JPS6128750B2 - - Google Patents

Info

Publication number
JPS6128750B2
JPS6128750B2 JP53056983A JP5698378A JPS6128750B2 JP S6128750 B2 JPS6128750 B2 JP S6128750B2 JP 53056983 A JP53056983 A JP 53056983A JP 5698378 A JP5698378 A JP 5698378A JP S6128750 B2 JPS6128750 B2 JP S6128750B2
Authority
JP
Japan
Prior art keywords
titanium nitride
gold
color tone
copper
color
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
Application number
JP53056983A
Other languages
Japanese (ja)
Other versions
JPS54148182A (en
Inventor
Nobuo Nishida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Citizen Watch Co Ltd
Original Assignee
Citizen Watch Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Citizen Watch Co Ltd filed Critical Citizen Watch Co Ltd
Priority to JP5698378A priority Critical patent/JPS54148182A/en
Priority to US05/912,548 priority patent/US4252862A/en
Priority to GB7826610A priority patent/GB2000812B/en
Priority to CH633978A priority patent/CH631040GA3/de
Priority to DE19782825513 priority patent/DE2825513A1/en
Priority to FR7822840A priority patent/FR2425210A1/en
Publication of JPS54148182A publication Critical patent/JPS54148182A/en
Priority to HK30884A priority patent/HK30884A/en
Priority to MY120/85A priority patent/MY8500120A/en
Publication of JPS6128750B2 publication Critical patent/JPS6128750B2/ja
Granted legal-status Critical Current

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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Physical Vapour Deposition (AREA)
  • Adornments (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

【発明の詳細な説明】 本発明は金及び金合金と同様な美しい色調を有
しすぐれた耐食性及び耐磨耗性を示す外装部品に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an exterior part that has a beautiful color tone similar to gold and gold alloys and exhibits excellent corrosion resistance and abrasion resistance.

時計用や装身具等の外装部品では装飾的要素で
ある色調と機能的要素である耐食性が同時に要求
され、特に金は古来この目的のために重宝され金
素材がそのまゝ加工されたり他金属の上に金メツ
キの形で被覆層を形成して使用されている。耐食
性が要求されない場合には金色を示すという意味
で１ミクロン以下の被覆層でも目的は達成される
が腕時計側やバンド、装身具では汗や水蒸気等に
対する高度の耐食性や長期の使用に耐える耐磨耗
性が色調と同時に要求されることから10ミクロン
以上の膜厚が必要である。金は非常に高価な金属
であるため十分な耐食性と耐磨耗性を有する外装
部品に使用するには制限があり、より安価で十分
な機能を発揮する金色の被覆層の開発が望まれて
いた。近時、イオンプレーテイングやスパツタリ
ング等のいわゆるPhysical Vapour Depotision
（以下PVDと略す）やChemical Vapour
Deposition（以下CVDと略す）によつてTiN、
TaN等の金色被膜が形成されるようになり安価で
機能的にすぐれた被覆層が実現されるようになつ
た。しかしながらこれらの被膜は一見金色ではあ
るが金そのものの色調と比較すると明らかに異な
り金固有の美しい色調を示さず装飾品における適
用が限定されていた。特に腕時計のケースやバン
ドでは金及び金合金の色調が好まれる傾向が強く
TiNやTaN等による被膜の耐食性や耐磨耗性が秀
れているにもかかわらずこの分野への応用に限界
があつた。特に腕時計のケースやバンドではデザ
イン的に対象とする部品の表面を鏡面及び粗面の
組み合わせで仕上げることが多く、その際鏡面上
と粗面上では同一被膜を形成しても色調が異なり
粗面上の色調が金又は金合金の色調とかけはなれ
る傾向が顕著であり問題とされていた。 For exterior parts such as watches and jewelry, color tone as a decorative element and corrosion resistance as a functional element are required at the same time.Gold has been particularly useful for this purpose since ancient times, and the gold material has been processed as it is, and other metals have been used. It is used by forming a covering layer in the form of gold plating on top. If corrosion resistance is not required, the purpose can be achieved with a coating layer of 1 micron or less in the sense of showing a golden color, but on the watch side, band, and accessories, it is highly corrosion resistant to sweat and water vapor, and wear resistant to withstand long-term use. Since quality and color are required at the same time, a film thickness of 10 microns or more is required. Since gold is a very expensive metal, there are restrictions on its use in exterior parts that have sufficient corrosion and abrasion resistance, and there is a desire to develop a gold-colored coating layer that is cheaper and has sufficient functionality. Ta. Recently, so-called physical vapor deposition such as ion plating and sputtering
(hereinafter abbreviated as PVD) and Chemical Vapor
TiN by deposition (hereinafter abbreviated as CVD)
Gold-colored coatings such as TaN began to be formed, making it possible to realize inexpensive and highly functional coating layers. However, although these coatings look gold at first glance, their color tone is clearly different from that of gold itself, and they do not exhibit the beautiful color tone characteristic of gold, so their application in decorative items has been limited. There is a strong tendency for gold and gold alloy tones to be preferred, especially for watch cases and bands.
Despite the excellent corrosion resistance and wear resistance of coatings made of TiN, TaN, etc., there are limits to their application in this field. In particular, for watch cases and bands, the surfaces of the parts targeted for design are often finished with a combination of mirror and rough surfaces.In this case, even if the same coating is formed on the mirror and rough surfaces, the color tones will be different on the rough surfaces. There is a noticeable tendency for the color tone of the upper layer to deviate from the color tone of gold or gold alloy, which has been considered a problem.

本発明はこれらの欠点を除去し耐食性にすぐれ
金及び金合金と同様の色調を広範囲にわたつて実
現できる外装部品を提供することを目的とする。 An object of the present invention is to eliminate these drawbacks and provide an exterior component that has excellent corrosion resistance and can achieve a color tone similar to that of gold and gold alloy over a wide range.

本発明は金属又は耐熱性基体上に窒化チタン被
膜を形成した被覆部品において該窒化チタン被膜
の少くとも表面層近傍にその色調を改良する目的
で窒化物を形成せず、かつ窒化チタンと化合しな
い金属すなわち銅、銀、パラジウム、白金を介在
させることを特徴とするものである。 The present invention provides coated parts in which a titanium nitride film is formed on a metal or heat-resistant substrate, in which nitride is not formed at least near the surface layer of the titanium nitride film for the purpose of improving the color tone, and the titanium nitride film is not combined with the titanium nitride film. It is characterized by the presence of metals such as copper, silver, palladium, and platinum.

以下、本発明を実施例に基づき説明する。 Hereinafter, the present invention will be explained based on examples.

実施例 １ ステンレススチールを腕時計ケースとして加工
後有機溶剤で洗浄しイオンプレーテイング装置に
配置する。イオンプレーテイング装置を２×
10-5Torrに排気後アルゴンガス５×10-3Torr迄
導入し配置した腕時計ケースに直流1KVの電圧を
印加してボンバードを行い続いて排気後窒素ガス
を導入し５×10-3Torrの圧力下でTiを電子ビー
ム加熱によつて蒸発させ該イオンプレーテイング
装置のフイラメントより放出された熱電子によつ
て発生したプラズマ中で窒素ガスと反応させ腕時
計ケースに黄色の窒化チタン被膜を形成する。窒
化チタン被膜形成開始後10分で該イオンプレーテ
イング装置内にあらかじめ配置しておいた銅を抵
抗加熱法によりボートで蒸発させ、窒化チタンの
被膜形成中に銅を含有させ10分間反応性イオンプ
レーテイングを行う。この際抵抗加熱ボートへの
電力を調整して銅の蒸発量を一定に維持した。こ
のようにして得た腕時計用ケースは従来の窒化チ
タン被膜での緑色を帯びた色調に対して淡い赤味
を帯びた美しい金色を示した。色調に関する詳細
な結果を第１図に示す。第１図は従来の窒化チタ
ン膜、純金、本発明による銅を含んだ窒化チタン
膜の波長対反射率を示す図で試料はいずれも鏡面
を採用した。曲線１は窒化チタンの色調で曲線２
は純金の色調、曲線３は窒化チタンに銅を20％含
有させた場合の色調を示す。赤味を帯びた色調を
示すことが測定結果からも明らかである。実施例
１の場合には基材がステンレススチールであるた
め耐食性がよく窒化チタン層は硬質であるため耐
磨耗性がすぐれ、一部銅が混入しても殆んど影響
がなく、すぐれた特性の安価な金色腕時計ケース
を提供することができた。又銅の含有率を変化さ
せれば微妙な金色を出現させることが可能で銅、
50％程度迄は耐食性、耐磨耗性に影響がなく利用
できることがわかつた。Example 1 After processing stainless steel as a wristwatch case, it was cleaned with an organic solvent and placed in an ion plating device. 2x ion plating equipment
After exhausting to 10 -5 Torr, argon gas was introduced to 5 × 10 -3 Torr, and a DC 1KV voltage was applied to the placed watch case to bombard it. After exhausting, nitrogen gas was introduced to 5 × 10 -3 Torr. Ti is evaporated by electron beam heating under pressure and reacts with nitrogen gas in the plasma generated by thermionic electrons emitted from the filament of the ion plating device to form a yellow titanium nitride film on the watch case. . Ten minutes after the start of titanium nitride film formation, the copper that had been placed in advance in the ion plating device was evaporated in a boat using a resistance heating method, and the copper was incorporated during the formation of the titanium nitride film and reactive ion plating was performed for 10 minutes. Perform teing. At this time, the amount of evaporated copper was maintained constant by adjusting the power to the resistance heating boat. The watch case thus obtained exhibited a beautiful gold color with a pale reddish tinge, as opposed to the greenish color of the conventional titanium nitride coating. Detailed results regarding color tone are shown in FIG. FIG. 1 is a diagram showing the reflectance versus wavelength of a conventional titanium nitride film, pure gold, and a copper-containing titanium nitride film according to the present invention, in which the samples each had a mirror surface. Curve 1 is the color tone of titanium nitride and curve 2
Curve 3 shows the color tone of pure gold, and curve 3 shows the color tone when titanium nitride contains 20% copper. It is clear from the measurement results that it exhibits a reddish color tone. In the case of Example 1, the base material is stainless steel, so it has good corrosion resistance, and the titanium nitride layer is hard, so it has excellent abrasion resistance, and even if some copper is mixed in, it has almost no effect and is excellent. We were able to provide a unique and inexpensive gold watch case. Also, by changing the content of copper, it is possible to create a subtle gold color.
It was found that it can be used up to about 50% without affecting corrosion resistance and abrasion resistance.

実施例 ２ 真鍮を腕時計ケースとして加工後電気化学メツ
キにより、ニツケルメツキ、クロムメツキを施し
て、その後反応性イオンプレーテイングによつて
実施例１と同様に窒化チタンを形成し、銀を被膜
の表面層に混入させた。真鍮は耐食性に乏しく外
装部品としてはそのまゝの状態で適用することは
困難であるがニツケルメツキ、クロムメツキを施
すことによつて耐食性が向上し、さらに硬質で金
色の窒化チタンを被覆することによつてすぐれた
特性の腕時計ケースを提供することができる。真
鍮はステンレススチールに比較して加工が容易な
ため複雑な加工を必要とするデザインに利用され
る。又窒化チタンの表面層近傍に銀を混入させた
ため第１図の曲線４の反射率がえられ白色味を帯
びた色調がえられた。Example 2 After processing brass as a watch case, electrochemical plating was applied to nickel plating and chrome plating, followed by reactive ion plating to form titanium nitride in the same manner as in Example 1, and silver on the surface layer of the coating. mixed in. Brass has poor corrosion resistance and is difficult to use as is for exterior parts, but its corrosion resistance can be improved by applying nickel plating or chrome plating, and it can also be coated with hard, golden titanium nitride. We can provide watch cases with excellent characteristics. Brass is easier to process than stainless steel, so it is used for designs that require complex processing. Furthermore, since silver was mixed near the surface layer of titanium nitride, a reflectance of curve 4 in FIG. 1 was obtained, and a whiteish color tone was obtained.

実施例において基材はステンレススチールと真
鍮の場合について述べたが、それ以外の銅合金、
アルミニウム合金等通常外装部品に使用している
すべての金属又は合金に対してこの発明は適用で
きる。又耐熱性の留意すれば金属以外のセラミツ
ク、プラスチツクに適用しても同様の効果があ
る。 In the examples, the base materials are stainless steel and brass, but other copper alloys,
The present invention is applicable to all metals or alloys commonly used for exterior parts, such as aluminum alloys. Furthermore, the same effect can be obtained when applied to ceramics and plastics other than metals, as long as heat resistance is taken into account.

又前記実施例では銅と銀を表面窒化チタン層に
含有させたが腕時計をはじめとして装飾的要素の
強い外装部材では微妙な色調の変化が要求され、
又歴史的、風土的差により世界的にも消費者の好
みが異り多様な色調の提供が必要であるので、
銅、銀以外にパラジウムおよび白金などの金属を
含有させ、多様な色調に対する要求に応じること
が可能である。 Further, in the above embodiment, copper and silver were contained in the surface titanium nitride layer, but for exterior parts with strong decorative elements such as wristwatches, a subtle change in color tone is required.
In addition, consumer tastes differ worldwide due to historical and cultural differences, and it is necessary to provide a variety of color tones.
By containing metals such as palladium and platinum in addition to copper and silver, it is possible to meet requests for various color tones.

又色調としては最外表面から１μｍ以下の層の
吸収、反射特性によつて規定されるため含有させ
る金属は表面層の近傍のみに分布していればよい
が、製造手段の均一化等のために、窒化チタンの
全層にわたつてこれらの金属を分布させてもよ
い。 In addition, since the color tone is determined by the absorption and reflection characteristics of the layer 1 μm or less from the outermost surface, it is sufficient that the metal to be included is distributed only in the vicinity of the surface layer, but in order to make the manufacturing method uniform, etc. Additionally, these metals may be distributed throughout the entire layer of titanium nitride.

又被膜形成後熱処理を施すことによつて色調の
微妙な変化、膜質の安定化をはかることもでき
る。 Further, by applying heat treatment after film formation, subtle changes in color tone and stabilization of film quality can be achieved.

以上述べたように本発明によれば窒化チタンの
表面層近傍に銅、銀、パラジウムおよび白金の中
から選ばれる少なくとも一種の金属を含有させ、
混入した金属の種類、混入比率等を変えることに
よつて広範囲の金色系の色調をうることができ、
腕時計をはじめとした装飾品のデザインの多様性
に答えることが可能となつた。又望み通りの金色
系の色調がえられ、窒化チタンの機能性の優秀さ
は認められながらも色調的に単調であるという欠
点をカバーでき広用範囲は極めて広い。 As described above, according to the present invention, at least one metal selected from copper, silver, palladium, and platinum is contained near the surface layer of titanium nitride,
By changing the type of metal mixed in, the mixing ratio, etc., a wide range of golden tones can be obtained.
It has become possible to respond to the diverse designs of decorative items such as wristwatches. In addition, the desired golden color tone can be obtained, and although the excellent functionality of titanium nitride is acknowledged, it can overcome the drawback of being monotonous in color tone, and has an extremely wide range of applications.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の一実施例における反射率と波
長の関係を示すグラフである。 １……窒化チタン、２……純金、３……窒化チ
タンに銅を含有、４……窒化チタンに銀を含有。 FIG. 1 is a graph showing the relationship between reflectance and wavelength in one embodiment of the present invention. 1...Titanium nitride, 2...Pure gold, 3...Titanium nitride contains copper, 4...Titanium nitride contains silver.

Claims (1)

【特許請求の範囲】[Claims] １ 窒化チタンと、銅、銀、パラジウムおよび白
金の中から選ばれる少なくとも一種の金属との混
合物層がイオンプレーテイング法により表面に形
成されていることを特徴とする金色外装部品。1. A golden exterior component, characterized in that a mixture layer of titanium nitride and at least one metal selected from copper, silver, palladium, and platinum is formed on the surface by an ion plating method.
JP5698378A 1977-06-10 1978-05-13 Golddcolor outer decorating part and its manufacture Granted JPS54148182A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP5698378A JPS54148182A (en) 1978-05-13 1978-05-13 Golddcolor outer decorating part and its manufacture
US05/912,548 US4252862A (en) 1977-06-10 1978-06-05 Externally ornamental golden colored part
GB7826610A GB2000812B (en) 1977-06-10 1978-06-09 Externally ornamental golden colour part
CH633978A CH631040GA3 (en) 1977-06-10 1978-06-09
DE19782825513 DE2825513A1 (en) 1977-06-10 1978-06-10 EXTERNAL GOLD TONE ITEM
FR7822840A FR2425210A1 (en) 1978-05-13 1978-08-02 Gold-coloured titanium nitride coating for watch cases etc. - contains aluminium, silicon, vanadium, silver, zinc, niobium or tin etc.
HK30884A HK30884A (en) 1977-06-10 1984-04-05 Corrosion resistant golden coloured coatings
MY120/85A MY8500120A (en) 1977-06-10 1985-12-30 Corrosion resistant golden coloured coatings

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5698378A JPS54148182A (en) 1978-05-13 1978-05-13 Golddcolor outer decorating part and its manufacture

Publications (2)

Publication Number Publication Date
JPS54148182A JPS54148182A (en) 1979-11-20
JPS6128750B2 true JPS6128750B2 (en) 1986-07-02

Family

ID=13042727

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5698378A Granted JPS54148182A (en) 1977-06-10 1978-05-13 Golddcolor outer decorating part and its manufacture

Country Status (2)

Country Link
JP (1) JPS54148182A (en)
FR (1) FR2425210A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5841152B2 (en) * 1979-02-01 1983-09-09 東洋製罐株式会社 Metal containers and their manufacturing method and equipment
FR2589484A1 (en) * 1985-11-04 1987-05-07 Asulab Sa OBJECT WITH PRECIOUS METAL COATING RESISTANT TO WEAR
CH713310B1 (en) 2016-12-23 2020-08-14 Swatch Group Res & Dev Ltd A method of coloring by coating a pale yellow color on a structural component or a component of a watch or jewelry trim.
EP3974405A1 (en) * 2020-09-25 2022-03-30 The Swatch Group Research and Development Ltd Ceramic decorative item

Also Published As

Publication number Publication date
FR2425210B1 (en) 1984-12-21
JPS54148182A (en) 1979-11-20
FR2425210A1 (en) 1979-12-07

Similar Documents

Publication Publication Date Title
US4252862A (en) Externally ornamental golden colored part
US5985469A (en) White decorative part and process for producing the same
JPS644841Y2 (en)
JP3262686B2 (en) Golden ornament and manufacturing method thereof
US7264668B2 (en) Decorative hard coating and method for manufacture
JPS5926664B2 (en) golden exterior parts
JPS6128750B2 (en)
JPH0461071B2 (en)
JPH0222452A (en) Ornamental member
JPH0751742B2 (en) Exterior parts for watches
JP2003183851A (en) Surface treatment method for ornament, ornament and watch
JPH03120355A (en) White personal ornament
JPS61127858A (en) Golden color external parts
JPS61133374A (en) Golden facing parts
JPH02310360A (en) Ornamental parts
CN1033177C (en) Product with golden surface
JP3244952B2 (en) Golden ornaments
CN118345360A (en) Preparation method of wear-resistant and oxidation-resistant coating on jewelry surface
JPH0730676Y2 (en) Gold exterior parts
JPS61163263A (en) Golden color exterior parts
JP2007254853A (en) Metallic oxide film, and member coated with the metallic oxide film
JPH03100161A (en) Colored hard noble metal film for ornamentation
JPH04329864A (en) External ornamental parts for timepiece
JPH0118610Y2 (en)
JPS61127863A (en) External parts