JP2010084224A - Method of manufacturing plated molded article using no nickel, and plated molded article - Google Patents
Method of manufacturing plated molded article using no nickel, and plated molded article Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 34
- 229910052759 nickel Inorganic materials 0.000 title description 17
- 238000007747 plating Methods 0.000 claims abstract description 207
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 71
- 239000011651 chromium Substances 0.000 claims abstract description 71
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 description 41
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 23
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000239290 Araneae Species 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000007815 allergy Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- -1 chromium sulfate) Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229910001128 Sn 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
- 239000012345 acetylating agent Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 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 1
- 238000009863 impact test Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 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
- 239000002994 raw material Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、各種の金属およびＡＢＳ、ＰＣ/ＡＢＳ、ナイロンなどの樹脂素材に対して、ニッケルを使用することなく良好な外観、耐食性および耐磨耗性を有するめっき皮膜を形成するめっき成形品の製造方法およびその方法によって得られためっき成形品に関する。 The present invention relates to a plated molded article that forms a plating film having good appearance, corrosion resistance and wear resistance without using nickel on various metals and resin materials such as ABS, PC / ABS, and nylon. The present invention relates to a manufacturing method and a plated molded product obtained by the method.
ニッケルめっきは優れた色調、耐食性などの特性を有し、クロムめっきを始めとする装飾めっきの下地めっきとしても使用される重要なめっき技術である。 Nickel plating has excellent characteristics such as color tone and corrosion resistance, and is an important plating technique used as a base plating for decorative plating such as chromium plating.
しかし、ニッケルめっきが施された装飾品などを身に付けた場合、汗などによってニッケルめっきが溶出することで肌にかぶれ、湿疹、炎症などを引き起こすこと（ニッケルアレルギー）が問題となっている。 However, when wearing a nickel-plated ornament or the like, there is a problem that the nickel plating is eluted by sweat or the like, causing skin irritation, eczema, inflammation, etc. (nickel allergy).
携帯電話、デジタルカメラなどの携帯機器を含む電化製品では、低コストあるいは軽量化のために成形品としてＡＢＳ，ＰＣ/ＡＢＳ、ナイロンなどに代表される樹脂が広く使用されている。これらの樹脂よりなるめっき成形品では、最外層に外観、耐磨耗性、耐食性の点で優れた特性を有するクロムめっきが使用される場合が多い。 In electrical appliances including mobile devices such as mobile phones and digital cameras, resins typified by ABS, PC / ABS, nylon and the like are widely used as molded articles for low cost or light weight. In plating molded products made of these resins, chrome plating having excellent characteristics in terms of appearance, wear resistance, and corrosion resistance is often used for the outermost layer.
このような場合においても下地層であるニッケルが外部に溶出しないこと、あるいはニッケルめっきを使用しないことが要求される。 Even in such a case, it is required that nickel as an underlayer does not elute to the outside or that nickel plating is not used.
現在、ニッケル代替めっきとしては、銅４０〜５５％、スズ（スペキュラム）合金皮膜が検討されており、ニッケルめっき使用しない樹脂めっき成形品の一般的な皮膜構造としては、樹脂素材/光沢硫酸銅/銅−スズ合金めっき/クロムめっきである。 Currently, 40-55% copper and tin (spectrum) alloy coatings are being investigated as nickel alternative plating, and the general coating structure of resin plating molded products that do not use nickel plating is resin materials / bright copper sulfate / Copper-tin alloy plating / chrome plating.
しかしながら、銅−スズ合金めっきは、銅（Ｅ０＝+0.337Ｖ）とスズ（Ｅ０＝-0.136Ｖ）の析出電位の差が大きく、合金めっきを得るためには析出電位を接近させる必要がある。このために、めっき浴中に錯化剤を添加することが必要となるが、銅−スズ合金めっき浴では、有害なシアンを錯化剤に使用したものが多くある。 However, copper-tin alloy plating has a large difference in precipitation potential between copper (E 0 = + 0.337 V) and tin (E 0 = −0.136 V), and it is necessary to bring the precipitation potential close to obtain alloy plating. is there. For this reason, it is necessary to add a complexing agent to the plating bath, but many copper-tin alloy plating baths use harmful cyanide as the complexing agent.
このシアンを含有する銅−スズ合金めっき浴を樹脂めっきに使用する場合、光沢硫酸銅めっき後に銅−スズ合金めっき浴（シアン含有）に浸漬すると、成形品表面と硫酸銅めっき皮膜の界面部分からシアンを含むめっき液のしみ込みが起こり、このことが原因となり、成形品表面/光沢硫酸銅めっき皮膜の間で剥離が発生する場合がある。 When this copper-tin alloy plating bath containing cyanide is used for resin plating, if it is immersed in a copper-tin alloy plating bath (containing cyan) after bright copper sulfate plating, from the interface between the molded product surface and the copper sulfate plating film Penetration of cyan-containing plating solution occurs, which may cause peeling between the surface of the molded product and the bright copper sulfate plating film.
近年では、有害なシアンを含有しない銅−スズ合金めっき浴（ピロリン酸浴など）が開発されており、この浴を使用した場合には、上記のめっき液の染み込みによる剥離に関する問題は解決される。 In recent years, copper-tin alloy plating baths (such as pyrophosphoric acid baths) that do not contain harmful cyanides have been developed, and when these baths are used, the above-mentioned problems relating to peeling due to penetration of the plating solution are solved. .
しかし、シアンを含有しない銅−スズ合金めっき浴においても以下に示すような問題が存在する。 However, the following problems also exist in a copper-tin alloy plating bath not containing cyan.
（１）シアン含有のめっき浴を使用して形成した皮膜と比較すると、めっき皮膜の硬度が低いため、必要な耐磨耗性を確保するためにめっき皮膜の膜厚を厚くすることが必要である。しかし、
（２）皮膜の応力がシアン含有のめっき浴からの皮膜と比較すると高いため、充分な耐磨耗性を確保するために膜厚を増加すると、皮膜にクラックが発生する。
(1) Compared to a film formed using a cyanide-containing plating bath, the plating film has a lower hardness, so it is necessary to increase the thickness of the plating film in order to ensure the necessary wear resistance. is there. But,
(2) Since the stress of the film is higher than that of a film from a cyan-containing plating bath, if the film thickness is increased in order to ensure sufficient wear resistance, cracks occur in the film.
（３）強い錯化剤であるシアンを使用していないため、めっき液が不安定であり、浴寿命が短くなり、生産コストが上がる。 (3) Since cyan, which is a strong complexing agent, is not used, the plating solution is unstable, the bath life is shortened, and the production cost is increased.
例えば、特開２００８−１４３１６９号公報（特許文献１）には、版母材と、その版母材の表面に設けられかつ表面に多数のグラビアセルが形成された銅めっき皮膜と、銅めっき皮膜の表面を被覆する３価クロムめっき液から得られるクロムめっき皮膜とを含み、クロムめっき皮膜を過熱水蒸気によって加熱処理したグラビア製版ロールが開示されている。 For example, Japanese Patent Laid-Open No. 2008-143169 (Patent Document 1) discloses a plate base material, a copper plating film provided on the surface of the plate base material, and having a number of gravure cells formed on the surface, and a copper plating film And a chromium plating film obtained from a trivalent chromium plating solution that coats the surface of the film, and a gravure platemaking roll in which the chromium plating film is heated with superheated steam.
しかし、この特許文献１では、３価クロムめっき皮膜を過熱水蒸気によって加熱処理することが必要であるので、生産性が低下する。また、得られた３価クロムめっき皮膜は、外観、耐食性および耐磨耗性が不十分である。
本発明は、上記した従来技術の問題点に鑑みてなされたものであり、その主な目的は従来のニッケルを使用しないめっきの問題点、特に、銅−スズ合金めっきを用いることなく、優れた外観、耐食性、耐磨耗性を有するめっき皮膜構造および工業的に使用可能な処理工程を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and the main purpose thereof is the problem of plating without using conventional nickel, particularly without using copper-tin alloy plating. An object is to provide a plating film structure having an appearance, corrosion resistance, and abrasion resistance, and a processing step that can be used industrially.
本発明者は、上記の目的を達成するべく、鋭意研究を重ねてきた。 The present inventor has intensively studied to achieve the above object.
その結果、ニッケルめっきを使用することなく、従来の膜構造と同等の外観、耐食性、耐磨耗性を有する皮膜構造および処理工程を見出し、ここに本発明を完成するに至った。 As a result, without using nickel plating, the present inventors have found a coating structure and processing steps having appearance, corrosion resistance, and abrasion resistance equivalent to those of a conventional film structure, and have completed the present invention.
すなわち、本発明は、以下の工程を包含する方法により、成形品の表面にめっきを処理するめっき成形品の製造方法であり、そのことにより上記目的が達成される。
（ａ）成形品表面に、光沢硫酸銅めっきによって銅めっき皮膜を形成する工程、
（ｂ）該銅めっき皮膜の表面に３価クロムめっきを行い第１のクロムめっき皮膜を形成する工程、
（ｃ）該第１のクロムめっき皮膜の表面に６価クロムめっきを行い、第２のクロムめっき皮膜を形成する工程。
That is, this invention is a manufacturing method of the plating molded product which processes plating on the surface of a molded product by the method including the following processes, and the said objective is achieved by it.
(A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating;
(B) forming a first chromium plating film by performing trivalent chromium plating on the surface of the copper plating film;
(C) A step of performing hexavalent chromium plating on the surface of the first chromium plating film to form a second chromium plating film.
一つの実施形態では、前記第１のクロムめっき皮膜の厚みが０．０５〜０．５μｍである。 In one embodiment, the thickness of the first chromium plating film is 0.05 to 0.5 μm.
一つの実施形態では、前記第２のクロムめっき皮膜の厚みが０．１〜３．０μｍである。 In one embodiment, the thickness of the second chromium plating film is 0.1 to 3.0 μm.
一つの実施形態では、前記３価クロムめっきを行う際の、３価クロムめっき浴に含まれるクロム濃度が１．０〜１０．０ｇ/Ｌである。 In one embodiment, the chromium concentration contained in the trivalent chromium plating bath when performing the trivalent chromium plating is 1.0 to 10.0 g / L.
一つの実施形態では、前記３価クロムめっきを行う際の、３価クロムめっき浴の酸化還元電位が１００〜２５０ｍＶである。 In one embodiment, the oxidation-reduction potential of the trivalent chromium plating bath when performing the trivalent chromium plating is 100 to 250 mV.
一つの実施形態では、前記３価クロムめっきを行う際の、３価クロムめっき浴のｐＨが２．０〜５．０である。 In one embodiment, the pH of the trivalent chromium plating bath when performing the trivalent chromium plating is 2.0 to 5.0.
また、本発明のめっき成形品は、上記いずれかの方法によって得られる。 Moreover, the plating molded article of the present invention can be obtained by any one of the above methods.
一つの実施形態では、前記成形品が携帯電話の操作用ボタンである。 In one embodiment, the molded article is a button for operating a mobile phone.
上記したように、有害なシアンを含有する、あるいは制御の困難である銅−スズ合金めっきを行うことなく、銅めっき皮膜上に直接クロムめっきを行うことにより、簡単に、低コストで問題となるニッケルめっきアレルギー対策を行うことが可能である。 As described above, it is easy and low-cost to perform chrome plating directly on the copper plating film without performing copper-tin alloy plating containing harmful cyanide or difficult to control. It is possible to take measures against nickel plating allergies.
銅−スズ合金めっき皮膜は、光沢硫酸銅めっき皮膜と比較して硬度が高いため、耐磨耗性試験などでは銅−スズ合金めっき皮膜が存在することは皮膜構造としては有利である。 Since the copper-tin alloy plating film has higher hardness than the bright copper sulfate plating film, the presence of the copper-tin alloy plating film is advantageous as a film structure in an abrasion resistance test or the like.
しかし、現状、銅−スズ合金めっき浴として安定な性能を示すものは有害なシアンを含有するシアン浴であり、排水処理、作業環境上からも好ましくない。近年では、錯化剤としてシアンを含有しないものも開発されてはいるが、実際の過酷な作業条件ではめっき浴の安定性などの点から問題がある。 However, what shows stable performance as a copper-tin alloy plating bath at present is a cyan bath containing harmful cyanide, which is not preferable from the viewpoint of waste water treatment and working environment. In recent years, those containing no cyanide have been developed as complexing agents, but there are problems in terms of the stability of the plating bath under actual severe working conditions.
光沢硫酸銅めっきは広く用いられているめっき浴であり、光沢剤を添加することで非常に良好な光沢外観を得ることができ、その浴管理も容易である。 Bright copper sulfate plating is a widely used plating bath, and by adding a brightening agent, a very good gloss appearance can be obtained, and the bath management is also easy.
耐磨耗性については、硫酸銅めっきによって形成された銅皮膜上に形成する高い硬度（1000Ｈｖ程度）を有する３価あるいは６価クロムめっき皮膜を厚く形成することで解決できる。 The wear resistance can be solved by forming a thick trivalent or hexavalent chromium plating film having a high hardness (about 1000 Hv) formed on a copper film formed by copper sulfate plating.
以下に、本発明を詳細に説明する。 The present invention is described in detail below.
本発明で使用する成形品は、ＡＢＳ樹脂、ＰＣ/ＡＢＳ樹脂、ナイロンなどの樹脂によって成形されたものがあげられる。例えば、射出成形された成形品があり、具体的には携帯電話、デジタルカメラの操作ボタンなどがある。 Examples of the molded article used in the present invention include those molded from resins such as ABS resin, PC / ABS resin, and nylon. For example, there are injection-molded molded products, specifically, cellular phones, digital camera operation buttons, and the like.
特に、ＡＢＳ樹脂にて形成された一次成形品と、該一次成形品の内側に二色成形によって成形された二次成形品とを有する２色成形品を使用することができる。２次成形品２はＰＣ等の透明な樹脂にて形成することもできる。また、樹脂素材以外に、各種の金属を対象として本発明の方法に従ってめっきすることもできる。 In particular, a two-color molded product having a primary molded product formed of ABS resin and a secondary molded product molded by two-color molding inside the primary molded product can be used. The secondary molded product 2 can also be formed of a transparent resin such as PC. In addition to the resin material, various metals can be plated according to the method of the present invention.
この成形品の表面に以下の工程によりめっき処理が行われる。
１）光沢硫酸銅めっき
図１に光沢硫酸銅めっきの概略工程を示す。
Plating treatment is performed on the surface of this molded product by the following steps.
1) Bright copper sulfate plating FIG. 1 shows a schematic process of bright copper sulfate plating.
成形品表面を脱脂し、水洗した後、クロム酸ー硫酸エッチングを行う。好ましいエッチング条件は図１に示したとおりである。 The surface of the molded product is degreased and washed with water, followed by chromic acid-sulfuric acid etching. Preferred etching conditions are as shown in FIG.
次に、成形品を水洗した後、中和、水洗を行い、プレディップし、次いで触媒化する。 Next, the molded product is washed with water, then neutralized and washed with water, pre-dipped, and then catalyzed.
触媒化した成形品を水洗した後、導体化し、水洗した後、電気銅めっきを行う。 After the catalyzed molded product is washed with water, it is made into a conductor, washed with water, and then subjected to electrolytic copper plating.
なお、上記光沢硫酸銅めっき方法は、一例であるので、その他の公知の方法に従って、実施してもよい。
２）銅めっきの浴種
装飾用に使用される銅めっきとしては、ほとんどが、硫酸銅であり、他のピロリン酸浴、シアン浴が使用されることはない。
In addition, since the said bright copper sulfate plating method is an example, you may implement according to another well-known method.
2) Copper plating bath type Most of the copper plating used for decoration is copper sulfate, and other pyrophosphoric acid baths and cyan baths are not used.
銅めっき浴に使用される光沢剤については、特に限定的でなく、必要な光沢を得ることができれば、従来より公知のものを使用可能である。 The brightener used in the copper plating bath is not particularly limited, and conventionally known brighteners can be used as long as necessary gloss can be obtained.
この段階で、光沢が不十分であれば、３価あるいは６価クロム処理後の光沢が出ない。
３）３価クロムめっきを行う必要性
硫酸銅めっきによって形成された皮膜上に、６価クロムめっきを直接製膜することは困難である。この理由は、６価クロムめっき浴のｐＨや酸化力が影響しているものと思われる。すなわち、一般的な、６価クロムめっき浴（サージェント浴）は、クロム酸２５０ｇ/Ｌ+９８％硫酸２．５ｇ/Ｌ程度の組成であり、ｐＨが低く、めっき浴の酸化力が高い（酸化還元電位が高い）ことが特徴である。このため、銅めっき皮膜が６価クロムめっき浴中に浸漬された時点で銅表面の酸化、溶解が起こるために正常に（きれいに）クロムめっきができないものと推測される。
At this stage, if the gloss is insufficient, the gloss after the trivalent or hexavalent chromium treatment is not obtained.
3) Necessity of performing trivalent chromium plating It is difficult to directly form hexavalent chromium plating on a film formed by copper sulfate plating. This is probably because the pH and oxidizing power of the hexavalent chromium plating bath are affected. That is, a general hexavalent chromium plating bath (sergeant bath) has a composition of about 250 g / L of chromic acid + 2.5 g / L of 98% sulfuric acid, has a low pH, and has a high oxidizing power of the plating bath (oxidation). The reduction potential is high). For this reason, when the copper plating film is immersed in a hexavalent chromium plating bath, it is presumed that the copper surface cannot be oxidized properly (cleanly) because the copper surface is oxidized and dissolved.
これに対して、３価クロムめっきでは、金属塩が３価クロム塩（硫酸クロムなど）であり、金属濃度も６価クロム浴と比較すると、低く、ＯＲＰ（酸化還元電位）も低い値を示す。３価クロムめっき浴は、一般にｐＨも３程度であり、３価クロムめっき浴中に銅めっき皮膜が浸漬された場合でも、銅めっき皮膜の酸化あるいは溶解が起こりにくいため、銅めっき皮膜上に３価クロムめっきは正常に製膜するものと思われる。
４）３価クロムめっき浴
３価クロムめっき浴は、以下（a）〜（ｇ）を含有することができる。
In contrast, in trivalent chromium plating, the metal salt is a trivalent chromium salt (such as chromium sulfate), the metal concentration is lower than that of the hexavalent chromium bath, and the ORP (redox potential) is also low. . The trivalent chromium plating bath generally has a pH of about 3, and even when the copper plating film is immersed in the trivalent chromium plating bath, oxidation or dissolution of the copper plating film hardly occurs. Divalent chromium plating seems to form normally.
4) Trivalent chromium plating bath The trivalent chromium plating bath may contain the following (a) to (g).
（a）クロム成分としては、硫酸クロム、塩基性硫酸クロム、塩化クロム、酢酸クロムなどの水溶性３価クロム化合物を含み、（ｂ）導電性塩として硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム、塩化ナトリウム、塩化カリウム、塩化アンモニウムなどを含み、（ｃ）クロムの酢化剤として、蟻酸、酢酸などのモノカルボン酸またはその塩、シュウ酸、マロン酸、マレイン酸などのジカルボン酸、クエン酸、リンゴ酸、グリコール酸などのヒドロキシカルボン酸、またはそれらの塩を含有することができる。 (A) The chromium component includes water-soluble trivalent chromium compounds such as chromium sulfate, basic chromium sulfate, chromium chloride, and chromium acetate. (B) Sodium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, Potassium chloride, ammonium chloride and the like, (c) as acetylating agent of chromium, monocarboxylic acid such as formic acid, acetic acid or the salt thereof, dicarboxylic acid such as oxalic acid, malonic acid, maleic acid, citric acid, malic acid, Hydroxycarboxylic acids such as glycolic acid, or salts thereof can be included.
さらに、（ｄ）ｐＨ緩衝剤として、ホウ酸、ホウ酸ナトリウムなどを含んでもよい。 Further, (d) boric acid, sodium borate and the like may be included as a pH buffering agent.
また、３価クロムめっき浴に含まれるクロム濃度は、１．０〜１０．０ｇ/Ｌが好ましい。さらに好ましくは、２．５〜４．０ｇ/Ｌである。 The chromium concentration contained in the trivalent chromium plating bath is preferably 1.0 to 10.0 g / L. More preferably, it is 2.5-4.0 g / L.
さらに、３価クロムめっき浴の酸化還元電位は、１００〜２５０ｍＶが好ましい。さらに好ましくは、１４０〜２００ｍＶである。 Furthermore, the redox potential of the trivalent chromium plating bath is preferably 100 to 250 mV. More preferably, it is 140-200 mV.
３価クロムめっき浴のｐＨは、２．０〜５．０が好ましい。さらに好ましくは、３．３〜３．８である。 The pH of the trivalent chromium plating bath is preferably 2.0 to 5.0. More preferably, it is 3.3-3.8.
市販品としては、奥野製薬工業製の「トップファインクロム」を使用することができる。 As a commercial product, “Top Fine Chrome” manufactured by Okuno Pharmaceutical Co., Ltd. can be used.
このめっき浴は、浴中の金属濃度が、３．５ｇ/Ｌと低く、浴のｐＨが３．５程度と高いため、浴のＯＲＰが低い（酸化力が弱い）ものである。さらに、めっき浴中の錯化剤量が少ないため、キレート効果による銅めっき皮膜溶解量も他社の３価クロムめっき浴と比較して低いことが確認されている。 In this plating bath, the metal concentration in the bath is as low as 3.5 g / L, and the pH of the bath is as high as about 3.5, so that the ORP of the bath is low (the oxidizing power is weak). Furthermore, since the amount of the complexing agent in the plating bath is small, it has been confirmed that the amount of copper plating film dissolved by the chelate effect is also lower than that of other trivalent chromium plating baths.
この３価クロムめっきによって形成される皮膜（クロムめっき皮膜）の厚みは０．０５〜０．５μｍが好ましい。さらに好ましくは、０．１〜０．３μｍである。 The thickness of the film (chromium plating film) formed by this trivalent chromium plating is preferably 0.05 to 0.5 μm. More preferably, it is 0.1-0.3 micrometer.
なお、ＯＲＰ（酸化還元電位）は次のようにして測定した。 The ORP (redox potential) was measured as follows.
ＯＲＰ測定には、アズワン株式会社製のラコムテスターＯＲＰ計を使用した。
測定結果は、以下に示す。
For ORP measurement, a Lacom Tester ORP meter manufactured by AS ONE Corporation was used.
The measurement results are shown below.
上記の３価クロムめっき浴はいずれもクロム酸塩に硫酸クロム（３価）を使用するタイプである。 All of the above trivalent chromium plating baths are of the type using chromium sulfate (trivalent) as chromate.
他社品の詳細な組成は不明であるが、トップファインクロムは、金属濃度およびＯＲＰが低いと思われる。
５）３価クロムめっき/６価クロムめっきの構造が必要である理由
ニッケルめっきが要求される部品は、人が触れる部分（携帯電話、デジタルカメラの操作ボタンなど）に用いられるため、ある程度の耐磨耗性が要求される。
Although the detailed composition of other companies' products is unknown, it seems that top fine chrome has a low metal concentration and ORP.
5) Reason why the structure of trivalent chrome plating / hexavalent chrome plating is necessary Parts that require nickel plating are used for parts that are touched by humans (cell phone, operation buttons of digital cameras, etc.). Abrasion is required.
一般的に３価クロムめっきの皮膜硬度は６価クロムめっきの皮膜硬度とほぼ同程度の９００〜１０００Ｈｖ程度を示す。 Generally, the film hardness of trivalent chromium plating is about 900 to 1000 Hv, which is almost the same as the film hardness of hexavalent chromium plating.
本発明の方法における、ニッケルめっきを使用しない工程では、銅−スズ合金めっきを行わないため、耐磨耗性を維持するために、クロムめっき皮膜の膜厚を１μｍ以上製膜することが望ましい。 In the method of the present invention, in which the nickel plating is not used, the copper-tin alloy plating is not performed. Therefore, in order to maintain the wear resistance, it is desirable to form a chromium plating film with a thickness of 1 μm or more.
現在、市販されている３価クロムめっき（硫酸クロムを使用するタイプ）は装飾用であり、厚く製膜すると外観不良（クモリなど）が発生する。
また、３価クロムめっき皮膜の製膜速度も６価クロムめっき皮膜と比較すると小さく（１/１０程度）、良好な光沢外観、耐摩耗性、耐食性、生産性を考慮すると、最外層には６価クロムめっき皮膜を用いることが好ましい。
６）基本的なめっき皮膜構造（膜厚など）
ＡＢＳ樹脂などで成形品を製造する場合には、光沢外観を得るために光沢硫酸銅めっき皮膜は、１０〜５０μｍ程度の膜厚が好ましい。さらに好ましくは２０〜４０μｍである。
Currently, commercially available trivalent chromium plating (a type using chromium sulfate) is for decoration, and when it is formed thick, poor appearance (such as spiders) occurs.
In addition, the film formation speed of the trivalent chromium plating film is smaller than that of the hexavalent chromium plating film (about 1/10), and considering the good gloss appearance, wear resistance, corrosion resistance, and productivity, the outermost layer is 6 It is preferable to use a valent chromium plating film.
6) Basic plating film structure (film thickness, etc.)
When a molded product is manufactured with ABS resin or the like, the bright copper sulfate plating film preferably has a thickness of about 10 to 50 μm in order to obtain a glossy appearance. More preferably, it is 20-40 micrometers.
３価クロムの膜厚は厚くする必要はなく、６価クロムめっきを正常に析出させるためのものであり、０．０５〜０．５μｍであれば十分である。特に好ましい３価クロムの膜厚は、０．１〜０．３μｍである。 The film thickness of the trivalent chromium does not need to be increased, but is for normally depositing hexavalent chromium plating, and 0.05 to 0.5 μm is sufficient. A particularly preferred film thickness of trivalent chromium is 0.1 to 0.3 μm.
この段階で皮膜表面にクモリなどが発生すると６価クロムめっき皮膜の外観にも影響するため、実際には必要最小限の膜厚にとどめることが望ましい。 At this stage, the occurrence of spider or the like on the surface of the film affects the appearance of the hexavalent chromium plating film, so it is actually desirable to limit the film thickness to the minimum necessary.
６価クロムめっき皮膜の膜厚は品物に要求される耐磨耗性との兼ね合いで決定される。耐磨耗性試験が厳しい場合には、厚く製膜（２μｍ以上など）することが必要となる。 The film thickness of the hexavalent chromium plating film is determined in consideration of the wear resistance required for the product. When the abrasion resistance test is severe, it is necessary to form a thick film (eg, 2 μm or more).
一般的には、６価クロムめっき皮膜の膜厚は０．１〜３．０μｍであり、特に好ましい膜厚は１．５〜２．５μｍである。 In general, the film thickness of the hexavalent chromium plating film is 0.1 to 3.0 μm, and the particularly preferable film thickness is 1.5 to 2.5 μm.
以下に実施例および比較例を挙げて本発明を説明する。 Hereinafter, the present invention will be described with reference to examples and comparative examples.
比較例１，２および実施例１〜３については、素材にＰＣ/ＡＢＳ樹脂の
２色成形品を使用した。
For Comparative Examples 1 and 2 and Examples 1 to 3, PC / ABS resin two-color molded products were used as materials.
この成形品についてクロム酸−硫酸エッチング処理を行い、成形品表面に親水性および微細孔を形成した後、直接硫酸銅めっきプロセス（奥野製薬工業製 トップＣＲＰプロセス）を用いて、触媒付与、導電化処理、直接硫酸銅めっきを行ったものを使用した。 This molded product is subjected to chromic acid-sulfuric acid etching treatment to form hydrophilicity and micropores on the surface of the molded product, and then, using a direct copper sulfate plating process (Okuno Pharmaceutical Co., Ltd. Top CRP process), catalyst application and electrical conductivity What processed and the direct copper sulfate plating was used.
実施例４については、ＳＰＣＣ鋼板を素材として使用した。
（比較例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる２色成形品を用いて、銅−スズ合金めっき（シアン含有）浴を用いて、銅−スズ合金めっき皮膜（膜厚５μｍ）を形成した。その後、成形品表面に３価クロムめっきを行い、０．１μｍ製膜した後、さらに６価クロムめっき（サージェント浴）を０．３μｍ製膜した。
（比較例２）
光沢硫酸銅めっき（膜厚２０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる２色成形品を用いて、銅−スズ合金めっき（ピロリン酸含有）浴を用いて、銅−スズ合金めっき皮膜（膜厚１０μｍ）を形成した。その後、成形品表面に３価クロムめっきを行い、０．１μｍ製膜した後、続いて６価クロムめっき（サージェント浴）を０．３μｍ製膜した。
（実施例１）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅−スズ合金めっきを行わずに、直接成形品表面に３価クロムめっきを行い、０．１μｍ製膜した。その後、耐食性、耐摩耗性を確保するため、さらに成形品表面に６価クロムめっき（サージェント浴）を２μｍ製膜した。
（実施例２）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅−スズ合金めっきを行わずに、直接３価クロムめっきを行い、０．３μｍ製膜した。その後、耐食性、耐摩耗性を確保するために、成形品表面に６価クロムめっき（サージェント浴）を２．５μｍ製膜した。
（実施例３）
光沢硫酸銅めっき（膜厚３０μｍ）を行ったＰＣ/ＡＢＳ樹脂よりなる成形品を用いて、銅−スズ合金めっきを行わずに、直接３価クロムめっきを行い、１．０μｍ製膜した。その後、水洗を行い、成形品表面に６価クロムめっき（サージェント浴）を１．５μｍ製膜した。
（実施例４）
ＳＰＣＣ鋼板に光沢硫酸銅めっき（膜厚２０μｍ）を行った後、３価クロムめっき浴を用いて、膜厚０．３μｍのクロムめっき皮膜を形成した。その後、水洗を行い、６価クロムめっき（サージェント浴）を１．５μｍ製膜した。
（評価方法）
１）皮膜外観：目視によりめっき成形品の表面にクモリなどの不良がないこと。
About Example 4, the SPCC steel plate was used as a raw material.
(Comparative Example 1)
Using a two-color molded product made of PC / ABS resin with bright copper sulfate plating (film thickness 30 μm), using a copper-tin alloy plating (cyan-containing) bath, copper-tin alloy plating film (film thickness 5 μm) ) Was formed. Thereafter, trivalent chromium plating was performed on the surface of the molded product to form a 0.1 μm film, and then a hexavalent chromium plating (sergeant bath) was further formed to 0.3 μm.
(Comparative Example 2)
Using a copper / tin alloy plating (containing pyrophosphoric acid) bath, a copper-tin alloy plating film (film thickness) using a two-color molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness 20 μm) 10 μm). Thereafter, trivalent chromium plating was performed on the surface of the molded product to form a film having a thickness of 0.1 μm, and then hexavalent chromium plating (sergeant bath) was formed to a thickness of 0.3 μm.
Example 1
Using a molded product made of PC / ABS resin with bright copper sulfate plating (film thickness 30μm), without performing copper-tin alloy plating, trivalent chromium plating is performed directly on the molded product surface to make 0.1μm Filmed. Thereafter, in order to ensure corrosion resistance and wear resistance, a hexavalent chromium plating (sergeant bath) was further formed to a thickness of 2 μm on the surface of the molded product.
(Example 2)
Using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm), trivalent chromium plating was directly performed without forming copper-tin alloy plating to form 0.3 μm. Thereafter, in order to ensure corrosion resistance and wear resistance, a hexavalent chromium plating (sergeant bath) was formed to a thickness of 2.5 μm on the surface of the molded product.
(Example 3)
Using a molded product made of PC / ABS resin subjected to bright copper sulfate plating (film thickness: 30 μm), trivalent chromium plating was directly performed to form a film of 1.0 μm without performing copper-tin alloy plating. Thereafter, washing with water was performed, and a hexavalent chromium plating (sergeant bath) was formed to a thickness of 1.5 μm on the surface of the molded product.
Example 4
After performing bright copper sulfate plating (film thickness 20 μm) on the SPCC steel plate, a chromium plating film having a film thickness of 0.3 μm was formed using a trivalent chromium plating bath. Thereafter, washing with water was performed to form a hexavalent chromium plating (sergeant bath) of 1.5 μm.
(Evaluation methods)
1) Appearance of film: Visually, the surface of the plated product is free from defects such as spiders.
２）クラック：実体顕微鏡観察によりめっき成形品の皮膜にクラックが認められないこと。 2) Cracks: No cracks are observed in the film of the plated product by observation with a stereoscopic microscope.
３）皮膜の剥離：めっき成形品表面の界面部分においてめっき皮膜の剥離やふくれが発生していないこと。 3) Film peeling: Plating film peeling or blistering does not occur at the interface part of the surface of the plated product.
４）塩水噴霧試験：めっき成形品を７２時間放置した後、めっき成形品表面にサビが発生していないこと。 4) Salt spray test: Rust does not occur on the surface of the plated product after the plated product is left for 72 hours.
５）消しゴム磨耗試験：市販の消しゴムを用いた磨耗試験によりめっき成形品の下地のめっき皮膜が露出しないこと。
６）打鍵試験：人工爪におる打撃試験で皮膜の剥離、磨耗のないこと。
5) Eraser abrasion test: The plating film on the base of the plated product is not exposed by an abrasion test using a commercially available eraser.
6) Keystroke test: No peeling or abrasion of the film in the impact test with an artificial nail.
上記実施例および比較例で得られた各めっき成形品について、上記試験項目を評価し、その結果を表１に示した。 The test items were evaluated for the respective plated molded articles obtained in the examples and comparative examples, and the results are shown in Table 1.
ニッケル代替めっきである銅−スズ合金めっきを樹脂めっきに適応した場合、比較例１で示すように、シアン浴を使用した場合には、樹脂/硫酸銅めっき皮膜界面へのめっき液の染み込みが原因と思われる剥離が観察された。 When copper-tin alloy plating, which is a nickel alternative plating, is applied to resin plating, as shown in Comparative Example 1, when a cyan bath is used, the penetration of the plating solution into the resin / copper sulfate plating film interface is the cause. A possible peeling was observed.
また、実施例２に示したように、シアンを使用しない銅−スズ合金めっき浴を使用した場合には、皮膜硬度がシアン浴を使用して形成した皮膜と比較して低いため膜厚を２倍程度にすることが必要である。この場合には、膜厚が増加することで高い皮膜応力によりクラックが発生した。 Further, as shown in Example 2, when a copper-tin alloy plating bath not using cyan was used, the film thickness was 2 because the film hardness was lower than that of a film formed using a cyan bath. It is necessary to double it. In this case, cracks were generated due to high film stress as the film thickness increased.
このように、樹脂めっきにおいて、ニッケルめっきの代替として銅−スズ合金めっきを使用した場合、外観、耐食性、耐摩耗性の全てを満足することは困難である。 Thus, in resin plating, when copper-tin alloy plating is used as an alternative to nickel plating, it is difficult to satisfy all of the appearance, corrosion resistance, and wear resistance.
これに対して、実施例１〜４で示した光沢硫酸銅めっき上に直接３価クロムめっきを行い、続いて６価クロムめっきを行った場合では、耐食性、耐磨耗性を満足させるための膜厚を厚くすることが必要であるが、外観、耐食性、耐磨耗性を満足することが可能である。 On the other hand, when trivalent chromium plating is directly performed on the bright copper sulfate plating shown in Examples 1 to 4, and then hexavalent chromium plating is performed, for satisfying corrosion resistance and wear resistance. Although it is necessary to increase the film thickness, it is possible to satisfy the appearance, corrosion resistance, and wear resistance.
加えて、比較的浴寿命が短く、管理が難しい銅−スズ合金めっきを使用することなく、ニッケルめっきを使用しない簡単な皮膜構造により生産コストも低減できる。 In addition, the production cost can be reduced by using a simple film structure that does not use nickel plating without using copper-tin alloy plating, which has a relatively short bath life and is difficult to manage.
Claims (9)
（ａ）成形品表面に、光沢硫酸銅めっきによって銅めっき皮膜を形成する工程、
（ｂ）該銅めっき皮膜の表面に３価クロムめっきを行い第１のクロムめっき皮膜を形成する工程、
（ｃ）該第１のクロムめっき皮膜の表面に６価クロムめっきを行い、第２のクロムめっき皮膜を形成する工程。 A method for producing a plated molded article in which plating is performed on the surface of the molded article by a method including the following steps:
(A) forming a copper plating film on the surface of the molded product by bright copper sulfate plating;
(B) forming a first chromium plating film by performing trivalent chromium plating on the surface of the copper plating film;
(C) A step of performing hexavalent chromium plating on the surface of the first chromium plating film to form a second chromium plating film.
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| CN102492968A (en) * | 2011-12-28 | 2012-06-13 | 尼尔金属(苏州)有限公司 | Copper plating method on brass base material |
| WO2012114737A1 (en) * | 2011-02-25 | 2012-08-30 | 株式会社太洋工作所 | Method for producing trivalent chromium-plated molded article and trivalent chromium-plated molded article |
| CN103060875A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material |
| CN103590082A (en) * | 2013-12-03 | 2014-02-19 | 厦门建霖工业有限公司 | Phosphor-less hexavalent chromium-less environmentally-friendly plastic electroplating method |
| WO2015037391A1 (en) * | 2013-09-12 | 2015-03-19 | 奥野製薬工業株式会社 | Trivalent chromium plating bath |
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| WO2012114737A1 (en) * | 2011-02-25 | 2012-08-30 | 株式会社太洋工作所 | Method for producing trivalent chromium-plated molded article and trivalent chromium-plated molded article |
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| CN103060875B (en) * | 2013-01-30 | 2015-06-03 | 昆明理工大学 | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material |
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| CN103590082B (en) * | 2013-12-03 | 2016-03-02 | 厦门建霖工业有限公司 | A kind of without phosphorus, non-hexavalent chromium environment friendly shape glue electro-plating method |
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