JP5657199B2 - Copper-zinc alloy electroplating bath - Google Patents
Copper-zinc alloy electroplating bath Download PDFInfo
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- JP5657199B2 JP5657199B2 JP2008227549A JP2008227549A JP5657199B2 JP 5657199 B2 JP5657199 B2 JP 5657199B2 JP 2008227549 A JP2008227549 A JP 2008227549A JP 2008227549 A JP2008227549 A JP 2008227549A JP 5657199 B2 JP5657199 B2 JP 5657199B2
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- zinc alloy
- zinc
- electroplating bath
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 45
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims description 45
- 238000009713 electroplating Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- -1 pyrophosphate ions Chemical class 0.000 claims description 8
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 238000007747 plating Methods 0.000 description 53
- 238000000034 method Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JJKVMNNUINFIRK-UHFFFAOYSA-N 4-amino-n-(4-methoxyphenyl)benzamide Chemical compound C1=CC(OC)=CC=C1NC(=O)C1=CC=C(N)C=C1 JJKVMNNUINFIRK-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000011641 cupric citrate Substances 0.000 description 1
- 235000019855 cupric citrate Nutrition 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は銅‐亜鉛合金電気めっき浴（以下、単に「めっき浴」とも称す）に関し、詳しくは、耐腐食性が向上した銅‐亜鉛合金めっき層を形成することができ、かつ、目的組成を有する均一で光沢のある銅‐亜鉛合金めっき層を幅広い電流密度で得ることができる銅‐亜鉛合金電気めっき浴に関する。 The present invention relates to a copper-zinc alloy electroplating bath (hereinafter, also simply referred to as “plating bath”). The present invention relates to a copper-zinc alloy electroplating bath capable of obtaining a uniform and shiny copper-zinc alloy plating layer with a wide current density.
現在、銅‐亜鉛合金めっきは、金属製品、プラスチック製品、セラミック製品等に真鍮色の金属光沢および色調を与えるため、装飾めっきとして工業的に広く用いられている。しかし、従来のめっき浴はシアン化合物を多量に含んでいるため、その毒性が大きな問題となっており、また、含シアン化合物廃液の処理負担も大きなものであった。 At present, copper-zinc alloy plating is widely used industrially as decorative plating in order to give a metallic luster and color tone of brass color to metal products, plastic products, ceramic products and the like. However, since the conventional plating bath contains a large amount of cyanide, its toxicity is a big problem, and the treatment load of the cyanide-containing waste liquid is also large.
かかる解決手段として、今日、シアン化合物を用いない銅‐亜鉛合金めっき方法が多数報告されている。例えば、逐次めっき方法は、黄銅めっきを被めっき製品に施すための実際的な方法であり、かかる方法においては、電着によって銅めっき層と亜鉛めっき層が被めっき製品表面に順次めっきされ、ついで、熱拡散工程が施される。逐次黄銅めっき方法の場合、ピロリン酸銅めっき溶液と酸性の硫酸亜鉛めっき溶液が通常使用されている（例えば、特許文献１）。 As a solution to this problem, many copper-zinc alloy plating methods that do not use cyanide have been reported today. For example, the sequential plating method is a practical method for applying brass plating to a product to be plated. In such a method, a copper plating layer and a zinc plating layer are sequentially plated on the surface of the product to be plated by electrodeposition. A thermal diffusion process is performed. In the sequential brass plating method, a copper pyrophosphate plating solution and an acidic zinc sulfate plating solution are usually used (for example, Patent Document 1).
また、錯化剤として酒石酸やグルコヘプトン酸を添加した硫酸銅および硫酸亜鉛を金属源とした浴を用いためっき浴が提案されている（例えば、特許文献２）。
しかしながら、特許文献１に記載されているような逐次めっき方法では、銅めっき層形成工程、亜鉛めっき層形成工程および熱拡散工程、と処理工程が多く、複雑であるため、作業効率が悪いという欠点がある。また、特許文献２に記載されている方法を用いた場合、シアン浴のような毒性の問題は解消するが、通常、ｐＨが１１以上という高ｐＨ領域でめっき処理がなされるため、元来低ｐＨ領域で良好なめっき層が得られる硫酸金属塩を浴中に含有している場合は、めっき層の付着力の低下が発生するという問題がある。 However, in the sequential plating method as described in Patent Document 1, there are many copper plating layer forming step, galvanized layer forming step and thermal diffusion step, and processing steps, and the process is complicated, so that the work efficiency is poor. There is. Further, when the method described in Patent Document 2 is used, the problem of toxicity such as a cyan bath is solved. However, since the plating treatment is usually performed in a high pH region where the pH is 11 or more, it is originally low. When the metal sulfate containing a good plating layer in the pH region is contained in the bath, there is a problem that the adhesion of the plating layer is reduced.
また、めっき層内にカルボン酸基を有する有機化合物が取り込まれることで、めっき下地金属が露出した際に、大気中の酸素および水分により銅‐亜鉛合金めっき層と下地金属との間で発生する腐食を促進するという問題も有している。 In addition, when an organic compound having a carboxylic acid group is incorporated into the plating layer, it is generated between the copper-zinc alloy plating layer and the base metal due to oxygen and moisture in the atmosphere when the plating base metal is exposed. It also has the problem of promoting corrosion.
そこで本発明の目的は、耐腐食性が向上した銅‐亜鉛合金めっき層を形成することができ、かつ、目的組成を有する均一で光沢のある銅‐亜鉛合金めっき層を幅広い電流密度で得ることができる銅‐亜鉛合金電気めっき浴を提供することにある。 Accordingly, an object of the present invention is to form a copper-zinc alloy plating layer with improved corrosion resistance and to obtain a uniform and shiny copper-zinc alloy plating layer having a target composition with a wide current density. An object of the present invention is to provide a copper-zinc alloy electroplating bath.
本発明者らは、上記課題を解決するために鋭意検討した結果、銅‐亜鉛合金電気めっき浴の構成を下記のとおりとすることにより、上記目的を達成す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。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by configuring the copper-zinc alloy electroplating bath as follows. It came to be completed.
すなわち、本発明の銅‐亜鉛合金電気めっき浴は、銅塩と、亜鉛塩と、ピロリン酸イオンとを含有する銅‐亜鉛合金電気めっき浴において、銅イオンおよび亜鉛イオンの総容積モル濃度Ｍ（ｍｏｌ／Ｌ）と添加するピロリン酸イオンの容積モル濃度Ｐ（ｍｏｌ／Ｌ）の比（Ｐ／Ｍ）が２．０〜３．２の範囲であり、かつ、カルボン酸基を有する有機化合物を含有せず、前記総容積モル濃度Ｍ（ｍｏｌ／Ｌ）が０．０３〜０．０８（ｍｏｌ／Ｌ）の範囲であるしないことを特徴とするものである。 That is, the copper-zinc alloy electroplating bath of the present invention is a copper-zinc alloy electroplating bath containing a copper salt, a zinc salt, and pyrophosphate ions. mol / L) and the molar ratio P (mol / L) of the pyrophosphate ion to be added (P / M) is in the range of 2.0 to 3.2, and an organic compound having a carboxylic acid group It is not contained, and the total volume molar concentration M (mol / L) is not in the range of 0.03 to 0.08 (mol / L).
また、本発明の金属コードは、本発明の銅‐亜鉛合金電気めっき浴を用いてめっき処理がなされた金属ワイヤを用いたことを特徴とするものである。 The metal cord of the present invention is characterized in that a metal wire plated using the copper-zinc alloy electroplating bath of the present invention is used.
本発明によれば、銅‐亜鉛合金電気めっき浴を上記構成にしたことにより、耐腐食性が向上した銅‐亜鉛合金めっき層を形成することができ、かつ、目的組成を有する均一で光沢のある銅‐亜鉛合金めっき層を幅広い電流密度で得ることが可能となった。 According to the present invention, the copper-zinc alloy electroplating bath is configured as described above, whereby a copper-zinc alloy plating layer with improved corrosion resistance can be formed, and a uniform and glossy composition having a target composition can be formed. It is possible to obtain a certain copper-zinc alloy plating layer with wide current density.
以下、本発明の好適な実施の形態について詳細に説明する。
本発明の銅‐亜鉛合金電気めっき浴は、銅塩と、亜鉛塩と、ピロリン酸イオンとを含有する銅‐亜鉛合金めっき浴である。本発明においては、めっき浴中に含まれる銅イオンおよび亜鉛イオンの総容積モル濃度Ｍ（ｍｏｌ／Ｌ）と添加するピロリン酸イオンの容積モル濃度Ｐ（ｍｏｌ／Ｌ）の比（Ｐ／Ｍ）を２．０〜３．２の範囲とすることが重要である。ピロリン酸イオンを錯化剤として用いることにより、めっき下地金属が露出した際の腐食を有機化合物が促進するというという問題を解決することができる。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The copper-zinc alloy electroplating bath of the present invention is a copper-zinc alloy plating bath containing a copper salt, a zinc salt, and pyrophosphate ions. In the present invention, the ratio (P / M) of the total molar volume M (mol / L) of copper ions and zinc ions contained in the plating bath to the molar volume P (mol / L) of pyrophosphate ions to be added. Is in the range of 2.0 to 3.2. By using pyrophosphate ions as a complexing agent, it is possible to solve the problem that the organic compound promotes corrosion when the plating base metal is exposed.
また、Ｐ／Ｍの範囲を２．０〜３．２とすることで、光沢のある均一な銅‐亜鉛合金めっき層を、低電流密度から高電流密度の範囲で得ることができる。本発明の効果を良好に得るためには、Ｐ／Ｍの範囲は、好適には２．５〜３．０である。 Moreover, by setting the range of P / M to 2.0 to 3.2, a glossy and uniform copper-zinc alloy plating layer can be obtained in a range of low current density to high current density. In order to obtain the effect of the present invention satisfactorily, the range of P / M is preferably 2.5 to 3.0.
銅塩としては、めっき浴の銅イオン源として公知のものであればいずれも使用可能であり、例えば、ピロリン酸銅、硫酸銅、塩化第２銅、スルファミン酸銅、酢酸第２銅、塩基性炭酸銅、臭化第２銅、ギ酸銅、水酸化銅、酸化第２銅、リン酸銅、ケイフッ化銅、ステアリン酸銅、クエン酸第２銅等を挙げることができ、これらのうち１種のみを用いてもよいし、２種以上を用いてもよい。 Any copper salt can be used as long as it is a known copper ion source for a plating bath. For example, copper pyrophosphate, copper sulfate, cupric chloride, copper sulfamate, cupric acetate, basic Examples include copper carbonate, cupric bromide, copper formate, copper hydroxide, cupric oxide, copper phosphate, copper fluorosilicate, copper stearate, cupric citrate, etc., one of these May be used alone, or two or more of them may be used.
亜鉛塩としては、めっき浴の亜鉛イオン源として公知のものであればいずれも使用可能であり、例えば、ピロリン酸亜鉛、硫酸亜鉛、塩化亜鉛、スルファミン酸亜鉛、酸化亜鉛、酢酸亜鉛、臭化亜鉛、塩基性炭酸亜鉛、シュウ酸亜鉛、リン酸亜鉛、ケイフッ化亜鉛、ステアリン酸亜鉛、乳酸亜鉛等を挙げることができ、これらのうち１種のみを用いてもよいし、２種以上を用いてもよい。 Any zinc salt may be used as long as it is a known zinc ion source for a plating bath. For example, zinc pyrophosphate, zinc sulfate, zinc chloride, zinc sulfamate, zinc oxide, zinc acetate, zinc bromide , Basic zinc carbonate, zinc oxalate, zinc phosphate, zinc fluorosilicate, zinc stearate, zinc lactate, etc., and only one of these may be used, or two or more may be used. Also good.
ピロリン酸イオン源としては、公知のものであればいずれでも使用可能であり、例えば、そのナトリウム塩、カリウム塩等を挙げることができる。 As the pyrophosphate ion source, any known one can be used, and examples thereof include a sodium salt and a potassium salt thereof.
また、本発明においては、銅イオンおよび亜鉛イオンの総容積モル濃度Ｍ（ｍｏｌ／Ｌ）が０．０３〜０．５０（ｍｏｌ／Ｌ）の範囲であることが好ましい。総容積モル濃度Ｍが０．０３（ｍｏｌ／Ｌ）未満であると、銅の析出が優先されてしまい、均一な銅‐亜鉛合金めっき層を得ることが難しくなる。一方、総容積モル濃度Ｍ（ｍｏｌ／Ｌ）が０．５０（ｍｏｌ／Ｌ）を超えると、銅‐亜鉛合金めっき層表面に十分な光沢が得られなくなってしまう。 Moreover, in this invention, it is preferable that the total volume molar concentration M (mol / L) of a copper ion and a zinc ion is the range of 0.03-0.50 (mol / L). If the total volume molarity M is less than 0.03 (mol / L), copper deposition is prioritized, making it difficult to obtain a uniform copper-zinc alloy plating layer. On the other hand, when the total volume molar concentration M (mol / L) exceeds 0.50 (mol / L), sufficient gloss cannot be obtained on the surface of the copper-zinc alloy plating layer.
さらに、本発明においては、めっき浴のｐＨは５〜１０の範囲であることが好ましい。ｐＨが１０を超えると、めっき液が不安定となり沈殿物が生じてしまい、均一な銅‐亜鉛合金めっき層を得ることが難しくなる。一方、ｐＨが５未満になると、ピロリン酸が加水分解され、やはり、均一な銅‐亜鉛合金めっき層を良好に得ることができなくなってしまう。また、ｐＨを５〜１０の範囲とすることで、硫酸金属塩による銅‐亜鉛合金めっき層の付着率を向上させることが可能となるという効果も得られる。 Furthermore, in this invention, it is preferable that pH of a plating bath is the range of 5-10. If the pH exceeds 10, the plating solution becomes unstable and precipitates are formed, making it difficult to obtain a uniform copper-zinc alloy plating layer. On the other hand, when the pH is less than 5, pyrophosphoric acid is hydrolyzed, so that a uniform copper-zinc alloy plating layer cannot be obtained satisfactorily. Moreover, the effect that it becomes possible to improve the adhesion rate of the copper-zinc alloy plating layer by a sulfate metal salt by making pH into the range of 5-10 is also acquired.
本発明の銅‐亜鉛合金電気めっき浴を使用して銅‐亜鉛合金めっき処理を施すに際しては、通常の電気めっき方法を採用することができる。例えば、浴温３０〜４０℃程度、無攪拌下あるいは機械攪拌下又は空気攪拌下で電気めっきすればよい。この際、陽極としては、通常の銅‐亜鉛合金の電気めっきに用いられるものであれば、いずれも使用できる。本発明の銅‐亜鉛合金電気めっき浴を用いることにより、耐腐食性が向上した銅‐亜鉛合金めっき層を形成することができ、かつ、目的組成を有する均一で光沢のある銅‐亜鉛合金めっき層を幅広い電流密度で得ることが可能となる。 In performing the copper-zinc alloy plating treatment using the copper-zinc alloy electroplating bath of the present invention, a normal electroplating method can be employed. For example, electroplating may be performed at a bath temperature of about 30 to 40 ° C. with no stirring, mechanical stirring, or air stirring. At this time, any anode can be used as long as it can be used for electroplating of a normal copper-zinc alloy. By using the copper-zinc alloy electroplating bath of the present invention, a copper-zinc alloy plating layer with improved corrosion resistance can be formed, and a uniform and glossy copper-zinc alloy plating having a target composition can be formed. Layers can be obtained with a wide range of current densities.
上記銅‐亜鉛合金電気めっき処理を行う前に、被めっき体には、常法に従ってバフ研磨、脱脂、希酸浸漬等の通常の前処理を施すことができ、あるいは光沢ニッケルめっき等の下地めっきを施すことも可能である。また、銅‐亜鉛合金めっき処理後には、水洗、湯洗、乾燥等の通常行われている操作を行ってもよく、さらに必要に応じて、重クロム酸希薄溶液への浸漬、クリヤー塗装等を行ってもよい。 Before performing the copper-zinc alloy electroplating treatment, the object to be plated can be subjected to normal pretreatment such as buffing, degreasing, dilute acid immersion, etc. according to a conventional method, or base plating such as bright nickel plating. It is also possible to apply. In addition, after the copper-zinc alloy plating treatment, usual operations such as water washing, hot water washing and drying may be performed, and if necessary, immersion in a dichromate dilute solution, clear coating, etc. You may go.
本発明においては、被めっき体としては特に制限されず、通常、銅‐亜鉛合金めっき処理が施されるものであれば、いずれでも使用でき、例えば、金属コードの製造に用いられる金属ワイヤ等の金属製品や、プラスチック製品、セラミックス製品等を挙げることができる。これらには、銅‐亜鉛合金めっき処理を施す前に、常法に従って下地めっきを施すのが好ましい。 In the present invention, the material to be plated is not particularly limited, and any metal can be used as long as it is usually subjected to a copper-zinc alloy plating treatment, such as a metal wire used for the production of a metal cord. Examples include metal products, plastic products, and ceramic products. These are preferably subjected to base plating according to a conventional method before the copper-zinc alloy plating treatment.
以下、本発明を実施例を用いてより詳細に説明する。
（実施例１〜３、参考例１〜５、比較例）
下記表１に示す浴組成を有する銅‐亜鉛合金電気めっき浴を調製し、下記表２中の条件に従い、被めっき体として、ニッケルめっきを施したステンレス鋼板に銅‐亜鉛合金めっき処理を施し、評価試験の試料とした。
Hereinafter, the present invention will be described in more detail with reference to examples.
(Examples 1-3, Reference Examples 1-5, Comparative Example)
A copper-zinc alloy electroplating bath having the bath composition shown in Table 1 below is prepared, and a nickel-plated stainless steel plate is subjected to a copper-zinc alloy plating treatment as an object to be plated according to the conditions in Table 2 below. Samples for evaluation tests were used.
得られた銅‐亜鉛合金めっき層の元素含有量をＸ線光電子分光分析装置（ＥＳＣＡ）により定量分析したところ、表１に示されているような銅原子％、亜鉛原子％であった。なお、ＥＳＣＡ分析の主要条件は下記のとおりであった。
使用機器：ＥＳＣＡ‐７５０ （株式会社 島津製作所製）
１．Ｘ線源 Ｍｇ製円錐状アノード
２．試料寸法 ６ｍｍφ
３．Ｘ線照射部分 試料全面
４．測定室真空度 ２×１０−５Ｐａ以下
５．Ｘ線出力 ８ｋＶ、３０ｍＡ
６．イオンエッチング
（１）使用ガス Ａｒガス、純度９９．９９９％
（２）アルゴンガス圧 ５×１０−４Ｐａ
（３）放電電流 ２０ｍＡ
（４）加速電圧 ２ｋＶ
（５）イオン電流 ８〜１２μＶ
（６）エッチングスピード ５０〜１００オングストローム／分
（７）エッチング時間 ３００秒
When the element content of the obtained copper-zinc alloy plating layer was quantitatively analyzed by an X-ray photoelectron spectrometer (ESCA), it was copper atom% and zinc atom% as shown in Table 1. The main conditions for ESCA analysis were as follows.
Equipment used: ESCA-750 (manufactured by Shimadzu Corporation)
1. X-ray source Mg conical anode2. Sample size 6mmφ
3. X-ray irradiation part Whole sample surface 4. 4. Vacuum degree of measurement chamber 2 × 10 −5 Pa or less X-ray output 8 kV, 30 mA
6). Ion etching (1) Gas used Ar gas, purity 99.999%
(2) Argon gas pressure 5 × 10 −4 Pa
(3) Discharge current 20mA
(4) Acceleration voltage 2kV
(5) Ion current 8-12μV
(6) Etching speed 50-100 angstrom / min (7) Etching time 300 seconds
（耐腐食性試験）
得られた銅‐亜鉛合金めっき層につき、積層後の接着強度ａ（Ｎ／ｃｍ）、および、沸騰水中に２時間保持した後の接着強度ｂ（Ｎ／ｃｍ）をＪＩＳ Ｃ６４８１に準拠して（引きはがし幅１ｍｍ）、測定した。得られた結果から下記式に基づき、劣化率（％）を求めた。
劣化率（％）＝｛（ａ−ｂ）／ａ｝×１００
この数値が小さいほど劣化が少なく、耐腐食性に優れていることを意味する。結果を表２に併せて示す。
(Corrosion resistance test)
With respect to the obtained copper-zinc alloy plating layer, the adhesive strength a (N / cm) after lamination and the adhesive strength b (N / cm) after being kept in boiling water for 2 hours in accordance with JIS C6481 ( The peel width was 1 mm) and measured. Based on the obtained result, the deterioration rate (%) was determined based on the following formula.
Deterioration rate (%) = {(ab) / a} × 100
A smaller value means less deterioration and better corrosion resistance. The results are also shown in Table 2.
表２の結果より、本発明の銅‐亜鉛合金電気めっき浴を用いることで、耐腐食性が向上した銅‐亜鉛合金めっき層を形成することができ、かつ、目的組成を有する均一で光沢のある銅‐亜鉛合金めっき層を幅広い電流密度で得ることができることが確かめられた。 From the results in Table 2, by using the copper-zinc alloy electroplating bath of the present invention, a copper-zinc alloy plating layer with improved corrosion resistance can be formed, and a uniform and glossy composition having a target composition can be obtained. It was confirmed that a certain copper-zinc alloy plating layer can be obtained with wide current density.
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