JP2015124434A - Tin-plated copper-alloy terminal material - Google Patents
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本発明は、自動車や民生機器等の電気配線の接続に使用されるコネクタ用端子、特に多ピンコネクタ用の端子として有用な錫めっき銅合金端子材に関するものである。 TECHNICAL FIELD The present invention relates to a tin-plated copper alloy terminal material useful as a connector terminal used for connection of electrical wiring of automobiles and consumer devices, particularly as a terminal for a multi-pin connector.
近年、自動車において電装機器の多機能・高集積化に伴い、使用するコネクタ端子の小型化、多ピン化が顕著になっている。コネクタには錫めっき銅合金材が広く使用されているが、コネクタの多ピン化により、端子差込時の摩擦抵抗が増え、生産性が低下することが懸念されている。そこで、錫めっき銅合金材の摩擦係数を小さくして単ピンあたりの挿入力を低減することが試みられている。 2. Description of the Related Art In recent years, with the increase in the number of functions and integration of electrical equipment in automobiles, miniaturization and increase in the number of pins of connector terminals to be used have become remarkable. Although tin-plated copper alloy materials are widely used for connectors, there is a concern that the increase in the number of pins of the connector will increase the frictional resistance when inserting the terminals, resulting in a decrease in productivity. Therefore, attempts have been made to reduce the insertion force per single pin by reducing the friction coefficient of the tin-plated copper alloy material.
例えば、錫めっき銅合金材の最表面に錫とは異なる結晶構造を持つ金属とすることで挿入力を低減させるもの（特許文献１）があるが、接触抵抗が増大する、ハンダ濡れ性が低下するといった問題があった。
特許文献２では、表面めっき層をＳｎめっき層とＡｇまたはＩｎを含むめっき層とをリフロー処理または熱拡散処理された層としている。
また、特許文献３では、Ｓｎめっき層の上にＡｇめっき層を形成して熱処理することにより、Ｓｎ−Ａｇ合金層を形成することが示されている。
これらの特許文献２，３記載の技術は、いずれも熱処理しＳｎ合金層としたものであり、表面全体が硬いＳｎ合金層で覆われているため、オス、メス両端子に用いた場合には摩擦抵抗の低減効果があるが、片側の端子が汎用のＳｎめっき材の場合、アブレシブ摩耗が発生してしまう問題があった。
For example, there is a metal that has a crystal structure different from that of tin on the outermost surface of a tin-plated copper alloy material (Patent Document 1), but the contact resistance increases and the solder wettability decreases. There was a problem such as.
In Patent Document 2, the surface plating layer is a Sn plating layer and a plating layer containing Ag or In that are subjected to a reflow process or a thermal diffusion process.
Patent Document 3 discloses that an Sn-Ag alloy layer is formed by forming an Ag plating layer on the Sn plating layer and performing heat treatment.
These technologies described in Patent Documents 2 and 3 are all heat-treated to form an Sn alloy layer, and the entire surface is covered with a hard Sn alloy layer, so when used for both male and female terminals, Although there is an effect of reducing frictional resistance, there is a problem that abrasive wear occurs when the terminal on one side is a general-purpose Sn plating material.
ここで、コネクタの挿入力Ｆは、メス端子がオス端子を圧し付ける力（接圧）をＰ、動摩擦係数をμとすると、通常オス端子は上下２方向からメス端子に挟まれるので、Ｆ＝２×μ×Ｐ となる。このＦを小さくするには、Ｐを小さくすることが有効だが、コネクタ嵌合時のオス・メス端子の電気的接続信頼性を確保するためにはいたずらに接圧を小さくすることができず、３Ｎ程度は必要とされる。多ピンコネクタでは、５０ピン／コネクタを超えるものもあるが、コネクタ全体の挿入力は１００Ｎ以下、できれば８０Ｎ以下、あるいは７０Ｎ以下が望ましいため、動摩擦係数μとしては、０．３以下が必要とされる。 Here, the insertion force F of the connector is such that the force (contact pressure) by which the female terminal presses the male terminal is P, and the dynamic friction coefficient is μ. 2 × μ × P. In order to reduce this F, it is effective to reduce P, but in order to ensure the electrical connection reliability of the male and female terminals when the connector is fitted, the contact pressure cannot be reduced unnecessarily. About 3N is required. Some multi-pin connectors exceed 50 pins / connector, but the insertion force of the entire connector is preferably 100 N or less, preferably 80 N or less, or 70 N or less, so that the dynamic friction coefficient μ is required to be 0.3 or less. The
従来より表層の摩擦抵抗を下げた端子材が開発されているが、オス、メス端子を嵌合する接続端子の場合、両者に同じ材種を用いることが少なく、特にオス端子は、黄銅を基材とした汎用のＳｎめっき付き端子材が広く用いられている。そのため、メス端子のみに低挿入力端子材を用いても、挿入力低減の効果が小さいといった問題があった。 Conventionally, terminal materials with lower surface friction resistance have been developed, but in the case of connection terminals that fit male and female terminals, the same material type is rarely used for both, and male terminals are based on brass. A general-purpose terminal material with Sn plating as a material is widely used. Therefore, even if a low insertion force terminal material is used only for the female terminal, there is a problem that the effect of reducing the insertion force is small.
本発明は、前述の課題に鑑みてなされたものであって、汎用のＳｎめっき端子材を用いた端子に対しても嵌合時の挿入力を低減することができる錫めっき銅合金端子材の提供を目的とする。 The present invention has been made in view of the above-described problems, and is a tin-plated copper alloy terminal material that can reduce the insertion force at the time of fitting even to a terminal using a general-purpose Sn-plated terminal material. For the purpose of provision.
発明者らは、端子材表層の摩擦抵抗を下げる手段として、ＣｕＳｎ金属層とＳｎ系表面層との界面の形状を制御し、Ｓｎ系表面層の直下に急峻な凹凸形状のＣｕＳｎ合金層を配置することで摩擦係数が小さくなることを見出した。但し、この低挿入力端子材を端子の一方にのみ用い、他方を汎用のＳｎめっき材とした場合、摩擦係数低減の効果が半減した。
いずれも最表面がＳｎめっきであるため、同種のＳｎどうしが接触することでＳｎの凝着が発生して摩擦係数低減の効果が半減する。特に、低挿入力端子材は、Ｓｎ系表面層の直下に硬いＣｕＳｎ合金層が配置されているため、汎用のＳｎめっき材の軟らかいＳｎ系表面層のＳｎが削れて凝着すると考えられる。
発明者らは鋭意研究した結果、最表面に薄くＡｇ被覆層を形成することで、低挿入力端子材の摩擦係数低減効果を確保しつつ、さらにＳｎの凝着を抑制し、他方の端子に汎用材を用いても摩擦抵抗の低減が可能となることを見出した。
The inventors have controlled the shape of the interface between the CuSn metal layer and the Sn-based surface layer as a means to lower the frictional resistance of the surface layer of the terminal material, and placed a steep uneven CuSn alloy layer directly under the Sn-based surface layer. It has been found that the friction coefficient is reduced by doing so. However, when this low insertion force terminal material was used for only one of the terminals and the other was a general-purpose Sn plating material, the effect of reducing the friction coefficient was reduced by half.
In any case, since the outermost surface is Sn plating, Sn adhesion occurs when Sn of the same kind is in contact with each other, and the effect of reducing the friction coefficient is halved. In particular, since the low insertion force terminal material has a hard CuSn alloy layer arranged immediately below the Sn-based surface layer, it is considered that Sn of the soft Sn-based surface layer of a general-purpose Sn plating material is scraped and adhered.
As a result of intensive research, the inventors have formed a thin Ag coating layer on the outermost surface, thereby ensuring the effect of reducing the friction coefficient of the low insertion force terminal material, and further suppressing the adhesion of Sn, and the other terminal. It was found that the frictional resistance can be reduced even by using a general-purpose material.
本発明の錫めっき銅合金端子材は、Ｃｕ合金からなる基材上表面にＳｎ系表面層が形成され、前記Ｓｎ系表面層と前記基材との間にＣｕＳｎ合金層が形成されており、前記Ｓｎ系表面層を溶解除去して、前記ＣｕＳｎ合金層を表面に現出させたときに測定される前記ＣｕＳｎ合金層の油溜り深さＲｖｋが０．２μｍ以上であり、かつ前記Ｓｎ系表面層の平均厚みが０．２μｍ以上０．６μｍ以下であり、前記Ｓｎ系表面層の最表面に０．０５μｍ以下の膜厚のＡｇ被覆層が形成され、表面の動摩擦係数が０．３以下であることを特徴とする。 In the tin-plated copper alloy terminal material of the present invention, an Sn-based surface layer is formed on the surface of a base material made of a Cu alloy, and a CuSn alloy layer is formed between the Sn-based surface layer and the base material. An oil reservoir depth Rvk of the CuSn alloy layer measured when the Sn-based surface layer is dissolved and removed so that the CuSn alloy layer appears on the surface is 0.2 μm or more, and the Sn-based surface The average thickness of the layer is 0.2 μm or more and 0.6 μm or less, an Ag coating layer having a thickness of 0.05 μm or less is formed on the outermost surface of the Sn-based surface layer, and the surface dynamic friction coefficient is 0.3 or less. It is characterized by being.
ＣｕＳｎ合金層の油溜まり深さＲｖｋを０．２μｍ以上、Ｓｎ系表面層の平均厚みを０．２μｍ以上０．６μｍ以下とし、Ｓｎ系表面層の最表面に０．０５μｍ以下のＡｇ被覆層を設けることで、動摩擦係数を０．３以下とすることができる。
ＣｕＳｎ合金層の油溜り深さＲｖｋは、０．２μｍ未満では、ＣｕＳｎ合金層の凹部内に存在するＳｎが少なくなるので、動摩擦係数が増大する。また、Ｓｎ系表面層の平均厚みを０．２μｍ以上０．６μｍ以下としたのは、０．２μｍ未満でははんだ濡れ性の低下、電気的接続信頼性の低下を招き、０．６μｍを超えるとＣｕＳｎ合金層の油溜り深さＲｖｋを０．２μｍ以上とすることができず、Ｓｎの占める厚さが大きくなるので動摩擦係数が増大するためである。
Ａｇ被覆層の膜厚が０．０５μｍを超えると、Ｓｎ系表面層とＣｕＳｎ合金層との特殊な界面形状による摩擦係数低減効果とＡｇ被覆層によるＳｎ凝着抑制効果とを同時に得ることができず、Ａｇ被覆層による凝着抑制効果のみであるため十分な摩擦係数低減効果が得られない。またＡｇ系被覆層を厚くするほどコスト高となる。このＡｇ被覆層の膜厚は０．００５μｍ以上とするのが好ましい。
ここで、表面の動摩擦係数は、本発明の錫めっき銅合金端子材同士の間ではもちろんのこと、最表面にＳｎめっき層を有する汎用のＳｎめっき端子材に対しても、０．３以下とされる。最表面にＳｎめっき層を有する汎用のＳｎめっき端子材とは、基材にＣｕめっき、Ｓｎめっきを施してリフロー処理することにより得られるが、ＣｕＳｎ合金層の油溜り深さＲｖｋが０．２μｍ未満であり、平均厚み０．２μｍ以上３μｍ以下のＳｎめっき層を最表面に有するＳｎめっき端子材、あるいは、リフロー処理することなく、基材に厚み０．５μｍ以上３μｍ以下のＳｎめっき層を形成したＳｎめっき端子材をいう。
The oil reservoir depth Rvk of the CuSn alloy layer is 0.2 μm or more, the average thickness of the Sn-based surface layer is 0.2 μm or more and 0.6 μm or less, and an Ag coating layer of 0.05 μm or less is formed on the outermost surface of the Sn-based surface layer. By providing, a dynamic friction coefficient can be 0.3 or less.
When the oil sump depth Rvk of the CuSn alloy layer is less than 0.2 μm, Sn existing in the recesses of the CuSn alloy layer decreases, and the dynamic friction coefficient increases. In addition, the average thickness of the Sn-based surface layer is set to 0.2 μm or more and 0.6 μm or less. If the thickness is less than 0.2 μm, solder wettability and electrical connection reliability are deteriorated. This is because the oil sump depth Rvk of the CuSn alloy layer cannot be 0.2 μm or more, and the thickness occupied by Sn increases, so that the dynamic friction coefficient increases.
When the film thickness of the Ag coating layer exceeds 0.05 μm, it is possible to simultaneously obtain the friction coefficient reduction effect due to the special interface shape between the Sn-based surface layer and the CuSn alloy layer and the Sn adhesion suppression effect due to the Ag coating layer. In addition, since only the adhesion suppression effect by the Ag coating layer is obtained, a sufficient friction coefficient reduction effect cannot be obtained. Further, the thicker the Ag-based coating layer, the higher the cost. The thickness of the Ag coating layer is preferably 0.005 μm or more.
Here, the dynamic friction coefficient of the surface is 0.3 or less for the general-purpose Sn plating terminal material having the Sn plating layer on the outermost surface as well as between the tin plating copper alloy terminal materials of the present invention. Is done. A general-purpose Sn-plated terminal material having a Sn plating layer on the outermost surface is obtained by applying a Cu plating or Sn plating to a base material and performing a reflow process. Sn plating terminal material having an Sn plating layer with an average thickness of 0.2 μm or more and 3 μm or less on the outermost surface, or forming a Sn plating layer with a thickness of 0.5 μm or more and 3 μm or less on the substrate without reflow treatment Sn-plated terminal material.
本発明の錫めっき銅合金端子材において、前記ＣｕＳｎ合金層の平均厚みが０．６μｍ以上１μｍ以下であるとよい。
ＣｕＳｎ合金層の平均厚みが０．６μｍ未満では油溜まり深さＲｖｋを０．２μｍ以上とすることが難しく、１μｍ以上の厚みに形成するためにはＳｎ系表面層を必要以上に厚くする必要があり不経済である。
In the tin-plated copper alloy terminal material of the present invention, the average thickness of the CuSn alloy layer may be 0.6 μm or more and 1 μm or less.
If the average thickness of the CuSn alloy layer is less than 0.6 μm, it is difficult to make the oil sump depth Rvk 0.2 μm or more. In order to form a thickness of 1 μm or more, it is necessary to make the Sn-based surface layer thicker than necessary. Yes, it is uneconomical.
本発明の錫めっき銅合金端子材において、前記基材が、０．５質量％以上５質量％以下のＮｉ、０．１質量％以上１．５質量％以下のＳｉを含有し、更に必要に応じてＺｎ，Ｓｎ，Ｆｅ，Ｍｇの群から選ばれた１種以上を合計で５質量％以下含有し、残部がＣｕ及び不可避不純物から構成されるとよい。 In the tin-plated copper alloy terminal material of the present invention, the base material contains 0.5 mass% to 5 mass% Ni, 0.1 mass% to 1.5 mass% Si, and further required. Accordingly, it is preferable that one or more selected from the group of Zn, Sn, Fe, and Mg is contained in a total amount of 5% by mass or less, and the balance is composed of Cu and inevitable impurities.
ＣｕＳｎ系表面層の油溜まり深さＲｖｋを０．２μｍ以上とするためには、ＣｕＳｎ合金層中にＮｉ及びＳｉが固溶することが必要である。この場合、Ｎｉ及びＳｉを含有している基材を用いれば、リフロー時に基材よりＮｉ及びＳｉをＣｕＳｎ合金層中に供給することができる。ただし、基材中のこれらＮｉ及びＳｉの含有量は、Ｎｉが０．５質量％未満、Ｓｉが０．１質量％未満では、それぞれＮｉ又はＳｉの効果が現れず、Ｎｉでは５質量％を越えると鋳造や熱間圧延時に割れを生じるおそれがあり、Ｓｉでは１．５質量％を超えると導電性が低下するため、Ｎｉは０．５質量％以上５質量％以下、Ｓｉは０．１質量％以上１．５質量％以下が好ましい。
Ｚｎ，Ｓｎは、強度、耐熱性向上のために添加するとよく、また、Ｆｅ，Ｍｇは、応力緩和特性向上のために添加するとよいが、合計で５質量％を超えると導電率が低下するので好ましくない。
In order to set the oil reservoir depth Rvk of the CuSn-based surface layer to 0.2 μm or more, it is necessary that Ni and Si dissolve in the CuSn alloy layer. In this case, if a base material containing Ni and Si is used, Ni and Si can be supplied from the base material into the CuSn alloy layer during reflow. However, the content of these Ni and Si in the substrate is such that when Ni is less than 0.5% by mass and Si is less than 0.1% by mass, the effect of Ni or Si does not appear. If it exceeds, there is a risk of cracking during casting or hot rolling, and if Si exceeds 1.5% by mass, the conductivity will decrease, so Ni is 0.5% by mass or more and 5% by mass or less, and Si is 0.1% by mass. The mass% is preferably 1.5% by mass or less.
Zn and Sn should be added to improve strength and heat resistance, and Fe and Mg should be added to improve stress relaxation characteristics. However, if the total exceeds 5% by mass, the conductivity will decrease. It is not preferable.
本発明の錫めっき銅合金端子材によれば、ＣｕＳｎ金属層とＳｎ系表面層との界面の凹凸形状を制御した低挿入力端子材のＳｎ系表面層の最表面に０．０５μｍ以下の膜厚のＡｇ被覆層を形成したことにより、汎用のＳｎめっき材との組み合わせで用いる場合でも、嵌合時の挿入力を低減することが可能となる。 According to the tin-plated copper alloy terminal material of the present invention, a film of 0.05 μm or less is formed on the outermost surface of the Sn-type surface layer of the low insertion force terminal material in which the uneven shape of the interface between the CuSn metal layer and the Sn-type surface layer is controlled. By forming a thick Ag coating layer, even when used in combination with a general-purpose Sn plating material, the insertion force during fitting can be reduced.
本発明の一実施形態の錫めっき銅合金端子材を説明する。
この錫めっき銅合金端子材は、図１の模式図に示すように、Ｃｕ合金からなる基材５上表面にＳｎ系表面層６が形成され、Ｓｎ系表面層６とＣｕ合金基材５との間にＣｕＳｎ合金層７が形成されており、Ｓｎ系表面層６を溶解除去して、ＣｕＳｎ合金層７を表面に現出させたときに測定されるＣｕＳｎ合金層７の油溜り深さＲｖｋが０．２μｍ以上であり、かつＳｎ系表面層６の平均厚みが０．２μｍ以上０．６μｍ以下であり、Ｓｎ系表面層６の最表面に０．０５μｍ以下の膜厚のＡｇ被覆層８が形成され、表面の動摩擦係数が０．３以下である。
The tin plating copper alloy terminal material of one Embodiment of this invention is demonstrated.
As shown in the schematic diagram of FIG. 1, this tin-plated copper alloy terminal material has a Sn-based surface layer 6 formed on the surface of a base material 5 made of a Cu alloy, and the Sn-based surface layer 6, the Cu alloy base material 5, The CuSn alloy layer 7 is formed between the two, and the Sn-based surface layer 6 is dissolved and removed, and the oil reservoir depth Rvk of the CuSn alloy layer 7 measured when the CuSn alloy layer 7 appears on the surface. Is 0.2 μm or more, the average thickness of the Sn-based surface layer 6 is 0.2 μm or more and 0.6 μm or less, and the Ag coating layer 8 having a thickness of 0.05 μm or less is formed on the outermost surface of the Sn-based surface layer 6. Are formed, and the dynamic friction coefficient of the surface is 0.3 or less.
基材は、Ｃｕ−Ｎｉ−Ｓｉ系合金、Ｃｕ−Ｎｉ−Ｓｉ−Ｚｎ系合金等、Ｎｉ及びＳｉを含有し、更に必要に応じてＺｎ，Ｓｎ，Ｆｅ，Ｍｇの群から選ばれた１種以上を合計で５質量％以下含有し、残部がＣｕ及び不可避不純物から構成される銅合金である。Ｎｉ及びＳｉを必須成分としたのは、後述するリフロー処理により形成されるＣｕＳｎ合金層の油溜まり深さＲｖｋ０．２μｍ以上にするために、リフロー時に基材よりＮｉ及びＳｉを供給し、ＣｕＳｎ合金層中にＮｉ及びＳｉを固溶させるためである。基材中のＮｉの含有量としては０．５質量％以上５質量％以下が、Ｓｉの含有量としては０．１質量％以上１．５質量％以下が好ましい。Ｎｉが０．５質量％未満ではＮｉの効果、Ｓｉが０．１質量％未満ではＳｉの効果がそれぞれ現れず、Ｎｉが５質量％を越えると鋳造や熱間圧延時に割れを生じるおそれがあり、Ｓｉが１．５質量％を超えると導電性が低下するためである。 The base material contains Ni and Si, such as a Cu—Ni—Si based alloy, a Cu—Ni—Si—Zn based alloy, and is further selected from the group of Zn, Sn, Fe, and Mg as required. The total is 5% by mass or less in total, and the balance is a copper alloy composed of Cu and inevitable impurities. Ni and Si are essential components because Ni and Si are supplied from the base material at the time of reflow in order to make the oil reservoir depth Rvk of 0.2 μm or more of the CuSn alloy layer formed by the reflow process described later, CuSn alloy This is because Ni and Si are dissolved in the layer. The Ni content in the substrate is preferably 0.5% by mass or more and 5% by mass or less, and the Si content is preferably 0.1% by mass or more and 1.5% by mass or less. If Ni is less than 0.5% by mass, the effect of Ni will not occur, and if Si is less than 0.1% by mass, the effect of Si will not appear. If Ni exceeds 5% by mass, cracking may occur during casting or hot rolling. This is because when Si exceeds 1.5% by mass, the conductivity is lowered.
また、Ｚｎ，Ｓｎは、強度、耐熱性を向上させ、Ｆｅ，Ｍｇは、応力緩和特性を向上させる。これらＺｎ，Ｓｎ，Ｆｅ，Ｍｇのいずれか１種以上を添加する場合は、その合計の含有量が５質量％を超えると導電性が低下するので好ましくない。特に、Ｚｎ，Ｓｎ，Ｆｅ，Ｍｇの全てを含むことが好ましい。 Zn and Sn improve strength and heat resistance, and Fe and Mg improve stress relaxation characteristics. When adding any one or more of these Zn, Sn, Fe, and Mg, if the total content exceeds 5% by mass, the conductivity decreases, which is not preferable. In particular, it is preferable to include all of Zn, Sn, Fe, and Mg.
ＣｕＳｎ合金層は、後述するように基材の上にＣｕめっき層とＳｎめっき層とを形成してリフロー処理することにより形成されたものであり、その大部分はＣｕ６Ｓｎ５であるが、基材との界面付近に、基材中のＮｉ及びＳｉとＣｕの一部が置換した（Ｃｕ，Ｎｉ，Ｓｉ）６Ｓｎ５合金が薄く形成される。また、このＣｕＳｎ合金層とＳｎ系表面層との界面は、凹凸状に形成され、その油溜り深さＲｖｋが０．２μｍ以上とされる。
この油溜まり深さＲｖｋは、ＪＩＳ Ｂ０６７１−２で規定される表面粗さ曲線の突出谷部平均深さであり、平均的な凹凸よりも深い部分がどの程度あるかを示す指標とされ、この値が大きければ、非常に深い谷部分の存在により、急峻な凹凸形状となっていることを示す。
このＣｕＳｎ合金層の平均厚みは０．６μｍ以上１μｍ以下であるとよく、０．６μｍ未満ではＣｕＳｎ合金層の油溜まり深さＲｖｋを０．２μｍ以上とすることが難しく、１μｍ以下と規定したのは、１μｍ以上の厚みに形成するためにはＳｎ系表面層を必要以上に厚くする必要があり不経済である。
なお、このＣｕＳｎ合金層の一部（Ｃｕ６Ｓｎ５）がＳｎ系表面層に露出していてもよい。その場合、各露出部の円相当直径が０．６μｍ以上２．０μｍ以下で、露出面積率は４０％以下とされ、その限られた範囲であれば、Ｓｎ系表面層の持つ優れた電気接続特性を損なうことはない。
The CuSn alloy layer is formed by forming a Cu plating layer and a Sn plating layer on a base material and performing a reflow treatment as will be described later. Most of the CuSn alloy layer is Cu 6 Sn 5 , A thin (Cu, Ni, Si) 6 Sn 5 alloy in which a part of Ni and Si and Cu in the base material is substituted is formed near the interface with the base material. In addition, the interface between the CuSn alloy layer and the Sn-based surface layer is formed in an uneven shape, and the oil sump depth Rvk is 0.2 μm or more.
This oil sump depth Rvk is the average depth of the projecting valley portion of the surface roughness curve defined in JIS B0671-2, and is an index indicating how much the portion is deeper than the average unevenness. A large value indicates a steep uneven shape due to the presence of a very deep valley.
The average thickness of the CuSn alloy layer is preferably 0.6 μm or more and 1 μm or less, and if it is less than 0.6 μm, it is difficult to make the oil reservoir depth Rvk of the CuSn alloy layer 0.2 μm or more, and it is defined as 1 μm or less. Is uneconomical because it is necessary to make the Sn-based surface layer thicker than necessary to form a thickness of 1 μm or more.
A part of this CuSn alloy layer (Cu 6 Sn 5 ) may be exposed on the Sn-based surface layer. In that case, the circle equivalent diameter of each exposed portion is 0.6 μm or more and 2.0 μm or less, and the exposed area ratio is 40% or less. There is no loss of properties.
Ｓｎ系表面層は平均厚みが０．２μｍ以上０．６μｍ以下に形成される。その厚みが０．２μｍ未満でははんだ濡れ性の低下、電気的接続信頼性の低下を招き、０．６μｍを超えると表層をＳｎとＣｕＳｎの複合構造とすることができず、Ｓｎだけで占められるので動摩擦係数が増大するためである。より好ましいＳｎ系表面層の平均厚みは０．２５μｍ以上０．５μｍ以下である。 The Sn-based surface layer has an average thickness of 0.2 μm or more and 0.6 μm or less. If the thickness is less than 0.2 μm, solder wettability and electrical connection reliability are reduced, and if it exceeds 0.6 μm, the surface layer cannot be made of a composite structure of Sn and CuSn, and is occupied only by Sn. This is because the dynamic friction coefficient increases. A more preferable average thickness of the Sn-based surface layer is 0.25 μm or more and 0.5 μm or less.
Ａｇ被覆層は、Ａｇからなる被覆層であり、後述するように、リフロー処理した後のＳｎ系表面層の上に形成され、膜厚が０．０５μｍ以下とされる。０．０５μｍを超える膜厚では、Ｓｎ系表面層とＣｕＳｎ合金層との特殊な界面形状による摩擦係数低減効果とＡｇ被覆層によるＳｎ凝着抑制効果とを同時に得ることができず、Ａｇ被覆層による凝着抑制効果のみであるため十分な摩擦係数低減効果が得られず、また、Ａｇ被覆層を厚くするほどコスト高となる。このＡｇ被覆層の膜厚は０．００５μｍ以上とするのが好ましい。 The Ag coating layer is a coating layer made of Ag, and is formed on the Sn-based surface layer after the reflow treatment as described later, and has a film thickness of 0.05 μm or less. When the film thickness exceeds 0.05 μm, the friction coefficient reduction effect due to the special interface shape between the Sn-based surface layer and the CuSn alloy layer and the Sn adhesion suppression effect due to the Ag coating layer cannot be obtained at the same time. The effect of reducing the friction coefficient is not obtained because of only the effect of suppressing adhesion due to, and the higher the Ag coating layer, the higher the cost. The thickness of the Ag coating layer is preferably 0.005 μm or more.
次に、この端子材の製造方法について説明する。
基材として、Ｃｕ−Ｎｉ−Ｓｉ系合金、Ｃｕ−Ｎｉ−Ｓｉ−Ｚｎ系合金等、Ｎｉ及びＳｉを含有し、更に必要に応じてＺｎ，Ｓｎ，Ｆｅ，Ｍｇの群から選ばれた１種以上を合計で５質量％以下含有し、残部がＣｕ及び不可避不純物から構成される銅合金からなる板材を用意する。この板材に脱脂、酸洗等の処理をすることによって表面を清浄にした後、Ｃｕめっき、Ｓｎめっきをこの順序で施す。
Next, the manufacturing method of this terminal material is demonstrated.
As a base material, Cu—Ni—Si alloy, Cu—Ni—Si—Zn alloy, etc., containing Ni and Si, and further, one kind selected from the group of Zn, Sn, Fe, Mg as required A plate material made of a copper alloy containing the above in total by 5% by mass or less and the balance of Cu and inevitable impurities is prepared. After the surface of the plate material is cleaned by degreasing, pickling, etc., Cu plating and Sn plating are performed in this order.
Ｃｕめっきは一般的なＣｕめっき浴を用いればよく、例えば硫酸銅（ＣｕＳＯ４）及び硫酸（Ｈ２ＳＯ４）を主成分とした硫酸銅浴等を用いることができる。めっき浴の温度は２０℃以上５０℃以下、電流密度は１Ａ／ｄｍ２以上２０Ａ／ｄｍ２以下とされる。このＣｕめっきにより形成されるＣｕめっき層の膜厚は０．０３μｍ以上０．１５μｍ以下とされる。０．０３μｍ未満では合金基材の影響が大きく、表層にまでＣｕＳｎ合金層が成長し、光沢度、はんだ濡れ性の低下を招き、０．１５μｍを超えると、リフロー時に基材よりＮｉが十分に供給されず、所望のＣｕＳｎ合金層の形状を得られないためである。 For Cu plating, a general Cu plating bath may be used. For example, a copper sulfate bath mainly composed of copper sulfate (CuSO 4 ) and sulfuric acid (H 2 SO 4 ) may be used. The temperature of the plating bath is 20 ° C. or more and 50 ° C. or less, and the current density is 1 A / dm 2 or more and 20 A / dm 2 or less. The film thickness of the Cu plating layer formed by this Cu plating is 0.03 μm or more and 0.15 μm or less. If it is less than 0.03 μm, the influence of the alloy base material is large, and the CuSn alloy layer grows to the surface layer, resulting in a decrease in glossiness and solder wettability. This is because the desired shape of the CuSn alloy layer cannot be obtained.
Ｓｎめっき層形成のためのめっき浴としては、一般的なＳｎめっき浴を用いればよく、例えば硫酸（Ｈ２ＳＯ４）と硫酸第一錫（ＳｎＳＯ４）を主成分とした硫酸浴を用いることができる。めっき浴の温度は１５℃以上３５℃以下、電流密度は１Ａ／ｄｍ２以上１０Ａ／ｄｍ２以下とされる。このＳｎめっき層の膜厚は０．６μｍ以上１．３μｍ以下とされる。Ｓｎめっき層の厚みが０．６μｍ未満であると、リフロー後のＳｎ系表面層が薄くなって電気接続特性が損なわれ、１．３μｍを超えると、表面へのＣｕＳｎ合金層の露出が少なくなって動摩擦係数を０．３以下にすることが難しい。 As a plating bath for forming the Sn plating layer, a general Sn plating bath may be used. For example, a sulfuric acid bath mainly composed of sulfuric acid (H 2 SO 4 ) and stannous sulfate (SnSO 4 ) is used. Can do. The temperature of the plating bath is 15 ° C. or more and 35 ° C. or less, and the current density is 1 A / dm 2 or more and 10 A / dm 2 or less. The film thickness of this Sn plating layer is 0.6 μm or more and 1.3 μm or less. When the thickness of the Sn plating layer is less than 0.6 μm, the Sn-based surface layer after reflow is thinned and the electrical connection characteristics are impaired. When the thickness exceeds 1.3 μm, the exposure of the CuSn alloy layer to the surface is reduced. Therefore, it is difficult to make the dynamic friction coefficient 0.3 or less.
リフロー処理条件としては、還元雰囲気中で基材の表面温度が２４０℃以上３６０℃以下となる条件で１秒以上１２秒以下の時間加熱し、急冷とされる。さらに望ましくは２６０℃以上３００℃以下で５秒以上１０秒以下の加熱後急冷である。この場合、保持時間は以下に示すようにＣｕめっき層及びＳｎめっき層のそれぞれの厚みに応じて１秒以上１２秒以下の範囲で適切な時間があり、めっき厚が薄いほど保持時間は少なく、厚くなると長い保持時間が必要になる。
＜基材温度を２４０℃以上３６０℃以下まで昇温後の保持時間＞
（１）Ｓｎめっき層の厚みが０．６μｍ以上０．８μｍ未満に対して、Ｃｕめっき層の厚みが０．０３以上０．０５μｍ未満の場合は１秒以上３秒以下、Ｃｕめっき層の厚みが０．０５μｍ以上０．０８μ未満の場合は１秒以上６秒以下、Ｃｕめっき層の厚みが０．０８μｍ以上０．１４μｍ以下の場合は６秒以上９秒以下
（２）Ｓｎめっき層の厚みが０．８μｍ以上１．０μｍ未満に対して、Ｃｕめっき層の厚みが０．０３以上０．０５μｍ未満の場合は３秒以上６秒以下、Ｃｕめっき層の厚みが０．０５μｍ以上０．０８μ未満の場合は３秒以上９秒以下、Ｃｕめっき層の厚みが０．０８μｍ以上０．１４μｍ以下の場合は６秒以上１２秒以下
（３）Ｓｎめっき層の厚みが１．０μｍ以上１．３μｍ以下に対して、Ｃｕめっき層の厚みが０．０３以上０．０５μｍ未満の場合は６秒以上９秒以下、Ｃｕめっき層の厚みが０．０５μｍ以上０．０８μ未満の場合は６秒以上１２秒以下、Ｃｕめっき層の厚みが０．０８μｍ以上０．１４μｍ以下の場合は９秒以上１２秒以下
２４０℃未満の温度、保持時間がこれら（１）〜（３）に示す時間未満の加熱ではＳｎの溶解が進まず、３６０℃を超える温度、保持時間が（１）〜（３）に示す時間を超える加熱ではＣｕＳｎ合金結晶が大きく成長してしまい所望の形状を得られず、またＣｕＳｎ合金層が表層にまで達し、表面に残留するＳｎ系表面層が少なくなり過ぎる（ＣｕＳｎ合金層の表面への露出率が大きくなり過ぎる）ためである。また、加熱条件が高いとＳｎ系表面層の酸化が進行して好ましくない。
As reflow treatment conditions, the substrate is heated for 1 second to 12 seconds in a reducing atmosphere under the condition that the surface temperature of the base material is 240 ° C. or higher and 360 ° C. or lower, and then rapidly cooled. More preferably, it is rapid cooling after heating at 260 to 300 ° C. for 5 to 10 seconds. In this case, as shown below, the holding time has an appropriate time in the range of 1 second to 12 seconds depending on the thickness of each of the Cu plating layer and the Sn plating layer, and the holding time is less as the plating thickness is thinner, Longer holding times are required as the thickness increases.
<Holding time after raising substrate temperature to 240 ° C. or higher and 360 ° C. or lower>
(1) Whereas the thickness of the Sn plating layer is 0.6 μm or more and less than 0.8 μm, the thickness of the Cu plating layer is 1 second or more and 3 seconds or less when the thickness of the Cu plating layer is 0.03 or more and less than 0.05 μm. When the thickness is 0.05 μm or more and less than 0.08 μm, it is 1 second or more and 6 seconds or less. When the thickness of the Cu plating layer is 0.08 μm or more and 0.14 μm or less, 6 seconds or more and 9 seconds or less. (2) Thickness of Sn plating layer Is 0.8 μm or more and less than 1.0 μm, and when the thickness of the Cu plating layer is 0.03 or more and less than 0.05 μm, the thickness of the Cu plating layer is 0.05 μm or more and 0.08 μm. Is less than 3 seconds and less than 9 seconds, and when the Cu plating layer thickness is between 0.08 μm and 0.14 μm, it is between 6 seconds and 12 seconds. (3) The Sn plating layer thickness is between 1.0 μm and 1.3 μm For the following, the thickness of the Cu plating layer is 0.03 or more When the thickness is less than 0.05 μm, it is 6 seconds or more and 9 seconds or less, and when the thickness of the Cu plating layer is 0.05 μm or more and less than 0.08 μ, the thickness of the Cu plating layer is 0.08 μm or more and 0.02 μm or less. In the case of 14 μm or less, the temperature is not less than 9 seconds and not more than 12 seconds. The temperature is not higher than 240 ° C. and the holding time is less than the time indicated in (1) to (3). However, when the heating exceeds the time shown in (1) to (3), the CuSn alloy crystal grows greatly and a desired shape cannot be obtained, and the CuSn alloy layer reaches the surface layer and remains on the surface. This is because there is too little (the exposure rate to the surface of the CuSn alloy layer becomes too large). Moreover, when heating conditions are high, the oxidation of the Sn-based surface layer proceeds, which is not preferable.
リフロー処理後の素材上にスパッタリング法やめっき法によってＡｇ層を被覆する。このＡｇ層の膜厚は前述したとおり０．０５μｍ以下とされる。 The Ag layer is coated on the material after the reflow treatment by a sputtering method or a plating method. The thickness of this Ag layer is 0.05 μm or less as described above.
そして、この端子材は、例えば図２に示すような形状のメス端子２に成形される。
このメス端子２は、図２に示す例では、全体としては角筒状に形成され、その一方端の開口部１５からオス端子１を嵌合することにより、このオス端子１を両側から挟持した状態に保持して接続される。メス端子２の内部には、嵌合されるオス端子１の一方の面に接触される弾性変形可能な接触片１６が設けられるとともに、この接触片１６に対向している側壁１７に、オス端子１の他方の面に接触する半球状の凸部１８がエンボス加工により内方に突出した状態に形成されている。接触片１６にも、凸部１８に対向するように山折り状の折り曲げ部１９が設けられている。これら凸部１８及び折り曲げ部１９は、オス端子１を嵌合したときにオス端子１に向けて凸となるように突出しており、該オス端子１に対する摺動部１１となる。
And this terminal material is shape | molded, for example in the female terminal 2 of a shape as shown in FIG.
In the example shown in FIG. 2, the female terminal 2 is formed in a rectangular tube shape as a whole, and the male terminal 1 is sandwiched from both sides by fitting the male terminal 1 from the opening 15 at one end thereof. It is connected in a state. Inside the female terminal 2, an elastically deformable contact piece 16 that is brought into contact with one surface of the fitted male terminal 1 is provided, and a male terminal is provided on the side wall 17 facing the contact piece 16. The hemispherical convex part 18 which contacts the other surface of 1 is formed in the state which protruded inward by embossing. The contact piece 16 is also provided with a mountain-folded bent portion 19 so as to face the convex portion 18. The protruding portion 18 and the bent portion 19 protrude so as to protrude toward the male terminal 1 when the male terminal 1 is fitted, and become the sliding portion 11 with respect to the male terminal 1.
なお、オス端子１に用いられる端子材は、図３に模式的に示すように、Ｃｕ合金からなる基材２１上表面にＳｎ系表面層２２が形成され、Ｓｎ系表面層２２とＣｕ合金基材２１との間にＣｕＳｎ合金層２３が形成された、一般的なリフロー処理材から構成される。このオス端子１において、Ｓｎ系表面層２２を溶解除去して、ＣｕＳｎ合金層２３を表面に現出させたときに測定されるＣｕＳｎ合金層２３の油溜り深さＲｖｋは０．２μｍ未満、通常は０．１５μｍ程度であり、かつＳｎ系表面層２２の平均厚みは０．２μｍ以上３μｍ以下である。
オス端子１は平板状に形成され、銅合金板にＣｕめっき及びＳｎめっきをこの順に施した後、リフロー処理することにより形成される。この場合、リフロー処理の加熱条件としては、一般には、２４０℃以上４００℃以下の温度で１秒以上２０秒以下の時間保持した後、急冷される。
なお、リフロー処理することなく、Ｃｕ合金からなる基材にＳｎめっきにより平均厚み０．５μｍ以上３μｍ以下のＳｎ系表面層を形成した端子材をオス端子材としてもよい。
As shown schematically in FIG. 3, the terminal material used for the male terminal 1 has an Sn-based surface layer 22 formed on the upper surface of a substrate 21 made of a Cu alloy, and the Sn-based surface layer 22 and the Cu alloy base. It is comprised from the general reflow processing material in which the CuSn alloy layer 23 was formed between the materials 21. In this male terminal 1, the Sn-based surface layer 22 is dissolved and removed, and the oil reservoir depth Rvk of the CuSn alloy layer 23 measured when the CuSn alloy layer 23 appears on the surface is less than 0.2 μm. Is about 0.15 μm, and the average thickness of the Sn-based surface layer 22 is not less than 0.2 μm and not more than 3 μm.
The male terminal 1 is formed in a flat plate shape, and is formed by subjecting a copper alloy plate to Cu plating and Sn plating in this order, and then reflow treatment. In this case, as a heating condition for the reflow treatment, in general, it is rapidly cooled after being held at a temperature of 240 ° C. or higher and 400 ° C. or lower for a time of 1 second or longer and 20 seconds or shorter.
In addition, it is good also considering the terminal material which formed Sn type | system | group surface layer with an average thickness of 0.5 micrometer or more and 3 micrometers or less by Sn plating to the base material which consists of Cu alloy, without performing reflow processing as a male terminal material.
このようなメス端子材及びオス端子材を用いて形成したコネクタは、メス端子２の開口部１５から接触片１６と側壁１７との間にオス端子１を挿入すると、接触片１６は二点鎖線で示す位置から実線で示す位置に弾性変形し、その折り曲げ部１９と凸部１８との間にオス端子１を挟持した状態に保持する。
前述したように、メス端子２は、ＣｕＳｎ合金層とＳｎ系表面層との界面を油溜り深さＲｖｋが０．２μｍ以上の急峻な凹凸形状に形成され、かつＳｎ系表面層の平均厚みが０．２μｍ以上０．６μｍ以下、Ｓｎ系表面層の最表面に０．０５μｍ以下の膜厚のＡｇ被覆層が形成されているので、メス端子２の凸部１８及び折り曲げ部１９の表面にＳｎが凝着することが抑制され、ＣｕＳｎ合金層とＳｎ系表面層との界面が急峻な凹凸形状に形成されていることによる動摩擦係数の低減効果が有効に発揮され、オス端子１が通常のリフロー処理によるＳｎ系表面層のものであっても、動摩擦係数を０．３以下にすることができる。
When the male terminal 1 is inserted between the contact piece 16 and the side wall 17 from the opening 15 of the female terminal 2 in the connector formed using such female terminal material and male terminal material, the contact piece 16 becomes a two-dot chain line. Is elastically deformed from the position indicated by the solid line to the position indicated by the solid line, and the male terminal 1 is held between the bent part 19 and the convex part 18.
As described above, in the female terminal 2, the interface between the CuSn alloy layer and the Sn-based surface layer is formed in a steep uneven shape with an oil sump depth Rvk of 0.2 μm or more, and the average thickness of the Sn-based surface layer is Since an Ag coating layer having a thickness of 0.2 μm or more and 0.6 μm or less and a thickness of 0.05 μm or less is formed on the outermost surface of the Sn-based surface layer, Sn is formed on the surface of the convex portion 18 and the bent portion 19 of the female terminal 2. Is suppressed, the effect of reducing the coefficient of dynamic friction due to the fact that the interface between the CuSn alloy layer and the Sn-based surface layer is formed in a steep concavo-convex shape is effectively exhibited, and the male terminal 1 is subjected to normal reflow. Even in the case of a Sn-based surface layer by treatment, the dynamic friction coefficient can be made 0.3 or less.
メス端子試験片として、板厚０．２５ｍｍの銅合金（Ｎｉ；０．５質量％以上５．０質量％以下−Ｚｎ；１．０質量％−Ｓｎ；０質量％以上０．５質量％以下―Ｓｉ；０．１質量％以上１．５質量％以下−Ｆｅ；０質量％以上０．０３質量％以下−Ｍｇ；０．００５質量％）を基材とし、Ｃｕめっき、Ｓｎめっきを順に施した後に、リフロー処理として、還元雰囲気中で、基材表面温度が２４０℃以上３６０℃以下の温度になるまで昇温し、３〜１５秒保持した後、水冷した。リフロー処理後、スパッタリング法によりＡｇ被覆層を形成した。比較例として、基材のＮｉ及びＳｉ濃度や、Ｃｕめっき厚、Ｓｎめっき厚を変量したもの、Ａｇ被覆層を形成しなかったものも作製した。
この場合、Ｃｕめっき及びＳｎめっきのめっき条件は、表１に示す通りとした。表１中、Ｄｋはカソードの電流密度、ＡＳＤはＡ／ｄｍ２の略である。
各めっき層の厚さ、リフロー条件は、表２に示す通りとした。
As a female terminal test piece, a copper alloy having a thickness of 0.25 mm (Ni: 0.5% by mass or more and 5.0% by mass or less -Zn; 1.0% by mass-Sn; 0% by mass or more and 0.5% by mass or less) -Si; 0.1% by mass or more and 1.5% by mass or less -Fe; 0% by mass or more and 0.03% by mass or less -Mg; 0.005% by mass) as a base material, followed by Cu plating and Sn plating in this order. Then, as a reflow treatment, the temperature of the substrate surface was raised in a reducing atmosphere until the substrate surface temperature reached 240 ° C. or higher and 360 ° C. or lower, held for 3 to 15 seconds, and then cooled with water. After the reflow treatment, an Ag coating layer was formed by a sputtering method. As comparative examples, the Ni and Si concentrations of the base material, the Cu plating thickness and the Sn plating thickness were varied, and the Ag coating layer was not formed.
In this case, the plating conditions for Cu plating and Sn plating were as shown in Table 1. In Table 1, Dk is an abbreviation of cathode current density and ASD is A / dm 2 .
The thickness of each plating layer and the reflow conditions were as shown in Table 2.
これらの試料について、リフロー後のＳｎ系表面層の厚み、ＣｕＳｎ合金層の厚み、ＣｕＳｎ合金層の油溜まり深さＲｖｋ、Ａｇ被覆層の厚みを測定した。
リフロー後のＳｎ系表面層及びＣｕＳｎ合金層の厚み、Ａｇ被覆層の厚みは、エスアイアイ・ナノテクノロジー株式会社製蛍光Ｘ線膜厚計（ＳＦＴ９４００）にて測定した。
Ｓｎ系表面層及びＣｕＳｎ合金層の厚みは、Ａｇ被覆層を形成する前の試料について、最初にリフロー後の試料の全Ｓｎ系表面層の厚みを測定した後、例えばレイボルド株式会社製のＬ８０等の、純ＳｎをエッチングしＣｕＳｎ合金を腐食しない成分からなるめっき被膜剥離用のエッチング液に数分間浸漬することによりＳｎ系表面層を除去し、その下層のＣｕＳｎ合金層を露出させ純Ｓｎ換算におけるＣｕＳｎ合金層の厚みを測定した後、（全Ｓｎ系表面層の厚み−純Ｓｎ換算におけるＣｕＳｎ合金層の厚み）をＳｎ系表面層の厚みと定義した。
ＣｕＳｎ合金層の油溜まり深さＲｖｋは、Ｓｎめっき被膜剥離用のエッチング液に浸漬してＳｎ系表面層を除去し、その下層のＣｕＳｎ合金層を露出させた後、株式会社キーエンス製レーザ顕微鏡(ＶＫ−Ｘ２００)を用い、対物レンズ１５０倍（測定視野９４μｍ×７０μｍ）の条件で、長手方向で５点、短手方向で５点、計１０点測定した値の平均値より求めた。
For these samples, the thickness of the Sn-based surface layer after reflow, the thickness of the CuSn alloy layer, the oil reservoir depth Rvk of the CuSn alloy layer, and the thickness of the Ag coating layer were measured.
The thickness of the Sn-based surface layer and the CuSn alloy layer after reflow and the thickness of the Ag coating layer were measured with a fluorescent X-ray film thickness meter (SFT 9400) manufactured by SII Nanotechnology.
The thicknesses of the Sn-based surface layer and the CuSn alloy layer were determined by measuring the thickness of all the Sn-based surface layers of the sample after the reflow for the sample before forming the Ag coating layer, for example, L80 manufactured by Reybold Co., Ltd. The Sn-based surface layer is removed by immersing it in an etching solution for stripping a plating film made of a component that does not corrode CuSn alloy by etching pure Sn, and the underlying CuSn alloy layer is exposed so as to be in pure Sn conversion. After measuring the thickness of the CuSn alloy layer, (the thickness of all Sn-based surface layers−the thickness of the CuSn alloy layer in terms of pure Sn) was defined as the thickness of the Sn-based surface layer.
The oil reservoir depth Rvk of the CuSn alloy layer was immersed in an etching solution for removing the Sn plating film to remove the Sn-based surface layer, and the underlying CuSn alloy layer was exposed. VK-X200) was obtained from the average value of the values measured at 10 points in total, 5 points in the longitudinal direction and 5 points in the short direction under the condition of 150 times the objective lens (measurement visual field 94 μm × 70 μm).
一方、オス端子試験片として、板厚０．２５ｍｍの銅合金（Ｃ２６００、Ｃｕ：７０質量％−Ｚｎ：３０質量％）を基材とし、Ｃｕめっき、Ｓｎめっきを順に施し、リフロー処理した。このオス端子材のリフロー条件としては、基材温度２７０℃、保持時間６秒とし、リフロー後のＳｎ系表面層の厚みは０．６μｍ、ＣｕＳｎ合金層の厚みは０．５μｍとした。このＣｕＳｎ合金層の油溜まり深さＲｖｋは０．１６μｍとした。
このオス端子試験片と、表２のメス端子試験片とを用いて動摩擦係数を測定した。
動摩擦係数については、株式会社トリニティーラボ製の摩擦測定機（μＶ１０００）を用い、両試験片間の摩擦力を測定して動摩擦係数を求めた。図４により説明すると、水平な台３１上にオス端子試験片３２を固定し、その上にメス端子試験片３３の半球凸面を置いてめっき面同士を接触させ、メス端子試験片３３に錘３４によって５００ｇｆの荷重Ｐをかけてオス端子試験片３２を押さえた状態とする。この荷重Ｐをかけた状態で、オス端子試験片３２を摺動速度８０ｍｍ／分で矢印により示した水平方向に１０ｍｍ引っ張ったときの摩擦力Ｆをロードセル３５によって測定した。その摩擦力Ｆの平均値Ｆａｖと荷重Ｐより動摩擦係数（＝Ｆａｖ／Ｐ）を求めた。
また、はんだ濡れ性として、試験片を１０ｍｍ幅に切り出し、活性フラックスを用いてメニスコグラフ法にてゼロクロスタイムを測定した。（はんだ浴温２６０℃のＳｎ−３％Ａｇ−０．５％Ｃｕはんだに浸漬させ、浸漬速度２ｍｍ／ｓｅｃ、浸漬深さ１ｍｍ、浸漬時間１０秒の条件にて測定した。）はんだゼロクロスタイムが３秒以下を○と評価し、３秒を超えた場合を×と評価した。
これらの測定結果、評価結果を表２に示す。
On the other hand, as a male terminal test piece, a copper alloy (C2600, Cu: 70% by mass—Zn: 30% by mass) having a plate thickness of 0.25 mm was used as a base material, and Cu plating and Sn plating were sequentially performed and reflow treatment was performed. The reflow conditions for this male terminal material were a substrate temperature of 270 ° C. and a holding time of 6 seconds, the thickness of the Sn-based surface layer after reflow was 0.6 μm, and the thickness of the CuSn alloy layer was 0.5 μm. The oil reservoir depth Rvk of this CuSn alloy layer was 0.16 μm.
The dynamic friction coefficient was measured using this male terminal test piece and the female terminal test piece of Table 2.
About the dynamic friction coefficient, the frictional force between both test pieces was measured using the friction measuring machine (microvolt 1000) by Trinity Lab Co., Ltd., and the dynamic friction coefficient was calculated | required. Referring to FIG. 4, a male terminal test piece 32 is fixed on a horizontal base 31, a hemispherical convex surface of a female terminal test piece 33 is placed thereon, and the plated surfaces are brought into contact with each other. Thus, a load P of 500 gf is applied to hold the male terminal test piece 32. With this load P applied, the frictional force F when the male terminal test piece 32 was pulled 10 mm in the horizontal direction indicated by the arrow at a sliding speed of 80 mm / min was measured by the load cell 35. A dynamic friction coefficient (= Fav / P) was obtained from the average value Fav of the friction force F and the load P.
Moreover, as solder wettability, the test piece was cut out to 10 mm width, and the zero cross time was measured by the menisograph method using the active flux. (Measured under the conditions of immersion in Sn-3% Ag-0.5% Cu solder with a solder bath temperature of 260 ° C., immersion rate of 2 mm / sec, immersion depth of 1 mm, and immersion time of 10 seconds.) The case where 3 seconds or less was evaluated as ◯, and the case where it exceeded 3 seconds was evaluated as x.
These measurement results and evaluation results are shown in Table 2.
この表２から明らかなように、実施例はいずれも動摩擦係数が０．３以下と小さく、良好なはんだ濡れ性を示した。
これに対して、各比較例は以下のような不具合が認められた。
比較例１、２はいずれもＡｇ被覆層がないので、動摩擦係数が大きい。比較例３は、Ａｇ被覆層の膜厚が大きいため、Ｓｎ系表面層とＣｕＳｎ合金層との特殊な界面形状による摩擦係数低減効果を十分に得ることができず動摩擦係数が大きい。比較例４はＣｕめっき厚が厚すぎ、また比較例５はリフロー保持時間が短すぎるため、ともにＲｖｋが小さく、Ａｇ層を施すだけでは低減効果はあるものの大きな効果は得られない。比較例６、７はＣｕＳｎ合金層が大きく成長しすぎてしまい、表面に残留するＳｎ系表面層が少なくなり過ぎるため、はんだ濡れ性が悪くなる。比較例８、９はＣｕＳｎ合金層の成長を促進する添加元素量が少ないため、十分な油溜まり深さＲｖｋが得られず、大きな効果が得られない。
図５は実施例５の動摩擦係数測定後のオス端子試験片の摺動面の顕微鏡写真であり、図６は比較例１の顕微鏡写真であり、図７は比較例４の顕微鏡写真である。これらの写真を比較してわかるように、実施例のものは、Ｓｎの凝着が抑制され摺動面が滑らかなのに対し、比較例はＳｎの凝着のため摺動面が粗い。メス側のＲｖｋが小さい比較例４は、Ａｇ被覆層があってもＳｎの凝着が発生し摺動面が粗くなっている。
As is apparent from Table 2, all of the examples had a small coefficient of dynamic friction of 0.3 or less and exhibited good solder wettability.
On the other hand, the following problems were recognized in each comparative example.
Since Comparative Examples 1 and 2 do not have an Ag coating layer, the dynamic friction coefficient is large. In Comparative Example 3, since the film thickness of the Ag coating layer is large, the effect of reducing the friction coefficient due to the special interface shape between the Sn-based surface layer and the CuSn alloy layer cannot be sufficiently obtained, and the dynamic friction coefficient is large. In Comparative Example 4, the Cu plating thickness is too thick, and in Comparative Example 5, the reflow holding time is too short. Therefore, both Rvk are small, and a large effect cannot be obtained only by applying an Ag layer. In Comparative Examples 6 and 7, the CuSn alloy layer grows too much, and the Sn-based surface layer remaining on the surface becomes too small, so that the solder wettability is deteriorated. In Comparative Examples 8 and 9, since the amount of the additive element that promotes the growth of the CuSn alloy layer is small, a sufficient oil sump depth Rvk cannot be obtained, and a great effect cannot be obtained.
5 is a photomicrograph of the sliding surface of the male terminal test piece after measurement of the dynamic friction coefficient of Example 5, FIG. 6 is a photomicrograph of Comparative Example 1, and FIG. 7 is a photomicrograph of Comparative Example 4. As can be seen from comparison of these photographs, in the example, Sn adhesion was suppressed and the sliding surface was smooth, whereas in the comparative example, the sliding surface was rough due to Sn adhesion. In Comparative Example 4 in which the Rvk on the female side is small, Sn adhesion occurs and the sliding surface becomes rough even with the Ag coating layer.
１ オス端子
２ メス端子
５ 基材
６ Ｓｎ系表面層
７ ＣｕＳｎ合金層
８ Ａｇ被覆層
１１ 摺動部
１５ 開口部
１６ 接触片
１７ 側壁
１８ 凸部
１９ 折り曲げ部
２１ 基材
２２ Ｓｎ系表面層
２３ ＣｕＳｎ合金層
３１ 台
３２ オス端子試験片
３３ メス端子試験片
３４ 錘
３５ ロードセル
DESCRIPTION OF SYMBOLS 1 Male terminal 2 Female terminal 5 Base material 6 Sn system surface layer 7 CuSn alloy layer 8 Ag coating layer 11 Sliding part 15 Opening part 16 Contact piece 17 Side wall 18 Convex part 19 Bending part 21 Base material 22 Sn system surface layer 23 CuSn Alloy layer 31 units 32 Male terminal test piece 33 Female terminal test piece 34 Weight 35 Load cell
Claims (3)
The base material contains 0.5% by mass or more and 5% by mass or less of Ni, 0.1% by mass or more and 1.5% by mass or less of Si, and, if necessary, a group of Zn, Sn, Fe, and Mg The tin-plated copper alloy terminal material according to claim 1 or 2, wherein one or more selected from the group consisting of 5% by mass or less is contained, and the balance is composed of Cu and inevitable impurities.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016056424A (en) * | 2014-09-11 | 2016-04-21 | 三菱マテリアル株式会社 | Tin-plated copper alloy terminal material and a method for manufacturing the same |
| JP6042577B1 (en) * | 2016-07-05 | 2016-12-14 | 有限会社 ナプラ | Multilayer preform sheet |
| WO2022219904A1 (en) * | 2021-04-13 | 2022-10-20 | Ｊｘ金属株式会社 | Male pin for connector and manufacturing method of male pin for connector |
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2013
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016056424A (en) * | 2014-09-11 | 2016-04-21 | 三菱マテリアル株式会社 | Tin-plated copper alloy terminal material and a method for manufacturing the same |
| JP6042577B1 (en) * | 2016-07-05 | 2016-12-14 | 有限会社 ナプラ | Multilayer preform sheet |
| JP2018001238A (en) * | 2016-07-05 | 2018-01-11 | 有限会社 ナプラ | Multilayer preform sheet |
| US9950496B2 (en) | 2016-07-05 | 2018-04-24 | Napra Co., Ltd. | Multi-layer preform sheet |
| WO2022219904A1 (en) * | 2021-04-13 | 2022-10-20 | Ｊｘ金属株式会社 | Male pin for connector and manufacturing method of male pin for connector |
| JP2022162913A (en) * | 2021-04-13 | 2022-10-25 | Ｊｘ金属株式会社 | Connector male pin, and production method of connector male pin |
| JP7394086B2 (en) | 2021-04-13 | 2023-12-07 | Ｊｘ金属株式会社 | Male pin for connector and method for manufacturing male pin for connector |
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