JP5419594B2 - Copper or copper alloy material with tin plating for connection parts used for connection with aluminum conductive members - Google Patents
Copper or copper alloy material with tin plating for connection parts used for connection with aluminum conductive members Download PDFInfo
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本発明は、例えば自動車用ワイヤーハーネス等に用いるアルミニウム電線やアルミニウム合金端子などのアルミニウム製導電部材と接続するコネクタ等に用いられる接続部品用錫めっき付銅又は銅合金材料に関する。 The present invention relates to a tin-plated copper or copper alloy material for connection parts used for connectors and the like connected to aluminum conductive members such as aluminum wires and aluminum alloy terminals used in, for example, automobile wire harnesses.
近年、自動車の電装化が進み、取り付けられる電子部品・電線が増加している。電子部品に使用される導電材料や電線には、導電性、強度、成形加工性、耐食性などの観点から銅又は銅合金が使用されており、一台あたり数十キログラムになっている。一方、近年の地球温暖化に代表される環境問題への取り組みに、自動車の小型・軽量化による燃費向上があり、電線や端子等の導電部材へのアルミニウム又はアルミニウム合金の適用が積極的に検討されている。 In recent years, electronic components of automobiles have been advanced, and electronic parts and electric wires to be attached are increasing. Copper or copper alloys are used for conductive materials and electric wires used for electronic parts from the viewpoints of conductivity, strength, moldability, corrosion resistance, etc., and each unit has several tens of kilograms. On the other hand, efforts to tackle environmental problems represented by global warming in recent years have improved fuel efficiency by reducing the size and weight of automobiles, and actively considering the application of aluminum or aluminum alloys to conductive members such as wires and terminals. Has been.
アルミニウム電線は、従来の銅線と異なり、表面に硬度が高く電気抵抗が高いアルミニウム酸化皮膜が形成されているため、端子とアルミニウム電線を接続する際、この酸化皮膜を破壊する必要がある。そのため、特許文献１のように、圧着部分に複数のインデントを付けた端子、特許文献２のように、アルミニウム電線と端子を超音波接合する技術が提案されている。 Unlike conventional copper wires, aluminum wires have an aluminum oxide film with high hardness and high electrical resistance formed on the surface. Therefore, when connecting a terminal and an aluminum wire, it is necessary to destroy the oxide film. For this reason, a technique in which an aluminum wire and a terminal are ultrasonically bonded as in Patent Document 1 and a terminal in which a plurality of indents are attached to a crimped portion as in Patent Document 1 and a terminal are proposed.
しかし、錫めっき付銅又は銅合金材料からなる端子とアルミニウム電線を接続する際、特許文献１の技術を適用しても、端子表面のめっき層の錫は、アルミニウム酸化皮膜に比べて軟らかいため、アルミニウム酸化皮膜が破壊されにくく、接触部の電気抵抗が大きくなりやすい。また、端子成形時にインデント加工を行うため、特殊な加工金型が必要となりコストアップになる。 However, when connecting the terminal made of tin-plated copper or copper alloy material and the aluminum electric wire, even if the technique of Patent Document 1 is applied, the tin of the plating layer on the terminal surface is softer than the aluminum oxide film, The aluminum oxide film is not easily destroyed and the electrical resistance of the contact portion tends to increase. In addition, since indent processing is performed at the time of terminal molding, a special processing die is required, which increases costs.
また、錫めっき付銅又は銅合金材料からなる端子とアルミニウム電線を接続する際、特許文献２の超音波接合技術を適用しても、錫とアルミニウムはほとんど固溶しないため、錫めっき表面にアルミニウム電線を接合することは困難である。そのため、端子のアルミニウム電線との接合部は銅又は銅合金素材を露出させた状態、端子嵌合部は錫めっき表面とする必要があり、端子成形後に端子嵌合部に錫めっきを施すか、もしくは、端子成形加工前に端子嵌合部に加工される部分の銅又は銅合金素材表面に部分的に錫めっきを行うなど、特殊なめっき工程が必要となる。また、超音波接合工程はコストアップ要因である。 In addition, when connecting a terminal made of tin-plated copper or a copper alloy material and an aluminum electric wire, even if the ultrasonic bonding technique of Patent Document 2 is applied, tin and aluminum are hardly dissolved, so that the surface of the tin plating has aluminum. It is difficult to join electric wires. Therefore, the joint portion of the terminal with the aluminum electric wire is in a state where the copper or copper alloy material is exposed, the terminal fitting portion needs to be a tin-plated surface, or the terminal fitting portion is tin-plated after terminal molding, Alternatively, a special plating process is required, for example, tin plating is partially performed on the surface of the copper or copper alloy material that is processed into the terminal fitting portion before the terminal forming process. In addition, the ultrasonic bonding process is a cost increase factor.
一方、アルミニウム電線と接続する端子材料としてアルミニウムを適用し、このアルミニウム端子に錫めっき付銅又は銅合金材料からなる端子を嵌合して接続する場合、両端子の嵌合部では硬度の低い錫めっき皮膜と硬度の高いアルミニウム酸化皮膜との接触となるため、この場合もアルミニウム酸化皮膜は破壊されず、接触部の電気抵抗が高くなりやすい。 On the other hand, when aluminum is applied as a terminal material to be connected to an aluminum electric wire and a terminal made of tin-plated copper or a copper alloy material is fitted and connected to the aluminum terminal, tin having low hardness at the fitting portion of both terminals Since the plating film is in contact with the aluminum oxide film having high hardness, the aluminum oxide film is not destroyed in this case, and the electrical resistance of the contact portion tends to be high.
アルミニウムを導電部材として利用する場合、アルミニウム酸化皮膜は電気抵抗が高く接触抵抗を増大させる。そのため、接点部として使用する場合、接触抵抗を低くするために、アルミニウム酸化皮膜を除去し、新生面で接触させることが重要である。しかし、アルミニウム表面の酸化皮膜は錫めっき皮膜に比べて非常に硬いため、一般的な錫めっき付き銅又は銅合金材料を用いた接続部材の場合、アルミニウム製導電部材に接触させても、錫めっき皮膜のみが削られ、アルミニウムの新生面が露出せず接触抵抗が高くなる。
アルミニウム酸化皮膜を除去するには両者を強く押し付けることが有効であるが、例えば錫めっき付銅又は銅合金材料からなる端子とアルミニウム電線の圧着の場合、アルミニウム電線が変形し断線する場合がある。また、錫めっき付銅又は銅合金材料からなる端子とアルミニウム製端子を嵌合させる場合、強く押し付けると端子挿入力が高くなり、作業性が低下する問題が発生する。
When aluminum is used as the conductive member, the aluminum oxide film has high electrical resistance and increases contact resistance. Therefore, when using as a contact part, in order to make a contact resistance low, it is important to remove an aluminum oxide film and to make it contact in a new surface. However, since the oxide film on the aluminum surface is much harder than the tin-plated film, in the case of a connecting member using a general tin-plated copper or copper alloy material, even if it is brought into contact with an aluminum conductive member, it is tin-plated. Only the film is shaved, and the new surface of the aluminum is not exposed and the contact resistance increases.
In order to remove the aluminum oxide film, it is effective to press both of them strongly. For example, in the case of crimping a terminal made of tin-plated copper or a copper alloy material and an aluminum wire, the aluminum wire may be deformed and disconnected. In addition, when fitting a terminal made of tin-plated copper or a copper alloy material and an aluminum terminal, if the terminal is pressed strongly, the terminal insertion force is increased, and the workability is lowered.
本発明は、上記従来の問題点に鑑みてなされたものであり、アルミニウム製の電線や端子等のアルミニウム製導電部材と接続する場合に、無理に強く接触させなくても、電気的信頼性（低い接触抵抗）を十分に確保できる、接続部品用錫めっき付銅又は銅合金材料を提供することを目的とする。 The present invention has been made in view of the above-described conventional problems. When connecting to an aluminum conductive member such as an aluminum wire or terminal, the electrical reliability ( An object of the present invention is to provide a tin-plated copper or copper alloy material for connection parts that can sufficiently ensure a low contact resistance.
本発明者らは、特定の表面被覆層構成を有する錫めっき付き銅又は銅合金材料を用いた場合、これをアルミニウムに対し軽く押し付けることで、アルミニウム酸化被膜を削り取ることができ、両者の接触抵抗が低くなることを見出した。本発明はこの知見に基づいてなされたものである。 When the present inventors used a tin-plated copper or copper alloy material having a specific surface coating layer configuration, the aluminum oxide film can be scraped off by lightly pressing it against aluminum, and the contact resistance between the two Was found to be lower. The present invention has been made based on this finding.
本発明に係る接続部品用錫めっき付銅又は銅合金材料は、特にアルミニウム製導電部材との接続に用いられる接続部品用材料であり、銅又は銅合金板条（板又は条）からなる母材の表面に、リフロー処理により形成されたＣｕ−Ｓｎ合金層とＳｎ層がこの順に形成され、Ｓｎ層の表面にＣｕ−Ｓｎ合金層の一部が露出し、Ｃｕ−Ｓｎ合金層の材料表面露出面積率が１０〜７５％、材料表面露出間隔が０．０１〜０．５ｍｍ、平均の厚さが０．２〜５．０μｍ、Ｃｕ含有量が２０〜７０ａｔ％であり、材料表面の算術平均粗さＲａが０．１５μｍ以上、３．０μｍ以下であることを特徴とする。本発明においてアルミニウム製導電部材のアルミニウムとは、純アルミニウムとアルミニウム合金の両方を含む意味で用いている。
Ｃｕ−Ｓｎ合金層とＳｎ層からなる表面被覆層が形成された領域は、母材の片面又は両面全体に及んでいてもよいし、片面又は両面の一部のみを占めているのでもよい。
The tin-plated copper or copper alloy material for connection parts according to the present invention is a connection part material particularly used for connection to an aluminum conductive member, and is a base material made of copper or a copper alloy plate (plate or strip). A Cu—Sn alloy layer and an Sn layer formed by reflow treatment are formed in this order on the surface of the Cu layer, a part of the Cu—Sn alloy layer is exposed on the surface of the Sn layer, and the surface of the material of the Cu—Sn alloy layer is exposed. The area ratio is 10 to 75%, the material surface exposure interval is 0.01 to 0.5 mm, the average thickness is 0.2 to 5.0 μm, the Cu content is 20 to 70 at%, and the arithmetic average of the material surface Roughness Ra is 0.15 μm or more and 3.0 μm or less. In the present invention, aluminum in an aluminum conductive member is used in the meaning including both pure aluminum and aluminum alloy.
The region where the surface coating layer composed of the Cu—Sn alloy layer and the Sn layer is formed may extend over one or both surfaces of the base material, or may occupy only a part of one surface or both surfaces.
この錫めっき付銅又は銅合金材料において、前記Ｓｎ層の平均の厚さが０．３〜６．０μｍであることが望ましい。母材表面とＣｕ−Ｓｎ合金層の間にさらにＮｉ層が形成されていてもよい。また、母材表面とＣｕ−Ｓｎ合金層の間（Ｎｉ層が形成されない場合）、あるいはＮｉ層とＣｕ−Ｓｎ合金層の間（Ｎｉ層が形成された場合）に、さらにＣｕ層を有していてもよい。
本発明において、Ｓｎ層、Ｃｕ層及びＮｉ層は、それぞれＳｎ、Ｃｕ、Ｎｉ金属のほか、Ｓｎ合金、Ｃｕ合金及びＮｉ合金を含む。
また、本発明において、銅又は銅合金板条からなる母材には、銅又は銅合金を被覆した板条が含まれる。例えば銅を被覆した鉄系材料の板条や、銅を被覆したアルミニウム系材料の板条である。
なお、以上述べた接続部品用銅又は銅合金材料の表面被覆層構成自体は公知である（例えば特開２００６−１８３０６８号公報参照）。
In the tin-plated copper or copper alloy material, it is desirable that the average thickness of the Sn layer is 0.3 to 6.0 μm. A Ni layer may be further formed between the surface of the base material and the Cu—Sn alloy layer. Further, a Cu layer is further provided between the surface of the base material and the Cu—Sn alloy layer (when the Ni layer is not formed) or between the Ni layer and the Cu—Sn alloy layer (when the Ni layer is formed). It may be.
In the present invention, the Sn layer, the Cu layer, and the Ni layer include Sn alloy, Cu alloy, and Ni alloy in addition to Sn, Cu, and Ni metal, respectively.
In the present invention, the base material made of copper or a copper alloy strip includes a strip coated with copper or a copper alloy. For example, it is a strip of iron-based material coated with copper or a strip of aluminum-based material coated with copper.
In addition, the surface coating layer structure itself of the copper or copper alloy material for connection parts described above is publicly known (see, for example, JP-A-2006-183068).
前記錫めっき付き銅又は銅合金材料は、銅又は銅合金板条からなる母材の表面に、Ｎｉめっき層（必要に応じて）、Ｃｕめっき層及びＳｎめっき層をこの順に形成した後、リフロー処理を行うことにより製造される。なお、本明細書において、リフロー処理前の表面被覆層を構成する各層について「めっき」という表現を付加し、リフロー処理後の表面被覆層を構成する各層と区別している。
Ｃｕ−Ｓｎ合金層は、リフロー処理においてＣｕめっき層とＳｎめっき層のＣｕとＳｎが相互拡散して形成されるが、その際にＣｕめっき層が全て消滅する場合と一部残留する場合の両方があり得る。前記Ｃｕ層はＣｕめっき層の一部が残留したものである。Ｃｕめっき層の厚さによっては、母材からもＣｕが供給される場合がある。
本発明において、Ｃｕめっき層、Ｓｎめっき層及びＮｉめっき層は、それぞれＣｕ、Ｓｎ、Ｎｉ金属のほか、Ｃｕ合金、Ｓｎ合金及びＮｉ合金を含む。
The tin-plated copper or copper alloy material is reflowed after forming a Ni plating layer (if necessary), a Cu plating layer, and a Sn plating layer in this order on the surface of the base material made of copper or a copper alloy sheet. Manufactured by processing. In the present specification, the expression “plating” is added to each layer constituting the surface coating layer before the reflow treatment to distinguish it from each layer constituting the surface coating layer after the reflow treatment.
The Cu-Sn alloy layer is formed by mutual diffusion of Cu and Sn in the Cu plating layer and the Sn plating layer in the reflow process. There can be. The Cu layer is a part of the Cu plating layer remaining. Depending on the thickness of the Cu plating layer, Cu may also be supplied from the base material.
In this invention, Cu plating layer, Sn plating layer, and Ni plating layer contain Cu alloy, Sn alloy, and Ni alloy other than Cu, Sn, and Ni metal, respectively.
本発明に係る錫めっき付銅又は銅合金材料は、表面に硬いＣｕ−Ｓｎ合金を露出させているため、アルミニウム系材料に軽く押し付けることで、表面のアルミニウム酸化皮膜を削り取ることが可能であり、接触抵抗が低くなる。
従って、本発明に係る錫めっき付き銅又は銅合金材料は、特にアルミニウム電線と圧着接続する端子用として、アルミニウム電線との高い接続信頼性を得ることができる。また、アルミニウムを使用した端子材と嵌合する場合、特に強く押し付けなくても、嵌合部において高い接触信頼性を得ることができる。
Since the copper or copper alloy material with tin plating according to the present invention exposes a hard Cu-Sn alloy on the surface, it is possible to scrape the aluminum oxide film on the surface by lightly pressing the aluminum-based material, Contact resistance is lowered.
Therefore, the copper or copper alloy material with tin plating according to the present invention can obtain high connection reliability with an aluminum electric wire, particularly for a terminal to be crimped to the aluminum electric wire. Moreover, when fitting with the terminal material which uses aluminum, even if it does not press especially strongly, high contact reliability can be acquired in a fitting part.
以下、本発明に係る錫めっき付き銅又は銅合金材料について、具体的に説明する。
（１）Ｃｕ−Ｓｎ合金層の材料表面露出面積率を１０〜７５％とした理由について述べる。なお、本発明では、Ｃｕ−Ｓｎ合金層の材料表面露出面積率を、材料の単位表面積あたりに露出するＣｕ−Ｓｎ合金層の表面積に１００をかけた値として算出する。Ｃｕ−Ｓｎ合金層の材料表面露出面積率が１０％未満では、アルミニウム表面酸化皮膜を削り取る面積が少なくなるため電気的信頼性が低くなる。一方７５％を超える場合には、経時や腐食などによる材料表面のＣｕの酸化物量などが多くなり、接触抵抗を増加させ易く、電気的接続の信頼性を維持することが困難となる。従って、Ｃｕ−Ｓｎ合金層の材料表面露出面積率を１０〜７５％に規定する。より望ましくは１０〜５０％である。
Hereinafter, the tin-plated copper or copper alloy material according to the present invention will be specifically described.
(1) The reason why the material surface exposed area ratio of the Cu—Sn alloy layer is set to 10 to 75% will be described. In the present invention, the material surface exposed area ratio of the Cu—Sn alloy layer is calculated as a value obtained by multiplying the surface area of the Cu—Sn alloy layer exposed per unit surface area of the material by 100. When the material surface exposed area ratio of the Cu—Sn alloy layer is less than 10%, the area where the aluminum surface oxide film is scraped is reduced, and thus the electrical reliability is lowered. On the other hand, if it exceeds 75%, the amount of Cu oxide on the surface of the material due to aging or corrosion increases, and it is easy to increase the contact resistance and it becomes difficult to maintain the reliability of electrical connection. Therefore, the material surface exposed area ratio of the Cu—Sn alloy layer is specified to be 10 to 75%. More desirably, it is 10 to 50%.
（２）材料表面のＣｕ−Ｓｎ合金層の平均の材料表面露出間隔を０．０１〜０．５ｍｍとした理由について述べる。なお、本発明では、Ｃｕ−Ｓｎ合金層の平均の材料表面露出間隔を、材料表面に描いた直線を横切るＣｕ−Ｓｎ合金層の平均の幅（前記直線に沿った長さ）とＳｎ層の平均の幅を足した値と定義する。Ｃｕ−Ｓｎ合金層の平均の材料表面露出間隔が０．０１ｍｍ未満では、高温酸化などの熱拡散による材料表面のＣｕの酸化物量が多くなり、接触抵抗を増加させ易く、電気的接続の信頼性を維持することが困難となる。一方、０．５ｍｍを超える場合には、特に小型端子に用いた際に低い摩擦係数を得ることが困難となる場合が生じてくる。また、一般的に端子が小型になれば、インデントやリブなどの電気接点部（挿抜部）の接触面積が小さくなるため、挿抜の際にＣｕ−Ｓｎ合金層の部分がアルミニウムと接触する確率が低下し、電気的信頼性を得ることが困難となる。従って、Ｃｕ−Ｓｎ合金層の平均の材料表面露出間隔を０．０１〜０．５ｍｍとすることが望ましい。
アルミニウム電線と端子の圧着を考えた場合、アルミニウム電線は細線を束ねた構造であるため、圧着部表面に電線長手方向に任意に直線を引いた場合、硬いＣｕ−Ｓｎ合金層が必ず露出していることが望ましい。電線長手方向でＣｕ−Ｓｎ合金層が露出していない箇所で電線と接触した場合、電線表面の酸化被膜が破壊されず、電気的接続の信頼性が得られない。錫めっき付き銅合金板条から端子を成形加工する場合、端子挿入方向（電線長手方向）と圧延方向は垂直な関係に加工することが多く、少なくとも圧延方向と垂直に直線を引いた場合、Ｃｕ−Ｓｎ合金層が必ず露出していれば良く、露出間隔は０．０１〜０．５ｍｍとすることが望ましい。
しかしながら、必ずしも電線長手方向と圧延方向の関係が垂直になるとは限らないので、より望ましくは、Ｃｕ−Ｓｎ合金層の平均の材料表面露出間隔を全ての方向において０．０１〜０．５ｍｍにする。これにより、挿抜の際のＣｕ−Ｓｎ合金層とアルミニウムの接触確率が増加する。さらに望ましくは０．０５〜０．３ｍｍである。
(2) The reason for setting the average material surface exposure interval of the Cu—Sn alloy layer on the material surface to 0.01 to 0.5 mm will be described. In addition, in this invention, the average width | variety (length along the said straight line) of the Cu-Sn alloy layer which cross | intersects the straight line drawn on the material surface with the average material surface exposure space | interval of a Cu-Sn alloy layer, and Sn layer. It is defined as the value obtained by adding the average width. When the average material surface exposure interval of the Cu-Sn alloy layer is less than 0.01 mm, the amount of Cu oxide on the material surface due to thermal diffusion such as high-temperature oxidation increases, the contact resistance is likely to increase, and the reliability of electrical connection It becomes difficult to maintain. On the other hand, when it exceeds 0.5 mm, it may be difficult to obtain a low coefficient of friction particularly when used for a small terminal. In general, if the terminal is made smaller, the contact area of an electrical contact portion (insertion / extraction portion) such as an indent or a rib is reduced. Therefore, there is a probability that the portion of the Cu-Sn alloy layer is in contact with aluminum at the time of insertion / extraction. It becomes difficult to obtain electrical reliability. Therefore, it is desirable that the average material surface exposure interval of the Cu—Sn alloy layer be 0.01 to 0.5 mm.
When considering the crimping of aluminum wires and terminals, the aluminum wires have a structure in which fine wires are bundled. Therefore, when a straight line is drawn arbitrarily in the longitudinal direction of the wires on the crimp surface, a hard Cu-Sn alloy layer is always exposed. It is desirable. When the Cu—Sn alloy layer is not exposed in the longitudinal direction of the electric wire and is in contact with the electric wire, the oxide film on the surface of the electric wire is not broken and the reliability of electrical connection cannot be obtained. When forming a terminal from a tin-plated copper alloy strip, the terminal insertion direction (wire longitudinal direction) and the rolling direction are often processed in a perpendicular relationship, and at least when a straight line is drawn perpendicular to the rolling direction, Cu The Sn alloy layer is necessarily exposed, and the exposure interval is preferably 0.01 to 0.5 mm.
However, since the relationship between the longitudinal direction of the electric wire and the rolling direction is not necessarily perpendicular, more preferably, the average material surface exposure interval of the Cu—Sn alloy layer is set to 0.01 to 0.5 mm in all directions. . Thereby, the contact probability of the Cu—Sn alloy layer and aluminum at the time of insertion / extraction increases. More desirably, the thickness is 0.05 to 0.3 mm.
（３）Ｃｕ−Ｓｎ合金層の平均の厚さを０．２〜５．０μｍとした理由について述べる。なお本発明では、Ｃｕ−Ｓｎ合金層の平均の厚さは、純Ｓｎ層を除去した後Ｃｕ−Ｓｎ合金層に含まれるＳｎ成分を蛍光Ｘ線膜厚計にて測定した厚さと定義する。（下記実施例に記載したＣｕ−Ｓｎ合金層の平均の厚さ測定方法は、この定義に準拠するものである）。Ｃｕ−Ｓｎ合金層の平均の厚さが０．２μｍ未満では、特に本発明のようにＣｕ−Ｓｎ合金層を材料表面に部分的に露出形成させる場合には、高温酸化などの熱拡散による材料表面のＣｕの酸化物量が多くなり、接触抵抗を増加させ易く、電気的接続の信頼性を維持することが困難となる。一方５．０μｍを超える場合には、経済的に不利であり、生産性も悪く、硬い層が厚く形成されるために成形加工性なども悪くなる。従って、Ｃｕ−Ｓｎ合金層の平均の厚さを０．２〜５．０μｍに規定する。より望ましくは０．３〜１．０μｍである。 (3) The reason why the average thickness of the Cu—Sn alloy layer is 0.2 to 5.0 μm will be described. In the present invention, the average thickness of the Cu—Sn alloy layer is defined as the thickness obtained by measuring the Sn component contained in the Cu—Sn alloy layer with a fluorescent X-ray film thickness meter after removing the pure Sn layer. (The method for measuring the average thickness of the Cu—Sn alloy layers described in the examples below is based on this definition). When the average thickness of the Cu—Sn alloy layer is less than 0.2 μm, particularly when the Cu—Sn alloy layer is partially exposed on the surface of the material as in the present invention, the material by thermal diffusion such as high temperature oxidation. The amount of Cu oxide on the surface increases, the contact resistance is likely to increase, and it becomes difficult to maintain the reliability of electrical connection. On the other hand, when the thickness exceeds 5.0 μm, it is economically disadvantageous, the productivity is poor, and the hard layer is formed thick, so that the moldability is deteriorated. Therefore, the average thickness of the Cu—Sn alloy layer is specified to be 0.2 to 5.0 μm. More desirably, the thickness is 0.3 to 1.0 μm.
（４）Ｃｕ−Ｓｎ合金層について、そのＣｕ含有量を２０〜７０ａｔ％とした理由について述べる。Ｃｕ含有量が２０〜７０ａｔ％のＣｕ−Ｓｎ合金層は、Ｃｕ６Ｓｎ５相を主体とする金属間化合物からなる。Ｃｕ６Ｓｎ５相はＳｎ層を形成するＳｎ又はＳｎ合金に比べて非常に硬く、それを材料の最表面に部分的に露出形成すると、アルミニウムと接触する際、アルミニウム酸化皮膜を除去することができる。さらに、本発明ではＣｕ６Ｓｎ５相がＳｎ層の表面に部分的に突出しているため、アルミニウム電線との圧着や、端子挿抜などにおける電気接点部の接触の際、硬いＣｕ６Ｓｎ５相で接触するため、アルミニウム酸化皮膜を軽い荷重で除去することができる。一方、Ｃｕ３Ｓｎ相はさらに硬く、アルミニウム酸化皮膜の除去には適しているが、Ｃｕ６Ｓｎ５相に比べてＣｕ含有量が多いため、これをＳｎ層の表面全面に露出させた場合には、経時や腐食などによる材料表面のＣｕの酸化物量などが多くなり、接触抵抗を増加させ易く、電気的接続の信頼性を維持することが困難となる。また、Ｃｕ３Ｓｎ相はＣｕ６Ｓｎ５相に比べて脆いために、成形加工性などが劣るという問題点がある。従って、Ｃｕ−Ｓｎ合金層の構成成分を、Ｃｕ含有量が２０〜７０ａｔ％のＣｕ−Ｓｎ合金に規定する。このＣｕ−Ｓｎ合金層には、Ｃｕ６Ｓｎ５相のみでなくＣｕ３Ｓｎ相が一部含まれていてもよく、母材及びＳｎめっき中の成分元素などが含まれていてもよい。しかし、Ｃｕ−Ｓｎ合金層のＣｕ含有量が２０ａｔ％未満では硬度が低く、アルミニウム酸化皮膜を除去することが困難となり、接触抵抗が増加する。一方Ｃｕ含有量が７０ａｔ％を超えるとＣｕ３Ｓｎ相の比率が高くなり経時や腐食などによる電気的接続の信頼性を維持することが困難となり、成形加工性なども悪くなる。従って、Ｃｕ−Ｓｎ合金層のＣｕ含有量を２０〜７０ａｔ％に規定する。より望ましくは４５〜６５ａｔ％である。 (4) Regarding the Cu—Sn alloy layer, the reason why the Cu content is set to 20 to 70 at% will be described. The Cu—Sn alloy layer having a Cu content of 20 to 70 at% is made of an intermetallic compound mainly composed of a Cu 6 Sn 5 phase. The Cu 6 Sn 5 phase is very hard compared to Sn or Sn alloy forming the Sn layer, and when it is partially exposed on the outermost surface of the material, it can remove the aluminum oxide film when it comes into contact with aluminum. it can. Further, in the present invention, since the Cu 6 Sn 5 phase partially protrudes from the surface of the Sn layer, the hard Cu 6 Sn 5 phase is used in contact with the electrical contact part in crimping with an aluminum electric wire or terminal insertion / extraction. Because of the contact, the aluminum oxide film can be removed with a light load. On the other hand, the Cu 3 Sn phase is harder and suitable for removing the aluminum oxide film, but has a higher Cu content than the Cu 6 Sn 5 phase, so that it is exposed to the entire surface of the Sn layer. Increases the amount of Cu oxide on the surface of the material due to aging or corrosion, etc., and tends to increase the contact resistance, making it difficult to maintain the reliability of electrical connection. Further, since the Cu 3 Sn phase is more fragile than the Cu 6 Sn 5 phase, there is a problem that molding processability is inferior. Therefore, the constituent component of the Cu—Sn alloy layer is defined as a Cu—Sn alloy having a Cu content of 20 to 70 at%. This Cu—Sn alloy layer may include not only the Cu 6 Sn 5 phase but also a part of the Cu 3 Sn phase, and may include a base material and component elements during Sn plating. However, if the Cu content of the Cu—Sn alloy layer is less than 20 at%, the hardness is low, and it becomes difficult to remove the aluminum oxide film, and the contact resistance increases. On the other hand, if the Cu content exceeds 70 at%, the ratio of the Cu 3 Sn phase becomes high, it becomes difficult to maintain the reliability of electrical connection due to aging or corrosion, and the moldability and the like deteriorate. Therefore, the Cu content of the Cu—Sn alloy layer is specified to be 20 to 70 at%. More desirably, it is 45 to 65 at%.
（５）材料表面の算術平均粗さＲａが０．１５μｍ以上、３．０μｍ以下とした理由について述べる。算術平均粗さＲａが０．１５μｍ未満の場合、Ｃｕ−Ｓｎ合金層の材料表面突出高さが全体に低く、アルミニウム系材料と接触した際、アルミニウム表面の酸化皮膜を除去する効果が小さくなり、接触信頼性が低下する。一方、算術平均粗さＲａが３．０μｍを超える場合、端子成形後加工後、高温環境に保持された時、材料表面のＣｕの酸化物量が多くなり、接触抵抗を増加させ易く、また耐食性も悪くなることから、電気的接続の信頼性を維持することが困難となる。従って、材料表面粗さは、算術平均粗さＲａが０．１５μｍ以上かつ３．０μｍ以下と規定する。より望ましくは０．１５〜２．０μｍである。
段落００１７で述べた通り、アルミニウム電線は細線を束ねた構造であるため、少なくとも圧延方向と垂直に測定した粗さが算術平均粗さＲａが０．１５μｍ以上かつ３．０μｍ以下であればよい。
しかしながら、必ずしも電線長手方向と圧延方向の関係が垂直になるとは限らないので、より望ましくは、全ての方向で測定した算術平均あらさＲａが０．１５μｍ以上かつ３．０μｍ以下であることが望ましい。より望ましくは０．１５〜２．０μｍである。
図１に本発明に係る錫めっき付銅又は銅合金材料（リフロー後）の断面構造を模式的に示す。Ｃｕ−Ｓｎ合金層ＹがＳｎ層Ｘの表面から突出している。算術平均粗さＲａが小さいとＣｕ−Ｓｎ合金層の突出が小さく、アルミニウム酸化皮膜が除去されにくく、算術平均粗さＲａが大きくなると、Ｃｕ−Ｓｎ合金層の露出面積が広くなり、電気的信頼性、耐食性が低下する。
(5) The reason why the arithmetic average roughness Ra of the material surface is 0.15 μm or more and 3.0 μm or less will be described. When the arithmetic average roughness Ra is less than 0.15 μm, the material surface protrusion height of the Cu—Sn alloy layer is low overall, and when it comes into contact with the aluminum-based material, the effect of removing the oxide film on the aluminum surface becomes small, Contact reliability decreases. On the other hand, when the arithmetic average roughness Ra exceeds 3.0 μm, the amount of Cu oxide on the surface of the material increases when it is kept in a high-temperature environment after processing after terminal molding, and it is easy to increase the contact resistance and also has corrosion resistance. Since it worsens, it becomes difficult to maintain the reliability of electrical connection. Therefore, the material surface roughness is defined as an arithmetic average roughness Ra of 0.15 μm or more and 3.0 μm or less. More desirably, the thickness is 0.15 to 2.0 μm.
As described in paragraph 0017, since the aluminum electric wire has a structure in which fine wires are bundled, the roughness measured at least perpendicular to the rolling direction may be an arithmetic average roughness Ra of 0.15 μm or more and 3.0 μm or less.
However, since the relationship between the wire longitudinal direction and the rolling direction is not always perpendicular, it is more desirable that the arithmetic average roughness Ra measured in all directions is 0.15 μm or more and 3.0 μm or less. More desirably, the thickness is 0.15 to 2.0 μm.
FIG. 1 schematically shows a cross-sectional structure of a tin-plated copper or copper alloy material (after reflow) according to the present invention. The Cu—Sn alloy layer Y protrudes from the surface of the Sn layer X. When the arithmetic average roughness Ra is small, the protrusion of the Cu—Sn alloy layer is small, and the aluminum oxide film is difficult to be removed. When the arithmetic average roughness Ra is large, the exposed area of the Cu—Sn alloy layer is widened and the electrical reliability is increased. And corrosion resistance are reduced.
（６）Ｓｎ層の平均の厚さを０．３〜６．０μｍとした理由について述べる。なお、本発明では、Ｓｎ層の平均の厚さは、試験材の皮膜中に含まれるＳｎ成分（Ｓｎ層の膜厚とＣｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚の和）を蛍光Ｘ線膜厚計にて測定した後、Ｓｎ層を除去しＣｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚を測定、試験材の皮膜中に含まれるＳｎ成分から、Ｃｕ−Ｓｎ合金層に含有されるＳｎ成分を差し引くことにより算出した値と定義する。（下記実施例に記載したＳｎ層の平均の厚さ測定方法は、この定義に準拠するものである）。Ｓｎ層の平均の厚さが０．３μｍ未満では、高温酸化などの熱拡散による材料表面のＣｕの酸化物量が多くなり、接触抵抗を増加させ易く、また耐食性も悪くなることから、電気的接続の信頼性を維持することが困難となる。一方６．０μｍを超える場合には、経済的に不利であり、生産性も悪くなる。従って、Ｓｎ層の平均の厚さを０．３〜６．０μｍに規定する。より望ましくは０．５〜３．０μｍである。Ｓｎ層がＳｎ合金からなる場合、Ｓｎ合金のＳｎ以外の構成成分としては、Ｐｂ、Ｂｉ、Ｚｎ、Ａｇ、Ｃｕなどが挙げられる。Ｐｂについては５０質量％未満、他の元素については１０質量％未満が望ましい。 (6) The reason for setting the average thickness of the Sn layer to 0.3 to 6.0 μm will be described. In the present invention, the average thickness of the Sn layer is the Sn component (the sum of the thickness of the Sn layer and the thickness of the Sn component contained in the Cu-Sn alloy layer) contained in the test material film. After measuring with a fluorescent X-ray film thickness meter, the Sn layer is removed and the film thickness of the Sn component contained in the Cu—Sn alloy layer is measured. From the Sn component contained in the film of the test material, the Cu—Sn alloy is measured. It is defined as a value calculated by subtracting the Sn component contained in the layer. (The method for measuring the average thickness of the Sn layer described in the examples below is based on this definition). If the average thickness of the Sn layer is less than 0.3 μm, the amount of Cu oxide on the surface of the material due to thermal diffusion such as high-temperature oxidation increases, and the contact resistance tends to increase and the corrosion resistance also deteriorates. It becomes difficult to maintain the reliability. On the other hand, if it exceeds 6.0 μm, it is economically disadvantageous and the productivity is also deteriorated. Therefore, the average thickness of the Sn layer is specified to be 0.3 to 6.0 μm. More desirably, the thickness is 0.5 to 3.0 μm. When the Sn layer is made of an Sn alloy, examples of constituents other than Sn of the Sn alloy include Pb, Bi, Zn, Ag, and Cu. Pb is preferably less than 50% by mass, and other elements are preferably less than 10% by mass.
（７）黄銅や丹銅のようなＺｎ含有Ｃｕ合金を母材として用いる場合などには、母材とＣｕ−Ｓｎ合金層の間にＣｕ層を有していてもよい。このＣｕ層はリフロー処理後にＣｕめっき層が残留したものである。Ｃｕ層は、Ｚｎやその他の母材構成元素の材料表面への拡散を抑制するのに役立ち、はんだ付け性などが改善されることが広く知られている。Ｃｕ層は厚くなりすぎると成形加工性などが劣化し、経済性も悪くなることから、Ｃｕ層の厚さは３．０μｍ以下が好ましい。Ｃｕ層には、母材に含まれる成分元素等が少量混入していてもよい。また、Ｃｕ層がＣｕ合金からなる場合、Ｃｕ合金のＣｕ以外の構成成分としてはＳｎ、Ｚｎ等が挙げられる。Ｓｎの場合は５０質量％未満、他の元素については５質量％未満が望ましい。 (7) When using a Zn-containing Cu alloy such as brass or red brass as a base material, a Cu layer may be provided between the base material and the Cu-Sn alloy layer. This Cu layer is a layer in which the Cu plating layer remains after the reflow treatment. It is widely known that the Cu layer is useful for suppressing the diffusion of Zn and other base material constituent elements to the material surface, and that the solderability is improved. If the Cu layer becomes too thick, the moldability and the like deteriorate and the economic efficiency also deteriorates. Therefore, the thickness of the Cu layer is preferably 3.0 μm or less. The Cu layer may contain a small amount of component elements contained in the base material. When the Cu layer is made of a Cu alloy, examples of constituent components other than Cu of the Cu alloy include Sn and Zn. In the case of Sn, less than 50% by mass, and for other elements, less than 5% by mass is desirable.
（８）また、母材とＣｕ−Ｓｎ合金層の間（Ｃｕ層がない場合）、又は母材とＣｕ層の間に、Ｎｉ層が形成されていてもよい。Ｎｉ層はＣｕや母材構成元素の材料表面への拡散を抑制して、高温長時間使用後も接触抵抗の上昇を抑制するとともに、Ｃｕ−Ｓｎ合金層の成長を抑制してＳｎ層の消耗を防止し、また亜硫酸ガス耐食性が向上することが知られている。また、Ｎｉ層自身の材料表面への拡散はＣｕ−Ｓｎ合金層やＣｕ層により抑制される。このことから、Ｎｉ層を形成した接続部品用材料は、耐熱性が求められる接続部品に特に適する。Ｎｉ層は厚くなりすぎると成形加工性などが劣化し、経済性も悪くなることから、Ｎｉ層の厚さは３．０μｍ以下が好ましい。Ｎｉ層には、母材に含まれる成分元素等が少量混入していてもよい。また、Ｎｉ層がＮｉ合金からなる場合、Ｎｉ合金のＮｉ以外の構成成分としては、Ｃｕ、Ｐ、Ｃｏなどが挙げられる。Ｃｕについては４０質量％以下、Ｐ、Ｃｏについては１０質量％以下が望ましい。 (8) Moreover, the Ni layer may be formed between the base material and the Cu—Sn alloy layer (when there is no Cu layer) or between the base material and the Cu layer. The Ni layer suppresses the diffusion of Cu and matrix constituent elements to the surface of the material, suppresses the increase in contact resistance even after high temperature use for a long time, suppresses the growth of the Cu—Sn alloy layer, and consumes the Sn layer. It is known that sulfur dioxide gas corrosion resistance is improved. Further, the diffusion of the Ni layer itself onto the material surface is suppressed by the Cu—Sn alloy layer or the Cu layer. For this reason, the connecting component material on which the Ni layer is formed is particularly suitable for connecting components that require heat resistance. If the Ni layer becomes too thick, the moldability and the like deteriorate, and the economic efficiency also deteriorates. Therefore, the thickness of the Ni layer is preferably 3.0 μm or less. A small amount of component elements contained in the base material may be mixed in the Ni layer. Further, when the Ni layer is made of a Ni alloy, Cu, P, Co and the like can be cited as constituent components other than Ni of the Ni alloy. For Cu, 40% by mass or less, and for P and Co, 10% by mass or less are desirable.
（９）本発明の材料表面におけるＳｎ層表面の凹凸は表面光沢を低下させ、摩擦係数や接触抵抗に悪影響を及ぼす場合があるため、なるべく平滑なほうが望ましい。母材表面の凹凸が激しい材料に被覆したＳｎ層の表面を平滑化する方法には、被覆層を形成させた後に研削、研磨などを行う機械的方法や、Ｓｎ層をリフロー処理する方法が挙げられるが、経済性や生産性を考慮すると、Ｓｎ層をリフロー処理する方法が望ましい。さらに、本発明のように、前記Ｃｕ−Ｓｎ合金層の一部を前記Ｓｎ層の表面に露出して形成させるには、リフロー処理以外の方法では製造が非常に困難となる。凹凸の激しい母材表面に直接に、あるいはＮｉめっき層やＣｕめっき層を介してＳｎめっき層を施した場合、めっきの均一電着性が良好であれば、Ｓｎめっき層表面は、母材の表面形態を反映して凹凸の激しい表面が得られてしまう。これにリフロー処理を施すと、溶融した表面凸部のＳｎが表面凹部に流動する作用により、Ｓｎ層の表面を平滑化でき、さらにリフロー処理中に形成されるＣｕ−Ｓｎ合金層の一部を前記Ｓｎ層の表面に露出して形成させることができる。またリフロー処理を施すことにより、耐ウィスカ性も向上する。なお、Ｃｕめっき層と溶融したＳｎめっき層の間に形成されるＣｕ−Ｓｎ拡散合金層は、通常、母材の表面形態を反映して成長する。ただし、リフロー処理条件が不適切だと、Ｓｎ層の表面に突出するＣｕ−Ｓｎ合金層の厚さが前記Ｃｕ−Ｓｎ合金層の平均の厚さと比較して極めて薄くなる場合がある。 (9) Since the irregularities on the surface of the Sn layer on the material surface of the present invention may reduce the surface gloss and adversely affect the friction coefficient and contact resistance, it is desirable to be as smooth as possible. Examples of the method of smoothing the surface of the Sn layer coated with a material having a rough surface of the base material include a mechanical method of performing grinding and polishing after forming the coating layer, and a method of reflowing the Sn layer. However, in consideration of economy and productivity, a method of reflowing the Sn layer is desirable. Further, as in the present invention, in order to form a part of the Cu—Sn alloy layer so as to be exposed on the surface of the Sn layer, it is very difficult to manufacture by a method other than the reflow treatment. When the Sn plating layer is applied directly on the surface of the base material with severe irregularities or through the Ni plating layer or the Cu plating layer, if the uniform electrodeposition of plating is good, the Sn plating layer surface is Reflecting the surface form, a highly uneven surface is obtained. When reflow treatment is applied to this, the surface of the Sn layer can be smoothed by the action of the molten surface convex portion Sn flowing into the surface concave portion, and a part of the Cu-Sn alloy layer formed during the reflow treatment can be removed. It can be formed exposed on the surface of the Sn layer. Moreover, whisker resistance is also improved by applying the reflow treatment. The Cu—Sn diffusion alloy layer formed between the Cu plating layer and the molten Sn plating layer usually grows reflecting the surface form of the base material. However, if the reflow treatment conditions are inappropriate, the thickness of the Cu—Sn alloy layer protruding from the surface of the Sn layer may be extremely thin compared to the average thickness of the Cu—Sn alloy layer.
図１において、銅又は銅合金母材Ａの一方の表面（図１において上側の表面）が粗面化され、他方の表面が従来材と同じく平滑である。粗面化した前記一方の表面では、表面の凹凸に沿って、数〜数十μｍ程度の径の粒子からなるＣｕ−Ｓｎ合金層Ｙが形成され、Ｓｎ層Ｘが溶融流動して平滑化しており、それに伴い、Ｃｕ−Ｓｎ合金層Ｙが一部材料表面に露出し、Ｓｎ層Ｘの表面から突出している。平滑な前記他方の表面では、従来材と同じく、Ｃｕ−Ｓｎ合金層Ｙの全面をＳｎ層Ｘが覆っている。
このように本発明の錫めっき付銅又は銅合金材料は、電気的接続の信頼性の維持に必要なＳｎ層を厚く形成させても、電気的接続の信頼性が比較的良好で、かつアルミニウム酸化皮膜を除去するのに効果的なＣｕ−Ｓｎ合金層を、材料表面に適正な条件で露出させているため、電気的接続の信頼性（低い接触抵抗）を維持することができる。
また、この錫めっき付銅又は銅合金材料は、少なくともアルミニウムと接触する部分の被覆層構成について、Ｃｕ含有量が２０〜７０ａｔ％で平均の厚さが０．２〜５．０μｍのＣｕ−Ｓｎ合金層と平均の厚さが０．３〜６．０μｍのＳｎ層がこの順に形成され、その材料表面はリフロー処理されていて、算術平均粗さＲａが０．１５μｍ以上３．０μｍ以下であり、前記Ｓｎ層の表面に前記Ｃｕ−Ｓｎ合金層の一部が露出して形成され、前記Ｃｕ−Ｓｎ合金層の材料表面露出面積率が１０〜７５％となっていればよく、アルミニウムと接触しない部分の被覆層構成は前記規定を満たしていなくてもよい。
In FIG. 1, one surface of copper or copper alloy base material A (the upper surface in FIG. 1) is roughened, and the other surface is smooth as in the conventional material. On the roughened one surface, a Cu—Sn alloy layer Y composed of particles having a diameter of several to several tens of μm is formed along the unevenness of the surface, and the Sn layer X melts and flows to be smoothed. Accordingly, a part of the Cu—Sn alloy layer Y is exposed on the surface of the material and protrudes from the surface of the Sn layer X. On the other smooth surface, the Sn layer X covers the entire surface of the Cu—Sn alloy layer Y as in the conventional material.
Thus, the tin-plated copper or copper alloy material of the present invention has relatively good electrical connection reliability even when the Sn layer necessary for maintaining the reliability of the electrical connection is formed thick, and aluminum. Since the Cu—Sn alloy layer effective for removing the oxide film is exposed on the surface of the material under appropriate conditions, the reliability of electrical connection (low contact resistance) can be maintained.
In addition, this tin-plated copper or copper alloy material is Cu-Sn having a Cu content of 20 to 70 at% and an average thickness of 0.2 to 5.0 [mu] m at least for the coating layer structure in contact with aluminum. An alloy layer and an Sn layer having an average thickness of 0.3 to 6.0 μm are formed in this order, the material surface is reflowed, and the arithmetic average roughness Ra is not less than 0.15 μm and not more than 3.0 μm It is sufficient that a part of the Cu-Sn alloy layer is exposed on the surface of the Sn layer, and the exposed area ratio of the material surface of the Cu-Sn alloy layer is 10 to 75%. The coating layer configuration of the portion that is not required does not have to satisfy the above definition.
以上述べた錫めっき付き銅又は銅合金材料は、銅又は銅合金板条からなる母材の表面を例えば機械的方法（圧延又は研磨）で粗面化処理したうえで、該母材表面に、Ｎｉめっき層（必要に応じて）、Ｃｕめっき層及びＳｎめっき層をこの順に形成した後、リフロー処理を行うことにより製造される。Ｎｉめっき層、Ｃｕめっき層及びＳｎめっき層が、それぞれＮｉ合金、Ｃｕ合金及びＳｎ合金からなる場合は、先にＮｉ層、Ｃｕ層及びＳｎ層に関して説明した各合金を用いることができる。なお、本発明に係る錫めっき付銅又は銅合金材料の製造には、前記特開２００６−１８３０６８号公報に記載された製造方法がそのまま適用できる。 The tin-plated copper or copper alloy material described above is obtained by roughening the surface of a base material made of copper or a copper alloy sheet by, for example, a mechanical method (rolling or polishing), It is manufactured by forming a Ni plating layer (if necessary), a Cu plating layer, and a Sn plating layer in this order, and then performing a reflow process. When the Ni plating layer, the Cu plating layer, and the Sn plating layer are made of a Ni alloy, a Cu alloy, and a Sn alloy, respectively, the alloys described above with respect to the Ni layer, the Cu layer, and the Sn layer can be used. In addition, the manufacturing method described in the said Unexamined-Japanese-Patent No. 2006-183068 can be applied as it is to manufacture of the tin-plated copper or copper alloy material according to the present invention.
以下の実施例により、要点を絞り、更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The following examples will focus on the essential points and will be described more specifically, but the present invention is not limited to these examples.
［銅合金母材の作製］
表１に、使用した銅合金（Ｎｏ．１、Ｎｏ．２）の化学成分を示す。本実施例においては、これらの銅合金板条を用い、機械的な方法（圧延又は研磨）で表面粗化処理を行い（試験Ｎｏ．１７は行わず）、ビッカース硬さＨｖ２００、厚さ０．２５ｍｍで、銅合金母材に仕上げた。この時の母材の算術平均粗さＲａは０．１〜４μｍであった。なお、この表面粗さは後述する［材料表面粗さ測定方法］で測定した。
さらに、Ｎｉめっき、Ｃｕめっき及びＳｎめっきを施した後、２８０℃で１０秒間のリフロー処理を行うことにより試験材Ｎｏ．１〜２１を得た。
[Preparation of copper alloy base material]
Table 1 shows chemical components of the copper alloys (No. 1 and No. 2) used. In this example, using these copper alloy strips, surface roughening was performed by a mechanical method (rolling or polishing) (no test No. 17 was performed), and Vickers hardness Hv200, thickness 0. A copper alloy base material was finished at 25 mm. The arithmetic mean roughness Ra of the base material at this time was 0.1 to 4 μm. This surface roughness was measured by [Material surface roughness measuring method] described later.
Furthermore, after applying Ni plating, Cu plating, and Sn plating, the test material No. 1-21 were obtained.
リフロー処理前の試験材について、Ｓｎめっき層、Ｃｕめっき層、Ｎｉめっき層の平均の厚さを、下記要領で測定した。その結果を表２に示す。
［Ｓｎめっき層の平均の厚さ測定方法］
蛍光Ｘ線膜厚計（セイコーインスツルメンツ株式会社；ＳＦＴ３２００）を用いて、リフロー処理前の試験材のＳｎめっきの平均厚さを算出した。測定条件は、検量線にＳｎ／母材の単層検量線又はＳｎ／Ｎｉ／母材の２層検量線を用い、コリメータ径をφ０．５ｍｍとした。
About the test material before a reflow process, the average thickness of Sn plating layer, Cu plating layer, and Ni plating layer was measured in the following way. The results are shown in Table 2.
[Method for measuring average thickness of Sn plating layer]
Using a fluorescent X-ray film thickness meter (Seiko Instruments Inc .; SFT3200), the average thickness of the Sn plating of the test material before the reflow treatment was calculated. The measurement conditions were a single layer calibration curve of Sn / base material or a two-layer calibration curve of Sn / Ni / base material for the calibration curve, and the collimator diameter was φ0.5 mm.
［Ｃｕめっきの平均の厚さ測定方法］
Ｃｕめっき後の試験材をミクロトーム法にて加工し、その断面をＳＥＭ（走査型電子顕微鏡）を用いて１０，０００倍の倍率で観察し、画像解析処理にて平均の厚さを算出した。なお、このＣｕめっき層の厚さは、リフロー処理後の試験材のＣｕ層の厚さを示す値ではなく、めっき皮膜の厚さである。
［Ｎｉめっき層の平均の厚さ測定方法］
蛍光Ｘ線膜厚計（セイコーインスツルメンツ株式会社；ＳＦＴ３２００）を用いて、リフロー処理前の試験材のＮｉめっきの平均厚さを算出した。測定条件は、検量線にＳｎ／Ｎｉ／母材の２層検量線を用い、コリメータ径をφ０．５ｍｍとした。なお、Ｎｉめっき層の平均の厚さはリフロー処理後（Ｎｉ層）もほとんど変化しない。
[Measuring method of average thickness of Cu plating]
The test material after Cu plating was processed by the microtome method, the cross section was observed at a magnification of 10,000 using a SEM (scanning electron microscope), and the average thickness was calculated by image analysis processing. In addition, the thickness of this Cu plating layer is not a value indicating the thickness of the Cu layer of the test material after the reflow treatment, but the thickness of the plating film.
[Measuring method of average thickness of Ni plating layer]
The average thickness of the Ni plating of the test material before the reflow treatment was calculated using a fluorescent X-ray film thickness meter (Seiko Instruments Inc .; SFT3200). The measurement conditions were Sn / Ni / base metal two-layer calibration curve for the calibration curve and the collimator diameter was φ0.5 mm. Note that the average thickness of the Ni plating layer hardly changes even after the reflow treatment (Ni layer).
続いて、リフロー処理後の試験材について、Ｃｕ−Ｓｎ合金層のＣｕ含有量、Ｃｕ−Ｓｎ合金層の平均の厚さ、Ｓｎ層の平均の厚さ、Ｃｕ−Ｓｎ合金層の材料表面露出面積率、Ｃｕ−Ｓｎ合金層の平均の材料表面露出間隔、及び材料表面粗さを下記要領で測定した。その結果を表３に示す。
［Ｃｕ−Ｓｎ合金層のＣｕ含有量測定方法］
まず、試験材をｐ−ニトロフェノール及び苛性ソーダを成分とする水溶液に１０分間浸漬し、Ｓｎ層を除去した。その後、ＥＤＸ（エネルギー分散型Ｘ線分光分析器）を用いて、Ｃｕ−Ｓｎ合金層のＣｕ含有量を定量分析により求めた。
Subsequently, for the test material after the reflow treatment, the Cu content of the Cu—Sn alloy layer, the average thickness of the Cu—Sn alloy layer, the average thickness of the Sn layer, and the material surface exposed area of the Cu—Sn alloy layer The average material surface exposure interval of the Cu—Sn alloy layer and the material surface roughness were measured as follows. The results are shown in Table 3.
[Method for measuring Cu content of Cu-Sn alloy layer]
First, the test material was immersed in an aqueous solution containing p-nitrophenol and caustic soda as components for 10 minutes to remove the Sn layer. Then, Cu content of a Cu-Sn alloy layer was calculated | required by quantitative analysis using EDX (energy dispersive X-ray-spectrometer).
［Ｃｕ−Ｓｎ合金層の平均の厚さ測定方法］
まず、試験材をｐ−ニトロフェノール及び苛性ソーダを成分とする水溶液に１０分間浸漬し、Ｓｎ層を除去した。その後、蛍光Ｘ線膜厚計（セイコーインスツルメンツ株式会社；ＳＦＴ３２００）を用いて、Ｃｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚を測定した。測定条件は、検量線にＳｎ／母材の単層検量線又はＳｎ／Ｎｉ／母材の２層検量線を用い、コリメータ径をφ０．５ｍｍとした。得られた値をＣｕ−Ｓｎ合金層の平均の厚さと定義して算出した。
[Measuring method of average thickness of Cu-Sn alloy layer]
First, the test material was immersed in an aqueous solution containing p-nitrophenol and caustic soda as components for 10 minutes to remove the Sn layer. Then, the film thickness of the Sn component contained in the Cu—Sn alloy layer was measured using a fluorescent X-ray film thickness meter (Seiko Instruments Inc .; SFT3200). The measurement conditions were a single layer calibration curve of Sn / base material or a two-layer calibration curve of Sn / Ni / base material for the calibration curve, and the collimator diameter was φ0.5 mm. The obtained value was calculated as the average thickness of the Cu—Sn alloy layer.
［Ｓｎ層の平均の厚さ測定方法］
まず、蛍光Ｘ線膜厚計（セイコーインスツルメンツ株式会社；ＳＦＴ３２００）を用いて、試験材のＳｎ層の膜厚とＣｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚の和を測定した。その後、ｐ−ニトロフェノール及び苛性ソーダを成分とする水溶液に１０分間浸漬し、Ｓｎ層を除去した。再度、蛍光Ｘ線膜厚計を用いて、Ｃｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚を測定した。測定条件は、検量線にＳｎ／母材の単層検量線又はＳｎ／Ｎｉ／母材の２層検量線を用い、コリメータ径をφ０．５ｍｍとした。得られたＳｎ層の膜厚とＣｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚の和から、Ｃｕ−Ｓｎ合金層に含有されるＳｎ成分の膜厚を差し引くことにより、Ｓｎ層の平均の厚さを算出した。
[Method for measuring average thickness of Sn layer]
First, the sum of the film thickness of the Sn layer of the test material and the film thickness of the Sn component contained in the Cu—Sn alloy layer was measured using a fluorescent X-ray film thickness meter (Seiko Instruments Inc .; SFT3200). Thereafter, the Sn layer was removed by immersing in an aqueous solution containing p-nitrophenol and caustic soda as components. Again, the film thickness of the Sn component contained in the Cu—Sn alloy layer was measured using a fluorescent X-ray film thickness meter. The measurement conditions were a single layer calibration curve of Sn / base material or a two-layer calibration curve of Sn / Ni / base material for the calibration curve, and the collimator diameter was φ0.5 mm. By subtracting the film thickness of the Sn component contained in the Cu-Sn alloy layer from the sum of the film thickness of the obtained Sn layer and the film thickness of the Sn component contained in the Cu-Sn alloy layer, the average of the Sn layers The thickness of was calculated.
［Ｃｕ−Ｓｎ合金層の材料表面露出面積率測定方法］
試験材の表面を、ＥＤＸ（エネルギー分散型Ｘ線分光分析器）を搭載したＳＥＭ（走査型電子顕微鏡）を用いて２００倍の倍率で観察し、得られた組成像の濃淡（汚れや傷等のコントラストは除く）から画像解析によりＣｕ−Ｓｎ合金層の材料表面露出面積率を測定した。図２にＮｏ．１の組成像を示す。図中、ＸはＳｎ層、Ｙは露出したＣｕ−Ｓｎ合金層である。
［Ｃｕ−Ｓｎ合金被覆層の平均の材料表面露出間隔測定方法］
試験材の表面を、ＥＤＸ（エネルギー分散型Ｘ線分光分析器）を搭載したＳＥＭ（走査型電子顕微鏡）を用いて２００倍の倍率で観察し、得られた組成像から、材料表面に引いた直線を横切るＣｕ−Ｓｎ合金被覆層の平均の幅（前記直線に沿った長さ）とＳｎ被覆層の平均の幅を足した値の平均を求めることにより、Ｃｕ−Ｓｎ合金被覆層の平均の材料表面露出間隔を測定した。測定方向（引いた直線の方向）は、表面粗化処理の際に行った圧延又は研磨方向に直角な方向とした。
[Measuring Method of Material Surface Exposed Area Ratio of Cu-Sn Alloy Layer]
The surface of the test material was observed at a magnification of 200 using an SEM (scanning electron microscope) equipped with EDX (energy dispersive X-ray spectrometer), and the resulting composition image was shaded (dirt, scratches, etc.). The ratio of the exposed surface area of the Cu—Sn alloy layer was measured by image analysis. In FIG. 1 shows a composition image. In the figure, X is a Sn layer, and Y is an exposed Cu—Sn alloy layer.
[Measuring method of average material surface exposure interval of Cu—Sn alloy coating layer]
The surface of the test material was observed at a magnification of 200 times using an SEM (scanning electron microscope) equipped with EDX (energy dispersive X-ray spectrometer), and was drawn on the material surface from the obtained composition image. By calculating the average of the value obtained by adding the average width (length along the straight line) of the Cu—Sn alloy coating layer crossing the straight line and the average width of the Sn coating layer, the average of the Cu—Sn alloy coating layer is obtained. The material surface exposure interval was measured. The measurement direction (the direction of the drawn straight line) was a direction perpendicular to the rolling or polishing direction performed during the surface roughening treatment.
［材料表面粗さ測定方法］
接触式表面粗さ計（株式会社東京精密；サーフコム１４００）を用いて、ＪＩＳ Ｂ０６０１−１９９４に基づいて測定した。表面粗さ測定条件は、カットオフ値を０．８ｍｍ、基準長さを０．８ｍｍ、評価長さを４．０ｍｍ、測定速度を０．３ｍｍ／ｓ、及び触針先端半径を５μｍＲとした。なお、表面粗さ測定方向は、表面粗化処理の際に行った圧延又は研磨方向に直角な方向（表面粗さが最も大きく出る方向）とした。
[Material surface roughness measurement method]
It measured based on JISB0601-1994 using the contact-type surface roughness meter (Tokyo Seimitsu; Surfcom 1400). The surface roughness measurement conditions were a cutoff value of 0.8 mm, a reference length of 0.8 mm, an evaluation length of 4.0 mm, a measurement speed of 0.3 mm / s, and a stylus tip radius of 5 μmR. The surface roughness measurement direction was a direction perpendicular to the rolling or polishing direction performed during the surface roughening treatment (the direction in which the surface roughness is maximized).
また、得られた試験材について、アルミニウム板との接触抵抗評価試験、高温放置後の接触抵抗評価試験を、下記の要領で行った。その結果を、表３及び表４に合わせて示す。
［アルミニウム板の接触抵抗評価試験］
嵌合型接続部品における電気接点のインデント部の形状を模擬し、図３に示すような摺動試験機（株式会社山崎精機研究所；ＣＲＳ−Ｂ１０５０ＣＨＯ）を用いて評価した。まず、アルミニウム板（Ａ１０５０：０．５ｍｍｔ，ビッカース硬さ：Ｈｖ４０）から切り出した板材のオス試験片１を水平な台２に固定し、その上に各試験材から切り出した半球加工材（内径をφ１．５ｍｍとした）のメス試験片３をおいて被覆層同士を接触させた。続いて、メス試験片３に４９ｍＮの荷重（錘４）をかけてオス試験片３を押さえ、オス試験片１とメス試験片３の間に定電流を印加し、ステッピングモータ５を用いてオス試験片１を水平方向に摺動させ（摺動距離を５０μｍ、摺動周波数を１Ｈｚとした）、摺動回数５回の抵抗を四端子法により、開放電圧２０ｍＶ、電流１０ｍＡの条件にて測定し、摺動時の平均抵抗値を測定チャートより読み取った。測定チャートの一例（試験Ｎｏ．１，１７）を図４に示す。なお、矢印は摺動方向である。
［高温放置後の接触抵抗評価試験］
各試験材に対し、大気中にて１６０℃×１２０ｈｒの熱処理を行った後、接触抵抗を四端子法により、開放電圧２０ｍＶ、電流１０ｍＡ、無摺動の条件にて測定した。
Moreover, about the obtained test material, the contact resistance evaluation test with an aluminum plate and the contact resistance evaluation test after leaving at high temperature were performed in the following manner. The results are shown in Table 3 and Table 4.
[Aluminum plate contact resistance evaluation test]
The shape of the indented portion of the electrical contact in the fitting-type connecting part was simulated and evaluated using a sliding tester (Yamazaki Seiki Laboratory Co., Ltd .; CRS-B1050CHO) as shown in FIG. First, a male test piece 1 of a plate material cut out from an aluminum plate (A1050: 0.5 mmt, Vickers hardness: Hv40) is fixed to a horizontal base 2, and a hemispherical processed material (inner diameter is cut out from each test material thereon) A female test piece 3 having a diameter of 1.5 mm was placed and the coating layers were brought into contact with each other. Subsequently, a load of 49 mN (weight 4) is applied to the female test piece 3 to hold the male test piece 3, a constant current is applied between the male test piece 1 and the female test piece 3, and the male is used using the stepping motor 5. The test piece 1 was slid in the horizontal direction (sliding distance was 50 μm, sliding frequency was 1 Hz), and the resistance of 5 times of sliding was measured by the four-terminal method under the conditions of an open voltage of 20 mV and a current of 10 mA. The average resistance value during sliding was read from the measurement chart. An example of the measurement chart (Test Nos. 1 and 17) is shown in FIG. The arrow indicates the sliding direction.
[Evaluation test for contact resistance after standing at high temperature]
Each test material was heat-treated at 160 ° C. for 120 hours in the air, and then contact resistance was measured by a four-terminal method under an open voltage of 20 mV, a current of 10 mA, and no sliding.
表３に示す結果について、次のように評価される。
Ｎｏ．１〜１１は、被覆層構成に関して本発明に規定する要件を満たし、アルミニウム板との接触抵抗が非常に低く、高温長時間放置後の接触抵抗についても優れた特性を示す。
一方、Ｎｏ．１２はＳｎ層及びＣｕ−Ｓｎ合金層の平均の厚さが薄く、Ｎｏ．１３はＣｕ−Ｓｎ合金層の平均の厚さが薄いため、高温放置後の接触抵抗が高い。また、Ｎｏ．１４は特性上問題は無いが、めっき厚さが厚いため製造コストが高くなる。
Ｎｏ．１５はＣｕ−Ｓｎ合金層内のＣｕ含有量が低く合金層の硬度が低いため、アルミニウムの酸化皮膜が破壊されず接触抵抗が高い。Ｎｏ．１６はＣｕ−Ｓｎ合金層内のＣｕ含有量が高いため、高温放置により表面までＣｕが拡散し、Ｃｕの酸化皮膜が表面に形成されるため高温放置後の接触抵抗が高い。
Ｎｏ．１７は粗面化処理を行わない通常母材を用いたため、Ｃｕ−Ｓｎ合金層が材料表面に露出せず、アルミニウムとの接触抵抗が高い。Ｎｏ．１８はＣｕ−Ｓｎ合金層の露出面積率が大きいため、高温酸化放置後の接触抵抗が高い。
Ｎｏ．１９はＣｕ−Ｓｎ合金層の露出間隔が広く、Ｃｕ−Ｓｎ合金層がメス試験片３とオス試験片１の接点部に存在していないため、アルミニウム板との接触抵抗が高い。
Ｎｏ．２０は材料の表面粗度が小さいため、アルミニウムの酸化皮膜が破壊されず接触抵抗が高い。Ｎｏ．２１は材料の表面粗度が大きいため、高温酸化放置後の接触抵抗が高くなる。
The results shown in Table 3 are evaluated as follows.
No. Nos. 1 to 11 satisfy the requirements stipulated in the present invention with respect to the coating layer structure, have very low contact resistance with an aluminum plate, and exhibit excellent characteristics in contact resistance after standing at high temperature for a long time.
On the other hand, no. No. 12 has a thin average thickness of the Sn layer and the Cu—Sn alloy layer. No. 13, since the average thickness of the Cu—Sn alloy layer is thin, the contact resistance after being left at high temperature is high. No. No. 14 has no problem in characteristics, but the manufacturing cost increases because the plating thickness is thick.
No. No. 15 has a low Cu content in the Cu—Sn alloy layer and a low hardness of the alloy layer, so that the aluminum oxide film is not destroyed and the contact resistance is high. No. No. 16 has a high Cu content in the Cu—Sn alloy layer, so that Cu diffuses to the surface when left at high temperature, and an oxide film of Cu is formed on the surface, so contact resistance after high temperature standing is high.
No. Since No. 17 used the normal base material which does not perform a roughening process, a Cu-Sn alloy layer is not exposed to the material surface, but contact resistance with aluminum is high. No. Since No. 18 has a large exposed area ratio of the Cu—Sn alloy layer, the contact resistance after being left at high temperature oxidation is high.
No. No. 19 has a wide exposure interval of the Cu—Sn alloy layer, and since the Cu—Sn alloy layer is not present at the contact portion between the female test piece 3 and the male test piece 1, the contact resistance with the aluminum plate is high.
No. No. 20 has a low surface roughness of the material, so that the aluminum oxide film is not destroyed and the contact resistance is high. No. No. 21 has a high surface roughness of the material, so that the contact resistance after leaving at high temperature is increased.
Ａ 母材
Ｘ Ｓｎ被覆層
Ｙ Ｃｕ−Ｓｎ合金被覆層
１ オス試験片
２ 台
３ メス試験片
４ 錘
５ ロードセル
A Base material X Sn coating layer Y Cu-Sn alloy coating layer 1 Male test piece 2 units 3 Female test piece 4 Weight 5 Load cell
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| DE102011084174A1 (en) * | 2011-10-07 | 2013-04-11 | Tyco Electronics Amp Gmbh | crimp |
| JP5587935B2 (en) * | 2012-03-30 | 2014-09-10 | Ｊｘ日鉱日石金属株式会社 | Sn plating material |
| JP2014002977A (en) * | 2012-06-20 | 2014-01-09 | Japan Aviation Electronics Industry Ltd | Surface structure of conductive member, and washer and crimp terminal including surface structure |
| TW201413068A (en) * | 2012-07-02 | 2014-04-01 | Mitsubishi Materials Corp | Tin-plated copper alloy terminal member with outstanding insertion and removal characteristics and method of manufacturing the same |
| JP5692192B2 (en) * | 2012-09-21 | 2015-04-01 | 株式会社オートネットワーク技術研究所 | Method for manufacturing connector terminal and method for manufacturing connector terminal material |
| US9748683B2 (en) | 2013-03-29 | 2017-08-29 | Kobe Steel, Ltd. | Electroconductive material superior in resistance to fretting corrosion for connection component |
| JP6134557B2 (en) * | 2013-03-29 | 2017-05-24 | Ｊｘ金属株式会社 | Copper strip or copper alloy strip and heat dissipating part provided with the strip |
| EP2799595A1 (en) * | 2013-05-03 | 2014-11-05 | Delphi Technologies, Inc. | Electric contact element |
| EP3051635B1 (en) * | 2015-01-30 | 2018-01-17 | TE Connectivity Germany GmbH | Electric contact means and electrical cable assembly for the automotive industry |
| JP6113822B1 (en) * | 2015-12-24 | 2017-04-12 | 株式会社神戸製鋼所 | Conductive material for connecting parts |
| CN116411202A (en) * | 2021-12-29 | 2023-07-11 | 无锡市蓝格林金属材料科技有限公司 | Copper-tin alloy wire and preparation method thereof |
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| JP2004014216A (en) * | 2002-06-05 | 2004-01-15 | Auto Network Gijutsu Kenkyusho:Kk | Wire connection terminal |
| JP4021734B2 (en) * | 2002-08-30 | 2007-12-12 | 矢崎総業株式会社 | Wire ultrasonic bonding method |
| JP3984539B2 (en) * | 2002-12-17 | 2007-10-03 | 株式会社オートネットワーク技術研究所 | Connector terminal and manufacturing method thereof |
| JP3926355B2 (en) * | 2004-09-10 | 2007-06-06 | 株式会社神戸製鋼所 | Conductive material for connecting parts and method for manufacturing the same |
| JP4024244B2 (en) * | 2004-12-27 | 2007-12-19 | 株式会社神戸製鋼所 | Conductive material for connecting parts and method for manufacturing the same |
| JP4255939B2 (en) * | 2004-09-17 | 2009-04-22 | 神鋼リードミック株式会社 | Press-fit terminal and manufacturing method thereof |
| JP4503620B2 (en) * | 2007-01-25 | 2010-07-14 | 株式会社神戸製鋼所 | Conductive material for connecting parts and method for manufacturing the same |
| JP5464792B2 (en) * | 2007-04-20 | 2014-04-09 | 株式会社神戸製鋼所 | Method for manufacturing mating connector terminal |
| JP2009099282A (en) * | 2007-10-12 | 2009-05-07 | Kobe Steel Ltd | Fitting type connector |
| JP4964795B2 (en) * | 2008-01-23 | 2012-07-04 | Ｊｘ日鉱日石金属株式会社 | Copper alloy tin plating strip with excellent wear resistance |
| JP5089451B2 (en) * | 2008-03-19 | 2012-12-05 | 古河電気工業株式会社 | Metal material for connector and manufacturing method thereof |
| JP5384382B2 (en) * | 2009-03-26 | 2014-01-08 | 株式会社神戸製鋼所 | Copper or copper alloy with Sn plating excellent in heat resistance and method for producing the same |
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