JP2002060999A - Plating method and plating product - Google Patents
Plating method and plating productInfo
- Publication number
- JP2002060999A JP2002060999A JP2000252554A JP2000252554A JP2002060999A JP 2002060999 A JP2002060999 A JP 2002060999A JP 2000252554 A JP2000252554 A JP 2000252554A JP 2000252554 A JP2000252554 A JP 2000252554A JP 2002060999 A JP2002060999 A JP 2002060999A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- solution
- electrolytic treatment
- fine particles
- plated
- 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000010419 fine particle Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 8
- 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 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 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
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 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
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 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
- 239000012670 alkaline solution 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
- 239000010974 bronze Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007772 electroless plating Methods 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
- 229910052742 iron Inorganic materials 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
- 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
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000005406 washing Methods 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、めっき方法および
めっき製品に関し、更に詳細には、表面保護めっきを施
した後で黒色の斑点を生じることのないめっき方法なら
びに当該方法により得られるめっき製品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plating method and a plated product, and more particularly to a plating method that does not produce black spots after surface protection plating, and a plated product obtained by the method. .
【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】本発明者らは先に、含フッ素化合物粒子を
含有する複合めっきにより、高級感ある渋い半光沢〜光
沢のめっき外観を持ちかつ、撥水性のあるめっき製品が
得られることを見出し、報告している（特願平１１−２
８５１５８号）。このようにして得られためっき製品
は、優れた外観および撥水性を有するため、商品価値の
高いものであるが、表面保護めっきとしてクロムめっき
を施した後の表面に黒色の斑点（いわゆる「シミ」）が
生じやすいという問題があることを見出した。The present inventors have previously found that a composite product containing fluorine-containing compound particles can provide a plated product having a high-grade, astringent, semi-glossy to glossy plating appearance and water repellency. Reported (Japanese Patent Application No. 11-2)
No. 85158). The plated product thus obtained has excellent appearance and water repellency, and therefore has high commercial value. However, black spots (so-called “stains”) appear on the surface after chromium plating as surface protective plating. ") Is likely to occur.
【０００４】このようなシミは、めっきされた製品の機
能には影響するものではないが、実際の製品の選択に当
たって、外観は大きな要素であり、このシミがめっき製
品の商品価値を引き下げるものであることはいうまでも
ない。[0004] Although such stains do not affect the function of the plated product, appearance is a major factor in selecting an actual product, and these stains reduce the commercial value of the plated product. Needless to say, there is.
【０００５】[0005]
【発明が解決しようとする課題】従って、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には、複合め
っきを施した後に表面保護めっきを施しても、シミを生
じることがなく、めっき製品の外観を損なわない技術の
提供が求められていた。Therefore, in order to obtain a composite plated product having excellent appearance as well as functionality, even if surface protection plating is performed after composite plating is applied, spots are not generated and plating is performed. There has been a demand for providing a technology that does not impair the appearance of the product.
【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、複合めっき工程と表面保護
めっき工程の間で電解処理を行うことで黒色斑点をなく
したり、減少させることができることを見出し、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 black spots can be eliminated or reduced by performing an electrolytic treatment between the composite plating step and the surface protection plating step. And found that the present invention was completed.
【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、これに電解処理を施し、更に表面保護
めっきを施すことを特徴とするめっき方法を提供するも
のである。That is, the present invention provides a plating method, which comprises subjecting a material to be plated to composite plating, subjecting the material to electrolytic treatment, and further performing surface protection plating.
【０００８】また本発明は、上記方法により得られるめ
っき製品を提供するものである。[0008] The present invention also provides a plated product obtained by the above method.
【０００９】[0009]
【発明の実施の形態】本発明のめっき方法は、被めっき
素材に常法に従い複合めっきを施し、次いで電解処理し
た後、表面保護めっきを施すことにより実施される。BEST MODE FOR CARRYING OUT THE INVENTION The plating method of the present invention is carried out by subjecting a material to be plated to composite plating according to a conventional method, followed by electrolytic treatment, and then to surface protection plating.
【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、ポリジメ
チルシロキサン（ＰＤＭＳ）、ポリプロピレン（ＰＰ）
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（Ｐ
ＴＦＥ）、フッ化ビニリデン樹脂、フッ化ビニル樹脂等
が挙げられる。[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 fine particles having a low surface energy include inorganic fine particles such as boron nitride, graphite, graphite fluoride, and molybdenum sulfide, fluorine-containing compounds, polydimethylsiloxane (PDMS), and polypropylene (PP).
And other organic polymer-based fine particles. Of these, polytetrafluoroethylene (P
TFE), vinylidene fluoride resin, vinyl fluoride resin and the like.
【００１１】本発明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 present invention is not particularly limited as long as it can coeutect in the plating solution. Generally, the fine particles having a particle size of 0.01 to 10 μm are used. preferable.
【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等を挙げることがで
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電解処理液に浸漬
し、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 a product to be plated subjected to composite plating in an electrolytic treatment solution and 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、電導性の高い溶液であれば酸性あるいはアルカリ
性のいずれの溶液でも良いが、特に酸性溶液としてはク
ロム酸および硫酸の混合溶液が好ましく、アルカリ性溶
液としては水酸化ナトリウム水溶液や、公知の電解脱脂
液（例えば、荏原ユージライト社製 Ｅ−２３）、ある
いはこれに更に水酸化ナトリウムを追加した溶液を使用
するのが好ましい。The electrolytic treatment solution used in the electrolytic treatment may be any of an acidic solution and an alkaline solution as long as it has a high conductivity. Particularly, the acidic solution is preferably a mixed solution of chromic acid and sulfuric acid. As the solution, it is preferable to use an aqueous solution of sodium hydroxide, a known electrolytic degreasing solution (for example, E-23 manufactured by Ebara Uzilite Co., Ltd.), or a solution in which sodium hydroxide is further added thereto.
【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１〜５００ｇ／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、クロム酸および硫酸の混合溶液を使用す
る場合には、クロム酸が１〜３００ｇ／Ｌ程度、硫酸が
０.０１〜３ｇ／Ｌ程度の濃度の水溶液を用いることが
好ましく、特にクロム酸が５〜５０ｇ／Ｌ程度、硫酸が
０.０５〜０.５ｇ／Ｌ程度の濃度の水溶液が好ましい。
更に、水酸化ナトリウムを使用する場合には水酸化ナト
リウムが１０〜１００ｇ／Ｌ程度の水溶液が好ましく、
公知の電解脱脂液を用いる場合は、その指定された量で
調製された溶液ないしこれに水酸化ナトリウムを５〜１
００ｇ／Ｌ程度追加した溶液が好ましい。When sodium hydroxide is used as the electrolytic treatment solution, it is preferable to use an aqueous solution having a concentration of about 1 to 500 g / L, particularly preferably about 10 to 100 g / L. When a mixed solution of chromic acid and sulfuric acid is used, it is preferable to use an aqueous solution having a concentration of about 1 to 300 g / L for chromic acid and about 0.01 to 3 g / L for sulfuric acid. An aqueous solution having a concentration of about 5 to 50 g / L and sulfuric acid of about 0.05 to 0.5 g / L is preferable.
Further, when sodium hydroxide is used, an aqueous solution of sodium hydroxide of about 10 to 100 g / L is preferable,
When a known electrolytic degreasing solution is used, sodium hydroxide is added to the solution prepared in the specified amount or sodium hydroxide.
A solution added by about 00 g / L is preferable.
【００１９】この電解処理は、電解処理液の温度を１０
〜８０℃程度とし、０.０１〜２０Ａ／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、０.２〜１０Ａ／ｄｍ
２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 0.01 to 20 A / dm 2 for about 5 seconds to 5 minutes. More preferably, a temperature of about 20 to 50 ° C., 0.2 to 10 A / dm
It may be performed at a current value of 2 for about 30 seconds to 2 minutes.
【００２０】本発明方法においては、上記電解処理後に
耐摩耗性や耐食性を向上させたり、外観をよくするため
に表面保護めっきを行う。In the method of the present invention, after the above-mentioned electrolytic treatment, surface protection plating is performed to improve abrasion resistance and corrosion resistance and to improve appearance.
【００２１】この表面保護めっきは、装飾性、耐食性、
耐摩耗性等を付与させるために行われるものであり、特
に制約されるものではないが、その例としては、クロム
めっき、金めっき、スズニッケル合金めっき、スズめっ
き、スズコバルト合金めっき等が挙げられる。これらの
めっきはいずれも周知なものであり、そのめっき条件は
一般的なもので良く、また膜厚もめっき製品の用途に応
じて適宜定められる。This surface protective plating has decorative properties, corrosion resistance,
It is performed to impart abrasion resistance and the like, and is not particularly limited. Examples thereof include chrome plating, gold plating, tin nickel alloy plating, tin plating, and tin cobalt alloy plating. . These platings are all well-known, and the plating conditions may be general ones, and the film thickness is appropriately determined according to the use of the plated product.
【００２２】なお、本発明方法において、表面保護めっ
きとしてクロムめっきを使用する場合は、クロムめっき
後の水洗液（薄いクロム酸水溶液となっている）を電解
処理液とし、これをクロムめっき槽の前に設けた電解処
理槽に送れば、クロム酸を含むめっき排液を減少させる
こともできるので、より経済的である。In the method of the present invention, when chromium plating is used as the surface protective plating, a washing solution (a thin chromic acid aqueous solution) after chromium plating is used as an electrolytic treatment solution, and this is used as a chromium plating tank. If the solution is sent to the previously provided electrolytic treatment tank, the plating effluent containing chromic acid can be reduced, which is more economical.
【００２３】以上説明した本発明方法によれば、従来の
方法である複合めっき後の表面保護めっきの際に生じる
黒色斑点を減少あるいは全くない状態にすることが可能
となる。According to the method of the present invention described above, it is possible to reduce or eliminate black spots generated during surface protection plating after composite plating, which is a conventional method.
【００２４】[0024]
【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
て発生する黒斑状のシミ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 method of the present invention can prevent black spots generated in composite plating, particularly in composite plating in which solid fine particles having low surface energy are co-deposited, 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.
【００２５】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。次の表面保護めっき工程にお
いて、複合めっき表面に付着した余分な固体微粒子ある
いは金属マトリックス表面や固体微粒子に吸着した界面
活性剤等が低電流部を中心に残存すると、それらの影響
により黒色のシミになると考えられる。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. In the next surface protection plating step, if extra solid fine particles adhering to the composite plating surface or surfactants adsorbed on the metal matrix surface or solid fine particles remain mainly in the low current area, they will cause black stains due to these effects. It is considered to be.
【００２６】これに対し、本発明方法では、電解処理に
より発生する水素ガスにより、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、黒色のしみ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 or the solid fine particles are caused by the hydrogen gas generated by the electrolytic treatment. It is considered that black spots are not substantially generated because they are removed.
【００２７】[0027]
【実施例】次に実施例、比較例および試験例を挙げ、本
発明を詳しく説明するが、本発明はこれら実施例等に何
ら制約されるものではない。EXAMPLES Next, the present invention will be described in detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples and the like.
【００２８】実 施 例 １ ベントカソードへのめっき（１）：ベントカソード（バ
フ研磨黄銅板）に前処理を行った後、電解ニッケル／Ｐ
ＴＦＥ複合めっき（テフジットプロセス：荏原ユージラ
イト社製）に５Ａ／ｄｍ２で３分間めっきを行った。次
いで、電解処理を行うために、２５℃の電解処理液（水
酸化ナトリウム：６０ｇ／Ｌ）に５Ａ／ｄｍ２で１分
間、陰極電解処理を行った。最後に表面保護めっきとし
てクロムめっき液（Ｋ−４０：荏原ユージライト社製）
に１８Ａ／ｄｍ２で４５秒間めっきを行った。EXAMPLE 1 Plating on Bent Cathode (1): After performing a pretreatment on the vent cathode (buff polished brass plate), electrolytic nickel / P
TFE composite plating (Tefujit process: manufactured by Ebara Eugerite Co.) was plated at 5 A / dm 2 for 3 minutes. Next, in order to perform the electrolytic treatment, a cathodic electrolytic treatment was performed at 25 A / dm 2 for 1 minute in an electrolytic treatment solution (sodium hydroxide: 60 g / L) at 25 ° C. Finally, a chromium plating solution (K-40: manufactured by Ebara Ujilight Co., Ltd.) as surface protection plating
Was plated at 18 A / dm 2 for 45 seconds.
【００２９】実 施 例 ２ ベントカソードへのめっき（２）：電解処理液をクロム
酸２０ｇ／Ｌおよび硫酸０.２ｇ／Ｌからなる溶液に変
え、さらに５Ａ／ｄｍ２で陰極電解処理を行う以外は、
実施例１と同様のめっき工程を行った。Example 2 Plating on bent cathode (2): Except that the electrolytic treatment solution was changed to a solution containing 20 g / L of chromic acid and 0.2 g / L of sulfuric acid, and the cathodic electrolytic treatment was performed at 5 A / dm 2. Is
The same plating process as in Example 1 was performed.
【００３０】実 施 例 ３ ベントカソードへのめっき（３）：電解処理液を水酸化
ナトリウム５０ｇ／ＬおよびＥ−２３* ５０ｇ／Ｌから
なる溶液に変えて陰極電解処理を行う以外は実施例１と
同様のめっき工程を行った。 * 荏原ユージライト社製電解脱脂剤Example 3 Plating on bent cathode (3): Example 1 except that the electrolytic treatment solution was changed to a solution containing 50 g / L of sodium hydroxide and 50 g / L of E-23 * to carry out the cathodic electrolytic treatment. The same plating process was performed. * Electrolytic degreasing agent manufactured by EBARA Eugerite
【００３１】比 較 例 １ ベントカソードへのめっき：陰極電解処理を行わない以
外は 実施例１と同様に電解ニッケル／ＰＴＦＥ複合め
っきをベントカソード上に析出させた。Comparative Example 1 Plating on bent cathode: Electrolytic nickel / PTFE composite plating was deposited on the bent cathode in the same manner as in Example 1 except that the cathodic electrolytic treatment was not performed.
【００３２】試 験 例 １ 上記実施例１〜３および比較例１で得られためっき製品
についてその外観を観察した。また、めっき平面部に水
滴を滴下し、めっき面と水滴との接触角を市販の接触角
測定器で測定した。それらの結果を表１に示す。Test Example 1 The appearance of the plated products obtained in Examples 1 to 3 and Comparative Example 1 was observed. Further, a water drop was dropped on the plating plane portion, and the contact angle between the plating surface and the water drop was measured with a commercially available contact angle measuring instrument. Table 1 shows the results.
【００３３】[0033]
【表１】 [Table 1]
【００３４】表１から明らかなように、本発明法によれ
ば複合めっき後の表面保護めっき前に電解処理を行うこ
とで、電解処理を行わないものにくらべて黒色斑点の少
ない光沢のある良好な外観が得られる。また、この電解
処理を行っても撥水性能は損なわれていなかった。As is clear from Table 1, according to the method of the present invention, by performing the electrolytic treatment before the surface protective plating after the composite plating, a glossy good with less black spots is obtained as compared with the one without the electrolytic treatment. Appearance is obtained. In addition, the water repellency was not impaired by the electrolytic treatment.
【００３５】以上の結果から、本発明方法により極低電
流部では若干の黒色斑点が残るものの、全体としては優
れた外観を得ることができることが明らかとなった。From the above results, it has been clarified that the method of the present invention can obtain an excellent appearance as a whole, though some black spots remain in the extremely low current portion.
【００３６】実 施 例 ４ 水栓金具へのめっき（１）：水栓金具（青銅鋳物）に前
処理を行った後、光沢ニッケルめっき液（＃６６：荏原
ユージライト製）に５Ａ／ｄｍ２で５分間めっきを行っ
た。次いで、サテン状ニッケルめっきを施すためにパー
ルブライト（ＬＰＷ社製）に５Ａ／ｄｍ２で５分間めっ
きを行った。その後、電解ニッケル／ＰＴＦＥ複合めっ
き液（テフジットプロセス：荏原ユージライト社製）に
５Ａ／ｄｍ２で３分間めっきを行った。Example 4 Plating on faucet fittings (1): After pretreatment of faucet fittings (bronze casting), 5 A / dm 2 was applied to bright nickel plating solution (# 66: Ebara Uzilite). For 5 minutes. Next, pearl bright (manufactured by LPW) was plated at 5 A / dm 2 for 5 minutes in order to apply a satin nickel plating. Thereafter, plating was performed at 5 A / dm 2 for 3 minutes on an electrolytic nickel / PTFE composite plating solution (Tefujit process: manufactured by Ebara Uzilite).
【００３７】次いで、電解処理を行うために、２５℃の
電解処理液（水酸化ナトリウム：６０ｇ／Ｌ）に５Ａ／
ｄｍ２で１分間、陰極電解処理を行った。最後に表面保
護めっきとしてクロムめっき液（Ｋ−４０：荏原ユージ
ライト社製）に１８Ａ／ｄｍ ２で３分間めっきを行っ
た。Next, in order to carry out the electrolytic treatment, at 25 ° C.
5A / in electrolytic treatment solution (sodium hydroxide: 60 g / L)
dm2For 1 minute. Finally, surface protection
Chromium plating solution (K-40: Ebara Eiji)
18A / dm 2Plating for 3 minutes
Was.
【００３８】実 施 例 ５ 水栓金具へのめっき（２）：電解処理液をクロム酸２０
ｇ／Ｌおよび硫酸０.２ｇ／Ｌからなる混合溶液に変
え、さらに０.５Ａ／ｄｍ２で陰極電解処理を行う以外
は、実施例４と同様のめっき工程を行った。Example 5 Plating on faucet fittings (2): Chromic acid 20
The same plating process as in Example 4 was performed, except that the mixed solution was changed to a mixed solution consisting of g / L and 0.2 g / L of sulfuric acid, and further subjected to cathodic electrolysis at 0.5 A / dm 2 .
【００３９】実 施 例 ６ 水栓金具へのめっき（３）：電解処理液を水酸化ナトリ
ウム５０ｇ／ＬおよびＥ−２３* ５０ｇ／Ｌからなる混
合溶液に変えて陰極電解処理を行う以外は、実施例４と
同様のめっき工程を行った。* 荏原ユージライト社製電
解脱脂剤Example 6 Plating on faucet fittings (3): Cathodic electrolytic treatment was performed except that the electrolytic treatment solution was changed to a mixed solution consisting of 50 g / L of sodium hydroxide and 50 g / L of E-23 * . The same plating process as in Example 4 was performed. * Electrolytic degreasing agent manufactured by EBARA Eugerite
【００４０】比 較 例 ２ 水栓金具へのめっき：陰極電解処理を行わない以外は、
実施例４と同様のめっき工程を行った。COMPARATIVE EXAMPLE 2 Plating on faucet fittings:
The same plating process as in Example 4 was performed.
【００４１】試 験 例 ２ 上記実施例４〜６および比較例２で得られためっき製品
についてその外観を観察した。また、めっき平面部に水
滴を滴下し、めっき面と水滴との接触角を市販の接触角
測定器で測定した。それらの結果を表２に示す。Test Example 2 The appearance of the plated products obtained in Examples 4 to 6 and Comparative Example 2 was observed. Further, a water drop was dropped on the plating plane portion, and the contact angle between the plating surface and the water drop was measured with a commercially available contact angle measuring instrument. Table 2 shows the results.
【００４２】[0042]
【表２】 [Table 2]
【００４３】表２の結果から、実際の製品においては、
本発明法により、黒色斑点のないサテン状の良好な外観
が得られることが明らかとなった。また、この電解処理
を行っても撥水性能は損なわれなかった。From the results in Table 2, in the actual product,
It has been clarified that the method of the present invention can provide a good satin appearance without black spots. Further, even when this electrolytic treatment was performed, the water repellency was not impaired.
【００４４】[0044]
【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した後、表面保護めっきを行
うことにより、電解処理を施さないものに比べて黒色斑
点が実質的に発生しない、良好な外観を有する複合めっ
き製品が得られる。 以 上According to the present invention, by subjecting a product to be plated subjected to composite plating to electrolytic treatment and then performing surface protection plating, black spots are substantially reduced as compared with those not subjected to electrolytic treatment. A composite plating product having a good appearance that does not occur is obtained. that's all
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西川 賢一 神奈川県藤沢市善行坂１−１−６ 荏原ユ ージライト株式会社中央研究所内 (72)発明者 今本 光男 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内 (72)発明者 河本 理之 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内 Ｆターム(参考） 4K024 AA02 AA03 AA07 AA11 AA21 AA23 AB02 AB03 AB12 BA09 BB15 DA02 DB04 DB10 GA02 GA04 GA16 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kenichi Nishikawa 1-1-6 Yoshiyukizaka, Fujisawa-shi, Kanagawa Ebara Ujilight Co., Ltd. Central Research Laboratory (72) Inventor Mitsuo Imamoto 2 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka No. 1-1, Toto Kiki Co., Ltd. (72) Inventor Noriyuki Kawamoto 2-1-1, Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka F-term in Toto Kiki Co., Ltd. 4K024 AA02 AA03 AA07 AA11 AA21 AA23 AB02 AB03 AB12 BA09 BB15 DA02 DB04 DB10 GA02 GA04 GA16
Claims (8)
これを電解処理し、更に表面保護めっきを施すことを特
徴とするめっき方法。After subjecting a material to be plated to composite plating,
A plating method comprising subjecting the resultant to electrolytic treatment and further performing surface protection plating.
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
記載のめっき方法。2. The 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、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項記載のめっき方
法。3. The plating method according to claim 2, wherein the solid fine particles having a low surface energy are fine particles of a fluorine-containing compound, a resin, boron nitride, molybdenum disulfide or graphite.
第１項記載のめっき方法。4. The plating method according to claim 1, wherein the electrolytic treatment is a cathodic electrolytic treatment.
を含有する溶液である請求項第４項記載のめっき方法。5. The plating method according to claim 4, wherein the solution used for the cathodic electrolysis is a solution containing chromic acid.
トリウムを含有する溶液である請求項第４項記載のめっ
き方法。6. The plating method according to claim 4, wherein the solution used for the cathodic electrolysis is a solution containing sodium hydroxide.
き、スズニッケル合金めっき、スズめっきまたはスズコ
バルト合金めっきから選ばれるめっきの何れかである請
求項第１項記載のめっき方法。7. The plating method according to claim 1, wherein the surface protection plating is any one selected from chromium plating, gold plating, tin nickel alloy plating, tin plating, and tin cobalt alloy plating.
のめっき方法により得られるめっき製品。8. A plated product obtained by the plating method according to any one of claims 1 to 7.
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|---|---|---|---|
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|---|---|---|---|
| JP2000252554A JP4627848B2 (en) | 2000-08-23 | 2000-08-23 | Plating method and plated product |
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| Publication Number | Publication Date |
|---|---|
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|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59145793A (en) * | 1983-02-08 | 1984-08-21 | Toppan Printing Co Ltd | Partial silver plating method |
| JPS61139695A (en) * | 1984-12-12 | 1986-06-26 | Hitachi Cable Ltd | Post treatment for silver plated product |
| JPH02232394A (en) * | 1989-03-06 | 1990-09-14 | Furukawa Electric Co Ltd:The | Anticorrosive treatment of plated material |
| JPH0598466A (en) * | 1991-10-08 | 1993-04-20 | Ebara Yuujiraito Kk | Nickel-chromium plating method and apparatus |
| JPH11193480A (en) * | 1997-12-26 | 1999-07-21 | Osaka Gas Co Ltd | Corrosion-resistant composite plating film and cooking utensil using the film |
| JPH11335859A (en) * | 1998-05-26 | 1999-12-07 | Protonics Kenkyusho:Kk | Composite gold plating film, its production and electrical contact having the composite gold plating film |
-
2000
- 2000-08-23 JP JP2000252554A patent/JP4627848B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59145793A (en) * | 1983-02-08 | 1984-08-21 | Toppan Printing Co Ltd | Partial silver plating method |
| JPS61139695A (en) * | 1984-12-12 | 1986-06-26 | Hitachi Cable Ltd | Post treatment for silver plated product |
| JPH02232394A (en) * | 1989-03-06 | 1990-09-14 | Furukawa Electric Co Ltd:The | Anticorrosive treatment of plated material |
| JPH0598466A (en) * | 1991-10-08 | 1993-04-20 | Ebara Yuujiraito Kk | Nickel-chromium plating method and apparatus |
| JPH11193480A (en) * | 1997-12-26 | 1999-07-21 | Osaka Gas Co Ltd | Corrosion-resistant composite plating film and cooking utensil using the film |
| JPH11335859A (en) * | 1998-05-26 | 1999-12-07 | Protonics Kenkyusho:Kk | Composite gold plating film, its production and electrical contact having the composite gold plating film |
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|---|---|
| JP4627848B2 (en) | 2011-02-09 |
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