JP2977503B2 - Copper-palladium alloy plating solution and plating substrate - Google Patents
Copper-palladium alloy plating solution and plating substrateInfo
- Publication number
- JP2977503B2 JP2977503B2 JP9044837A JP4483797A JP2977503B2 JP 2977503 B2 JP2977503 B2 JP 2977503B2 JP 9044837 A JP9044837 A JP 9044837A JP 4483797 A JP4483797 A JP 4483797A JP 2977503 B2 JP2977503 B2 JP 2977503B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- palladium
- plating solution
- plating
- compound
- 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.)
- Expired - Lifetime
Links
- 238000007747 plating Methods 0.000 title claims description 89
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 title claims description 24
- 229910001252 Pd alloy Inorganic materials 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000001447 alkali salts Chemical class 0.000 claims description 8
- -1 ammonium palladium compound Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000005749 Copper compound Substances 0.000 claims description 7
- 150000001880 copper compounds Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 6
- 201000005299 metal allergy Diseases 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000537 White brass Inorganic materials 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、光沢性、耐蝕性等
のある銅−パラジウム系合金メッキ液及びメッキ基材に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plating solution of a copper-palladium alloy having glossiness and corrosion resistance and a plating substrate.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、金属製の眼鏡フレームや腕時計外装部品等に白色メ
ッキを施そうとする場合等にはニッケルメッキが多用さ
れている。2. Description of the Related Art Conventionally, nickel plating has been frequently used when white plating is to be applied to a metal spectacle frame, a wristwatch exterior part, or the like.
【０００３】しかしながら、ニッケルは金属アレルギー
の主な原因となるものであって、金属アレルギーを起こ
し易い人はニッケルメッキによる白色メッキが施された
物品を利用することができないという問題があるため、
これに代わる代替えメッキの開発が望まれている。[0003] However, nickel is a major cause of metal allergy, and there is a problem that a person who is susceptible to metal allergy cannot use articles plated with white by nickel plating.
The development of alternative plating is desired.
【０００４】一方、銅と亜鉛とを含有せしめた銅−亜鉛
系の合金メッキ液（白色黄銅メッキ液）や、銅とスズと
を含有せしめた銅−スズ系の合金メッキ液（スペキュラ
ムメッキ液）によっても白色メッキを施すことができ
る。On the other hand, a copper-zinc alloy plating solution containing copper and zinc (white brass plating solution) and a copper-tin alloy plating solution containing copper and tin (speculum plating solution) White plating.
【０００５】しかしながら、白色黄銅メッキは耐蝕性が
悪いという不具合があり、スペキュラムメッキは光沢
性、合金比率、メッキ厚づけ性が安定しないという不具
合があるため、これらのメッキ液は用途が限定されてい
た。However, white brass plating has a problem that corrosion resistance is poor, and speculum plating has a problem that brightness, alloy ratio and plating thickness are not stable. Was.
【０００６】本出願人は、上記従来技術の有する問題に
鑑みて金属アレルギーを誘発する虞のあるニッケルメッ
キに代え、光沢が良く白色優美であるとともに耐蝕性や
厚づけ性等にも優れた白色合金メッキを提供すべく鋭意
研究を重ねた結果、本発明を完成するに至った。[0006] In view of the problems of the prior art described above, the present applicant has replaced nickel plating, which may induce metal allergy, with a white color which is excellent in glossiness, graceful whiteness, corrosion resistance, thickness and the like. As a result of intensive studies to provide alloy plating, the present invention has been completed.
【０００７】[0007]
【課題を解決するための手段】本発明は、（１）遊離シ
アン濃度が４０〜６０ｇ／Ｌであり且つ水酸化アルカリ
でｐＨが１２以上となるように調製された、可溶性銅化
合物、可溶性アンモニウムパラジウム化合物及び可溶性
第二スズアルカリ化合物を含有する銅−パラジウム系合
金メッキ液に、アルカリ塩を含有させるとともに、可溶
性亜鉛化合物を金属亜鉛換算で０．００１ｍｇ／Ｌ〜１
ｇ／Ｌ含有せしめたことを特徴とする銅−パラジウム系
合金メッキ液、（２）可溶性銅化合物がＣｕＣＮであ
り、その含有量が金属銅換算で２０〜５０ｇ／Ｌである
上記（１）記載の銅−パラジウム系合金メッキ液、
（３）可溶性アンモニウムパラジウム化合物が〔Ｐｄ
（ＮＨ3 ）4 〕（ＣＮ）2 であり、その含有量が金属パ
ラジウム換算で５〜２０ｇ／Ｌである上記（１）又は
（２）記載の銅−パラジウム系合金メッキ液、（４）可
溶性第二スズアルカリ化合物がＮａＳｎＯ3 であり、そ
の含有量が金属スズ換算で５〜２０ｇ／Ｌである上記
（１）、（２）又は（３）記載の銅−パラジウム系合金
メッキ液、（５）アルカリ塩がＫＮａＣ4 Ｏ6 であり、
その含有量が５〜２００ｇ／Ｌである上記（１）、
（２）、（３）又は（４）記載の銅−パラジウム系合金
メッキ液、（６）上記（１）、（２）、（３）、（４）
又は（５）記載の銅−パラジウム系合金メッキ液により
表面の一部又は全部にメッキ被膜が施されたメッキ基材
であり、メッキ被膜中に銅４６〜６６重量％、パラジウ
ム４５〜２５重量％を含有し、残成分がスズ及び亜鉛で
あることを特徴とする銅−パラジウム系合金メッキ基材
を要旨とする。DISCLOSURE OF THE INVENTION The present invention relates to (1) a soluble copper compound and a soluble ammonium compound which are prepared so as to have a free cyanide concentration of 40 to 60 g / L and a pH of 12 or more with alkali hydroxide. An alkali salt is contained in a copper-palladium alloy plating solution containing a palladium compound and a soluble stannic alkali compound, and a soluble zinc compound is contained in an amount of 0.001 mg / L to 1 in terms of zinc metal.
g / L; a copper-palladium alloy plating solution, wherein (2) the soluble copper compound is CuCN and the content thereof is 20 to 50 g / L in terms of metallic copper. Copper-palladium alloy plating solution,
(3) When the soluble ammonium palladium compound is [Pd
(NH 3 ) 4 ] (CN) 2 , the content of which is 5 to 20 g / L in terms of metal palladium, the copper-palladium alloy plating solution according to the above (1) or (2), (4) soluble The copper-palladium alloy plating solution according to the above (1), (2) or (3), wherein the stannic alkali compound is NaSnO 3 and the content thereof is 5 to 20 g / L in terms of metal tin. ) The alkali salt is KNaC 4 O 6 ,
(1) whose content is 5-200 g / L,
(2), the copper-palladium alloy plating solution according to (3) or (4), (6) the above (1), (2), (3), (4)
Or a plating base material in which a plating film is applied to a part or all of the surface with the copper-palladium alloy plating solution according to (5), wherein 46 to 66% by weight of copper and 45 to 25% by weight of palladium in the plating film And a balance of tin and zinc, wherein the balance is tin and zinc.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【０００９】本発明の銅−パラジウム系合金メッキ液に
含有せしめる可溶性銅化合物としては、例えば、シアン
化第一銅、シアン化第一銅カリウム、シアン化第一銅ナ
トリウム等を用いることができる。本発明では薬品入手
の容易さの点でシアン化第一銅（ＣｕＣＮ）を用いるの
が好ましい。As the soluble copper compound to be contained in the copper-palladium alloy plating solution of the present invention, for example, cuprous cyanide, potassium cuprous cyanide, sodium cuprous cyanide and the like can be used. In the present invention, it is preferable to use cuprous cyanide (CuCN) from the viewpoint of easy availability of chemicals.
【００１０】可溶性銅化合物の含有量は、金属銅に換算
した量で２０〜５０ｇ／Ｌであるのが好ましく、２０ｇ
／Ｌ未満であるとレベリング光沢性の低下をきたしてし
まい、５０ｇ／Ｌよりも多くなると銅の析出が過剰にな
りメッキの色調が銅色となってしまう。[0010] The content of the soluble copper compound is preferably 20 to 50 g / L in terms of metallic copper, and is preferably 20 g / L.
If it is less than / L, the leveling gloss will decrease, and if it is more than 50 g / L, the precipitation of copper will be excessive and the color tone of the plating will be copper.
【００１１】また、可溶性アンモニウムパラジウム化合
物としては、例えば、〔Ｐｄ（ＮＨ3 ）4 〕（Ｃ
Ｎ）2 、ＰｄＣｌ2 （ＮＨ3 ）2 、Ｐｄ（ＮＯ2 ）
2 （ＮＨ3 ）2等を用いることができる。本発明ではメ
ッキ液の安定性、老化防止の点で〔Ｐｄ（ＮＨ3 ）4 〕
（ＣＮ）2 を用いるのが好ましい。Examples of the soluble ammonium palladium compound include, for example, [Pd (NH 3 ) 4 ] (C
N) 2 , PdCl 2 (NH 3 ) 2 , Pd (NO 2 )
2 (NH 3 ) 2 or the like can be used. In the present invention, [Pd (NH 3 ) 4 ] is used in terms of stability of plating solution and prevention of aging.
It is preferred to use (CN) 2 .
【００１２】可溶性アンモニウムパラジウム化合物の含
有量は、金属パラジウムに換算した量で５〜２０ｇ／Ｌ
であるのが好ましく、５ｇ／Ｌ未満であると電流効率の
低下をきたしてしまい、２０ｇ／Ｌよりも多くなるとパ
ラジウムの析出が増えてしまうため採算上好ましくな
い。The content of the soluble ammonium palladium compound is 5 to 20 g / L in terms of metal palladium.
Is preferably less than 5 g / L, the current efficiency is lowered, and if it is more than 20 g / L, the precipitation of palladium increases, which is not profitable.
【００１３】また、可溶性第二スズアルカリ化合物とし
ては、例えば、Ｎａ2 ＳｎＯ3 、ＮａＮＨ4 ＳｎＯ3 、
ＫＮＨ4 ＳｎＯ3 等を用いることができる。本発明では
安価に入手できるという点でＮａ2 ＳｎＯ3 を用いるの
が好ましい。The soluble stannic alkali compounds include, for example, Na 2 SnO 3 , NaNH 4 SnO 3 ,
KNH 4 SnO 3 or the like can be used. In the present invention, it is preferable to use Na 2 SnO 3 because it can be obtained at low cost.
【００１４】可溶性第二スズアルカリ化合物の含有量
は、金属スズに換算した量で５〜２０ｇ／Ｌであるのが
好ましく、含有量が５ｇ／Ｌ未満であると光沢の低下を
きたし、２０ｇ／Ｌよりも多くなるとスズの析出が増
え、メッキの物性も悪くなるため好ましくない。尚、本
発明では第一スズ塩は使用することができない。The content of the soluble stannic alkali compound is preferably 5 to 20 g / L in terms of metal tin, and if the content is less than 5 g / L, the gloss is reduced, and the content is 20 g / L. If it exceeds L, the precipitation of tin increases, and the physical properties of plating deteriorate, which is not preferable. In the present invention, stannous salts cannot be used.
【００１５】本発明にあっては上記可溶性銅化合物、可
溶性アンモニウムパラジウム化物及び可溶性第二スズア
ンモニウム化合物に加え、アルカリ塩とともに可溶性亜
鉛化合物をメッキ液中に含有させる。In the present invention, in addition to the above-mentioned soluble copper compound, soluble ammonium palladium compound and soluble stannic ammonium compound, a soluble zinc compound is contained in the plating solution together with an alkali salt.
【００１６】本発明においてアルカリ塩は金属錯塩安定
剤として作用する。該アルカリ塩には、例えば、ＫＮａ
Ｃ4 Ｏ6 、Ｎａ4 Ｐ2 Ｏ7 等を用いることができる。本
発明では安定性の点でＫＮａＣ4 Ｏ6 を用いるのが好ま
しい。In the present invention, the alkali salt acts as a metal complex salt stabilizer. The alkali salt includes, for example, KNa
C 4 O 6 , Na 4 P 2 O 7 and the like can be used. In the present invention, it is preferable to use KNaC 4 O 6 from the viewpoint of stability.
【００１７】アルカリ塩の含有量は５〜２００ｇ／Ｌで
あるのが好ましく、５ｇ／Ｌ未満であると第二スズ化合
物の溶解安定性が悪くなり、２００ｇ／Ｌよりも多くな
ると光沢範囲が狭くなり良好な光沢が得られ難くなって
しまう。The content of the alkali salt is preferably from 5 to 200 g / L, and if it is less than 5 g / L, the dissolution stability of the stannic compound becomes poor, and if it exceeds 200 g / L, the gloss range becomes narrow. And it becomes difficult to obtain good gloss.
【００１８】また、可溶性亜鉛化合物としては、例え
ば、Ｋ2 Ｚｎ（ＣＮ）4 、Ｎａ2 Ｚｎ（ＣＮ）4 、Ｚｎ
（ＣＮ）2 等を用いることができる。本発明では入手の
容易さの点でＺｎ（ＣＮ）2 を用いるのが好ましい。Examples of the soluble zinc compound include K 2 Zn (CN) 4 , Na 2 Zn (CN) 4 , Zn
(CN) 2 or the like can be used. In the present invention, it is preferable to use Zn (CN) 2 from the viewpoint of availability.
【００１９】可溶性亜鉛化合物の含有量は、金属亜鉛に
換算した量で０．００１ｍｇ／Ｌ〜１ｍｇ／Ｌであるの
が好ましく、含有量が０．００１ｍｇ／Ｌ未満であると
メッキの光沢安定性が悪くなり、１ｇ／Ｌよりも多くな
るとメッキの物性が悪くなってしまう。The content of the soluble zinc compound is preferably 0.001 mg / L to 1 mg / L in terms of zinc metal, and if the content is less than 0.001 mg / L, the gloss stability of the plating is reduced. , And if it exceeds 1 g / L, the physical properties of the plating deteriorate.
【００２０】また、本発明メッキ液にあっては、メッキ
液中の遊離シアン濃度が４０〜６０ｇ／Ｌとなるように
調製する。メッキ液中の遊離シアン濃度が４０ｇ／Ｌ未
満ではメッキの光沢が安定せず、６０ｇ／Ｌよりも多く
なるとメッキの色調がブロンズ色となってしまうため好
ましくない。The plating solution of the present invention is prepared so that the free cyanide concentration in the plating solution is 40 to 60 g / L. If the free cyanide concentration in the plating solution is less than 40 g / L, the gloss of the plating is not stable, and if it exceeds 60 g / L, the color tone of the plating becomes undesirably bronze.
【００２１】更に、本発明メッキ液のｐＨは、水酸化ア
ルカリで１２以上、好ましくは１２．５以上となるよう
に調製される。ｐＨが１２未満の場合は第二スズ化合物
の溶解安定性や、メッキの光沢性が悪くなってしまう。
本発明メッキ液のｐＨを調製する水酸化アルカリとして
は、例えば、ＮＨ4 ＯＨ、ＮａＯＨ、ＫＯＨ等を用いる
ことができる。Further, the pH of the plating solution of the present invention is adjusted to 12 or more, preferably 12.5 or more, with alkali hydroxide. When the pH is less than 12, the dissolution stability of the stannic compound and the luster of the plating deteriorate.
As the alkali hydroxide for adjusting the pH of the plating solution of the present invention, for example, NH 4 OH, NaOH, KOH and the like can be used.
【００２２】このような本発明の銅−パラジウム系合金
メッキ液を用いて被メッキ物に白色メッキを施すには、
例えば、電圧１〜１０Ｖ、電流密度０．１〜１０Ａ／ｄ
ｍ2等の条件で、従来公知の方法により行うことができ
る。In order to apply white plating to an object to be plated using the copper-palladium alloy plating solution of the present invention,
For example, voltage 1-10V, current density 0.1-10A / d
It can be carried out by a conventionally known method under conditions such as m 2 .
【００２３】また、本発明の銅−パラジウム系合金メッ
キ基材は上記したようなメッキ液を用いて、その表面の
一部又は全部に銅−パラジウム系合金メッキ被膜を形成
したものであり、該メッキ被膜中には、銅４６〜６６重
量％、パラジウム４５〜２５重量％を含有し、残成分が
スズ及び亜鉛である。The copper-palladium-based alloy plating substrate of the present invention is obtained by forming a copper-palladium-based alloy plating film on a part or all of the surface thereof by using the plating solution as described above. The plating film contains 46 to 66% by weight of copper and 45 to 25% by weight of palladium, and the remaining components are tin and zinc.
【００２４】本発明メッキ基材の具体的な形態には、眼
鏡フレーム、腕時計の外装部品、装身具、筆記用具、置
物類等を挙げることができる。また、本発明メッキ基材
には必要に応じてその最表面に金、パラジウム等の貴金
属を用いた仕上げメッキ層を設けることもできる。Specific examples of the plating base material of the present invention include eyeglass frames, exterior parts of wristwatches, accessories, writing utensils, ornaments, and the like. Further, the plating base material of the present invention may be provided with a finish plating layer using a noble metal such as gold or palladium on the outermost surface, if necessary.
【００２５】[0025]
【実施例】次に具体的な実施例を挙げて本発明をより詳
細に説明するが、本発明はこれらに限定されるものでは
ない。Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.
【００２６】実施例１ 長さ１０ｃｍ×幅１５ｃｍ×厚み０．１ｃｍの黄銅素材
からなる板状の試験片に、アルカリ脱脂（マクダット
社：ＷＳＰ）、電解脱脂（マクダット社：ＤＥＷ）、酸
浸積（５重量％硫酸）の順に一般の銅合金用の処理と同
様の前処理を施した後、下記組成の本発明銅−パラジウ
ム系合金メッキ液を用いて、該メッキ液の温度を５５℃
とし、電圧３Ｖ、電流密度５Ａ／ｄｍ2 で３０分間陰極
電解してメッキを施したところ、試験片上に良好な光沢
を有する白色優美なメッキ被膜が５μｍの厚さで形成さ
れた。Example 1 A plate-like test piece made of a brass material having a length of 10 cm, a width of 15 cm and a thickness of 0.1 cm was subjected to alkaline degreasing (McDat: WSP), electrolytic degreasing (McDat: DEW), and acid immersion. (5% by weight sulfuric acid) in this order, after performing the same pretreatment as the treatment for general copper alloys, using a copper-palladium alloy plating solution of the present invention having the following composition, and raising the temperature of the plating solution to 55 ° C.
When plating was performed by performing cathodic electrolysis at a voltage of 3 V and a current density of 5 A / dm 2 for 30 minutes, a white and elegant plating film having good gloss was formed on the test piece with a thickness of 5 μm.
【００２７】また、メッキの施された試験片を１８０度
折り曲げたところ、メッキ被膜には割れも入らず、剥離
もなく耐摩耗性も良好なものであった。尚、メッキ被膜
の組成を分析してみたところ、銅が５１重量％、パラジ
ウムが４０重量％含まれており、残りはスズと亜鉛であ
った。When the plated test piece was bent at 180 degrees, the plated coating did not crack, did not peel off, and had good wear resistance. When the composition of the plating film was analyzed, it was found that 51% by weight of copper and 40% by weight of palladium were contained, and the balance was tin and zinc.
【００２８】 ＜銅−パラジウム系合金メッキ液組成＞ ＣｕＣＮ ・・・２０ｇ／Ｌ（金属銅換算） 〔Ｐｄ（ＮＨ3 ）4 〕（ＣＮ）2 ・・・２０ｇ／Ｌ（金属パラジウム換算） ＺｎＣＮ ・・・0.１ｇ／Ｌ（金属亜鉛換算） Ｎａ2 ＳｎＯ3 ・・・１０ｇ／Ｌ（金属スズ換算） ＫＮａＣ4 Ｏ6 ・・・３０ｇ／Ｌ 遊離シアン濃度 ・・・４０ｇ／Ｌ ｐＨ ・・・１２<Copper-palladium alloy plating solution composition> CuCN: 20 g / L (in terms of metallic copper) [Pd (NH 3 ) 4 ] (CN) 2 :: 20 g / L (in terms of metallic palladium) ZnCN 0.1 g / L (in terms of metallic zinc) Na 2 SnO 3 ··· 10 g / L (in terms of metallic tin) KNaC 4 O 6 ··· 30 g / L Free cyanide concentration ··· 40 g / L pH ··· 12
【００２９】比較例１ 実施例１のメッキ液中のシアン化パラジウムアミンの代
わりにシアン化パラジウムカリウムを含有せしめた以外
は実施例１で用いたメッキ液と同様のメッキ液を用い、
実施例１と同様の方法で試験片にメッキを施したとこ
ろ、試験片上にはクモリのある白色のメッキ被膜が５μ
ｍの膜厚で形成され、実施例１とは大きく異なる結果で
あった。Comparative Example 1 A plating solution similar to the plating solution used in Example 1 was used except that palladium potassium cyanide was contained in place of the palladium cyanide amine in the plating solution of Example 1.
When a test piece was plated in the same manner as in Example 1, a white plating film having cloudiness was 5 μm on the test piece.
m, and the result was significantly different from that of Example 1.
【００３０】比較例２ 実施例１のメッキ液からシアン化亜鉛を除いた以外は実
施例１で用いたメッキ液と同様のメッキ液を用い、実施
例１と同様の方法で試験片にメッキを施したところ、試
験片上には白色のメッキ被膜が５μｍの膜厚で形成され
たが、該メッキ被膜には完全な光沢が得られず、部分的
に光沢ムラが確認され、実施例１とは大きく異なる結果
であった。Comparative Example 2 A test piece was plated in the same manner as in Example 1 using the same plating solution as used in Example 1 except that zinc cyanide was removed from the plating solution of Example 1. As a result, a white plated film having a thickness of 5 μm was formed on the test piece, but complete gloss was not obtained on the plated film, and uneven gloss was partially observed. The results were very different.
【００３１】比較例３ 実施例１のメッキ液からロッシェル塩を除いた以外は実
施例１で用いたメッキ液と同様のメッキ液を用い、実施
例１と同様の方法で試験片にメッキを施したところ、試
験片上には白色のメッキ被膜が５μｍの膜厚で形成され
たが、その後メッキ液が濁り、更に再度別の試験片に同
じ条件でメッキを施したところ、今度はメッキ被膜の光
沢がなくなり、安定しない結果となってしまい、実施例
１とは大きく異なる結果であった。COMPARATIVE EXAMPLE 3 A test piece was plated in the same manner as in Example 1 by using the same plating solution as used in Example 1 except that Rochelle salt was removed from the plating solution of Example 1. As a result, a white plating film having a thickness of 5 μm was formed on the test piece, but thereafter the plating solution became turbid, and another test piece was plated again under the same conditions. Disappeared, resulting in an unstable result, which was significantly different from Example 1.
【００３２】比較例４ 実施例１のメッキ液から第二スズ酸ナトリウムを除いた
以外は実施例１で用いたメッキ液と同様のメッキ液を用
い、実施例１と同様の方法で試験片にメッキを施したと
ころ、試験片上には白色のメッキ被膜が５μｍの膜厚で
形成されたが、該メッキ被膜には光沢ムラがあり、実施
例１とは大きく異なる結果であった。COMPARATIVE EXAMPLE 4 A test piece was prepared in the same manner as in Example 1 except that sodium stannate was removed from the plating solution of Example 1. As a result of plating, a white plating film was formed on the test piece with a thickness of 5 μm. However, the plating film had uneven gloss, which was significantly different from that of Example 1.
【００３３】実施例２〜４ 次に、実施例１と同様のメッキ液を用い、メッキ処理時
の電流密度を変えた以外は実施例１と同様の方法で試験
片にメッキを施し、得られたメッキ被膜の組成を分析し
た。その関係を表１に示す。Examples 2 to 4 Next, a test piece was plated in the same manner as in Example 1 except that the plating solution was changed and the current density during plating was changed using the same plating solution. The composition of the plated coating was analyzed. Table 1 shows the relationship.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】以上説明したように、本発明銅−パラジ
ウム系合金メッキ液及びメッキ基材は、金属アレルギー
の原因となるニッケル塩やコバルト塩を含んでいないた
め金属アレルギーを起こし易い人でも容易に扱うことが
できるのみならず、メッキの色調を著しく異ならせず光
沢が良く白色優美であるとともに耐蝕性や厚づけ性等に
も優れた白色合金メッキが得られ、しかも貴金属を多量
に含んでいないので厚いメッキ被膜を安価に且つ容易に
得ることができる。As described above, the copper-palladium alloy plating solution and the plating substrate of the present invention do not contain a nickel salt or a cobalt salt which causes metal allergy, so that even a person who is liable to cause metal allergy can easily do so. In addition to being able to handle, the color tone of the plating is not remarkably changed, and the white alloy plating which is excellent in gloss and white and has excellent corrosion resistance and thickening property is obtained, and contains a large amount of precious metals. Therefore, a thick plating film can be easily obtained at low cost.
Claims (6)
且つ水酸化アルカリでｐＨが１２以上となるように調製
された、可溶性銅化合物、可溶性アンモニウムパラジウ
ム化合物及び可溶性第二スズアルカリ化合物を含有する
銅−パラジウム系合金メッキ液に、アルカリ塩を含有さ
せるとともに、可溶性亜鉛化合物を金属亜鉛換算で０．
００１ｍｇ／Ｌ〜１ｇ／Ｌ含有せしめたことを特徴とす
る銅−パラジウム系合金メッキ液。1. A soluble copper compound, a soluble ammonium palladium compound and a soluble stannic alkali compound prepared so that the free cyanide concentration is 40 to 60 g / L and the pH is adjusted to 12 or more with alkali hydroxide. The copper-palladium alloy plating solution to be added contains an alkali salt and a soluble zinc compound is added in an amount of 0.1 in metal zinc equivalent.
A copper-palladium alloy plating solution containing 001 mg / L to 1 g / L.
有量が金属銅換算で２０〜５０ｇ／Ｌである請求項１記
載の銅−パラジウム系合金メッキ液。2. The copper-palladium alloy plating solution according to claim 1, wherein the soluble copper compound is CuCN, and the content thereof is 20 to 50 g / L in terms of metallic copper.
〔Ｐｄ（ＮＨ3 ）4 〕（ＣＮ）2 であり、その含有量が
金属パラジウム換算で５〜２０ｇ／Ｌである請求項１又
は２記載の銅−パラジウム系合金メッキ液。3. The copper-palladium according to claim 1, wherein the soluble ammonium palladium compound is [Pd (NH 3 ) 4 ] (CN) 2 , and the content thereof is 5 to 20 g / L in terms of metal palladium. System alloy plating solution.
Ｏ3 であり、その含有量が金属スズ換算で５〜２０ｇ／
Ｌである請求項１、２又は３記載の銅−パラジウム系合
金メッキ液。4. The method according to claim 1, wherein the soluble stannic alkali compound is NaSn.
O 3 whose content is 5 to 20 g /
4. The copper-palladium alloy plating solution according to claim 1, wherein L is L.
含有量が５〜２００ｇ／Ｌである請求項１、２、３又は
４記載の銅−パラジウム系合金メッキ液。5. The copper-palladium alloy plating solution according to claim 1, wherein the alkali salt is KNaC 4 O 6 and the content thereof is 5 to 200 g / L.
ラジウム系合金メッキ液により表面の一部又は全部にメ
ッキ被膜が施されたメッキ基材であり、メッキ被膜中に
銅４６〜６６重量％、パラジウム４５〜２５重量％を含
有し、残成分がスズ及び亜鉛であることを特徴とする銅
−パラジウム系合金メッキ基材。6. A plating base material having a plating film applied to a part or all of its surface with the copper-palladium alloy plating solution according to claim 1, 2, 3 or 4. A copper-palladium-based alloy-plated substrate containing 46 to 66% by weight and 45 to 25% by weight of palladium, with the balance being tin and zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9044837A JP2977503B2 (en) | 1997-02-13 | 1997-02-13 | Copper-palladium alloy plating solution and plating substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9044837A JP2977503B2 (en) | 1997-02-13 | 1997-02-13 | Copper-palladium alloy plating solution and plating substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10219467A JPH10219467A (en) | 1998-08-18 |
| JP2977503B2 true JP2977503B2 (en) | 1999-11-15 |
Family
ID=12702596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9044837A Expired - Lifetime JP2977503B2 (en) | 1997-02-13 | 1997-02-13 | Copper-palladium alloy plating solution and plating substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2977503B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017055553A1 (en) * | 2015-09-30 | 2017-04-06 | Coventya S.P.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3964189B2 (en) * | 2001-11-22 | 2007-08-22 | 住友大阪セメント株式会社 | Electroless plating catalyst and metal plating pattern forming method |
| AT514818B1 (en) | 2013-09-18 | 2015-10-15 | W Garhöfer Ges M B H Ing | Deposition of Cu, Sn, Zn coatings on metallic substrates |
-
1997
- 1997-02-13 JP JP9044837A patent/JP2977503B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017055553A1 (en) * | 2015-09-30 | 2017-04-06 | Coventya S.P.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate |
| EP3150744B1 (en) * | 2015-09-30 | 2020-02-12 | COVENTYA S.p.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy layer, method for electrochemical deposition of said alloy layer, substrate comprising said alloy layer and uses of the coated substrate |
| EP3356579B1 (en) * | 2015-09-30 | 2020-03-11 | Coventya S.p.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10219467A (en) | 1998-08-18 |
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