 hours or more, good corrosion resistance.

[實施例6] 將電鍍時間設成15秒，並令Zn鍍層之厚度為1µm以上，除此之外，以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 6] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 1 except that the plating time was set to 15 seconds and the thickness of the Zn plating layer was 1 μm or more.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達144小時，耐蝕性良好。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 1. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long. 144 hours, good corrosion resistance.

[實施例7] 於前置處理後且於形成Sn鍍層前，於基材上形成厚度0.3μm之Ni鍍層，之後形成厚度0.3μm之Cu鍍層後，將電鍍時間設成14秒，形成厚度0.7μm之Sn鍍層，除此之外，以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。另，上述Ni鍍層係於含80g/L之胺磺酸鎳、45g/L之硼酸之Ni渡液中，以前置處理後之基材(被鍍敷材)為陰極且以Ni電極板為陽極，於電流密度5A/dm2 、液溫50℃下進行15秒電鍍而形成者，Cu鍍層則係於含110g/L之硫酸銅與100g/L之硫酸的Cu鍍液中，以鍍Ni完畢之被鍍敷材為陰極且以Cu電極板為陽極，在電流密度5A/dm2 、液溫30℃下進行12秒電鍍而形成者。[Example 7] After the pre-treatment and before the formation of the Sn plating layer, a Ni plating layer having a thickness of 0.3 μm was formed on the substrate, and then a Cu plating layer having a thickness of 0.3 μm was formed, and then the plating time was set to 14 seconds to form a thickness of 0.7. A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 1 except that the Sn plating layer of μm was used. Further, the Ni plating layer is applied to a Ni-containing liquid containing 80 g/L of nickel sulfamate and 45 g/L of boric acid, and the substrate (the plated material) after the pretreatment is a cathode and the Ni electrode plate is used as an anode. It was formed by electroplating for 15 seconds at a current density of 5 A/dm 2 and a liquid temperature of 50 ° C. The Cu plating layer was formed in a Cu plating solution containing 110 g/L of copper sulfate and 100 g/L of sulfuric acid to complete Ni plating. The plated material was a cathode, and the Cu electrode plate was used as an anode, and was formed by electroplating for 12 seconds at a current density of 5 A/dm 2 and a liquid temperature of 30 °C.

以與實施例1相同之方法分析該迴流處理後之Sn鍍敷材，結果確認了Sn鍍敷材之基材表面形成有Ni層與(由Cu-Sn合金構成之)Cu-Sn合金層，該Cu-Sn合金層表面則形成有由Sn構成之Sn層。另，Cu鍍層之Cu因迴流處理而擴散成Cu-Sn合金層，Cu層則未觀察到。又，以與實施例1相同之方法測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.4μm。此外，以螢光X射線膜厚計(Seiko Instruments Inc.製)測定Ni層之厚度，結果為0.3μm。The Sn plating material after the reflow treatment was analyzed in the same manner as in Example 1. As a result, it was confirmed that a Ni layer and a Cu-Sn alloy layer (consisting of Cu-Sn alloy) were formed on the surface of the substrate of the Sn plating material. On the surface of the Cu-Sn alloy layer, an Sn layer made of Sn is formed. Further, Cu of the Cu plating layer was diffused into a Cu-Sn alloy layer by reflow treatment, and the Cu layer was not observed. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured in the same manner as in Example 1. As a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.4 μm. Further, the thickness of the Ni layer was measured by a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.) and found to be 0.3 μm.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 1. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long. 192 hours or more, good corrosion resistance.

[實施例8] 使用由50mm×50mm×0.25mm大小之Cu-Zn合金構成之平板狀導體基材(含30質量%之Zn且殘餘部分為Cu之銅合金C2600之基材)，於前置處理後且於形成Sn鍍層前，在基材上形成厚度1.0μm之Cu鍍層，除此之外以與實施例1相同之方法製出形成有Zn鍍層之Sn鍍敷材。另，上述Cu鍍層係於含110g/L之硫酸銅與100g/L之硫酸的Cu鍍液中，以基材為陰極且以Cu電極板為陽極，在電流密度5A/dm2 、液溫30℃下進行電鍍40秒而形成者。[Example 8] A flat conductor substrate composed of a Cu-Zn alloy of 50 mm × 50 mm × 0.25 mm (a substrate containing 30% by mass of Zn and a copper alloy C2600 having a residual portion) was used in the front. After the treatment, a Cu plating layer having a thickness of 1.0 μm was formed on the substrate before the formation of the Sn plating layer, and a Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 1. Further, the Cu plating layer is used in a Cu plating solution containing 110 g/L of copper sulfate and 100 g/L of sulfuric acid, and the substrate is used as a cathode and the Cu electrode plate is used as an anode at a current density of 5 A/dm 2 and a liquid temperature of 30 The plating was carried out at ° C for 40 seconds.

以與實施例1相同之方法分析該迴流處理後之Sn鍍敷材，結果確認了Sn鍍敷材之基材表面形成有Cu層與(由Cu-Sn合金構成之)Cu-Sn合金層，該Cu-Sn合金層表面則形成有由Sn構成之Sn層。又，以與實施例1相同之方法測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm。此外，以電解式膜厚計(中央製作所股份有限公司製Thickness Tester TH-11)測定Cu層之厚度，結果為0.7μm。The Sn plating material after the reflow treatment was analyzed in the same manner as in Example 1. As a result, it was confirmed that a Cu layer and a Cu-Sn alloy layer (consisting of Cu-Sn alloy) were formed on the surface of the substrate of the Sn plating material. On the surface of the Cu-Sn alloy layer, an Sn layer made of Sn is formed. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured in the same manner as in Example 1. As a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.7 μm. Further, the thickness of the Cu layer was measured by an electrolytic film thickness meter (Thickness Tester TH-11 manufactured by Konica Minolta Co., Ltd.) and found to be 0.7 μm.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 1. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long. 192 hours or more, good corrosion resistance.

[比較例1] 迴流處理後之Sn鍍敷材不進行電解脫脂與酸洗，而未於Sn鍍敷材表面形成Ni鍍層及Zn鍍層，除此之外以與實施例1相同之方法製出Sn鍍敷材。[Comparative Example 1] The Sn plating material after the reflow treatment was produced in the same manner as in Example 1 except that the electrolytic coating was not subjected to electrolytic degreasing and pickling, and the Ni plating layer and the Zn plating layer were not formed on the surface of the Sn plating material. Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行耐蝕性評價，結果，至發生氣體為止之時間短至2小時，耐蝕性差。The corrosion resistance of the Sn plating material thus produced was evaluated in the same manner as in Example 1. As a result, the time until the gas generation was as short as 2 hours, and the corrosion resistance was inferior.

[比較例2] 迴流處理後之Sn鍍敷材不進行電解脫脂與酸洗，而未於Sn鍍敷材表面形成Ni鍍層，除此之外以與實施例1相同之方法製出Sn鍍敷材。[Comparative Example 2] Sn plating was performed in the same manner as in Example 1 except that the Sn plating material after the reflow treatment was not subjected to electrolytic degreasing and pickling, and a Ni plating layer was not formed on the surface of the Sn plating material. material.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行(初期之)密著性評價，結果，雖然山摺彎曲加工部未有Zn鍍層剝離，但如圖4A及圖4B所示，經模具刮擦之直線部與谷摺彎曲加工部則有Zn鍍層剝離，密著性不佳。With respect to the Sn plating material thus produced, the (initial) adhesion evaluation was carried out in the same manner as in Example 1. As a result, although the Zn plating layer was not peeled off in the mountain bending portion, as shown in FIGS. 4A and 4B It is shown that the straight portion and the valley bending portion which are scraped by the mold are peeled off by the Zn plating layer, and the adhesion is poor.

[比較例3] 除未於Sn鍍敷材表面形成Ni鍍層之外，以與實施例1相同之方法製出Sn鍍敷材。[Comparative Example 3] An Sn plating material was produced in the same manner as in Example 1 except that the Ni plating layer was not formed on the surface of the Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行(初期之)密著性評價，結果，雖然山摺彎曲加工部未有Zn鍍層剝離，但經模具刮擦之直線部與谷摺彎曲加工部則有Zn鍍層剝離，密著性不佳。With respect to the Sn plating material thus produced, the (initial) adhesion evaluation was carried out in the same manner as in Example 1. As a result, although the Zn plating layer was not peeled off in the mountain bending portion, the straight portion was scraped by the mold. The Zn plating layer is peeled off from the valley bending portion, and the adhesion is poor.

[比較例4] 令電鍍時間為290秒而在Sn鍍敷材上形成厚度10μm之Ni鍍層，除此之外以與實施例1相同之方法製出形成有Zn之Sn鍍敷材。[Comparative Example 4] A Sn-plated material on which Zn was formed was produced in the same manner as in Example 1 except that the plating time was 290 seconds and a Ni plating layer having a thickness of 10 μm was formed on the Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例1相同之方法進行(初期之)密著性評價，結果，雖然山摺彎曲加工部未有Zn鍍層剝離，但經模具刮擦之直線部與谷摺彎曲加工部則有Zn鍍層剝離，密著性不佳。With respect to the Sn plating material thus produced, the (initial) adhesion evaluation was carried out in the same manner as in Example 1. As a result, although the Zn plating layer was not peeled off in the mountain bending portion, the straight portion was scraped by the mold. The Zn plating layer is peeled off from the valley bending portion, and the adhesion is poor.

茲將該等實施例及比較例之Sn鍍敷材的製造條件及特性示於表1~表3。另，於表3中，密著性良好時以○表示，有剝離現象而密著性不佳時則以×表示。The manufacturing conditions and characteristics of the Sn plating materials of the examples and the comparative examples are shown in Tables 1 to 3. In addition, in Table 3, when the adhesion is good, it is represented by ○, and when there is a peeling phenomenon and the adhesion is poor, it is represented by ×.

[表1] [Table 1]

[表2] [Table 2]

[表3] [table 3]

[實施例9] 首先，準備50mm×50mm×0.25mm大小且由Cu-Ni-Sn-P合金構成之平板狀導體基材(含1.0質量%之Ni、0.9質量%之Sn與0.05質量%之P且殘餘部分為Cu之銅合金基材)(DOWA METALTECH Co.,Ltd.製NB-109EH)。[Example 9] First, a flat conductor substrate composed of a Cu-Ni-Sn-P alloy having a size of 50 mm × 50 mm × 0.25 mm (containing 1.0% by mass of Ni, 0.9% by mass of Sn and 0.05% by mass) was prepared. P and the residual portion is a copper alloy substrate of Cu) (NB-109EH manufactured by DOWA METALTECH Co., Ltd.).

其次，就前置處理而言，將基材(被鍍敷材)以鹼性電解脫脂液進行10秒電解脫脂後進行水洗，之後，浸漬於100g/L之硫酸，酸洗後水洗。Next, in the pretreatment, the substrate (plated material) was electrolytically degreased in an alkaline electrolytic degreasing liquid for 10 seconds, and then washed with water, and then immersed in 100 g/L of sulfuric acid, pickled, and washed with water.

接著，於含有60g/L之硫酸錫(II)、75g/L之硫酸、30g/L之甲酚磺酸與1g/L之β萘酚之Sn鍍液中，以基材為陰極，Sn電極板為陽極，於電流密度5A/dm2 、液溫25℃下進行20秒電鍍，藉此於基材表面形成厚度1μm之Sn鍍層，獲得Sn鍍敷材。Next, in a Sn plating solution containing 60 g/L of tin (II) sulfate, 75 g/L of sulfuric acid, 30 g/L of cresolsulfonic acid and 1 g/L of β-naphthol, the substrate is used as a cathode, and the Sn electrode is used. The plate was an anode, and electroplating was carried out for 20 seconds at a current density of 5 A/dm 2 and a liquid temperature of 25 ° C to form a Sn plating layer having a thickness of 1 μm on the surface of the substrate to obtain a Sn plating material.

接著，將所得Sn鍍敷材洗淨乾燥後，進行熱處理(迴流處理)。該迴流處理係於2個近紅外線加熱器(HYBEC CORPORATION.製HYP-8N，額定電壓100V，額定功率560W，平行照射型)以間隔25mm對向配置，並將Sn鍍敷材配置於該等近紅外線加熱器之中央部位，令設定電流值為10.8A，於大氣環境下加熱Sn鍍敷材13秒使Sn鍍層表面熔融後，立刻浸漬於25℃水槽內冷卻。Next, the obtained Sn plating material is washed and dried, and then subjected to heat treatment (reflow treatment). The reflow treatment was carried out in two near-infrared heaters (HYP-8N, manufactured by HYBEC CORPORATION, rated voltage: 100 V, rated power: 560 W, parallel illumination type) at an interval of 25 mm, and Sn plating materials were placed in the vicinity. In the center of the infrared heater, the set current value was 10.8 A, and the Sn plating material was heated in an atmosphere for 13 seconds to melt the surface of the Sn plating layer, and then immersed in a 25 ° C water tank for cooling.

以聚焦離子束(FIB)切斷該迴流處理後之Sn鍍敷材，使與Sn鍍敷材之軋延方向呈垂直之截面露出，並以電場放射型歐傑電子能譜分析裝置(FE-AES)分析該截面。結果，確認了Sn鍍敷材之基材表面形成有Cu-Sn合金所構成之Cu-Sn合金層，且該Cu-Sn合金層表面形成有由Sn構成之Sn層。此外，以電解式膜厚計(中央製作所股份有限公司製Thickness Tester TH-11)測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm。The Sn plating material after the reflow treatment is cut by a focused ion beam (FIB), and a cross section perpendicular to the rolling direction of the Sn plating material is exposed, and an electric field emission type Auger electron spectroscopy analyzer (FE- AES) analyzes the section. As a result, it was confirmed that a Cu-Sn alloy layer composed of a Cu-Sn alloy was formed on the surface of the substrate of the Sn plating material, and a Sn layer made of Sn was formed on the surface of the Cu-Sn alloy layer. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured by an electrolytic film thickness meter (Thickness Tester TH-11 manufactured by Konica Minolta Co., Ltd.), and as a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.7 μm.

接著，將膠帶貼附於迴流處理後之Sn鍍敷材之一側面的全面上將之遮蔽後，將該Sn鍍敷材浸漬於40g/L之氫氧化鈉水溶液並以10A/dm2 進行30秒電解脫脂，再浸漬於100g/L硫酸120秒，酸洗後進行水洗。Next, the tape was attached to the entire surface of one side of the Sn plating material after the reflow treatment, and then the Sn plating material was immersed in a 40 g/L sodium hydroxide aqueous solution and carried out at 10 A/dm 2 . The solution was electrolytically degreased, immersed in 100 g/L of sulfuric acid for 120 seconds, and washed with water after washing.

接著，於含有80g/L之胺磺酸鎳及50g/L之硼酸的Ni鍍浴(胺磺酸浴)中，以(已於一側面之全面上貼附膠帶遮蔽之)Sn鍍敷材為陰極，並以Ni電極板為陽極，於電流密度10A/dm2 、液溫50℃下進行電鍍6秒，藉此，於Sn鍍敷材之另一面上形成Ni鍍層。以螢光X射線膜厚計(Seiko Instruments Inc.製)測定該Ni鍍層之厚度，結果為0.2μm。Next, in a Ni plating bath (amine sulfonic acid bath) containing 80 g/L of nickel sulfamate and 50 g/L of boric acid, the Sn plating material (which has been covered with a tape on one side) is The cathode was plated with a Ni electrode plate as an anode at a current density of 10 A/dm 2 and a liquid temperature of 50 ° C for 6 seconds, whereby a Ni plating layer was formed on the other surface of the Sn plating material. The thickness of the Ni plating layer was measured by a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.) and found to be 0.2 μm.

其次，於由含有200g/L之硫酸鋅與30g/L之硫酸銨之水溶液所形成之Zn鍍浴(硫酸浴)中，以(於一面之全面上貼附膠帶遮蔽之)鍍Ni後之Sn鍍敷材為陰極，以Zn電極板為陽極，於電流密度20A/dm2 、液溫50℃下進行30秒電鍍，藉此於已形成在Sn鍍敷材另一面之Ni鍍層的表面上形成Zn鍍層。以螢光X射線膜厚計(Seiko Instruments Inc.製)測定該Zn鍍層之厚度，結果為3μm。Next, in a Zn plating bath (sulfuric acid bath) formed of an aqueous solution containing 200 g/L of zinc sulfate and 30 g/L of ammonium sulfate, Sn coated with Ni (masked on one side of the entire surface) plated sheet as a cathode and an anode electrode plate Zn, plating for 30 seconds at 20A / dm 2, a liquid temperature of 50 deg.] C to a current density, to thereby formed on the surface of the formed sheet Sn plating the other surface of the Ni plating layer Zn plating. 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.

以聚焦離子束(FIB)加工觀察裝置將已如前述般形成Zn鍍層之Sn鍍敷材切斷，使Sn鍍敷材之與軋延方向垂直之截面露出，再以電界放射型歐傑電子能譜分析裝置(FE-AES)分析該截面。結果，確定了Sn鍍敷材之基材表面形成有Cu-Sn合金構成之Cu-Sn合金層，且該Cu-Sn合金層表面形成有Sn構成之Sn層，該Sn層表面形成有Ni鍍層，該Ni鍍層表面則形成有Zn鍍層。此外，從掃描離子顯微鏡像(SIM像)測定該等層之厚度，確認了Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm，Ni鍍層之厚度為0.2μm，Zn鍍層之厚度為3μm。The Sn plating material which has formed the Zn plating layer as described above is cut by a focused ion beam (FIB) processing observation apparatus, and the cross section perpendicular to the rolling direction of the Sn plating material is exposed, and then the electric radiation type Auger electron energy is used. The cross section was analyzed by a spectral analysis device (FE-AES). As a result, it was confirmed that a Cu-Sn alloy layer composed of a Cu-Sn alloy was formed on the surface of the substrate of the Sn plating material, and a Sn layer composed of Sn was formed on the surface of the Cu-Sn alloy layer, and a Ni plating layer was formed on the surface of the Sn layer. A Zn plating layer is formed on the surface of the Ni plating layer. Further, the thickness of the layers was measured from a scanning ion microscope image (SIM image), and it was confirmed that 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 was 0.2 μm, and the thickness of the Zn plating layer was The thickness is 3 μm.

此外，對截取自形成有Zn鍍層之Sn鍍敷材且30mm×10mm×0.25mm大小之試驗片施加10kN之荷重，以最小彎曲半徑R與板厚t之比R/t會成為1.0之方式施行遵照JIS H3110之90°W彎曲，將該試驗片埋入樹脂後，朝對試驗片之長向呈平行之方向(相對於90°W彎曲之彎曲軸呈垂直方向)切斷，並以雷射顯微鏡(KEYENCE CORPORATION.製VK-X100)放大該截面，觀察經模具刮擦之直線部、谷摺彎曲加工部與山摺彎曲加工部，並以目測評價Zn鍍層有無剝離。結果，任一部分皆無Zn鍍層剝離，密著性(初期密著性)良好。Further, a load of 10 kN was applied to a test piece of a size of 30 mm × 10 mm × 0.25 mm taken from a Sn plating material on which a Zn plating layer was formed, and the ratio R/t of the minimum bending radius R to the thickness t was 1.0. According to the 90°W bending of JIS H3110, the test piece is embedded in the resin, and is cut in a direction parallel to the longitudinal direction of the test piece (vertical direction with respect to the bending axis of the 90° W bending), and is laser-exposed. A microscope (VK-X100 manufactured by KEYENCE CORPORATION) was used to enlarge the cross section, and the straight portion, the valley bending portion, and the mountain bending portion which were scraped by the mold were observed, and the presence or absence of peeling of the Zn plating layer was visually evaluated. As a result, no part of the Zn plating layer was peeled off, and the adhesion (initial adhesion) was good.

此外，以截取自已形成Zn鍍層之Sn鍍敷材且50mm×10mm×0.25mm大小之試驗片的Zn鍍層為外側，並以該Sn鍍敷材將直徑0.8mm、長度30mm之純鋁單線(A1070)歛縫後，浸漬於5質量%之NaCl水溶液中，並以電蝕(卑金屬會發生溶解之異種金屬接觸腐蝕)所引起之氣體發生時間來評價耐蝕性。結果，至發生氣體為止之時間長達192時間以上，耐食性良好。Further, a Zn plating layer of a test piece of a size of 50 mm × 10 mm × 0.25 mm which was cut out from a Sn plating material having a Zn plating layer was taken as an outer side, and a pure aluminum single wire having a diameter of 0.8 mm and a length of 30 mm was used as the Sn plating material (A1070). After the caulking, the corrosion resistance was evaluated by immersing in a 5 mass% NaCl aqueous solution and gas generation time caused by electrolytic etching (contact metal corrosion in which the metal was dissolved). As a result, the time until the gas generation was as long as 192 times or longer, and the food resistance was good.

此外，使用微小維氏硬度計(Mitutoyo Corporation.製HM-200)，並令測定荷重為0.005kgf，遵照JIS Z2244來測定形成有Zn鍍層之Sn鍍敷材之表面維氏硬度HV，結果為HV55。Further, a Vickers hardness HV of the surface of the Sn plating material on which the Zn plating layer was formed was measured in accordance with JIS Z2244 using a micro Vickers hardness tester (HM-200, manufactured by Mitutoyo Corporation) and a measurement load of 0.005 kgf, and the result was HV55. .

又，就形成有Zn鍍層之Sn鍍敷材之表面粗度而言，從接觸式表面粗度計(小坂研究所股份有限公司製SURFCORDER SE4000)所測得之結果，遵照JIS B0601算出顯示表面粗度之參數，即算術平均粗度Ra，結果，形成有Zn鍍層之Sn鍍敷材的算術平均粗度Ra為0.14μm。In addition, the surface roughness of the Sn plating material in which the Zn plating layer was formed was calculated from the contact surface roughness meter (SURFCORDER SE4000 manufactured by Otaru Research Co., Ltd.), and the display surface was calculated in accordance with JIS B0601. The parameter of the degree, that is, the arithmetic mean roughness Ra, as a result, the arithmetic mean roughness Ra of the Sn plating material on which the Zn plating layer was formed was 0.14 μm.

此外，就形成Zn鍍層之Sn鍍敷材的光澤度而言，使用光澤度計(SAKATA INX CORPORATION.製RD918)測定視感反射濃度，結果光澤度為0.15。In addition, the glossiness of the Sn plating material on which the Zn plating layer was formed was measured by using a gloss meter (RD918 manufactured by SAKATA INX CORPORATION), and the glossiness was 0.15.

此外，對截取自形成有Zn鍍層之Sn鍍敷材且30mm×10mm×0.25mm大小之試驗片施加10kN之荷重，以最小彎曲半徑R與板厚t之比R/t會成為1.0之方式施行遵照JIS H3110之90°W彎曲，並以雷射顯微鏡(KEYENCE CORPORATION.製VK-X100)放大觀察山摺彎曲加工部之表面。茲將其顯微鏡照片顯示於圖5。圖5所示，確認了山摺彎曲加工部表面並未發生深度皺痕。又，使用雷射顯微鏡(KEYENCE CORPORATION.製VK-X100)(截止值0.08mm)算出山摺彎曲加工部表面之算術平均粗度Ra，結果為0.7μm。另，該山摺彎曲加工部表面之算術平均粗度Ra宜在1.7μm以下，更宜為1.5μm以下。Further, a load of 10 kN was applied to a test piece of a size of 30 mm × 10 mm × 0.25 mm taken from a Sn plating material on which a Zn plating layer was formed, and the ratio R/t of the minimum bending radius R to the thickness t was 1.0. The surface of the mountain bending portion was observed by a laser microscope (VK-X100 manufactured by KEYENCE CORPORATION) in accordance with the 90°W bending of JIS H3110. A photo of the microscope is shown in Figure 5. As shown in Fig. 5, it was confirmed that deep wrinkles did not occur on the surface of the mountain bending portion. Further, the arithmetic mean roughness Ra of the surface of the mountain bending portion was calculated using a laser microscope (VK-X100, manufactured by KEYENCE CORPORATION) (cutoff value: 0.08 mm), and found to be 0.7 μm. Further, the arithmetic mean roughness Ra of the surface of the mountain bent portion is preferably 1.7 μm or less, more preferably 1.5 μm or less.

[實施例10] 除了將電鍍時間設為420秒而將Zn鍍層之厚度製成40μm之外，以與實施例9相同方法製出形成有Zn鍍層之Sn鍍敷材。[Example 10] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the plating time was 420 seconds and the thickness of the Zn plating layer was 40 μm.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為51，算術平均粗度Ra為1.2μm，光澤度為0.12，山摺彎曲加工部表面之算術平均粗度Ra為1.2μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 192 hours or more, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the beveled portion of the Sn plating material were obtained, and as a result, the Vickers hardness HV was 51, and the arithmetic mean roughness Ra was obtained. The thickness was 1.2 μm, the gloss was 0.12, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 1.2 μm.

[實施例11] 除了將電鍍時間設為10秒而將Zn鍍層之厚度製成1μm之外，以與實施例9相同方法製出形成有Zn鍍層之Sn鍍敷材。[Example 11] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the plating time was set to 10 seconds and the thickness of the Zn plating layer was set to 1 μm.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達144小時，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為62.5，算術平均粗度Ra為0.11μm，光澤度為0.17，山摺彎曲加工部表面之算術平均粗度Ra為1.0μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 144 hours, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the mountain bending portion were obtained, and the Vickers hardness HV was 62.5, and the arithmetic mean roughness Ra was obtained. The thickness was 0.11 μm, the gloss was 0.17, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 1.0 μm.

[實施例12] 除了將電鍍時間設為90秒而於Sn鍍敷材上形成厚度3μm之Ni鍍層之外，以與實施例9相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 12] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the plating time was 90 seconds and a Ni plating layer having a thickness of 3 μm was formed on the Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為55，算術平均粗度Ra為0.14μm，光澤度為0.15，山摺彎曲加工部表面之算術平均粗度Ra為0.7μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 192 hours or more, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the beveled portion of the Sn plating material were obtained, and as a result, the Vickers hardness HV was 55, and the arithmetic mean roughness Ra was obtained. The thickness was 0.14 μm, the gloss was 0.15, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 0.7 μm.

[實施例13] 除了將電鍍時間設為3秒而於Sn鍍敷材上形成厚度0.1μm之Ni鍍層之外，以與實施例9相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Example 13] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the plating time was set to 3 seconds to form a Ni plating layer having a thickness of 0.1 μm on the Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為55，算術平均粗度Ra為0.14μm，光澤度為0.15，山摺彎曲加工部表面之算術平均粗度Ra為0.7μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 192 hours or more, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the beveled portion of the Sn plating material were obtained, and as a result, the Vickers hardness HV was 55, and the arithmetic mean roughness Ra was obtained. The thickness was 0.14 μm, the gloss was 0.15, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 0.7 μm.

[實施例14] 使用50mm×50mm×0.25mm大小且由Cu-Zn合金構成之平板狀導體基材(含30質量%之Zn且殘餘部分為Cu之銅合金C2600之基材)，於前置處理後且於形成Sn鍍層前，於基材上形成厚度0.6μm之Cu鍍層，除此之外，以與實施例9相同之方法製出形成有Zn鍍層之Sn鍍敷材。另，上述Cu鍍層係於含110g/L之硫酸銅與100g/L之硫酸的Cu鍍液中，以基材為陰極且以Cu電極板為陽極，於電流密度5A/dm2 、液溫30℃下進行40秒電鍍而形成者。[Example 14] A flat conductor substrate composed of a Cu-Zn alloy (a base material containing 30% by mass of Zn and a residual portion of Cu alloy C2600) was used in front of a 50 mm × 50 mm × 0.25 mm size. After the treatment, a Cu plating layer having a thickness of 0.6 μm was formed on the substrate before the formation of the Sn plating layer, and a Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9. Also, in the Cu-based Cu plating bath containing 110g / L of copper sulfate 100g / L of sulfuric acid, to the substrate as a cathode and an anode electrode plate to Cu, the current density of 5A / dm 2, a liquid temperature of 30 It was formed by plating for 40 seconds at °C.

以與實施例9相同之方法分析該迴流處理後之Sn鍍敷材，結果確認了Sn鍍敷材之基材表面形成有Cu層與(由Cu-Sn合金構成之)Cu-Sn合金層，該Cu-Sn合金層表面則形成有由Sn構成之Sn層。又，以與實施例9相同之方法測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.7μm。此外，以電解式膜厚計(中央製作所股份有限公司製Thickness Tester TH-11)測定Cu層之厚度，結果為0μm。The Sn plating material after the reflow treatment was analyzed in the same manner as in Example 9. As a result, it was confirmed that a Cu layer and a Cu-Sn alloy layer (consisting of a Cu-Sn alloy) were formed on the surface of the substrate of the Sn plating material. On the surface of the Cu-Sn alloy layer, an Sn layer made of Sn is formed. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured in the same manner as in Example 9. As a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.7 μm. Further, the thickness of the Cu layer was measured by an electrolytic film thickness meter (Thickness Tester TH-11 manufactured by Konica Minolta Co., Ltd.), and it was 0 μm.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為55，算術平均粗度Ra為0.14μm，光澤度為0.15，山摺彎曲加工部表面之算術平均粗度Ra為0.7μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 192 hours or more, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the beveled portion of the Sn plating material were obtained, and as a result, the Vickers hardness HV was 55, and the arithmetic mean roughness Ra was obtained. The thickness was 0.14 μm, the gloss was 0.15, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 0.7 μm.

[實施例15] 於前置處理後且於形成Sn鍍層前，於基材上形成厚度0.3μm之Ni鍍層，之後形成厚度0.3μm之Cu鍍層後，將電鍍時間設成14秒，形成厚度0.7μm之Sn鍍層，除此之外，以與實施例9相同之方法製出形成有Zn鍍層之Sn鍍敷材。另，上述Ni鍍層係於含80g/L之胺磺酸鎳及45g/L之硼酸之Ni渡液中，以前置處理後之基材(被鍍敷材)為陰極且以Ni電極板為陽極，於電流密度5A/dm2 、液溫50℃下進行15秒電鍍而形成者，Cu鍍層則係於含110g/L之硫酸銅與100g/L之硫酸的Cu鍍液中，以鍍Ni完畢之被鍍敷材為陰極且以Cu電極板為陽極，在電流密度5A/dm2 、液溫30℃下進行12秒電鍍而形成者。[Example 15] After the pre-treatment and before the formation of the Sn plating layer, a Ni plating layer having a thickness of 0.3 μm was formed on the substrate, and then a Cu plating layer having a thickness of 0.3 μm was formed, and then the plating time was set to 14 seconds to form a thickness of 0.7. A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the Sn plating layer of μm was used. Further, the Ni plating layer is used in a Ni-containing liquid containing 80 g/L of nickel sulfamate and 45 g/L of boric acid, and the substrate (the plated material) after the pretreatment is a cathode and the Ni electrode plate is used as an anode. It was formed by electroplating for 15 seconds at a current density of 5 A/dm 2 and a liquid temperature of 50 ° C. The Cu plating layer was formed in a Cu plating solution containing 110 g/L of copper sulfate and 100 g/L of sulfuric acid to complete Ni plating. The plated material was a cathode, and the Cu electrode plate was used as an anode, and was formed by electroplating for 12 seconds at a current density of 5 A/dm 2 and a liquid temperature of 30 °C.

以與實施例9相同之方法分析該迴流處理後之Sn鍍敷材，結果確認了Sn鍍敷材之基材表面形成有Ni層與(由Cu-Sn合金構成之)Cu-Sn合金層，該Cu-Sn合金層表面則形成有由Sn構成之Sn層。另，Cu鍍層之Cu因迴流處理而擴散成Cu-Sn合金層，Cu層則未觀察到。又，以與實施例9相同之方法測定Cu-Sn合金層與Sn層之厚度，結果Cu-Sn合金層之厚度為0.6μm，Sn層之厚度為0.4μm。此外，以螢光X射線膜厚計(Seiko Instruments Inc.製)測定Ni層之厚度，結果為0.3μm。The Sn plating material after the reflow treatment was analyzed in the same manner as in Example 9. As a result, it was confirmed that a Ni layer and a Cu-Sn alloy layer (consisting of a Cu-Sn alloy) were formed on the surface of the substrate of the Sn plating material. On the surface of the Cu-Sn alloy layer, an Sn layer made of Sn is formed. Further, Cu of the Cu plating layer was diffused into a Cu-Sn alloy layer by reflow treatment, and the Cu layer was not observed. Further, the thickness of the Cu-Sn alloy layer and the Sn layer was measured in the same manner as in Example 9. As a result, the thickness of the Cu-Sn alloy layer was 0.6 μm, and the thickness of the Sn layer was 0.4 μm. Further, the thickness of the Ni layer was measured by a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.) and found to be 0.3 μm.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性與耐蝕性之評價，結果，無Zn鍍層剝離，密著性良好，此外，至發生氣體為止之時間長達192小時以上，耐蝕性良好。又，求出該Sn鍍敷材之維氏硬度HV、算術平均粗度Ra、光澤度及山摺彎曲加工部表面之算術平均粗度Ra，結果維氏硬度HV為55，算術平均粗度Ra為0.14μm，光澤度為0.15，山摺彎曲加工部表面之算術平均粗度Ra為0.7μm。With respect to the Sn plating material thus produced, adhesion and corrosion resistance were evaluated in the same manner as in Example 9. As a result, the Zn-free plating layer was peeled off, the adhesion was good, and the time until the gas generation was long 192 hours or more, good corrosion resistance. Further, the Vickers hardness HV, the arithmetic mean roughness Ra, the glossiness, and the arithmetic mean roughness Ra of the surface of the beveled portion of the Sn plating material were obtained, and as a result, the Vickers hardness HV was 55, and the arithmetic mean roughness Ra was obtained. The thickness was 0.14 μm, the gloss was 0.15, and the arithmetic mean roughness Ra of the surface of the mountain bent portion was 0.7 μm.

[比較例5] 迴流處理後之Sn鍍敷材不進行電解脫脂與酸洗，而未於Sn鍍敷材表面形成Ni鍍層及Zn鍍層，除此之外以與實施例9相同之方法製出Sn鍍敷材。[Comparative Example 5] The Sn plating material after the reflow treatment was produced in the same manner as in Example 9 except that electrolytic degreasing and pickling were not performed, and a Ni plating layer and a Zn plating layer were not formed on the surface of the Sn plating material. Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行耐蝕性評價，結果，至發生氣體為止之時間極短僅24小時，耐蝕性差。The corrosion resistance of the Sn plating material thus produced was evaluated in the same manner as in Example 9. As a result, the time until the gas generation was extremely short was only 24 hours, and the corrosion resistance was inferior.

[比較例6] 除未於Sn鍍敷材表面形成Ni鍍層之外，以與實施例9相同之方法製作出Sn鍍敷材。[Comparative Example 6] A Sn plating material was produced in the same manner as in Example 9 except that the Ni plating layer was not formed on the surface of the Sn plating material.

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性評價，結果，雖然山摺彎曲加工部未有Zn鍍層剝離，但經模具刮擦之直線部與谷摺彎曲加工部則有Zn鍍層剝離，密著性不佳。The Sn plating material produced in this manner was evaluated for adhesion in the same manner as in Example 9. As a result, although the Zn plating layer was not peeled off in the mountain bending portion, the straight portion and the valley bent by the mold were bent. In the processed portion, the Zn plating layer is peeled off, and the adhesion is poor.

[比較例7] 將電鍍時間設成290秒而在Sn鍍敷材上形成厚度10μm之Ni鍍層，除此之外，以與實施例9相同之方法製出形成有Zn鍍層之Sn鍍敷材。[Comparative Example 7] A Sn plating material on which a Zn plating layer was formed was produced in the same manner as in Example 9 except that the plating time was set to 290 seconds to form a Ni plating layer having a thickness of 10 μm on the Sn plating material. .

針對如此製出之Sn鍍敷材，以與實施例9相同之方法進行密著性評價，結果，雖然山摺彎曲加工部未有Zn鍍層剝離，但經模具刮擦之直線部與谷摺彎曲加工部則有Zn鍍層剝離，密著性不佳。The Sn plating material produced in this manner was evaluated for adhesion in the same manner as in Example 9. As a result, although the Zn plating layer was not peeled off in the mountain bending portion, the straight portion and the valley bent by the mold were bent. In the processed portion, the Zn plating layer is peeled off, and the adhesion is poor.

茲將該等實施例及比較例之Sn鍍敷材之製造條件及特性顯示於表4~表6。另，於表6中，密著性良好時以○表示，有剝離現象而密著性不佳時則以×表示。The manufacturing conditions and characteristics of the Sn plating materials of the examples and the comparative examples are shown in Tables 4 to 6. In addition, in Table 6, when the adhesion is good, it is represented by ○, and when there is a peeling phenomenon and the adhesion is not good, it is represented by ×.

[表4] [Table 4]

[表5] [table 5]

[表6] [Table 6]

10‧‧‧基材10‧‧‧Substrate

12‧‧‧含Sn層12‧‧‧Sn layer

14‧‧‧Ni鍍層14‧‧‧Ni plating

16‧‧‧Zn鍍層16‧‧‧Zn coating

18‧‧‧基底層18‧‧‧ basal layer

121‧‧‧Cu-Sn合金層121‧‧‧Cu-Sn alloy layer

122‧‧‧Sn層122‧‧‧Sn layer

181‧‧‧Ni層181‧‧‧Ni layer

182‧‧‧Cu層182‧‧‧Cu layer

圖1係一截面圖，其概略顯示本發明之Sn鍍敷材之第1及第2實施形態。 圖2係一截面圖，其概略顯示本發明之Sn鍍敷材之第1及第2實施形態之變形例。 圖3A係截取自實施例1之Sn鍍敷材之試驗片於彎曲90°W後(經模具刮擦之)直線部的顯微鏡照片。 圖3B係截取自實施例1之Sn鍍敷材之試驗片於彎曲90°W後之谷摺彎曲加工部的顯微鏡照片。 圖4A係截取自比較例2之Sn鍍敷材之試驗片於彎曲90°W後(經模具刮擦之)直線部的顯微鏡照片。 圖4B係截取自比較例2之Sn鍍敷材之試驗片於彎曲90°W後之谷摺彎曲加工部的顯微鏡照片。 圖5係截取自實施例9之Sn鍍敷材之試驗片於彎曲90°W後之山摺彎曲加工部表面的顯微鏡照片。Fig. 1 is a cross-sectional view schematically showing first and second embodiments of the Sn plating material of the present invention. Fig. 2 is a cross-sectional view schematically showing a modification of the first and second embodiments of the Sn plating material of the present invention. Fig. 3A is a photomicrograph of a straight portion taken from a test piece of the Sn plating material of Example 1 after being bent at 90 °W (scratched by a mold). Fig. 3B is a micrograph of a valley bending portion of the test piece taken from the Sn plating material of Example 1 after bending at 90 °W. Fig. 4A is a photomicrograph of a straight portion taken from a test piece of the Sn plating material of Comparative Example 2 after being bent at 90 °W (scratched by a mold). 4B is a micrograph of a valley bending portion of the test piece taken out from the Sn plating material of Comparative Example 2 after bending at 90°W. Fig. 5 is a photomicrograph of the surface of the mountain bent portion after the test piece of the Sn plating material of Example 9 was cut at 90 °W.

Claims (15)

一種Sn鍍敷材，特徵在於其係於銅或銅合金所構成之基材表面形成有含Sn層者； 其中，含Sn層係由Cu-Sn合金層與Sn層構成，該Sn層係由形成在該Cu-Sn合金層表面之Sn構成且厚度5μm以下，含Sn層表面形成有Ni鍍層，且該Ni鍍層表面形成有Zn鍍層作為最表層。A Sn plating material characterized in that a Sn-containing layer is formed on a surface of a substrate composed of copper or a copper alloy; wherein the Sn-containing layer is composed of a Cu-Sn alloy layer and a Sn layer, and the Sn layer is composed of The surface of the Cu-Sn alloy layer is made of Sn and has a thickness of 5 μm or less. The surface of the Sn-containing layer is formed with a Ni plating layer, and the surface of the Ni plating layer is formed with a Zn plating layer as the outermost layer. 如請求項1之Sn鍍敷材，其中前述Cu-Sn合金層之厚度為0.2~2μm。The Sn plating material of claim 1, wherein the thickness of the Cu-Sn alloy layer is 0.2 to 2 μm. 如請求項1之Sn鍍敷材，其中前述Ni鍍層之厚度為0.01~5μm。The Sn plating material of claim 1, wherein the thickness of the Ni plating layer is 0.01 to 5 μm. 如請求項1之Sn鍍敷材，其中前述Zn鍍層之厚度為0.5~40μm。The Sn plating material of claim 1, wherein the Zn plating layer has a thickness of 0.5 to 40 μm. 如請求項1之Sn鍍敷材，其中前述基材與前述含Sn層之間形成有基底層。The Sn plating material of claim 1, wherein a base layer is formed between the substrate and the Sn-containing layer. 如請求項5之Sn鍍敷材，其中前述基底層係含有Cu及Ni中至少一者之層。The Sn plating material of claim 5, wherein the base layer contains a layer of at least one of Cu and Ni. 如請求項1之Sn鍍敷材，其僅於前述基材之一側表面之含Sn層表面上隔著Ni鍍層形成有Zn鍍層來作為最表層，前述基材另一側面之含Sn層則作為最表層來形成。The Sn plating material according to claim 1, wherein the Sn-containing layer is formed on the surface of the Sn-containing layer on one side surface of the substrate on the surface of the Sn-containing layer via the Ni plating layer as the outermost layer, and the Sn-containing layer on the other side of the substrate. It is formed as the outermost layer. 如請求項1之Sn鍍敷材，其中前述Zn鍍層之維氏硬度HV為80以下。The Sn plating material of claim 1, wherein the Zn plating layer has a Vickers hardness HV of 80 or less. 如請求項8之Sn鍍敷材，其中前述Zn鍍層表面之算術平均粗度Ra為0.1~3.0μm。The Sn plating material of claim 8, wherein the surface of the Zn plating layer has an arithmetic mean roughness Ra of 0.1 to 3.0 μm. 如請求項8之Sn鍍敷材，其中前述Zn鍍層表面之光澤度為1.2以下。The Sn plating material of claim 8, wherein the surface of the Zn plating layer has a gloss of 1.2 or less. 如請求項8之Sn鍍敷材，其中前述Ni鍍層形成於前述含Sn層之部分表面上。The Sn plating material of claim 8, wherein the Ni plating layer is formed on a portion of the surface of the Sn-containing layer. 一種Sn鍍敷材之製造方法，特徵在於： 於銅或銅合金所構成之基材表面形成Sn鍍層後，藉由熱處理形成含Sn層來製造鍍敷材，該含Sn層係由Cu-Sn合金層與Sn層構成，該Sn層係由形成在該Cu-Sn合金層表面之Sn構成； 並且，該製造方法係令Sn層之厚度在5μm以下，且於含Sn層表面形成Ni鍍層後，於該Ni鍍層表面形成Zn鍍層來作為最表層。A method for producing a Sn plating material, characterized in that: after forming a Sn plating layer on a surface of a substrate made of copper or a copper alloy, a Sn-containing layer is formed by heat treatment to produce a plating material consisting of Cu-Sn The alloy layer is composed of a Sn layer composed of Sn formed on the surface of the Cu-Sn alloy layer; and the manufacturing method is such that the thickness of the Sn layer is 5 μm or less and the Ni plating layer is formed on the surface of the Sn-containing layer. A Zn plating layer is formed on the surface of the Ni plating layer as the outermost layer. 如請求項12之Sn鍍敷材之製造方法，其中前述Zn鍍層係藉由在硫酸浴中進行電鍍而形成。The method for producing a Sn plating material according to claim 12, wherein the Zn plating layer is formed by electroplating in a sulfuric acid bath. 一種電線連接用端子，特徵在於其係一將Sn鍍敷材用作材料之連接端子，且該Sn鍍敷材係於銅或銅合金所構成之基材表面形成有含Sn層者，該含Sn層係由Cu-Sn合金層與Sn層構成，該Sn係由形成在該Cu-Sn合金層表面之Sn構成且厚度5μm以下；並且 該電線連接用端子係於其與電線連接之連接部以外的部分，在含Sn層表面形成有Ni鍍層，該Ni鍍層表面則形成有Zn鍍層。A terminal for connecting electric wires, characterized in that a Sn plating material is used as a connection terminal of a material, and the Sn plating material is formed on a surface of a substrate composed of copper or a copper alloy, and a Sn-containing layer is formed. The Sn layer is composed of a Cu-Sn alloy layer and a Sn layer composed of Sn formed on the surface of the Cu-Sn alloy layer and having a thickness of 5 μm or less; and the terminal for wire connection is connected to the connection portion with the electric wire. In the other portion, a Ni plating layer is formed on the surface of the Sn-containing layer, and a Zn plating layer is formed on the surface of the Ni plating layer. 如請求項14之電線連接用端子，其中前述Zn鍍層之維氏硬度HV為80以下。The terminal for electric wire connection of claim 14, wherein the Zn plating layer has a Vickers hardness HV of 80 or less.
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