JP2021091939A - Sn PLATING MATERIAL AND PRODUCTION METHOD THEREOF - Google Patents

Sn PLATING MATERIAL AND PRODUCTION METHOD THEREOF Download PDF

Info

Publication number
JP2021091939A
JP2021091939A JP2019223550A JP2019223550A JP2021091939A JP 2021091939 A JP2021091939 A JP 2021091939A JP 2019223550 A JP2019223550 A JP 2019223550A JP 2019223550 A JP2019223550 A JP 2019223550A JP 2021091939 A JP2021091939 A JP 2021091939A
Authority
JP
Japan
Prior art keywords
phase
layer
plating
plating material
outermost layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2019223550A
Other languages
Japanese (ja)
Other versions
JP7404053B2 (en
Inventor
雄太 笹井
Yuta Sakai
雄太 笹井
裕貴 ▲高▼橋
裕貴 ▲高▼橋
Hirotaka Takahashi
隆夫 冨谷
Takao Tomitani
隆夫 冨谷
宏人 成枝
Hiroto Narueda
宏人 成枝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dowa Metaltech Co Ltd
Original Assignee
Dowa Metaltech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dowa Metaltech Co Ltd filed Critical Dowa Metaltech Co Ltd
Priority to JP2019223550A priority Critical patent/JP7404053B2/en
Publication of JP2021091939A publication Critical patent/JP2021091939A/en
Application granted granted Critical
Publication of JP7404053B2 publication Critical patent/JP7404053B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Electroplating Methods And Accessories (AREA)

Abstract

To provide an Sn plating material with good corrosion resistivity having its surface of high reflection density and the production method thereof when the Sn plating material is used as a terminal material to be connected to an electric cable made of aluminum or aluminum alloy by crimping such as swaging.SOLUTION: An Ni plating film (preferably with an average thickness of 0.1-1.0 μm) is formed on the surface of a base material made of copper or copper alloy. A Zn plating film (preferably with an average thickness of 0.1-6.0 μm) is formed on the surface of the Ni plating film. An Sn plating film (preferably with an average thickness of 0.1-6.0 μm) on the surface of the Zn plating film. Afterwards, an outermost surface layer made of the Sn layer and a plurality of Zn layers is formed on the surface of the base material through the Ni layer by heating (or reflow treatment) at a temperature of the fusion point (232°C) of Sn or higher. Part of the Zn layer of the outermost surface layer is exposed to the surface of the outermost surface layer.SELECTED DRAWING: Figure 1

Description

本発明は、Ｓｎめっき材およびその製造方法に関し、特に、ワイヤーハーネスなどの電線に接続される端子などの材料として使用されるＳｎめっき材およびその製造方法に関する。 The present invention relates to a Sn plating material and a method for manufacturing the same, and more particularly to a Sn plating material used as a material such as a terminal connected to an electric wire such as a wire harness and a method for manufacturing the Sn plating material.

従来、車両用のワイヤーハーネスなどの電線として銅または銅合金からなる電線が使用され、その電線に接続される端子などの材料として、銅または銅合金にＳｎめっきを施したＳｎめっき材が使用されている。 Conventionally, an electric wire made of copper or a copper alloy is used as an electric wire such as a wire harness for a vehicle, and a Sn plating material obtained by Sn-plating copper or a copper alloy is used as a material such as a terminal connected to the electric wire. ing.

近年、車両の軽量化による燃費効率の向上のため、車両用のワイヤーハーネスなどの電線として、銅または銅合金より比重の小さいアルミニウムまたはアルミニウム合金からなる電線が使用されている。 In recent years, in order to improve fuel efficiency by reducing the weight of a vehicle, an electric wire made of aluminum or an aluminum alloy having a smaller specific gravity than copper or a copper alloy has been used as an electric wire such as a wire harness for a vehicle.

しかし、アルミニウムまたはアルミニウム合金からなる電線にＳｎめっき材からなる端子を加締めなどの圧着加工により接続すると、電位差の大きい異種金属の接触によるガルバニック腐食（卑な金属が溶解する異種金属接触腐食）が生じる可能性がある。 However, when a terminal made of Sn-plated material is connected to an electric wire made of aluminum or an aluminum alloy by crimping or other crimping process, galvanic corrosion (corrosion of dissimilar metals in which a base metal dissolves) occurs due to contact of dissimilar metals having a large potential difference. It can occur.

そのため、接続部分に防食剤や樹脂を塗布して異種金属接触腐食を防止しているが、生産性が低下し、製造コストが高くなる。 Therefore, an anticorrosive agent or a resin is applied to the connecting portion to prevent galvanic corrosion of dissimilar metals, but the productivity is lowered and the manufacturing cost is increased.

また、異種金属接触腐食を防止する端子として、電線の一端に露出した第一の金属（アルミニウム系材料）からなる芯線を加締め接続する芯線バレル部を有する電線接続部を備え、第一の金属よりもイオン化傾向が小さい第二の金属（銅系材料）により形成された端子であって、芯線バレル部が芯線を加締める前に、イオン化傾向が第一の金属と第二の金属の間である第三の金属（亜鉛）で電線接触部がめっき処理され、芯線バレル部における接続面のめっき層が加締め時に破壊される端子が提案されている（例えば、特許文献１参照）。 Further, as a terminal for preventing contact corrosion between dissimilar metals, a wire connecting portion having a core wire barrel portion for crimping and connecting a core wire made of a first metal (aluminum-based material) exposed at one end of the wire is provided, and the first metal. It is a terminal formed of a second metal (copper-based material) that has a lower ionization tendency than that of the first metal and the second metal before the core wire barrel crimps the core wire. A terminal has been proposed in which the wire contact portion is plated with a third metal (zinc) and the plating layer on the connecting surface in the core wire barrel portion is destroyed during crimping (see, for example, Patent Document 1).

また、銅又は銅合金からなる基材の上にニッケル含有率が５〜５０質量％の亜鉛ニッケル合金層を０．１〜５．０μｍの厚さで形成し、この亜鉛ニッケル合金層の上に錫めっきを施して錫層を形成した後、４０℃以上１６０℃以下で３０分以上保持して亜鉛ニッケル合金層の合金を錫層に拡散させることにより、錫めっき付き銅端子材を製造する方法が提案されている（例えば、特許文献２参照）。 Further, a zinc-based alloy layer having a nickel content of 5 to 50% by mass is formed on a base material made of copper or a copper alloy to a thickness of 0.1 to 5.0 μm, and the zinc-based alloy layer is placed on the zinc-nickel alloy layer. A method for producing a tin-plated copper terminal material by tin-plating to form a tin layer and then holding it at 40 ° C. or higher and 160 ° C. or lower for 30 minutes or longer to diffuse the alloy of the zinc-based alloy layer into the tin layer. Has been proposed (see, for example, Patent Document 2).

特開２０１３−１３４８９１号公報（段落番号０００８、００２２）Japanese Unexamined Patent Publication No. 2013-134891 (paragraph numbers 0008 and 0022) 特開２０１７−１１０２９０号公報（段落番号００１０−００１６）JP-A-2017-110290 (paragraph number 0010-0016)

しかし、特許文献１の端子では、電線接触部が第三の金属（亜鉛）でめっき処理され、加締め時にめっき層が破壊されるように非常に薄いめっき層を形成する必要があるので、長期間にわたって異種金属接触腐食を防止することが困難である。また、端子の材料として一般的に使用されているＳｎめっき材の表面に異種金属接触腐食防止層としてＺｎめっき層を形成しても、Ｚｎめっき層の密着性が悪く、Ｓｎめっき材を端子の材料として使用した場合に、端子形状に加工する際にＺｎめっき層が剥離し易くなることがわかった。 However, in the terminal of Patent Document 1, the wire contact portion is plated with a third metal (zinc), and it is necessary to form a very thin plating layer so that the plating layer is destroyed during crimping. It is difficult to prevent galvanic corrosion of dissimilar metals over a period of time. Further, even if a Zn plating layer is formed as a dissimilar metal contact corrosion prevention layer on the surface of a Sn plating material generally used as a terminal material, the adhesion of the Zn plating layer is poor, and the Sn plating material is used for the terminal. It was found that when used as a material, the Zn plating layer is easily peeled off when processing into a terminal shape.

また、特許文献２の方法により製造された錫めっき付き銅端子材は、表面に光沢がなく（表面の反射濃度が低く）、銅端子を製造する際のプレスなどの工程において、外観センサが表面欠陥を誤検出するおそれがある。 Further, the tin-plated copper terminal material manufactured by the method of Patent Document 2 has no gloss on the surface (the reflection density on the surface is low), and the appearance sensor is on the surface in a process such as pressing when manufacturing the copper terminal. There is a risk of erroneous detection of defects.

したがって、本発明は、このような従来の問題点に鑑み、Ｓｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、耐食性が良好であり且つ表面の反射濃度が高いＳｎめっき材およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention has good corrosion resistance when the Sn plating material is used as a terminal material for connecting to an electric wire made of aluminum or an aluminum alloy by crimping or other crimping. It is an object of the present invention to provide a Sn plating material having a high surface reflection density and a method for producing the same.

本発明者らは、上記課題を解決するために鋭意研究した結果、銅または銅合金からなる基材の表面にＮｉめっき皮膜を形成し、このＮｉめっき皮膜の表面にＺｎめっき皮膜を形成し、このＺｎめっき皮膜の表面にＳｎめっき皮膜を形成した後、Ｓｎの融点以上の温度で加熱することにより、Ｓｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、耐食性が良好であり且つ表面の反射濃度が高いＳｎめっき材を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have formed a Ni-plated film on the surface of a base material made of copper or a copper alloy, and formed a Zn-plated film on the surface of the Ni-plated film. After forming a Sn plating film on the surface of this Zn plating film, the Sn plating material is connected to an electric wire made of aluminum or an aluminum alloy by crimping or other crimping process by heating at a temperature equal to or higher than the melting point of Sn. It has been found that when used as a material, a Sn plating material having good corrosion resistance and a high surface reflection density can be produced, and the present invention has been completed.

すなわち、本発明によるＳｎめっき材の製造方法は、銅または銅合金からなる基材の表面にＮｉめっき皮膜を形成し、このＮｉめっき皮膜の表面にＺｎめっき皮膜を形成し、このＺｎめっき皮膜の表面にＳｎめっき皮膜を形成した後、Ｓｎの融点以上の温度で加熱することを特徴とする。 That is, in the method for producing a Sn plating material according to the present invention, a Ni plating film is formed on the surface of a base material made of copper or a copper alloy, a Zn plating film is formed on the surface of the Ni plating film, and the Zn plating film is formed. After forming a Sn plating film on the surface, it is characterized by heating at a temperature equal to or higher than the melting point of Sn.

このＳｎめっき材の製造方法において、Ｎｉめっき皮膜の平均厚さが０．１〜１．０μｍ、Ｚｎめっき皮膜の平均厚さが０．１〜６．０μｍ、Ｓｎめっき皮膜の平均厚さが０．１〜６．０μｍであるのが好ましい。また、上記の加熱により、基材の表面にＮｉ層を介してＳｎ相と複数のＺｎ相とからなる最表層を形成し、この最表層のＺｎ相の一部を最表層の表面に露出させるのが好ましく、複数のＺｎ相をＳｎ相内で互いに離間して形成するのがさらに好ましい。この場合、最表層の表面に露出したＺｎ相が占める面積の割合が１〜９０面積％であるのが好ましく、最表層が５〜９０質量％のＺｎを含むのが好ましい。また、最表層の表面に露出したＺｎ相の長径が０．１〜５．０μｍ、短径が０．１〜５．０μｍであり、アスペクト比が１．０〜５．０であるのが好ましい。 In this method for producing a Sn plating material, the average thickness of the Ni plating film is 0.1 to 1.0 μm, the average thickness of the Zn plating film is 0.1 to 6.0 μm, and the average thickness of the Sn plating film is 0. It is preferably .1 to 6.0 μm. Further, by the above heating, an outermost layer composed of a Sn phase and a plurality of Zn phases is formed on the surface of the base material via a Ni layer, and a part of the Zn phase of the outermost layer is exposed on the surface of the outermost layer. It is preferable that a plurality of Zn phases are formed so as to be separated from each other in the Sn phase. In this case, the ratio of the area occupied by the Zn phase exposed on the surface of the outermost layer is preferably 1 to 90 area%, and the outermost layer preferably contains 5 to 90% by mass of Zn. Further, it is preferable that the major axis of the Zn phase exposed on the surface of the outermost layer is 0.1 to 5.0 μm, the minor axis is 0.1 to 5.0 μm, and the aspect ratio is 1.0 to 5.0. ..

また、本発明によるＳｎめっき材は、銅または銅合金からなる基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層のＺｎ相の一部が最表層の表面に露出していることを特徴とする。 Further, in the Sn plating material according to the present invention, a Ni layer is formed on the surface of a base material made of copper or a copper alloy, and an outermost layer composed of a Sn phase and a plurality of Zn phases is formed on the surface of the Ni layer. A part of the Zn phase of the outermost layer is exposed on the surface of the outermost layer.

このＳｎめっき材において、複数のＺｎ相がＳｎ相内で互いに離間して形成されているのが好ましい。また、最表層の表面に露出したＺｎ相が占める面積の割合が１〜９０面積％であるのが好ましく、最表層が５〜９０質量％のＺｎを含むのが好ましい。また、最表層の表面に露出したＺｎ相の長径が０．１〜５．０μｍ、短径が０．１〜５．０μｍであり、アスペクト比が１．０〜５．０であるのが好ましい。また、Ｎｉ層の平均厚さが０．１〜１．０μｍであるのが好ましく、最表層の平均厚さが０．２〜７．０μｍであるのが好ましい。また、最表層の表面の反射濃度が０．３以上であるのが好ましい。 In this Sn plating material, it is preferable that a plurality of Zn phases are formed so as to be separated from each other in the Sn phase. Further, the ratio of the area occupied by the Zn phase exposed on the surface of the outermost layer is preferably 1 to 90 area%, and the outermost layer preferably contains 5 to 90% by mass of Zn. Further, it is preferable that the major axis of the Zn phase exposed on the surface of the outermost layer is 0.1 to 5.0 μm, the minor axis is 0.1 to 5.0 μm, and the aspect ratio is 1.0 to 5.0. .. The average thickness of the Ni layer is preferably 0.1 to 1.0 μm, and the average thickness of the outermost layer is preferably 0.2 to 7.0 μm. Further, the reflection density on the surface of the outermost layer is preferably 0.3 or more.

本発明によれば、Ｓｎめっき材をアルミニウムまたはアルミニウム合金からなる電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、耐食性が良好であり且つ表面の反射濃度が高いＳｎめっき材を製造することができる。 According to the present invention, when the Sn plating material is used as a terminal material for connecting to an electric wire made of aluminum or an aluminum alloy by crimping or other crimping, Sn plating has good corrosion resistance and a high surface reflection density. The material can be manufactured.

実施例１のＳｎめっき材の断面を模式的に示す図である。It is a figure which shows typically the cross section of the Sn plating material of Example 1. 実施例３のＳｎめっき材の断面の５，０００倍の走査イオン顕微鏡像（ＳＩＭ像）である。It is a scanning ion microscope image (SIM image) of 5,000 times the cross section of the Sn plating material of Example 3.

本発明によるＳｎめっき材の製造方法の実施の形態では、銅または銅合金からなる基材の表面に（好ましくは平均厚さ０．１〜１．０μｍ、さらに好ましくは０．２〜０．５μｍの）Ｎｉめっき皮膜を形成し、このＮｉめっき皮膜の表面に（好ましくは平均厚さ０．１〜６．０μｍ、さらに好ましくは０．５〜３．０μｍの）Ｚｎめっき皮膜を形成し、このＺｎめっき皮膜の表面に（好ましくは平均厚さ０．１〜６．０μｍ、さらに好ましくは０．５〜３．０μｍの）Ｓｎめっき皮膜を形成した後、Ｓｎの融点（２３２℃）以上の温度で加熱（リフロー処理）することにより、基材の表面にＮｉ層を介してＳｎ相（８５質量％以上Ｓｎを含み、残部がＺｎ（またはＺｎとＮｉ）である相）と複数のＺｎ相（８５質量％以上のＺｎを含み、残部がＳｎ（またはＳｎとＮｉ）である相）とからなる最表層を形成し、この最表層の複数のＺｎ相をＳｎ相内で互いに離間（または当接）して形成し且つＺｎ相の一部を最表層の表面に露出させる。この最表層の表面に露出したＺｎ相が占める面積の割合は好ましくは１〜９０面積％（さらに好ましくは１．５〜８６面積％）であり、最表層は好ましくは５〜９０質量％（さらに好ましくは１０〜９０質量％）のＺｎを含む。また、最表層の表面に露出したＺｎ相の長径は、好ましくは０．１〜５．０μｍ（さらに好ましくは０．１〜３．０μｍ）、短径は、好ましくは０．１〜５．０μｍ（さらに好ましくは０．１〜３．０μｍ）であり、アスペクト比は、好ましくは１．０〜５．０（さらに好ましくは１．０〜３．５）である。なお、このアスペクト比が高過ぎると、Ｓｎめっき材を電線に加締めなどの圧着加工により接続する端子の材料として使用した場合に、端子の接続部の表面にＳｎ相が存在し難く、接触信頼性が不十分になるおそれがある。 In the embodiment of the method for producing a Sn plating material according to the present invention, on the surface of a base material made of copper or a copper alloy (preferably an average thickness of 0.1 to 1.0 μm, more preferably 0.2 to 0.5 μm). A Ni plating film is formed, and a Zn plating film (preferably with an average thickness of 0.1 to 6.0 μm, more preferably 0.5 to 3.0 μm) is formed on the surface of the Ni plating film. After forming a Sn plating film (preferably an average thickness of 0.1 to 6.0 μm, more preferably 0.5 to 3.0 μm) on the surface of the Zn plating film, the temperature is equal to or higher than the melting point of Sn (232 ° C.). By heating (reflowing) with, a Sn phase (a phase containing 85% by mass or more of Sn and the balance being Zn (or Zn and Ni)) and a plurality of Zn phases (a phase containing 85% by mass or more of Sn) and a plurality of Zn phases (a phase containing 85% by mass or more of Sn) and a plurality of Zn phases (a phase containing 85% by mass or more of Sn on the surface of the base material via a Ni layer) The outermost layer is formed of a phase containing 85% by mass or more of Zn and the balance is Sn (or Sn (or Sn and Ni)), and the plurality of Zn phases in the outermost layer are separated (or abutted) from each other in the Sn phase. ) And a part of the Zn phase is exposed on the surface of the outermost layer. The proportion of the area occupied by the Zn phase exposed on the surface of the outermost layer is preferably 1 to 90 area% (more preferably 1.5 to 86 area%), and the outermost layer is preferably 5 to 90% by mass (further). It preferably contains 10 to 90% by mass) of Zn. The major axis of the Zn phase exposed on the surface of the outermost layer is preferably 0.1 to 5.0 μm (more preferably 0.1 to 3.0 μm), and the minor axis is preferably 0.1 to 5.0 μm. (More preferably 0.1 to 3.0 μm), and the aspect ratio is preferably 1.0 to 5.0 (more preferably 1.0 to 3.5). If this aspect ratio is too high, it is difficult for the Sn phase to exist on the surface of the terminal connection portion when the Sn plating material is used as a terminal material to be connected to the electric wire by crimping or other crimping, and the contact reliability is high. There is a risk of insufficient sex.

また、本発明によるＳｎめっき材の実施の形態は、銅または銅合金からなる基材の表面に（好ましくは平均厚さ０．１〜１．０μｍ、さらに好ましくは０．２〜０．５μｍの）Ｎｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる（好ましくは平均厚さ０．２〜７．０μｍ、さらに好ましくは０．５〜６．０μｍの）最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間（または当接）して形成され且つＺｎ相の一部が最表層の表面に露出している。この最表層の表面に露出したＺｎ相が占める面積の割合は好ましくは１〜９０面積％（さらに好ましくは１．５〜８６面積％）であり、最表層は好ましくは５〜９０質量％（さらに好ましくは１０〜９０質量％）のＺｎを含む。また、最表層の表面に露出したＺｎ相の長径は、好ましくは０．１〜５．０μｍ（さらに好ましくは０．１〜３．０μｍ）、短径は、好ましくは０．１〜５．０μｍ（さらに好ましくは０．１〜３．０μｍ）であり、アスペクト比は、好ましくは１．０〜５．０（さらに好ましくは１．０〜３．５）である。また、最表層の表面の反射濃度が０．３以上であるの好ましく、０．４以上であるのがさらに好ましく、０．７以上であるのが最も好ましい。 Further, in the embodiment of the Sn plating material according to the present invention, the surface of the base material made of copper or a copper alloy (preferably an average thickness of 0.1 to 1.0 μm, more preferably 0.2 to 0.5 μm). ) A Ni layer is formed, and the surface of the Ni layer is composed of a Sn phase and a plurality of Zn phases (preferably having an average thickness of 0.2 to 7.0 μm, more preferably 0.5 to 6.0 μm). A surface layer is formed, and a plurality of Zn phases of the outermost layer are formed so as to be separated (or abutted) from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. The proportion of the area occupied by the Zn phase exposed on the surface of the outermost layer is preferably 1 to 90 area% (more preferably 1.5 to 86 area%), and the outermost layer is preferably 5 to 90% by mass (further). It preferably contains 10 to 90% by mass) of Zn. The major axis of the Zn phase exposed on the surface of the outermost layer is preferably 0.1 to 5.0 μm (more preferably 0.1 to 3.0 μm), and the minor axis is preferably 0.1 to 5.0 μm. (More preferably 0.1 to 3.0 μm), and the aspect ratio is preferably 1.0 to 5.0 (more preferably 1.0 to 3.5). Further, the reflection density on the surface of the outermost layer is preferably 0.3 or more, more preferably 0.4 or more, and most preferably 0.7 or more.

以下、本発明によるＳｎめっき材およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the Sn plating material according to the present invention and the method for producing the same will be described in detail.

［実施例１］
まず、５０ｍｍ×５０ｍｍ×０．２０ｍｍの大きさのＣｕ−Ｎｉ−Ｓｎ−Ｐ系合金からなる平板状の導体基材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の基材）（ＤＯＷＡメタルテック株式会社製のＮＢ−１０９）を用意した。 [Example 1]
First, a flat plate-shaped conductor base material (1.0 mass% Ni, 0.9 mass% Sn, and 0.05) made of a Cu—Ni—Sn—P alloy having a size of 50 mm × 50 mm × 0.20 mm. A copper alloy base material containing mass% P and the balance being Cu) (NB-109 manufactured by DOWA Metaltech Co., Ltd.) was prepared.

次に、前処理として、基材（被めっき材）をアルカリ電解脱脂液により１０秒間電解脱脂を行った後に水洗し、その後、１００ｇ／Ｌの硫酸に浸漬して酸洗した後に水洗した。 Next, as a pretreatment, the base material (material to be plated) was electrolytically degreased with an alkaline electrolytic degreasing solution for 10 seconds and then washed with water, then immersed in 100 g / L sulfuric acid, pickled and then washed with water.

次に、前処理後の基材（被めっき材）の一方の面以外の部分にマスキングテープを貼り付けた後、３４２ｇ／Ｌのスルファミン酸ニッケルと４５ｇ／Ｌのホウ酸を含むＮｉめっき液中において、前処理後の基材（被めっき材）を陰極とし、Ｎｉ板を陽極として、電流密度４Ａ／ｄｍ２、液温５５℃で２６秒間電気めっきを行うことにより、基材上に平均厚さ０．３μｍのＮｉめっき層を形成した。 Next, after a masking tape is attached to a portion other than one surface of the base material (material to be plated) after pretreatment, it is contained in a Ni plating solution containing 342 g / L nickel sulfamate and 45 g / L boric acid. In, the pretreated base material (material to be plated) is used as a cathode, and a Ni plate is used as an anode, and electroplating is performed at a current density of 4 A / dm 2 and a liquid temperature of 55 ° C. for 26 seconds to obtain an average thickness on the base material. A 0.3 μm Ni plating layer was formed.

次に、２００ｇ／Ｌの硫酸亜鉛と３０ｇ／Ｌの硫酸アンモニウムを含む水溶液からなるＺｎめっき浴（硫酸浴）中において、Ｎｉめっき後の基材を陰極とし、Ｚｎ板を陽極として、電流密度１０Ａ／ｄｍ２、液温５０℃で１２秒間電気めっきを行うことにより、Ｎｉめっき層の表面に平均厚さ０．３μｍのＺｎめっき層を形成した。 Next, in a Zn plating bath (sulfate bath) consisting of an aqueous solution containing 200 g / L of zinc sulfate and 30 g / L of ammonium sulfate, the base material after Ni plating is used as a cathode and the Zn plate is used as an anode, and the current density is 10 A /. By electroplating at dm 2 and a liquid temperature of 50 ° C. for 12 seconds, a Zn plating layer having an average thickness of 0.3 μm was formed on the surface of the Ni plating layer.

次に、１６ｇ／Ｌのメタンスルホン酸錫と９６ｇ／Ｌのメタンスルホン酸と４０ｍＬ／Ｌの添加剤（石原ケミカル株式会社製のＵＴＢ ＰＦ−１９０Ｓ）を含むＳｎめっき液中において、Ｚｎめっき後の基材を陰極とし、Ｓｎ板を陽極として、電流密２Ａ／ｄｍ２、液温５０℃で４２秒間電気めっきを行うことにより、Ｚｎめっき層の表面に平均厚さ０．３μｍのＳｎめっき層を形成した後、マスキングテープを剥がしてＳｎめっき材を得た。 Next, in a Sn plating solution containing 16 g / L tin methanesulfonate, 96 g / L methanesulfonic acid and 40 mL / L additive (UTB PF-190S manufactured by Ishihara Chemical Co., Ltd.), after Zn plating. By electroplating the base material as a cathode and the Sn plate as an anode at a current density of 2 A / dm 2 and a liquid temperature of 50 ° C. for 42 seconds, a Sn plating layer having an average thickness of 0.3 μm is formed on the surface of the Zn plating layer. After the formation, the masking tape was peeled off to obtain a Sn plating material.

次に、得られたＳｎめっき材を洗浄して乾燥した後、熱処理（リフロー処理）を行った。このリフロー処理では、２つの近赤外線ヒーター（株式会社ハイベック製のＨＹＰ−８Ｎ、定格電圧１００Ｖ、定格電力５６０Ｗ、平行照射タイプ）を２５ｍｍ離間して対向するように配置し、これらの近赤外線ヒーターの中央部にＳｎめっき材を配置して、設定電流値を１０．８Ａとして、大気雰囲気においてＳｎめっき材を（最高到達温度６５０℃で）１４秒間加熱してＳｎめっき層の表面を溶融させた直後に２５℃の水槽内に浸漬して冷却した。なお、最高到達温度は、遠赤外線ヒータの中央部にＫ熱電対の先端を当接させて測定した。 Next, the obtained Sn plating material was washed and dried, and then heat-treated (reflow treatment) was performed. In this reflow processing, two near-infrared heaters (HYP-8N manufactured by Hi-Beck Co., Ltd., rated voltage 100V, rated power 560W, parallel irradiation type) are arranged so as to face each other with a distance of 25 mm, and these near-infrared heaters are used. Immediately after the Sn plating material is placed in the center, the set current value is set to 10.8A, and the Sn plating material is heated for 14 seconds (at the maximum ultimate temperature of 650 ° C.) for 14 seconds to melt the surface of the Sn plating layer. It was cooled by immersing it in a water tank at 25 ° C. The maximum temperature reached was measured by bringing the tip of the K thermocouple into contact with the central portion of the far-infrared heater.

このようにしてリフロー処理を行ったＳｎめっき材を集束イオンビーム（ＦＩＢ）加工観察装置（日本電子株式会社製のＪＩＢ−４０００）により切断して、Ｓｎめっき材の圧延方向に垂直な断面を露出させ、その断面をＦＩＢ加工観察装置に付属する走査イオン顕微鏡（ＳＩＭ）により観察した。その結果、この断面の走査イオン顕微鏡像（ＳＩＭ像）により、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、このＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ０．６μｍであることが確認された。 The Sn plating material reflowed in this way is cut by a focused ion beam (FIB) processing observation device (JIB-4000 manufactured by JEOL Ltd.) to expose the cross section of the Sn plating material perpendicular to the rolling direction. The cross section was observed with a scanning ion microscope (SIM) attached to the FIB processing observation device. As a result, a Ni layer is formed on the surface of the base material of the Sn plating material by the scanning ion microscope image (SIM image) of this cross section, and the outermost layer composed of the Sn phase and a plurality of Zn phases is formed on the surface of the Ni layer. It was confirmed that the plurality of Zn phases in the outermost layer were formed so as to be separated from each other in the Sn phase, and a part of the Zn phase was exposed on the surface of the outermost layer. Moreover, when the thickness of the Ni layer and the outermost layer was measured from this SIM image, it was confirmed that the thickness of the Ni layer was 0.3 μm and the thickness of the outermost layer was 0.6 μm.

また、リフロー処理後のＳｎめっき材の表面を観察することにより、Ｓｎめっき材の表面のＺｎ相が占める面積の割合（面積率（面積％））を算出した。このＳｎめっき材の表面のＺｎ相の面積率は、試験片の表面に卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により加速電圧１５ｋＶで電子線を照射して反射電子検出器から得られた（倍率５００倍の）反射電子組成（ＣＯＭＰＯ）像を、画像解析アプリケーション（画像編集・加工ソフトＧＩＭＰ２．１０．６）を使用して、（全ピクセルのうち最も高い輝度を２５５、最も低い輝度を０とすると、輝度が１２７以下のピクセルが黒、輝度が１２７を超えるピクセルが白になるように）階調を二値化し、（８５質量％以上のＳｎを含む）Ｓｎ相の部分（白い部分）と（８５質量％以上のＺｎを含む）Ｚｎ相の部分（黒い部分）に分離して、画像全体のピクセル数Ｘに対するＺｎ相の部分のピクセル数Ｙの比Ｙ／Ｘとして算出した。その結果、Ｓｎめっき材の表面のＺｎ相が占める面積の割合（面積率）は、３６．２面積％であった。 Further, by observing the surface of the Sn plating material after the reflow treatment, the ratio of the area occupied by the Zn phase on the surface of the Sn plating material (area ratio (area%)) was calculated. The area ratio of the Zn phase on the surface of the Sn plating material is obtained from a reflected electron detector by irradiating the surface of the test piece with an electron beam at an acceleration voltage of 15 kV with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Co., Ltd.). Using an image analysis application (image editing / processing software GIMP2.10.6), a reflected electron composition (COMPO) image (at a magnification of 500 times) was used to obtain the highest brightness of all pixels of 255 and the lowest brightness. When is 0, the gradation is binarized (so that pixels with a brightness of 127 or less are black and pixels with a brightness of more than 127 are white), and the Sn phase portion (including Sn of 85% by mass or more) is white. It was separated into a Zn phase portion (black portion) (including a Zn of 85% by mass or more) and calculated as a ratio Y / X of the number of pixels Y of the Zn phase portion to the number of pixels X of the entire image. As a result, the ratio (area ratio) of the area occupied by the Zn phase on the surface of the Sn plating material was 36.2 area%.

また、リフロー処理後のＳｎめっき材の表面を卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により、加速電圧１５ｋＶ、倍率１００倍で観察し、この観察領域において最表層中のＺｎの量を上記の卓上電子顕微鏡に付属するエネルギー分散型Ｘ線分析装置（Ｏｘｆｏｒｄ社製のＡＺｔｅｃ Ｏｎｅ）により求めたところ、５１．０質量％であった。 Further, the surface of the Sn plating material after the reflow treatment was observed with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 15 kV and a magnification of 100 times, and the amount of Zn in the outermost layer in this observation region was observed. It was 51.0% by mass as determined by an energy dispersive X-ray analyzer (AZtec One manufactured by Oxford) attached to the above-mentioned tabletop electron microscope.

また、リフロー処理後のＳｎめっき材の表面を観察することにより、Ｓｎめっき材の表面のＺｎ相の長径（Ｚｎ相が内接する長方形の面積が最小となる長方形の長辺の長さ）と、短径（その長方形の短辺の長さ）を測定し、短径に対する長径の比（長径／短径（アスペクト比））を算出した。このＳｎめっき材の表面のＺｎ相の長径および短辺は、試験片の表面に卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により加速電圧１５ｋＶで電子線を照射して反射電子検出器から得られた（倍率２０００倍の）反射電子組成（ＣＯＭＰＯ）像を、画像解析アプリケーション（画像編集・加工ソフトＧＩＭＰ２．１０．６）を使用して、（全ピクセルのうち最も高い輝度を２５５、最も低い輝度を０とすると、輝度が１２７以下のピクセルが黒、輝度が１２７を超えるピクセルが白になるように）階調を二値化し、（８５質量％以上のＳｎを含む）Ｓｎ相の部分（白い部分）と（８５質量％以上のＺｎを含む）Ｚｎ相の部分（黒い部分）に分離して、２０個のＺｎ相について、それぞれの長径と短径を測定して、それぞれの平均値をＺｎ相の長径および短径とし、アスペクト比（長径／短径）を算出した。その結果、Ｚｎ相の長径は２．０μｍ、短径は１．３μｍであり、アスペクト比は１．６であった。 Further, by observing the surface of the Sn plating material after the reflow treatment, the major axis of the Zn phase on the surface of the Sn plating material (the length of the long side of the rectangle that minimizes the area of the rectangle inscribed by the Zn phase) is determined. The minor axis (the length of the short side of the rectangle) was measured, and the ratio of the major axis to the minor axis (major axis / minor axis (aspect ratio)) was calculated. The major axis and short side of the Zn phase on the surface of this Sn plating material are obtained by irradiating the surface of the test piece with an electron beam at an acceleration voltage of 15 kV with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Co., Ltd.) from a reflected electron detector. Using the image analysis application (image editing / processing software GIMP2.10.6), the obtained reflected electron composition (COMPO) image (at a magnification of 2000 times) was used to obtain the highest brightness (255, highest of all pixels). When the low brightness is 0, the gradation is binarized (so that pixels with a brightness of 127 or less are black and pixels with a brightness of more than 127 are white), and the Sn phase portion (including Sn of 85% by mass or more). Separated into a Zn phase part (black part) (containing 85% by mass or more of Zn) and measured the major axis and minor axis of each of the 20 Zn phases, and the average value of each. The major axis and the minor axis of the Zn phase were set to, and the aspect ratio (major axis / minor axis) was calculated. As a result, the major axis of the Zn phase was 2.0 μm, the minor axis was 1.3 μm, and the aspect ratio was 1.6.

なお、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部を卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により、加速電圧１５ｋＶ、倍率５０００倍で観察し、この卓上電子顕微鏡に付属するエネルギー分散型Ｘ線分析装置（Ｏｘｆｏｒｄ社製のＡＺｔｅｃ Ｏｎｅ）を使用して、Ｓｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９０．９質量％のＳｎと７．４質量％のＺｎと１．７質量％のＮｉからなる相であり、Ｚｎ相は、９５．９質量％のＺｎと２．４質量％のＳｎと１．７質量％のＮｉからなる相であった。 The central part of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was measured by a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Co., Ltd.) at an acceleration voltage of 15 kV and a magnification of 5000 times. After observing, the composition of the central part of each of the Sn phase and the Zn phase was determined by point analysis using the energy dispersive X-ray analyzer (AZtec One manufactured by Oxford) attached to this tabletop electron microscope. The Sn phase is a phase composed of 90.9 mass% Sn, 7.4 mass% Zn and 1.7 mass% Ni, and the Zn phase is 95.9 mass% Zn and 2.4 mass%. It was a phase composed of Sn and 1.7% by mass of Ni.

また、リフロー処理後のＳｎめっき材から切り出した５０ｍｍ×１０ｍｍ×０．２０ｍｍの大きさの試験片の最表層（Ｓｎ相およびＺｎ相）を外側にして、このＳｎめっき材により直径０．８ｍｍ、長さ３０ｍｍの純アルミニウム単線（Ａ１０７０）を加締めた後、５質量％のＮａＣｌ水溶液中に浸漬し、ガルバニック腐食（卑な金属が溶解する異種金属接触腐食）によるガスの発生時間によって耐食性を評価した。その結果、ガスが発生するまでの時間は２４時間と長く、耐食性が良好であった。 Further, with the outermost surface layers (Sn phase and Zn phase) of the test piece having a size of 50 mm × 10 mm × 0.20 mm cut out from the Sn plating material after the reflow treatment on the outside, the Sn plating material has a diameter of 0.8 mm. After crimping a pure aluminum single wire (A1070) with a length of 30 mm, it is immersed in a 5 mass% NaCl aqueous solution, and corrosion resistance is evaluated by the gas generation time due to galvanic corrosion (corrosion of dissimilar metals in which base metals dissolve). did. As a result, the time until gas was generated was as long as 24 hours, and the corrosion resistance was good.

また、リフロー処理後のＳｎめっき材の表面の反射濃度（絶対濃度）をマクベス濃度計（Ｍａｃｂｅｔｈ社製のＲＤ−９１８）により測定したところ、１．６であった。 Further, the reflection density (absolute density) on the surface of the Sn plating material after the reflow treatment was measured by a Macbeth densitometer (RD-918 manufactured by Macbeth) and found to be 1.6.

［実施例２］
電気めっき時間を２０秒間として平均厚さ０．５μｍのＺｎめっき層を形成し、電気めっき時間を７０秒間として平均厚さ０．５μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 2]
The same as in Example 1 except that a Zn plating layer having an average thickness of 0.5 μm was formed with an electroplating time of 20 seconds and a Sn plating layer having an average thickness of 0.5 μm was formed with an electroplating time of 70 seconds. After obtaining the Sn plating material by the method, a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ１．１μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 1.1 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、２０．８面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 20.8 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、３７．４質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 37.4% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は２．０μｍ、短径は１．４μｍであり、アスペクト比は１．５であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 2. The minor axis was 1.0 μm, the minor axis was 1.4 μm, and the aspect ratio was 1.5.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９５．０質量％のＳｎと３．１質量％のＺｎと１．９質量％のＮｉからなる相であり、Ｚｎ相は、９４．８質量％のＺｎと３．１質量％のＳｎと２．１質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 95. It is a phase consisting of 0.0% by mass Sn, 3.1% by mass Zn and 1.9% by mass Ni, and the Zn phase is 94.8% by mass Zn, 3.1% by mass Sn and 2. It was a phase composed of 1% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は７２時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 72 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．３であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.3.

［実施例３］
電気めっき時間を３５秒間として平均厚さ０．４μｍのＮｉめっき層を形成し、電気めっき時間を２０秒間として平均厚さ０．５μｍのＺｎめっき層を形成し、電気めっき時間を１４０秒間として平均厚さ１．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 3]
A Ni plating layer with an average thickness of 0.4 μm is formed with an electroplating time of 35 seconds, a Zn plating layer with an average thickness of 0.5 μm is formed with an electroplating time of 20 seconds, and an average with an electroplating time of 140 seconds. A Sn plating material was obtained by the same method as in Example 1 except that a Sn plating layer having a thickness of 1.0 μm was formed, and then a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。なお、このＳｎめっき材の断面のＳＩＭ像を図２に示す。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．４μｍであり、最表層の厚さ１．５μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. A SIM image of a cross section of this Sn plating material is shown in FIG. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.4 μm, and the thickness of the outermost layer was 1.5 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、１８．７面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 18.7 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、３３．５質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 33.5% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は２．９μｍ、短径は１．９μｍであり、アスペクト比は１．６であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 2. The minor axis was 1.9 μm, the aspect ratio was 1.6.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９２．２質量％のＳｎと６．６質量％のＺｎと１．２質量％のＮｉからなる相であり、Ｚｎ相は、９５．５質量％のＺｎと３．１質量％のＳｎと１．４質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 92. It is a phase composed of .2% by mass Sn, 6.6% by mass Zn and 1.2% by mass Ni, and the Zn phase is 95.5% by mass Zn, 3.1% by mass Sn and 1. It was a phase composed of 4% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は１４４時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 144 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．０であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.0.

［実施例４］
電気めっき時間を１７秒間として平均厚さ０．２μｍのＮｉめっき層を形成し、電気めっき時間を２０秒間として平均厚さ０．５μｍのＺｎめっき層を形成し、電気めっき時間を４２０秒間として平均厚さ３．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 4]
A Ni plating layer with an average thickness of 0.2 μm is formed with an electroplating time of 17 seconds, a Zn plating layer with an average thickness of 0.5 μm is formed with an electroplating time of 20 seconds, and an average with an electroplating time of 420 seconds. A Sn plating material was obtained by the same method as in Example 1 except that a Sn plating layer having a thickness of 3.0 μm was formed, and then a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．２μｍであり、最表層の厚さ３．２μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.2 μm, and the thickness of the outermost layer was 3.2 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、５．０面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 5.0 area% was calculated. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、１３．９質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 13.9% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は０．７μｍ、短径は０．３μｍであり、アスペクト比は２．２であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 0. The minor axis was 0.7 μm, the minor axis was 0.3 μm, and the aspect ratio was 2.2.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９１．９質量％のＳｎと６．９質量％のＺｎと１．２質量％のＮｉからなる相であり、Ｚｎ相は、９５．５質量％のＺｎと３．６質量％のＳｎと０．９質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 91. It is a phase consisting of 9.9% by mass Sn, 6.9% by mass Zn and 1.2% by mass Ni, and the Zn phase is 95.5% by mass Zn, 3.6% by mass Sn and 0. It was a phase composed of 9% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は７２時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 72 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、０．７であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 0.7.

［実施例５］
電気めっき時間を２０秒間として平均厚さ０．５μｍのＺｎめっき層を形成し、電気めっき時間を７００秒間として平均厚さ５．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 5]
The same as in Example 1 except that a Zn plating layer having an average thickness of 0.5 μm was formed with an electroplating time of 20 seconds and a Sn plating layer having an average thickness of 5.0 μm was formed with an electroplating time of 700 seconds. After obtaining the Sn plating material by the method, a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ５．３μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 5.3 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、１．５面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 1.5 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、１１．７質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 11.7% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は０．７μｍ、短径は０．ｌ２μｍであり、アスペクト比は３．２であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 0. .7 μm, minor axis is 0. It was l2 μm and had an aspect ratio of 3.2.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９６．６質量％のＳｎと３．４質量％のＺｎからなる相であり、Ｚｎ相は、９５．６質量％のＺｎと４．４質量％からなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 96. It was a phase composed of 6.6% by mass of Sn and 3.4% by mass of Zn, and the Zn phase was a phase composed of 95.6% by mass of Zn and 4.4% by mass.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は７２時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 72 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、０．６であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 0.6.

［実施例６］
電気めっき時間を４０秒間として平均厚さ１．０μｍのＺｎめっき層を形成し、電気めっき時間を１４０秒間として平均厚さ１．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 6]
The same as in Example 1 except that a Zn plating layer having an average thickness of 1.0 μm was formed with an electroplating time of 40 seconds and a Sn plating layer having an average thickness of 1.0 μm was formed with an electroplating time of 140 seconds. After obtaining the Sn plating material by the method, a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ２．１μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 2.1 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、９．１面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 9.1 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、１８．０質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 18.0% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は１．５μｍ、短径は０．９μｍであり、アスペクト比は２．１であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 1. The minor axis was 0.5 μm, the minor axis was 0.9 μm, and the aspect ratio was 2.1.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９２．３質量％のＳｎと６．９質量％のＺｎと０．８質量％のＮｉからなる相であり、Ｚｎ相は、９５．７質量％のＺｎと２．３質量％のＳｎと２．０質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 92. It is a phase consisting of 3.3% by mass Sn, 6.9% by mass Zn and 0.8% by mass Ni, and the Zn phase is 95.7% by mass Zn, 2.3% by mass Sn and 2. It was a phase composed of 0% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は１２０時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 120 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．３であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.3.

［実施例７］
電気めっき時間を８７秒間として平均厚さ１．０μｍのＮｉめっき層を形成し、電気めっき時間を４０秒間として平均厚さ１．０μｍのＺｎめっき層を形成し、電気めっき時間を１４０秒間として平均厚さ１．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 7]
A Ni plating layer with an average thickness of 1.0 μm is formed with an electroplating time of 87 seconds, a Zn plating layer with an average thickness of 1.0 μm is formed with an electroplating time of 40 seconds, and an average with an electroplating time of 140 seconds. A Sn plating material was obtained by the same method as in Example 1 except that a Sn plating layer having a thickness of 1.0 μm was formed, and then a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは１．０μｍであり、最表層の厚さ２．０μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 1.0 μm, and the thickness of the outermost layer was 2.0 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、８．８面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 8.8 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、１７．６質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 17.6% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は２．０μｍ、短径は１．２μｍであり、アスペクト比は１．８であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 2. The minor axis was 2.0 μm, the minor axis was 1.2 μm, and the aspect ratio was 1.8.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９１．６質量％のＳｎと７．１質量％のＺｎと１．３質量％のＮｉからなる相であり、Ｚｎ相は、９５．６質量％のＺｎと２．８質量％のＳｎと１．６質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 91. It is a phase consisting of 1.6% by mass Sn, 7.1% by mass Zn and 1.3% by mass Ni, and the Zn phase is 95.6% by mass Zn, 2.8% by mass Sn and 1. It was a phase composed of 6% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は１２０時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 120 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．３であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.3.

［実施例８］
電気めっき時間を８０秒間として平均厚さ２．０μｍのＺｎめっき層を形成した以外は、実施例３と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 8]
A Sn plating material was obtained by the same method as in Example 3 except that a Zn plating layer having an average thickness of 2.0 μm was formed with an electroplating time of 80 seconds, and then a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．４μｍであり、最表層の厚さ３．２μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.4 μm, and the thickness of the outermost layer was 3.2 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、４．０面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 4.0 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、１０．８質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 10.8% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は１．１μｍ、短径は０．７μｍであり、アスペクト比は１．８であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 1. The minor axis was 0.1 μm, the minor axis was 0.7 μm, and the aspect ratio was 1.8.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９４．０質量％のＳｎと５．３質量％のＺｎと０．７質量％のＮｉからなる相であり、Ｚｎ相は、９７．１質量％のＺｎと２．１質量％のＳｎと０．８質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 94. It is a phase consisting of 0.0% by mass Sn, 5.3% by mass Zn and 0.7% by mass Ni, and the Zn phase is 97.1% by mass Zn, 2.1% by mass Sn and 0. It was a phase composed of 8% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は１２０時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 120 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．５であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.5.

［実施例９］
電気めっき時間を１７秒間として平均厚さ０．２μｍのＮｉめっき層を形成し、電気めっき時間を２００秒間として平均厚さ５．０μｍのＺｎめっき層を形成した以外は、実施例２と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Example 9]
The same as in Example 2 except that a Ni plating layer having an average thickness of 0.2 μm was formed with an electroplating time of 17 seconds and a Zn plating layer having an average thickness of 5.0 μm was formed with an electroplating time of 200 seconds. After obtaining the Sn plating material by the method, a reflow treatment was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに当接して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．２μｍであり、最表層の厚さ５．５μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed in contact with each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thickness of the Ni layer and the outermost layer was measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.2 μm, and the thickness of the outermost layer was 5.5 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、２０．８面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 20.8 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、４９．５質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 49.5% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は１．８μｍ、短径は１．０μｍであり、アスペクト比は２．２であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 1. The minor axis was 0.8 μm, the minor axis was 1.0 μm, and the aspect ratio was 2.2.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９６．８質量％のＳｎと３．２質量％のＺｎからなる相であり、Ｚｎ相は、９６．６質量％のＺｎと３．４質量％のＳｎからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 96. It was a phase composed of 0.8% by mass Sn and 3.2% by mass Zn, and the Zn phase was a phase composed of 96.6% by mass Zn and 3.4% by mass Sn.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は４８時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 48 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．５であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.5.

［実施例１０］
電気めっき時間を３５秒間として平均厚さ０．４μｍのＮｉめっき層を形成し、電気めっき時間を８０秒間として平均厚さ２．０μｍのＺｎめっき層を形成し、電気めっき時間を１４０秒間として平均厚さ１．０μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、加熱時間を１８秒間とした以外は、実施例１と同様の方法により、リフロー処理を行った。 [Example 10]
A Ni plating layer with an average thickness of 0.4 μm is formed with an electroplating time of 35 seconds, a Zn plating layer with an average thickness of 2.0 μm is formed with an electroplating time of 80 seconds, and an average with an electroplating time of 140 seconds. By the same method as in Example 1 except that a Sn plating layer having a thickness of 1.0 μm was formed, the heating time was set to 18 seconds after obtaining the Sn plating material. , Reflow processing was performed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに離間して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ３．０μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed so as to be separated from each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 3.0 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、６０．１面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 60.1 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、６６．８質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 66.8% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は０．８μｍ、短径は０．５μｍであり、アスペクト比は１．７であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 0. The minor axis was 0.8 μm, the minor axis was 0.5 μm, and the aspect ratio was 1.7.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９３．４質量％のＳｎと６．０質量％のＺｎと０．６質量％のＮｉからなる相であり、Ｚｎ相は、９８．３質量％のＺｎと１．２質量％のＳｎと０．５質量％のＮｉからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 93. It is a phase consisting of 0.4% by mass Sn, 6.0% by mass Zn and 0.6% by mass Ni, and the Zn phase is 98.3% by mass Zn, 1.2% by mass Sn and 0. It was a phase composed of 5% by mass of Ni.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は１２０時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 120 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．５であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.5.

［実施例１１］
電気めっき時間を１７秒間として平均厚さ０．２μｍのＮｉめっき層を形成し、電気めっき時間を２００秒間として平均厚さ５．０μｍのＺｎめっき層を形成し、電気めっき時間を７０秒間として平均厚さ０．５μｍのＳｎめっき層を形成した以外は、実施例１と同様の方法により、Ｓｎめっき材を得た後、実施例１０と同様の方法により、リフロー処理を行った。 [Example 11]
A Ni plating layer with an average thickness of 0.2 μm is formed with an electroplating time of 17 seconds, a Zn plating layer with an average thickness of 5.0 μm is formed with an electroplating time of 200 seconds, and an average with an electroplating time of 70 seconds. A Sn-plated material was obtained by the same method as in Example 1 except that a Sn-plated layer having a thickness of 0.5 μm was formed, and then a reflow treatment was performed by the same method as in Example 10.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面を分析したところ、Ｓｎめっき材の基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層の複数のＺｎ相がＳｎ相内で互いに当接して形成され且つＺｎ相の一部が最表層の表面に露出していることが確認された。また、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ５．６μｍであることが確認された。 When the cross section of the Sn plating material subjected to the reflow treatment in this manner was analyzed by the same method as in Example 1, a Ni layer was formed on the surface of the base material of the Sn plating material, and the surface of the Ni layer was formed. An outermost layer composed of a Sn phase and a plurality of Zn phases is formed, and the plurality of Zn phases of the outermost layer are formed in contact with each other in the Sn phase, and a part of the Zn phase is exposed on the surface of the outermost layer. It was confirmed that there was. Further, when the thicknesses of the Ni layer and the outermost layer were measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 5.6 μm. It was confirmed that there was.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、８５．３面積％であった。 Further, when the surface of the Sn plating material after the reflow treatment was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, 85.3 area%. Met.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の最表層中のＺｎの量を求めたところ、８９．１質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, it was 89.1% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材の表面のＺｎ相の長径および短径の平均値を算出し、アスペクト比（長径／短径）を算出したところ、Ｚｎ相の長径は２．３μｍ、短径は１．４μｍであり、アスペクト比は２．０であった。 Further, when the average value of the major axis and the minor axis of the Zn phase on the surface of the Sn plating material was calculated by the same method as in Example 1 and the aspect ratio (major axis / minor axis) was calculated, the major axis of the Zn phase was 2. The minor axis was 1.3 μm, the minor axis was 1.4 μm, and the aspect ratio was 2.0.

なお、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面に露出しているＳｎ相とＺｎ相のそれぞれの中央部の組成を点分析により求めたところ、Ｓｎ相は、９４．５質量％のＳｎと５．５質量％のＺｎからなる相であり、Ｚｎ相は、９７．０質量％のＺｎと３．０質量％のＳｎからなる相であった。 When the composition of the central portion of each of the Sn phase and the Zn phase exposed on the surface of the Sn plating material after the reflow treatment was determined by the same method as in Example 1, the Sn phase was 94. It was a phase composed of 5.5% by mass Sn and 5.5% by mass Zn, and the Zn phase was a phase composed of 97.0% by mass Zn and 3.0% by mass Sn.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は７２時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was as long as 72 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．４であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.4.

［比較例１］
Ｎｉめっき層とＺｎめっき層を形成しなかった以外は、実施例３と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Comparative Example 1]
A reflow treatment was performed after obtaining a Sn-plated material by the same method as in Example 3 except that the Ni-plated layer and the Zn-plated layer were not formed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は２４時間より短く、耐食性が良好でなかった。 When the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1 for the Sn plating material subjected to the reflow treatment in this way, the time until gas was generated was It was shorter than 24 hours and the corrosion resistance was not good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．７であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.7.

［比較例２］
Ｚｎめっき層を形成しなかった以外は、実施例３と同様の方法により、Ｓｎめっき材を得た後、リフロー処理を行った。 [Comparative Example 2]
A reflow treatment was performed after obtaining a Sn plating material by the same method as in Example 3 except that the Zn plating layer was not formed.

このようにしてリフロー処理を行ったＳｎめっき材について、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層の厚さを測定したところ、０．３μｍであることが確認された。 When the thickness of the Ni layer was measured from the SIM image of the cross section of the Sn plating material subjected to the reflow treatment in this manner by the same method as in Example 1, it was confirmed that the thickness was 0.3 μm.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は２４時間より短く、耐食性が良好でなかった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material after the reflow treatment was evaluated by the same method as in Example 1, the time until gas was generated was shorter than 24 hours, and the corrosion resistance was not good.

また、実施例１と同様の方法により、リフロー処理後のＳｎめっき材の表面の反射濃度を測定したところ、１．６であった。 Further, the reflection density on the surface of the Sn plating material after the reflow treatment was measured by the same method as in Example 1 and found to be 1.6.

［比較例３］
実施例６と同様の方法によりＳｎめっき材を得た後、リフロー処理を行わなかった。 [Comparative Example 3]
After obtaining the Sn plating material by the same method as in Example 6, the reflow treatment was not performed.

このＳｎめっき材について、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ２．０μｍであることが確認された。 When the thickness of the Ni layer and the outermost layer of this Sn plating material was measured from the SIM image of the cross section by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the thickness of the outermost layer was 0.3 μm. It was confirmed that it was 2.0 μm.

また、実施例１と同様の方法により、Ｓｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、０面積％であった。 Further, when the surface of the Sn plating material was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, it was 0 area%.

また、実施例１と同様の方法により、Ｓｎめっき材の最表層中のＺｎの量を求めたところ、０．２質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material was determined by the same method as in Example 1, it was 0.2% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は２４時間より短く、耐食性が良好でなかった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material was evaluated by the same method as in Example 1, the time until gas was generated was shorter than 24 hours, and the corrosion resistance was not good.

また、実施例１と同様の方法により、Ｓｎめっき材の表面の反射濃度を測定したところ、０．２と低かった。 Moreover, when the reflection density on the surface of the Sn plating material was measured by the same method as in Example 1, it was as low as 0.2.

［比較例４］
実施例６と同様の方法によりＳｎめっき材を得た後、リフロー処理に代えて、１６０℃で６０分間加熱する熱処理を行った。 [Comparative Example 4]
After obtaining the Sn plating material by the same method as in Example 6, heat treatment was performed by heating at 160 ° C. for 60 minutes instead of the reflow treatment.

この熱処理後のＳｎめっき材について、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ２．１μｍであることが確認された。 When the thickness of the Ni layer and the outermost layer was measured from the SIM image of the cross section of the Sn plating material after this heat treatment by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the outermost layer was found to be 0.3 μm. It was confirmed that the thickness of was 2.1 μm.

また、実施例１と同様の方法により、Ｓｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、０面積％であった。 Further, when the surface of the Sn plating material was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, it was 0 area%.

また、実施例１と同様の方法により、Ｓｎめっき材の最表層中のＺｎの量を求めたところ、２．７質量％であった。 Further, when the amount of Zn in the outermost surface layer of the Sn plating material was determined by the same method as in Example 1, it was 2.7% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は７２時間と長く、耐食性が良好であった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material was evaluated by the same method as in Example 1, the time until gas was generated was as long as 72 hours, and the corrosion resistance was good.

また、実施例１と同様の方法により、Ｓｎめっき材の表面の反射濃度を測定したところ、０．２と低かった。 Moreover, when the reflection density on the surface of the Sn plating material was measured by the same method as in Example 1, it was as low as 0.2.

［比較例５］
Ｚｎめっき層の形成に代えて、３２ｇ／Ｌの塩化亜鉛と６６ｇ／Ｌの塩化ニッケルと２４０ｇ／Ｌの塩化アンモニウムと１００ｍＬ／Ｌの添加剤（株式会社大和化成研究所製のダインジンアロイＡＤ２）と４２ｇ／Ｌのアンモニア（２５％）を含む水溶液からなるＺｎ−Ｎｉ合金めっき浴中において、Ｎｉめっき後の基材を陰極とし、Ｎｉ板を陽極として、電流密度４Ａ／ｄｍ２、液温４５℃で１５０秒間電気めっきを行うことにより、Ｎｉめっき層の表面に平均厚さ１．０μｍのＺｎ−Ｎｉ合金めっき層を形成した以外は、実施例６と同様の方法によりＳｎめっき材を得た後、リフロー処理に代えて、１６０℃で６０分間加熱する熱処理を行った。 [Comparative Example 5]
Instead of forming the Zn plating layer, 32 g / L of zinc chloride, 66 g / L of nickel chloride, 240 g / L of ammonium chloride and 100 mL / L of additives (Dynezin alloy AD2 manufactured by Daiwa Kasei Laboratory Co., Ltd.) In a Zn—Ni alloy plating bath consisting of an aqueous solution containing 42 g / L of ammonia (25%), the base material after Ni plating is used as a cathode, the Ni plate is used as an anode, the current density is 4 A / dm 2 , and the liquid temperature is 45. A Sn plating material was obtained by the same method as in Example 6 except that a Zn—Ni alloy plating layer having an average thickness of 1.0 μm was formed on the surface of the Ni plating layer by electroplating at ° C. for 150 seconds. After that, instead of the reflow treatment, a heat treatment was performed by heating at 160 ° C. for 60 minutes.

この熱処理後のＳｎめっき材について、実施例１と同様の方法により、断面のＳＩＭ像からＮｉ層と最表層の厚さを測定したところ、Ｎｉ層の厚さは０．３μｍであり、最表層の厚さ２．０μｍであることが確認された。 When the thickness of the Ni layer and the outermost layer was measured from the SIM image of the cross section of the Sn plating material after this heat treatment by the same method as in Example 1, the thickness of the Ni layer was 0.3 μm, and the outermost layer was found to be 0.3 μm. It was confirmed that the thickness of was 2.0 μm.

また、実施例１と同様の方法により、Ｓｎめっき材の表面を観察して、Ｚｎ相が占める面積の割合（面積率（面積％））を算出したところ、０面積％であった。 Further, when the surface of the Sn plating material was observed by the same method as in Example 1 and the ratio of the area occupied by the Zn phase (area ratio (area%)) was calculated, it was 0 area%.

また、実施例１と同様の方法により、Ｓｎめっき材の最表層中のＺｎの量を求めたところ、２．６質量％であった。 Further, when the amount of Zn in the outermost layer of the Sn plating material was determined by the same method as in Example 1, it was 2.6% by mass.

また、実施例１と同様の方法により、Ｓｎめっき材から切り出した試験片の耐食性を評価したところ、ガスが発生するまでの時間は２４時間より短く、耐食性が良好でなかった。 Further, when the corrosion resistance of the test piece cut out from the Sn plating material was evaluated by the same method as in Example 1, the time until gas was generated was shorter than 24 hours, and the corrosion resistance was not good.

また、実施例１と同様の方法により、Ｓｎめっき材の表面の反射濃度を測定したところ、０．２と低かった。 Moreover, when the reflection density on the surface of the Sn plating material was measured by the same method as in Example 1, it was as low as 0.2.

これらの実施例および比較例で得られたＳｎめっき材の製造条件および特性を表１〜表３に示す。 Tables 1 to 3 show the production conditions and characteristics of the Sn plating materials obtained in these Examples and Comparative Examples.

Figure 2021091939
Figure 2021091939

Figure 2021091939
Figure 2021091939

Figure 2021091939
Figure 2021091939

１０ 基材
１２ Ｎｉ層
１４ 最表層
１４ａ Ｓｎ相
１４ｂ Ｚｎ相 10 Base material 12 Ni layer 14 Outermost layer 14a Sn phase 14b Zn phase

Claims (17)

銅または銅合金からなる基材の表面にＮｉめっき皮膜を形成し、このＮｉめっき皮膜の表面にＺｎめっき皮膜を形成し、このＺｎめっき皮膜の表面にＳｎめっき皮膜を形成した後、Ｓｎの融点以上の温度で加熱することを特徴とする、Ｓｎめっき材の製造方法。 A Ni plating film is formed on the surface of a base material made of copper or a copper alloy, a Zn plating film is formed on the surface of the Ni plating film, a Sn plating film is formed on the surface of the Zn plating film, and then the melting point of Sn is formed. A method for producing a Sn plating material, which comprises heating at the above temperature. 前記Ｎｉめっき皮膜の平均厚さが０．１〜１．０μｍであることを特徴とする、請求項１に記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to claim 1, wherein the average thickness of the Ni plating film is 0.1 to 1.0 μm. 前記Ｚｎめっき皮膜の平均厚さが０．１〜６．０μｍであることを特徴とする、請求項１または２に記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to claim 1 or 2, wherein the average thickness of the Zn plating film is 0.1 to 6.0 μm. 前記Ｓｎめっき皮膜の平均厚さが０．１〜６．０μｍであることを特徴とする、請求項１乃至３のいずれかに記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to any one of claims 1 to 3, wherein the Sn plating film has an average thickness of 0.1 to 6.0 μm. 前記加熱により、前記基材の表面にＮｉ層を介してＳｎ相と複数のＺｎ相とからなる最表層を形成し、この最表層のＺｎ相の一部を最表層の表面に露出させることを特徴とする、請求項１乃至４のいずれかに記載のＳｎめっき材の製造方法。 By the heating, an outermost layer composed of a Sn phase and a plurality of Zn phases is formed on the surface of the base material via a Ni layer, and a part of the Zn phase of the outermost layer is exposed on the surface of the outermost layer. The method for producing a Sn plating material according to any one of claims 1 to 4, which is characteristic. 前記加熱により、前記複数のＺｎ相をＳｎ相内で互いに離間して形成することを特徴とする、請求項５に記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to claim 5, wherein the plurality of Zn phases are formed so as to be separated from each other in the Sn phase by the heating. 前記最表層の表面に露出したＺｎ相が占める面積の割合が１〜９０面積％であることを特徴とする、請求項５または６に記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to claim 5 or 6, wherein the ratio of the area occupied by the Zn phase exposed on the surface of the outermost layer is 1 to 90 area%. 前記最表層が５〜９０質量％のＺｎを含むことを特徴とする、請求項５乃至７のいずれかに記載のＳｎめっき材の製造方法。 The method for producing a Sn plating material according to any one of claims 5 to 7, wherein the outermost surface layer contains 5 to 90% by mass of Zn. 前記最表層の表面に露出したＺｎ相の長径が０．１〜５．０μｍ、短径が０．１〜５．０μｍであり、アスペクト比が１．０〜５．０であることを特徴とする、請求項５乃至８のいずれかに記載のＳｎめっき材の製造方法。 The Zn phase exposed on the surface of the outermost layer has a major axis of 0.1 to 5.0 μm, a minor axis of 0.1 to 5.0 μm, and an aspect ratio of 1.0 to 5.0. The method for producing a Sn plating material according to any one of claims 5 to 8. 銅または銅合金からなる基材の表面にＮｉ層が形成され、このＮｉ層の表面にＳｎ相と複数のＺｎ相とからなる最表層が形成され、この最表層のＺｎ相の一部が最表層の表面に露出していることを特徴とする、Ｓｎめっき材。 A Ni layer is formed on the surface of a base material made of copper or a copper alloy, and an outermost layer composed of a Sn phase and a plurality of Zn phases is formed on the surface of the Ni layer, and a part of the Zn phase of the outermost layer is the most. A Sn plating material characterized by being exposed on the surface of the surface layer. 前記複数のＺｎ相がＳｎ相内で互いに離間して形成されていることを特徴とする、請求項１０に記載のＳｎめっき材。 The Sn plating material according to claim 10, wherein the plurality of Zn phases are formed so as to be separated from each other in the Sn phase. 前記最表層の表面に露出したＺｎ相が占める面積の割合が１〜９０面積％であることを特徴とする、請求項１０または１１に記載のＳｎめっき材。 The Sn plating material according to claim 10 or 11, wherein the ratio of the area occupied by the Zn phase exposed on the surface of the outermost layer is 1 to 90 area%. 前記最表層が５〜９０質量％のＺｎを含むことを特徴とする、請求項１０乃至１２のいずれかに記載のＳｎめっき材。 The Sn plating material according to any one of claims 10 to 12, wherein the outermost surface layer contains 5 to 90% by mass of Zn. 前記Ｎｉ層の平均厚さが０．１〜１．０μｍであることを特徴とする、請求項１０乃至１３のいずれかに記載のＳｎめっき材。 The Sn plating material according to any one of claims 10 to 13, wherein the average thickness of the Ni layer is 0.1 to 1.0 μm. 前記最表層の平均厚さが０．２〜７．０μｍであることを特徴とする、請求項１０乃至１４のいずれかに記載のＳｎめっき材。 The Sn plating material according to any one of claims 10 to 14, wherein the average thickness of the outermost layer is 0.2 to 7.0 μm. 前記最表層の表面の反射濃度が０．３以上であることを特徴とする、請求項１０乃至１５のいずれかに記載のＳｎめっき材。 The Sn plating material according to any one of claims 10 to 15, wherein the reflection density on the surface of the outermost layer is 0.3 or more. 前記最表層の表面に露出したＺｎ相の長径が０．１〜５．０μｍ、短径が０．１〜５．０μｍであり、アスペクト比が１．０〜５．０であることを特徴とする、請求項１０乃至１６のいずれかに記載のＳｎめっき材。 The Zn phase exposed on the surface of the outermost layer has a major axis of 0.1 to 5.0 μm, a minor axis of 0.1 to 5.0 μm, and an aspect ratio of 1.0 to 5.0. The Sn plating material according to any one of claims 10 to 16.
JP2019223550A 2019-12-11 2019-12-11 Sn plating material and its manufacturing method Active JP7404053B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019223550A JP7404053B2 (en) 2019-12-11 2019-12-11 Sn plating material and its manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2019223550A JP7404053B2 (en) 2019-12-11 2019-12-11 Sn plating material and its manufacturing method

Publications (2)

Publication Number Publication Date
JP2021091939A true JP2021091939A (en) 2021-06-17
JP7404053B2 JP7404053B2 (en) 2023-12-25

Family

ID=76311871

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2019223550A Active JP7404053B2 (en) 2019-12-11 2019-12-11 Sn plating material and its manufacturing method

Country Status (1)

Country Link
JP (1) JP7404053B2 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002317233A (en) 2001-04-20 2002-10-31 Nippon Steel Corp Hot dip tin-zinc based plated steel sheet
JP2008248332A (en) 2007-03-30 2008-10-16 Nikko Kinzoku Kk Tin-plated strip and its production method
JP6449690B2 (en) 2015-03-12 2019-01-09 株式会社Uacj Conductive material with Sn plating layer
JP6501039B2 (en) 2017-01-30 2019-04-17 三菱マテリアル株式会社 Connector terminal material and terminal and wire end structure
JP6978287B2 (en) 2017-11-16 2021-12-08 Ｄｏｗａメタルテック株式会社 Plating material

Also Published As

Publication number Publication date
JP7404053B2 (en) 2023-12-25

Similar Documents

Publication Publication Date Title
JP6734185B2 (en) Sn plated material and manufacturing method thereof
JP6740635B2 (en) Tin-plated copper terminal material, its manufacturing method, and wire terminal structure
JP5025387B2 (en) Conductive material for connecting parts and method for manufacturing the same
JP6304447B2 (en) Tin-plated copper terminal material and terminal and wire terminal structure
US10985485B2 (en) Tin-plated product and method for producing same
TWI719093B (en) Manufacturing method of tinned copper terminal material
TW201812108A (en) Tinned copper terminal material, terminal, and electrical wire end part structure
JP6940380B2 (en) Sn plating material and its manufacturing method
CN110214203B (en) Terminal material for connector, terminal and wire end part structure
JP7187162B2 (en) Sn-plated material and its manufacturing method
JP2018147777A (en) Anticorrosive terminal material and anticorrosive terminal and wire terminal structure
KR102385215B1 (en) Sn plating material and manufacturing method thereof
CN110997984B (en) Tin-plated copper terminal material, terminal and wire terminal part structure
JP6086531B2 (en) Silver plating material
JP5185759B2 (en) Conductive material and manufacturing method thereof
JP7404053B2 (en) Sn plating material and its manufacturing method
JP2019011503A (en) Anticorrosion terminal material, manufacturing method thereof, anticorrosion terminal and wire terminal part structure
JP2019011504A (en) Anticorrosion terminal material, manufacturing method thereof, anticorrosion terminal and wire terminal part structure
JP6839952B2 (en) Sn plating material and its manufacturing method
JP2018147778A (en) Anticorrosive terminal material, anticorrosive terminal, and wire terminal structure
JP2020056090A (en) Anticorrosive terminal material, manufacturing method therefor, and anticorrosive terminal and wire terminal part structure
JP2018016878A (en) Manufacturing method of tin plating copper terminal material
JP2024077764A (en) Method for manufacturing silver-coated material, silver-coated material and current-carrying component
JP2014164939A (en) Crimp terminal

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20221026

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20230809

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20230822

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20231005

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20231205

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20231213

R150 Certificate of patent or registration of utility model

Ref document number: 7404053

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150