JP2004060050A - Electroless composite plating bath and electroless composite plating method - Google Patents
Electroless composite plating bath and electroless composite plating method Download PDFInfo
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- JP2004060050A JP2004060050A JP2003150764A JP2003150764A JP2004060050A JP 2004060050 A JP2004060050 A JP 2004060050A JP 2003150764 A JP2003150764 A JP 2003150764A JP 2003150764 A JP2003150764 A JP 2003150764A JP 2004060050 A JP2004060050 A JP 2004060050A
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- composite plating
- plating bath
- electroless composite
- electroless
- ion
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、無電解複合めっき浴及び無電解複合めっき方法に関する。さらに詳しくは、無電解めっき（化学めっき）により、金属めっき皮膜中にフッ素樹脂等の微粒子等を複合共析させることが可能な無電解複合めっき浴及び無電解複合めっき方法に関する。
【０００２】
【従来の技術】
従来より、無電解金属めっき浴にフッ素樹脂、ナイロン、ポリエチレン、黒鉛、フッ化黒鉛、二硫化モリブデン、窒化ホウ素等の微粒子等を分散した複合めっき浴が知られている。そして、この複合めっき浴に被めっき体を浸漬させて無電解複合めっきを行うことにより、被めっき体の表面に化学的に金属皮膜を析出させるとともに、この金属皮膜中に微粒子や短繊維を共析させて、金属マトリックス中に上記微粒子等を分散させた複合めっき皮膜を得る手段が知られている。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）の微粒子を無電解ニッケル−リン（Ｎｉ−Ｐ）めっき液中に分散した複合めっき浴を用いることで、Ｎｉ−Ｐめっき皮膜中にＰＴＦＥの微粒子が共析したＮｉ−Ｐ／ＰＴＦＥ複合めっき皮膜が得られる。このＮｉ−Ｐ／ＰＴＦＥ複合めっき皮膜は、ニッケル金属の諸物性と共に、ＰＴＦＥの持つ低摩擦性や非粘着性を併せ持つめっき皮膜となる。
【０００３】
ところで、ＰＴＦＥに代表されるフッ素樹脂、黒鉛、フッ化黒鉛等の微粒子は、撥水性及び疎水性が強く、そのままでは、金属めっき浴中に分散させることができないため、該微粒子等を均一にめっき皮膜中に共析させることは非常に困難であった。そこで、従来より、界面活性剤を分散助剤として用いて微粒子等をめっき浴に分散させる手段が用いられている。この分散助剤である界面活性剤としては、カチオン性界面活性剤、使用されるめっき浴のｐＨにおいてカチオン性を示す両性界面活性剤及び非イオン性界面活性剤等の界面活性剤が使用されており、例えば、特許文献１、特許文献２、特許文献３、特許文献４、特許文献５、特許文献６、特許文献７等には、これら界面活性剤が使用された複合めっき浴が開示されている。
【０００４】
この界面活性剤の中では、カチオン性界面活性剤、中でも分子内にＣ−Ｆ結合を持つフッ素含有カチオン性界面活性剤が適していると考えられており（特許文献６等参照）、当該界面活性剤が主として使用されていた。しかし、これらの多くは次の式（２）及びその誘導体
【化２】
Ｒｆ−ＳＯ２−Ｙ …… （２）
（Ｒｆはフッ素置換アルキル基またはアルケニル基、Ｙはアミド基、水酸基またはハロゲンをそれぞれ示す）
で表される構造を持つ塩または誘導体であるが、近年、Ｒｆ−ＳＯ２−Ｙが人体や環境に対して有害であるという問題があり、かかる界面活性剤の使用及び製造は禁止されつつある。
【０００５】
一方、フッ素を含有しない界面活性剤についても、特許文献８、特許文献９、特許文献１０等に開示があり、また、非特許文献１にも、当該界面活性剤についての研究報告がされている。しかし、これらのフッ素を含有しないカチオン性界面活性剤を使用した複合めっき浴は、フッ素含有カチオン性界面活性剤（フルオロ炭素型）と比較して、めっき皮膜の部分的な未析出（カジリ）や部分的な黒色化が起こり易いため、めっき皮膜が不均一となり、皮膜性能を著しく低下させるという問題があった。更に、これらの複合めっき浴に使用されるカチオン性界面活性剤は、腐食性が高く、かつ、生分解性も良くないという環境上の問題も有していた。
【０００６】
また、複合めっき浴に使用する両性界面活性剤としては、アルキルベタイン両性界面活性剤やエチレンオキサイドを有するアルキルベタイン両性界面活性剤が知られているが、これらを含むめっき浴も、無電解ニッケル浴の使用温度においてはＰＴＦＥ等の微粒子の凝集が起こり易いため、良好なめっき皮膜を得ることができない場合があった。また、凝集の発生を抑制するためには、かかる両性界面活性剤の過剰の添加や、さらにノニオン系界面活性剤、カチオン系界面活性剤の併用を必要としていた。この結果、該微粒子の分散性が向上する一方で、界面活性剤の過剰な添加によるめっき皮膜の不均一や析出不良が発生し、皮膜性能を著しく低下させるという問題が起こっていた。更に、このめっき浴を連続使用した場合にあっては、該微粒子と界面活性剤の蓄積や、さらにはめっき浴の老化によって、ピット等の皮膜の不均一性が発生するという問題もあった。
【０００７】
このように、無電解複合めっきでは、めっき浴中での微粒子の良好な分散状態を維持するために、界面活性剤を分散助剤として添加することが必要であるが、一方では、添加された界面活性剤が、無めっき部や部分的な黒色部を生じさせる等、外観と機能性を低下させてしまうという問題を有していた。また、界面活性剤を添加した無電解複合めっき浴を用い、連続して無電解複合めっきを実施した場合にあっては、めっき浴の連続使用によるＰＴＦＥ等の微粒子と界面活性剤の蓄積やめっき浴の老化によって、微粒子のめっき皮膜への異常吸着やめっき皮膜中に均一に分散しない等の問題が起こり、皮膜性能を著しく低下させてしまっていた。さらに、めっき浴の使用にあたっては、添加する界面活性剤の有害性や環境性も考慮しなければならないという問題もあった。
【０００８】
【特許文献１】
特開昭４９−２６１３３号公報
【特許文献２】
特開昭４９−５８３２号公報
【特許文献３】
特開昭５２−５６０２６号公報
【特許文献４】
特開昭５２−５６１４７号公報
【特許文献５】
特開昭５２−１３０４３４号公報
【特許文献６】
特開昭５４−１５９３４３号公報
【特許文献７】
特開２０００−２０４４８２号公報
【特許文献８】
特許第３１３９２３９号公報
【特許文献９】
特開昭６２−５０２５５２号公報
【特許文献１０】
特開２０００−２０４４８２号公報
【非特許文献１】
ＴＲＡＮＳＡＣＴＩＯＮＳ ｏｆ ＴＨＥ ＩＮＳＴＩＴＵＴＥ ｏｆ ＭＥＴＡＬ ＦＩＮＩＳＨＩＮＧ １９９４， ７２（２）， 第５５〜５７頁
【０００９】
【発明が解決しようとする課題】
従って、フッ素樹脂等の撥水性ないし疎水性微粒子を添加しても、これら微粒子の凝集が起こらずめっき浴中に良好に分散し、めっきによりこれら微粒子が均一に分散した複合めっき皮膜が得られ、更には、連続使用が可能で、人体に対する有害性が低く、環境に対する負荷の低い無電解複合めっき浴の提供が求められていた。
【００１０】
【課題を解決するための手段】
本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、特定の構造を有する化合物を無電解複合めっき浴中に分散剤として含有させることにより、かかる課題を解決できることを見出し、本発明を完成した。
【００１１】
すなわち本発明は、金属イオン、水不溶性材料、還元剤及び界面活性剤を含有する複合めっき浴において、界面活性剤として下記式（１）で示される化合物を含有せしめたことを特徴とする無電解複合めっき浴を提供するものである。
【００１２】
【化３】
【００１３】
また、本発明は、上記の無電解複合めっき浴中に被めっき体を浸漬させることによりめっきすることを特徴とする無電解複合めっき方法を提供するものである。
【００１４】
【発明の実施の形態】
本明細書において、「無電解複合めっき浴」とは、水不溶性材料をめっき浴中に分散させためっき浴のことをいい、また、「無電解複合めっき」とは、無電解めっきにより、該材料を金属とともに被めっき体の表面に共析せしめ、金属の持つ物性と水不溶性材料の持つ物性を同時に奏させることが可能なめっき皮膜を形成することをいう。
【００１５】
本発明の無電解複合めっき浴は、上記したように、特定の界面活性剤、水不溶性物質、還元剤及び金属イオンを基本めっき組成として含有するものであるが、かかる界面活性剤は、下記式（１）で表されるものである。
【００１６】
【化４】
【００１７】
式（１）で表される化合物は、無電解複合めっき浴中の酸性度が酸性から弱酸性の条件下において、実質的にカチオン性を示すという特徴をもつ両性界面活性剤である。
【００１８】
この化合物（１）は、構造中に脂肪酸アミドアルキル基を有するものである。この脂肪酸部分（Ｒ１ＣＯ−）の例としては、ヤシ油脂肪酸、パーム核油脂肪酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等から導かれたものが挙げられる。本発明の無電解複合めっき浴においては、当該脂肪酸部分は、ラウリン酸よりもアルキル鎖の長いミスチリン酸やパルミチン酸を含むヤシ油脂肪酸やパーム核油脂肪酸から導いたものであることが、めっき浴中における安定性やめっき浴使用時の熱安定性等という点で好ましい。
【００１９】
また、化合物（１）の基Ｒ２ 及びＲ３ における炭素数１〜６のアルキル基の例としては、メチル、エチル、プロピル、ブチル、ペンチル、へキシル等が、炭素数１〜６のヒドロキシアルキル基の例としては、ヒドロキシメチル、ヒドロキシエチル、ヒドロキシプロピル、ヒドロキシブチル、ヒドロキシペンチル、ヒドロキシへキシル等が、炭素数１〜６のアルコキシル基の例としては、メトキシル、エトキシル、プロポキシル、ブトキシル、ペンチルオキシル、へキシルオキシル等がそれぞれ挙げられる。このうち、化合物が容易に入手できる等の理由から、低級アルキル基、特にメチル基であることが好ましい。
【００２０】
上記の化合物（１）の例としては、例えば、ニッサンアノンＢＤＣ−ＳＦ、ニッサンアノンＢＤＦ−ＳＦ（いずれも日本油脂（株）製）、アデカアンホートＰＢ−３０Ｌ（旭電化工業（株）製）、エナジコールＣ−３０Ｂ、エナジコールＬ−３０Ｂ（いずれもライオン（株）製）等として市販されている脂肪酸アミドプロピルジメチル酢酸ベタインを挙げることができ、これらは容易に入手することができる。
【００２１】
本発明の無電解複合めっき浴において、界面活性剤としての化合物（１）の使用濃度は、めっき浴の組成において、１０００ｍｇ／Ｌ以下であることが好ましく、２０〜６００ｍｇ／Ｌであることがより好ましい。
【００２２】
本発明の無電解複合めっき浴においては、化合物（１）のほか、本発明の効果を損なわない範囲で他の種類の界面活性剤、例えば、カチオン性界面活性剤や、めっき浴の水素イオン条件下で実質的にカチオン性を示す両性界面活性剤を添加することができる。このような界面活性剤としては、具体的には、ラウリルトリメチルアンモニウムクロライド（例えば、コータミン２４：花王（株）製）やジメチルアルキルベタイン（例えば、ニッサンアノンＢＦ：日本油脂（株）製）等を挙げることができ、その一種又は二種を併用することができる。
【００２３】
更に、本発明の無電解複合めっき浴には、本発明の効果を損なわない範囲で、ポリオキシエチレンアルキルエーテル系非イオン界面活性剤（例えば、エマルゲン１０９Ｐ：花王（株）製）等の非イオン性界面活性剤や、アルキルアリルポリエーテルスルホン酸ナトリウム（例えば、ＴＲＩＴＯＮ Ｘ−２００：ＵＮＩＯＮ ＣＡＲＢＩＤＥ社製）等のアニオン性界面活性剤のそれぞれ一種又は二種とも併用することができる。
【００２４】
本発明の無電解複合めっき浴は、上記の化合物（１）を界面活性剤として含有せしめる以外は、通常の無電解複合めっき浴に配合する成分、すなわち、金属イオン、水不溶性材料および還元剤を常法に従って溶解ないし分散させることにより調製することができる。
【００２５】
本発明の無電解複合めっき浴で使用することができる金属イオンとしては、ニッケルイオン、コバルトイオン、銅イオン、金イオン、鉄イオン、パラジウムイオン、スズイオン、白金イオン、ロジウムイオン等が挙げられ、これらを有する硫酸塩や塩化物等、水溶性の金属塩の形態で用いることができる。無電解複合めっき浴中のこれらの金属イオンの濃度は、通常使用されうる濃度で用いればよいが、めっき浴の組成において０．１〜１００ｇ／Ｌが好ましく、１．０〜５０ｇ／Ｌがより好ましい。
【００２６】
また、本発明の無電解複合めっき浴に用いられる水不溶性材料としては、一般に複合めっきで使用されるものであれば特に制限はなく、無電解複合めっき浴の種類や該めっきにより得られるめっき皮膜の用途等に応じて適宜選定することができるが、本発明は、撥水性ないし疎水性の水不溶性材料、例えば、ＰＴＦＥ（ポリテトラフルオロエチレン）、ＰＦＡ（テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体）、フッ化ピッチ等のフッ素樹脂やフッ素化合物、ナイロン、ポリエチレン、黒鉛、フッ化黒鉛、二硫化モリブデン、窒化ホウ素、炭化ケイ素等に対して使用することにより、特に優れた効果を得ることができる。なお、水不溶性材料は、一種類を単独で使用してもよく、又は二種以上を組み合わせて使用しても良い。
【００２７】
なお、上記ＰＴＦＥの例としては、ルブリカントＬ−１７０Ｊ、Ｌ−１７２Ｊ（ともに旭硝子（株）製）、ルブロンＬ−２、Ｌ−５（ともにダイキン工業（株）製）、ゾニールＭＰ−１１００、ＭＰ−１２００、ＴＬＰ１０Ｆ−１（ともにデュポン社製）等の商品名で市販されている微粒子を挙げることができ、これらが使用できる。
【００２８】
これらの水不溶性材料は、微粒子状の形態であることが好ましく、無電解複合めっき浴中で適度に分散し、まためっき皮膜において金属マトリックス中に共析しうる程度の粒子径のものであれば特に制約はないが、一般には、１００μｍ以下、好ましくは０．１〜１０μｍの大きさのものを使用すればよい。更に、長さが１００μｍ以下、好ましくは、５〜１００μｍの短繊維状の形態であってもよい。
【００２９】
本発明の無電解複合めっき浴における、上記水不溶性材料の含有量は、めっき浴の組成において、５００ｇ／Ｌ以下であることが好ましく、１〜１０ｇ／Ｌであることがより好ましい。
【００３０】
更に、本発明の無電解複合めっき浴で使用することができる還元剤としては、次亜リン酸ナトリウム、ジメチルアミンボラン、ヒドラジン等の次亜リン酸塩や、アミンボラン類またはヒドラジン塩等が挙げられる。無電解複合めっき浴中のこれらの還元剤の濃度は、使用する還元剤の種類や析出させる金属により相違するが、めっき浴の組成中１〜１００ｇ／Ｌが好ましく、２〜３０ｇ／Ｌがより好ましい。
【００３１】
本発明の無電解複合めっき浴の調製にあたっては、上記の必須成分の他、本発明の効果を妨げない範囲で、錯化剤を添加することが好ましい。
【００３２】
使用できる錯化剤としては、リンゴ酸、乳酸、コハク酸、プロピオン酸、マロン酸、アジピン酸、クエン酸、酢酸、グリシン、グルコン酸、グリコール酸等の有機酸やこれらの水溶性塩の一種を単独で、又は二種以上を組み合わせて用いることができる。無電解複合めっき浴中のこれらの錯化剤の濃度は、めっき浴の組成において１〜１００ｇ／Ｌが好ましく、１０〜４０ｇ／Ｌがより好ましい。
【００３３】
また、本発明の無電解複合めっき浴には、本発明の効果を損なわない範囲で、必要に応じて、無電解めっき浴に通常使用される安定剤、反応促進剤、付きまわり改善効果を目的とした成分等を適宜添加することができる。
【００３４】
この安定剤としては、例えば、鉛イオンを含む化合物（例えば硝酸鉛）等を使用することができ、また、反応促進剤としても、硫黄化合物、アルコール類、カルボン酸等を使用することができる。さらに、付きまわり改善効果を有する各種の酸化剤等も添加することができる。
【００３５】
かくして調製される本発明の無電解複合めっき浴を使用して無電解複合めっきを実施するには、通常の無電解めっきで用いられる手段に従えばよく、例えば、水不溶性材料が均一に分散された無電解複合めっき浴に対して、被めっき体を浸漬させることにより、被めっき体の表面に対して、水不溶性材料が均一に分散された複合めっき皮膜を形成させることができる。
【００３６】
また、無電解複合めっきを実施する場合には、無電解複合めっき浴の酸性度をｐＨ１〜７とすることが好ましく、３〜５とすることがより好ましい。無電解複合めっき浴のｐＨをこの範囲にすることにより、効率的な金属イオンの還元反応が進行し、複合めっき皮膜の析出速度が良好となるという効果が得られる。めっき浴のｐＨ調整のためには、塩酸、硫酸、スルファミン酸、硝酸等の酸や水酸化ナトリウム、水酸化アンモニウム溶液等のアルカリをｐＨ調整剤として適宜添加することができる。
【００３７】
さらに、無電解複合めっきの実施にあたっては、無電解複合めっき浴の浴温を４０〜９５℃とすればよく、８５〜９０℃とすることが好ましい。
【００３８】
更にまた、必要により無電解複合めっき浴を攪拌したり、被めっき体を揺動等させることにより、無電解複合めっきを効率よく行うことができ、また、めっき皮膜の外観及び性能をより優れたものとすることができる。これらの無電解複合めっき浴の攪拌手段や被めっき体の揺動手段等については、通常用いられる手段を適宜行えばよい。
【００３９】
以上説明した無電解複合めっき方法において、好ましい態様の一つとしては、例えば、下記組成のＰＦＴＥを含有するＮｉ−Ｐ無電解複合めっきを使用しためっき方法が挙げられる。この方法では、被めっき体として、鋼板（例えば、ブライト鋼板（ＳＰＣＣ−ＳＢ））を用意し、これを液温を８５から９０℃、ｐＨを４から５とした下記組成の無電解複合めっき浴に３０から６０分程度浸漬させて無電解複合めっきを行うことにより、被めっき体の表面にＮｉ／ＰＴＦＥの複合めっき皮膜が形成される。この方法によれば、５ないし２０μｍの複合めっき皮膜が、被めっき体の表面部に形成されることになり、また、その際のＰＴＦＥの析出量は、数ないし約３０容量％程度となる。
【００４０】
（ 無電解複合めっき浴組成 ）
硫酸ニッケル６水和物 ２５〜３０ｇ／Ｌ
脂肪酸アミドプロピルジメチル酢酸ベタイン ２０〜６００ｍｇ／Ｌ
（界面活性剤）
ＰＴＦＥ（水不溶性材料：平均粒子径約０．３μｍ） １〜１０ｇ／Ｌ
リンゴ酸（錯化剤） １０〜５０ｇ／Ｌ
乳酸（錯化剤） １０〜５０ｇ／Ｌ
コハク酸（錯化剤） １０〜５０ｇ／Ｌ
次亜りん酸ナトリウム１水和物（還元剤） ２０〜５０ｇ／Ｌ
【００４１】
なお、本発明の無電解複合めっき浴を用いて無電解複合めっきを行うにあたっては、めっきの進行により、金属イオンが還元剤によって金属に還元され、また、水不溶性材料が共析するにつれても、めっき浴中の金属イオン濃度、還元剤濃度及び水不溶性材料濃度が低下し、またｐＨも低下することになる。従って、連続的に又は適当な時間ごとに、無電解複合めっき浴中に水溶性金属塩、還元剤、水不溶性材料及びｐＨ調整剤等を補給して、それらの濃度をもとの濃度に戻すことが好ましい。
【００４２】
この場合においては、金属イオン濃度の低下量、還元剤の低下量、水不溶性材料の低下量及びｐＨの変化量と、無電解複合めっき皮膜の析出量は互いにほぼ比例関係にあると考えられる。また、析出速度は初期のめっき浴濃度が同じであれば、同一めっき条件においてほぼ一定であると考えられるので、初期のめっき浴濃度が同じで同一のめっき条件の場合は、一定間隔ごとに一定量の水溶性金属塩、還元剤、水不溶性材料及びｐＨ調整剤等を別途補給することにより、無電解複合めっき浴の濃度をほぼもとに戻すことができる。
【００４３】
また、連続的又は適当な時間ごとに、無電解複合めっき浴中の金属イオン濃度やｐＨを測定し、その測定結果に応じて、めっき浴中に水溶性金属塩、還元剤、水不溶性材料及びｐＨ調整剤等を補給するようにしてもよい。更に、めっき浴中の水不溶性材料濃度や錯化剤、その他の成分の濃度を分析して、濃度調整を行ってもよい。
【００４４】
本発明の無電解複合めっき浴は、かかる水溶性金属塩等の補給を行うことにより、少なくても２ターン、一般には、３〜４ターン程度まで良好に無電解複合めっきを続けることができ、連続的に無電解複合めっき浴を使用しても、表面が平滑で均一性に優れためっき皮膜を与えることができるものである。また、析出速度のや共析量の低下も少なく、めっき皮膜の性能も安定したものである。ここで、「１ターン」とは、本発明の無電解複合めっき浴中の初期金属イオン濃度に相当する量の金属析出が生じた時点におけるめっき浴の老化度を示す指標であり、すなわち、例えば、無電解複合めっき浴中の初期金属イオン濃度が５ｇ／Ｌであるとした場合、５ｇ／Ｌの金属析出が生じた時点を１ターンとするものである。よって、この場合には、２５ｇ／Ｌの金属析出が生じた時点が５ターンとなる。
【００４５】
【実施例】
次に実施例を挙げ、本発明をさらに詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。
【００４６】
実 施 例 １
めっき浴使用温度におけるＰＴＦＥの分散性：
下記のめっき浴組成において、表１に示される８種類の界面活性剤（参考品１〜８）をそれぞれ添加して、本発明品１〜３及び比較品１〜５の無電解複合めっき浴を調製した。
【００４７】
（ 無電解複合めっき浴組成 ）
成 分 含有量
１． 硫酸ニッケル６水和物 ２５ｇ／Ｌ
２． 次亜りん酸ナトリウム１水和物 ３０ｇ／Ｌ
３． リンゴ酸 ２５ｇ／Ｌ
４． 乳酸 ２０ｇ／Ｌ
５． コハク酸 ５ｇ／Ｌ
６． 硼砂 ５ｇ／Ｌ
７． 硝酸鉛（安定剤） 適量
８． 表１の界面活性剤 １５０ｍｇ／Ｌ
９． ＰＴＦＥ＊１ ４．０ｇ／Ｌ
（平均一次粒子径：０．３μｍ）
＊１： ＭＰ１１００（Ｄｕｐｏｎｔ社製）
【００４８】
（ 使用した界面活性剤 ）
【表１】
これらの８種類の無電解複合めっき浴について、硫酸あるいは水酸化アンモニウム溶液を用いてめっき浴のｐＨを５．０に調整した。次いで、このめっき浴の温度を９０℃（めっき浴の使用温度に相当する）まで上昇させた場合における、水不溶性材料であるＰＴＦＥ（ポリテトラフルオロエチレン）の分散状態を比較・評価した。結果を表２に示す。
【００５０】
（ 結 果 ）
【表２】
表２の結果より、本発明品１〜３及び比較品１、２の無電解複合めっき浴中のＰＴＦＥは、めっき浴の温度を９０℃まで加温した場合、良好な分散状態を示すことが示された。一方、比較品３〜５の無電解複合めっき浴では、めっき浴を９０℃まで昇温中または昇温後まもなく、ＰＴＦＥの凝集が発生することが確認された。
【００５２】
実 施 例 ２
無電解複合めっき試験（１）：
サンプルとして鉄板（サイズ：５０ｍｍ×１００ｍｍ×０．８ｍｍ）を用い、このサンプルを被めっき体として、実施例１で調製した本発明品１〜３及び比較品１〜５の無電解複合めっき浴に浸漬させ、下記のめっき条件にて無電解複合めっきを行った。
【００５３】
（ めっき条件 ）
めっき浴のｐＨ（注） ： ４．９
めっき浴の温度 ： ９０℃
めっき時間 ： ６０分
攪拌条件 ： 緩やかな機械攪拌
（注）硫酸あるいは水酸化アンモニウム溶液を用いてｐＨを調製した。
【００５４】
この無電解複合めっき後のサンプルに対して、めっき皮膜の外観及びＰＴＦＥの共析量を、それぞれ下記の評価基準により判定した。また、めっき皮膜の析出速度についても、常法を用いて測定した。結果を表３に示す。
【００５５】
（ 評価基準：皮膜外観 ）
皮膜の外観を目視にて観察した。
判 定 内 容
◎ ： 暗灰色で均一
○ ： 暗灰色でやや均一
△ ： 暗灰色で不均一
× ： ニッケル光沢色で不均一
【００５６】
（ ＰＴＦＥの共析量 ）
判 定 共 析 量
◎ ： ２５容量％以上
○ ： ２０容量％以上２５容量％未満
△ ： １５容量％以上２０容量％未満
× ： １５容量％未満
【００５７】
（ 結 果 ）
【表３】
表３の結果からわかるように、本発明品１〜３の無電解複合めっき浴を使用しためっきサンプルの皮膜外観及びＰＴＦＥの共析量は良好であり、また、複合めっき皮膜の析出速度も優れたものであった。一方、比較品１の無電解複合めっき浴を使用したものについては、皮膜外観及び共析量は本発明品とほぼ同等であったが、析出速度が若干劣り、また、比較品２の無電解複合めっき浴を使用したものは、共析量や析出速度について本発明品レベルには達しなかった。更に、比較品３〜５の無電解複合めっき浴を使用したものについては、皮膜外観が良好ではなく、また、十分なＰＴＦＥの共析量を得ることができなかった。
【００５９】
実 施 例 ３
無電解複合めっき試験（２）（めっき浴の連続使用試験）：
表２及び表３の結果から、無電解複合めっき浴建浴時（０ターン）において、ＰＴＦＥがめっき浴中で良好な分散性を示し、かつ、得られためっき皮膜の特性も優れていた本発明品１〜３及び比較品１、２の無電解複合めっき浴について、連続使用試験を行った。連続使用試験は、めっき浴を連続使用（１、２、３ターン時）して無電解複合めっきを行ない、各ターンごとのめっき皮膜の皮膜外観、ＰＴＦＥ共析量及び析出速度を、下記の評価基準を用いて判定することにより行った。結果を表４に示す。
【００６０】
（ 皮膜外観 ）
判 定 内 容
◎ ： 梨地調の良好な均一外観である
○ ： 梨地調が僅かに粗い均一外観
△ ： 僅かにピットが生じている
× ： 皮膜全面にＰＴＦＥ粒子の異常吸着が起こっている
×× ： 皮膜全面に著しいピットが生じている
【００６１】
（ ＰＴＦＥ共析量 ）
判 定 共 析 量
◎ ： ２５容量％以上
○ ： ２０容量％以上２５容量％未満
△ ： １５容量％以上２０容量％未満
× ： １５容量％未満
【００６２】
（ 析出速度 ）
各ターン時の析出速度を、実施例２と同様の方法でそれぞれ測定し、この測定値を、下記評価基準を用いて、実施例２で得られた結果に対する各ターン時の析出速度の低下割合を評価した。
判 定 低下割合
○ ： ２０％未満
△ ： ２０％以上４０％未満
× ： ４０％以上
【００６３】
（ 結 果 ）
【表４】
表４の結果からわかるように、本発明品１及び２の無電解複合めっき浴は、めっき浴を連続的に使用しても、外観が良好なめっき皮膜を与えることができ、無電解複合めっきにおける析出速度や共析量の低下も極めて少ないものであった。また、本発明品３の無電解複合めっき浴は、従来品（フッ素含有カチオン界面活性剤含有）である比較品１の無電解複合めっき浴とほぼ同レベルであった。一方、比較品２の無電解複合めっき浴は、上記めっき浴を使用したものと比べてめっき皮膜外観に劣るものであり、めっき浴の連続使用には適さないものであった。
【００６５】
【発明の効果】
本発明の無電解複合めっき浴は、めっき浴中に水不溶性材料の微粒子が均一に分散し、表面が平滑で均一性に優れためっき皮膜を与えることができるものであり、また、めっきにおける該微粒子の共析量や析出速度等のめっき性能も優れたものである。
【００６６】
さらに、本発明の無電解複合めっき浴は、無電解複合めっきを連続的に使用しても、上記性能の低下が少なく、更にまた、使用される界面活性剤は、易生分解性を示し、刺激性も少ないため、人体や環境も配慮したものであり、安全面、環境面でも優れたものである。
【００６７】
従って、本発明の無電解複合めっき浴及び無電解複合めっき方法は、シャフト、軸受け、メタルマスク、スライドレール、ベアリング、ボルト、ナット、金型、アイロンベース、アイロン台、鋸、鋏、カッターや包丁等の工業用品または家庭用品、天板等の調理器具用部材、キッチンバッグ等の台所用品並びに台所部材、水道蛇口などの水洗金具全般、水道やガスのコック部品全般等の無電解複合めっきとして、有利に使用することができるものである。
以 上[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electroless composite plating bath and an electroless composite plating method. More specifically, the present invention relates to an electroless composite plating bath and an electroless composite plating method capable of co-depositing fine particles such as fluororesin in a metal plating film by electroless plating (chemical plating).
[0002]
[Prior art]
2. Description of the Related Art Composite plating baths in which fine particles such as fluororesin, nylon, polyethylene, graphite, graphite fluoride, molybdenum disulfide, boron nitride, and the like are dispersed in an electroless metal plating bath have been known. Then, the object to be plated is immersed in the composite plating bath to perform electroless composite plating, whereby a metal film is chemically deposited on the surface of the object to be plated, and fine particles and short fibers are simultaneously contained in the metal film. Means for obtaining a composite plating film in which the fine particles and the like are dispersed in a metal matrix by precipitation are known. For example, by using a composite plating bath in which fine particles of polytetrafluoroethylene (PTFE) are dispersed in an electroless nickel-phosphorus (Ni-P) plating solution, fine particles of PTFE are codeposited in the Ni-P plating film. A Ni-P / PTFE composite plating film is obtained. This Ni-P / PTFE composite plating film becomes a plating film having both the low friction property and the non-adhesive property of PTFE, together with various physical properties of nickel metal.
[0003]
By the way, fine particles such as fluororesin, graphite, and fluorinated graphite represented by PTFE have strong water repellency and hydrophobicity, and cannot be dispersed in a metal plating bath as it is, so that the fine particles are uniformly plated. It was very difficult to cause eutectoid in the film. Therefore, conventionally, means for dispersing fine particles and the like in a plating bath using a surfactant as a dispersing aid has been used. As the surfactant which is the dispersing aid, cationic surfactants, surfactants such as amphoteric surfactants and nonionic surfactants which show cationicity at the pH of the plating bath used, and the like are used. For example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, and Patent Literature 7 disclose composite plating baths using these surfactants. I have.
[0004]
Among these surfactants, cationic surfactants, in particular, fluorine-containing cationic surfactants having a C—F bond in the molecule are considered to be suitable (see Patent Document 6 and the like). Activators were mainly used. However, many of them are of the following formula (2) and its derivatives
Embedded image
Rf-SO 2 -Y ... (2)
(Rf is a fluorine-substituted alkyl group or alkenyl group, Y is an amide group, a hydroxyl group or a halogen, respectively)
Is a salt or a derivative having a structure represented by the following formula. 2 -Y is harmful to humans and the environment, and the use and production of such surfactants are being banned.
[0005]
On the other hand, surfactants containing no fluorine are also disclosed in Patent Literature 8, Patent Literature 9, Patent Literature 10, and the like, and Non-Patent Literature 1 also reports research on the surfactant. . However, compared to the fluorine-containing cationic surfactant (fluorocarbon type), the composite plating bath using the fluorine-free cationic surfactant has a partial non-precipitation (galling) of the plating film and Since partial blackening is likely to occur, there is a problem that the plating film becomes non-uniform and the film performance is remarkably reduced. Furthermore, the cationic surfactants used in these composite plating baths also have environmental problems such as high corrosiveness and poor biodegradability.
[0006]
Also, as the amphoteric surfactant used in the composite plating bath, an alkyl betaine amphoteric surfactant and an alkyl betaine amphoteric surfactant having ethylene oxide are known, and a plating bath containing these is also an electroless nickel bath. At the use temperature, fine particles such as PTFE are likely to aggregate, so that a good plating film may not be obtained in some cases. In addition, in order to suppress the occurrence of aggregation, it has been necessary to add an excessive amount of the amphoteric surfactant or to use a combination of a nonionic surfactant and a cationic surfactant. As a result, while the dispersibility of the fine particles is improved, non-uniformity or poor deposition of the plating film due to excessive addition of the surfactant occurs, and there has been a problem that the film performance is remarkably reduced. Furthermore, when this plating bath is used continuously, there is a problem that the accumulation of the fine particles and the surfactant and the aging of the plating bath cause non-uniformity of the film such as pits.
[0007]
As described above, in the electroless composite plating, it is necessary to add a surfactant as a dispersing aid in order to maintain a good dispersion state of the fine particles in the plating bath. There has been a problem that the surfactant deteriorates the appearance and functionality, such as producing a non-plated portion or a partial black portion. In the case where the electroless composite plating is continuously performed using an electroless composite plating bath to which a surfactant is added, accumulation of fine particles such as PTFE and a surfactant due to continuous use of the plating bath or plating is performed. Due to the aging of the bath, problems such as abnormal adsorption of fine particles to the plating film and non-uniform dispersion in the plating film have occurred, and the film performance has been significantly reduced. Furthermore, when using the plating bath, there is a problem that the harmfulness and environmental properties of the added surfactant must be considered.
[0008]
[Patent Document 1]
JP-A-49-26133
[Patent Document 2]
JP-A-49-5832
[Patent Document 3]
JP-A-52-56026
[Patent Document 4]
JP-A-52-56147
[Patent Document 5]
JP-A-52-130434
[Patent Document 6]
JP-A-54-159343
[Patent Document 7]
JP 2000-204482 A
[Patent Document 8]
Japanese Patent No. 3139239
[Patent Document 9]
JP-A-62-502552
[Patent Document 10]
JP 2000-204482 A
[Non-patent document 1]
TRANSACTIONS of THE INSTITUTE of METAL FINISHING 1994, 72 (2), pp. 55-57.
[0009]
[Problems to be solved by the invention]
Therefore, even if water-repellent or hydrophobic fine particles such as a fluororesin are added, these fine particles do not agglomerate and are well dispersed in a plating bath, and a composite plating film in which these fine particles are uniformly dispersed by plating is obtained. Further, there has been a demand for an electroless composite plating bath which can be used continuously, has low harm to the human body, and has a low environmental load.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that by incorporating a compound having a specific structure as a dispersant in an electroless composite plating bath, such problems can be solved. Completed the invention.
[0011]
That is, the present invention provides a composite plating bath containing a metal ion, a water-insoluble material, a reducing agent and a surfactant, wherein a compound represented by the following formula (1) is contained as a surfactant. A composite plating bath is provided.
[0012]
Embedded image
[0013]
The present invention also provides an electroless composite plating method characterized in that plating is performed by immersing a body to be plated in the above electroless composite plating bath.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present specification, “electroless composite plating bath” refers to a plating bath in which a water-insoluble material is dispersed in a plating bath, and “electroless composite plating” refers to a plating bath formed by electroless plating. This means that the material is co-deposited with the metal on the surface of the object to be plated to form a plating film capable of simultaneously exhibiting the properties of the metal and the properties of the water-insoluble material.
[0015]
As described above, the electroless composite plating bath of the present invention contains a specific surfactant, a water-insoluble substance, a reducing agent, and a metal ion as a basic plating composition. This is represented by (1).
[0016]
Embedded image
[0017]
The compound represented by the formula (1) is an amphoteric surfactant having the characteristic that it exhibits substantially cationic properties under the condition where the acidity in the electroless composite plating bath is acidic to weakly acidic.
[0018]
This compound (1) has a fatty acid amide alkyl group in the structure. This fatty acid moiety (R 1 Examples of CO-) include those derived from coconut oil fatty acids, palm kernel oil fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid and the like. In the electroless composite plating bath of the present invention, the fatty acid portion is derived from coconut oil fatty acid or palm kernel oil fatty acid including mystyric acid or palmitic acid having an alkyl chain longer than lauric acid, This is preferred from the viewpoints of stability during use and thermal stability when using a plating bath.
[0019]
Further, the group R of the compound (1) 2 And R 3 Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include hydroxymethyl, hydroxyethyl, and hydroxy. Examples of the alkoxyl group having 1 to 6 carbon atoms such as propyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl include methoxyl, ethoxyl, propoxyl, butoxyl, pentyloxyl and hexyloxyl. Of these, a lower alkyl group, particularly a methyl group, is preferred because the compound can be easily obtained.
[0020]
Examples of the above compound (1) include, for example, Nissan Anone BDC-SF, Nissan Anon BDF-SF (all manufactured by Nippon Oil & Fats Co., Ltd.), Adeka Ankhort PB-30L (manufactured by Asahi Denka Kogyo Co., Ltd.), Enazicol Fatty acid amidopropyldimethyl acetate betaine which is commercially available as C-30B, Enazicol L-30B (all manufactured by Lion Corporation) and the like can be mentioned, and these can be easily obtained.
[0021]
In the electroless composite plating bath of the present invention, the concentration of the compound (1) used as a surfactant is preferably 1000 mg / L or less, more preferably 20 to 600 mg / L, in the composition of the plating bath. preferable.
[0022]
In the electroless composite plating bath of the present invention, in addition to the compound (1), other types of surfactants such as a cationic surfactant and hydrogen ion conditions of the plating bath can be used as long as the effects of the present invention are not impaired. An amphoteric surfactant which exhibits substantially cationic properties below can be added. Specific examples of such a surfactant include lauryltrimethylammonium chloride (eg, Cotamine 24: manufactured by Kao Corporation) and dimethylalkyl betaine (eg, Nissan Anone BF: manufactured by NOF Corporation). And one or two of them can be used in combination.
[0023]
Further, the electroless composite plating bath of the present invention may contain a nonionic surfactant such as a polyoxyethylene alkyl ether-based nonionic surfactant (for example, Emulgen 109P: manufactured by Kao Corporation) within a range that does not impair the effects of the present invention. One or two of anionic surfactants and anionic surfactants such as sodium alkyl allyl polyether sulfonate (for example, TRITON X-200: manufactured by Union Carbide) can be used in combination.
[0024]
The electroless composite plating bath of the present invention comprises, except that the above-mentioned compound (1) is contained as a surfactant, the components to be blended in a general electroless composite plating bath, that is, metal ions, a water-insoluble material and a reducing agent. It can be prepared by dissolving or dispersing according to a conventional method.
[0025]
Examples of metal ions that can be used in the electroless composite plating bath of the present invention include nickel ions, cobalt ions, copper ions, gold ions, iron ions, palladium ions, tin ions, platinum ions, rhodium ions, and the like. Can be used in the form of a water-soluble metal salt such as a sulfate or a chloride having The concentration of these metal ions in the electroless composite plating bath may be a concentration that can be generally used, but is preferably 0.1 to 100 g / L, more preferably 1.0 to 50 g / L in the composition of the plating bath. preferable.
[0026]
The water-insoluble material used in the electroless composite plating bath of the present invention is not particularly limited as long as it is generally used in composite plating, and the type of electroless composite plating bath and the plating film obtained by the plating are not limited. The present invention is applicable to water-repellent or hydrophobic water-insoluble materials such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer). ), Fluorine compounds such as pitch fluoride, fluorine compounds, nylon, polyethylene, graphite, graphite fluoride, molybdenum disulfide, boron nitride, silicon carbide, etc., to obtain particularly excellent effects. it can. The water-insoluble material may be used alone or in a combination of two or more.
[0027]
Examples of the above-mentioned PTFE include Lubricant L-170J and L-172J (both manufactured by Asahi Glass Co., Ltd.), Lubron L-2 and L-5 (both manufactured by Daikin Industries, Ltd.), Zonyl MP-1100, MP Fine particles commercially available under trade names such as -1200 and TLP10F-1 (both manufactured by DuPont) can be used, and these can be used.
[0028]
These water-insoluble materials are preferably in the form of fine particles, and are appropriately dispersed in an electroless composite plating bath, and have a particle diameter of such a degree that they can be co-deposited in a metal matrix in a plating film. Although there is no particular limitation, a material having a size of generally 100 μm or less, preferably 0.1 to 10 μm may be used. Further, it may be in the form of a short fiber having a length of 100 μm or less, preferably 5 to 100 μm.
[0029]
The content of the water-insoluble material in the electroless composite plating bath of the present invention is preferably 500 g / L or less, more preferably 1 to 10 g / L, in the composition of the plating bath.
[0030]
Further, examples of the reducing agent that can be used in the electroless composite plating bath of the present invention include sodium hypophosphite, dimethylamine borane, hypophosphites such as hydrazine, and amine boranes or hydrazine salts. . The concentration of these reducing agents in the electroless composite plating bath varies depending on the type of the reducing agent used and the metal to be deposited, but is preferably 1 to 100 g / L, more preferably 2 to 30 g / L in the composition of the plating bath. preferable.
[0031]
In preparing the electroless composite plating bath of the present invention, it is preferable to add a complexing agent in addition to the above-mentioned essential components as long as the effects of the present invention are not impaired.
[0032]
Examples of complexing agents that can be used include organic acids such as malic acid, lactic acid, succinic acid, propionic acid, malonic acid, adipic acid, citric acid, acetic acid, glycine, gluconic acid, and glycolic acid, and one type of water-soluble salts thereof. They can be used alone or in combination of two or more. The concentration of these complexing agents in the electroless composite plating bath is preferably from 1 to 100 g / L, more preferably from 10 to 40 g / L, in the composition of the plating bath.
[0033]
In addition, the electroless composite plating bath of the present invention has a stabilizer, a reaction accelerator, and an effect of improving the throwing power, which are usually used in the electroless plating bath, if necessary, as long as the effects of the present invention are not impaired. Can be added as appropriate.
[0034]
As the stabilizer, for example, a compound containing lead ions (for example, lead nitrate) or the like can be used. As the reaction accelerator, a sulfur compound, alcohols, carboxylic acid, or the like can be used. Further, various oxidizing agents having a throwing power improving effect can be added.
[0035]
In order to carry out the electroless composite plating using the electroless composite plating bath of the present invention thus prepared, it is sufficient to follow the means used in ordinary electroless plating, for example, the water-insoluble material is uniformly dispersed. By dipping the object to be plated in the electroless composite plating bath, a composite plating film in which the water-insoluble material is uniformly dispersed can be formed on the surface of the object to be plated.
[0036]
When performing electroless composite plating, the acidity of the electroless composite plating bath is preferably adjusted to pH 1 to 7, more preferably 3 to 5. By setting the pH of the electroless composite plating bath in this range, an effect is obtained in that the reduction reaction of the metal ions proceeds efficiently and the deposition rate of the composite plating film is improved. To adjust the pH of the plating bath, an acid such as hydrochloric acid, sulfuric acid, sulfamic acid or nitric acid, or an alkali such as sodium hydroxide or ammonium hydroxide solution can be appropriately added as a pH adjuster.
[0037]
Further, in performing the electroless composite plating, the bath temperature of the electroless composite plating bath may be set to 40 to 95 ° C, and preferably 85 to 90 ° C.
[0038]
Furthermore, if necessary, the electroless composite plating bath can be agitated, or the object to be plated can be shaken or the like, so that the electroless composite plating can be performed efficiently, and the appearance and performance of the plating film are more excellent. Things. As the stirring means for these electroless composite plating baths, the rocking means for the object to be plated, and the like, any commonly used means may be used.
[0039]
In the above-described electroless composite plating method, as one of preferred embodiments, for example, a plating method using Ni-P electroless composite plating containing PFTE having the following composition is exemplified. In this method, a steel plate (for example, a bright steel plate (SPCC-SB)) is prepared as an object to be plated, and is electroless composite plating bath having the following composition with a liquid temperature of 85 to 90 ° C. and a pH of 4 to 5. By performing the electroless composite plating by immersion in the substrate for about 30 to 60 minutes, a composite plating film of Ni / PTFE is formed on the surface of the body to be plated. According to this method, a composite plating film having a thickness of 5 to 20 μm is formed on the surface of the object to be plated, and the amount of PTFE deposited at this time is about several to about 30% by volume.
[0040]
(Electroless composite plating bath composition)
Nickel sulfate hexahydrate 25-30g / L
Fatty acid amidopropyldimethyl betaine 20-600mg / L
(Surfactant)
PTFE (water-insoluble material: average particle diameter of about 0.3 μm) 1 to 10 g / L
Malic acid (complexing agent) 10-50 g / L
Lactic acid (complexing agent) 10-50 g / L
Succinic acid (complexing agent) 10-50 g / L
Sodium hypophosphite monohydrate (reducing agent) 20-50 g / L
[0041]
In performing the electroless composite plating using the electroless composite plating bath of the present invention, as the plating proceeds, metal ions are reduced to metal by a reducing agent, and as the water-insoluble material is eutectoid, The metal ion concentration, the reducing agent concentration, and the water-insoluble material concentration in the plating bath decrease, and the pH also decreases. Therefore, the water-soluble metal salt, the reducing agent, the water-insoluble material, the pH adjuster, etc. are replenished to the electroless composite plating bath continuously or at appropriate intervals, and the concentrations thereof are returned to the original concentrations. Is preferred.
[0042]
In this case, it is considered that the reduction amount of the metal ion concentration, the reduction amount of the reducing agent, the reduction amount of the water-insoluble material, the change amount of the pH, and the deposition amount of the electroless composite plating film are almost proportional to each other. In addition, the deposition rate is considered to be substantially constant under the same plating conditions if the initial plating bath concentration is the same, so that if the initial plating bath concentration is the same and the plating conditions are the same, the deposition rate is constant at regular intervals. By separately replenishing the water-soluble metal salt, the reducing agent, the water-insoluble material, the pH adjuster, and the like, the concentration of the electroless composite plating bath can be almost returned to the original.
[0043]
Also, continuously or at an appropriate time, the metal ion concentration and pH in the electroless composite plating bath are measured, and according to the measurement result, a water-soluble metal salt, a reducing agent, a water-insoluble material and A pH adjuster or the like may be supplied. Further, the concentration may be adjusted by analyzing the concentration of the water-insoluble material, the concentration of the complexing agent, and other components in the plating bath.
[0044]
The electroless composite plating bath of the present invention can continue the electroless composite plating satisfactorily up to at least 2 turns, generally about 3 to 4 turns by supplying such a water-soluble metal salt. Even if the electroless composite plating bath is used continuously, a plating film having a smooth surface and excellent uniformity can be provided. Further, the deposition rate and the amount of eutectoid do not decrease much, and the performance of the plating film is stable. Here, "one turn" is an index indicating the aging degree of the plating bath at the time when the amount of metal deposition corresponding to the initial metal ion concentration in the electroless composite plating bath of the present invention has occurred, that is, for example, Assuming that the initial metal ion concentration in the electroless composite plating bath is 5 g / L, the time at which 5 g / L of metal is deposited is one turn. Therefore, in this case, the point at which the metal deposition of 25 g / L occurs is 5 turns.
[0045]
【Example】
Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
[0046]
Example 1
Dispersibility of PTFE at plating bath operating temperature:
In the following plating bath compositions, eight types of surfactants (reference products 1 to 8) shown in Table 1 were respectively added to form electroless composite plating baths of products 1 to 3 of the present invention and comparative products 1 to 5. Prepared.
[0047]
(Electroless composite plating bath composition)
Component Content
1. Nickel sulfate hexahydrate 25g / L
2. Sodium hypophosphite monohydrate 30g / L
3. Malic acid 25g / L
4. Lactic acid 20g / L
5. Succinic acid 5g / L
6. Borax 5g / L
7. Lead nitrate (stabilizer)
8. Surfactant of Table 1 150mg / L
9. PTFE * 1 4.0g / L
(Average primary particle diameter: 0.3 μm)
* 1: MP1100 (manufactured by Dupont)
[0048]
(Surfactant used)
[Table 1]
With respect to these eight electroless composite plating baths, the pH of the plating bath was adjusted to 5.0 using sulfuric acid or ammonium hydroxide solution. Next, the dispersion state of PTFE (polytetrafluoroethylene), which is a water-insoluble material, when the temperature of the plating bath was raised to 90 ° C. (corresponding to the use temperature of the plating bath) was compared and evaluated. Table 2 shows the results.
[0050]
(Result)
[Table 2]
From the results in Table 2, it can be seen that PTFE in the electroless composite plating baths of the products 1 to 3 of the present invention and the comparative products 1 and 2 show a good dispersion state when the temperature of the plating bath is heated to 90 ° C. Indicated. On the other hand, in the electroless composite plating baths of Comparative Products 3 to 5, it was confirmed that PTFE agglomeration occurred during or immediately after the temperature of the plating bath was raised to 90 ° C.
[0052]
Example 2
Electroless composite plating test (1):
An iron plate (size: 50 mm x 100 mm x 0.8 mm) was used as a sample, and this sample was used as an object to be plated in the electroless composite plating baths of inventive products 1 to 3 and comparative products 1 to 5 prepared in Example 1. It was immersed, and electroless composite plating was performed under the following plating conditions.
[0053]
(Plating conditions)
PH of plating bath (Note): 4.9
Plating bath temperature: 90 ° C
Plating time: 60 minutes
Stirring conditions: gentle mechanical stirring
(Note) The pH was adjusted using a sulfuric acid or ammonium hydroxide solution.
[0054]
For the sample after the electroless composite plating, the appearance of the plating film and the eutectoid content of PTFE were determined according to the following evaluation criteria. In addition, the deposition rate of the plating film was measured using a conventional method. Table 3 shows the results.
[0055]
(Evaluation criteria: film appearance)
The appearance of the film was visually observed.
Judgment contents
◎: Dark gray and uniform
○: Dark gray and slightly uniform
△: Dark gray and uneven
×: non-uniform with bright nickel color
[0056]
(Eutectoid amount of PTFE)
Judgment amount
◎: 25% by volume or more
: 20% by volume or more and less than 25% by volume
△: 15% by volume or more and less than 20% by volume
×: less than 15% by volume
[0057]
(Result)
[Table 3]
As can be seen from the results in Table 3, the film appearance of the plating samples using the electroless composite plating baths of the present invention products 1 to 3 and the eutectoid content of PTFE are good, and the deposition rate of the composite plating film is also excellent. It was. On the other hand, in the case of the comparative product 1 using the electroless composite plating bath, the film appearance and the amount of eutectoid were almost the same as those of the product of the present invention, but the deposition rate was slightly inferior. In the case of using the composite plating bath, the eutectoid amount and the deposition rate did not reach the level of the present invention. Furthermore, in the case of using the electroless composite plating baths of Comparative Examples 3 to 5, the film appearance was not good, and a sufficient eutectoid amount of PTFE could not be obtained.
[0059]
Example 3
Electroless composite plating test (2) (continuous use test of plating bath):
From the results in Tables 2 and 3, it can be seen that PTFE exhibited good dispersibility in the plating bath when the electroless composite plating bath was built (0 turns), and the properties of the resulting plating film were also excellent. Continuous use tests were performed on the electroless composite plating baths of Invention Products 1 to 3 and Comparative Products 1 and 2. In the continuous use test, electroless composite plating was performed using the plating bath continuously (at 1, 2, and 3 turns), and the film appearance, the PTFE eutectoid amount, and the deposition rate of the plating film for each turn were evaluated as follows. The determination was made by using a standard. Table 4 shows the results.
[0060]
(Film appearance)
Judgment contents
◎: Pear-skin tone with good uniform appearance
○: Uniform appearance with a slightly rough satin finish
△: Slight pits
×: Abnormal adsorption of PTFE particles on the entire surface of the film
XX: significant pits are formed on the entire surface of the film
[0061]
(PTFE eutectoid amount)
Judgment amount
◎: 25% by volume or more
: 20% by volume or more and less than 25% by volume
△: 15% by volume or more and less than 20% by volume
×: less than 15% by volume
[0062]
(Deposition rate)
The deposition rate at each turn was measured in the same manner as in Example 2, and the measured value was used to evaluate the reduction rate of the deposition rate at each turn with respect to the result obtained in Example 2 using the following evaluation criteria. Was evaluated.
Judgment decrease rate
○: less than 20%
△: 20% or more and less than 40%
×: 40% or more
[0063]
(Result)
[Table 4]
As can be seen from the results in Table 4, the electroless composite plating baths of the present invention products 1 and 2 can provide a plating film having a good appearance even when the plating bath is continuously used, and the electroless composite plating The decrease in the precipitation rate and the amount of eutectoid was extremely small. The electroless composite plating bath of the product 3 of the present invention was almost at the same level as the electroless composite plating bath of the comparative product 1 which is a conventional product (containing a fluorine-containing cationic surfactant). On the other hand, the electroless composite plating bath of Comparative Product 2 was inferior in plating film appearance as compared with the one using the above plating bath, and was not suitable for continuous use of the plating bath.
[0065]
【The invention's effect】
The electroless composite plating bath of the present invention is capable of uniformly dispersing the fine particles of the water-insoluble material in the plating bath, providing a plating film having a smooth surface and excellent uniformity. The plating performance such as the eutectoid amount of fine particles and the deposition rate is also excellent.
[0066]
Furthermore, the electroless composite plating bath of the present invention, even when electroless composite plating is continuously used, the above-mentioned performance is less reduced, and further, the surfactant used exhibits easy biodegradability, Since it is less irritating, it takes into consideration the human body and the environment, and is also excellent in safety and environment.
[0067]
Therefore, the electroless composite plating bath and the electroless composite plating method of the present invention can be applied to shafts, bearings, metal masks, slide rails, bearings, bolts, nuts, dies, iron bases, ironing boards, saws, scissors, cutters and kitchen knives. It is advantageous as electroless composite plating for industrial or household products, cooking utensils such as top boards, kitchen utensils such as kitchen bags, kitchen components, flushing fittings such as water taps, and faucet parts for water and gas. It can be used for:
that's all
Claims (8)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257460A (en) * | 2005-03-15 | 2006-09-28 | Ebara Udylite Kk | Electroless nickel-composite plating bath and electroless nickel alloy-composite plating bath |
| JP2009288463A (en) * | 2008-05-29 | 2009-12-10 | Tokai Rubber Ind Ltd | Method for manufacturing metallic mold, metallic mold and developing roll for electrophotographic apparatus |
| JP2012092416A (en) * | 2010-09-30 | 2012-05-17 | Eyetec Co Ltd | Method for forming composite plating film |
-
2003
- 2003-05-28 JP JP2003150764A patent/JP3979968B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257460A (en) * | 2005-03-15 | 2006-09-28 | Ebara Udylite Kk | Electroless nickel-composite plating bath and electroless nickel alloy-composite plating bath |
| JP2009288463A (en) * | 2008-05-29 | 2009-12-10 | Tokai Rubber Ind Ltd | Method for manufacturing metallic mold, metallic mold and developing roll for electrophotographic apparatus |
| JP2012092416A (en) * | 2010-09-30 | 2012-05-17 | Eyetec Co Ltd | Method for forming composite plating film |
Also Published As
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| JP3979968B2 (en) | 2007-09-19 |
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