JPH06146059A - Palladium-cobalt-indium alloy plating bath - Google Patents
Palladium-cobalt-indium alloy plating bathInfo
- Publication number
- JPH06146059A JPH06146059A JP30271792A JP30271792A JPH06146059A JP H06146059 A JPH06146059 A JP H06146059A JP 30271792 A JP30271792 A JP 30271792A JP 30271792 A JP30271792 A JP 30271792A JP H06146059 A JPH06146059 A JP H06146059A
- Authority
- JP
- Japan
- Prior art keywords
- liter
- palladium
- cobalt
- indium
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 34
- 229910000846 In alloy Inorganic materials 0.000 title claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- -1 sulfuric acid compound Chemical class 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 7
- 150000002471 indium Chemical class 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052763 palladium Inorganic materials 0.000 abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 13
- 239000010941 cobalt Substances 0.000 abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 206010020751 Hypersensitivity Diseases 0.000 abstract description 3
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 3
- 230000007815 allergy Effects 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 208000026935 allergic disease Diseases 0.000 abstract 1
- 235000019646 color tone Nutrition 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 238000009713 electroplating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- AEPKDRAICDFPEY-UHFFFAOYSA-L palladium(2+);dinitrite Chemical compound [Pd+2].[O-]N=O.[O-]N=O AEPKDRAICDFPEY-UHFFFAOYSA-L 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- VSEUCCPAJZHJSX-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;indium(3+) Chemical compound [In+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VSEUCCPAJZHJSX-UHFFFAOYSA-K 0.000 description 1
- BCSZNBYWPPFADT-UHFFFAOYSA-N 4-(1,2,4-triazol-4-ylmethyl)benzonitrile Chemical compound C1=CC(C#N)=CC=C1CN1C=NN=C1 BCSZNBYWPPFADT-UHFFFAOYSA-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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- DFJDEYXPDYCTPT-UHFFFAOYSA-H [In+3].S(N)([O-])(=O)=O.[In+3].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O Chemical compound [In+3].S(N)([O-])(=O)=O.[In+3].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O DFJDEYXPDYCTPT-UHFFFAOYSA-H 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- JYMHDNVZJJANCR-UHFFFAOYSA-J cobalt(2+) tetrasulfamate Chemical compound S(N)([O-])(=O)=O.[Co+2].[Co+2].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O JYMHDNVZJJANCR-UHFFFAOYSA-J 0.000 description 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- GHGNQWNTEPHORR-UHFFFAOYSA-L cobalt;dichlorocobalt Chemical compound [Co].Cl[Co]Cl GHGNQWNTEPHORR-UHFFFAOYSA-L 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、パラジウム・コバルト
・インジウム合金めっき浴に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a palladium-cobalt-indium alloy plating bath.
【０００２】[0002]
【従来の技術】電気めっきは金属の装飾、防錆、耐磨耗
用として古くから行われている方法であり、特に貴金属
めっきは光沢性に富み、装飾目的に、眼鏡フレーム、時
計外装部品等にしばしば施されている。とりわけ、白色
系めっきは優美さ、繊細さが表現され、他の貴金属めっ
きと同様広く一般に好まれている。2. Description of the Related Art Electroplating is a method that has been used for a long time for metal decoration, rust prevention, and abrasion resistance. Particularly, precious metal plating has a high gloss, and for decoration purposes, eyeglass frames, watch exterior parts, etc. Often applied to. In particular, white-based plating expresses elegance and delicacy, and like other precious metal platings, is widely popular.
【０００３】従来、貴金属による白色系めっきとしては
一般に、パラジウム・ニッケル合金めっきが頻用されて
いる。パラジウム単体でも白色を出すことは可能である
が、めっき皮膜の耐蝕性に難があり、これを向上させる
ためにはニッケルを含有させる必要があった。ところ
が、このニッケルが多くの人間に対し接触アレルギーを
引き起こすことが近年明らかになり、特に欧州において
は、ニッケルを含む製品に対し販売を禁止する国も出て
きており、このパラジウム・ニッケル合金めっきに代わ
る、貴金属による白色系めっきの開発が待たれていたの
である。Conventionally, palladium-nickel alloy plating has been frequently used as the white plating with a noble metal. Although it is possible to obtain white color even with palladium alone, the corrosion resistance of the plating film is poor, and in order to improve this, it was necessary to add nickel. However, it has become clear in recent years that this nickel causes contact allergies in many humans, and in particular in Europe, some countries have banned the sale of products containing nickel. The development of white-based plating with an alternative precious metal was awaited.
【０００４】[0004]
【解決すべき技術的課題】本発明は、貴金属による白色
系めっきに、上記のごとき問題があったことに鑑みてな
されたものであり、ニッケルを含まずとも耐蝕性に優れ
た白色系貴金属めっきが可能なパラジウム・コバルト・
インジウム合金めっき浴を提供することを技術的課題と
するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems in white-based plating with a noble metal, and white-based noble metal plating excellent in corrosion resistance even without containing nickel. Capable of palladium / cobalt /
It is a technical subject to provide an indium alloy plating bath.
【０００５】[0005]
【課題解決のために採用した手段】本発明はめっき浴に
おいて、カルボン酸１０〜２００g/リットルと硫酸化合物ま
たは亜硫酸化合物１〜２００g/リットルとパラジウム塩とし
てパラジウム１〜５０g/リットルとコバルト塩としてコバル
ト１〜５０g/リットルとインジウム塩としてインジウム0.1
〜３０g/リットルとを含有し、ｐＨを６〜１１にするという
手段を採用することにより前述の技術的課題を解決した
のである。Means adopted for solving the problems In the present invention, in a plating bath, 10 to 200 g / liter of carboxylic acid, 1 to 200 g / liter of sulfuric acid compound or sulfite compound, 1 to 50 g / liter of palladium salt as palladium salt, and cobalt as cobalt salt. 1-50g / l and indium 0.1 as indium salt
The above-mentioned technical problem was solved by adopting a means of containing -30 g / liter and adjusting pH to 6-11.
【０００６】以上の組成を有するめっき浴を、めっき浴
温度１５〜７０℃、電流密度 0.1〜５Ａ/dm2、陰極材料
としてカーボンあるいはチタン白金を用いて、めっき処
理を行うのである。The plating bath having the above composition is plated at a plating bath temperature of 15 to 70 ° C., a current density of 0.1 to 5 A / dm 2 , and carbon or titanium platinum as a cathode material.
【０００７】上記のカルボン酸、及び硫酸化合物または
亜硫酸化合物は、金属イオンの錯化並びにめっき浴の電
導性を向上させる作用があり、これらの濃度が高いほど
インジウムが優先して析出するが、それぞれ２００g/リッ
トル以上にした場合、析出物に色ムラを生じ著しく光沢が
低下するため、実用には適さない。The above-mentioned carboxylic acid and sulfuric acid compound or sulfurous acid compound have an action of improving the complexation of metal ions and the conductivity of the plating bath. The higher the concentration of these is, the more preferentially indium is deposited. When the amount is 200 g / liter or more, color unevenness is caused in the precipitate and the gloss is remarkably reduced, which is not suitable for practical use.
【０００８】また、ここに言うパラジウム塩とは、ジク
ロロテトラアンミンパラジウム、塩化第一パラジウム、
塩化パラジウムアンモニウム、塩化パラジウムナトリウ
ム、亜硝酸パラジウム、ジアミノ亜硝酸パラジウム等を
指し、例えば青化パラジウムカリウムのようなパラジウ
ムの青酸化合物では、光沢が乏しくなり「曇り」を生じ
てしまい実用には適さない。このパラジウム塩は、析出
物の主成分であるパラジウムの供給源であり、その濃度
によって析出成分中のパラジウム含有率は比例的に変化
する。しかし、浴中のパラジウム濃度が５０g/リットルを越
えると析出不良を起こし、１g/リットル未満では、光沢のな
い曇った析出物になり実用的でない。The palladium salt referred to herein is dichlorotetraamminepalladium, palladium (I) chloride,
Palladium ammonium chloride, sodium palladium chloride, palladium nitrite, diaminopalladium nitrite, etc. are not suitable for practical use because, for example, a hydrocyanic acid compound of palladium such as potassium palladium bromide will cause poor gloss and "cloudiness". . This palladium salt is a supply source of palladium, which is the main component of the precipitate, and the palladium content in the precipitate component changes proportionally depending on its concentration. However, when the concentration of palladium in the bath exceeds 50 g / liter, poor deposition occurs, and when it is less than 1 g / liter, it is not practical because it becomes a dull and cloudy deposit.
【０００９】また、ここに言うコバルト塩とは、塩化コ
バルト、硫酸コバルト、スルファミン酸コバルト、クエ
ン酸コバルト等を指し、例えは青化コバルトのような青
酸化合物では、光沢が乏しくなり「曇り」を生じてしま
い実用には適さない。このコバルト塩は析出物の主成分
であるコバルトの供給源であり、パラジウム塩の場合と
同様、濃度によって析出成分中のコバルト含有率は比例
的に変化する。しかし浴中のコバルト濃度が５０g/リットル
を越えると「曇り」を生じ、逆に１g/リットル未満では、析
出物の応力が増大し実用に供することはできない。The term "cobalt salt" as used herein refers to cobalt chloride, cobalt sulfate, cobalt sulfamate, cobalt citrate, etc. For example, a cyanide compound such as cobalt cyanide has poor gloss and causes "cloudiness". It occurs and is not suitable for practical use. This cobalt salt is a supply source of cobalt, which is the main component of the precipitate, and similarly to the case of the palladium salt, the cobalt content in the precipitate component changes in proportion to the concentration. However, when the cobalt concentration in the bath exceeds 50 g / liter, "cloudy" occurs, and when it is less than 1 g / liter, the stress of the precipitate increases and it cannot be put to practical use.
【００１０】また、ここに言うインジウム塩とは、塩化
インジウム、硫酸インジウム、スルファミン酸インジウ
ム、クエン酸インジウム等を指し、例えば、ホウフッ化
インジウムのようなインジウムのフッ化物では安定した
析出は得られない。このインジウム塩は、析出物の主成
分であるインジウムの供給源であり、パラジウム塩の場
合と同様、濃度によって析出成分中のインジウム含有率
は比例的に変化する。しかし、浴中のインジウム濃度
が、0.1 g/リットル未満の場合では「曇り」を生じ、逆に３
０g/リットル以上では、析出物の応力が極端に大きくなり実
用に供することはできない。The indium salt referred to herein means indium chloride, indium sulfate, indium sulfamate, indium citrate, etc. For example, stable precipitation cannot be obtained with a fluoride of indium such as indium borofluoride. . This indium salt is a supply source of indium, which is the main component of the precipitate, and the indium content in the precipitate component proportionally changes depending on the concentration, as in the case of the palladium salt. However, when the concentration of indium in the bath is less than 0.1 g / liter, "cloudy" occurs, and conversely 3
When it is 0 g / liter or more, the stress of the precipitate becomes extremely large and it cannot be put to practical use.
【００１１】更にまた、本発明においてｐＨは重要な働
きをする。ｐＨを６以下にした場合には、析出物が粗く
なることから「焦げ」を生じ、また、ｐＨ１１以上では
「曇り」を生じてしまう。Furthermore, the pH plays an important role in the present invention. When the pH is set to 6 or less, the precipitate becomes coarse and thus "burnt" occurs, and when the pH is 11 or more, "cloudy" occurs.
【００１２】[0012]
【実施例】以下、本発明にかかる実施例について説明す
る。 実施例１ 酒石酸ナトリウム １５０g/リットル 硫酸ナトリウム ６０g/リットル 塩化パラジウムアンモニウム パラジウムとして ３０g/リットル スルファミン酸コバルト コバルトとして ４０g/リットル 硫酸インジウム インジウムとして ５g/リットル サッカリン （光沢剤） ４g/リットル １,4ブチンジオール （光沢剤） 0.3 g/リットル 上記組成の溶液に、水酸化ナトリウムを加えてｐＨを１
０とし、液温５０℃、陰極電流密度 1.5Ａ/dm2の条件に
て電気めっき処理を行ったところ、白色のパラジウム・
コバルト・インジウム合金めっきが得られた。EXAMPLES Examples according to the present invention will be described below. Example 1 Sodium tartrate 150 g / liter Sodium sulfate 60 g / liter Palladium ammonium chloride Palladium 30 g / liter Cobalt sulfamate Cobalt 40 g / liter Indium sulfate Indium 5 g / liter Saccharin (brightener) 4 g / liter 1,4 butynediol ( Brightener) 0.3 g / liter To the solution of the above composition, add sodium hydroxide to adjust the pH to 1
When the electroplating treatment was performed under the conditions of 0, the liquid temperature of 50 ° C., and the cathode current density of 1.5 A / dm 2 , white palladium.
A cobalt / indium alloy plating was obtained.
【００１３】実施例２ クエン酸 １８０g/リットル 亜硫酸ナトリウム １００g/リットル ジアミノ亜硝酸パラジウム パラジウムとして ３g/リットル 塩化コバルト コバルトとして ５g/リットル スルファミン酸インジウム インジウムとして ２０g/リットル サッカリン （光沢剤） ４g/リットル ギ酸 （光沢剤） 0.5 cc/リットル 上記組成の溶液に、アンモニア水を加えてｐＨを 6.5と
し、液温２５℃、陰極電流密度 0.5Ａ/dm2の条件にて電
気めっき処理を行ったところ、薄灰色のパラジウム・コ
バルト・インジウム合金めっきが得られた。Example 2 Citric acid 180 g / liter Sodium sulfite 100 g / liter Diamino palladium Nitrite Palladium 3 g / liter Cobalt chloride Cobalt 5 g / liter Indium sulfamate Indium 20 g / liter Saccharin (brightener) 4 g / liter Formic acid ( (Brightener) 0.5 cc / liter To the solution of the above composition, ammonia water was added to adjust the pH to 6.5, and electroplating was performed under the conditions of a liquid temperature of 25 ° C. and a cathode current density of 0.5 A / dm 2 , and a light gray As a result, a palladium / cobalt / indium alloy plating was obtained.
【００１４】本実施例めっき浴で得られためっき皮膜
は、電気炉で２８０℃にて６０分間、加熱処理しても変
色することはなく、また５０％塩酸・５０％硫酸に１０
分間以上浸漬しても、その表面に酸化膜が生じたり、変
色したりすることはなかった。The plating film obtained in the plating bath of this example did not discolor even if it was heated at 280 ° C. for 60 minutes in an electric furnace, and was diluted with 50% hydrochloric acid / 50% sulfuric acid to 10%.
No oxide film was formed on the surface or discoloration occurred even after immersion for more than a minute.
【００１５】[0015]
【本発明の効果】以上、実施例をもって説明したとお
り、本発明パラジウム・コバルト・インジウム合金めっ
き浴によるめっき皮膜は、白色から薄灰色に至る色調を
呈し、なおかつ耐蝕性において、パラジウム・ニッケル
合金めっきに優るものであるため、アレルギー要因とな
るニッケルを含まない貴金属白色系めっきの可能なめっ
き浴としてその実用的価値は頗る高いものがある。As described above with reference to the examples, the plating film of the palladium / cobalt / indium alloy plating bath of the present invention exhibits a color tone ranging from white to light gray, and the corrosion resistance is palladium / nickel alloy plating. Therefore, it has a very high practical value as a plating bath capable of plating white precious metal that does not contain nickel, which is a cause of allergies.
【００１６】また、本発明めっき浴によるめっき皮膜
は、低応力なため、例えば眼鏡フレームに使用されるチ
タン材のようなニッケルを含まない部品の表面にも直
接、めっき処理することも可能になるのである。Further, since the plating film formed by the plating bath of the present invention has a low stress, it is possible to directly plate the surface of a nickel-free component such as a titanium material used for eyeglass frames. Of.
Claims (1)
合物または亜硫酸化合物１〜２００g/リットルとパラジウム
塩としてパラジウム１〜５０g/リットルとコバルト塩として
コバルト１〜５０g/リットルとインジウム塩としてインジウ
ム 0.1〜３０g/リットルとを含むｐＨが６〜１１であること
を特徴とするパラジウム・コバルト・インジウム合金め
っき浴。1. A carboxylic acid of 10 to 200 g / liter and a sulfuric acid compound or a sulfite compound of 1 to 200 g / liter, a palladium salt of 1 to 50 g / liter, a cobalt salt of 1 to 50 g / liter and an indium salt of indium of 0.1 to 10 g / liter. A palladium-cobalt-indium alloy plating bath having a pH of 6 to 11 including 30 g / liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30271792A JPH06146059A (en) | 1992-11-12 | 1992-11-12 | Palladium-cobalt-indium alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30271792A JPH06146059A (en) | 1992-11-12 | 1992-11-12 | Palladium-cobalt-indium alloy plating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06146059A true JPH06146059A (en) | 1994-05-27 |
Family
ID=17912329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30271792A Pending JPH06146059A (en) | 1992-11-12 | 1992-11-12 | Palladium-cobalt-indium alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06146059A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8460533B2 (en) | 2006-12-15 | 2013-06-11 | Rohm And Haas Electronic Materials Llc | Indium compositions |
| US8491773B2 (en) | 2008-04-22 | 2013-07-23 | Rohm And Haas Electronic Materials Llc | Method of replenishing indium ions in indium electroplating compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62139893A (en) * | 1985-12-12 | 1987-06-23 | リ−ロ−ナル インコ−ポレ−テツド | Alkaline plating bath and electrodeposition method for electrodeposition of palladium or palladium alloy |
| JPH04160145A (en) * | 1990-10-24 | 1992-06-03 | Seiko Epson Corp | Exterior parts for watches |
-
1992
- 1992-11-12 JP JP30271792A patent/JPH06146059A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62139893A (en) * | 1985-12-12 | 1987-06-23 | リ−ロ−ナル インコ−ポレ−テツド | Alkaline plating bath and electrodeposition method for electrodeposition of palladium or palladium alloy |
| JPH04160145A (en) * | 1990-10-24 | 1992-06-03 | Seiko Epson Corp | Exterior parts for watches |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8460533B2 (en) | 2006-12-15 | 2013-06-11 | Rohm And Haas Electronic Materials Llc | Indium compositions |
| US9206519B2 (en) | 2006-12-15 | 2015-12-08 | Rohm And Haas Electronic Materials Llc | Indium compositions |
| US8491773B2 (en) | 2008-04-22 | 2013-07-23 | Rohm And Haas Electronic Materials Llc | Method of replenishing indium ions in indium electroplating compositions |
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