JP5848168B2 - Silver plating material - Google Patents

Silver plating material Download PDF

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JP5848168B2
JP5848168B2 JP2012056586A JP2012056586A JP5848168B2 JP 5848168 B2 JP5848168 B2 JP 5848168B2 JP 2012056586 A JP2012056586 A JP 2012056586A JP 2012056586 A JP2012056586 A JP 2012056586A JP 5848168 B2 JP5848168 B2 JP 5848168B2
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silver plating
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plating layer
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圭介 篠原
圭介 篠原
雅史 尾形
雅史 尾形
宮澤　寛
寛 宮澤
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Dowa Metaltech Co Ltd
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本発明は、銀めっき材に関し、特に、車載用や民生用の電気配線に使用されるコネクタ、スイッチ、リレーなどの接点や端子部品の材料として使用される銀めっき材に関する。   The present invention relates to a silver plating material, and more particularly, to a silver plating material used as a material for contacts and terminal parts such as connectors, switches, and relays used in in-vehicle and consumer electrical wiring.

従来、コネクタやスイッチなどの接点や端子部品などの材料として、銅または銅合金などの比較的安価で耐食性や機械的特性などに優れた素材に、電気特性や半田付け性などの必要な特性に応じて、錫、銀、金などのめっきを施しためっき材が使用されている。   Conventionally, as a material for contacts and terminal parts such as connectors and switches, a relatively inexpensive material such as copper or copper alloy, which has excellent corrosion resistance and mechanical properties, and the necessary characteristics such as electrical characteristics and solderability. Accordingly, plating materials plated with tin, silver, gold or the like are used.

銅または銅合金などの素材に錫めっきを施した錫めっき材は、安価であるが、高温環境下における耐食性に劣っている。また、これらの素材に金めっきを施した金めっき材は、耐食性に優れ、信頼性が高いが、コストが高くなる。一方、これらの素材に銀めっきを施した銀めっき材は、金めっき材と比べて安価であり、錫めっき材と比べて耐食性に優れている。   A tin-plated material obtained by tin-plating a material such as copper or a copper alloy is inexpensive, but has poor corrosion resistance in a high-temperature environment. In addition, gold plating materials obtained by applying gold plating to these materials are excellent in corrosion resistance and high in reliability, but cost is high. On the other hand, silver plating materials obtained by performing silver plating on these materials are cheaper than gold plating materials and have excellent corrosion resistance compared to tin plating materials.

また、コネクタやスイッチなどの接点や端子部品などは、コネクタの挿抜やスイッチの摺動に伴う耐摩耗性も要求され、さらに、エンジン周辺などの高温環境下で使用される場合には、高温環境下における信頼性（耐熱性）も要求される。   Also, contacts and terminal parts such as connectors and switches are required to have wear resistance due to connector insertion / removal and switch sliding, and when used in a high temperature environment such as around the engine, Reliability (heat resistance) below is also required.

銀めっき材の耐摩耗性を向上させるために、銀めっき層中にアンチモンやビスマスなどの元素を含有させることによって、銀めっき材の硬度を向上させる方法が知られている。しかし、この方法で硬度を向上させた銀めっき材は、素材またはその上に形成された下地層が銅または銅合金からなる場合に、高温環境下で使用すると、銅が拡散して銀めっきの表面にＣｕＯが形成され、接触抵抗が上昇するという問題がある。   In order to improve the wear resistance of the silver plating material, a method of improving the hardness of the silver plating material by adding an element such as antimony or bismuth in the silver plating layer is known. However, the silver plating material whose hardness has been improved by this method is such that when the material or the underlying layer formed on it is made of copper or a copper alloy, the copper diffuses when used in a high temperature environment. There is a problem that CuO is formed on the surface and the contact resistance increases.

このように銀めっき層中にアンチモンなどを添加した銀めっき材において、耐熱性を向上させるために、銅または銅合金部材の表面の少なくとも一部に、アンチモン濃度が０．１質量％以下の銀または銀合金層を形成し、この銀または銀合金層の上に、最表層としてビッカース硬度Ｈｖ１４０以上の銀合金層を形成する方法が提案されている（例えば、特許文献１参照）。   Thus, in order to improve heat resistance in the silver plating material which added antimony etc. in the silver plating layer, silver with an antimony concentration of 0.1% by mass or less is formed on at least a part of the surface of the copper or copper alloy member. Alternatively, a method has been proposed in which a silver alloy layer is formed and a silver alloy layer having a Vickers hardness of Hv140 or higher is formed as the outermost layer on the silver or silver alloy layer (see, for example, Patent Document 1).

特開２００７−７９２５０号公報（段落番号００１０）JP 2007-79250 A (paragraph number 0010)

しかし、特許文献１のような最表面として銀合金層が形成された銅または銅合金部材では、高温環境下における信頼性（耐熱性）が十分ではなく、また、銀めっき材を複雑な形状や小型のコネクタやスイッチなどの接点や端子部品に加工すると、銀めっき材に割れが生じて、素材が露出してしまうという問題がある。   However, in the copper or copper alloy member in which the silver alloy layer is formed as the outermost surface as in Patent Document 1, the reliability (heat resistance) in a high temperature environment is not sufficient, and the silver plating material has a complicated shape or When processing into contacts and terminal parts such as small connectors and switches, there is a problem that the silver plating material is cracked and the material is exposed.

したがって、本発明は、このような従来の問題点に鑑み、耐熱性、耐摩耗性および曲げ加工性に優れた銀めっき材を提供することを目的とする。   Therefore, in view of such a conventional problem, an object of the present invention is to provide a silver plating material excellent in heat resistance, wear resistance and bending workability.

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、結晶方位を制御した第１の銀めっき層を素材上に形成した後、具体的には、第１の銀めっき層の（銀結晶中の主要な配向モードである）｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度（Ｘ線回折ピークの積分強度）の和に対する｛２００｝面のＸ線回折強度の占める割合（以下、「｛２００｝配向強度比」という）を高めて４０％以上にした第１の銀めっき層を素材上に形成した後、この第1の銀めっき層上にビッカース硬度Ｈｖ１４０以上の第２の銀めっき層を形成することにより、耐熱性、耐摩耗性および曲げ加工性に優れた銀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 intensive studies to solve the above-mentioned problems, the present inventors have formed a first silver plating layer with controlled crystal orientation on the material, and specifically, the first silver plating layer ( {For the sum of X-ray diffraction intensities (integrated intensities of X-ray diffraction peaks) of {111} plane, {200} plane, {220} plane, and {311} plane, which are the main orientation modes in silver crystals) The first silver plating layer having a proportion of the X-ray diffraction intensity of the 200} plane (hereinafter referred to as “{200} orientation intensity ratio”) increased to 40% or more is formed on the material, and then the first It has been found that by forming a second silver plating layer having a Vickers hardness of Hv140 or higher on the silver plating layer, a silver plating material excellent in heat resistance, wear resistance and bending workability can be produced. It came to be completed.

すなわち、本発明による銀めっき材は、素材上に｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度の和に対する｛２００｝面のＸ線回折強度の割合が４０％以上である第１の銀めっき層が形成され、この第1の銀めっき層上にビッカース硬度Ｈｖ１４０以上の第２の銀めっき層が形成されていることを特徴とする。   That is, the silver-plated material according to the present invention has an X-ray diffraction of {200} plane with respect to the sum of X-ray diffraction intensities of {111} plane, {200} plane, {220} plane and {311} plane on the material. A first silver plating layer having a strength ratio of 40% or more is formed, and a second silver plating layer having a Vickers hardness of Hv140 or more is formed on the first silver plating layer.

この銀めっき材において、第２の銀めっき層が０．５質量％以上のアンチモンを含むのが好ましい。また、素材が銅または銅合金からなるのが好ましく、素材が銅または銅合金以外からなる場合には、素材と第１の銀めっき層の間に銅または銅合金からなる下地層が形成されているのが好ましい。   In this silver plating material, it is preferable that the second silver plating layer contains 0.5% by mass or more of antimony. Moreover, it is preferable that the material is made of copper or a copper alloy, and when the material is made of other than copper or a copper alloy, an underlayer made of copper or a copper alloy is formed between the material and the first silver plating layer. It is preferable.

また、本発明による接点または端子部品は、上記の銀めっき材を材料として用いたことを特徴とする。   The contact or terminal component according to the present invention is characterized by using the above-mentioned silver plating material as a material.

本発明によれば、耐熱性、耐摩耗性および曲げ加工性に優れた銀めっき材を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the silver plating material excellent in heat resistance, abrasion resistance, and bending workability can be provided.

本発明による銀めっき材の実施の形態を概略的に示す断面図である。It is sectional drawing which shows schematically embodiment of the silver plating material by this invention. 比較例１の銀めっき材概略的に示す断面図である。It is sectional drawing which shows the silver plating material of the comparative example 1 roughly. 比較例２の銀めっき材概略的に示す断面図である。It is sectional drawing which shows the silver plating material of the comparative example 2 roughly. 比較例３の銀めっき材概略的に示す断面図である。It is sectional drawing which shows the silver plating material of the comparative example 3 roughly. 比較例４の銀めっき材概略的に示す断面図である。It is sectional drawing which shows the silver plating material of the comparative example 4 roughly. 比較例５の銀めっき材概略的に示す断面図である。It is sectional drawing which shows the silver plating material of the comparative example 5 roughly.

本発明による銀めっき材の実施の形態では、図１に示すように、素材１２上に｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度の和に対する｛２００｝面のＸ線回折強度の割合が４０％以上である第１の銀めっき層１４が形成され、この第1の銀めっき層１４上にビッカース硬度Ｈｖ１４０以上の第２の銀めっき層１６が形成されている。この銀めっき材１０において、第２の銀めっき層１６が０．５質量％以上のアンチモンを含むのが好ましい。また、素材１２が銅または銅合金からなるのが好ましく、素材１２が銅または銅合金以外からなる場合には、素材１２と第１の銀めっき層１４の間に銅または銅合金からなる下地層が形成されているのが好ましい。また、第１の銀めっき層１４の膜厚と第２の銀めっき層１６の膜厚の比が１：１〜３：１であるのが好ましい。   In the embodiment of the silver plating material according to the present invention, as shown in FIG. 1, the X-ray diffraction intensity of each of the {111} plane, {200} plane, {220} plane, and {311} plane on the material 12 is shown. A first silver plating layer 14 having a ratio of the X-ray diffraction intensity of the {200} plane to the sum of 40% or more is formed, and a second silver plating having a Vickers hardness Hv 140 or more is formed on the first silver plating layer 14. Layer 16 is formed. In this silver plating material 10, it is preferable that the second silver plating layer 16 contains 0.5% by mass or more of antimony. Moreover, it is preferable that the raw material 12 consists of copper or a copper alloy, and when the raw material 12 consists of other than copper or a copper alloy, the base layer which consists of a copper or copper alloy between the raw material 12 and the 1st silver plating layer 14 Is preferably formed. Moreover, it is preferable that ratio of the film thickness of the 1st silver plating layer 14 and the film thickness of the 2nd silver plating layer 16 is 1: 1-3: 1.

このような銀めっき材１０は、素材１２上に｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度の和に対する｛２００｝面のＸ線回折強度の割合が４０％以上である第１の銀めっき層１４を形成した後、この第1の銀めっき層１４上に（好ましくは０．５質量％以上のアンチモンを含むとともに）ビッカース硬度Ｈｖ１４０以上の第２の銀めっき層１６を形成することによって製造することができる。   Such a silver plating material 10 has an X-ray diffraction on the {200} plane with respect to the sum of the X-ray diffraction intensities of the {111} plane, {200} plane, {220} plane, and {311} plane on the material 12. After the first silver plating layer 14 having a strength ratio of 40% or more is formed, the Vickers hardness Hv 140 or more is formed on the first silver plating layer 14 (preferably containing 0.5% by mass or more of antimony). It can manufacture by forming the 2nd silver plating layer 16 of this.

具体的には、第１の銀めっき層１４は、５〜１５ｍｇ／Ｌのセレンを含み且つフリーシアンに対する銀の質量比が０．９〜１．８である第１の銀めっき浴中において電気めっきを行うことによって素材上に形成するこができる。なお、電気めっきの際の液温は、好ましくは１０〜４０℃、さらに好ましくは１５〜３０℃であり、電流密度は、好ましくは１〜１５Ａ／ｄｍ２、さらに好ましくは３〜１０Ａ／ｄｍ２である。 Specifically, the first silver plating layer 14 contains 5 to 15 mg / L of selenium and has an electric power in a first silver plating bath in which the mass ratio of silver to free cyan is 0.9 to 1.8. It can form on a raw material by plating. The liquid temperature during electroplating is preferably 10 to 40 ° C., more preferably 15 to 30 ° C., and the current density is preferably 1 to 15 A / dm 2 , more preferably 3 to 10 A / dm 2. It is.

この第１の銀めっき層１４を形成するための第１の銀めっき浴として、シアン化銀カリウム（ＫＡｇ（ＣＮ）２）と、シアン化カリウム（ＫＣＮ）と、３〜３０ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）とからなり、この銀めっき浴中のセレン濃度が５〜１５ｍｇ／Ｌであり且つフリーシアンに対する銀の質量比が０．９〜１．８である銀めっき浴を使用するのが好ましい。 As a first silver plating bath for forming the first silver plating layer 14, potassium cyanide (KAg (CN) 2 ), potassium cyanide (KCN), and 3-30 mg / L potassium selenocyanate ( It is preferable to use a silver plating bath having a selenium concentration in this silver plating bath of 5 to 15 mg / L and a mass ratio of silver to free cyan of 0.9 to 1.8.

なお、銀めっき材の第１の銀めっき層は、銀を含むめっき層であり、５〜１５ｍｇ／Ｌのセレンを含み且つフリーシアンに対する銀の質量比が０．９〜１．８である銀めっき浴中において電気めっきを行うことによって、｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度の和に対する｛２００｝面のＸ線回折強度の占める割合が４０％以上になるように形成することができれば、銀合金のめっき層でもよい。   The first silver plating layer of the silver plating material is a plating layer containing silver, silver containing 5 to 15 mg / L selenium and having a mass ratio of silver to free cyan of 0.9 to 1.8. By electroplating in the plating bath, the X-ray diffraction intensity of the {200} plane relative to the sum of the X-ray diffraction intensities of the {111} plane, {200} plane, {220} plane, and {311} plane A silver alloy plating layer may be used as long as it can be formed so as to have an occupation ratio of 40% or more.

また、第２の銀めっき層は、５０〜１５０ｇ／Ｌのシアン化銀力リウムと、９０〜１５０ｇ／Ｌのシアン化力リウムと、１０〜５０ｇ／Ｌの酒石酸ナトリウムカリウム四水和物と、３〜２０ｇ／Ｌの酒石酸アンチモンカリウムからなる第２の銀めっき液中において電気めっきを行うことによって第１の銀めっき層の表面に形成するのが好ましい。なお、電気めっきの際の液温は、好ましくは１０〜４０℃、さらに好ましくは１５〜３０℃であり、電流密度は、好ましくは１〜１０Ａ／ｄｍ２、さらに好ましくは３〜１０Ａ／ｄｍ２である。 The second silver plating layer is composed of 50 to 150 g / L silver cyanide, 90 to 150 g / L cyanide, 10 to 50 g / L potassium sodium tartrate tetrahydrate, It is preferable to form it on the surface of the first silver plating layer by performing electroplating in a second silver plating solution comprising 3 to 20 g / L of antimony potassium tartrate. The liquid temperature during electroplating is preferably 10 to 40 ° C., more preferably 15 to 30 ° C., and the current density is preferably 1 to 10 A / dm 2 , more preferably 3 to 10 A / dm 2. It is.

以下、本発明による銀めっき材の実施例について詳細に説明する。   Hereinafter, the example of the silver plating material by this invention is described in detail.

［実施例１］
まず、素材（被めっき材）として６７ｍｍ×５０ｍｍ ×０．３ｍｍの純銅板を用意し、この被めっき材とＳＵＳ板をアルカリ脱脂液に入れ、被めっき材を陰極とし、ＳＵＳ板を陽極として、電圧５Ｖで３０秒間電解脱脂を行い、水洗した後、３％硫酸中で１５秒間酸洗を行った。 [Example 1]
First, a 67 mm × 50 mm × 0.3 mm pure copper plate is prepared as a material (material to be plated), the material to be plated and the SUS plate are put in an alkaline degreasing solution, the material to be plated is used as a cathode, and the SUS plate is used as an anode. Electrolytic degreasing was performed at a voltage of 5 V for 30 seconds, followed by washing with water and then pickling in 3% sulfuric acid for 15 seconds.

次に、３ｇ／Ｌのシアン化銀カリウムと９０ｇ／Ｌのシアン化カリウムからなる銀ストライクめっき浴中において、被めっき材を陰極とし、白金で被覆したチタン電極板を陽極として、スターラにより４００ｒｐｍで撹拌しながら電流密度２．５Ａ／ｄｍ２で１０秒間電気めっき（銀ストライクめっき）を行った。 Next, in a silver strike plating bath made of 3 g / L potassium potassium cyanide and 90 g / L potassium cyanide, the material to be plated is used as a cathode, and a titanium electrode plate coated with platinum is used as an anode, and stirred with a stirrer at 400 rpm. Then, electroplating (silver strike plating) was performed at a current density of 2.5 A / dm 2 for 10 seconds.

次に、１１１ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と、１２０ｇ／Ｌのシアン化カリウム（ＫＣＮ）と、１８ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）からなる銀めっき浴中において、被めっき材を陰極とし、銀電極板を陽極として、スターラにより４００ｒｐｍで撹拌しながら液温１８℃において電流密度５Ａ／ｄｍ２で銀めっき層（第１の銀めっき層）の膜厚が２μｍになるまで電気めっき（第１の銀めっき）を行った。 Next, in a silver plating bath composed of 111 g / L of potassium potassium cyanide (KAg (CN) 2 ), 120 g / L of potassium cyanide (KCN), and 18 mg / L of potassium selenocyanate (KSeCN) Using the material as the cathode and the silver electrode plate as the anode, stirring at 400 rpm with a stirrer until the film thickness of the silver plating layer (first silver plating layer) reaches 2 μm at a current density of 5 A / dm 2 at a liquid temperature of 18 ° C. Electroplating (first silver plating) was performed.

次に、１２０ｇ／Ｌのシアン化銀力リウムと、１２０ｇ／Ｌのシアン化力リウムと、３０ｇ／Ｌの酒石酸ナトリウムカリウム四水和物と、７ｇ／Ｌの酒石酸アンチモンカリウムからなる銀めっき液中において、被めっき材を陰極とし、銀電極板を陽極として、スターラにより４００ｒｐｍで損拝しながら液温２０℃において電流密度５Ａ／ｄｍ２で（第１の銀めっき層と第２の銀めっき層の）合計の銀めっき層の膜厚が３μｍになるまで電気めっき（第２の銀めっき）を行った。 Next, in a silver plating solution comprising 120 g / L silver cyanide, 120 g / L potassium cyanide, 30 g / L sodium potassium tartrate tetrahydrate, and 7 g / L antimony potassium tartrate. The material to be plated is a cathode, the silver electrode plate is an anode, and the current density is 5 A / dm 2 at a liquid temperature of 20 ° C. while being lost at 400 rpm by a stirrer (first silver plating layer and second silver plating layer) (Ii) Electroplating (second silver plating) was performed until the total silver plating layer thickness was 3 μm.

このようにして、図１に示すように、素材１２上に形成された第１の銀めっき層１４上に第２の銀めっき層１６が形成された銀めっき材１０を作製し、この銀めっき材１０について、第１の銀めっき層１４の｛２００｝配向強度比を算出し、第２の銀めっき層１６中のＳｂ含有量を算出し、第２の銀めっき層１６ビッカース硬度を測定するとともに、銀めっき材１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。   Thus, as shown in FIG. 1, the silver plating material 10 in which the second silver plating layer 16 is formed on the first silver plating layer 14 formed on the material 12 is produced, and this silver plating is performed. For the material 10, the {200} orientation strength ratio of the first silver plating layer 14 is calculated, the Sb content in the second silver plating layer 16 is calculated, and the Vickers hardness of the second silver plating layer 16 is measured. At the same time, the contact resistance, bending workability and wear resistance of the silver-plated material 10 before and after the heat resistance test were evaluated.

銀めっき材１０の第１の銀めっき層１４の｛２００｝配向強度比は、素材１２上に第１の銀めっき層１４を形成した後に第２の銀めっき層１６を形成しないで作製した銀めっき材について、Ｘ線回折（ＸＲＤ）分析装置（理学電気株式会社製のＲＩＮＴ−３Ｃ）により、管球Ｃｕ、管電圧３０ｋＶ、管電流３０ｍＡ、サンプリング幅０．０２０°の条件で、モノクロメータとガラスの試料ホルダを使用して得られたＸ線回折パターンから、第１の銀めっき層１４の｛１１１｝面、｛２００｝面、｛２２０｝面および｛３１１｝面の各々のＸ線回折ピークの積分強度を求めて、その合計に対して｛２００｝面のＸ線回折ピークの積分強度が占める割合として算出した。その結果、第１の銀めっき層１４の｛２００｝配向強度比は６６％であった。   The {200} orientation strength ratio of the first silver plating layer 14 of the silver plating material 10 is the silver produced without forming the second silver plating layer 16 after forming the first silver plating layer 14 on the material 12. With respect to the plated material, a monochromator was used with an X-ray diffraction (XRD) analyzer (RINT-3C manufactured by Rigaku Corporation) under the conditions of tube Cu, tube voltage 30 kV, tube current 30 mA, and sampling width 0.020 °. From the X-ray diffraction pattern obtained using the glass sample holder, the X-ray diffraction of each of the {111} plane, {200} plane, {220} plane and {311} plane of the first silver plating layer 14 The integrated intensity of the peak was determined and calculated as the ratio of the integrated intensity of the {200} plane X-ray diffraction peak to the total. As a result, the {200} orientation strength ratio of the first silver plating layer 14 was 66%.

銀めっき材１０の第２の銀めっき層１６中のＳｂ含有量は、銀めっき材１０から切り出した試験片中のＡｇ含有量（Ｘ質量％）およびＳｂ含有量（Ｙ質量％）をＩＣＰ装置（ジャーレルアッシュ社製ＩＲＩＳ／ＡＲ）を用いてプラズマ分光分析法によって求め、Ｙ／（Ｘ＋Ｙ）として算出した。その結果、第２の銀めっき層１６中のＳｂ含有量は１．３質量％であった。   The Sb content in the second silver plating layer 16 of the silver plating material 10 is obtained by calculating the Ag content (X mass%) and the Sb content (Y mass%) in the test piece cut out from the silver plating material 10 as an ICP device. It was calculated | required by the plasma spectroscopy analysis method using (JIREL-ASH company IRIS / AR), and computed as Y / (X + Y). As a result, the Sb content in the second silver plating layer 16 was 1.3% by mass.

銀めっき材１０の第２の銀めっき層１６のビッカース硬度は、素材１２上に第１の銀めっき層１４を形成しないで第２の銀めっき層１６を形成して作製した銀めっき材について、微小硬度計（株式会社ミツトヨ製のＨＭ２２１）を使用して、荷重１０ｇｆを１５秒間加えて、ＪＩＳ Ｚ２２４４に従って測定した。その結果、第２の銀めっき層１６のビッカース硬度Ｈｖは１７０であった。   The Vickers hardness of the second silver plating layer 16 of the silver plating material 10 is about the silver plating material produced by forming the second silver plating layer 16 on the material 12 without forming the first silver plating layer 14. Using a micro hardness tester (HM221 manufactured by Mitutoyo Corporation), a load of 10 gf was applied for 15 seconds, and the measurement was performed according to JIS Z2244. As a result, the Vickers hardness Hv of the second silver plating layer 16 was 170.

銀めっき材１０の耐熱性は、銀めっき材１０を乾燥機（アズワン社製のＯＦ４５０）により１５０℃で７２時間加熱する耐熱試験の前後に、電気接点シミュレータ（山崎精機研究所製のＣＲＳ−１）により荷重５０ｇｆで接触抵抗を測定することによって評価した。その結果、銀めっき材１０の接触抵抗は、耐熱試験前では１．２ｍΩ、耐熱試験後では１３．１ｍΩであり、耐熱試験後の接触抵抗も１５ｍΩ以下と良好であり、耐熱試験後の接触抵抗の上昇が抑制されていた。   The heat resistance of the silver-plated material 10 is determined by the electric contact simulator (CRS-1 manufactured by Yamazaki Seiki Laboratories) before and after the heat resistance test in which the silver-plated material 10 is heated at 150 ° C. for 72 hours with a dryer (OF450 manufactured by ASONE). ) To measure the contact resistance with a load of 50 gf. As a result, the contact resistance of the silver plating material 10 is 1.2 mΩ before the heat test, 13.1 mΩ after the heat test, and the contact resistance after the heat test is 15 mΩ or less, and the contact resistance after the heat test is good. The rise of was suppressed.

銀めっき材１０の曲げ加工性は、ＪＩＳ Ｚ２２４８のＶブロック法に準じて、銀めっき材１０を素材１２の圧延方向に対して垂直方向にＲ＝０．１で９０度に折り曲げた後、その折り曲げた箇所を顕微鏡（キーエンス社製のデジタルマイクロスコープＶＨＸ−１０００）により１０００倍に拡大して観察し、その割れの有無によって評価した。その結果、割れは観察されず、曲げ加工性は良好であった。   The bending workability of the silver-plated material 10 is determined by bending the silver-plated material 10 at 90 degrees with R = 0.1 in the direction perpendicular to the rolling direction of the material 12 according to JIS Z2248 V-block method. The bent portion was observed with a microscope (digital microscope VHX-1000 manufactured by Keyence Corporation) at a magnification of 1000 times, and was evaluated based on the presence or absence of the crack. As a result, no cracks were observed and the bending workability was good.

銀めっき材１０の耐摩耗性は、電気接点シミユレータ（山崎精機研究所製のＣＲＳ−１）を使用して、荷重５０ｇｆ、摺動速度５０ｍｍ／分、摺動距離２ｍｍで銀めっき材１０上で銀リベットを摺動させ、銀めっきが摩耗して素地が露出するまでの摺動回数（摺動耐久回数）を測定することによって評価した。その結果、摺動耐久回数は３１０回であり、耐摩耗性は良好であった。   The wear resistance of the silver-plated material 10 is determined on the silver-plated material 10 using an electrical contact simulator (CRS-1 manufactured by Yamazaki Seiki Laboratories) at a load of 50 gf, a sliding speed of 50 mm / min, and a sliding distance of 2 mm. Silver rivets were slid and evaluated by measuring the number of sliding times (sliding durability times) until the silver plating was worn and the substrate was exposed. As a result, the sliding durability was 310 times and the wear resistance was good.

［比較例１］
第１の銀めっきと第２の銀めっきの代わりに、１１１ｇ／Ｌのシアン化銀カリウムと、１２０ｇ／Ｌのシアン化カリウムと、７３ｍｇ／Ｌのセレノシアン酸カリウムからなる銀めっき浴中において、被めっき材を陰極とし、銀電極板を陽極として、スターラにより４００ｒｐｍで撹拌しながら液温２５℃において電流密度５Ａ／ｄｍ２で銀めっき層の膜厚が３μｍになるまで電気めっき（従来の銀めっきと同様の銀めっき）を行った以外は、実施例１と同様の方法により、図２に示すように、素材１２上に（従来の銀めっきと同様の方法により）銀めっき層１８が形成された銀めっき材１１０を作製した。 [Comparative Example 1]
In place of the first silver plating and the second silver plating, a material to be plated in a silver plating bath comprising 111 g / L of potassium cyanide cyanide, 120 g / L of potassium cyanide, and 73 mg / L of potassium selenocyanate And a silver electrode plate as an anode, electroplating until the film thickness of the silver plating layer reaches 3 μm at a current density of 5 A / dm 2 at a liquid temperature of 25 ° C. while stirring at 400 rpm with a stirrer (similar to conventional silver plating) The silver plating layer 18 was formed on the material 12 (by the same method as the conventional silver plating) as shown in FIG. A plating material 110 was produced.

このようにして作製した銀めっき材１１０について、銀めっき層１８の｛２００｝配向強度比を算出し、銀めっき層１８のビッカース硬度を測定するとともに、銀めっき材１１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。その結果、銀めっき層１８の｛２００｝配向強度比は７％、ビッカース硬度Ｈｖは１２０であった。また、銀めっき材１１０の接触抵抗は、耐熱試験前では１．４ｍΩ、耐熱試験後では２０．５ｍΩであり、耐熱試験後の接触抵抗は１５ｍΩより高く、耐熱試験後の接触抵抗が上昇していた。また、銀めっき材１１０の曲げ加工性試験では、めっきが割れて素地の露出が観察され、曲げ加工性は良好ではなかった。さらに、銀めっき材１１０の耐摩耗性試験では、摺動耐久回数は１２０回であり、耐摩耗性は良好ではなかった。   For the silver plating material 110 produced in this way, the {200} orientation strength ratio of the silver plating layer 18 is calculated, the Vickers hardness of the silver plating layer 18 is measured, and the contact resistance before and after the heat resistance test of the silver plating material 110. The bending workability and wear resistance were evaluated. As a result, the {200} orientation strength ratio of the silver plating layer 18 was 7%, and the Vickers hardness Hv was 120. Moreover, the contact resistance of the silver plating material 110 is 1.4 mΩ before the heat test, and 20.5 mΩ after the heat test. The contact resistance after the heat test is higher than 15 mΩ, and the contact resistance after the heat test is increased. It was. Moreover, in the bending workability test of the silver plating material 110, plating was cracked and the substrate was exposed, and the bending workability was not good. Furthermore, in the wear resistance test of the silver plating material 110, the sliding durability was 120 times, and the wear resistance was not good.

［比較例２］
第１の銀めっき層の膜厚が３μｍになるまで電気めっき（第１の銀めっき）を行って、第２の銀めっきを行わなかった以外は、実施例１と同様の方法により、実施例１と同様の方法により、図３に示すように、素材１２上に第１の銀めっき層１４’が形成された銀めっき材２１０を作製した。 [Comparative Example 2]
In the same manner as in Example 1 except that electroplating (first silver plating) was performed until the film thickness of the first silver plating layer reached 3 μm, and the second silver plating was not performed. 1, a silver plating material 210 in which a first silver plating layer 14 ′ was formed on the material 12 was produced as shown in FIG. 3.

このようにして作製した銀めっき材２１０について、第１の銀めっき層１４’の｛２００｝配向強度比を算出し、第１の銀めっき層１４’のビッカース硬度を測定するとともに、銀めっき材２１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。その結果、第１の銀めっき層１４’の｛２００｝配向強度比は６６％、ビッカース硬度Ｈｖは１１０であった。また、銀めっき材２１０の接触抵抗は、耐熱試験前では１．２ｍΩ、耐熱試験後では４．８ｍΩであり、耐熱試験後の接触抵抗は５ｍΩ以下と非常に良好であり、耐熱試験後の接触抵抗の上昇が抑制されていた。また、銀めっき材２１０の曲げ加工性試験では、割れは観察されず、曲げ加工性は良好であった。しかし、銀めっき材２１０の耐摩耗性試験では、摺動耐久回数は１００回であり、耐摩耗性は良好ではなかった。   For the silver plating material 210 thus produced, the {200} orientation strength ratio of the first silver plating layer 14 ′ is calculated, the Vickers hardness of the first silver plating layer 14 ′ is measured, and the silver plating material The contact resistance, bending workability, and wear resistance before and after the 210 heat test were evaluated. As a result, the {200} orientation strength ratio of the first silver plating layer 14 ′ was 66%, and the Vickers hardness Hv was 110. Further, the contact resistance of the silver plating material 210 is 1.2 mΩ before the heat test, and 4.8 mΩ after the heat test, and the contact resistance after the heat test is 5 mΩ or less, which is very good. The increase in resistance was suppressed. Further, in the bending workability test of the silver plating material 210, no crack was observed, and the bending workability was good. However, in the wear resistance test of the silver plating material 210, the number of sliding durability was 100, and the wear resistance was not good.

［比較例３］
第１の銀めっきを行わず、第２の銀めっき層の膜厚が３μｍになるまで電気めっき（第２の銀めっき）を行った以外は、実施例１と同様の方法により、実施例１と同様の方法により、図４に示すように、素材１２上に第２の銀めっき層１６’が形成された銀めっき材３１０を作製した。 [Comparative Example 3]
Example 1 was carried out in the same manner as in Example 1 except that electroplating (second silver plating) was performed until the film thickness of the second silver plating layer was 3 μm without performing the first silver plating. 4, a silver plating material 310 in which a second silver plating layer 16 ′ was formed on the material 12 was produced.

このようにして作製した銀めっき材３１０について、第２の銀めっき層１６’の｛２００｝配向強度比を算出し、第２の銀めっき層１６’のビッカース硬度を測定するとともに、銀めっき材３１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。その結果、第２の銀めっき層１６’の｛２００｝配向強度比は７％、ビッカース硬度Ｈｖは１７０であった。また、銀めっき材３１０の接触抵抗は、耐熱試験前では２．０ｍΩ、耐熱試験後では４２．９ｍΩであり、耐熱試験後の接触抵抗は１５ｍΩより高く、耐熱試験後の接触抵抗が上昇していた。また、銀めっき材３１０の曲げ加工性試験では、めっきが割れて素地の露出が観察され、曲げ加工性は良好ではなかった。なお、銀めっき材３１０の耐摩耗性試験では、摺動耐久回数は３００回であり、耐摩耗性は良好であった。   With respect to the silver plating material 310 thus produced, the {200} orientation strength ratio of the second silver plating layer 16 ′ is calculated, the Vickers hardness of the second silver plating layer 16 ′ is measured, and the silver plating material The contact resistance, bending workability and wear resistance before and after the heat resistance test of 310 were evaluated. As a result, the {200} orientation strength ratio of the second silver plating layer 16 ′ was 7%, and the Vickers hardness Hv was 170. Moreover, the contact resistance of the silver plating material 310 is 2.0 mΩ before the heat test, and 42.9 mΩ after the heat test. The contact resistance after the heat test is higher than 15 mΩ, and the contact resistance after the heat test is increased. It was. Moreover, in the bending workability test of the silver plating material 310, plating was cracked and the substrate was exposed, and the bending workability was not good. In the wear resistance test of the silver plating material 310, the sliding durability was 300 times, and the wear resistance was good.

［比較例４］
第１の銀めっきの代わりに、１１１ｇ／Ｌのシアン化銀カリウムと、１２０ｇ／Ｌのシアン化カリウムと、７３ｍｇ／Ｌのセレノシアン酸カリウムからなる銀めっき浴中において、被めっき材を陰極とし、銀電極板を陽極として、スターラにより４００ｒｐｍで撹拌しながら液温２５℃において電流密度５Ａ／ｄｍ２で銀めっき層の膜厚が２μｍになるまで電気めっき（従来の銀めっきと同様の銀めっき）を行った以外は、実施例１と同様の方法により、図５に示すように、素材１２上に形成された（従来の銀めっきと同様の方法により）銀めっき層１８’上に第２の銀めっき層１６が形成された銀めっき材４１０を作製した。 [Comparative Example 4]
In place of the first silver plating, in a silver plating bath comprising 111 g / L of potassium cyanide cyanide, 120 g / L of potassium cyanide, and 73 mg / L of potassium selenocyanate, the material to be plated is used as a cathode, and a silver electrode Electroplating (silver plating similar to conventional silver plating) at a current density of 5 A / dm 2 and a silver plating layer thickness of 2 μm while stirring at 400 rpm with a stirrer using the plate as the anode Except for the above, the second silver plating is performed on the silver plating layer 18 'formed on the material 12 by the same method as in Example 1 (as in the conventional silver plating) as shown in FIG. A silver plating material 410 on which the layer 16 was formed was produced.

このようにして作製した銀めっき材４１０について、銀めっき層１８’の｛２００｝配向強度比を算出し、第２の銀めっき層１６のビッカース硬度を測定するとともに、銀めっき材４１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。なお、銀めっき層１８’の｛２００｝配向強度比は、素材１２上に銀めっき層１８’を形成した後に第２の銀めっき層１６を形成しないで作製した銀めっき材について算出し、第２の銀めっき層１６のビッカース硬度は、素材１２上に銀めっき層１８’を形成しないで第２の銀めっき層１６を形成して作製した銀めっき材について測定した。その結果、銀めっき層１８’の｛２００｝配向強度比は７％、第２の銀めっき層１６のビッカース硬度Ｈｖは１７０であった。また、銀めっき材４１０の接触抵抗は、耐熱試験前では１．５ｍΩ、耐熱試験後では３２．０ｍΩであり、耐熱試験後の接触抵抗は１５ｍΩより高く、耐熱試験後の接触抵抗が上昇していた。また、銀めっき材４１０の曲げ加工性試験では、めっきが割れて素地の露出が観察され、曲げ加工性は良好ではなかった。なお、銀めっき材４１０の耐摩耗性試験では、摺動耐久回数は２９０回であり、耐摩耗性は良好であった。   For the silver plating material 410 thus produced, the {200} orientation strength ratio of the silver plating layer 18 ′ is calculated, the Vickers hardness of the second silver plating layer 16 is measured, and the heat resistance test of the silver plating material 410 is performed. The contact resistance before and after, bending workability and wear resistance were evaluated. The {200} orientation strength ratio of the silver plating layer 18 ′ is calculated for a silver plating material produced without forming the second silver plating layer 16 after forming the silver plating layer 18 ′ on the material 12, The Vickers hardness of the second silver plating layer 16 was measured on a silver plating material produced by forming the second silver plating layer 16 without forming the silver plating layer 18 ′ on the material 12. As a result, the {200} orientation strength ratio of the silver plating layer 18 ′ was 7%, and the Vickers hardness Hv of the second silver plating layer 16 was 170. Moreover, the contact resistance of the silver plating material 410 is 1.5 mΩ before the heat test, and 32.0 mΩ after the heat test. The contact resistance after the heat test is higher than 15 mΩ, and the contact resistance after the heat test is increased. It was. Further, in the bending workability test of the silver plating material 410, the plating was cracked and the substrate was exposed, and the bending workability was not good. In the wear resistance test of the silver plating material 410, the number of sliding durability was 290 times, and the wear resistance was good.

［比較例５］
第１の銀めっきと第２の銀めっきの順序を逆にして、第２の銀めっき層の膜厚が２μｍになるまで電気めっき（第２の銀めっき）を行った後に、（第２の銀めっき層と第１の銀めっき層の）合計の銀めっき層の膜厚が３μｍになるまで電気めっき（第１の銀めっき）を行った以外は、実施例１と同様の方法により、図６に示すように、素材１２上に形成された第２の銀めっき層１６上に第１の銀めっき層１４が形成された銀めっき材５１０を作製した。 [Comparative Example 5]
The order of the first silver plating and the second silver plating is reversed, and after electroplating (second silver plating) until the film thickness of the second silver plating layer becomes 2 μm, (second According to the same method as in Example 1, except that the electroplating (first silver plating) was performed until the total thickness of the silver plating layer (the silver plating layer and the first silver plating layer) became 3 μm. As shown in FIG. 6, a silver plating material 510 in which the first silver plating layer 14 was formed on the second silver plating layer 16 formed on the material 12 was produced.

このようにして作製した銀めっき材５１０について、第２の銀めっき層１６の｛２００｝配向強度比を算出し、第１の銀めっき層１４のビッカース硬度を測定するとともに、銀めっき材５１０の耐熱試験前後の接触抵抗、曲げ加工性および耐摩耗性を評価した。なお、第２の銀めっき層１６の｛２００｝配向強度比は、素材１２上に第２の銀めっき層１６を形成した後に第１の銀めっき層１４を形成しないで作製した銀めっき材について算出し、第１の銀めっき層１４のビッカース硬度は、素材１２上に第２の銀めっき層１６を形成しないで第１の銀めっき層１４を形成して作製した銀めっき材について測定した。その結果、第２の銀めっき層１６の｛２００｝配向強度比は７％、第１の銀めっき層１４のビッカース硬度Ｈｖは１１０であった。また、銀めっき材５１０の接触抵抗は、耐熱試験前では１．５ｍΩ、耐熱試験後では１２．０ｍΩであり、耐熱試験後の接触抵抗は１５ｍΩ以下と良好であり、耐熱試験後の接触抵抗の上昇が抑制されていた。しかし、銀めっき材５１０の曲げ加工性試験では、めっきが割れて素地の露出が観察され、曲げ加工性は良好ではなかった。また、銀めっき材５１０の耐摩耗性試験では、摺動耐久回数は１３０回であり、耐摩耗性は良好ではなかった。   About the silver plating material 510 produced in this way, the {200} orientation strength ratio of the second silver plating layer 16 is calculated, and the Vickers hardness of the first silver plating layer 14 is measured. The contact resistance, bending workability and wear resistance before and after the heat test were evaluated. Note that the {200} orientation strength ratio of the second silver plating layer 16 is the same as the silver plating material produced without forming the first silver plating layer 14 after forming the second silver plating layer 16 on the material 12. The Vickers hardness of the first silver plating layer 14 calculated was measured for a silver plating material produced by forming the first silver plating layer 14 without forming the second silver plating layer 16 on the material 12. As a result, the {200} orientation strength ratio of the second silver plating layer 16 was 7%, and the Vickers hardness Hv of the first silver plating layer 14 was 110. Moreover, the contact resistance of the silver plating material 510 is 1.5 mΩ before the heat test, and 12.0 mΩ after the heat test. The contact resistance after the heat test is 15 mΩ or less, and the contact resistance after the heat test is good. The rise was suppressed. However, in the bending workability test of the silver plating material 510, the plating was cracked and the substrate was exposed, and the bending workability was not good. Further, in the wear resistance test of the silver plating material 510, the sliding durability was 130 times, and the wear resistance was not good.

これらの実施例および比較例の結果を表１に示す。   The results of these examples and comparative examples are shown in Table 1.

Figure 0005848168
Figure 0005848168

本発明による銀めっき材は、車載用や民生用の電気配線に使用されるコネクタ、スイッチ、リレーなどの接点や端子部品の材料として使用することができる。特に、スイッチ用のバネ接点部材の材料の他、携帯電話や電気機器のリモコンなどのスイッチの材料として使用することができる。また、大電流が流れて発熱量が大きいハイブリッド電気自動車（ＨＥＶ）の充電端子や高圧コネクタなどの材料としても使用することができる。   The silver-plated material according to the present invention can be used as a material for contacts and terminal parts such as connectors, switches, and relays used in in-vehicle and consumer electrical wiring. In particular, it can be used as a material for a switch such as a mobile phone or a remote controller of an electric device in addition to a material for a spring contact member for the switch. It can also be used as a material for charging terminals and high voltage connectors of hybrid electric vehicles (HEV) that generate a large amount of heat and generate a large amount of heat.

１０、１１０、２１０、３１０、４１０、５１０ 銀めっき材
１２ 素材
１４、１４’ 第１の銀めっき層
１６、１６’ 第２の銀めっき層
１８、１８’ 従来の銀めっきと同様の方法により形成された銀めっき層 10, 110, 210, 310, 410, 510 Silver plating material 12 Material 14, 14 'First silver plating layer 16, 16' Second silver plating layer 18, 18 'Formed by the same method as conventional silver plating Silver plating layer

Claims (5)

素材上に｛１１１｝面と｛２００｝面と｛２２０｝面と｛３１１｝面の各々のＸ線回折強度の和に対する｛２００｝面のＸ線回折強度の割合が４０％以上である第１の銀めっき層が形成され、この第1の銀めっき層上にビッカース硬度Ｈｖ１４０以上の第２の銀めっき層が形成されていることを特徴とする、銀めっき材。 The ratio of the X-ray diffraction intensity of the {200} plane to the sum of the X-ray diffraction intensities of the {111} plane, {200} plane, {220} plane, and {311} plane on the material is 40% or more. 1. A silver-plated material, wherein a silver-plated layer of 1 is formed, and a second silver-plated layer having a Vickers hardness of Hv140 or higher is formed on the first silver-plated layer. 前記第２の銀めっき層が０．５質量％以上のアンチモンを含むことを特徴とする、請求項１に記載の銀めっき材。 The silver plating material according to claim 1, wherein the second silver plating layer contains 0.5% by mass or more of antimony. 前記素材が銅または銅合金からなることを特徴とする、請求項１または２に記載の銀めっき材。 The silver plating material according to claim 1, wherein the material is made of copper or a copper alloy. 前記素材と前記第１の銀めっき層の間に銅または銅合金からなる下地層が形成されていることを特徴とする、請求項１または２に記載の銀めっき材。 The silver plating material according to claim 1 or 2, wherein a base layer made of copper or a copper alloy is formed between the material and the first silver plating layer. 請求項１乃至４のいずれかに記載の銀めっき材を材料として用いたことを特徴とする、接点または端子部品。 A contact or terminal component, wherein the silver plating material according to any one of claims 1 to 4 is used as a material.
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