JPS5943545B2 - watch case - Google Patents
watch caseInfo
- Publication number
- JPS5943545B2 JPS5943545B2 JP6632276A JP6632276A JPS5943545B2 JP S5943545 B2 JPS5943545 B2 JP S5943545B2 JP 6632276 A JP6632276 A JP 6632276A JP 6632276 A JP6632276 A JP 6632276A JP S5943545 B2 JPS5943545 B2 JP S5943545B2
- Authority
- JP
- Japan
- Prior art keywords
- case
- watch case
- stainless steel
- ion
- coated
- 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
- 239000000463 material Substances 0.000 claims description 13
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 238000007733 ion plating Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
本発明は、腕時計用ケースの材料及びその表面処理に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a material for a watch case and a surface treatment thereof.
従来これに類する材質の時計ケースは、ほとんどがステ
ンレス・スチールであり、そのステンレスの表面には自
然に数１０オングストロームの不働態層が形成されてい
る。即ち、強制的に不働態処理を行う事なくケース面に
キズがつけぱ不働態層が形成される。しかるにステンレ
スの加工は材料の粘さともからみ非常に困難である。更
に好むと好まざるとにかかわらず不働態層を形成するが
故に、ステンレス上への湿式メッキによる貴金属層の形
成等が困難であり、ステンレス素材の色調とは別の色調
を持つた化学的に安定なケースを安価に作る事は容易で
なかつた。これはファッション性のあるデザインが重視
される製品である腕時計用ケースでは大きな制約条件が
ある。ステンレス表面に形成される不働態層は湿式メッ
キに対しては障害となるが、酸化物あるいは窒化物など
の化合物被膜を蒸着する場合には有効な中間層となる。Conventional watch cases made of similar materials are mostly stainless steel, and a passive layer of several tens of angstroms is naturally formed on the surface of the stainless steel. That is, a passive layer is formed by scratching the case surface without forcibly performing passivation treatment. However, processing stainless steel is extremely difficult due to the viscosity of the material. Furthermore, because a passive layer is formed whether you like it or not, it is difficult to form a precious metal layer on stainless steel by wet plating, and it is difficult to form a noble metal layer on stainless steel because it has a color tone different from that of the stainless steel material. It was not easy to make a stable case at low cost. This is a major constraint for watch cases, which are products that place emphasis on fashionable design. Although the passive layer formed on the stainless steel surface is an obstacle to wet plating, it becomes an effective intermediate layer when depositing a compound film such as an oxide or nitride.
したがつてステンレスの表面に例えば窒化チタニウムの
ような化合物を密着性良く被覆することができる。一方
、加工性に優れた黄銅材の表面に化合物被膜を密着性良
く被覆することは極めて困難である。Therefore, the surface of stainless steel can be coated with a compound such as titanium nitride with good adhesion. On the other hand, it is extremely difficult to coat the surface of a brass material with excellent workability with a compound film with good adhesion.
そこで本発明の目的は、加工性に優れた黄銅材で作成し
た時計ケースの表面に硬質で黄金色を呈する窒化チタニ
ウムを被覆することである。上記目的のため本発明にお
いては、黄銅材で作成してケースの表面に不働態層を形
成し易い金属としてＮｉあるいはＮｉ合金を被覆し、そ
の表面に不働態層を形成したのちイオンブレーティング
法により窒化チタニウムを被覆するようにした。以下実
施例に基づき説明する。実施例において使用したイオン
ブレーティング装置を第１図に示す。第１図において、
１は真空槽、２は排気口、３はニードルバルブ、４はカ
ソード電極、５は被着基材、６は蒸発源、□は直流源、
８は蒸発用電源、９は絶縁材から成つている。Therefore, an object of the present invention is to coat the surface of a watch case made of a brass material with excellent workability with titanium nitride, which is hard and has a golden color. For the above purpose, in the present invention, the case is made of brass material and coated with Ni or Ni alloy as a metal that easily forms a passive layer on the surface of the case, and after forming a passive layer on the surface, ion blating is applied. It was then coated with titanium nitride. The following will be explained based on examples. FIG. 1 shows the ion blating device used in the examples. In Figure 1,
1 is a vacuum chamber, 2 is an exhaust port, 3 is a needle valve, 4 is a cathode electrode, 5 is an adhesion substrate, 6 is an evaporation source, □ is a DC source,
8 is an evaporation power source, and 9 is an insulating material.
先ず機械加工により黄銅材で時計ケース基材を作成し、
カソード電極を兼ねた治具４に取付け、ニードルバルブ
３を通して酸素を導入し、酸素分圧２×１０−２Ｔｏｒ
ｒの雰囲気の下で治具４に直流のマイナスＯ、５にりを
印加しつつニッケルを２分間イオンブレーティングし、
続いて酸素分圧を８×１０−２Ｔｏｒｒまで上げつつ、
治具にかかる直流電圧をマイナス１Ｋｖまで増加して約
８分間イオンブレーティングし、続いて酸素ガスの導入
を止め、別のニードルバルブ３’より窒素ガスを導入し
、５×１０−３Ｔｏｒｒにバランスさせつつチタニウム
を蒸発させてイオンプレーテイングした所第２図に示す
構成の黄金色を持つた外観色調のケースが形成された。
硬度を測定した所マイクロビツカースでＨｖ−６００あ
り、室温の１０％ＨＮＯ３溶液中に３日間浸漬しても腐
蝕、変色等発生せず化学的に安定なフアツシヨン性に富
んだケースを作る事が出来た。尚電気化学的な安定性も
考え、黄銅製時計ケース基材とＮｉ層との間にＴｌ，Ｔ
ａ，Ｃｒ等の金属層を設ける事と不働態層を形成する金
属層としてＮ１以外にＮｉ−ＣＯ合金を使用する事を行
つたが、より安定なケースになつた。First, we created the watch case base material from brass material by machining.
It is attached to a jig 4 that also serves as a cathode electrode, and oxygen is introduced through the needle valve 3 to create an oxygen partial pressure of 2 x 10-2 Torr.
In an atmosphere of
Subsequently, while increasing the oxygen partial pressure to 8 x 10-2 Torr,
The DC voltage applied to the jig was increased to -1 Kv and ion blating was performed for about 8 minutes, then the introduction of oxygen gas was stopped, nitrogen gas was introduced from another needle valve 3', and the balance was adjusted to 5 x 10-3 Torr. When the titanium was evaporated and ion plating was carried out under the same conditions, a case with a golden yellow exterior color was formed as shown in FIG.
The hardness of the case was measured as Hv-600 for microvits, and even if it was immersed in a 10% HNO3 solution at room temperature for 3 days, no corrosion or discoloration would occur, making it possible to create a chemically stable and highly durable case. done. In addition, considering electrochemical stability, Tl, T is added between the brass watch case base material and the Ni layer.
A more stable case was obtained by providing a metal layer such as a, Cr, etc. and using a Ni--CO alloy in place of N1 as the metal layer forming the passive layer.
実施例としては直流電圧を印加するイオンプレーテイン
グ方式いわゆるＭＡＴＴＯＸ方式で説明しているがこれ
を他のイオンプレーテイング方式である高周波励起式イ
オンプレーテイング及び熱電子放射型の、例えば多陰極
方式イオンプレーテイングで行つても実施例と同等もし
くは、それ以上の効果をあげる事は明らかである。As an example, an ion plating method that applies a DC voltage, the so-called MATTOX method, is explained, but this is also applicable to other ion plating methods such as radio frequency excitation ion plating and thermionic emission type, such as multi-cathode ion plating. It is clear that even if plating is used, the effect is equal to or greater than that of the embodiment.
更に被着基材として時計部品に対して示したが時計と同
様常時携帯され、フアツシヨン性の強いデザインの重要
視されるライター、メガネフレーム、ボタン、ハンドバ
ツグカバン等の止め金、万年筆、ボールペン、等の貴金
属湿式メツキに当該真空被膜形成法を適用しても時計と
同様の効果をあげる事は明らかである。In addition, although it is shown for watch parts as an adhering base material, it is also used for lighters, eyeglass frames, buttons, clasps for handbags, fountain pens, ballpoint pens, etc., which are always carried around like watches and have a highly fashionable design. It is clear that applying the vacuum film formation method to wet plating of precious metals such as the above will produce the same effect as that of watches.
第１図は、本発明の実施例に使用したイオンプレーテイ
ング装置の概略図、第２図は、本発明によるケースの断
面図である。
１０・・・・・・ケース基材、１１・・・・・・不働態
層を有する金属層、１２・・・・・・窒化チタニウム被
膜。FIG. 1 is a schematic diagram of an ion plating apparatus used in an embodiment of the present invention, and FIG. 2 is a sectional view of a case according to the present invention. 10...Case base material, 11...Metal layer having a passive layer, 12...Titanium nitride coating.
Claims (1)
たのちその表面を酸素ガス存在下でのグロー放電により
不働態化処理し、しかるのちイオンブレーティング法に
より窒化チタニウムを被覆してなることを特徴とする腕
時計用ケース。1 The surface of a brass base material is coated with Ni or Ni alloy, the surface is passivated by glow discharge in the presence of oxygen gas, and then titanium nitride is coated with ion blating. A distinctive watch case.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6632276A JPS5943545B2 (en) | 1976-06-07 | 1976-06-07 | watch case |
| DE2705225A DE2705225C2 (en) | 1976-06-07 | 1977-02-08 | Ornamental part for clocks etc. |
| US05/945,292 US4226082A (en) | 1976-06-07 | 1978-09-25 | Ornamental part for watches and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6632276A JPS5943545B2 (en) | 1976-06-07 | 1976-06-07 | watch case |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52149157A JPS52149157A (en) | 1977-12-12 |
| JPS5943545B2 true JPS5943545B2 (en) | 1984-10-23 |
Family
ID=13312473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6632276A Expired JPS5943545B2 (en) | 1976-06-07 | 1976-06-07 | watch case |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5943545B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5893869A (en) * | 1981-12-01 | 1983-06-03 | Seiko Instr & Electronics Ltd | External parts for decoration |
| JPH06295644A (en) * | 1993-04-08 | 1994-10-21 | Nippon Steel Corp | Vacuum arc treatment method and pretreatment method |
-
1976
- 1976-06-07 JP JP6632276A patent/JPS5943545B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52149157A (en) | 1977-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4226082A (en) | Ornamental part for watches and method of producing the same | |
| US4707238A (en) | Method of processing a metal surface | |
| JPS61231164A (en) | Personal ornament having colored surface | |
| US4713150A (en) | Process for preparing a part for color anodization | |
| JPS5943545B2 (en) | watch case | |
| JPS5938442Y2 (en) | Golden portable exterior parts | |
| JP2820451B2 (en) | Jewelry | |
| JP2001295074A (en) | Ornmental material formed with hardened layer and method for manufacturing the same | |
| JPH0751742B2 (en) | Exterior parts for watches | |
| GB2186000A (en) | A method of processing a metal surface | |
| JP3244952B2 (en) | Golden ornaments | |
| JPH03120355A (en) | White personal ornament | |
| JPH08120481A (en) | Decorative member | |
| JPS5945754B2 (en) | Exterior parts for watches | |
| JPH05156425A (en) | Ornamental member and its production | |
| JP2001294955A (en) | Golden ornaments | |
| US20240158905A1 (en) | Protective coating for a copper allow substrate and corresponding process | |
| JPH069006Y2 (en) | Precious metal ornaments | |
| JPS61231163A (en) | Personal ornament having colored surface | |
| JP3020985B2 (en) | Exterior parts having a gold layer | |
| JPS61127858A (en) | Golden color external parts | |
| JPS62109964A (en) | Ornamental ion plating method | |
| JPH03100161A (en) | Colored hard noble metal film for ornamentation | |
| JPH02217460A (en) | Outer ornament parts for watch | |
| JP2719560B2 (en) | Exterior parts having a gold layer |