JPH0210876B2 - - Google Patents
Info
- Publication number
- JPH0210876B2 JPH0210876B2 JP59204659A JP20465984A JPH0210876B2 JP H0210876 B2 JPH0210876 B2 JP H0210876B2 JP 59204659 A JP59204659 A JP 59204659A JP 20465984 A JP20465984 A JP 20465984A JP H0210876 B2 JPH0210876 B2 JP H0210876B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- base layer
- plating
- intermediate metal
- metal
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 238000007747 plating Methods 0.000 claims description 37
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 8
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 95
- 239000010931 gold Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000005240 physical vapour deposition Methods 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910001020 Au alloy Inorganic materials 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003353 gold alloy Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910003468 tantalcarbide Inorganic materials 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- -1 TiN Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】
〔技術分野〕
この発明は、金色・黒色等の美麗な色調を有す
ると共に、表面硬度に優れた外装部品に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an exterior component that has a beautiful color tone such as gold or black and has excellent surface hardness.
メガネフレーム、時計バンド、装身具等の外装
部品には、長時間優れた装飾的効果が求められる
ので、優れた色調と共に、傷がつき難くかつ耐食
性の良い表面処理が求められている。
Exterior parts such as eyeglass frames, watch bands, and accessories are required to have excellent decorative effects over a long period of time, so they are required to have surface treatments that are scratch-resistant and have good corrosion resistance, as well as excellent color tone.
このような条件を満たす外装部品およびその製
造方法として、従来例えば特公昭59−26664号公
報の金色外装部品で開示されたものがある。 As an exterior component and a method for manufacturing the same that meet these conditions, there is a conventional one disclosed in Japanese Patent Publication No. 59-26664 titled "Golden exterior component".
この従来の外装部品は、ステンレススチール等
からなる時計バンド用等の基材に、金色に近似し
た色を有しかつ硬質な窒化チタン（TiN）、窒化
タンタル（TaN）等の硬質金属化合物からなる
ベース層が設けられ、このベース層上に、美麗な
色調を形成するための金あるいは金合金からなる
表面層が形成されたものである。 This conventional exterior part consists of a base material for a watch band made of stainless steel, etc., and a hard metal compound, such as titanium nitride (TiN) or tantalum nitride (TaN), which has a color similar to gold and is hard. A base layer is provided, and a surface layer made of gold or a gold alloy is formed on this base layer to form a beautiful color tone.
このような外装部品の表面層は高価な金属材料
で形成されているので、材料の無駄が少ない電気
メツキ法で作成されることが望ましい。また電気
メツキ法で作成された層は色調も安定している利
点がある。 Since the surface layer of such an exterior component is formed of an expensive metal material, it is desirable to create it by electroplating, which reduces waste of material. Furthermore, layers created by electroplating have the advantage of stable color tone.
ところが、前記従来の外装部品では、TiN等
の金属化合物からなる硬質で緻密なベース層上に
直接表面層が設けられているため、電気化学メツ
キ法で表面層を形成すると表面層とベース層との
密着強度が不足する。 However, in the conventional exterior parts mentioned above, the surface layer is provided directly on a hard and dense base layer made of a metal compound such as TiN, so when the surface layer is formed by electrochemical plating, the surface layer and base layer are separated. Adhesion strength is insufficient.
このため、従来の外装部品にあつては、経時的
に、表面層が剥離して長期の使用に耐えない問題
があつた。 For this reason, conventional exterior parts had a problem in that the surface layer peeled off over time, making them unusable for a long period of time.
この発明は上記事情に鑑みてなされたもので、
硬質金属化合物からなるベース層とメツキ法で形
成された表面層との密着性を向上でき長期間良好
な外観品質を維持する外装部品を提供することを
目的とする。 This invention was made in view of the above circumstances,
The purpose of the present invention is to provide an exterior part that can improve the adhesion between a base layer made of a hard metal compound and a surface layer formed by a plating method and maintain good appearance quality for a long period of time.
この発明の外装部品は、外装部品の表面を形成
するメツキ層と、該メツキ層と近似色を呈する硬
質金属化合物によつて形成されたベース層との間
に、透明性を有し純金属あるいは金属合金を主体
としかつ上記ベース層との界面においてこれら純
金属あるいは金属合金がベース層をなす硬質金属
化合物と混合状態にある中間金属層が介在せしめ
られてなるものである。
The exterior component of the present invention has a transparent material between a plating layer forming the surface of the exterior component and a base layer formed of a hard metal compound exhibiting a similar color to the plating layer. The intermediate metal layer is mainly composed of a metal alloy and is interposed at the interface with the base layer, in which these pure metals or metal alloys are in a mixed state with the hard metal compound forming the base layer.
前記中間金属層の厚さは、一般的には500Å以
下であることが望ましい。 The thickness of the intermediate metal layer is generally preferably 500 Å or less.
この発明の外装部品にあつては、ベース層とメ
ツキ層との間に中間金属層が設けられている。こ
の中間金属層とベース層とは、界面の部分で混合
しているので互いに強固に密着する。また、中間
金属層は主に純金属あるいは金属合金からなるも
のなので、層をなす金属は、電気化学メツキ法に
より与えられる低いエネルギーでも中間金属層内
に拡散浸透してゆくことができる。従つて、この
中間金属層上に形成されたメツキ層は中間金属層
と強固に密着したものとなる。そして、外装部品
の表面をなすメツキ層と基板上に形成されたベー
ス層とは、中間金属層を介して強固に密着する。
In the exterior component of the present invention, an intermediate metal layer is provided between the base layer and the plating layer. Since the intermediate metal layer and the base layer are mixed at the interface, they adhere firmly to each other. Furthermore, since the intermediate metal layer is mainly made of pure metal or metal alloy, the metal forming the layer can diffuse into the intermediate metal layer even with low energy provided by the electrochemical plating method. Therefore, the plating layer formed on the intermediate metal layer is firmly adhered to the intermediate metal layer. Then, the plating layer forming the surface of the exterior component and the base layer formed on the substrate are tightly adhered to each other through the intermediate metal layer.
以下、実施例に沿つてこの発明を詳しく説明す
る。
Hereinafter, this invention will be explained in detail with reference to Examples.
図に示すものは、この発明の外装部品の断面で
ある。この外装部品は、基材１の表面にまずベー
ス層２が形成され、このベース層２の上に中間金
属層３とメツキ層４が順次形成されたなるもので
ある。 What is shown in the figure is a cross section of the exterior component of the present invention. In this exterior component, a base layer 2 is first formed on the surface of a base material 1, and an intermediate metal layer 3 and a plating layer 4 are sequentially formed on this base layer 2.
基材１は、ステンレス鋼、チタン、真ちゆう、
あるいはアルミニウム等、種々の金属またはそれ
らの合金あるいは非金属からなるもので、メガネ
フレーム、時計枠、時計バンド等の所望の形状に
形成されてなるものである。 Base material 1 is stainless steel, titanium, brass,
Alternatively, it is made of various metals such as aluminum, alloys thereof, or non-metals, and is formed into a desired shape such as an eyeglass frame, a watch frame, or a watch band.
基板１上に形成されたベース層２は、硬質金属
化合物からなる層であつて、後述するメツキ層と
近似した色調を有しかつ高い表面硬度を有する硬
質金属化合物により好適に形成される。そのよう
な硬質金属化合物の例としては、たとえば金色に
近似する色調を程す窒化チタン（TiN）、炭化タ
ンタル（TaC）、黒色を程する窒化タンタル
（TaN）、炭化チタン（TiC）、炭化クロム
（Cr3C2・Cr7C3・Cr23C9）などが挙げられる。こ
れら硬質金属化合物によりベース層２を形成する
には、一般にイオンプレーテイング法、スパツタ
リング法、真空蒸着法などの物理蒸着法が用いら
れる。 The base layer 2 formed on the substrate 1 is a layer made of a hard metal compound, and is preferably formed of a hard metal compound having a color tone similar to that of the plating layer described later and having high surface hardness. Examples of such hard metal compounds include titanium nitride (TiN) and tantalum carbide (TaC), which have a color similar to gold, tantalum nitride (TaN), which has a black color, titanium carbide (TiC), and chromium carbide. ( Cr3C2 ・ Cr7C3・Cr23C9 ) , etc. To form the base layer 2 from these hard metal compounds, physical vapor deposition methods such as ion plating, sputtering, and vacuum evaporation are generally used.
ベース層２上の中間金属層３は、純金属または
金属合金からなるものである。この中間金属層３
と上記ベース層２との界面において、これら純金
属あるいは金属合金はベース層２をなす硬質化合
物と混合した状態になつている。この中間金属層
３は、上記ベース層２を形成した物理蒸着法と同
一の物理蒸着法で形成されることが望ましいが、
高エネルギーで蒸気を蒸着させることができるス
パツタリング法等を利用すれば、必ずしも中間金
属層３をベース層と同じ方法で形成する必要はな
い。 The intermediate metal layer 3 on the base layer 2 is made of pure metal or a metal alloy. This intermediate metal layer 3
At the interface between the base layer 2 and the base layer 2, these pure metals or metal alloys are in a mixed state with the hard compound forming the base layer 2. This intermediate metal layer 3 is preferably formed by the same physical vapor deposition method as that used to form the base layer 2;
If a sputtering method or the like that allows vapor deposition with high energy is used, it is not necessarily necessary to form the intermediate metal layer 3 by the same method as the base layer.
この中間金属層３をなす純金属、金属合金とし
ては、例えば、ニツケル（Ni）、パラジウム
（Pd）、白金（Pt）、イリジウム（Ir）、金（Au）、
銀（Ag）、銅（Cu）、ロジウム（Rh）、インジウ
ム（In）など種々の金属あるいはそれらの合金が
挙げられる。この中間金属層３は、前記ベース層
２が透けて見える厚さに形成されている。そのた
めには、この中間金属層３の厚さを500Å以下さ
らに望ましくは70Å以下に設定することが望まし
い。このように中間金属層３を透明に形成すると
メツキ層４と近似した色調に形成されたベース層
２によつてメツキ層４の色調を補うことができる
ので、メツキ層４を薄く形成しても、外装部品の
色調を所望の色調とすることができる。他方この
中間金属３が薄すぎると斑になつて後述するメツ
キ層４の密着が不均一となるので、この中間金属
層３は50Å以上の厚さであることが望ましい。 Examples of pure metals and metal alloys forming the intermediate metal layer 3 include nickel (Ni), palladium (Pd), platinum (Pt), iridium (Ir), gold (Au),
Examples include various metals such as silver (Ag), copper (Cu), rhodium (Rh), and indium (In), or alloys thereof. This intermediate metal layer 3 is formed to such a thickness that the base layer 2 can be seen through it. For this purpose, it is desirable to set the thickness of this intermediate metal layer 3 to 500 Å or less, more preferably 70 Å or less. When the intermediate metal layer 3 is formed transparent in this way, the color tone of the plating layer 4 can be supplemented by the base layer 2 formed in a color tone similar to that of the plating layer 4, so even if the plating layer 4 is formed thinly. , the color tone of the exterior parts can be made into a desired color tone. On the other hand, if the intermediate metal layer 3 is too thin, it will become uneven and the adhesion of the plating layer 4, which will be described later, will be non-uniform, so it is desirable that the intermediate metal layer 3 has a thickness of 50 Å or more.
この中間金属層３上には、通常の電気化学メツ
キ法によりメツキ層４が形成される。このメツキ
層４を形成する金属等には種々のものを利用でき
る。例えば、所望する色調が金色である場合に
は、金あるいは金合金等が用いられる。また所望
する色調が黒色である場合には黒ロジウム、黒ル
テニウム等が用いられる。このメツキ層４は、
0.1μｍ〜10μｍ程度に形成されていれば、この外
装部品の色調を所望のものとすることができる。 A plating layer 4 is formed on this intermediate metal layer 3 by a normal electrochemical plating method. Various metals can be used to form the plating layer 4. For example, if the desired color tone is gold, gold or a gold alloy is used. Furthermore, when the desired color tone is black, black rhodium, black ruthenium, etc. are used. This plating layer 4 is
If the thickness is about 0.1 μm to 10 μm, the color tone of this exterior component can be desired.
本発明の外装部品を作成して密着性等の試験を
行い、本発明の効果を確認した。
Exterior components of the present invention were prepared and tested for adhesion, etc., to confirm the effects of the present invention.
まず、研磨されたステンレス鋼製時計バンドを
溶剤で洗浄して乾燥した。 First, a polished stainless steel watch band was cleaned with a solvent and dried.
次に、この時計バンドをイオンプレーテイング
装置の基板にセツトして、まずベース層２を、つ
いで中間金属層３を形成した。 Next, this watch band was set on a substrate of an ion plating device, and first a base layer 2 and then an intermediate metal layer 3 were formed.
ベース層２の形成は常法に従い次の手順で行な
つた。まず、イオンプレーテイング装置（以下、
PVD装置と略称する）にアルゴン（Ar）を注入
してイオンボンバートをした後、PVD装置内を
高真空（10-5〜10-7Torr）に排気し、基板に数
百ボルトの電圧を印加して、イオン化したチタン
（Ti）を時計バンドに付着せしめた、Tiが時計バ
ンドに強く付着して均一なTi膜が得られた後、
基板電圧を下げ、PVD装置内に窒素ガス（N2）
を導入し、PVD装置内の圧力を約10-6Torrとし
て、イオン化されたTiとN2とを反応せしめ、金
に近似した色調を呈する窒化チタン（TiN）を
時計バンドに付着せしめた。これを所定時間行
い、膜厚1μｍ〜2μｍのベース層２を形成した。
つづいて、同一のPVD装置内でニツケル（Ni）
をイオン化して、このイオン化されたニツケル
（Ni）を時計バンドに付着せしめた。これを所定
時間行い、50Å〜70Åの厚さ中間金属層３を形成
した。 The base layer 2 was formed according to the following procedure according to a conventional method. First, the ion plating device (hereinafter referred to as
After injecting argon (Ar) into the PVD equipment (abbreviated as PVD equipment) and performing ion bombardment, the inside of the PVD equipment is evacuated to a high vacuum (10 -5 to 10 -7 Torr), and a voltage of several hundred volts is applied to the substrate. The ionized titanium (Ti) was applied to the watch band. After Ti was strongly attached to the watch band and a uniform Ti film was obtained,
Lower the substrate voltage and introduce nitrogen gas (N 2 ) into the PVD equipment.
By introducing a PVD system at a pressure of approximately 10 -6 Torr, ionized Ti and N 2 were reacted, and titanium nitride (TiN), which has a color similar to gold, was deposited on the watch band. This was carried out for a predetermined period of time to form a base layer 2 having a thickness of 1 μm to 2 μm.
Next, nickel (Ni) was produced in the same PVD equipment.
was ionized and the ionized nickel (Ni) was attached to a watch band. This was carried out for a predetermined period of time to form an intermediate metal layer 3 having a thickness of 50 Å to 70 Å.
次に、このように中間金属層３が形成された時
計バンドに、電気化学メツキ法により金合金より
なるメツキ層４を形成した。金合金をメツキする
には、まず時計バンドを脱脂し、ついでこれを有
機酸（クエン酸）で処理して活性化し、この後、
クエン酸浴中で金メツキを行つた。形成されたメ
ツキ層４の厚さは、約0.3μｍであつた。 Next, a plating layer 4 made of a gold alloy was formed on the watch band with the intermediate metal layer 3 formed thereon by an electrochemical plating method. To plate gold alloy, the watch band is first degreased, then treated with an organic acid (citric acid) to activate it;
Gold plating was carried out in a citric acid bath. The thickness of the plating layer 4 formed was about 0.3 μm.
このように表面処理された時計バンドを各種試
験に供した。次に試験の内容とその結果を述べ
る。 The watch bands surface-treated in this manner were subjected to various tests. Next, the content of the test and its results will be described.
ａ 人工汗全漬試験
次の組成からなる人工汗液を40℃に保ち、こ
れに時計バンドを浸漬した。a) Artificial sweat total immersion test An artificial sweat solution having the following composition was kept at 40°C, and a watch band was immersed in it.
塩化ナトリウム 9.9ｇ／
硫化ナトリウム 0.8ｇ／
尿 素 1.7ｇ／
アンモニア水 0.18ｇ／
乳 酸 1.1ｇ／
遮 糖 0.22ｇ／
残り純水
24時間後時計バンドを取り出し外観を観察し
たところ異常は全くなかつた。また、このもの
にセロテープを密着させ急激にはがしてみた
が、金合金からなるメツキ層４の剥離は生じな
かつた。Sodium chloride 9.9g / Sodium sulfide 0.8g / Urea 1.7g / Ammonia water 0.18g / Lactic acid 1.1g / Sugar blocker 0.22g / Remaining pure water After 24 hours, I took out the watch band and observed the appearance, and there was no abnormality at all. . In addition, cellophane tape was applied closely to this material and then rapidly peeled off, but the plating layer 4 made of gold alloy did not peel off.
ｂ 折り曲げ試験
上記時計バンドを分解して得られた各駒を、
万力を用いて60゜〜90゜に折り曲げて外観を観察
した。b Bending test Each piece obtained by disassembling the above watch band was
The appearance was observed by bending it at an angle of 60° to 90° using a vise.
全部の駒を試験したが、外観には亀裂等の異
状は全く見られなかつた。また、この折り曲げ
部にセロテープを密着せしめた後このセテープ
を急速に剥がしたが、メツキ層４の剥離は生じ
なかつた。 All the pieces were tested, and no abnormalities such as cracks were found in their appearance. Further, after adhering cellophane tape to the bent portion, the cellophane tape was rapidly peeled off, but no peeling of the plating layer 4 occurred.
ｃ 塩水試験
時計バンドを、常温の３％NaCl溶液に浸漬
した。c Salt water test The watch band was immersed in a 3% NaCl solution at room temperature.
48時間後、時計バンドを取り出し錆の発生の
有無を観察したが、錆は全く発生していなかつ
た。 After 48 hours, the watch band was removed and observed for rust, but no rust was found.
ｄ 摩耗試験
耐摩耗試験機を用いて時計バンドの摩耗試験
を行つた。試験条件は、荷重500ｇ、摩耗回数
15000回とした。d Wear test A wear test of the watch band was conducted using an abrasion tester. Test conditions are load 500g, number of wear
It was set to 15,000 times.
試験後の時計バンドの外観を観察したとこ
ろ、メツキ層４は傷ついていたが、ベース層２
をなすTiNの色調がメツキ層４をなす金合金
の色調と同一であり、しかも中間金属層３は膜
厚が薄いため透明なので、メツキ層４の傷はほ
とんど目立たなかつた。 When we observed the appearance of the watch band after the test, we found that the plating layer 4 was damaged, but the base layer 2 was damaged.
The color tone of the TiN forming the plating layer 4 is the same as the color tone of the gold alloy forming the plating layer 4, and since the intermediate metal layer 3 is thin and transparent, the scratches on the plating layer 4 were hardly noticeable.
また、チタン製のメガネフレームについても
同様の表面処理を行ない、上記試験に供したと
ころ、ステンレス鋼製時計バンドと同様良好な
結果が得られた。 Furthermore, when a titanium eyeglass frame was subjected to the same surface treatment and subjected to the above test, good results were obtained similar to the stainless steel watch band.
以上説明したように、この発明の外装部品は、
表面を形成するメツキ層と該メツキ層と近似色を
程する硬質金属化合物によつて形成されたベース
層との間に、透明性を有し、純金属あるいは金属
合金を主体とし、かつ上記ベース層との界面にお
いて、これら純金属あるいは金属合金がベース層
をなす硬質金属化合物と混合状態にある透明性中
間金属層が介在せしめられてなるものなので、中
間金属層を介して、高度の高いTiN、TiC、
TaN、TaC、Cr23C8等の硬質金属化合物からな
るベース層上に、美麗で安定した色調を有しかつ
経済的に形成できるメツキ層を、強固に密着せし
めることができる。従つて、この外装部品は、美
麗で安定した色調を有し、傷つき難く、かつ安価
に生産できるという利点に加え、剥離などの問題
が生じることがなく、長期間良好な外観品質を維
持し得るという長所を有するものとなる。
As explained above, the exterior parts of this invention are
Between the plating layer forming the surface and the base layer formed of a hard metal compound having a color similar to that of the plating layer, the base layer is transparent, is mainly made of pure metal or metal alloy, and is made of a base layer as described above. At the interface with the TiN layer, a transparent intermediate metal layer in which these pure metals or metal alloys are mixed with the hard metal compound forming the base layer is interposed. ,TiC,
A plating layer that has a beautiful and stable color tone and can be formed economically can be tightly adhered to a base layer made of a hard metal compound such as TaN, TaC, Cr 23 C 8 , etc. Therefore, this exterior part has the advantage of having a beautiful and stable color tone, being hard to damage, and being able to be produced at low cost.In addition, it does not cause problems such as peeling and can maintain good appearance quality for a long period of time. It has the advantage of.
しかもこの発明の外装部品は、中間金属層が透
明に形成されているので、メツキ層が傷付いた場
合はメツキ層と近似色を呈するベース層の色調が
損傷部に表われる。従つてこの発明の外装部品は
メツキ層の傷が目立たず、この点でも長期間良好
な外観品質を維持し得るものとなる。 Moreover, in the exterior component of the present invention, since the intermediate metal layer is formed to be transparent, if the plating layer is damaged, the color tone of the base layer, which has a color similar to that of the plating layer, will appear in the damaged area. Therefore, in the exterior component of the present invention, scratches on the plating layer are not noticeable, and in this respect as well, good appearance quality can be maintained for a long period of time.
図は、第１の発明の外装部品を示す断面図であ
る。
１……基材、２……ベース層、３……中間金属
層、４……メツキ層。
The figure is a sectional view showing the exterior component of the first invention. 1... Base material, 2... Base layer, 3... Intermediate metal layer, 4... Plating layer.
Claims (1)
似色を呈する硬質金属化合物によつて形成された
ベース層との間に、透明性を有し、純金属あるい
は金属合金を主体としかつ上記ベース層との界面
においてこれら純金属あるいは金属合金がベース
層をなす硬質金属化合物と混合状態にある中間金
属層が介在せしめられていることを特徴とする外
装部品。 ２ 上記中間金属層の厚さが500Å以下であるこ
とを特徴とする特許請求の範囲第１項の外装部
品。[Scope of Claims] 1. Between the plating layer forming the surface and the base layer formed of a hard metal compound exhibiting a similar color to the plating layer, a pure metal or a metal alloy having transparency is provided. An exterior component characterized in that an intermediate metal layer is interposed at the interface with the base layer in which these pure metals or metal alloys are mixed with a hard metal compound constituting the base layer. 2. The exterior component according to claim 1, wherein the intermediate metal layer has a thickness of 500 Å or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59204659A JPS6184392A (en) | 1984-09-29 | 1984-09-29 | Surface treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59204659A JPS6184392A (en) | 1984-09-29 | 1984-09-29 | Surface treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6184392A JPS6184392A (en) | 1986-04-28 |
| JPH0210876B2 true JPH0210876B2 (en) | 1990-03-09 |
Family
ID=16494157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59204659A Granted JPS6184392A (en) | 1984-09-29 | 1984-09-29 | Surface treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6184392A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61104097A (en) * | 1984-10-23 | 1986-05-22 | Iwasaki Mekki:Kk | Armored part |
| JPS6353267A (en) * | 1986-08-22 | 1988-03-07 | Nippon Dento Kogyo Kk | Plating method |
| JPH02173267A (en) * | 1988-12-27 | 1990-07-04 | Natl Res Inst For Metals | Formation of composite film having wear resistance and electrical conductivity |
| JP2005146304A (en) * | 2003-11-12 | 2005-06-09 | Citizen Watch Co Ltd | Decorative part having decorative film, and its production method |
| WO2009038151A1 (en) * | 2007-09-19 | 2009-03-26 | Citizen Holdings Co., Ltd. | Ornament parts |
| JP7238468B2 (en) * | 2019-02-28 | 2023-03-14 | セイコーエプソン株式会社 | watch exterior parts and watches |
| DE102019109188B4 (en) | 2019-04-08 | 2022-08-11 | Umicore Galvanotechnik Gmbh | Use of an electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
| CN110396708A (en) * | 2019-08-07 | 2019-11-01 | 东莞市合航精密科技有限公司 | A kind of corrosion resistance coating of silver combined plating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204660A (en) * | 1983-05-10 | 1984-11-20 | T Hasegawa Co Ltd | Pulverization of water-soluble natural pigment |
-
1984
- 1984-09-29 JP JP59204659A patent/JPS6184392A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204660A (en) * | 1983-05-10 | 1984-11-20 | T Hasegawa Co Ltd | Pulverization of water-soluble natural pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6184392A (en) | 1986-04-28 |
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