JP3322211B2 - Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating film - Google Patents
Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating filmInfo
- Publication number
- JP3322211B2 JP3322211B2 JP14407598A JP14407598A JP3322211B2 JP 3322211 B2 JP3322211 B2 JP 3322211B2 JP 14407598 A JP14407598 A JP 14407598A JP 14407598 A JP14407598 A JP 14407598A JP 3322211 B2 JP3322211 B2 JP 3322211B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating
- composite
- fluorine
- polymer compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Chemically Coating (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は複合金めっき処理技
術に属し、例えば、電気接点表面のめっき処理等に特に
適した複合金めっき処理技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite gold plating technique, and more particularly, to a composite gold plating technique particularly suitable for plating a surface of an electric contact.
【０００２】[0002]
【従来の技術】コネクタ、プリント回路基板、機器スリ
ップリング、スイッチ、バッテリその他の電流輸送デバ
イスには、電子機器の接続若しくは断続を可能にする電
気接点が用いられている。これら電気接点の接触面に
は、安定した接続若しくは断続を維持するための各種表
面処理がなされており、通常、接触電気抵抗が低く且つ
耐摩耗性に優れた貴金属めっきが用いられる。そして、
特に信頼性が要求される電気接点には、前記貴金属めっ
きの中でも汚染により酸化被膜等が生成する心配の少な
い金めっきが用いられる。2. Description of the Related Art Electrical contacts for connecting or disconnecting electronic equipment are used in connectors, printed circuit boards, equipment slip rings, switches, batteries and other current transport devices. The contact surfaces of these electric contacts are subjected to various surface treatments for maintaining stable connection or intermittent connection. Usually, noble metal plating having low contact electric resistance and excellent wear resistance is used. And
Particularly, for the electrical contact requiring reliability, gold plating, which is less likely to form an oxide film due to contamination among the noble metal plating, is used.
【０００３】このように前記接触面を金めっき処理する
場合は、まず素地金属をニッケルめっき処理又はコバル
トめっき処理することで下地層を作成し、その上から金
めっき処理することが一般的である。これら下地層は、
金めっきの密着性を向上させるとともに該金めっきに孔
が生じた場合にも素地金属の腐食を防止し、更にはその
高い硬度により金めっきの耐摩耗性を向上させる。When the contact surface is subjected to gold plating as described above, it is general that a base metal is first subjected to nickel plating or cobalt plating to form an underlayer, and then gold plating is performed thereon. . These underlayers
In addition to improving the adhesion of the gold plating, corrosion of the base metal is prevented even when holes are formed in the gold plating, and the high hardness improves the wear resistance of the gold plating.
【０００４】また、前記金めっき処理としては、近年、
無電解金めっき法が多く用いられている。該無電解金め
っき法は電流を使用しないため素地表面上の電流密度分
布を考慮する必要がなく、めっき浴を管理するだけで均
一な厚みで均質な金めっき皮膜が得られるといった特徴
がある。In recent years, the gold plating process has been
Electroless gold plating is often used. Since the electroless gold plating method does not use a current, there is no need to consider the current density distribution on the surface of the substrate, and a characteristic is that a uniform gold plating film having a uniform thickness can be obtained only by controlling the plating bath.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、以上の
如き優れた金めっき処理を施した電気接点も、水分、そ
の他の汚れが付着する可能性が高い環境下で使用される
場合には容易に電気瞬断等の接触不良が生じていた。However, the electrical contacts which have been subjected to the excellent gold plating as described above can easily be used in an environment where there is a high possibility that moisture or other dirt is likely to adhere. Poor contact such as instantaneous interruption has occurred.
【０００６】本発明はかかる現況に鑑みてなされたもの
で、汚れが付着し難く付着しても容易に除去できるとと
もに金本来の低い接触電気抵抗及び優れた耐摩耗性を維
持できる電気接点の金めっき処理技術を提供せんとする
ものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and it is difficult to adhere dirt, and it is possible to easily remove dirt and to maintain the original low contact electric resistance and excellent wear resistance of gold. It is intended to provide plating processing technology.
【０００７】[0007]
【課題を解決するための手段】本発明者は前述の課題を
解決するにあたり鋭意検討を進めた結果、ニッケルめっ
きに対して既に実績のあるフッ素系高分子化合物を金と
複合させることで金めっき皮膜表面上に撥水性をもたせ
ることができ、更に、最終的に熱処理を施すことによっ
て１４０度の水の接触角と１．０Ω以下の接触電気抵抗
を同時に実現にできるとの予測に基づき、本発明を完成
するに至った。Means for Solving the Problems As a result of diligent studies for solving the above-mentioned problems, the present inventor has developed a gold plating by combining a fluorine-based polymer compound that has already been used for nickel plating with gold. Based on the prediction that water repellency can be imparted to the surface of the film, and that the contact angle of water and the contact electric resistance of 1.0 Ω or less can be simultaneously realized by finally performing the heat treatment. The invention has been completed.
【０００８】すなわち本発明は、金又はフッ素系高分子
化合物との付着性が向上する下地層を上面に設けた素材
にめっき処理を施して金並びにフッ素系高分子化合物を
共析させた複合金めっき皮膜であって、前記下地層を、
無電解めっき処理によりニッケル並びにフッ素系高分子
化合物が共析した複合ニッケルめっき層とし、２２０〜
３６０℃の熱処理を施したことを特徴とする複合金めっ
き皮膜を提供する。ここに、前記熱処理温度は使用する
フッ素系高分子化合物の溶融温度に密接に関連付けられ
たものであり、例えば該フッ素系高分子化合物としてＰ
ＴＦＥを用いた場合には３３０〜３６０℃が好ましい範
囲となる。[0008] That is, the present invention provides a composite gold in which gold and a fluoropolymer are co-deposited by subjecting a material provided with an underlayer on the upper surface thereof having improved adhesion to gold or a fluoropolymer to a plating treatment. A plating film, wherein the underlayer is
A composite nickel plating layer in which nickel and a fluorine-based polymer compound were codeposited by electroless plating,
Provided is a composite gold-plated film obtained by performing a heat treatment at 360 ° C. Here, the heat treatment temperature is closely related to the melting temperature of the fluorine-based polymer used, and for example, P is used as the fluorine-based polymer.
When TFE is used, a preferable range is 330 to 360 ° C.
【０００９】このような複合金めっき皮膜にあっては、
前記熱処理によりフッ素系高分子化合物が溶融し表面上
で網目状に結合することで、該表面上に十分な撥水性及
び低摩擦性をもたらし、水分等の汚れが付着することを
未然に防止するとともに万一汚れが付着したとしても容
易に剥離させる。また、前記下地層内のフッ素系高分子
化合物がその表面移行性によって複合金めっき皮膜に拡
散移行し、結果として該複合金めっき皮膜の撥水性を増
大させる。そして前記下地層のニッケルが前記複合金め
っき皮膜の密着性を向上させるとともに、熱処理によっ
て前記複合ニッケルめっき層の硬度が増大することで前
記複合金めっき皮膜の機械的強度が増大し耐久性が向上
する。In such a composite gold plating film,
The heat treatment causes the fluorine-based polymer compound to melt and bond in a network on the surface, thereby providing sufficient water repellency and low friction on the surface, and preventing the attachment of dirt such as moisture. Also, even if dirt adheres, it is easily peeled off. Further, the fluorine-based polymer compound in the underlayer diffuses and transfers to the composite gold plating film due to its surface migration property, and as a result, the water repellency of the composite gold plating film increases. The nickel of the underlayer improves the adhesion of the composite gold plating film, and the heat treatment increases the hardness of the composite nickel plating layer, thereby increasing the mechanical strength of the composite gold plating film and improving the durability. I do.
【００１０】また本発明は、金又はフッ素系高分子化合
物との付着性が向上する下地層を上面に設けた素材にめ
っき処理を施して金並びにフッ素系高分子化合物を共析
させた複合金めっき皮膜であって、前記下地層を置換金
めっき処理してなる第１金系めっき層と、該第１金系め
っき層表面をめっき処理して金とフッ素系高分子化合物
を共析させた第２金系めっき層とからなり、２２０〜３
６０℃の熱処理を施したことを特徴とする複合金めっき
皮膜をも提供する。ここに、前記金との付着性が向上す
る下地層とは通常金めっきの下地処理として用いられる
ニッケルストライク等の前処理以外に、例えば素材表面
をスパッタリングやエッチングしてなる表面層をも含む
ものである。[0010] The present invention also provides a composite gold obtained by subjecting a material provided with an underlayer on the upper surface thereof having improved adhesion to gold or a fluorine-based polymer compound to a plating treatment to co-deposit gold and a fluorine-based polymer compound. A plating film, wherein a first gold-based plating layer obtained by subjecting the base layer to displacement gold plating, and a surface of the first gold-based plating layer being subjected to plating to cause gold and a fluorine-based polymer compound to be eutectoid. 220-3
Also provided is a composite gold-plated film characterized by having been subjected to a heat treatment at 60 ° C. Here, the underlayer having improved adhesion to gold includes, in addition to a pretreatment such as nickel strike, which is usually used as a base treatment for gold plating, also includes a surface layer formed by, for example, sputtering or etching the material surface. .
【００１１】このような複合金めっき皮膜にあっては、
上記と同様、前記熱処理によりフッ素系高分子化合物が
溶融し表面上で網目状に結合することで、該表面上に十
分な撥水性及び低摩擦性をもたらし、水分等の汚れが付
着することを未然に防止するとともに万一汚れが付着し
たとしても容易に剥離させる。また、前記置換金めっき
処理とは、めっき浴中に浸漬したイオン化傾向の大きい
金属が溶出する際に遊離する電子によって浴中の金イオ
ンを還元析出させる成膜技術であって、金によって下地
層が完全に被覆された時点で反応が停止する。したがっ
て、前記置換金めっき処理のみでは厚い皮膜を得ること
ができないが、本発明の場合には該第１金系めっき層の
上に第２金系めっき層を形成しているので、複合金めっ
き皮膜全体の厚みが調整され、下地層の露出度を減少さ
せている。[0011] In such a composite gold plating film,
In the same manner as described above, the fluorine-based polymer compound is melted by the heat treatment and bonded in a network on the surface, thereby providing sufficient water repellency and low frictional properties on the surface to prevent dirt such as moisture from adhering. Prevent it from happening and make it easy to peel off any dirt. Further, the displacement gold plating treatment is a film formation technique in which gold ions in the bath are reduced and precipitated by electrons released when a metal having a high ionization tendency immersed in a plating bath is eluted, The reaction stops when is completely covered. Therefore, a thick film cannot be obtained only by the displacement gold plating treatment, but in the case of the present invention, since the second gold plating layer is formed on the first gold plating layer, the composite gold plating The thickness of the entire coating is adjusted to reduce the degree of exposure of the underlayer.
【００１２】ここで、前記下地層がニッケル並びにフッ
素系高分子化合物を共析してなる複合ニッケルめっき層
である場合には、該下地層を置換金めっき処理した前記
第１金系めっき層には該下地層のフッ素系高分子化合物
が析出することとなり、結果的に前記複合金めっき皮膜
の表面上に析出するフッ素系高分子化合物の量が増大し
て撥水性が向上する。Here, when the underlayer is a composite nickel plating layer obtained by eutectoidizing nickel and a fluorine-based polymer compound, the underlayer is replaced with the first gold-based plating layer by displacement gold plating. Means that the fluorine-based polymer compound of the underlayer is deposited, and as a result, the amount of the fluorine-based polymer compound deposited on the surface of the composite gold plating film is increased, and the water repellency is improved.
【００１３】以上の複合金めっき皮膜は、水の接触角に
して１００〜１４０度の撥水性を有していることが好ま
しい。ここに、水の接触角は、図３に示す如く、複合金
めっき皮膜２１の表面２１ｅにおける水滴２２の接線２
２ｆが前記表面２１ｅとの間でなす角αで定義され、該
接触角αが１００度より小さいと表面上に汚れ等が付着
しやすく付着した汚れは容易に落とすことができない。
この水の接触角が大きいほど撥水性に優れていることに
なるが、該撥水性は複合金めっき皮膜表面及びその近傍
に位置する絶縁性のフッ素系高分子化合物によるもので
あり、本発明においては１００〜１４０度が好ましい範
囲である。The above-described composite gold plating film preferably has a water repellency of 100 to 140 degrees as a contact angle of water. Here, the contact angle of water is, as shown in FIG. 3, the tangential line 2 of the water droplet 22 on the surface 21e of the composite gold plating film 21.
2f is defined by an angle α formed between the surface 21e and the surface 21e. If the contact angle α is smaller than 100 degrees, dirt or the like easily adheres to the surface and the adhered dirt cannot be easily removed.
The greater the contact angle of water, the better the water repellency, but the water repellency is due to the insulating fluorine-based polymer compound located on the surface of the composite gold plating film and in the vicinity thereof. Is a preferable range of 100 to 140 degrees.
【００１４】本発明は、これら複合金めっき皮膜を製造
する方法として、素材表面上の不純物を除去する洗浄工
程と、前記洗浄した素材に無電解めっき処理を施してニ
ッケル並びにフッ素系高分子化合物を共析させた複合ニ
ッケルめっき層からなる下地層を形成する下地処理工程
と、前記下地処理した素材にめっき処理を施して金並び
にフッ素系高分子化合物を共析させた複合金めっき皮膜
を形成する複合金めっき処理工程と、前記複合金めっき
皮膜を２２０〜３６０℃で熱処理する熱処理工程とから
なる製造方法を提供する。ここに、前記洗浄工程は、通
常の金めっき処理で行われる脱脂、酸洗い、水洗い等を
必要に応じて行うものであり、また、前記洗浄工程以外
の各工程間でも必要に応じて水洗い等簡単な洗浄を行
う。According to the present invention, as a method of producing these composite gold plating films, a washing step of removing impurities on the surface of the material, and electroless plating of the washed material to remove nickel and a fluorine-based polymer compound. An undercoat treatment step of forming an undercoat layer comprising an eutectoid composite nickel plating layer; and forming a composite gold plating film in which gold and a fluorine-based polymer compound are eutectoidally subjected to plating treatment. Provided is a manufacturing method comprising a composite gold plating treatment step and a heat treatment step of heat treating the composite gold plating film at 220 to 360 ° C. Here, the washing step is to perform degreasing, pickling, washing with water and the like performed in a normal gold plating process as needed, and also washing with water between steps other than the washing step as necessary. Perform a simple wash.
【００１５】このような製造方法にあっては、表面に十
分な撥水性及び低摩擦性を有する複合金めっき皮膜が実
現できる。下地処理工程により形成された前記下地層と
しての複合ニッケルめっき層には十分量のフッ素系高分
子化合物が共析しており、該フッ素系高分子化合物は前
記複合ニッケルめっき層上に形成される複合金めっき皮
膜内に拡散浸透してその表面に十分な撥水性を齎す。ま
た該複合ニッケルめっき層は前記熱処理により極度に硬
化するため、該複合ニッケルめっき層上に形成される複
合金めっき皮膜の機械的強度が増大する。そしてニッケ
ルは金との密着性に優れており、前記複合金めっき皮膜
の剥離を未然に防止する。According to such a manufacturing method, a composite gold plating film having sufficient water repellency and low friction on the surface can be realized. A sufficient amount of a fluorine-based polymer compound is eutectoid in the composite nickel plating layer as the base layer formed in the base treatment step, and the fluorine-based polymer compound is formed on the composite nickel plating layer. It diffuses and penetrates into the composite gold plating film to bring about sufficient water repellency on its surface. Further, since the composite nickel plating layer is extremely hardened by the heat treatment, the mechanical strength of the composite gold plating film formed on the composite nickel plating layer increases. Nickel has excellent adhesion to gold, and prevents peeling of the composite gold plating film.
【００１６】また、本発明は、素材表面上の不純物を除
去する洗浄工程と、前記洗浄した素材に表面処理を施し
て金又はフッ素系高分子化合物の付着性が向上する下地
層を形成する下地処理工程と、前記下地処理した素材に
置換金めっき処理を施して金を析出させた第１金系めっ
き層を形成する置換金めっき処理ステップと、前記第１
金系めっき層表面にめっき処理を施して金並びにフッ素
系高分子化合物を共析させた第２金系めっき層を形成す
る複合金めっき処理ステップとからなる複合金めっき処
理工程と、前記複合金めっき皮膜を２２０〜３６０℃で
熱処理する熱処理工程とからなる複合金めっき皮膜の製
造方法をも提供する。ここに、前記下地処理工程は前述
の複合金めっき皮膜の場合と同様、ニッケルストライク
等の通常行われる前処理以外に、例えば素材表面をスパ
ッタリングやエッチングすることも含まれる。The present invention also provides a cleaning step of removing impurities on the surface of the material, and a surface treatment of the cleaned material to form an underlayer that improves the adhesion of gold or a fluorine-based polymer compound. A treatment step, a displacement gold plating process step of subjecting the base-treated material to a displacement gold plating process to form a first gold-based plating layer in which gold is deposited, and
A composite gold plating process step of: performing a plating process on the surface of a gold-based plating layer to form a second gold-based plating layer in which gold and a fluorine-based polymer compound are co-deposited; There is also provided a method for producing a composite gold plating film, comprising a heat treatment step of heat-treating the plating film at 220 to 360 ° C. Here, similarly to the case of the above-described composite gold plating film, the undercoating step includes, for example, sputtering or etching the surface of the material, in addition to the usual pretreatment such as nickel strike.
【００１７】このような製造方法にあっては、上記と同
様、表面に十分な撥水性及び低摩擦性を有する複合金め
っき皮膜が実現できるとともに、このような複合金めっ
き処理工程により形成された複合金めっき皮膜は下地層
の金属を金に置き換えた前記第１金系めっき層が該下地
層と強固に密着しており、さらに該第１金系めっき層上
に形成される第２金系めっき層も金の上に成膜すること
となるため、全体として密着性が向上する。また前記第
１金系めっき層は下地層を完全に被覆した時点で成膜を
終了するので厚い層を得ることができないが、前記第２
金系めっき層により複合金めっき皮膜全体の厚みが調整
され、下地層の露出度を減少させている。According to such a production method, a composite gold plating film having sufficient water repellency and low friction on the surface can be realized as described above, and the composite gold plating film formed by such a composite gold plating process can be realized. In the composite gold plating film, the first gold-based plating layer in which the metal of the underlying layer is replaced with gold is firmly adhered to the underlying layer, and a second gold-based plating layer formed on the first gold-based plating layer Since the plating layer is also formed on gold, the adhesion is improved as a whole. In addition, since the first gold-based plating layer is completely formed when the underlying layer is completely covered, a thick layer cannot be obtained.
The thickness of the entire composite gold plating film is adjusted by the gold plating layer, thereby reducing the degree of exposure of the underlayer.
【００１８】ここで、前記下地層がニッケル並びにフッ
素系高分子化合物を共析してなる複合ニッケルめっき層
である場合には、該下地層を置換金めっき処理した前記
第１金系めっき層には該下地層のフッ素系高分子化合物
が析出することとなり、結果的に複合金めっき皮膜の表
面に析出するフッ素系高分子化合物の量が増大して撥水
性が向上する。Here, when the underlayer is a composite nickel plating layer obtained by eutectoidizing nickel and a fluorine-based polymer compound, the underlayer is replaced with the first gold-based plating layer subjected to displacement gold plating. Means that the fluorine-based polymer compound of the underlayer is deposited, and as a result, the amount of the fluorine-based polymer compound deposited on the surface of the composite gold plating film is increased, and the water repellency is improved.
【００１９】以上の製造方法によると、複合金めっき皮
膜の表面に水の接触角にして１００〜１４０度の撥水性
が得られる。According to the above manufacturing method, a water repellency of 100 to 140 degrees in terms of a contact angle of water can be obtained on the surface of the composite gold plating film.
【００２０】そして、以上にしてなる複合金めっき皮膜
を電気接点の表面皮膜として用いた場合には、該電気接
点の表面上には金本来の低い接触電気抵抗に加えて優れ
た撥水性、耐摩耗性及び耐食性が齎される。具体的に
は、水の接触角にして１００〜１４０度の撥水性が実現
され、汚れ等が付着しやすい環境下において微弱な電流
を扱う場合にも、電気瞬断を未然に防止し安定した通電
性を確保できる。When the composite gold plating film formed as described above is used as a surface film of an electric contact, the surface of the electric contact has excellent water repellency and resistance in addition to the low contact electric resistance inherent to gold. Abrasion and corrosion resistance are provided. Specifically, a water repellency of 100 to 140 degrees as a contact angle of water is realized, and even when a weak current is handled in an environment where dirt or the like easily adheres, electrical instantaneous interruption is prevented beforehand and stable. Conductivity can be ensured.
【００２１】[0021]
【発明の実施の形態】次に本発明の詳細を図示した実施
例に基づき説明する。図１に示す如く、複合金めっき皮
膜１は金又はフッ素系高分子化合物との付着性が向上す
る下地層３を上面に設けた電気接点２にめっき処理を施
して、金６ａ並びにフッ素系高分子化合物微粒子６ｃを
共析して形成され、本実施例における前記下地層３は、
ニッケルめっき液中にフッ素系高分子化合物微粒子を界
面活性剤で分散させためっき液を用いて電気接点２表面
に無電解めっき処理を施しニッケル４ｂとフッ素系高分
子化合物微粒子４ｃを共析させて形成した複合ニッケル
めっき層４であり、前記複合金めっき皮膜１は、該複合
ニッケルめっき層４を置換金めっき処理してなる第１金
系めっき層５と、金めっき液中にフッ素系高分子化合物
微粒子を界面活性剤で分散させためっき液を用いて前記
第１金系めっき層５表面に無電解めっき処理を施し金６
ａとフッ素系高分子化合物微粒子６ｃを共析させて形成
した第２金系めっき層６とから構成されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will now be described with reference to the illustrated embodiments. As shown in FIG. 1, a composite gold plating film 1 is subjected to a plating process on an electric contact 2 provided with an underlayer 3 on the upper surface thereof, which improves the adhesion to gold or a fluorine-based polymer compound, to form a gold layer 6a and a fluorine-based high layer. The underlayer 3 in the present embodiment is formed by eutecting molecular compound fine particles 6c.
Electroless plating is performed on the surface of the electrical contact 2 using a plating solution in which fluorine-based polymer compound fine particles are dispersed in a nickel plating solution with a surfactant, and nickel 4b and fluorine-based polymer compound fine particles 4c are co-deposited. The composite nickel plating layer 1 is formed, and the composite gold plating film 1 includes a first gold plating layer 5 obtained by subjecting the composite nickel plating layer 4 to displacement gold plating, and a fluoropolymer in a gold plating solution. Electroless plating is performed on the surface of the first gold-based plating layer 5 using a plating solution in which compound fine particles are dispersed with a surfactant, and gold 6
a and the second gold-based plating layer 6 formed by co-depositing the fluorine-based polymer compound fine particles 6c.
【００２２】前記フッ素系高分子化合物としては、炭化
水素基の水素部分を全て若しくはその一部をフッ素に置
換したパーフルオロアルキル基若しくはポリフルオロア
ルキル基を有する高分子化合物が好ましく、その中でも
ポリテトラフルオロエチレン、ポリクロロトリフルオロ
エチレン、ポリフッ化ビニリデン、テトラフルオロエチ
レン−ヘキサフルオロプロピレン共重合体の１種若しく
は２種以上を用いることが好ましい。特に、前記ポリテ
トラフルオロエチレン（以下、単に「ＰＴＦＥ」と称
す。）を用いることが入手しやすい点で好ましい。As the above-mentioned fluorine-based polymer compound, a polymer compound having a perfluoroalkyl group or a polyfluoroalkyl group in which all or a part of the hydrogen portion of a hydrocarbon group is substituted with fluorine is preferable. It is preferable to use one or more of fluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoropropylene copolymer. In particular, it is preferable to use the polytetrafluoroethylene (hereinafter, simply referred to as “PTFE”) because it is easily available.
【００２３】また、前記ニッケルめっき液は、還元剤と
しての次亜リン酸塩及び錯化剤を添加することで前記複
合ニッケルめっき層４中にリンを均一に析出するものが
好ましい。このようにリンを均一に析出することで複合
ニッケルめっき層４の耐食性が著しく向上する。It is preferable that the nickel plating solution uniformly precipitates phosphorus in the composite nickel plating layer 4 by adding a hypophosphite and a complexing agent as a reducing agent. By thus uniformly depositing phosphorus, the corrosion resistance of the composite nickel plating layer 4 is significantly improved.
【００２４】前記複合金めっき皮膜１の構成要素である
第１金系めっき層５は、置換金めっき処理により前記複
合ニッケルめっき層４表面及びその近傍のニッケル４ｂ
を金５ａに置換して形成されるため、その主成分は金５
ａ及びフッ素系高分子化合物微粒子５ｃとなり、金とフ
ッ素系高分子化合物の複合皮膜を実現している。The first gold-based plating layer 5, which is a component of the composite gold plating film 1, is subjected to displacement gold plating to form a nickel 4b on the surface of the composite nickel plating layer 4 and in the vicinity thereof.
Is replaced with gold 5a, and its main component is gold 5a.
a and the fluorine-based polymer compound fine particles 5c to realize a composite film of gold and a fluorine-based polymer compound.
【００２５】しかし、前記置換金めっき処理は、めっき
液中に浸漬した複合ニッケルめっき層４のニッケル４ｂ
が溶出する際に遊離する電子によって溶液中の金イオン
を還元析出するものであり、前記複合ニッケルめっき層
４表面が完全に金５ａで被覆された時点で反応が停止す
るため達成される層の厚みには限界がある。そこで、本
実施例においては前記第１金系めっき層５表面に更に無
電解金めっき処理を施した第２金系めっき層６が形成さ
れる。前記無電解金めっき処理において金めっき液中の
フッ素系高分子化合物微粒子を分散させる界面活性剤と
しては、カチオン系活性剤１Ｆ若しくはノニオン・カチ
オン混合系活性剤を使用することが好ましい。このよう
な活性剤は金めっき浴中でのフッ素系高分子化合物の凝
集を最小限に抑え、結果として前記第２金系めっき層６
に略３０体積％のフッ素系高分子化合物を共析させるこ
とが可能となる。However, the displacement gold plating is performed by the nickel 4b of the composite nickel plating layer 4 immersed in a plating solution.
Is used for reducing and precipitating gold ions in the solution by the electrons released when eluting. The reaction is stopped when the surface of the composite nickel plating layer 4 is completely covered with gold 5a. There is a limit to the thickness. Therefore, in this embodiment, a second gold-based plating layer 6 is further formed on the surface of the first gold-based plating layer 5 by electroless gold plating. As the surfactant for dispersing the fluorine-containing polymer compound fine particles in the gold plating solution in the electroless gold plating treatment, it is preferable to use a cationic surfactant 1F or a nonionic / cation mixed surfactant. Such an activator minimizes aggregation of the fluorine-based polymer compound in the gold plating bath, and as a result, the second gold-based plating layer 6
Approximately 30% by volume of a fluorine-based polymer compound can be co-deposited.
【００２６】以上にしてなる複合金めっき皮膜１を有す
る電気接点２は、２２０〜３６０℃の熱処理を施すこと
で該表面に水の接触角で１００〜１４０度の撥水性、
２．５〜３．０×１０-6Ω・ｃｍの固有抵抗及び０．０
５〜１．０Ωの接触電気抵抗を実現しており、表面に水
分その他の汚れが付着することを防止しつつ、金めっき
本来の低接触電気抵抗を達成し、電気瞬断を未然に防止
して安定した通電性を確保できる。前記接触電気抵抗と
は、接触針により前記複合金めっき皮膜に加える荷重を
２〜８ｇまで変化させた際の接触抵抗をミリオームメー
タで読み取ったものである。また、前記熱処理によって
複合金めっき皮膜１の下地層３である複合ニッケルめっ
き層４の機械的強度が著しく向上するため、該複合金め
っき皮膜１の耐摩耗性及び耐久性が向上する。The electrical contact 2 having the composite gold plating film 1 formed as described above is subjected to a heat treatment at 220 to 360 ° C. so that the surface has a water repellency of 100 to 140 degrees in terms of a contact angle of water.
2.5-3.0 × 10 −6 Ω · cm specific resistance and 0.0
Achieving a contact electric resistance of 5 to 1.0 Ω, preventing the adhesion of moisture and other dirt to the surface, achieving the original low contact electric resistance of gold plating, and preventing electrical momentary interruption. As a result, stable electric conductivity can be secured. The contact electric resistance is obtained by reading the contact resistance with a milliohm meter when the load applied to the composite gold plating film by a contact needle is changed from 2 to 8 g. Moreover, the mechanical strength of the composite nickel plating layer 4 which is the underlayer 3 of the composite gold plating film 1 is significantly improved by the heat treatment, so that the wear resistance and durability of the composite gold plating film 1 are improved.
【００２７】尚、本発明における下地層は複合ニッケル
めっき層４に限定されるものではなく、例えばニッケル
合金めっき層やコバルト合金めっき層も金との付着性が
向上する点で好ましい実施例である。また、前記第２金
系めっき層６に関しても、無電解めっき処理に限らず電
解金めっき処理を施してなるものも好ましい。The underlayer in the present invention is not limited to the composite nickel plating layer 4. For example, a nickel alloy plating layer or a cobalt alloy plating layer is a preferred embodiment in that the adhesion to gold is improved. . Also, the second gold-based plating layer 6 is not limited to the electroless plating process, but may preferably be one that has been subjected to an electrolytic gold plating process.
【００２８】次に、本発明の複合金めっき皮膜の製造方
法を図２に基づいて説明する。Next, a method for producing a composite gold plating film of the present invention will be described with reference to FIG.
【００２９】本実施例においては、先ず洗浄工程７にお
いて電気接点１２表面上の不純物１２ｄを除去する。具
体的には、浸漬脱脂剤を使用したアルカリ浸漬脱脂を
常温で５分間行ない、水酸化ナトリウムを加えた電解
脱脂剤を使用して陰極電解脱脂を常温で５分間行ない、
１０重量％の塩酸を使用した酸洗を常温で１分間行な
い、塩化ニッケルと塩酸を使用したニッケルストライ
クを常温で１分間行なう。尚、これら各処理を終了する
毎に水洗を行なう。In this embodiment, first, in the cleaning step 7, the impurities 12d on the surface of the electrical contact 12 are removed. Specifically, alkali immersion degreasing using an immersion degreasing agent is performed at room temperature for 5 minutes, and cathodic electrolytic degreasing is performed at room temperature for 5 minutes using an electrolytic degreasing agent to which sodium hydroxide is added,
Pickling using 10% by weight of hydrochloric acid is performed at room temperature for 1 minute, and nickel strike using nickel chloride and hydrochloric acid is performed at room temperature for 1 minute. Note that washing is performed each time these processes are completed.
【００３０】次に、ＰＴＦＥ微粒子を界面活性剤で分散
させた無電解Ｎｉ−Ｐめっき浴を用いて複合ニッケルめ
っき層１４を形成する下地処理工程８を行なう。めっき
処理時の浴条件は、浴温が８８〜９２℃、好ましくは
９０〜９１℃、浴比が０．５〜１．５ｄｍ2／Ｌ、好
ましくは略０．８ｄｍ2／Ｌ、ニッケル濃度が４．６
〜５．１ｇ／Ｌ、好ましくは４．９〜５．０ｇ／Ｌ、
ｐＨが４．８〜５．２、好ましくは４．９〜５．１であ
る。この下地処理工程８によって略２．０μｍ厚の複合
ニッケルめっき層１４が形成され、該複合ニッケルめっ
き層１４には略３２体積％のＰＴＦＥ微粒子１４ｃが含
有する。Next, a base treatment step 8 of forming a composite nickel plating layer 14 using an electroless Ni-P plating bath in which PTFE fine particles are dispersed with a surfactant is performed. The bath conditions during the plating treatment are as follows: a bath temperature of 88 to 92 ° C, preferably 90 to 91 ° C, a bath ratio of 0.5 to 1.5 dm 2 / L, preferably about 0.8 dm 2 / L, and a nickel concentration of 4.6
To 5.1 g / L, preferably 4.9 to 5.0 g / L,
pH is 4.8-5.2, preferably 4.9-5.1. The composite nickel plating layer 14 having a thickness of approximately 2.0 μm is formed by the undercoating process 8, and the composite nickel plating layer 14 contains approximately 32% by volume of PTFE fine particles 14c.
【００３１】次に、下地層である前記複合ニッケルめっ
き層１４表面に金並びにフッ素系高分子化合物を共析さ
せる複合金めっき処理工程９Ａ，９Ｂを行なう。該複合
金めっき処理工程は、第１金系めっき層１５を形成する
置換金めっき処理ステップ９Ａと、ＰＴＦＥ微粒子をカ
チオン系活性剤１Ｆで分散させた無電解金めっき浴を用
いて第２金系めっき層１６を形成する複合金めっき処理
ステップ９Ｂの２つのステップからなる。具体的には、
前記置換金めっき処理ステップ９Ａは、有機酸金を含有
した置換型金めっき浴を使用する。浴条件は、浴温が
略８０℃、浴比が略１．０ｄｍ2／Ｌ、金濃度が
２．０ｇ／Ｌ、ｐＨが６〜８である。この置換金めっ
き処理ステップ９Ａによって前記複合ニッケルめっき層
１４表面及びその近傍のニッケルが金に置換し、略０．
２５μｍ厚の第１金系めっき層１５が作成されると同時
に、前記複合ニッケルめっき層１４の厚みは減少する。
この第１金系めっき層１５には当然のことながら略３２
体積％のＰＴＦＥ微粒子１５ｃが含有している。Next, composite gold plating treatment steps 9A and 9B for eutecting gold and a fluorine-based polymer compound on the surface of the composite nickel plating layer 14 as an underlayer are performed. The composite gold plating process includes a displacement gold plating step 9A for forming the first gold-based plating layer 15 and a second gold-based plating bath using an electroless gold plating bath in which PTFE fine particles are dispersed with a cationic activator 1F. It comprises two steps of a composite gold plating step 9B for forming the plating layer 16. In particular,
In the displacement gold plating step 9A, a displacement gold plating bath containing organic acid gold is used. The bath conditions are a bath temperature of about 80 ° C., a bath ratio of about 1.0 dm 2 / L, a gold concentration of 2.0 g / L, and a pH of 6 to 8. By the replacement gold plating step 9A, the nickel on the surface of the composite nickel plating layer 14 and the vicinity thereof is replaced with gold, and the nickel is substantially removed.
At the same time that the first gold-based plating layer 15 having a thickness of 25 μm is formed, the thickness of the composite nickel plating layer 14 is reduced.
The first gold-based plating layer 15 naturally has approximately 32
It contains the PTFE fine particles 15c by volume.
【００３２】また、前記複合金めっき処理ステップ９Ｂ
は、ＰＴＦＥ微粒子を含有した自己触媒型ノンシアン無
電解金めっき浴を使用する。浴条件は、浴温が７０〜
９０℃、浴比が略１．０ｄｍ2／Ｌ、金濃度が１．
０〜３．０ｇ／Ｌ、ｐＨが６．５〜１０である。この
複合金めっき処理ステップ９Ｂによって略０．７５μｍ
の第２金系めっき層１６が作成される。The composite gold plating step 9B
Uses an autocatalytic non-cyanide electroless gold plating bath containing PTFE fine particles. The bath conditions are as follows:
90 ° C., bath ratio of about 1.0 dm 2 / L, gold concentration of 1.
0-3.0 g / L, pH is 6.5-10. Approximately 0.75 μm by this composite gold plating step 9B.
Is formed.
【００３３】そして、本発明の最大の特徴である熱処理
工程１０としては、電気接点１２、複合ニッケルめっき
層１４（下地層）及び複合金めっき皮膜１１を２２０〜
３６０℃でベーキングして複合金めっき皮膜１１中のＰ
ＴＦＥ微粒子を溶融、拡散、更には表面上で網目状に結
合させた後、冷却固化する。これにより、複合金めっき
皮膜１１の表面上に水の接触角で略１４０度の十分な撥
水性が生じる。本発明者はＳＥＭ写真により前記表面上
に直径約０．２μｍのＰＴＦＥ微粒子１６ｃが多数存在
していることを確認している。In the heat treatment step 10 which is the most important feature of the present invention, the electric contact 12, the composite nickel plating layer 14 (underlying layer) and the composite gold plating film 11
Baking at 360 ° C., P in composite gold plating film 11
The TFE fine particles are melted, diffused, further bonded in a network on the surface, and then cooled and solidified. As a result, a sufficient water repellency of approximately 140 degrees at a contact angle of water occurs on the surface of the composite gold plating film 11. The present inventor has confirmed from the SEM photograph that a large number of PTFE fine particles 16c having a diameter of about 0.2 μm exist on the surface.
【００３４】本発明の複合金めっき皮膜はフッ素系高分
子化合物を表面上に被覆するのではなく内部から表面に
移行析出させているため、該表面は金本来の輝きを維持
しており、特に汗等の汚れが付着し易い時計、眼鏡等の
装飾金めっきとして使用することも好ましい。In the composite gold plating film of the present invention, the fluoropolymer compound is not coated on the surface but migrates and precipitates from the inside to the surface, so that the surface maintains the original brightness of gold. It is also preferable to use it as decorative gold plating for watches, glasses and the like to which dirt such as sweat easily adheres.
【００３５】次に、複合金めっき皮膜の撥水性を実験に
基づいて説明する。Next, the water repellency of the composite gold plating film will be described based on experiments.
【００３６】（実験１） 実施例１として、Ｎｉ／Ｐ−ＰＴＦＥ複合めっき層から
なる下地層上に置換金めっき処理ステップ及びＰＴＦＥ
微粒子を分散させた電解金めっき浴を用いた複合金めっ
き処理ステップからなる複合金めっき処理を施した複合
金めっき皮膜、及び実施例２〜１０として、Ｎｉ／Ｐめ
っき層からなる下地層上に置換金めっき処理ステップ及
びＰＴＦＥ微粒子を分散させた無電解金めっき浴を用い
た複合金めっき処理ステップからなる複合金めっき処理
を施した複合金めっき皮膜を用いて、ＰＴＦＥ微粒子の
共析量を調べる実験を行なった。前記実施例１における
複合金めっき処理は、シアン化第一金カリウム、クエン
酸カリウム及びクエン酸を含有した厚付け純金めっき浴
を使用した。浴条件は、金板又はチタン上白金めっき板
を陽極として、浴温が６５〜７５℃、電流密度が
０．５〜２Ａ／ｄｍ2、好ましくは略１Ａ／ｄｍ2、金
濃度が略８．２ｇ／Ｌ、ｐＨが５．６〜６．２であ
る。前記ＰＴＦＥ微粒子の分散に用いる界面活性剤とし
ては、実施例１〜４にカチオン系活性剤Ｆを使用し、実
施例５〜７にカチオン系活性剤１Ｆを使用し、実施例８
〜１０にはノニオン・カチオン混合系活性剤を使用し
た。洗浄工程としては、浸漬脱脂剤３０ｇ／Ｌを用い
たアルカリ浸漬脱脂を常温で５分間、水酸化ナトリウ
ム５０ｇ／Ｌ及び電解脱脂剤５０ｇ／Ｌを用いた陰極電
解脱脂を常温で５分間、ニッケルストライクを常温で
１分間を行なった。熱処理工程における温度はいずれも
３５０℃とした。(Experiment 1) As Example 1, a displacement gold plating step and PTFE were performed on an underlayer composed of a Ni / P-PTFE composite plating layer.
On a composite gold plating film subjected to a composite gold plating treatment comprising a composite gold plating treatment step using an electrolytic gold plating bath in which fine particles are dispersed, and, as Examples 2 to 10, on a base layer composed of a Ni / P plating layer Investigating the eutectoid amount of PTFE fine particles using a composite gold plating film that has been subjected to a composite gold plating treatment comprising a displacement gold plating treatment step and a composite gold plating treatment step using an electroless gold plating bath in which PTFE fine particles are dispersed. An experiment was performed. In the composite gold plating treatment in Example 1, a thick pure gold plating bath containing potassium gold (I) cyanide, potassium citrate, and citric acid was used. The bath conditions are as follows. A bath temperature is 65 to 75 ° C., a current density is 0.5 to 2 A / dm 2 , preferably approximately 1 A / dm 2 , and a gold concentration is approximately 8. 2 g / L, pH 5.6-6.2. As a surfactant used for dispersion of the PTFE fine particles, a cationic surfactant F was used in Examples 1 to 4, and a cationic surfactant 1F was used in Examples 5 to 7.
For No. 10 to 10, nonionic / cation mixed activators were used. The washing process includes: alkaline immersion degreasing using 30 g / L of immersion degreaser at room temperature for 5 minutes; cathodic electrolytic degreasing using 50 g / L of sodium hydroxide and 50 g / L of electrolytic degreaser at room temperature for 5 minutes; For 1 minute at room temperature. The temperature in each of the heat treatment steps was 350 ° C.
【００３７】実験結果は、実施例１については膜厚が
１．０μｍ、水の接触角が１４０度となり、実施例２〜
１０については表１に示している。The experimental results show that Example 1 had a film thickness of 1.0 μm and a contact angle of water of 140 °.
10 is shown in Table 1.
【００３８】[0038]
【表１】 [Table 1]
【００３９】表１より、無電解金めっき浴に界面活性剤
としてカチオン系活性剤Ｆを使用した場合、ＰＴＦＥ分
散量が１ｇ／Ｌの実施例２においては１．１μｍ以上の
膜厚が得られたが、水の接触角は８５度であり、ＰＴＦ
Ｅ分散量が５ｇ／Ｌの実施例４においては水の接触角が
１２８度と十分な撥水性を示したが、膜厚は０．５４３
μｍであった。一方、カチオン系活性剤１Ｆを使用した
場合には、実施例５〜７の何れにおいても１．１μｍ以
上の膜厚と１３０度以上の水の接触角を同時に達成し
た。更に、ノニオン・カチオン混合系活性剤を使用した
場合には、実施例８〜１０の何れにおいても１．１μｍ
以上の十分な膜厚を達成しているが、ＰＴＦＥの分散量
が１５ｇ／Ｌ以上である実施例９及び１０においてはＰ
ＴＦＥ共析量が２０体積％より少なくなり、水の接触角
も１００度より小さくなった。As shown in Table 1, when the cationic surfactant F was used as a surfactant in the electroless gold plating bath, a film thickness of 1.1 μm or more was obtained in Example 2 in which the PTFE dispersion amount was 1 g / L. However, the contact angle of water is 85 degrees and PTF
In Example 4 in which the amount of dispersion of E was 5 g / L, the contact angle of water was 128 degrees, indicating sufficient water repellency, but the film thickness was 0.543.
μm. On the other hand, when the cationic activator 1F was used, in all of Examples 5 to 7, a film thickness of 1.1 μm or more and a contact angle of water of 130 ° or more were simultaneously achieved. Further, when a nonionic / cation mixed activator was used, in all of Examples 8 to 10, 1.1 μm
Although the above-mentioned sufficient film thickness is achieved, in Examples 9 and 10 in which the dispersion amount of PTFE is 15 g / L or more, P
The amount of TFE eutectoid was less than 20% by volume, and the contact angle of water was also less than 100 degrees.
【００４０】[0040]
【発明の効果】以上にしてなる本発明の複合金めっき皮
膜は、２２０〜３６０℃の熱処理によってフッ素系高分
子化合物が溶融し表面上で網目状に結合するため、該表
面上に十分な撥水性及び低摩擦性をもたらし、水分等の
汚れが付着することを未然に防止できるとともに万一汚
れが付着したとしても容易に剥離できる。According to the composite gold plating film of the present invention thus constituted, the fluorine-based polymer compound is melted by heat treatment at 220 to 360 ° C. and is bonded in a mesh on the surface. Water and low friction properties are provided, so that contamination such as moisture can be prevented from adhering, and even if dirt adheres, it can be easily peeled off.
【００４１】下地層が無電解めっき処理によりニッケル
並びにフッ素系高分子化合物が共析した複合ニッケルめ
っき層であると、前記下地層内のフッ素系高分子化合物
がその表面移行性によって複合金めっき皮膜に拡散移行
し、結果として該複合金めっき皮膜の撥水性を増大でき
る。そして、ニッケルにより前記複合金めっき皮膜の密
着性が向上するとともに、熱処理により前記複合ニッケ
ルめっき層の硬度が増大し、複合金めっき皮膜の機械的
強度が増大して耐久性を向上できる。When the underlayer is a composite nickel plating layer in which nickel and a fluorine-based polymer compound are codeposited by electroless plating, the fluorine-based polymer compound in the underlayer is transferred to the composite gold plating film due to its surface migration. , And as a result, the water repellency of the composite gold plating film can be increased. Then, the adhesion of the composite gold plating film is improved by nickel, and the hardness of the composite nickel plating layer is increased by the heat treatment, and the mechanical strength of the composite gold plating film is increased to improve the durability.
【００４２】複合金めっき皮膜が、下地層を置換金めっ
き処理してなる第１金系めき層と、該第１金系めっき層
表面をめっき処理して金とフッ素系高分子化合物を共析
させた第２金系めっき層とからなることで、複合金めっ
き皮膜の密着性が増し剥離を未然に防止できる。また、
ここで前記下地層がニッケル並びにフッ素系高分子化合
物を共析してなる複合ニッケルめっき層である場合に
は、該下地層を置換金めっき処理した前記第１金系めっ
き層には該下地層のフッ素系高分子化合物が析出するこ
ととなり、結果的に前記複合金めっき皮膜の表面上に析
出するフッ素系高分子化合物の量が増大して撥水性を向
上できる。The composite gold plating film has a first gold plating layer obtained by subjecting an underlayer to displacement gold plating, and the surface of the first gold plating layer is subjected to a plating treatment to deposit gold and a fluoropolymer compound. With the second gold-based plating layer, the adhesion of the composite gold plating film is increased, and peeling can be prevented. Also,
Here, when the underlayer is a composite nickel plating layer obtained by eutectoidizing nickel and a fluorine-based polymer compound, the undercoat layer is replaced with the first gold-based plating layer. Is deposited, and as a result, the amount of the fluorine-based polymer compound deposited on the surface of the composite gold plating film is increased, and the water repellency can be improved.
【００４３】そして、以上の複合金めっき皮膜は水の接
触角にして１００〜１４０度の撥水性が得られる。The above composite gold plating film has a water repellency of 100 to 140 degrees in terms of the contact angle of water.
【００４４】また、前記複合金めっき皮膜を電気接点の
表面皮膜として用いると、該電気接点は耐食性、密着性
及び耐摩耗性に優れるとともに、汚れ等が付着しやすい
環境下で微弱な電流を扱う場合にも電気瞬断を未然に防
止して安定した通電性を確保できる。When the composite gold plating film is used as a surface film of an electric contact, the electric contact is excellent in corrosion resistance, adhesion and abrasion resistance, and handles a weak current in an environment where dirt and the like are apt to adhere. Even in this case, stable electrical conduction can be secured by preventing electrical momentary interruption.
【図１】本発明に係る複合金めっき皮膜を示す簡略断面
説明図。FIG. 1 is a simplified sectional explanatory view showing a composite gold plating film according to the present invention.
【図２】本発明に係る複合金めっき皮膜の製造方法を示
す簡略説明図。FIG. 2 is a simplified explanatory view showing a method for producing a composite gold plating film according to the present invention.
【図３】水の接触角の定義を示す説明図。FIG. 3 is an explanatory view showing a definition of a contact angle of water.
１、１１ 複合金めっき皮膜 ２、１２ 電気接点 ３ 下地層 ４、１４ 複合ニッケルめっき層 ５、１５ 第１金系めっき層 ６、１６ 第２金系めっき層 ７ 洗浄工程 ８ 下地処理工程 ９Ａ 置換金めっき処理ステップ ９Ｂ 複合金めっき処理ステップ １０ 熱処理工程 ２１ 複合金めっき皮膜 ２２ 水滴 ４ｂ ニッケル ４ｃ、５ｃ、６ｃ フッ素系高分子微粒子 １４ｃ、１５ｃ、１６ｃ ＰＴＦＥ微粒子 １２ｄ 汚れ ２１ｅ 表面 ２２ｆ 接線 DESCRIPTION OF SYMBOLS 1, 11 Composite gold plating film 2, 12 Electrical contact 3 Underlayer 4, 14 Composite nickel plating layer 5, 15 First gold-based plating layer 6, 16 Second gold-based plating layer 7 Cleaning process 8 Base treatment process 9A Substituted gold Plating Step 9B Composite Gold Plating Step 10 Heat Treatment Step 21 Composite Gold Plating Film 22 Water Drop 4b Nickel 4c, 5c, 6c Fluoropolymer Fine Particles 14c, 15c, 16c PTFE Fine Particles 12d Soil 21e Surface 22f Tangential Line
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｒ 13/03 Ｈ０１Ｒ 13/03 Ａ (56)参考文献 特開 平６−108260（ＪＰ，Ａ) 特開 昭61−195570（ＪＰ，Ａ) 特開 平７−235461（ＪＰ，Ａ) 特開 平６−108296（ＪＰ，Ａ) 特開 平８−283955（ＪＰ，Ａ) 特開 平６−108295（ＪＰ，Ａ) 特開 平６−108294（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/52 C23C 18/44 C25D 15/02 H01H 1/00 H01R 13/03 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification symbol FI H01R 13/03 H01R 13/03 A (56) References JP-A-6-108260 (JP, A) JP-A-61-195570 ( JP, A) JP-A-7-235461 (JP, A) JP-A-6-108296 (JP, A) JP-A-8-283955 (JP, A) JP-A-6-108295 (JP, A) JP Hei 6-108294 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 18/52 C23C 18/44 C25D 15/02 H01H 1/00 H01R 13/03
Claims (9)
が向上する下地層を上面に設けた素材にめっき処理を施
して金並びにフッ素系高分子化合物を共析させた複合金
めっき皮膜であって、前記下地層を、無電解めっき処理
によりニッケル並びにフッ素系高分子化合物が共析した
複合ニッケルめっき層とし、２２０〜３６０℃の熱処理
を施したことを特徴とする複合金めっき皮膜。1. A composite gold-plated film obtained by subjecting a material provided with an underlayer on the upper surface thereof having improved adhesion to gold or a fluorine-based polymer compound to a plating treatment to co-deposit gold and a fluorine-based polymer compound. A composite gold plating film, wherein the underlayer is a composite nickel plating layer in which nickel and a fluorine-based polymer compound are codeposited by electroless plating, and is subjected to a heat treatment at 220 to 360 ° C.
が向上する下地層を上面に設けた素材にめっき処理を施
して金並びにフッ素系高分子化合物を共析させた複合金
めっき皮膜であって、前記下地層を置換金めっき処理し
てなる第１金系めっき層と、該第１金系めっき層表面を
めっき処理して金とフッ素系高分子化合物を共析させた
第２金系めっき層とからなり、２２０〜３６０℃の熱処
理を施したことを特徴とする複合金めっき皮膜。2. A composite gold plating film obtained by subjecting a material provided with an underlayer on the upper surface thereof having improved adhesion to gold or a fluorine-based polymer compound to a plating treatment and co-depositing gold and a fluorine-based polymer compound. A first gold-based plating layer obtained by subjecting the underlayer to displacement gold plating; and a second gold-based metal obtained by plating the surface of the first gold-based plating layer to co-deposit gold and a fluorine-based polymer compound. A composite gold plating film comprising a base plating layer and subjected to a heat treatment at 220 to 360 ° C.
が向上する下地層を上面に設けた素材にめっき処理を施
して金並びにフッ素系高分子化合物を共析させた複合金
めっき皮膜であって、前記下地層を、無電解めっき処理
によりニッケル並びにフッ素系高分子化合物が共析した
複合ニッケルめっき層とし、前記下地層を置換金めっき
処理してなる第１金系めっき層と、該第１金系めっき層
表面をめっき処理して金とフッ素系高分子化合物を共析
させた第２金系めっき層とからなり、２２０〜３６０℃
の熱処理を施したことを特徴とする複合金めっき皮膜。3. A composite gold plating film obtained by subjecting a material provided with an underlayer on the upper surface thereof having improved adhesion to gold or a fluorine-based polymer compound to a plating treatment and eutecting gold and a fluorine-based polymer compound. A first gold-based plating layer obtained by subjecting the base layer to a composite nickel plating layer in which nickel and a fluorine-based polymer compound are codeposited by electroless plating, and the base layer being subjected to displacement gold plating; A second gold-based plating layer in which the surface of the first gold-based plating layer is plated and gold and a fluorine-based polymer compound are co-deposited;
A composite gold plating film characterized by having been subjected to a heat treatment.
あることを特徴とする請求項１〜３の何れか１項に記載
の複合金めっき皮膜。4. The composite gold plating film according to claim 1, wherein a contact angle of water on the surface is 100 to 140 degrees.
と、 前記洗浄した素材に無電解めっき処理を施してニッケル
並びにフッ素系高分子化合物を共析させた複合ニッケル
めっき層からなる下地層を形成する下地処理工程と、 前記下地処理した素材にめっき処理を施して金並びにフ
ッ素系高分子化合物を共析させた複合金めっき皮膜を形
成する複合金めっき処理工程と、 前記複合金めっき皮膜を２２０〜３６０℃で熱処理する
熱処理工程と、 からなる複合金めっき皮膜の製造方法。5. A cleaning step of removing impurities on the surface of the material, and an underlying layer comprising a composite nickel plating layer obtained by subjecting the washed material to electroless plating to cause eutectoid nickel and a fluorine-based polymer compound. An undercoat treatment step to form; a plating treatment on the undertreated material to form a composite gold plating film in which gold and a fluoropolymer compound are eutectoid; and A heat treatment step of performing a heat treatment at 220 to 360 ° C .;
と、 前記洗浄した素材に表面処理を施して金又はフッ素系高
分子化合物の付着性が向上する下地層を形成する下地処
理工程と、 前記下地処理した素材に置換金めっき処理を施して金を
析出させた第１金系めっき層を形成する置換金めっき処
理ステップと、前記第１金系めっき層表面にめっき処理
を施して金並びにフッ素系高分子化合物を共析させた第
２金系めっき層を形成する複合金めっき処理ステップと
からなる複合金めっき処理工程と、 前記複合金めっき皮膜を２２０〜３６０℃で熱処理する
熱処理工程と、 からなる複合金めっき皮膜の製造方法。6. A cleaning step of removing impurities on the surface of the material, and a surface treatment step of performing a surface treatment on the cleaned material to form an underlayer that improves the adhesion of gold or a fluorine-based polymer compound. A replacement gold plating step of forming a first gold-based plating layer by depositing gold by subjecting the base-treated material to replacement gold plating, and performing a plating process on the surface of the first gold-based plating layer to obtain gold and A composite gold plating treatment step comprising a composite gold plating treatment step of forming a second gold plating layer in which a fluorine-based polymer compound is codeposited; and a heat treatment step of subjecting the composite gold plating film to a heat treatment at 220 to 360 ° C. A method for producing a composite gold plating film comprising:
と、 前記洗浄した素材に無電解めっき処理を施してニッケル
並びにフッ素系高分子化合物を共析させた複合ニッケル
めっき層からなる下地層を形成する下地処理工程と、 前記下地処理した素材に置換金めっき処理を施して金を
析出させた第１金系めっき層を形成する置換金めっき処
理ステップと、前記第１金系めっき層表面にめっき処理
を施して金並びにフッ素系高分子化合物を共析させた第
２金系めっき層を形成する複合金めっき処理ステップと
からなる複合金めっき処理工程と、 前記複合金めっき皮膜を２２０〜３６０℃で熱処理する
熱処理工程と、 からなる複合金めっき皮膜の製造方法。7. A cleaning step of removing impurities on the surface of the material, and an underlayer comprising a composite nickel plating layer obtained by subjecting the washed material to electroless plating to cause eutectoid nickel and a fluorine-based polymer compound. Forming a first gold-based plating layer in which gold is deposited by subjecting the base-treated material to replacement gold plating; and forming a first gold-based plating layer on the surface of the first gold-based plating layer. A composite gold plating process step of performing a plating process to form a second gold-based plating layer in which gold and a fluorine-based polymer compound are codeposited, and forming the composite gold plating film in a range of 220 to 360. A heat treatment step of heat treatment at a temperature of ℃, and a method of manufacturing a composite gold plating film comprising:
なる請求項５〜７の何れか１項に記載の複合金めっき皮
膜の製造方法。8. The method for producing a composite gold plating film according to claim 5, wherein the contact angle of water on the surface is 100 to 140 degrees.
めっき皮膜を表面に有する電気接点。9. An electric contact having a composite gold plating film according to claim 1 on the surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14407598A JP3322211B2 (en) | 1998-05-26 | 1998-05-26 | Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14407598A JP3322211B2 (en) | 1998-05-26 | 1998-05-26 | Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001385853A Division JP2002241954A (en) | 2001-12-19 | 2001-12-19 | Composite gold plating film, production method therefor and electric contact having the composite gold plating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11335859A JPH11335859A (en) | 1999-12-07 |
| JP3322211B2 true JP3322211B2 (en) | 2002-09-09 |
Family
ID=15353703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14407598A Expired - Lifetime JP3322211B2 (en) | 1998-05-26 | 1998-05-26 | Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3322211B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4627848B2 (en) * | 2000-08-23 | 2011-02-09 | 荏原ユージライト株式会社 | Plating method and plated product |
| JP2003305743A (en) * | 2002-04-12 | 2003-10-28 | Sumitomo Rubber Ind Ltd | Mold for golf ball, manufacturing method therefor, and golf ball manufacturing method |
| JP4391440B2 (en) | 2005-04-05 | 2009-12-24 | ジョンソン・エンド・ジョンソン株式会社 | Bipolar tweezers |
| JP4599565B2 (en) * | 2006-10-23 | 2010-12-15 | 国立大学法人信州大学 | Electrolytic plating method and electrolytic plating solution |
| DE102011083469A1 (en) * | 2011-09-27 | 2013-03-28 | Sb Limotive Company Ltd. | Battery module comprising a plurality of battery cells and motor vehicle |
-
1998
- 1998-05-26 JP JP14407598A patent/JP3322211B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11335859A (en) | 1999-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5461988B2 (en) | Metal laminated polyimide substrate and manufacturing method thereof | |
| CN1318647C (en) | Metal-plated material and method for preparation, and electric and electronic parts using same | |
| JP4372835B1 (en) | Conductive member and manufacturing method thereof | |
| JP4319247B1 (en) | Conductive member and manufacturing method thereof | |
| TWI225322B (en) | Terminal having ruthenium layer and a connector with the terminal | |
| JP5570285B2 (en) | Catalyst aqueous solution used in electroless plating method, method for preparing the catalyst aqueous solution, electroless plating method using the catalyst aqueous solution, and metal object to be plated provided with a metal film formed using the electroless plating method | |
| JPH01306574A (en) | Sn or sn alloy clad material | |
| Antler | The application of palladium in electronic connectors | |
| JP3322211B2 (en) | Composite gold plating film, method for producing the same, and electrical contact having the composite gold plating film | |
| JP5325734B2 (en) | Conductive member and manufacturing method thereof | |
| JP2006028635A (en) | Method for manufacturing surface treated copper foil for microfabrication circuit substrate | |
| JP2670348B2 (en) | Sn or Sn alloy coating material | |
| JP5621570B2 (en) | Conductive material with Sn plating and manufacturing method thereof | |
| JP2002241954A (en) | Composite gold plating film, production method therefor and electric contact having the composite gold plating film | |
| JP3442764B1 (en) | Connector terminals and connectors | |
| JP2010090400A (en) | Electroconductive material and method for manufacturing the same | |
| JP2006104504A (en) | Electroless plating pre-treatment method and surface metallizing method for polyimide resin, and flexible printed circuit board and manufacturing method for the same | |
| JP3454232B2 (en) | Composite plating film | |
| JPH04318997A (en) | Copper foil for printed circuit and manufacture thereof | |
| JP4294363B2 (en) | Two-layer flexible copper-clad laminate and method for producing the two-layer flexible copper-clad laminate | |
| JP7302364B2 (en) | Connector terminal materials and connector terminals | |
| JP3909035B2 (en) | Plating pretreatment liquid and plating pretreatment method | |
| JP3709142B2 (en) | Copper foil for printed wiring board and method for producing the same | |
| CA2327801A1 (en) | Copper on polymer component having improved adhesion | |
| JPH07243085A (en) | Production of metal-clad polyimide substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080628 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100628 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110628 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110628 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120628 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120628 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130628 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130628 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140628 Year of fee payment: 12 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |