JP2002061000A - Composite plating method and composite plated article - Google Patents
Composite plating method and composite plated articleInfo
- Publication number
- JP2002061000A JP2002061000A JP2000253592A JP2000253592A JP2002061000A JP 2002061000 A JP2002061000 A JP 2002061000A JP 2000253592 A JP2000253592 A JP 2000253592A JP 2000253592 A JP2000253592 A JP 2000253592A JP 2002061000 A JP2002061000 A JP 2002061000A
- Authority
- JP
- Japan
- Prior art keywords
- composite plating
- composite
- plating method
- electrolytic treatment
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 34
- 239000010419 fine particle Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 27
- 239000000243 solution Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001096 P alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、複合めっき方法お
よび複合めっき製品に関し、更に詳細には、複合めっき
を施した後で変色等の問題が生じることのない複合めっ
き方法ならびに当該方法により得られる複合めっき製品
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite plating method and a composite plating product, and more particularly, to a composite plating method which does not cause a problem such as discoloration after composite plating and a method obtained by the method. Related to composite plating products.
【０００２】[0002]
【従来の技術】従来より、めっき皮膜に機械的、電子・
電磁気的、光学的、熱的および化学的特性を持たせる目
的で、種々の固体微粒子をめっき皮膜に共析させる複合
めっきが行われている。それらの複合めっきに用いられ
る固体微粒子としては金属酸化物、窒化物、炭化物、硫
化物、フッ化物等の金属化合物ならびに含フッ素樹脂等
の有機ポリマーが知られている。2. Description of the Related Art Conventionally, mechanical, electronic,
For the purpose of imparting electromagnetic, optical, thermal, and chemical properties, composite plating in which various solid fine particles are codeposited on a plating film has been performed. As solid fine particles used for such composite plating, metal compounds such as metal oxides, nitrides, carbides, sulfides and fluorides, and organic polymers such as fluororesins are known.
【０００３】このような複合めっきにより、めっきによ
り得られる金属皮膜に、金属のみでは得られない特有の
効果を付与することが可能であるが、めっき後に表面に
変色ムラを生じ、仕上がり外観が大幅に低下するという
問題があった。[0003] By such a composite plating, it is possible to provide a metal film obtained by plating with a special effect that cannot be obtained by using only metal, but after plating, discoloration unevenness occurs on the surface, and the finished appearance is greatly reduced. There was a problem that it was lowered.
【０００４】このような仕上がり外観の低下は、めっき
された製品の機能には全く影響するものではないため、
従来、ほとんど無視されていたが、実際の製品の選択に
当たって、外観も選択要素の一つであり、めっき製品の
商品価値を引き上げるためにはその解消が求められるこ
とはいうまでもない。[0004] Since such a reduction in the finished appearance does not affect the function of the plated product at all,
In the past, it was almost neglected, but in actual product selection, appearance is also one of the selection factors, and it goes without saying that it must be eliminated in order to increase the commercial value of plated products.
【０００５】[0005]
【発明が解決しようとする課題】従って、めっき後の表
面の変色ムラの発生を防止することができる、機能性と
同時に外観も優れた複合めっき製品を得るための技術の
提供が求められていた。Accordingly, there has been a need to provide a technique for obtaining a composite plated product which can prevent the occurrence of discoloration unevenness on the surface after plating and which has both excellent functionality and excellent appearance. .
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記実状
に鑑み鋭意研究したところ、上記変色ムラの発生の大き
な原因は複合めっき工程において析出固型微粒子ととも
にめっき表面に付着する有機物であること、およびこれ
を防ぐためには電解処理を行えばよいことを見出し、本
発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and found that the major cause of the occurrence of the discoloration unevenness is an organic substance adhering to the plating surface together with precipitated solid fine particles in the composite plating step. The present inventors have found that an electrolytic treatment may be performed to prevent this, and have completed the present invention.
【０００７】すなわち本発明は、被めっき素材に複合め
っきを施した後、これを電解処理することを特徴とする
複合めっき方法を提供するものである。That is, the present invention provides a composite plating method, which comprises subjecting a material to be plated to composite plating and then subjecting the material to electrolytic treatment.
【０００８】また本発明は、上記方法により得られる複
合めっき製品を提供するものである。[0008] The present invention also provides a composite plating product obtained by the above method.
【０００９】[0009]
【発明の実施の形態】本発明の複合めっき方法は、被め
っき素材に常法に従い複合めっきを施し、次いでこれを
電解処理することにより実施される。BEST MODE FOR CARRYING OUT THE INVENTION The composite plating method of the present invention is performed by subjecting a material to be plated to composite plating according to a conventional method, and then subjecting the material to electrolytic treatment.
【００１０】本発明方法でいう複合めっきとは、固体微
粒子をめっき液中に分散させためっき液を利用して行う
めっきであり、固体微粒子を金属と共に共析せしめ、金
属の持つ物性と固体微粒子の持つ物性を同時に奏させる
ことを目的とするものをいう。使用される固体微粒子は
特に制約はないが、特に表面エネルギーの低い固体微粒
子を分散粒子とする複合めっきの場合に本発明方法の効
果が高い。このような表面エネルギーの低い固体微粒子
の例としては、窒化ホウ素、黒鉛、フッ化黒鉛、硫化モ
リブデン等の無機系微粒子や含フッ素化合物、シリコー
ン樹脂、ポリプロピレン樹脂等の有機ポリマー系微粒子
が挙げられる。このうち、含フッ素化合物としては、ポ
リテトラフッ化エチレン（ＰＴＦＥ）、フッ化ビニリデ
ン樹脂、フッ化ビニル樹脂等が、またシリコーン樹脂と
しては、ポリジメチルシロキサン等がそれぞれ挙げられ
る。[0010] The composite plating referred to in the method of the present invention is plating performed by using a plating solution in which solid fine particles are dispersed in a plating solution. Means to simultaneously exhibit the physical properties possessed by The solid fine particles to be used are not particularly limited, but the effect of the method of the present invention is particularly high in the case of composite plating using solid fine particles having low surface energy as dispersed particles. Examples of such solid particles having a low surface energy include inorganic particles such as boron nitride, graphite, graphite fluoride, and molybdenum sulfide, and organic polymer particles such as a fluorine-containing compound, a silicone resin, and a polypropylene resin. Among them, examples of the fluorine-containing compound include polytetrafluoroethylene (PTFE), vinylidene fluoride resin, and vinyl fluoride resin, and examples of the silicone resin include polydimethylsiloxane.
【００１１】本発明の複合めっきにおいて使用される固
体微粒子の粒径は、めっき液中で共析しうる大きさであ
れば特に制約はないが、一般には、０.０１〜１０μｍ
のものを使用することが好ましい。The particle size of the solid fine particles used in the composite plating of the present invention is not particularly limited as long as it can coeutect in the plating solution, but is generally 0.01 to 10 μm.
It is preferable to use
【００１２】また、一般に上記したような表面エネルギ
ーの低い固体微粒子をめっき液に分散させるに当たって
は分散助剤として界面活性剤を添加することが一般的で
あるが、本発明においてはその利用を排除するものでな
い。逆に、後記するように界面活性剤を配合した複合め
っきに対してより効果が高いものである。本発明方法の
複合めっきにおいて分散助剤として使用される界面活性
剤としては、例えば、ＦＣ−１３４（住友スリーエム社
製）、Ｆ１５０（大日本インキ化学社製）等のカチオン
系界面活性剤、トリトンＸ−１００（ユニオンカーバイ
ド社製）等のノニオン系界面活性剤などを挙げることが
できる。In general, when dispersing the solid fine particles having a low surface energy as described above in a plating solution, a surfactant is generally added as a dispersing agent, but the use of the surfactant is excluded in the present invention. Not something to do. Conversely, as will be described later, it is more effective for composite plating containing a surfactant. Examples of the surfactant used as a dispersing aid in the composite plating of the method of the present invention include cationic surfactants such as FC-134 (manufactured by Sumitomo 3M) and F150 (manufactured by Dainippon Ink and Chemicals), and Triton. Non-ionic surfactants such as X-100 (manufactured by Union Carbide) can be used.
【００１３】一方、上記固体微粒子を分散させることに
より、複合めっき液を形成することのできるめっき液
（基本めっき浴）としては、上記微粒子を分散、共析さ
せることのできるものであれば電解、無電解のいずれの
浴を用いても良い。具体的に基本めっき浴の例として
は、ニッケル、ニッケルリン合金、ニッケル鉄合金、
銅、鉄、亜鉛、亜鉛ニッケル合金等のめっき浴が挙げら
れる。また、無電解めっきの具体例としては、ニッケル
リン合金、ニッケルホウ素合金、ニッケルコバルト合
金、ニッケルタングステン合金等のめっき浴が挙げられ
る。On the other hand, as a plating solution (basic plating bath) capable of forming a composite plating solution by dispersing the solid fine particles, an electrolytic solution, which can disperse and eutect the fine particles, Either electroless bath may be used. Specifically, examples of the basic plating bath include nickel, nickel phosphorus alloy, nickel iron alloy,
Plating baths of copper, iron, zinc, zinc-nickel alloys and the like can be mentioned. Further, specific examples of the electroless plating include a plating bath of a nickel phosphorus alloy, a nickel boron alloy, a nickel cobalt alloy, a nickel tungsten alloy, or the like.
【００１４】より具体的な複合めっきの例としては、エ
ンルーブ８５０プロセス（無電解ニッケル／ＰＴＦＥ複
合めっき：荏原ユージライト社製）、テフジットプロセ
ス（電解ニッケル／ＰＴＦＥ複合めっき：荏原ユージラ
イト社製）等の名称で市販されている複合めっきが挙げ
られる。[0014] More specific examples of composite plating include an Enlube 850 process (electroless nickel / PTFE composite plating: manufactured by Ebara Ugelite) and a Tefujit process (electrolytic nickel / PTFE composite plating: manufactured by Ebara Ujilite). And other commercially available composite platings.
【００１５】なお、本発明で複合めっきが施される被め
っき素材としては、金属や、プラスチックを常法により
導電化した素材そのものであっても良く、また、これら
の素材上に、公知の銅めっき、ニッケルめっき等を行っ
たものであっても良く、更に素材またはめっきを施した
素材をサテン状下地加工したものであっても良い。The material to be subjected to the composite plating in the present invention may be a metal or a material itself obtained by making a plastic conductive by an ordinary method. The material may be plated, nickel-plated, or the like, or may be a material or a plated material that has been subjected to a satin base processing.
【００１６】本発明方法における電解処理は、上記の複
合めっきを行った後に行なわれる。この電解処理は、複
合めっきを施された被めっき製品をアルカリ性または中
性の電解処理液に浸漬し、好ましくは陰極電解すること
により行われる。The electrolytic treatment in the method of the present invention is performed after performing the above-described composite plating. This electrolytic treatment is performed by immersing the product to be plated, which has been subjected to the composite plating, in an alkaline or neutral electrolytic treatment solution, preferably by performing cathodic electrolysis.
【００１７】この電解処理に用いられる電解処理液とし
ては、水酸化ナトリウム、水酸化カリウム等のアルカリ
金属化合物水溶液または硫酸ナトリウム、塩化ナトリウ
ム、クエン酸ナトリウム、硫酸カリウム等のアルカリ金
属塩水溶液や、硫酸アンモニウム、クエン酸アンモニウ
ム等のアンモニウム塩水溶液、あるいは公知の電解脱脂
液（例えば、荏原ユージライト社製 Ｅ−２３、ＯＰ−
２２３等）を使用するのが好ましい。Examples of the electrolytic treatment solution used in the electrolytic treatment include an aqueous solution of an alkali metal compound such as sodium hydroxide and potassium hydroxide, or an aqueous solution of an alkali metal salt such as sodium sulfate, sodium chloride, sodium citrate and potassium sulfate; , An ammonium salt aqueous solution such as ammonium citrate, or a known electrolytic degreasing solution (for example, E-23, OP-
223) is preferably used.
【００１８】電解処理液として水酸化ナトリウムを使用
する場合には１〜２００ｇ／Ｌ程度の濃度の水溶液を用
いることが好ましく、特に１０〜１００ｇ／Ｌ程度が好
ましい。また、硫酸アンモニウムを使用する場合には１
〜２００ｇ／Ｌ程度の濃度の水溶液を用いることが好ま
しく、特に１０〜１００ｇ／Ｌ程度の濃度の水溶液が好
ましい。更に、公知の電解脱脂液を用いる場合は、その
指定された量で調製された溶液が好ましい。When sodium hydroxide is used as the electrolytic treatment liquid, it is preferable to use an aqueous solution having a concentration of about 1 to 200 g / L, particularly preferably about 10 to 100 g / L. When ammonium sulfate is used, 1
It is preferable to use an aqueous solution having a concentration of about 200 g / L, particularly an aqueous solution having a concentration of about 10 to 100 g / L. Further, when a known electrolytic degreasing solution is used, a solution prepared in the specified amount is preferable.
【００１９】なお、上記の電解処理液には、更にエチレ
ンジアミン四酢酸、エチレンジアミン等の錯化剤、１,
４−ブチンジオール、プロパギルアルコール等の鉄等の
金属イオン析出抑制剤を添加することもできる。更にま
た、電解時のミストの発生や、飛散を防止するために界
面活性剤を添加することもできる。The above-mentioned electrolytic treatment solution further contains a complexing agent such as ethylenediaminetetraacetic acid or ethylenediamine,
A metal ion precipitation inhibitor such as iron such as 4-butynediol and propargyl alcohol can also be added. Further, a surfactant can be added to prevent generation of mist and scattering during electrolysis.
【００２０】この電解処理は、電解処理液の温度を１０
〜８０℃程度とし、０.１〜２０Ａ／ｄｍ２の電流値
で、５秒〜５分間程度陰極電解を行えばよい。更に好ま
しくは２０〜５０℃程度の温度、１〜１０Ａ／ｄｍ２の
電流値で、３０秒〜２分間程度行えばよいIn this electrolytic treatment, the temperature of the electrolytic treatment solution is set at 10
The cathode electrolysis may be performed at a current value of 0.1 to 20 A / dm 2 for about 5 seconds to 5 minutes. More preferably, the heating may be performed at a temperature of about 20 to 50 ° C. and a current value of 1 to 10 A / dm 2 for about 30 seconds to 2 minutes.
【００２１】以上のように、複合めっき後に電解処理を
行ない、常法に従って水洗、乾燥を行うことにより、表
面保護めっきやその他の表面保護処理を行うことなく変
色や変色ムラの発生を防ぐことが可能となる。なお、よ
り長い変色防止効果を得るために、クロム酸浸漬（例え
ば、２５ｇ／ｌのクロム酸に１分程度浸漬）や電解クロ
メート処理（例えば、Ｅ−５００（荏原ユージライト株
式会社製）中、０.５Ａ／ｄｍ２で１分間電解）等を行
うこともできる。As described above, by performing electrolytic treatment after composite plating, washing with water and drying according to a conventional method, it is possible to prevent discoloration and uneven discoloration without performing surface protection plating and other surface protection treatments. It becomes possible. In order to obtain a longer discoloration prevention effect, immersion in chromic acid (for example, immersion in 25 g / l chromic acid for about 1 minute) or electrolytic chromate treatment (for example, E-500 (manufactured by Ebara Ujilight Co., Ltd.) (Electrolysis at 0.5 A / dm 2 for 1 minute) and the like.
【００２２】[0022]
【作用】本発明方法により、複合めっき、特に表面エネ
ルギーが低い固体微粒子を共析させる複合めっきにおい
て発生する変色を防ぐことのできる作用機序は次のよう
に考えられている。すなわち、複合めっき液中に懸濁さ
せようとする固体微粒子のめっき液に対する濡れ性が悪
かったり、めっき液中に容易に懸濁しない場合、分散助
剤として界面活性剤を添加することが行われる。表面エ
ネルギーが低い固体微粒子にあっては、特に界面活性剤
の添加量を多くする必要がある。The mechanism by which the discoloration that occurs in the composite plating, particularly in the composite plating in which solid fine particles having a low surface energy are codeposited by the method of the present invention, is considered as follows. That is, when the solid fine particles to be suspended in the composite plating solution have poor wettability to the plating solution or do not easily suspend in the plating solution, a surfactant is added as a dispersing aid. . In the case of solid fine particles having a low surface energy, it is particularly necessary to increase the amount of the surfactant added.
【００２３】そして、添加された界面活性剤の一部は、
金属マトリックス表面や固体微粒子に吸着され、更にめ
っき被膜中に共析される。そして、このように吸着され
た有機物や析出した金属面は、めっき後の空気や種々の
ガスとの接触により反応し、変色の原因となるものと考
えられる。A part of the added surfactant is
It is adsorbed on the surface of the metal matrix and solid fine particles, and is eutectoid in the plating film. It is considered that the organic substance and the precipitated metal surface thus adsorbed react with each other by contact with air or various gases after plating and cause discoloration.
【００２４】これに対し、本発明方法では、電解処理に
より、複合めっき表面に付着していた余分な固体微粒
子、また金属マトリックス表面や固体微粒子に吸着して
いた界面活性剤が除去されるため、これらによる変色が
実質的に発生しないものと考えられる。On the other hand, in the method of the present invention, extra solid fine particles adhering to the composite plating surface and a surfactant adsorbed on the metal matrix surface and the solid fine particles are removed by the electrolytic treatment. It is considered that discoloration due to these does not substantially occur.
【００２５】[0025]
【実施例】次に実施例を挙げ、本発明を詳しく説明する
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。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
【００２６】実 施 例 １ ハルセル板による試験（１）：ハルセル板（バフ研磨黄
銅板）に前処理を行った後、８８℃の無電解ニッケル／
ＰＴＦＥ複合めっき浴（エンルーブ８５０プロセス：荏
原ユージライト社製）に３０分間浸漬し、複合めっきを
行った。次いで、表１に示す電解液および温度で、５Ａ
／ｄｍ２で１分間陰極電解処理を行なった。EXAMPLE 1 Test with Hull Cell Plate (1): After pretreatment of Hull cell plate (buff polished brass plate), electroless nickel at 88 ° C.
It was immersed in a PTFE composite plating bath (Enlube 850 process: manufactured by Ebara Uzilite) for 30 minutes to perform composite plating. Then, at the electrolyte and temperature shown in Table 1, 5A
/ Dm 2 for 1 minute.
【００２７】この電解処理後、洗浄、乾燥したハルセル
板の外観を目視で観察し、変色ムラの有無を下記基準に
より評価した。この結果も表１に示す、After the electrolytic treatment, the appearance of the washed and dried Hull cell plate was visually observed, and the presence or absence of discoloration unevenness was evaluated according to the following criteria. This result is also shown in Table 1,
【００２８】変色ムラ評価基準： 評 価 評 価 内 容 ◎ 変色ムラが全く認められない。 ○ 変色ムラが僅かに認められる。 △ 変色ムラがある程度認められる。 × 変色ムラが認められる。Evaluation criteria for discoloration unevenness: Evaluation Evaluation content ◎ No discoloration unevenness is recognized at all.ム ラ Discoloration unevenness is slightly observed. Δ Discoloration unevenness is observed to some extent. C: Discoloration unevenness is observed.
【００２９】[0029]
【表１】 [Table 1]
【００３０】この結果から明らかなように、電解処理す
ることにより、変色ムラの発生を有効に抑制することが
できた。As is clear from the results, the occurrence of discoloration unevenness could be effectively suppressed by the electrolytic treatment.
【００３１】実 施 例 ２ ハルセル板による試験（２）：無電解ニッケル／ＰＴＦ
Ｅ複合めっき（エンルーブ８５０プロセス：荏原ユージ
ライト社製）に代えて電解ニッケル／ＰＴＦＥ複合めっ
き（テフジットプロセス：荏原ユージライト社製）を用
い、５Ａ／ｄｍ２で５分間電解めっきする以外は、実施
例１と同様にして複合めっきを行った。実施例と同様に
ハルセル板の外観を目視で観察し、上記基準により変色
ムラを評価した。この結果を表２に示す。Example 2 Test using Hull cell plate (2): Electroless nickel / PTF
Except that electrolytic nickel / PTFE composite plating (Tefujit process: manufactured by EBARA Eugelite) is used instead of E composite plating (Enlube 850 process: manufactured by EBARA Eugelite) and electrolytic plating is performed at 5 A / dm 2 for 5 minutes. Composite plating was performed in the same manner as in Example 1. The appearance of the Hull cell plate was visually observed in the same manner as in the examples, and the discoloration unevenness was evaluated based on the above criteria. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】この結果から明らかなように、電解めっき
による複合めっきであっても電解処理により、変色ムラ
の発生を有効に抑制することができた。As is clear from the results, even in the case of composite plating by electrolytic plating, the occurrence of discoloration unevenness could be effectively suppressed by the electrolytic treatment.
【００３４】比 較 例 １ 浸漬処理による変色ムラの防止試験：実施例１と同様、
ハルセル板に前処理および無電解ニッケル／ＰＴＦＥ複
合めっきを行った後、表３に示す条件の浸漬液に１分間
浸漬し、変色ムラの発生を実施例１の評価基準に従って
評価した。この結果を表３に示す。Comparative Example 1 Test for Prevention of Discoloration Unevenness by Immersion Treatment: As in Example 1,
After the pretreatment and the electroless nickel / PTFE composite plating were performed on the Hull cell plate, the plate was immersed in an immersion liquid under the conditions shown in Table 3 for 1 minute, and the occurrence of discoloration unevenness was evaluated according to the evaluation criteria of Example 1. Table 3 shows the results.
【００３５】[0035]
【表３】 [Table 3]
【００３６】この結果から明らかなように、アルカリ
性、酸性のいずれの浸漬液を使用した場合でも変色ムラ
の発生を抑制することはできなかった。As is evident from the results, it was not possible to suppress the occurrence of discoloration unevenness when using either an alkaline or acidic immersion liquid.
【００３７】実 施 例 ３ 後処理の併用：実施例１と同様に前処理および無電解ニ
ッケル／ＰＴＦＥ複合めっきを行ったハルセルを、２５
℃の６０ｇ／ｌの水酸化ナトリウム溶液中、５Ａ／ｄｍ
２で１分間陰極電解を行った。次いで後処理として、こ
れを２５ｇ／ｍｌのクロム酸溶液（２５℃）に１分間浸
漬した。水洗、乾燥を行った後、前の実施例と同様にし
て変色ムラの発生を評価したところ、変色ムラの発生は
僅かに認められる程度であった。この後処理をしたもの
は、同条件で電解処理をしただけのものと比べ、耐変色
性に優れたものであった。Example 3 Combination of post-treatment: A hull cell subjected to pre-treatment and electroless nickel / PTFE composite plating in the same manner as
5A / dm in 60 g / l sodium hydroxide solution at 60 ° C
2 for 1 minute. Next, this was immersed in a 25 g / ml chromic acid solution (25 ° C.) for 1 minute as a post-treatment. After washing with water and drying, the occurrence of discoloration unevenness was evaluated in the same manner as in the previous example. The occurrence of discoloration unevenness was slightly recognized. Those subjected to the post-treatment had better discoloration resistance than those subjected to the electrolytic treatment only under the same conditions.
【００３８】また、クロム酸溶液への浸漬に代え、後処
理として電解クロメート処理（エバクロ−５００（荏原
ユージライト株式会社製）、０.５Ａ／ｄｍ２、１分）
を行ったものも、耐変色性に優れたものであった。In addition, instead of immersion in a chromic acid solution, electrolytic chromate treatment (Evacro-500 (manufactured by Ebara Ujilight Co., Ltd.), 0.5 A / dm 2 , 1 minute) is performed as a post-treatment
Was also excellent in discoloration resistance.
【００３９】[0039]
【発明の効果】本発明によれば、複合めっきを施した被
めっき製品に電解処理を施こすことにより、変色ムラの
発生を有意に抑制することができる。従って、外観の良
好な複合めっき製品を得る方法として広く使用すること
ができるものである。 以 上According to the present invention, the occurrence of discoloration unevenness can be significantly suppressed by subjecting a product to be plated subjected to composite plating to electrolytic treatment. Therefore, it can be widely used as a method for obtaining a composite plating product having a good appearance. that's all
Claims (7)
これを電解処理することを特徴とする複合めっき方法。After subjecting a material to be plated to composite plating,
A composite plating method comprising subjecting this to electrolytic treatment.
面エネルギーの低い固体微粒子を界面活性剤により分散
させた分散粒子を含有するめっき液である請求項第１項
記載の複合めっき方法。2. The composite plating method according to claim 1, wherein the plating solution used for the composite plating is a plating solution containing dispersed particles obtained by dispersing solid fine particles having a low surface energy with a surfactant.
フッ素化合物、シリコーン樹脂、ポリプロピレン樹脂、
窒化ホウ素、二硫化モリブデンまたは黒鉛の微粒子であ
る請求項第２項記載の複合めっき方法。3. A solid fine particle having a low surface energy comprises a fluorine-containing compound, a silicone resin, a polypropylene resin,
3. The composite plating method according to claim 2, wherein the composite plating method is fine particles of boron nitride, molybdenum disulfide or graphite.
第１項記載の複合めっき方法。4. The composite plating method according to claim 1, wherein the electrolytic treatment is a cathodic electrolytic treatment.
ルカリ金属化合物、アルカリ金属塩またはアンモニウム
塩を主成分とするものである請求項第１項または第２項
記載の複合めっき方法。5. The composite plating method according to claim 1, wherein the electrolytic treatment solution used in the electrolytic treatment contains an alkali metal compound, an alkali metal salt or an ammonium salt as a main component.
オン析出抑制剤および／または界面活性剤を含有するも
のである請求項第５項記載の複合めっき方法。6. The composite plating method according to claim 5, wherein the electrolytic treatment solution further contains a chelating agent, a metal ion precipitation inhibitor and / or a surfactant.
のめっき方法により得られる複合めっき製品。7. A composite plated product obtained by the plating method according to any one of claims 1 to 6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| JP2010222707A (en) * | 2010-06-07 | 2010-10-07 | Shinshu Univ | Electroless plating method and electroless plating solution |
| US10570518B2 (en) | 2016-08-03 | 2020-02-25 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite plating film |
-
2000
- 2000-08-24 JP JP2000253592A patent/JP2002061000A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| JP4599565B2 (en) * | 2006-10-23 | 2010-12-15 | 国立大学法人信州大学 | Electrolytic plating method and electrolytic plating solution |
| JP2010222707A (en) * | 2010-06-07 | 2010-10-07 | Shinshu Univ | Electroless plating method and electroless plating solution |
| US10570518B2 (en) | 2016-08-03 | 2020-02-25 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite plating film |
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