JPH0559193B2 - - Google Patents
Info
- Publication number
- JPH0559193B2 JPH0559193B2 JP59065518A JP6551884A JPH0559193B2 JP H0559193 B2 JPH0559193 B2 JP H0559193B2 JP 59065518 A JP59065518 A JP 59065518A JP 6551884 A JP6551884 A JP 6551884A JP H0559193 B2 JPH0559193 B2 JP H0559193B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- ion plating
- black
- torr
- gas
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Adornments (AREA)
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はイオンプレーテイング被膜の製法に係
り、特には腕時計、時計バンド、指輪等の外装部
品の基体材料に黒色色調のイオンプレーテイング
被膜を施す方法に関するものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to a method for producing an ion plating film, and in particular, a method for applying a black-toned ion plating film to the base material of exterior parts such as wristwatches, watch bands, rings, etc. It is related to.
従来の技術
近年、腕時計には高級感のある独特の色彩と色
調を求める傾向が強く、それに応じて基体材料に
対する着色メツキ、染色、塗装などの各種加工方
法が実施されてきたが、これらの方法ではイ）高
級感が得られない、ロ）耐食性に乏しく、変色、
剥離、傷つきやすい、ハ）加工が面倒で、公害上
の問題がある、などの不利欠点を伴なうものがあ
り、いずれも満足できるものではなかつた。Conventional Technology In recent years, there has been a strong trend for wristwatches to have unique colors and tones that give a sense of luxury, and in response to this, various processing methods have been implemented on the base material, such as color plating, dyeing, and painting. A) It does not give a sense of luxury, and B) It has poor corrosion resistance and discoloration.
Some of them have disadvantages such as easy peeling and scratching, c) troublesome processing, and pollution problems, and none of them are satisfactory.
本発明の目的は、かかる不利欠点をもたない方
法としてイオンプレーテイングによる新規な黒色
色調の被膜の製法を提案するものである。 The object of the present invention is to propose a new method for producing black-toned coatings by ion plating as a method that does not have these disadvantages.
すなわち、本発明は、窒化チタンと炭化チタン
の混合からなるイオンプレーテイング被膜の製法
において、メタン、アセチレン、エチレン、プロ
パンの中の１種の鎖式炭化水素を10〜15％混合し
た窒素とアルゴンとからなる、８×10-4〜５×
10-3Torrの混合ガス雰囲気中でチタンを蒸発さ
せ、チタン蒸発源とカソードの基本表面間に20〜
200Vの直流電圧を印加し、イオンプレーテイン
グにより該表面に黒色色調の超硬質被膜を形成さ
せることを特徴とするイオンプレーテイング被膜
の製法である。 That is, the present invention provides a method for producing an ion plating film consisting of a mixture of titanium nitride and titanium carbide, using nitrogen and argon mixed with 10 to 15% of one type of chain hydrocarbon among methane, acetylene, ethylene, and propane. consisting of 8×10 -4 ~5×
Evaporate the titanium in a mixed gas atmosphere of 10 -3 Torr, with 20 ~
This is a method for producing an ion plating film characterized by applying a DC voltage of 200 V and forming an ultra-hard film with a black tone on the surface by ion plating.
以下本発明を詳しく説明すると、本発明におけ
るイオンプレーテイング法は、チタンを蒸発源と
し、反応ガスには１種の鎖式炭化水素を10〜15％
混合した窒素を使用し、アルゴンとの混合ガス雰
囲気中で行うのである。反応ガスが窒素のみの場
合、得られる被膜の色調は黄色の濃淡が変化する
だけであるが、鎖式炭化水素を混合することによ
つて、光沢のある黒色色調が得られる。鎖式炭化
水素としては入手が容易で経済的なメタン、アセ
チレン、エチレン、プロパンなどが適当である。
これらは基体に要求される黒色被膜の色調によつ
て任意選択し、混合割合を調整すればよい。ま
た、窒素と鎖式炭化水素の混合ガスのうちの鎖式
炭化水素が10％以下になると黒黄色から徐々に黄
色となり、15％以上になると黒灰色から徐々に灰
色となり、所望の黒色色調を得ることができな
い。また、深黒色色調を得るために、鎖式炭化水
素のうちメタンを使用する場合は、15％の上限に
近い割合でガスを導入することが望ましく、アセ
チレンやエチレンを使用する場合は、11〜14％ガ
スを導入することが望ましく、プロパンを使用す
る場合は、10％の下限に近い割合でガスを導入す
ることが望ましい。 To explain the present invention in detail below, the ion plating method of the present invention uses titanium as an evaporation source and contains 10 to 15% of one type of chain hydrocarbon as a reaction gas.
It uses a mixture of nitrogen and is carried out in a mixed gas atmosphere with argon. When the reactant gas is only nitrogen, the color tone of the resulting film changes only in the shade of yellow, but by mixing a chain hydrocarbon, a glossy black tone can be obtained. Suitable chain hydrocarbons include methane, acetylene, ethylene, and propane, which are easily available and economical.
These may be arbitrarily selected depending on the color tone of the black film required for the substrate, and the mixing ratio may be adjusted. In addition, when the chain hydrocarbon content of the mixed gas of nitrogen and chain hydrocarbons is less than 10%, the color changes from black-yellow to gradually yellow, and when it exceeds 15%, the black-gray color gradually changes to gray, achieving the desired black tone. can't get it. In addition, in order to obtain a deep black tone, when using methane among chain hydrocarbons, it is desirable to introduce the gas at a rate close to the upper limit of 15%, and when using acetylene or ethylene, it is preferable to introduce the gas at a rate close to the upper limit of 15%. It is desirable to introduce 14% gas, and if propane is used, it is desirable to introduce gas at a rate close to the lower limit of 10%.
つぎに、添付図面により本発明をさらに具体的
に説明する。 Next, the present invention will be explained in more detail with reference to the accompanying drawings.
第１図は、本発明の実施に用いる、イオンプレ
ーテイング装置の１例である。 FIG. 1 shows an example of an ion plating apparatus used to implement the present invention.
真空室１内に基本ホルダー２および下方にチタ
ン蒸発源３を配置し、これにカソード電源４を接
続し正極側を接地する。 A basic holder 2 and a titanium evaporation source 3 are placed in a vacuum chamber 1 below, a cathode power source 4 is connected to this, and the positive electrode side is grounded.
基体ホルダー２によく洗浄した基体６を取り付
け、排気系７から排気して真空室１内を２×10-5
Torr以下の真空度とする。ついでガス導入口８
からアルゴンを導入し、３×10-3Torrになつた
とき20〜200Vの電圧カソード電源４を接続しボ
ンバードを行つた後、エチレンを13％混合した窒
素との混合ガスを導入して８×10-4〜５×10-3
Torrになつたとき、蒸発駆動電源１１をはたら
かせてチタン蒸発源３からチタンを蒸発させる。 Attach the well-cleaned substrate 6 to the substrate holder 2, evacuate from the exhaust system 7, and vacuum the inside of the vacuum chamber 1 to 2×10 -5
The degree of vacuum should be less than Torr. Then gas inlet 8
When the temperature reached 3×10 -3 Torr, the cathode power source 4 with a voltage of 20 to 200 V was connected to perform bombardment, and then a mixed gas with nitrogen mixed with 13% ethylene was introduced to increase the temperature to 8× 10 -4 ~5×10 -3
When the temperature reaches Torr, the evaporation drive power source 11 is activated to evaporate titanium from the titanium evaporation source 3.
蒸発したチタンは、正電位のアノード電極１０
によりイオン化され、スイツチ５を接するとカソ
ード電源４の電圧により基体ホルダー、基体が負
電位となり、チタンイオンは基体に衝突し、被膜
を形成する。 The evaporated titanium is transferred to the positive potential anode electrode 10.
When the switch 5 is brought into contact with the titanium ions, the voltage of the cathode power source 4 causes the substrate holder and the substrate to have a negative potential, and the titanium ions collide with the substrate to form a film.
このとき、接地された熱電子フイラメント１
２，１３をフイラメント加熱電源１４，１５によ
り加熱して熱電子を放出させることによりイオン
化が促進される。この場合の被膜はチタンと混合
ガスの反応によつて生成された窒化チタンと炭化
チタンの混合からなる超硬質の光沢のある黒色色
調である。したがつて優れた装飾性と高級感のあ
る外装部品が得られる。 At this time, the grounded thermionic filament 1
2 and 13 are heated by filament heating power sources 14 and 15 to emit thermoelectrons, thereby promoting ionization. The coating in this case is an ultra-hard, glossy black color consisting of a mixture of titanium nitride and titanium carbide produced by the reaction of titanium and a mixed gas. Therefore, an exterior component with excellent decorativeness and a high-class feel can be obtained.
つぎに本発明の実施例について説明するが、本
発明はこれに限定されず広く他の部品にも応用さ
れることはもちろんである。 Next, embodiments of the present invention will be described, but it goes without saying that the present invention is not limited thereto and can be widely applied to other parts.
実施例 １
SUS316製の腕時計ケースを試料とし、第１図
の装置の基体ホルダー２に取り付け、真空室内を
３×10-5Torrに排気後アルゴンを導入し、ガス
圧を３×10-3Torrとしてカソード電源４から80V
電圧を印加、100℃、10分間ボンバードにより表
面を清浄化した。Example 1 A watch case made of SUS316 was used as a sample, and it was attached to the base holder 2 of the apparatus shown in Figure 1. After the vacuum chamber was evacuated to 3 x 10 -5 Torr, argon was introduced and the gas pressure was increased to 3 x 10 -3 Torr. As cathode power 4 to 80V
A voltage was applied and the surface was cleaned by bombardment at 100°C for 10 minutes.
つぎに、エチレンを13％混合した窒素をアルゴ
ンに加えて、ガス圧を８×10-4Torrに維持しな
がら、チタンを蒸発駆動電源１１により蒸発さ
せ、基体ホルダー２と蒸発源３との間に50Vの直
流電圧を印加して100℃、25分間イオンプレーテ
イングを行つたところ、試料の表面に光沢のある
美しい色調の黒色被膜のケースが得られた。 Next, nitrogen mixed with 13% ethylene is added to argon, and while maintaining the gas pressure at 8×10 -4 Torr, titanium is evaporated by the evaporation drive power source 11 between the substrate holder 2 and the evaporation source 3. When ion plating was performed at 100℃ for 25 minutes by applying a DC voltage of 50V to the sample, a case with a glossy and beautiful black coating was obtained on the surface of the sample.
このようにして得られた腕時計ケースは、人工
汗48時間の浸漬試験後も腐食が認められず、250
℃加熱、急冷後も異常がなく、耐摩擦性試験も良
好な結果であつた。 The watch case obtained in this way showed no corrosion even after a 48-hour immersion test in artificial sweat, and
There were no abnormalities after heating and quenching at °C, and good results were obtained in the abrasion resistance test.
実施例 ２
BS材にニツケルメツキした腕時計ケースを試
料とし、実施例１と同じ真空室内で同じようにボ
ンバードした。Example 2 A watch case made of nickel plated BS material was used as a sample and bombarded in the same vacuum chamber as in Example 1.
つぎにアルゴンにメタン15％混合した窒素を加
えて、ガス圧を５×10-3Torrに維持し、チタン
を蒸発駆動電源１１により蒸発させ、基体ホルダ
ー２と蒸発源との間に100Vの直流電圧を印加し、
100℃、20分間イオンプレーテイングを行つたと
ころ、紫黒色の美しい色調の被膜のケースが得ら
れた。 Next, nitrogen mixed with 15% methane is added to argon, the gas pressure is maintained at 5 × 10 -3 Torr, titanium is evaporated by the evaporation drive power supply 11, and 100V DC is applied between the substrate holder 2 and the evaporation source. Apply voltage,
When ion plating was performed at 100°C for 20 minutes, a case with a beautiful purple-black color was obtained.
このようにして得られたケースを実施例１と同
様に試験したところ良好な結果であつた。 When the case thus obtained was tested in the same manner as in Example 1, good results were obtained.
発明の効果
以上の実施例から明らかなように、メタン、ア
セチレン、エチレン、プロパンの中の１種の鎖式
炭化水素を10〜15％混合した窒素とアルゴンとか
らなる、８×10-4〜５×10-3Torrの混合ガス雰
囲気中でチタンを蒸発させ、チタン蒸発源とカソ
ードの基体表面間に20〜200Vの直流電圧を印加
させる本願発明の製法により、従来得られなかつ
た黒色色調の超硬性被膜が得られ、装飾性に優れ
た高級感のある外装部品が提供できる。Effects of the Invention As is clear from the above examples, 8×10 -4 ~ The manufacturing method of the present invention, in which titanium is evaporated in a mixed gas atmosphere of 5 × 10 -3 Torr and a DC voltage of 20 to 200 V is applied between the titanium evaporation source and the cathode substrate surface, produces a black tone that could not be obtained conventionally. A superhard coating can be obtained, and a high-class exterior component with excellent decorative properties can be provided.
第１図は本発明の実施に用いるイオンプレーテ
イング装置の概略説明図である。
１……真空室、２……基体ホルダー、３……チ
タン蒸発源、４……カソード電源、５……スイツ
チ、６……基体、７……排気系、８……ガス導入
口、９……アノード電源、１０……アノード電
極、１１……蒸発駆動電源、１２，１３……熱電
子フイラメント、１４，１５……フイラメント加
熱電源。
FIG. 1 is a schematic explanatory diagram of an ion plating apparatus used for carrying out the present invention. DESCRIPTION OF SYMBOLS 1... Vacuum chamber, 2... Substrate holder, 3... Titanium evaporation source, 4... Cathode power supply, 5... Switch, 6... Substrate, 7... Exhaust system, 8... Gas inlet, 9... ... Anode power supply, 10 ... Anode electrode, 11 ... Evaporation drive power supply, 12, 13 ... Thermionic filament, 14, 15 ... Filament heating power supply.
Claims (1)
ンプレーテイング被膜の製法において、メタン、
アセチレン、エチレン、プロパンの中の１種の鎖
式炭化水素を10〜15％混合した窒素とアルゴンと
からなる、８×10-4〜５×10-3Torrの混合ガス
雰囲気中でチタンを蒸発させ、チタン蒸発源とカ
ソードの基本表面間に20〜200Vの直流電圧を印
加し、イオンプレーテイングにより該表面に黒色
色調の超硬質被膜を形成させることを特徴とする
イオンプレーテイング被膜の製法。1 In the method of manufacturing an ion plating film made of a mixture of titanium nitride and titanium carbide, methane,
Evaporate titanium in a mixed gas atmosphere of 8×10 -4 to 5×10 -3 Torr consisting of nitrogen and argon mixed with 10 to 15% of one type of chain hydrocarbon among acetylene, ethylene, and propane. A method for producing an ion plating film, which comprises applying a DC voltage of 20 to 200 V between the titanium evaporation source and the basic surface of the cathode to form a black-toned ultra-hard film on the surface by ion plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6551884A JPS60208472A (en) | 1984-04-02 | 1984-04-02 | Production of ion plating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6551884A JPS60208472A (en) | 1984-04-02 | 1984-04-02 | Production of ion plating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60208472A JPS60208472A (en) | 1985-10-21 |
| JPH0559193B2 true JPH0559193B2 (en) | 1993-08-30 |
Family
ID=13289328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6551884A Granted JPS60208472A (en) | 1984-04-02 | 1984-04-02 | Production of ion plating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60208472A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63310957A (en) * | 1987-06-10 | 1988-12-19 | Seiko Instr & Electronics Ltd | External parts |
| AU648258B2 (en) * | 1990-06-29 | 1994-04-21 | Niigata Engineering Co., Ltd. | Method of forming titanium nitride film and vessel coated by same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51128562A (en) * | 1975-05-01 | 1976-11-09 | Orient Watch Co Ltd | Forming method of carbonic metal coating for surface of watch |
| JPS5485214A (en) * | 1977-12-21 | 1979-07-06 | Suwa Seikosha Kk | Armor for personal watch |
-
1984
- 1984-04-02 JP JP6551884A patent/JPS60208472A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60208472A (en) | 1985-10-21 |
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