JP2013093228A - Connector and manufacturing method therefor, and plating method of silver - Google Patents
Connector and manufacturing method therefor, and plating method of silver Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 171
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 112
- 239000004332 silver Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 112
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 44
- 239000011701 zinc Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 37
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 102
- 239000000243 solution Substances 0.000 description 31
- 239000002585 base Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 14
- 238000003384 imaging method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- VLGWYKOEXANHJT-UHFFFAOYSA-N methylsulfanol Chemical compound CSO VLGWYKOEXANHJT-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GFLFYBVNHUWFJJ-UHFFFAOYSA-M CS[O-].[Ag+] Chemical compound CS[O-].[Ag+] GFLFYBVNHUWFJJ-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 nickel and zinc Chemical compound 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Electrical Connectors (AREA)
Abstract
Description
本発明は、銅又は銅合金製の母材上に銀のめっき層を備えたコネクタ、該コネクタの製造への適用に好適な銀のめっき方法、及び該めっき方法を適用したコネクタの製造方法に関する。 The present invention relates to a connector having a silver plating layer on a base material made of copper or a copper alloy, a silver plating method suitable for application to the manufacture of the connector, and a connector manufacturing method to which the plating method is applied. .
高出力モータ等の配線や端子では、大電流が流れることがあり、このような用途に対応したコネクタとしては、銅又は銅合金製の母材上に銀めっき層を備えたものが好適である。
しかし、このようなコネクタでは、めっき層の表面に銅が析出することがある。そして、析出した銅は、経時と共に酸化されて電気抵抗値が大きい酸化銅となるため、コネクタの接触抵抗が大きくなり、電気的接続能が低下してしまう。
In a wiring or terminal of a high output motor or the like, a large current may flow, and as a connector corresponding to such an application, a connector provided with a silver plating layer on a base material made of copper or copper alloy is suitable. .
However, in such a connector, copper may be deposited on the surface of the plating layer. And since the deposited copper is oxidized with time and becomes copper oxide having a large electric resistance value, the contact resistance of the connector is increased, and the electrical connection ability is lowered.
上記のように銅が析出する理由は、使用時のコネクタに大電流が流れることでコネクタが発熱したり、コネクタが高温環境に曝されるなどして、コネクタの温度が上昇すると、銀めっき層中の銀の結晶粒の境界（以下、「結晶粒界」と略記することがある）を介して、母材を構成する銅が拡散し、銀めっき層の表面に到達するためであると考えられる。 The reason why copper precipitates as described above is that when a large current flows through the connector during use, the connector generates heat or the connector is exposed to a high temperature environment, and the temperature of the connector rises. It is thought that the copper constituting the base material diffuses and reaches the surface of the silver plating layer through the boundary of the silver crystal grains in the inside (hereinafter sometimes abbreviated as “crystal grain boundary”). It is done.
そこで、コネクタの実用性を損なうことなく、このような銅の析出を防止するものとして、銀めっき層を母材に近い下層側の第一層と、第一層の上層側の第二層との二層構造とし、第二層よりも第一層の銀の結晶粒径を大きくした銀めっき層が開示されている（特許文献１参照）。かかる銀めっき層によれば、銀の結晶粒径が大きい第一層により、母材からの銅の拡散が抑制され、銀の結晶粒径が小さい第二層により、めっき層の硬度が高くなり、耐摩耗性が向上するとされている。 Therefore, as a means for preventing such copper precipitation without impairing the practicality of the connector, the first layer on the lower layer side close to the base material and the second layer on the upper layer side of the first layer A silver plating layer is disclosed in which a silver crystal grain size of the first layer is larger than that of the second layer (see Patent Document 1). According to such a silver plating layer, the diffusion of copper from the base material is suppressed by the first layer having a large crystal grain size of silver, and the hardness of the plating layer is increased by the second layer having a small crystal grain size of silver. It is said that the wear resistance is improved.
しかし、特許文献１に記載の銀めっき層は、二層構造とするために、その形成過程でめっき条件を変更する、すなわちめっきを二回行う必要があり、工程数が増加し、作業も煩雑化するという問題点があった。 However, since the silver plating layer described in Patent Document 1 has a two-layer structure, it is necessary to change the plating conditions in the formation process, that is, it is necessary to perform the plating twice, which increases the number of steps and makes the operation complicated. There was a problem of becoming.
本発明は、上記事情に鑑みてなされたものであり、表面への銅の析出が抑制された銀のめっき層を備えたコネクタ、前記めっき層を簡便に形成できる銀のめっき方法、及び該めっき方法を適用したコネクタの製造方法を提供することを課題とする。 The present invention has been made in view of the above circumstances, and includes a connector provided with a silver plating layer in which copper deposition on the surface is suppressed, a silver plating method capable of easily forming the plating layer, and the plating. It is an object of the present invention to provide a method for manufacturing a connector to which the method is applied.
上記課題を解決するため、
本発明は、銅又は銅合金製の母材上に、亜鉛を含有する銀のめっき層を備えたことを特徴とするコネクタを提供する。
To solve the above problem,
The present invention provides a connector comprising a silver-plated layer containing zinc on a base material made of copper or a copper alloy.
かかるコネクタは、亜鉛を含有する銀のめっき層を備えたことで、温度が上昇してもめっき層表面への銅の析出が抑制され、良好な電気的接続能を長期間維持できる。 Such a connector is provided with a silver plating layer containing zinc, so that even if the temperature rises, copper deposition on the surface of the plating layer is suppressed, and good electrical connection ability can be maintained for a long time.
また、本発明は、亜鉛を含有するめっき液を用いた電気めっきにより、銅又は銅合金製の母材上に、亜鉛を含有する銀のめっき層を形成することを特徴とする銀のめっき方法を提供する。 Further, the present invention provides a silver plating method comprising forming a silver plating layer containing zinc on a base material made of copper or a copper alloy by electroplating using a plating solution containing zinc I will provide a.
かかる銀のめっき方法によれば、亜鉛を含有するめっき液を用いた電気めっきを行うことにより、形成された銀のめっき層は、温度が上昇してもその表面への銅の析出が抑制され、良好な品質を長期間維持できる。また、めっき液の種類が異なる点以外は、従来と同様の方法で電気めっきを行えるので、工程数の増加や作業の煩雑化を伴うことがなく、極めて簡便にめっき層を形成できる。 According to such a silver plating method, by performing electroplating using a plating solution containing zinc, the formed silver plating layer suppresses copper deposition on the surface even when the temperature rises. Good quality can be maintained for a long time. Moreover, since electroplating can be performed by a method similar to the conventional method except that the types of plating solutions are different, the plating layer can be formed very easily without increasing the number of steps and complicating work.
本発明の銀のめっき方法においては、前記めっき液の亜鉛の含有量が０．１〜１０ｐｐｍであることが好ましい。 In the silver plating method of the present invention, the zinc content of the plating solution is preferably 0.1 to 10 ppm.
前記めっき液の亜鉛の含有量が上記範囲であることで、形成されためっき層は、導電性等の特性を損なうことなく、表面への銅の析出抑制効果が一層優れたものとなる。 When the zinc content of the plating solution is within the above range, the formed plating layer has a further excellent effect of suppressing the precipitation of copper on the surface without impairing properties such as conductivity.
また、本発明は、銅又は銅合金製の母材上に、亜鉛を含有する銀のめっき層を備えたコネクタの製造方法であって、上記本発明の銀のめっき方法で前記めっき層を形成する工程を有することを特徴とするコネクタの製造方法を提供する。 Further, the present invention is a method for manufacturing a connector comprising a silver plating layer containing zinc on a base material made of copper or a copper alloy, wherein the plating layer is formed by the silver plating method of the present invention. The manufacturing method of the connector characterized by having the process to do is provided.
かかる製造方法によれば、上記本発明の銀のめっき方法を適用するので、良好な電気的接続能を長期間維持できるコネクタを簡便な方法で得られる。 According to this manufacturing method, since the silver plating method of the present invention is applied, a connector capable of maintaining good electrical connection ability for a long period of time can be obtained by a simple method.
本発明によれば、表面への銅の析出が抑制された銀のめっき層を備えたコネクタ、前記めっき層を簡便に形成できる銀のめっき方法、及び該めっき方法を適用したコネクタの製造方法を提供できる。 According to the present invention, there is provided a connector provided with a silver plating layer in which copper deposition on the surface is suppressed, a silver plating method capable of easily forming the plating layer, and a method of manufacturing a connector to which the plating method is applied. Can be provided.
＜銀のめっき方法＞
本発明に係る銀のめっき方法（以下、単に「めっき方法」と略記することがある）は、亜鉛を含有するめっき液を用いた電気めっきにより、銅又は銅合金製の母材上に、亜鉛を含有する銀のめっき層（以下、「銀めっき層」又は「めっき層」と記載することがある）を形成することを特徴とする。
本発明において、「母材上に銀めっき層を形成する」とは、母材表面に直接銀めっき層を形成する場合だけでなく、母材表面に後述するストライクめっき層等の中間層を形成し、この中間層の表面に銀めっき層を形成する場合も含む概念とする。
<Silver plating method>
The silver plating method according to the present invention (hereinafter simply abbreviated as “plating method”) is obtained by electroplating with a plating solution containing zinc on a base material made of copper or a copper alloy. It is characterized by forming a silver plating layer (hereinafter sometimes referred to as “silver plating layer” or “plating layer”).
In the present invention, “to form a silver plating layer on a base material” means not only the case of forming a silver plating layer directly on the surface of the base material, but also an intermediate layer such as a strike plating layer to be described later on the surface of the base material. The concept includes a case where a silver plating layer is formed on the surface of the intermediate layer.
銀めっき層を形成する母材の材質は、銅又は銅合金であり、母材は単層及び複数層のいずれでもよく、複数層の場合、これらの層を構成する材質の種類及び組み合わせは任意に選択できる。
また、銅及び銅合金以外の材質からなる基材の表面に積層された銅又は銅合金を、母材としてもよい。
The material of the base material forming the silver plating layer is copper or a copper alloy, and the base material may be either a single layer or a plurality of layers. In the case of a plurality of layers, the type and combination of materials constituting these layers are arbitrary. Can be selected.
Moreover, it is good also considering the copper or copper alloy laminated | stacked on the surface of the base material which consists of materials other than copper and a copper alloy as a base material.
銅と合金を構成する金属元素としては、亜鉛、ニッケル、アルミニウム、スズ、金、鉄が例示でき、銅合金は公知のものでよい。 Examples of the metal element constituting the alloy with copper include zinc, nickel, aluminum, tin, gold, and iron, and the copper alloy may be a known one.
銀めっき層は、亜鉛を含有するめっき液を用いる点以外は、従来と同様の方法で電気めっきを行うことにより形成できる。したがって、特殊なめっき条件は不要であり、工程数の増加及び作業の煩雑化を伴うことがないので、極めて簡便に銀めっき層を形成できる。 The silver plating layer can be formed by performing electroplating by the same method as in the prior art except that a plating solution containing zinc is used. Therefore, special plating conditions are not necessary, and the number of steps is not increased and the work is not complicated, so that a silver plating layer can be formed very easily.
前記めっき液は、亜鉛を含有していればよいが、亜鉛の含有量は、質量比で０．１〜１０ｐｐｍであることが好ましい。亜鉛の含有量が０．１ｐｐｍ以上であることで、形成される銀めっき層は、表面への銅の析出抑制効果がより優れたものとなる。また、亜鉛の含有量が１０ｐｐｍ以下であることで、形成される銀めっき層は、銀としての性質を残しつつ、表面の導電性等の特性がより良好となる。 Although the said plating solution should just contain zinc, it is preferable that content of zinc is 0.1-10 ppm by mass ratio. When the zinc content is 0.1 ppm or more, the formed silver plating layer has a more excellent effect of suppressing the precipitation of copper on the surface. In addition, when the zinc content is 10 ppm or less, the formed silver plating layer has better properties such as surface conductivity while leaving the properties as silver.
電気めっきでは、例えば、まず銀めっきの対象となる母材の表面を洗浄し、特に疎水性の汚れを除去する。この時の洗浄方法としては、電解洗浄（電解脱脂）、酸洗浄（酸洗）、アルカリ洗浄、溶剤洗浄等が例示でき、これらを一種単独で、又は二種以上を組み合わせて行い、洗浄する。 In electroplating, for example, first, the surface of a base material to be silver-plated is washed to remove hydrophobic dirt. Examples of the cleaning method at this time include electrolytic cleaning (electrolytic degreasing), acid cleaning (pickling), alkali cleaning, solvent cleaning, and the like, and these are performed alone or in combination of two or more.
銀めっき層の形成前には、母材の表面にストライクめっきを行うことが好ましい。このようにすることで、母材の表面に中間層としてストライクめっき層が形成され、このストライクめっき層を介して形成された銀めっき層は、表面が滑らかになるなど、品質がより向上する。また、母材と銀めっき層との密着性がより向上する。
ストライクめっき層の厚さは、０．１μｍ以下であることが好ましい。
Prior to the formation of the silver plating layer, strike plating is preferably performed on the surface of the base material. By doing in this way, a strike plating layer is formed as an intermediate layer on the surface of the base material, and the quality of the silver plating layer formed through this strike plating layer is further improved, such as a smooth surface. Moreover, the adhesiveness of a base material and a silver plating layer improves more.
The thickness of the strike plating layer is preferably 0.1 μm or less.
ストライクめっきは従来と同様の方法で行えばよく、母材の材質等を考慮して、適宜条件を調節すればよい。例えば、ストライクめっきを行うためのめっき液（以下、「ストライクめっき液」と略記することがある）は、銀を含有することが好ましい。また、ストライクめっき液は、銀ではなくニッケル、亜鉛等の銀以外の金属を含有していてもよく、銀と銀以外の金属とを共に含有していてもよい。
ストライクめっき液が亜鉛を含有する場合、その含有量は、上記の亜鉛を含有するめっき液（以下、ストライクめっき液と区別するために、「本めっき液」と略記することがある）と同様でよい。
The strike plating may be performed by a method similar to the conventional one, and the conditions may be appropriately adjusted in consideration of the material of the base material. For example, a plating solution for performing strike plating (hereinafter sometimes abbreviated as “strike plating solution”) preferably contains silver. Moreover, the strike plating solution may contain metals other than silver, such as nickel and zinc, instead of silver, and may contain both silver and metals other than silver.
When the strike plating solution contains zinc, the content thereof is the same as that of the above-described zinc-containing plating solution (hereinafter sometimes abbreviated as “main plating solution” in order to be distinguished from the strike plating solution). Good.
ストライクめっき液が銀を含有する場合、ストライクめっきは、陽極としてイリジウム電極又は白金電極を用い、めっき浴の温度を好ましくは２０〜３０℃、電流密度を好ましくは２〜５Ａ／ｄｍ２、電流を流す時間を好ましくは２０〜６０秒として、行うことができる。 When the strike plating solution contains silver, strike plating uses an iridium electrode or a platinum electrode as the anode, the temperature of the plating bath is preferably 20 to 30 ° C., the current density is preferably 2 to 5 A / dm 2 , and the current is supplied. The flowing time is preferably 20 to 60 seconds.
銀めっき層を形成するための電気めっき（以下、ストライクめっきと区別するために、「本めっき」と略記することがある）は、亜鉛を含有する本めっき液を用いる点以外は、従来と同様の方法で行えばよい。例えば、陽極として９９．９９％以上の銀電極を用い、めっき浴の温度を好ましくは２０〜４５℃、電流密度を好ましくは０．５〜５Ａ／ｄｍ２として行うことができる。電流を流す時間は、目的とする銀めっき層の厚さが得られるように、適宜調節すればよい。 Electroplating for forming a silver plating layer (hereinafter sometimes abbreviated as “main plating” to be distinguished from strike plating) is the same as in the prior art except that a main plating solution containing zinc is used. It is sufficient to do this. For example, a silver electrode of 99.99% or more is used as the anode, the temperature of the plating bath is preferably 20 to 45 ° C., and the current density is preferably 0.5 to 5 A / dm 2 . What is necessary is just to adjust suitably time to send an electric current so that the thickness of the target silver plating layer may be obtained.
本発明に係るめっき方法によれば、従来のめっき液に代えて、亜鉛を含有するめっき液を用いる点以外は、従来と同様の方法で銀めっき層を形成できる。そして、かかる銀めっき層は、後述するように、表面への銅の析出が抑制されたものである。また、上記説明からも明らかなように、本発明に係るめっき方法では、先に述べた「特開２００８−１６９４０８号公報」で開示されているような、銀の結晶粒径を大きくする操作が不要なので、形成された銀めっき層は、耐摩耗性にも優れたものである。したがって、良好な品質の銀めっき層を、工程数の増加や作業の煩雑化を伴うことなく、極めて簡便に形成できる。 According to the plating method of the present invention, the silver plating layer can be formed by the same method as in the prior art except that a plating solution containing zinc is used instead of the conventional plating solution. And as this silver plating layer mentions later, precipitation of copper to the surface is suppressed. Further, as apparent from the above description, in the plating method according to the present invention, an operation for increasing the crystal grain size of silver as disclosed in the above-mentioned “Japanese Patent Laid-Open No. 2008-169408” is performed. Since it is unnecessary, the formed silver plating layer has excellent wear resistance. Therefore, a silver plating layer of good quality can be formed very easily without increasing the number of steps and complication of work.
＜コネクタ及びその製造方法＞
本発明に係るコネクタは、銅又は銅合金製の母材上に、亜鉛を含有する銀めっき層を備えたことを特徴とする。
コネクタが備える銀めっき層は、例えば、上記のめっき方法で形成できる。すなわち、本発明に係るコネクタは、上記のめっき方法で銀めっき層を形成する工程を有する方法で製造でき、銀めっき層を形成する工程以外は、従来と同様の方法で行えばよい。
<Connector and manufacturing method thereof>
The connector according to the present invention includes a silver plating layer containing zinc on a base material made of copper or a copper alloy.
The silver plating layer with which a connector is provided can be formed with said plating method, for example. That is, the connector according to the present invention can be manufactured by a method having a step of forming a silver plating layer by the above plating method, and may be performed by a method similar to the conventional method except for the step of forming a silver plating layer.
銅又は銅合金製の母材は、コネクタに適した形状を有するものであり、公知の方法で成形でき、それ以外の点は、上記の銀のめっき方法で説明したものと同様である。 The base material made of copper or a copper alloy has a shape suitable for a connector and can be formed by a known method, and the other points are the same as those described in the above silver plating method.
前記銀めっき層の亜鉛の含有量は、めっき液（本めっき液）の亜鉛の含有量で調節でき、通常は、めっき液の亜鉛の含有量よりもやや低下すると考えられる。本発明においては、前記銀めっき層の亜鉛の含有量は、質量比で０．０５〜５ｐｐｍであることが好ましく、このような範囲とすることで、上記の銀のめっき方法で説明した、優れた効果を奏する。 The zinc content of the silver plating layer can be adjusted by the zinc content of the plating solution (main plating solution), and is usually considered to be slightly lower than the zinc content of the plating solution. In the present invention, the zinc content of the silver plating layer is preferably 0.05 to 5 ppm in terms of mass ratio, and by making such a range, the excellent silver plating method described above can be achieved. Has an effect.
本発明に係るコネクタは、銀めっき層が亜鉛を含有することにより、温度上昇によって銀めっき層の表面には、結晶粒界を介してこの亜鉛が優先的に析出し、母材を構成する銅の析出が抑制される。析出した亜鉛は酸化されて酸化亜鉛になるが、これは導電性物質であり、電気抵抗値が小さく、しかも透明であるため、電気的特性や外観異常（変色）が抑制され、銀めっき層は良好な品質を長期間維持できる。また、銀めっき層は、先に説明したように、耐摩耗性にも優れる。したがって、かかる銀めっき層を備えたコネクタは、良好な電気的接続能を長期間維持できる。 In the connector according to the present invention, when the silver plating layer contains zinc, the zinc preferentially precipitates on the surface of the silver plating layer through a grain boundary due to a temperature rise, and constitutes a base material. Is suppressed. The deposited zinc is oxidized to become zinc oxide, which is a conductive substance, has a small electrical resistance value, and is transparent, so electrical characteristics and appearance abnormality (discoloration) are suppressed, and the silver plating layer is Good quality can be maintained for a long time. Further, as described above, the silver plating layer is excellent in wear resistance. Therefore, a connector provided with such a silver plating layer can maintain a good electrical connection ability for a long period of time.
以下、具体的実施例により、本発明についてさらに詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
本実施例では、以下に示すめっき液を使用した。
（ストライクめっき液）
大和化成社製「ＧＰＥ−ＳＴ」：メタンスルフェン酸（ＣＨ３ＳＯＨ）７質量％、メタンスルフェン酸銀（ＣＨ３ＳＯＡｇ）２質量％、錯化剤２０質量％、残部水
（めっき液）
大和化成社製「ＧＰＥ−ＰＬ」：メタンスルフェン酸１０質量％、メタンスルフェン酸銀２０質量％、添加剤０．２質量％、残部水
In this example, the following plating solution was used.
(Strike plating solution)
“GPE-ST” manufactured by Daiwa Kasei Co., Ltd .: 7% by mass of methanesulfenic acid (CH 3 SOH), 2% by mass of silver methanesulfenate (CH 3 SOAg), 20% by mass of complexing agent, remaining water (plating solution)
“GPE-PL” manufactured by Daiwa Kasei Co., Ltd .: 10% by mass of methanesulfenic acid, 20% by mass of silver methanesulfenate, 0.2% by mass of additive, remaining water
＜銅製母材上への銀めっき層の形成＞
［実施例１］
以下に示す手順により、銅製の母材上に銀めっき層を形成した。母材としては大きさが１０ｍｍ×３０ｍｍ×１０ｍｍの無酸素銅ブロックを使用した。
まず、１０質量％水酸化ナトリウム（ＮａＯＨ）水溶液中に、陽極としてニッケル板を、陰極として前記銅ブロックを、それぞれ設置し、室温において、電流密度２．５Ａ／ｄｍ２で６０秒間直流電流を流すことで、銅ブロック表面を電解脱脂した。
次いで、電解脱脂後の銅ブロックを水洗した後、１０質量％メタンスルフェン酸水溶液を用いて、この水洗後の電解脱脂済み銅ブロックを室温で６０秒間酸洗した。
<Formation of silver plating layer on copper base material>
[Example 1]
A silver plating layer was formed on a copper base material by the following procedure. An oxygen-free copper block having a size of 10 mm × 30 mm × 10 mm was used as the base material.
First, a nickel plate as an anode and the copper block as a cathode are placed in a 10% by mass sodium hydroxide (NaOH) aqueous solution, and a direct current is passed at a current density of 2.5 A / dm 2 for 60 seconds at room temperature. Thus, the copper block surface was electrolytically degreased.
Next, after the electrolytic degreasing copper block was washed with water, the electrolytically degreased copper block after the water washing was pickled at room temperature for 60 seconds using a 10% by mass methanesulfenic acid aqueous solution.
次いで、酸洗後の銅ブロックを水洗した後、前記ストライクめっき液（「ＧＰＥ−ＳＴ」）中に、陽極として酸化イリジウム電極を、陰極としてこの酸洗及び水洗後の前記銅ブロックを、それぞれ設置し、室温において、電流密度２．５Ａ／ｄｍ２で３０秒間直流電流を流すことで、銅ブロック表面に対してストライクめっきを行った。形成したストライクめっき層（ストライク銀めっき層）の厚さは、０．０２〜０．０３μｍであった。 Next, after washing the pickled copper block with water, the strike plating solution ("GPE-ST") is provided with the iridium oxide electrode as the anode and the picked and washed copper block as the cathode, respectively. Then, strike plating was performed on the surface of the copper block by passing a direct current for 30 seconds at a current density of 2.5 A / dm 2 at room temperature. The thickness of the formed strike plating layer (strike silver plating layer) was 0.02 to 0.03 μm.
次いで、ストライクめっき済み銅ブロックを水洗した。また、亜鉛の濃度が１質量％となるように、金属亜鉛（Ｚｎ）を１０質量％メタンスルフェン酸水溶液に添加し、得られた亜鉛含有水溶液を、前記めっき液（「ＧＰＥ−ＰＬ」）に１質量％添加して、亜鉛の含有量が１ｐｐｍである亜鉛含有本めっき液を調製した。そして、この本めっき液中に、陽極として銀板を、陰極として水洗後の前記ストライクめっき済み銅ブロックを、それぞれ設置し、４０℃、電流密度４Ａ／ｄｍ２で４８０秒間直流電流を流すことで銀めっきを行い、銅ブロック上に銀めっき層を形成した。形成した銀めっき層は、ストライクめっき層も含めて厚さが２０μｍであった。 Next, the strike-plated copper block was washed with water. Further, metal zinc (Zn) is added to a 10% by mass methanesulfenic acid aqueous solution so that the concentration of zinc is 1% by mass, and the obtained zinc-containing aqueous solution is used as the plating solution (“GPE-PL”) The zinc-containing main plating solution having a zinc content of 1 ppm was prepared. In this plating solution, a silver plate is used as an anode, and the strike-plated copper block after washing as a cathode is installed, and a direct current is applied at 40 ° C. and a current density of 4 A / dm 2 for 480 seconds. Silver plating was performed to form a silver plating layer on the copper block. The formed silver plating layer including the strike plating layer had a thickness of 20 μm.
［比較例１］
金属亜鉛を使用せず、前記亜鉛含有本めっき液に代えて、前記めっき液（「ＧＰＥ−ＰＬ」）を使用したこと以外は、実施例１と同様に銅ブロック上に銀めっき層を形成した。形成したストライクめっき層の厚さは０．０２〜０．０３μｍであり、銀めっき層は、このストライクめっき層も含めて厚さが２０μｍであった。
[Comparative Example 1]
A silver plating layer was formed on the copper block in the same manner as in Example 1 except that metal zinc was not used and the plating solution (“GPE-PL”) was used instead of the zinc-containing main plating solution. . The formed strike plating layer had a thickness of 0.02 to 0.03 μm, and the silver plating layer including the strike plating layer had a thickness of 20 μm.
＜銀めっき層の評価＞
上記実施例及び比較例で形成した銀めっき層の表面を、オージェ電子分光法（Ａｕｇｅｒ Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ：ＡＥＳ）で分析した。元素の検出結果を表１に示す。
次いで、銀めっき層を形成した銅ブロックを、大気中、１６０℃で１６８時間加熱処理した後、再度、銀めっき層の表面をオージェ電子分光法で分析した。元素の検出結果を表１に示す。
また、実施例１の銅ブロックについて、銀めっき層表面の撮像データを図１に示す。図１（ａ）は加熱処理前、（ｂ）は加熱処理後のそれぞれの撮像データである。そして、比較例１の銅ブロックについて、銀めっき層表面の撮像データを図２に示す。図２（ａ）は加熱処理前、（ｂ）は加熱処理後のそれぞれの撮像データである。これら撮像データは、デジタルカメラで銀めっき層表面を直接撮影することにより取得した。
<Evaluation of silver plating layer>
The surface of the silver plating layer formed in the above Examples and Comparative Examples was analyzed by Auger Electron Spectroscopy (AES). The element detection results are shown in Table 1.
Next, the copper block on which the silver plating layer was formed was heat-treated at 160 ° C. for 168 hours in the atmosphere, and then the surface of the silver plating layer was analyzed again by Auger electron spectroscopy. The element detection results are shown in Table 1.
Moreover, about the copper block of Example 1, the imaging data of the silver plating layer surface are shown in FIG. FIG. 1A shows image data before heat treatment, and FIG. 1B shows image data after heat treatment. And about the copper block of the comparative example 1, the imaging data of the silver plating layer surface are shown in FIG. FIG. 2A shows the respective imaging data before the heat treatment, and FIG. 2B shows the respective image data after the heat treatment. These imaging data were acquired by directly photographing the surface of the silver plating layer with a digital camera.
上記結果から明らかなように、加熱処理前の銀めっき層の表面からは、実施例１及び比較例１のいずれにおいても、炭素（Ｃ）、酸素（Ｏ）、銀（Ａｇ）が検出されたのに対し、銅（Ｃｕ）は検出されなかった。検出された炭素及び酸素は、銀めっき層の表面に付着していた有機物の汚れに由来すると考えられる。 As is clear from the above results, carbon (C), oxygen (O), and silver (Ag) were detected from the surface of the silver plating layer before the heat treatment in both Example 1 and Comparative Example 1. On the other hand, copper (Cu) was not detected. It is considered that the detected carbon and oxygen are derived from organic contaminants attached to the surface of the silver plating layer.
一方、実施例１では、加熱処理後の銀めっき層の表面から、炭素、酸素、銀に加え、亜鉛が新たに検出されたものの、銅は検出されなかった。これは、図１からも明らかなように、加熱処理前後で、銀めっき層の表面において、色味の変化をはじめとする外観の変化が見られなかったことと整合していた。実施例１では、銀めっき層の表面が、加熱処理後も加熱処理前と同様の銀光沢を有していた。このように、実施例１では、加熱処理後の銀めっき層において、表面への銅の析出が顕著に抑制されていた。 On the other hand, in Example 1, in addition to carbon, oxygen, and silver, zinc was newly detected from the surface of the silver plating layer after the heat treatment, but copper was not detected. As is clear from FIG. 1, this was consistent with the fact that no change in appearance such as a change in color was observed on the surface of the silver plating layer before and after the heat treatment. In Example 1, the surface of the silver plating layer had the same silver luster after the heat treatment as before the heat treatment. Thus, in Example 1, precipitation of copper on the surface was remarkably suppressed in the silver plating layer after the heat treatment.
これに対して、比較例１では、加熱処理後の銀めっき層の表面から、炭素、酸素、銀に加え、銅が新たに検出された。これは、図２からも明らかなように、銀めっき層の表面が、加熱処理前には銀光沢を有していたのに対し、加熱処理後は大半で赤銅色を帯びており、色味の劇的な変化が見られたことと整合していた。このように、比較例１では、加熱処理後の銀めっき層において、表面への銅の析出が顕著であった。 In contrast, in Comparative Example 1, copper was newly detected from the surface of the silver plating layer after the heat treatment, in addition to carbon, oxygen, and silver. As is apparent from FIG. 2, the surface of the silver plating layer had a silver luster before the heat treatment, whereas the surface of the silver plating layer had a bronze color after the heat treatment. This was consistent with the dramatic changes that were seen. As described above, in Comparative Example 1, copper deposition on the surface was remarkable in the silver plating layer after the heat treatment.
本発明は、電気・電子部品に利用可能であり、特に、温度上昇を伴うコネクタへの適用に好適である。 The present invention can be used for electrical / electronic components, and is particularly suitable for application to a connector that is accompanied by a temperature rise.
Claims (4)
請求項２又は３に記載の銀のめっき方法で前記めっき層を形成する工程を有することを特徴とするコネクタの製造方法。 On a base material made of copper or copper alloy, a manufacturing method of a connector provided with a silver plating layer containing zinc,
A method for manufacturing a connector, comprising the step of forming the plating layer by the silver plating method according to claim 2.
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