JP2004143489A - Composite electroplating bath, and composite electroplating method - Google Patents
Composite electroplating bath, and composite electroplating method Download PDFInfo
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- JP2004143489A JP2004143489A JP2002307867A JP2002307867A JP2004143489A JP 2004143489 A JP2004143489 A JP 2004143489A JP 2002307867 A JP2002307867 A JP 2002307867A JP 2002307867 A JP2002307867 A JP 2002307867A JP 2004143489 A JP2004143489 A JP 2004143489A
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- Prior art keywords
- plating bath
- ion
- electro
- composite plating
- plating
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000009713 electroplating Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 171
- 239000002198 insoluble material Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 28
- 239000010419 fine particle Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
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- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims 1
- 229910001430 chromium ion Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
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- 239000003093 cationic surfactant Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
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- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
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- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、電気複合めっき浴及び電気複合めっき方法に関する。更に詳しくは、金属めっき皮膜中にフッ素樹脂等の水不溶性材料を複合共析させることが可能な電気複合めっき浴及び電気複合めっき方法に関する。
【０００２】
【従来の技術】
従来より、電気めっき浴中に、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や短繊維を分散させて電気複合めっき浴とし、このめっき浴に被めっき体を浸漬させて電気めっきを行うことにより、電気的に金属皮膜を還元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、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。
【０００３】
例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）の微粒子を電気ニッケルめっき浴中に分散した複合めっき浴を用いることにより、ニッケルめっき皮膜中にＰＴＦＥ微粒子が分散したニッケル／ＰＴＦＥ複合めっき皮膜を得ることができることが知られており、このニッケル／ＰＴＦＥ複合めっき皮膜は、ニッケル金属の諸物性とともに、ＰＴＦＥの有する低摩擦性や非粘着性を併せ持っためっき皮膜となる。
【０００４】
ところで、ＰＴＦＥに代表されるフッ素樹脂や、黒鉛、フッ化黒鉛などの微粒子は、その高い撥水性や疎水性のために、直接一般のめっき浴中に分散させることができず、これら微粒子が均一に分散しためっき皮膜を得ることは非常に困難であった。そこで、めっき浴に上記微粒子の他、カチオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤等の界面活性剤を分散助剤として配合し、微粒子を分散させた複合めっき浴が広く使用されている。
【０００５】
例えば、ＰＴＦＥに代表されるフッ素樹脂や、黒鉛、フッ化黒鉛等の、撥水性や疎水性が高い微粒子に対する分散助剤としては、フッ素含有カチオン性界面活性剤が好適とされてきた（特開昭４９−５８３２号公報、特開昭５２−５６１４７号公報、特開昭５２−５６０２６号公報、特開昭５４−１５９３４３号公報、特開昭５０−２１２９９号公報等）。この中でも、分子内にＣ−Ｆ結合のパーフルオロアルキル基（フルオロ炭素型）を持つフッ素含有カチオン性界面活性剤が分散助剤として高い性能を有しているとされ、当該界面活性剤が広く使用されていた。
【０００６】
しかし、電気複合めっき浴においては、添加する界面活性剤の種類や添加量により、めっき時の液攪拌や揺動による影響を受けやすくなるため、めっき皮膜の部分的な外観の黒色化や未析出部が発生し、皮膜が不均一となって皮膜性能を低下させるという問題があった。また、界面活性剤の使用により、めっき皮膜の高電流密度部分にコゲが発生し易くなることから、めっき皮膜の性能を著しく低下させることもあった。従って、通常のめっき作業においては、めっき液循環等の液攪拌や液の流動方向及び流動速度に注意する必要があり、これが作業効率を大幅に低下させてしまう原因ともなっていた。特に、複雑な形状の被めっき物では、この問題が著しかった。
【０００７】
前記したフッ素含有カチオン性界面活性剤を使用した場合においても、電気めっき時に高電流密度部分にコゲが発生し易く、皮膜性能を著しく低下させるという問題があり、液循環等の液攪拌や液の流動方向及び流動速度に注意して作業を行わなければならず、作業効率の低下は甘受せざるを得なかった。
【０００８】
更に、フッ素含有カチオン性界面活性剤の多くは、次の式（ＩＩ）で表される化合物、その塩またはその誘導体であるが、近年、式（ＩＩ）の化合物が人体や環境に対して有害であるということが判明したため、かかる界面活性剤の使用及び製造は禁止されつつある。
【０００９】
【化２】
Ｒｆ−ＳＯ２ −Ｙ ……（ＩＩ）
（式中、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）
【００１０】
一方、フッ素を含有しないカチオン性界面活性剤を用い、ＰＴＦＥに代表されるフッ素樹脂や、黒鉛等の、撥水性、疎水性が強い微粒子を分散させた電気複合めっき浴が報告されている（特公平４−２８７９７号公報等）。また、フッ素を含有しない界面活性剤と、フッ素樹脂等のフッ素化合物以外の水不溶性材料を使用した複合めっき浴も報告されている（特開昭５２−１３０４３４号公報等）。この報告によれば、フッ素含有界面活性剤だけでなく、フッ素を含有しないカチオン性界面活性剤も微粒子の分散には有効であるとしている。更に、必要に応じて、水不溶性材料の微粒子を疎水性の有機化合物で被覆した後、前記疎水性の有機化合物に対し親和性を有するカチオン性界面活性剤を使用する手段等の報告もされていた（特公平５２−２５３７５公報、特公昭５２−４１７３３公報等）。
【００１１】
しかしながら、これらの界面活性剤も、前記したフッ素含有カチオン性界面活性剤以上にめっき時の液攪拌や揺動による影響を受け易くなるため、黒色の外観ムラやめっき皮膜の未析出が発生し易く、また微粒子の分散安定性や皮膜中の微粒子共析量の安定性にも問題があった。更に、一般には、カチオン性界面活性剤は、腐蝕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あり、めっき浴の環境面への配慮も必要とされていた。
【００１２】
【発明が解決しようとする課題】
従って、めっき浴中にフッ素樹脂等の撥水性ないし疎水性の微粒子を添加しても、これらが電気めっき時の液攪拌や揺動による影響を受けにくくし、めっき皮膜の黒色化や外観ムラやめっき皮膜の未析出等の問題の発生を防止する手段の提供が求められていた。そしてこの手段は、同時に、めっき浴中においては微粒子分散を安定し、めっき皮膜中では微粒子共析量が安定で良好であり、高電流密度部分においてコゲが発生を防止できることや、人体に対する安全性が高く、環境面においても優れたものであるような電気複合めっき浴を提供するものであることが求められていた。
【００１３】
【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電気複合めっき浴中に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。
【００１４】
すなわち本発明は、界面活性剤、金属イオン及び水不溶性材料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（Ｉ）で示される化合物を含有せしめたことを特徴とする電気複合めっき浴を提供するものである。
【化３】
【００１５】
また本発明は、被めっき体を上記電気複合めっき浴に浸漬し、電気めっきすることを特徴とする電気複合めっき方法を提供するものである。
【００１６】
【発明の実施の形態】
本明細書において、「電気複合めっき浴」とは、水不溶性材料を金属めっき浴中に分散させためっき浴のことをいい、また、「電気複合めっき」とは、電気めっきにより、該材料と金属を被めっき体の表面に共析せしめ、金属のもつ物性と水不溶性材料のも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。
【００１７】
本発明の電気複合めっき浴は、上記したように、特定の界面活性剤、金属イオン及び水不溶性物質を基本めっき浴組成として含有するものである。
【００１８】
本発明の電気複合めっき浴において使用される界面活性剤は、下記式（Ｉ）で表される化合物である。
【化４】
【００１９】
式（Ｉ）で表される化合物は、電気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。
【００２０】
この化合物（Ｉ）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が、この脂肪酸部分（Ｒ１−ＣＯ−）は、炭素数が８から２１の脂肪酸から導かれたものであり、具体的な例としては、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、ステアリン酸等の脂肪酸から導かれたものが挙げられる。
【００２１】
この脂肪酸部分としては、Ｒ１で示されるアルキル部分が長いものの方が、電気めっき時における液攪拌や揺動による影響を受けにくくなるため、部分的な外観の黒色化やめっき皮膜の未析出部の発生、皮膜の不均一性の発生及び高電流密度部分におけるコゲの発生を防止ないし抑制することができるという点で好ましい。例えば、ラウリン酸から導いた脂肪酸部分を有するよりもアルキル鎖の長いミリスチン酸、パルミチン酸、ステアリン酸や、ミリスチン酸、パルミチン酸、ステアリン酸等を含有するヤシ油脂肪酸、パーム核油脂肪酸等から導いた脂肪酸部分を有するものを用いることにより、液攪拌や揺動による影響を受けにくくすることができる。
【００２２】
一方、化合物（Ｉ）の基Ｒ２、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、ヘキシル等が、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、ヒドロキシヘキシル等が、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、ヘキシルオキシル等がそれぞれ挙げられるが、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。
【００２３】
本発明の電気複合めっき浴における界面活性剤としての化合物（Ｉ）の使用濃度は、めっき浴の組成において、５０００ｍｇ／Ｌ以下であることが好ましく、２０〜１０００ｍｇ／Ｌであることがより好ましい。
【００２４】
また、本発明の電気複合めっき浴には、化合物（Ｉ）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）等が挙げられ、その一種を単独で、または二種以上を組み合わせて用いることができる。
【００２５】
更に、本発明の電気複合めっき浴には、本発明の効果を損なわない範囲で、ポリオキシエチレン系非イオン性界面活性剤（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等のそれぞれ一種を単独で、または二種以上を組み合わせて使用することができる。
【００２６】
本発明の電気複合めっき浴においては、界面活性剤としての上記化合物（Ｉ）のほか、通常の電気複合めっき浴に配合される金属イオンや水不溶性材料が使用される。
【００２７】
本発明の電気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、銀イオン、鉄イオン、パラジウムイオン、白金イオン、スズイオン、タングステン、亜鉛イオン、クロムイオン及びロジウムイオン等が挙げられる。これらの金属イオン源としては、スルファミン酸塩、硫酸塩や塩化物等、水溶性の金属塩を用いることができる。電気複合めっき浴中のこれら金属イオンの濃度は、通常使用されうる濃度とすればよいが、一般に、めっき浴組成において０．１〜１０００ｇ／Ｌが好ましく、１．０〜５００ｇ／Ｌがより好ましい。
【００２８】
また、本発明の電気複合めっき浴に用いられる水不溶性材料としては、一般に複合めっきに使用されるものであれば特に制限はなく、電気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に応じて適宜選定することができ、これらの水不溶性材料は、一種類を単独で使用してもよく、また、二種以上を組み合わせて使用してもよい。
【００２９】
本発明は、特に、撥水性ないし疎水性の水不溶性材料を使用する場合において有効である。このような、撥水性ないし疎水性の水不溶性材料としては、例えばＰＴＦＥ、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（ＰＦＡ）、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、酸化チタン、二酸化ケイ素、アルミナ、炭化ケイ素等を例示することができる。
【００３０】
更に、これらの水不溶性材料は、微粒子状であっても短繊維状であっても良いが、微粒子状の形態であることが好ましい。微粒子状である場合の粒子径も、電気複合めっき浴中で適度に分散し、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限はないが、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。また、短繊維状である場合は、長さが１００μｍ以下、好ましくは５〜１００μｍ程度であることが好ましい。
【００３１】
なお、ＰＴＦＥの微粒子としては、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、ＴＬＰ−１０Ｆ−１（全てデュポン社製）等の商品名で市販されているので、これらを用いることもできる。
【００３２】
本発明の電気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１０００ｇ／Ｌ以下であることが好ましく、１〜３００ｇ／Ｌであることがより好ましい。
【００３３】
本発明の電気複合めっき浴の調製は、上記した各成分を混合する等、通常の手段を用いて行えばよい。
【００３４】
なお、本発明の電気複合めっき浴には、上記した基本成分の他に、本発明の効果を妨げない範囲において、電気複合めっきに使用される添加剤を任意成分として適宜加えることができる。
【００３５】
この添加剤としては、例えば、光沢化剤、平滑化剤、湿潤剤、応力減少剤などが挙げられ、スルホン酸基等を有する硫黄化合物や、単結合または多重結合を有し、かつヒドロキシ基やカルボニル基、カルボキシル基等を有する有機化合物（例えば、ブチンジオールに代表される多価アルコール類等や、ポリエチレングリコールに代表されるポリエーテル化合物等）、単結合または多重結合を有し、かつアミノ基、ニトロ基またはアゾ基等の一種若しくは二種以上を有する窒素化合物（例えば、ヤヌスグリーンＢに代表されるフェナンジン系染料等）が、上記した金属イオンの用途に応じて使用される。例えば、ニッケルめっきを実施する場合にあっては、サッカリンやブチンジオールなど、通常電気めっきに使用されているめっき光沢剤を使用することができる。
【００３６】
また、金属めっき皮膜の電気的還元において、金属の還元雰囲気および金属めっき界面でめっき皮膜を効率的かつ均一に析出させることができるｐＨ緩衝剤を必要に応じて使用することができる。具体的には、ホウ酸やホウ砂等のホウ素化合物、クエン酸やマロン酸等の有機酸等の、通常電気めっきに使用されているｐＨ緩衝剤等が挙げられる。
【００３７】
更に、亜りん酸、亜りん酸ナトリウム、次亜りん酸、次亜りん酸ナトリウム等のリン供与物質を、めっき皮膜の外観向上、内部応力緩和、硬さ物性向上などのめっき皮膜の物性向上を目的として適宜使用することができる。
【００３８】
かくして調製される本発明の電気複合めっき浴を用いて電気複合めっきを実施するには、通常の電気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電気複合めっき浴に、被めっき体を浸漬させ、電気めっきすることにより、被めっき体の表面に、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。
【００３９】
電気複合めっきを実施するにあたっては、被めっき体に対して、油分除去のための脱脂や酸化皮膜除去のための酸活性等の前処理を施しておくことが好ましい。特に、被めっき体が導電性を有しないものである場合等には、エッチングやキャタライジング等による触媒付与や、無電解めっき、スパッタリングや蒸着等の前処理を施し、被めっき体に導電性を付与しておくことが好ましい。
【００４０】
電気複合めっきを実施する場合のめっき条件は、特に制約はなく、通常の複合めっきの場合と同様にすればよい。
【００４１】
例えば、めっき時の陰極電流密度は、めっき浴中の金属イオンの濃度やその種類により適宜決定され、該金属めっき浴で通常設定される電流密度を用いればよいが、一般に、０．０５〜２０Ａ／ｄｍ２程度とし、１〜１０Ａ／ｄｍ２とすることが好ましい。また、めっき浴のｐＨを１〜７程度とし、３〜５とすることが好ましい。更に、めっき浴の浴温を、１０〜８０℃程度とすればよく、２０〜６０℃とすることがより好ましい。
【００４２】
更にまた、必要により電気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、電気複合めっきを効率よく行なうことができ、また、めっき皮膜の外観及び物性を優れたものとして、本発明の効果を十分に発揮させることができるので好ましい。これらの電気複合めっき浴の攪拌手段や被めっき体の揺動手段等に関しては、通常用いられる手段を適宜行なえばよい。
【００４３】
以上説明した本発明の電気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、水不溶性材料としてＰＴＦＥを含有する下記組成の電気ニッケル複合めっき浴を使用した電気めっき方法が挙げられる。
【００４４】
この方法では、被めっき体として、常法により前処理が施された鋼板（例えば、ブライト鋼板（ＳＰＣＣ−ＳＢ））を用意し、これを浴温３０〜７０℃、ｐＨを４〜５とした下記組成の電気ニッケル複合めっき浴に浸漬し、陰極の電流密度を０．５〜１０Ａ／ｄｍ２として１０分程度めっきすることにより、被めっき体の表面部に、厚さが１ないし２０μｍのＮｉ／ＰＴＦＥの複合めっき皮膜を形成することができる。また、その際におけるＰＴＦＥの共析量は、めっき皮膜に対して数ないし約４０容量％となる。
【００４５】
（ 電気複合めっき浴組成 ）
成 分 濃 度
スルファミン酸ニッケル ３５０〜６００ｇ／Ｌ
塩化ニッケル ５〜９０ｇ／Ｌ
ホウ酸（ｐＨ緩衝剤） ３０〜５０ｇ／Ｌ
光沢剤 適 量
脂肪酸アミドプロピルベタイン ２０〜１０００ｍｇ／Ｌ
（界面活性剤）
ＰＴＦＥ １〜１００ｇ／Ｌ
（水不溶性材料：平均粒子径約０．３μｍ）
【００４６】
なお、本発明の電気複合めっき浴を用いて電気複合めっきを行なうにあたっては、めっきの進行によって水不溶性材料がめっき皮膜中に共析するにつれて、電気複合めっき浴中の水不溶性材料の濃度が低下することとなる。従って、本発明の効果を十分に発揮させるように電気めっきを行うには、連続的に、または適当な間隔ごとに該水不溶性材料を補給して、めっき浴中の水不溶性材料の濃度を上記した一定範囲内に保つようにすることが好ましい。
【００４７】
【実施例】
次に実施例を挙げ、本発明を更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。
【００４８】
実 施 例 １
めっき浴に対するＰＴＦＥの分散性の確認：
下記の電気複合めっき浴組成において、表１に示される１１種類の界面活性剤（参考品１〜１１）をそれぞれ添加して、本発明品１〜６及び比較品１〜５の電気複合めっき浴を調製した。
【００４９】
（ 電気複合めっき浴組成 ）
成 分 濃 度
スルファミン酸ニッケル ４００ｇ／Ｌ
塩化ニッケル ４０ｇ／Ｌ
ホウ酸 ４０ｇ／Ｌ
サッカリン（光沢剤） 適量
表１に記載の界面活性剤 ５００ｍｇ／Ｌ
ＰＴＦＥ＊１ ２０ｇ／Ｌ
（平均粒子径：約０．３μｍ）
＊１：ゾニールＭＰ−１１００（デュポン社製）
【００５０】
（ 使用した界面活性剤 ）
【表１】
これらの１１種類の電気複合めっき浴について、スルファミン酸水溶液あるいは炭酸ニッケルを用いて、めっき浴のｐＨを４．２に調整した後、めっき浴の温度を５０℃（このめっき浴の使用温度に相当する）まで上昇させた。このめっき浴を１Ｌ容のビーカーに取り、３０分間放置した後の、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。
【００５２】
（ 結 果 ）
【表２】
表２の結果より、本発明品１〜６及び比較品１〜３の電気複合めっき浴中のＰＴＦＥは、めっき浴を５０℃まで加温した場合であっても良好な分散を示すことが示された。一方、比較品４及び５の電気複合めっき浴では、めっき浴の調整後間もなくＰＴＦＥの凝集が発生し、めっき浴に対するＰＴＦＥの分散性が悪いことが確認された。
【００５４】
実 施 例 ２
電気複合めっき試験（１）：
被めっきサンプルとして、真鍮板（サイズ：６０ｍｍ×１００ｍｍ×０．３ｍｍ）を用いた。このサンプルに対し、マーベライトＭプロセス（荏原ユージライト（株））を用いて、下記の条件に従い下地めっきとして電気光沢ニッケルめっきを施した。
【００５５】
（ 下地めっき条件 ）
めっき浴のｐＨ（注） ： ４．５（注）
めっき浴の温度 ： ５５℃
めっき時間 ： １０分
攪拌条件 ： 空気攪拌
陰極電流密度 ： ４Ａ／ｄｍ２
（注）硫酸水溶液もしくは炭酸ニッケルを用いてｐＨを調整した
【００５６】
上記のようにしてサンプルに対して下地めっきを施した後、実施例１で調製した本発明品１〜６及び比較品１〜３の電気複合めっき浴を用いて、下記のめっき条件にてハルセル試験を行い、めっき皮膜の外観と高電流密度部のコゲの発生状態を観察した。
【００５７】
（ めっき条件 ）
めっき浴のｐＨ（注） ： ４．２
めっき浴の温度 ： ５０℃
めっき時間 ： ２分３０秒
攪拌条件 ： マグネティックスターラーによる攪拌（３００ｒｐｍ）
陰極電流 ： ３Ａ
（注）スルファミン酸水溶液もしくは炭酸ニッケルを用いてｐＨを調整した
【００５８】
実 施 例 ３
電気複合めっき試験（２）：
被めっきサンプルとして、ステンレス板（サイズ：６０ｍｍ×１００ｍｍ×０．３ｍｍ）を用いた。このサンプルに対し、まず、実施例２で示した手段により下地めっきを施した後、実施例１で調製した本発明品１〜６及び比較品１〜３の電気複合めっき浴を用いて、下記のめっき条件にて電気複合めっきを行い、めっき皮膜のＰＴＦＥ共析量を測定した。
【００５９】
（ めっき条件 ）
めっき浴のｐＨ（注） ： ４．２
めっき浴の温度 ： ５０℃
めっき時間 ： ２０分
攪拌条件 ： マグネティックスターラーによる攪拌（３００ｒｐｍ）
陰極電流密度 ： ４Ａ／ｄｍ２
（注）スルファミン酸水溶液もしくは炭酸ニッケルを用いてｐＨを調整した
【００６０】
実施例２及び３により得られた電気複合めっき後のサンプルに対し、めっき皮膜の外観、高電流密度部分でのコゲの発生状態、ＰＴＦＥの共析量について、それぞれ下記の評価基準により判定した。結果を表３に表す。
【００６１】
（ 評価基準：めっき皮膜外観）
ハルセル試験後のサンプル外観を目視にて確認した。
（ 評価基準：高電流密度部分のコゲの発生 ）
ハルセル試験後のサンプルの下から３０ｍｍの位置での、高電流密度側端面からのコゲの発生距離を測定した。
（評価基準：ＰＴＦＥの共析量）
（ 結 果 ）
【表３】
表３の結果からわかるように、本発明品１〜６の複合めっき浴を使用しためっきサンプルの皮膜外観は良好であり、また、高電流密度部分でのコゲの発生も防止ないし抑制されているものであった。さらに、めっき皮膜のＰＴＦＥ共析量も十分なレベルであった。
【００６６】
一方、比較品１の複合めっき浴を用いてめっきを行ったサンプルは、皮膜の外観及びＰＴＦＥ共析量は良好であるが、高電流密度部分でのコゲの発生が著しかった。また、比較品２及び３は、高電流密度部分でのコゲの発生は抑制されてはいるが、皮膜外観は不均一であり、かつ、十分なＰＴＦＥ共析量が得られなかった。
【００６７】
【発明の効果】
本発明の電気複合めっき浴は、めっき浴中に水不溶性材料の微粒子が均一に分散し、また、めっきにおけるめっき皮膜中の微粒子の共析量も優れたものであり、かつ、高電流密度部分のコゲの発生を防止ないし抑制することができるものである。従って、本発明の電気複合めっき浴によれば、めっき皮膜に良好な外観を与えるとともに優れた機能性を付与することができる。更に、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、人体や環境に配慮したものであり、安全面や環境面にも優れたものである。
【００６８】
従って、本発明の電気複合めっき浴及び電気複合めっき方法は、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電気複合めっきとして、有利に使用することができる。
以 上[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electro-composite plating bath and an electro-composite plating method. More specifically, the present invention relates to an electro-composite plating bath and an electro-composite plating method capable of co-depositing a water-insoluble material such as a fluororesin in a metal plating film.
[0002]
[Prior art]
Conventionally, fine particles and short fibers such as fluororesin, nylon, polyethylene, graphite, graphite fluoride, molybdenum disulfide, and boron nitride are dispersed in an electroplating bath to form an electrocomposite plating bath, and the plating bath is plated. By performing electroplating by immersing the body, a metal coating is reduced and precipitated electrically, and fine particles and short fibers are co-deposited in this metal film, and the above-mentioned fine particles and the like are dispersed in a metal matrix. Means for obtaining are known.
[0003]
For example, by using a composite plating bath in which polytetrafluoroethylene (PTFE) fine particles are dispersed in an electric nickel plating bath, a nickel / PTFE composite plating film in which PTFE fine particles are dispersed in a nickel plating film can be obtained. It is known that this nickel / PTFE composite plating film is a plating film having both the low friction property and the non-adhesive property of PTFE as well as the physical properties of nickel metal.
[0004]
By the way, fine particles such as fluororesin represented by PTFE, graphite, and fluorinated graphite cannot be directly dispersed in a general plating bath because of their high water repellency and hydrophobicity. It was very difficult to obtain a plating film dispersed in the coating. Accordingly, composite plating baths in which fine particles are dispersed by mixing a surfactant such as a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant as a dispersing aid in addition to the fine particles in the plating bath are widely used. It is used.
[0005]
For example, as a dispersing aid for fine particles having high water repellency and high hydrophobicity such as a fluororesin represented by PTFE, graphite, and fluorinated graphite, a fluorine-containing cationic surfactant has been considered to be suitable (Japanese Patent Application Laid-Open (JP-A) No. 2002-110572). JP-A-49-5832, JP-A-52-56147, JP-A-52-56026, JP-A-54-159343, JP-A-50-21299, and the like. Among them, a fluorine-containing cationic surfactant having a C-F bond perfluoroalkyl group (fluorocarbon type) in the molecule is said to have high performance as a dispersing aid, and the surfactant is widely used. Had been used.
[0006]
However, depending on the type and amount of surfactant added, the electroplating bath is susceptible to liquid agitation and rocking during plating, so that the plating film has a partial appearance with blackening or non-precipitation. There was a problem that a portion was generated and the film became non-uniform, thereby deteriorating the film performance. In addition, since the use of the surfactant makes it easy to generate kogation in a high current density portion of the plating film, the performance of the plating film may be significantly reduced. Therefore, in the ordinary plating operation, it is necessary to pay attention to the liquid stirring and the flow direction and the flow speed of the plating solution, and this has caused the work efficiency to be greatly reduced. In particular, this problem was remarkable in an object to be plated having a complicated shape.
[0007]
Even when the above-mentioned fluorine-containing cationic surfactant is used, kogation is easily generated in a high current density portion during electroplating, and there is a problem that the film performance is significantly reduced. The work has to be performed while paying attention to the flow direction and the flow speed, and the reduction in work efficiency has to be accepted.
[0008]
Further, many of the fluorine-containing cationic surfactants are compounds represented by the following formula (II), salts thereof or derivatives thereof, but in recent years, compounds of the formula (II) are harmful to humans and the environment. The use and manufacture of such surfactants is being banned.
[0009]
Embedded image
Rf-SO 2 -Y (II)
(In the formula, Rf represents a fluorine-substituted alkyl group or alkenyl group, and Y represents an amide group, a hydroxyl group, or a halogen, respectively.)
[0010]
On the other hand, there has been reported an electro-composite plating bath in which fine particles having strong water repellency and hydrophobicity, such as a fluororesin represented by PTFE and graphite, are dispersed by using a cationic surfactant containing no fluorine (see, for example, Japanese Patent Application Laid-Open No. H11-163873). Japanese Patent Publication No. Hei 4-28797). A composite plating bath using a surfactant containing no fluorine and a water-insoluble material other than a fluorine compound such as a fluorine resin has also been reported (Japanese Patent Application Laid-Open No. 52-130434). According to this report, not only a fluorine-containing surfactant but also a fluorine-free cationic surfactant is effective for dispersing fine particles. Further, if necessary, it has been reported that, after coating the fine particles of the water-insoluble material with a hydrophobic organic compound, a means of using a cationic surfactant having an affinity for the hydrophobic organic compound is provided. (JP-B-52-25375, JP-B-52-41733, etc.).
[0011]
However, these surfactants are also more susceptible to liquid agitation and rocking during plating than the above-mentioned fluorine-containing cationic surfactants, so that black appearance unevenness and non-precipitation of the plating film easily occur. In addition, there were also problems in the dispersion stability of the fine particles and the stability of the eutectoid amount of the fine particles in the film. Further, in general, cationic surfactants have environmental problems such as high corrosiveness and poor biodegradability, and therefore, consideration has to be given to the environmental aspects of the plating bath.
[0012]
[Problems to be solved by the invention]
Therefore, even if water-repellent or hydrophobic fine particles such as fluororesin are added to the plating bath, they are hardly affected by the liquid agitation or shaking during the electroplating, and the blackening of the plating film and the appearance unevenness are prevented. There has been a demand for provision of means for preventing the occurrence of problems such as non-precipitation of plating films. At the same time, this means that the dispersion of fine particles in the plating bath is stable, the amount of fine particles eutectoid in the plating film is stable and good, and that kogation can be prevented from occurring in high current density areas, and safety to the human body. Therefore, it has been demanded to provide an electro-composite plating bath which is high in environmental performance and is also excellent in environmental aspects.
[0013]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that such a problem can be solved by including a compound having a specific structure in an electrocomposite plating bath, and completed the present invention. .
[0014]
That is, the present invention provides an electroplating bath comprising a compound represented by the following formula (I) as a surfactant in a composite plating bath containing a surfactant, a metal ion and a water-insoluble material. To provide.
Embedded image
[0015]
The present invention also provides an electro-composite plating method characterized by immersing a body to be plated in the electro-composite plating bath and electroplating the object.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present specification, the “electro-composite plating bath” refers to a plating bath in which a water-insoluble material is dispersed in a metal plating bath. This means that a metal is eutectoidally deposited on the surface of a body to be plated to form a plating film capable of simultaneously exhibiting the properties of a metal and the properties of a water-insoluble material.
[0017]
As described above, the electrocomposite plating bath of the present invention contains a specific surfactant, a metal ion, and a water-insoluble substance as a basic plating bath composition.
[0018]
The surfactant used in the electro-composite plating bath of the present invention is a compound represented by the following formula (I).
Embedded image
[0019]
The compound represented by the formula (I) is an amphoteric surfactant having a characteristic that it exhibits a substantially cationic property under an acidic to weakly acidic condition in an electroplating bath.
[0020]
The compound (I) has a fatty acid amide alkyl group in the structure. The fatty acid portion (R 1 —CO—) is derived from a fatty acid having 8 to 21 carbon atoms. Typical examples include those derived from fatty acids such as coconut oil fatty acids, palm kernel oil fatty acids, lauric acid, myristic acid, palmitic acid and stearic acid.
[0021]
As the fatty acid moiety, towards the alkyl moiety represented by R 1 is long, it becomes hardly affected by the liquid stirred or rocking during electroplating, partial undeposited portion of blackening and plating film appearance This is preferable in that the occurrence of slag, the occurrence of non-uniformity of the film, and the occurrence of kogation in a high current density portion can be prevented or suppressed. For example, it is derived from coconut oil fatty acids, palm kernel oil fatty acids, and the like containing myristic acid, palmitic acid, stearic acid, and myristic acid, palmitic acid, stearic acid, and the like having an alkyl chain longer than that having a fatty acid portion derived from lauric acid. The use of a compound having a fatty acid moiety can reduce the effects of liquid stirring and shaking.
[0022]
On the other hand, examples of the alkyl group having 1 to 6 carbon atoms in the groups R 2 and R 3 of the compound (I) include methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. Examples of the group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. Examples of the alkoxyl group having 1 to 6 carbon atoms include methoxyl, ethoxyl, propoxyl, butoxyl, and pentyloxyl. Hexyloxyl, etc., but a lower alkyl group, particularly a methyl group, is preferred because the compound can be easily obtained.
[0023]
The concentration of compound (I) used as a surfactant in the electrocomposite plating bath of the present invention is preferably 5000 mg / L or less, more preferably 20 to 1000 mg / L, in the composition of the plating bath.
[0024]
The electro-composite plating bath of the present invention may contain, in addition to the compound (I), other types of surfactants such as a cationic surfactant and hydrogen ion conditions of the plating bath, 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 lauryl trimethyl ammonium chloride (for example, Cotamine 24: manufactured by Kao Corporation) and dimethylalkyl betaine (for example, Nissan Anone BF: manufactured by NOF Corporation). And one kind thereof can be used alone, or two or more kinds can be used in combination.
[0025]
Furthermore, in the electro-composite plating bath of the present invention, a non-ionic surfactant such as a polyoxyethylene-based non-ionic surfactant (for example, Emulgen 109P: manufactured by Kao Corporation) or the like may be used as long as the effects of the present invention are not impaired. Agents or anionic surfactants such as sodium alkyl allyl polyether sulfonate (for example, TRITON X-200: manufactured by Union Carbide) can be used alone or in combination of two or more.
[0026]
In the electro-composite plating bath of the present invention, in addition to the compound (I) as a surfactant, a metal ion or a water-insoluble material mixed in a usual electro-composite plating bath is used.
[0027]
Metal ions that can be used in the electro-composite plating bath of the present invention include nickel ions, cobalt ions, copper ions, gold ions, silver ions, iron ions, palladium ions, platinum ions, tin ions, tungsten, zinc ions, and chromium. And rhodium ions. As these metal ion sources, water-soluble metal salts such as sulfamate, sulfate and chloride can be used. The concentration of these metal ions in the electro-composite plating bath may be a concentration that can be generally used, but is generally preferably 0.1 to 1000 g / L, more preferably 1.0 to 500 g / L in the plating bath composition. .
[0028]
The water-insoluble material used for the electro-composite plating bath of the present invention is not particularly limited as long as it is generally used for composite plating, and the type of electro-composite plating bath and the use of the plating film obtained by the plating are not limited. These water-insoluble materials may be used alone or in a combination of two or more.
[0029]
The present invention is particularly effective when a water-repellent or hydrophobic water-insoluble material is used. Examples of such a water-repellent or hydrophobic water-insoluble material include PTFE, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), fluorine resin such as pitch fluoride, fluorine compound, nylon, polyethylene, and the like. Graphite, graphite fluoride, molybdenum disulfide, boron nitride, titanium oxide, silicon dioxide, alumina, silicon carbide and the like can be exemplified.
[0030]
Further, these water-insoluble materials may be in the form of fine particles or short fibers, but are preferably in the form of fine particles. The particle diameter in the case of fine particles is not particularly limited as long as it is appropriately dispersed in the electro-composite plating bath and has such a particle diameter that it can be co-deposited in the metal matrix in the plating film. In the following, it is preferable to use one having a size of 0.1 to 10 μm. In the case of a short fiber, the length is preferably 100 μm or less, and more preferably about 5 to 100 μm.
[0031]
The fine particles of 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, and MP- Since they are commercially available under the trade names such as 1200 and TLP-10F-1 (all manufactured by DuPont), these can also be used.
[0032]
The content of the water-insoluble material in the electrocomposite plating bath of the present invention is preferably 1,000 g / L or less, more preferably 1 to 300 g / L, in the composition of the plating bath.
[0033]
The preparation of the electro-composite plating bath of the present invention may be carried out using ordinary means such as mixing the above-mentioned components.
[0034]
In addition, in addition to the above-mentioned basic components, additives used for electro-composite plating can be appropriately added to the electro-composite plating bath of the present invention as an optional component within a range not to impair the effects of the present invention.
[0035]
Examples of the additive include a brightener, a smoothing agent, a wetting agent, a stress reducing agent, and the like, a sulfur compound having a sulfonic acid group or the like, a single or multiple bond, and a hydroxy group or a An organic compound having a carbonyl group, a carboxyl group, or the like (for example, a polyhydric alcohol represented by butynediol, a polyether compound represented by polyethylene glycol, or the like), a single bond or a multiple bond, and an amino group A nitrogen compound having one or more of a nitro group, an azo group, or the like (for example, a phenazine dye represented by Janus Green B, etc.) is used depending on the use of the metal ion described above. For example, in the case of performing nickel plating, a plating brightener usually used for electroplating, such as saccharin or butynediol, can be used.
[0036]
Further, in the electrical reduction of the metal plating film, a pH buffer agent capable of depositing the plating film efficiently and uniformly in the reducing atmosphere of the metal and at the metal plating interface can be used as required. Specific examples thereof include a pH buffering agent usually used for electroplating, such as a boron compound such as boric acid and borax, and an organic acid such as citric acid and malonic acid.
[0037]
Further, phosphorus-donating substances such as phosphorous acid, sodium phosphite, hypophosphorous acid, and sodium hypophosphite are used to improve the properties of the plating film, such as improving the appearance of the plating film, relaxing internal stress, and improving the hardness properties. It can be appropriately used for the purpose.
[0038]
In order to carry out the electro-composite plating using the electro-composite plating bath of the present invention thus prepared, a method used in ordinary electro-plating may be used, for example, an electro-composite plating in which a water-insoluble material is uniformly dispersed. By dipping the object to be plated in the bath and performing electroplating, 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.
[0039]
In performing the electro-composite plating, it is preferable that the object to be plated is subjected to a pretreatment such as degreasing for removing oil and acid activity for removing an oxide film. In particular, when the object to be plated has no conductivity, a catalyst is applied by etching, catalyzing, or the like, and a pretreatment such as electroless plating, sputtering, or vapor deposition is performed so that the object to be plated has conductivity. It is preferable to provide it.
[0040]
There are no particular restrictions on the plating conditions for performing the electro-composite plating, and the plating conditions may be the same as in the case of ordinary composite plating.
[0041]
For example, the cathode current density at the time of plating is appropriately determined depending on the concentration and type of metal ions in the plating bath, and the current density usually set in the metal plating bath may be used. / Dm 2 and preferably 1 to 10 A / dm 2 . Further, the pH of the plating bath is preferably about 1 to 7, and preferably 3 to 5. Further, the bath temperature of the plating bath may be about 10 to 80 ° C, and more preferably 20 to 60 ° C.
[0042]
Furthermore, if necessary, the electric composite plating bath can be efficiently stirred by stirring the electric composite plating bath or shaking the object to be plated, and the appearance and physical properties of the plating film can be improved. It is preferable because the effects of the present invention can be sufficiently exhibited. As for the stirring means of these electro-composite plating baths and the swinging means of the object to be plated, means generally used may be appropriately used.
[0043]
In the above-described electro-composite plating method of the present invention, as one of preferred embodiments, for example, an electro-plating method using an electro-nickel composite plating bath containing PTFE as a water-insoluble material and having the following composition is exemplified.
[0044]
In this method, as an object to be plated, a steel plate (for example, a bright steel plate (SPCC-SB)) that has been subjected to a pretreatment by an ordinary method is prepared, and the bath temperature is set to 30 to 70 ° C. and the pH is set to 4 to 5. Immersion in an electro-nickel composite plating bath having the following composition, plating at a current density of the cathode of 0.5 to 10 A / dm 2 for about 10 minutes, to form a Ni having a thickness of 1 to 20 μm on the surface of the body to be plated. / PTFE composite plating film can be formed. The eutectoid amount of PTFE at that time is several to about 40% by volume based on the plating film.
[0045]
(Electro-composite plating bath composition)
Component concentration Nickel sulfamate 350-600 g / L
Nickel chloride 5-90g / L
Boric acid (pH buffer) 30-50g / L
Brightener Appropriate amount fatty acid amidopropyl betaine 20-1000mg / L
(Surfactant)
PTFE 1-100g / L
(Water-insoluble material: average particle size about 0.3 μm)
[0046]
In performing the electro-composite plating using the electro-composite plating bath of the present invention, the concentration of the water-insoluble material in the electro-composite plating bath decreases as the water-insoluble material co-deposits in the plating film as the plating proceeds. Will be done. Therefore, in order to perform electroplating so as to sufficiently exert the effects of the present invention, the water-insoluble material is replenished continuously or at appropriate intervals, and the concentration of the water-insoluble material in the plating bath is adjusted as described above. It is preferable to keep the temperature within a certain range.
[0047]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0048]
Example 1
Confirmation of dispersibility of PTFE in plating bath:
In the following electrocomposite plating bath compositions, 11 types of surfactants (reference products 1 to 11) shown in Table 1 were respectively added, and electrocomposite plating baths of inventive products 1 to 6 and comparative products 1 to 5 were added. Was prepared.
[0049]
(Electro-composite plating bath composition)
Component concentration Nickel sulfamate 400g / L
Nickel chloride 40g / L
Boric acid 40g / L
Saccharin (brightener) Suitable amount of surfactant described in Table 1 500 mg / L
PTFE * 1 20g / L
(Average particle size: about 0.3 μm)
* 1: Zonyl MP-1100 (manufactured by DuPont)
[0050]
(Surfactant used)
[Table 1]
The pH of the plating bath was adjusted to 4.2 using an aqueous sulfamic acid solution or nickel carbonate for these 11 types of electrocomposite plating baths, and then the temperature of the plating bath was set to 50 ° C. (corresponding to the operating temperature of this plating bath). To do). This plating bath was placed in a 1-L beaker and allowed to stand for 30 minutes, after which the dispersion state of PTFE (polytetrafluoroethylene) as a water-insoluble material was compared and evaluated. Table 2 shows the results.
[0052]
(Result)
[Table 2]
The results in Table 2 show that PTFE in the electro-composite plating baths of the present invention products 1 to 6 and the comparative products 1 to 3 show good dispersion even when the plating bath is heated to 50 ° C. Was done. On the other hand, in the electro-composite plating baths of Comparative Products 4 and 5, PTFE agglomeration occurred shortly after the preparation of the plating bath, and it was confirmed that the dispersibility of PTFE in the plating bath was poor.
[0054]
Example 2
Electro-composite plating test (1):
As a sample to be plated, a brass plate (size: 60 mm × 100 mm × 0.3 mm) was used. This sample was subjected to electrobright nickel plating as a base plating under the following conditions using a Mavelite M process (EBARA Ujilight Co., Ltd.).
[0055]
(Undercoat plating conditions)
Plating bath pH (Note): 4.5 (Note)
Plating bath temperature: 55 ° C
Plating time: 10 minutes Stirring conditions: Air stirring Cathode current density: 4 A / dm 2
(Note) The pH was adjusted using a sulfuric acid aqueous solution or nickel carbonate.
After undercoating the sample as described above, Hull cell was prepared under the following plating conditions using the electro-composite plating baths of inventive products 1 to 6 and comparative products 1 to 3 prepared in Example 1. A test was conducted to observe the appearance of the plating film and the occurrence of kogation in the high current density portion.
[0057]
(Plating conditions)
PH of plating bath (Note): 4.2
Plating bath temperature: 50 ° C
Plating time: 2 minutes 30 seconds Stirring conditions: Stirring with a magnetic stirrer (300 rpm)
Cathode current: 3A
(Note) The pH was adjusted using an aqueous solution of sulfamic acid or nickel carbonate.
Example 3
Electro-composite plating test (2):
A stainless plate (size: 60 mm × 100 mm × 0.3 mm) was used as a sample to be plated. First, the sample was subjected to base plating by the means shown in Example 2, and then using the electro-composite plating baths of inventive products 1 to 6 and comparative products 1 to 3 prepared in Example 1, The electro-composite plating was performed under the following plating conditions, and the PTFE eutectoid amount of the plating film was measured.
[0059]
(Plating conditions)
PH of plating bath (Note): 4.2
Plating bath temperature: 50 ° C
Plating time: 20 minutes Stirring conditions: Stirring with magnetic stirrer (300 rpm)
Cathode current density: 4 A / dm 2
(Note) The pH was adjusted using an aqueous solution of sulfamic acid or nickel carbonate.
With respect to the samples after electro-composite plating obtained in Examples 2 and 3, the appearance of the plating film, the state of occurrence of kogation in the high current density portion, and the eutectoid content of PTFE were determined according to the following evaluation criteria. The results are shown in Table 3.
[0061]
(Evaluation criteria: plating film appearance)
The appearance of the sample after the Hull cell test was visually confirmed.
(Evaluation criteria: kogation in high current density area)
The distance at which the kogation was generated from the end face on the high current density side at a position 30 mm from the bottom of the sample after the Hull cell test was measured.
(Evaluation criteria: eutectoid amount of PTFE)
(Result)
[Table 3]
As can be seen from the results in Table 3, the appearance of the coating film of the plating samples using the composite plating baths of the present invention products 1 to 6 was good, and the occurrence of kogation in the high current density portion was also prevented or suppressed. Was something. Further, the PTFE eutectoid content of the plating film was also at a sufficient level.
[0066]
On the other hand, in the sample which was plated using the composite plating bath of Comparative Product 1, the appearance of the film and the amount of PTFE eutectoid were good, but the occurrence of kogation in the high current density portion was remarkable. In Comparative Examples 2 and 3, although the occurrence of kogation in the high current density portion was suppressed, the film appearance was not uniform, and a sufficient amount of PTFE eutectoid was not obtained.
[0067]
【The invention's effect】
The electro-composite plating bath of the present invention is characterized in that fine particles of the water-insoluble material are uniformly dispersed in the plating bath, and the eutectoid content of the fine particles in the plating film in plating is excellent, and the high current density portion Can be prevented or suppressed. Therefore, according to the electro-composite plating bath of the present invention, it is possible to give a plating film a good appearance and to impart excellent functionality. Furthermore, the surfactant used is readily biodegradable and less irritating, so that it is considered for the human body and the environment, and is excellent in safety and environment.
[0068]
Therefore, the electro-composite plating bath and the electro-composite plating method of the present invention can be used for industrial applications such as shafts, bearings, metal masks, slide rails, bearings, bolts, nuts, dies, iron bases, ironing boards, saws, scissors, cutters and kitchen knives. It is advantageously used as an electro-composite plating for household or household products, cooking utensils such as top boards, kitchen utensils such as kitchen bags, kitchen components, flushing fittings such as water faucets, and faucet parts for water and gas. be able to.
that's all
Claims (7)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040451A1 (en) * | 2009-09-29 | 2011-04-07 | Ntn株式会社 | Sliding member |
| JP2011074952A (en) * | 2009-09-29 | 2011-04-14 | Ntn Corp | Slide bearing |
| JP2011137538A (en) * | 2009-12-04 | 2011-07-14 | Ntn Corp | Sliding member |
| CN104109895A (en) * | 2014-07-09 | 2014-10-22 | 哈尔滨工程大学 | Method for forming high-corrosion-resistant nickel and chromium composite coating on steel surface |
| CN110878421A (en) * | 2018-09-06 | 2020-03-13 | 南京农业大学 | Preparation of high-hydrophobicity Ni-Co-P-BN (h) -Al2O3Electrochemical method for binary nano composite coating |
| CN113445107A (en) * | 2021-06-28 | 2021-09-28 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
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2002
- 2002-10-23 JP JP2002307867A patent/JP3771210B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040451A1 (en) * | 2009-09-29 | 2011-04-07 | Ntn株式会社 | Sliding member |
| JP2011074952A (en) * | 2009-09-29 | 2011-04-14 | Ntn Corp | Slide bearing |
| JP2011137538A (en) * | 2009-12-04 | 2011-07-14 | Ntn Corp | Sliding member |
| CN104109895A (en) * | 2014-07-09 | 2014-10-22 | 哈尔滨工程大学 | Method for forming high-corrosion-resistant nickel and chromium composite coating on steel surface |
| CN110878421A (en) * | 2018-09-06 | 2020-03-13 | 南京农业大学 | Preparation of high-hydrophobicity Ni-Co-P-BN (h) -Al2O3Electrochemical method for binary nano composite coating |
| CN110878421B (en) * | 2018-09-06 | 2023-11-24 | 南京农业大学 | Preparation of high-hydrophobicity Ni-Co-P-BN (h) -Al 2 O 3 Electrochemical method of binary nano composite coating |
| CN113445107A (en) * | 2021-06-28 | 2021-09-28 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
| CN113445107B (en) * | 2021-06-28 | 2022-05-13 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
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