JPS648719B2 - - Google Patents
Info
- Publication number
- JPS648719B2 JPS648719B2 JP16657781A JP16657781A JPS648719B2 JP S648719 B2 JPS648719 B2 JP S648719B2 JP 16657781 A JP16657781 A JP 16657781A JP 16657781 A JP16657781 A JP 16657781A JP S648719 B2 JPS648719 B2 JP S648719B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- microns
- nickel
- gold
- tin
- 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
Links
- 238000007747 plating Methods 0.000 claims description 48
- 229910000531 Co alloy Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001096 P alloy Inorganic materials 0.000 claims description 6
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- -1 Au-Ni-In Inorganic materials 0.000 description 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】
本発明は、時計用外装部品に関するものであ
る。更に詳しくは、金めつきした時計用外装部品
の耐食性を著しく向上せしめたものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an exterior part for a timepiece. More specifically, it significantly improves the corrosion resistance of gold-plated watch exterior parts.
従来、時計用外装部品の金めつきは、時計ケー
スを例にたとえ説明するとニツケル、ニツケル−
コバルト合金の下地めつきを１〜５ミクロン施
し、その上にAu−Ag、Au−Cu、Au−Ni−In、
Au−Pdなどの金合金めつきを５ミクロン程度施
していた。 Conventionally, the gold plating of exterior parts for watches has been applied using nickel and nickel metal plating, using a watch case as an example.
A cobalt alloy undercoat of 1 to 5 microns is applied, and then Au-Ag, Au-Cu, Au-Ni-In,
Gold alloy plating such as Au-Pd was applied to about 5 microns.
しかしこれらは、すじ目仕上げの様に表面が凹
凸状になつている場合は、すじ目の谷部にめつき
が完全に被覆されにくいため、苛酷な使用環境下
では、腐食され易いという問題があつた。 However, when the surface is uneven like a lined finish, it is difficult for the plating to completely cover the valleys of the lines, making it susceptible to corrosion under harsh usage environments. It was hot.
そこで一般的には、下地めつきまたは、金めつ
きの厚みを厚くしたりあるいは、透明樹脂をコー
テイングする方法が採られていたが、前記方法で
は、めつき厚を厚くすると素地に施こされるすじ
目仕上げの目付けが消え外観が損なわれたり、透
明樹脂のコーテイングでは、キズ、ハガレなどが
生じ耐久品質に劣るなどの欠点があつた。 Generally, methods have been adopted to increase the thickness of the base plating or gold plating, or to coat the base with transparent resin. There were drawbacks such as the streak finish's weight disappearing and the appearance being impaired, and the transparent resin coating causing scratches and peeling, resulting in poor durability.
本発明は、上記欠点に鑑み下地めつきにより耐
食性が従来のものより向上出来ないものか鋭意研
究した結果、金めつきの下地めつきとしてニツケ
ル−リン合金めつきを施し、更にスズ−コバルト
合金めつきを施すことにより耐食性が飛躍的に向
上することがわかつた。 In view of the above-mentioned drawbacks, as a result of intensive research into whether the corrosion resistance could be improved by under-plating compared to conventional ones, the present invention was developed by applying nickel-phosphorus alloy plating as the under-plating for gold plating, and further applying tin-cobalt alloy plating. It was found that corrosion resistance was dramatically improved by applying the coating.
即ち本発明は、下地めつきとしてニツケル−リ
ン合金めつきを施し、更にその上にスズ−コバル
ト合金めつき層を形成させた後、金めつきを行う
ことにより耐食性を著しく向上せしめた時計用外
装部品を得ることに成功したものである。 That is, the present invention provides a watch that has significantly improved corrosion resistance by applying nickel-phosphorus alloy plating as a base plating, further forming a tin-cobalt alloy plating layer thereon, and then gold plating. We succeeded in obtaining exterior parts.
本発明によれば、ニツケル−リン合金めつき
は、電解めつき、無電解めつきいずれの方法でも
よくすじ目仕上げの様なものは、無電解めつき法
が好ましい。また析出部のリン濃度は、５〜15％
が適当である。またスズ−コバルト合金めつきに
ついては、組成がスズ80〜86％のものが最も耐食
性により結果を与えることが認められた。 According to the present invention, nickel-phosphorus alloy plating can be performed by either electrolytic plating or electroless plating, and for streak finishing, electroless plating is preferred. In addition, the phosphorus concentration in the precipitation area is 5 to 15%.
is appropriate. Regarding tin-cobalt alloy plating, it was found that a tin composition of 80 to 86% gave the best results in corrosion resistance.
以下、実施例に従つて本発明を詳細に説明す
る。 Hereinafter, the present invention will be explained in detail according to Examples.
実施例 １
黄銅材を鍛造後表面加工して時計用ケースを作
り、トリクレン、アルカリ脱脂更に酸洗後、下地
めつきとして、ニツケル−リン合金めつき３ミク
ロン施し、更にその上にスズ−コバルト合金めつ
き0.5ミクロンを施した。この下地めつきに用い
ためつき浴、めつき条件を下記に示す。Example 1 A watch case was made by forging a brass material and then surface-processing it. After degreasing with trichloride and alkali and pickling, a nickel-phosphorus alloy plating of 3 microns was applied as a base plating, and then a tin-cobalt alloy was applied on top of that. A plating of 0.5 micron was applied. The plating bath and plating conditions used for this base plating are shown below.
＜めつき液組成＞
塩化コバルト 40g/
塩化第一スズ 40g/
ピロリン酸カリ 200g/
添加剤 適 量
＜めつき条件＞
電流密度 0.5A／ｄm2
時 間 ５分
浴 温 60℃
pH ９
次に金ストライクを施し、更に14カラツトの
Au−Ag合金めつき３ミクロン、更にその上に23
カラツトAu−Ni−In合金めつきを２ミクロン施
した。
<Plating solution composition> Cobalt chloride 40g/Stannous chloride 40g/Potassium pyrophosphate 200g/Additives Appropriate amount <Plating conditions> Current density 0.5A/dm 2 hours 5 minutes Bath temperature 60℃ pH 9 Next, gold With a strike and an additional 14 carats.
Au-Ag alloy plating 3 microns, furthermore 23
Carat Au-Ni-In alloy plating of 2 microns was applied.
この様にして得られた時計ケースと、従来のめ
つき方法で得られた時計ケースにつき、人工汗浸
漬試験７日間、塩水噴霧試験５日間の耐食性試験
を行つた所、従来のめつき方法で得られた時計ケ
ースは、すじ目仕上げ部分に点状の腐食が生じた
のに対し、上記方法で得られた時計ケースは、全
く異常が認められなかつた。 Corrosion resistance tests were conducted on the watch cases obtained in this way and the watch cases obtained using the conventional plating method, including a 7-day artificial sweat immersion test and a 5-day salt spray test. In the obtained watch case, dot-like corrosion occurred in the lined finished portion, whereas in the watch case obtained by the above method, no abnormality was observed at all.
実施例 ２
洋白材を鍛造後表面加工して時計ケースを作り
トリクレン、アルカリ脱脂更に酸洗い後、下地め
つきとして、まず下記に示すめつき浴、めつき条
件でニツケル−リン合金めつきを無電解めつき法
で２ミクロン施した。Example 2 A watch case was made by forging the surface of nickel silver material, degreasing it with alkali and pickling, and then applying nickel-phosphorus alloy plating under the plating bath and plating conditions shown below. It was applied to a thickness of 2 microns using an electroless plating method.
＜めつき液組成＞
塩化ニツケル 50g/
次亜リン酸ナトリウム 10g/
クエン酸ナトリウム 10g/
＜めつき条件＞
浴 温 90℃
時 間 10分
pH ４
更にその上に下記に示すめつき浴、めつき条件
でスズ−コバルト合金めつきを0.3ミクロン施し
た。<Plating liquid composition> Nickel chloride 50g/ Sodium hypophosphite 10g/ Sodium citrate 10g/ <Plating conditions> Bath temperature 90℃ Time 10 minutes pH 4 Furthermore, on top of that, use the plating bath shown below for plating. Tin-cobalt alloy plating was applied to a thickness of 0.3 microns under these conditions.
＜めつき液組成＞
塩化コバルト 350g/
フツ化第一スズ 50g/
酸性フツ化アンモン 20g/
添加剤 適 量
＜めつき条件＞
電流密度 1A／ｄm2
時 間 ２分
浴 温 65℃
pH ２
次に金ストライクを施し、更に16カラツトAu
−Cu合金めつき３ミクロン、また更に23カラツ
トAu−Ni−In合金めつき２ミクロンを施した。<Plating solution composition> Cobalt chloride 350g/Stannic fluoride 50g/Acidic ammonium fluoride 20g/Additive appropriate amount <Plating conditions> Current density 1A/dm 2 hours 2 minutes Bath temperature 65℃ pH 2 Next Gold strike and additional 16 karat Au
-Cu alloy plating of 3 microns, and a further 23 carat Au-Ni-In alloy plating of 2 microns.
この様にして得られた時計ケースを実施例１と
同様の耐食試験を行なつた所、腐食、変色などの
異常は全く認められなかつた。 When the watch case thus obtained was subjected to the same corrosion resistance test as in Example 1, no abnormalities such as corrosion or discoloration were observed.
以上の実施例では、本発明の一部について述べ
たものであり、下地めつきの厚さについては、更
に増減が可能である。スズ−コバルト合金めつき
の厚さは、0.2ミクロン以上あればよい。 The above embodiments describe only a part of the present invention, and the thickness of the base plating can be further increased or decreased. The thickness of the tin-cobalt alloy plating may be 0.2 microns or more.
以上の如く本発明によれば、従来の金めつきで
は得られなかつた高耐食性の時計用外装部品を得
ることが可能となつた。 As described above, according to the present invention, it has become possible to obtain a highly corrosion-resistant watch exterior part that could not be obtained by conventional gold plating.
Claims (1)
きを施し、更にその上にスズ−コバルト合金めつ
き層を形成させた後、金めつきをしたことを特徴
とする時計用外装部品。1. An exterior part for a watch, characterized in that a nickel-phosphorus alloy plating is applied as a base plating, a tin-cobalt alloy plating layer is further formed thereon, and then gold plating is applied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16657781A JPS5867890A (en) | 1981-10-19 | 1981-10-19 | Outer parts for watch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16657781A JPS5867890A (en) | 1981-10-19 | 1981-10-19 | Outer parts for watch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5867890A JPS5867890A (en) | 1983-04-22 |
| JPS648719B2 true JPS648719B2 (en) | 1989-02-15 |
Family
ID=15833842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16657781A Granted JPS5867890A (en) | 1981-10-19 | 1981-10-19 | Outer parts for watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5867890A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7644907B2 (en) | 2006-12-28 | 2010-01-12 | Schlumberger Technology Corporation | Drum for a well access line |
| KR100854505B1 (en) | 2007-02-23 | 2008-08-26 | (주)해빛정보 | Plating layer using w-co and sn-co and method for plating the same |
| EP3171229A1 (en) * | 2015-11-19 | 2017-05-24 | Nivarox-FAR S.A. | Clock component |
-
1981
- 1981-10-19 JP JP16657781A patent/JPS5867890A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5867890A (en) | 1983-04-22 |
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