JPS62236345A - Electronic wrist watch - Google Patents
Electronic wrist watchInfo
- Publication number
- JPS62236345A JPS62236345A JP7785286A JP7785286A JPS62236345A JP S62236345 A JPS62236345 A JP S62236345A JP 7785286 A JP7785286 A JP 7785286A JP 7785286 A JP7785286 A JP 7785286A JP S62236345 A JPS62236345 A JP S62236345A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- rare earth
- plated
- electroless copper
- earth iron
- 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
- 210000000707 wrist Anatomy 0.000 title abstract 2
- 238000007747 plating Methods 0.000 claims abstract description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 12
- 239000010949 copper Substances 0.000 abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 2
- ICBPURKUPVLVCM-UHFFFAOYSA-N 1,5-dimethyl-2-phenylpyrazol-3-one;2-hydroxy-2-phenylacetic acid Chemical class OC(=O)C(O)C1=CC=CC=C1.CN1C(C)=CC(=O)N1C1=CC=CC=C1 ICBPURKUPVLVCM-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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000001509 sodium citrate Substances 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、希土類鉄系磁石をロータにした電子腕時計
において、ロータの表面処理に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to surface treatment of a rotor in an electronic wristwatch whose rotor is a rare earth iron magnet.
（発明の概要）
この発明は、希土類鉄系磁石のロータに無電解銅めっき
を下地めっきすることにより、めっき密着性、耐食性を
向上させたらのである。(Summary of the Invention) The present invention improves plating adhesion and corrosion resistance by base-plating the rotor of a rare earth iron magnet with electroless copper plating.
（従来の技術）
従来、電子腕時計のロータは、Ｓｎ＋ −Ｃｏ系磁石が
用いられてきたが、コスト、磁石特性等の点で有利な希
土類鉄系磁石ロータを用いる気運がある。(Prior Art) Conventionally, Sn + -Co magnets have been used for the rotors of electronic wristwatches, but there is a trend to use rare earth iron magnet rotors, which are advantageous in terms of cost, magnetic properties, and the like.
しかし、希を類鉄系磁石は、Ｓｍ−ｃｏ系に比べ耐食性
に劣り、変色、錆などが生じゃすく何んらかの表面処理
を施す必要があり、一部亜鉛クロメートなどで解決しよ
うとする提案がある。However, rare iron-based magnets have poorer corrosion resistance than Sm-co magnets, and are prone to discoloration and rust, requiring some kind of surface treatment. I have a suggestion to do so.
（発明が解決しようとする問題点）
希土類鉄系磁石は、酸、アルカリ溶液に対し弱く、通常
のめっき処理では処理ｒ程中表面が侵される。また、焼
結合金であるため本質的に穴だらけの内部構造を有して
おり、見掛上めっきがついても経時的に内部から薬品等
がしみ出し、めっきがツクしたり、変色、錆が生じるな
ど問題があった。本発明は、上記のような問題点を解決
しめっき密着性、耐良性に優れた希土類鉄系磁石ロータ
を有する電子腕時計を提供するものである。(Problems to be Solved by the Invention) Rare earth iron magnets are sensitive to acids and alkaline solutions, and the surface of the magnet is attacked during the normal plating process. In addition, since it is a sintered alloy, it has an internal structure that is essentially full of holes, so even if it appears to be plated, chemicals, etc. will seep out from inside over time, causing the plating to become dull, discolored, and rusted. There were problems such as the occurrence of The present invention solves the above-mentioned problems and provides an electronic wristwatch having a rare earth iron magnet rotor with excellent plating adhesion and good resistance.
（問題点を解決するための手段）
上記問題点を解決するため、各種めっき浴のなかから、
めっきまわり性がよく、かつ希土類鉄系含金を侵さない
ものについて検討した結果、常温近辺でめっき可能な無
電解銅めっきがめつき性にすぐれていることを見い出し
た。すなわち、本発明は、脱脂、除錆した希土類鉄系［
１−夕に無電解銅めっきを下地めっきとし、次に所望す
る仕上げめっきの形成を可能にしたものである。無電解
銅めっきは、常温近辺でめっき可能なホルマリンを還元
剤とする化学鋼めっき浴が適している。(Means for solving the problem) In order to solve the above problem, from among various plating baths,
As a result of examining materials that have good plating properties and do not attack rare earth iron-based metals, it was discovered that electroless copper plating, which can be plated at around room temperature, has excellent plating properties. That is, the present invention provides degreased and rust-removed rare earth iron [
1- In the evening, electroless copper plating is used as a base plating, and then a desired finish plating can be formed. For electroless copper plating, a chemical steel plating bath using formalin as a reducing agent, which can be plated at around room temperature, is suitable.
また、めっきまわり性をよくするため、あらかじめ、塩
化第一錫溶液による感受性化、塩化パラジウム溶液での
活性化を行なうことが好ましい。Furthermore, in order to improve plating coverage, it is preferable to sensitize with a stannous chloride solution and activate with a palladium chloride solution in advance.
（作用）
上記のようにして処理された希土類鉄系磁石のロータは
、表面の凹凸にち銅めっきがト分つきま・１ わり、
素材を侵すことがなく、下地め・きとして良好なもので
ある。無電解銅めっきの厚みは１ミクロン以上形成する
ことにより、各種の仕上げめっきに耐えるものである。(Function) The rotor of the rare earth iron magnet treated as described above has copper plating on it due to the unevenness of the surface.
It does not attack the material and is good as a base finish. By forming the electroless copper plating to a thickness of 1 micron or more, it can withstand various finishing platings.
このようにして得た希土類鉄系磁石のロータは、電子腕
時計用として機能上、耐食性上満足出来るものである。The thus obtained rare earth iron magnet rotor is functionally and corrosion resistant for use in electronic wristwatches.
［実施例−１］
Ｎｄ −Ｂ −Ｆｅ系の磁石用焼結合金から成形した電
子腕時計用ロータを、アルカリ脱脂、酸洗いした後、塩
化第一錫溶液と塩化パラジウム溶液で感受性化、および
活性化を行い表面調整した。[Example-1] A rotor for an electronic wristwatch molded from a Nd-B-Fe-based sintered alloy for magnets was degreased with alkaline and pickled, and then sensitized and activated with a stannous chloride solution and a palladium chloride solution. The surface was adjusted by
塩化第一錫溶液
塩化パラジウム溶液
次にすばやく、純水で超音波洗浄をした後、無電解銅め
っきを１ミクロン形成した。Stannous chloride solution Palladium chloride solution Next, after quick ultrasonic cleaning with pure water, 1 micron electroless copper plating was formed.
［無電解銅めっき］
組成、条件
１ｉＩＪ［２９ｇ／ｊ！
ａツセル塩 １４０ ｇ／ｌ水酸化ナトリ
ウム ４０ ９／ｊ！ホルマリン（３７％）
１６６ ｇ／Ｊ１）１１ １１
．５温度 ２０ ℃
その後、湯洗、水洗し仕上げめっきとして無電解ニッケ
ルめっきを２ミクロン施し電子腕時計用ロータとした。[Electroless copper plating] Composition, conditions 1iIJ [29g/j! a Tussel salt 140 g/l Sodium hydroxide 40 9/j! Formalin (37%)
166 g/J1) 11 11
．． 5 Temperature: 20° C. Thereafter, it was washed with hot water and water, and electroless nickel plating of 2 microns was applied as a final plating to prepare a rotor for an electronic wristwatch.
［無電解ニッケルめっき］
組成１条件
塩化ニッケル ５０ ９／Ｉ！次亜りん酸ナト
リウム １０ ９／Ｉ！くえん酸ナトリウム １０
Ｊ／ＪｐＨ４
温度 ９０ ℃
このようにして得たロータは、恒温高湿試験（４０℃Ｘ
９５％、１００Ｈｒ）を行った結果、めっきのフクレ、
変色、錆の発生もなく良好であった。[Electroless nickel plating] Composition 1 condition Nickel chloride 50 9/I! Sodium hypophosphite 10 9/I! Sodium citrate 10
J/JpH4 Temperature: 90°C The rotor thus obtained was subjected to a constant temperature and high humidity test (40°C
95%, 100Hr) As a result, plating blisters,
It was in good condition with no discoloration or rust.
［実施例−２１
実施例−１と同様に感受性化、活性化処理したＮｄ−Ｂ
−ｒ’ｅ系ロータを、純水で超音波洗浄した後無電解
鋼めっきを１ミクロン形成した。[Example-21 Nd-B sensitized and activated in the same manner as in Example-1
- After the r'e rotor was ultrasonically cleaned with pure water, 1 micron of electroless steel plating was formed.
無電解銅めっき液
高速無電解銅めっき液 ＭＫ−４５０
（空回化学工業製）
温度 ２５℃
ついで、水洗後、シアン化亜鉛めっき浴で、３ミクロン
の亜鉛めっきを施し、更にクローメート処理を行い腕時
計用ロータとした。Electroless copper plating solution High-speed electroless copper plating solution MK-450 (manufactured by Kuai Kagaku Kogyo) Temperature: 25℃ Next, after washing with water, 3 micron zinc plating is applied in a cyanide zinc plating bath, and further chromate treatment is performed. It was used as a rotor for
シアン化亜鉛めっき
組成１条件 −
シアン化亜鉛 ６０ ｇ／Ｊ
シアン化ソーダ ４０ ｇ／Ｊ
か性ソーダ ９０ ９＃！
温度 ２５ ℃
電流密度 ３ Ａ／ム
このようにして得た〇−タを恒温高湿試験（４０℃Ｘ９
５％、２００Ｈｒ）行った結果、変色、錆の発生は全く
な（、まためっき密着性ら良好であった。Zinc cyanide plating composition 1 condition - Zinc cyanide 60 g/J Sodium cyanide 40 g/J Caustic soda 90 9#! Temperature: 25°C Current density: 3 A/mu
5% for 200 hours), there was no discoloration or rust (and the plating adhesion was good).
（発明の効果）
以上述べてきたように本発明によれば、下地めっきに常
温近辺でめっき可能な無電解銅めっきを施すことにより
、めっき密着性、耐食性に優れたＮｄ−１３−ｒ’ｅ系
のロータを有する電子腕時計を提供できるものである。(Effects of the Invention) As described above, according to the present invention, by applying electroless copper plating that can be plated at around room temperature to the base plating, Nd-13-r'e has excellent plating adhesion and corrosion resistance. Accordingly, it is possible to provide an electronic wristwatch having a rotor of this type.
なお本発明は、実施例以外の希土類鉄系磁石の表面処理
としても同様な効果を得ることが可能である。また仕上
げめりぎとして、無電解ニッケルめっき、亜鉛クロメー
ト以外の各種めっきにも適用することが可能でその効果
は大きい。Note that the present invention can obtain similar effects by surface treatment of rare earth iron magnets other than those in the examples. Furthermore, as a finishing layer, it can be applied to various platings other than electroless nickel plating and zinc chromate, and its effects are great.
Claims (2)
を下地めっきとしたことを特徴とする電子腕時計。(1) An electronic wristwatch characterized by having a rotor made of a rare earth iron magnet as a base plating of electroless steel plating.
０％のＲ（但しＲはＹを含む希土類元素の少なくとも一
種）、２〜２８％のＢ、および残部および不可避の不純
物からなる特許請求の範囲第１項記載の電子腕時計。(2) The rare earth iron-based magnet has an atomic percentage of 8 to 3
The electronic wristwatch according to claim 1, comprising 0% R (where R is at least one kind of rare earth element including Y), 2 to 28% B, and the balance and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7785286A JPS62236345A (en) | 1986-04-04 | 1986-04-04 | Electronic wrist watch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7785286A JPS62236345A (en) | 1986-04-04 | 1986-04-04 | Electronic wrist watch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62236345A true JPS62236345A (en) | 1987-10-16 |
Family
ID=13645589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7785286A Pending JPS62236345A (en) | 1986-04-04 | 1986-04-04 | Electronic wrist watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62236345A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304713A (en) * | 1988-06-02 | 1989-12-08 | Shin Etsu Chem Co Ltd | Manufacture of corrosion-resistant rare earth magnet |
| JPH03283607A (en) * | 1990-03-30 | 1991-12-13 | Shin Etsu Chem Co Ltd | Manufacture of anticorrosive rare earth magnet |
| US5314756A (en) * | 1991-11-27 | 1994-05-24 | Hitachi Metals, Ltd. | Permanent magnet of rare-earth-element/transition-metal system having improved corrosion resistance and manufacturing method thereof |
| WO1999054986A1 (en) * | 1998-04-23 | 1999-10-28 | Citizen Watch Co., Ltd. | Rotor of small-sized motor |
| US6357116B1 (en) | 1997-09-25 | 2002-03-19 | Hess Engineering, Inc. | Method for assembly of vehicle wheels |
-
1986
- 1986-04-04 JP JP7785286A patent/JPS62236345A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304713A (en) * | 1988-06-02 | 1989-12-08 | Shin Etsu Chem Co Ltd | Manufacture of corrosion-resistant rare earth magnet |
| JPH03283607A (en) * | 1990-03-30 | 1991-12-13 | Shin Etsu Chem Co Ltd | Manufacture of anticorrosive rare earth magnet |
| US5314756A (en) * | 1991-11-27 | 1994-05-24 | Hitachi Metals, Ltd. | Permanent magnet of rare-earth-element/transition-metal system having improved corrosion resistance and manufacturing method thereof |
| CN1057631C (en) * | 1991-11-27 | 2000-10-18 | 日立金属株式会社 | Rare-earth element/transition metal series permanent magnet having improved anticorrosion performance and manufacture thereof |
| US6357116B1 (en) | 1997-09-25 | 2002-03-19 | Hess Engineering, Inc. | Method for assembly of vehicle wheels |
| WO1999054986A1 (en) * | 1998-04-23 | 1999-10-28 | Citizen Watch Co., Ltd. | Rotor of small-sized motor |
| US6677692B1 (en) | 1998-04-23 | 2004-01-13 | Citizen Watch Co., Ltd. | Rotor of small-sized motor |
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