JPH062934B2 - Jewelry that has a colored surface - Google Patents
Jewelry that has a colored surfaceInfo
- Publication number
- JPH062934B2 JPH062934B2 JP6606885A JP6606885A JPH062934B2 JP H062934 B2 JPH062934 B2 JP H062934B2 JP 6606885 A JP6606885 A JP 6606885A JP 6606885 A JP6606885 A JP 6606885A JP H062934 B2 JPH062934 B2 JP H062934B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- accessory
- tin
- jewelry
- nickel
- 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
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (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、表面の有色をイオンプレーティング法により
実現する銅合金からなる装身具に関するものである。TECHNICAL FIELD The present invention relates to an accessory made of a copper alloy whose surface is colored by an ion plating method.
表面にイオンプレーティング法による窒化チタン等の有
色被膜を形成する銅合金からなる装身具の従来技術とし
て、銅合金の表面に下地層としてニッケル等の金属をメ
ッキ処理により形成し、イオンプレーティング法によ
り、前記下地層の上に窒化チタン等の有色被膜を形成し
たものがある。As a conventional technique of an accessory made of a copper alloy that forms a colored film such as titanium nitride on the surface by the ion plating method, a metal such as nickel is formed as a base layer on the surface of the copper alloy by plating, and the In some cases, a colored film such as titanium nitride is formed on the underlayer.
また、表面にイオンプレーティング法による窒化チタン
等の有色被膜を形成した銅合金からなる装身具として、
前記従来技術の他に特公昭５９−４５７５４号公報の様
に、銅合金の表面に下地層としてニッケル層をメッキ処
理により形成し、更に該ニッケル層の上にクロム層をメ
ッキ処理により形成し、イオンプレーティング法により
前記クロム層の上に窒化チタン等の有色被膜を形成した
ものもある。Also, as an accessory made of a copper alloy on the surface of which a colored coating such as titanium nitride is formed by an ion plating method,
In addition to the above-mentioned prior art, as in Japanese Patent Publication No. 59-45754, a nickel layer is formed as a base layer on the surface of a copper alloy by plating, and a chromium layer is further formed on the nickel layer by plating. There is also one in which a colored film such as titanium nitride is formed on the chromium layer by an ion plating method.
銅合金の表面の下地層にイオンプレーティング法により
有色被膜を形成して表面に有色を呈する装身具と、銅合
金からなる装身具の表面に、メッキ処理によりニッケル
層を形成し、更にニッケル層の上にメッキ処理により金
層を形成した従来技術で製作した装身具の耐食性を比較
すると、イオンプレーティング法による前者はメッキ処
理により金層を形成した後者よりも劣っている。また、
特公昭５９−４５７５４号公報による装身具は、ニッケ
ル等の下地層の上にイオンプレーティング法により有色
被膜を形成した装身具と比較すれば耐食性がかなりすぐ
れており、実用としては差支えない程度の耐食性を有し
ている。しかし特公昭５９−４５７５４号の装身具は、
下地層の形成に使用したクロムメッキ液は、形成したク
ロム層の表面に付着した残りやすいので、完全に除去す
るための洗浄工程の管理がめんどうであった。また、ク
ロムメッキ液が洗浄工程に於て取りきれず、クロム層の
表面に残査として残った状態で、イオンプレーティング
法で窒化チタン等の有色被膜を形成すると、クロムメッ
キ液が残査として残った上に形成された窒化チタン等の
有色被膜との密着が悪くなる。更には、クロムメッキの
公害などの問題があった。An accessory that forms a colored film by forming a colored coating on the underlayer on the surface of a copper alloy by the ion plating method, and a nickel layer is formed by plating on the surface of the accessory made of a copper alloy. Comparing the corrosion resistance of the accessory manufactured by the prior art in which the gold layer is formed by plating, the former by the ion plating method is inferior to the latter by which the gold layer is formed by plating. Also,
The accessory according to Japanese Examined Patent Publication No. 59-45754 has considerably excellent corrosion resistance as compared with the accessory in which a colored coating is formed on the underlayer of nickel or the like by the ion plating method, and the corrosion resistance is practically acceptable. Have However, the accessory of Japanese Patent Publication No. 59-45754 is
Since the chrome plating solution used for forming the underlayer is likely to remain on the surface of the formed chrome layer, it is troublesome to control the cleaning process for complete removal. Also, when the chromium plating solution cannot be completely removed in the cleaning process and remains as a residue on the surface of the chromium layer, and a colored film such as titanium nitride is formed by the ion plating method, the chromium plating solution remains as a residue. Adhesion with the colored film such as titanium nitride formed on the remaining portion deteriorates. Further, there is a problem such as pollution of chrome plating.
本発明は、表面に有色を呈するイオンプレーティング法
による従来技術の装身具の問題点をなくし、金メッキ仕
様と同等の耐食性を有し、有色被膜の密着が優れた装身
具を提供することを目的とする。An object of the present invention is to eliminate the problems of the jewelry of the prior art by the ion plating method that exhibits a color on the surface, have the corrosion resistance equivalent to the gold plating specification, and provide the jewelry with excellent adhesion of the colored film. .
本発明は、銅合金からなる装身具の表面にニッケル層を
下地層として形成した上にスズコバルト合金層を形成
し、更にイオンプレーティング法により前記スズコバル
ト合金層の上に窒化チタン等の有色被膜を形成したもの
である。The present invention forms a tin-cobalt alloy layer on a nickel layer formed as a base layer on the surface of an accessory made of a copper alloy, and further forms a colored coating such as titanium nitride on the tin-cobalt alloy layer by an ion plating method. It was done.
装身具の表面がニッケル層、スズコバルト合金層、有色
被膜の３層からなり、ニッケル層とニッケル層の上面の
スズコバルト合金層により、有色被膜との密着及び耐食
性を一段と向上させる。The surface of the accessory comprises a nickel layer, a tin-cobalt alloy layer, and a colored coating. The nickel layer and the tin-cobalt alloy layer on the upper surface of the nickel layer further improve the adhesion to the colored coating and the corrosion resistance.
以下、本発明の実施例を図面に基づいて説明する。図面
は、本発明の実施例であり、表面に有色を呈する装身具
の要部断面図である。１は装身具、２はニッケル層、３
はスズコバルト合金層、４は窒化チタン層である。Embodiments of the present invention will be described below with reference to the drawings. Drawing is an example of the present invention, and is an important section sectional view of accessories which shows a color on the surface. 1 is jewelry, 2 is nickel layer, 3
Is a tin cobalt alloy layer, and 4 is a titanium nitride layer.
黄銅からなる装身具１を、トリクレン洗浄、アルカリ脱
脂、酸洗の通常メッキの前処理を行い、次に下地層とし
て、ニッケルメッキ処理によりニッケル層２を５μ形成
し、更にその上にスズコバルトメッキ処理によりスズコ
バルト合金層３を0.5μ形成した。尚、本実施例におい
てニッケル層２を５μ、スズコバルト合金層３を0.5μ
としたのは下記理由による。ニッケル層２のニッケル厚
としては１〜１０μの範囲が良く、膜厚が１μより薄い
と耐食性に不安があり、１０μより厚いと耐食性は充分
だがエッヂ部が電流密度の関係により特にニッケルの析
出が多く丸みを帯びて外観的に好ましくないことがあ
る。又スズコバルト合金層３のスズコバルト合金厚は0.
1〜５μの範囲が良く膜厚が0.1μより薄いと耐食性に不
安があり、５μより厚いと経済的に好ましくない。すな
わち前記数値に限定されなくても実施できるが、耐食性
その他の理由により前記の様にニッケル層を１〜１０μ
スズコバルト合金層を0.1〜５μとすることが好まし
い。次にこのメッキに用いたメッキ液の組成及びメッキ
条件を示すと下記の通りである。The jewelry 1 made of brass is subjected to pretreatments such as trichlene washing, alkaline degreasing and pickling, and then a nickel layer 2 of 5 μm is formed as a base layer by nickel plating, and tin cobalt plating is further performed thereon. Thus, a tin-cobalt alloy layer 3 having a thickness of 0.5 μm was formed. In this embodiment, the nickel layer 2 is 5 μm and the tin-cobalt alloy layer 3 is 0.5 μm.
The reason is as follows. The nickel thickness of the nickel layer 2 is preferably in the range of 1 to 10 μ, and if the film thickness is less than 1 μ, there is concern about corrosion resistance. If the thickness is more than 10 μ, corrosion resistance is sufficient, but nickel deposits particularly on the edge part due to current density. It may have a lot of roundness and may be unfavorable in appearance. The tin-cobalt alloy layer 3 has a tin-cobalt alloy thickness of 0.
If it is in the range of 1 to 5μ and the film thickness is thinner than 0.1μ, there is concern about corrosion resistance, and if it is thicker than 5μ, it is economically unfavorable. That is, it can be carried out without being limited to the above-mentioned numerical values, but the nickel layer is added in an amount of 1 to 10 μm as described above due to corrosion resistance and other reasons.
It is preferable that the tin-cobalt alloy layer has a thickness of 0.1 to 5 μm. Next, the composition of the plating solution used for this plating and the plating conditions are as follows.
ニッケルメッキ 液 組 成 硫酸ニッケル ２５０ g/ 塩化ニッケル ５０ g/ 硼 酸 ４０ g/ 添加剤 １５ ml/ メッキ条件 電流密度 ５ A/dm2 浴 温 ４５℃ ｐＨ 4.0 時 間 ５分 スズコバルトメッキ 液 組 成 スコバロイ メッキ条件 電流密度 1.0A/dm2 浴 温 ３５℃ ｐＨ 3.5 時 間 ４分 次に、スズコバルト合金層３を形成した装身具１を、イ
オンプレーティング装置のベルジャー内にセットし、真
空中でボンバードを行い装身具１の表面の洗浄を行っ
た。Composition of nickel plating solution Nickel sulfate 250 g / Nickel chloride 50 g / Boric acid 40 g / Additive 15 ml / Plating conditions Current density 5 A / dm 2 Bath temperature 45 ° C pH 4.0 hours 5 minutes Tin cobalt plating solution composition Scoballoy plating conditions Current density 1.0A / dm 2 bath Temperature 35 ° C pH 3.5 hours 4 minutes Next, the accessory 1 with the tin-cobalt alloy layer 3 formed is set in the bell jar of the ion plating device and bombarded in vacuum. The surface of the accessory 1 was washed.
次に、ベルジャー内を不活性ガスであるＡｒガスと反応
性ガスであるＮ２ガスの混合雰囲気で真空度2.0×１０
-3Torrにし、電圧（3.0kV５０ｍＡ）を印加し、プラズ
マを発生させ金属チタンを電子ビームで加熱蒸発させ、
装身具１のスズコバルト合金層３の上面に、窒化チタン
層４の有色被膜を0.3μ形成した。前記実施例による装
身具を試験したところ、耐食性がすぐれ、しかもクロム
を使用しないので特公昭５９−４５７５４号の様な作業
性や公害などの問題もなかった。Next, the degree of vacuum in the bell jar was set to 2.0 × 10 in a mixed atmosphere of Ar gas as an inert gas and N 2 gas as a reactive gas.
-3 Torr, voltage (3.0 kV 50 mA) is applied, plasma is generated and metallic titanium is heated and evaporated by an electron beam,
On the upper surface of the tin-cobalt alloy layer 3 of the accessory 1, a 0.3 μm colored coating of the titanium nitride layer 4 was formed. When the accessory according to the above-mentioned example was tested, it was excellent in corrosion resistance and there was no problem of workability and pollution as in Japanese Patent Publication No. 59-45754 because it does not use chromium.
尚、窒化チタンは黄金色を呈するがガスあるいは蒸発さ
せる金属の種類を変えることによってグレー色、黒色等
の色を出すことが可能な事はいうまでもない。It should be noted that titanium nitride has a golden color, but it goes without saying that it is possible to produce a color such as gray or black by changing the type of gas or metal to be evaporated.
またガスの種類としては、Ａｒ−Ｎｉ混合ガスのみでな
く、不活性ガスとしてＨｌ、反応性ガスとしてＯ2、Ｃ2
Ｈ2、ＣＨ3等がある。又金属の種類としてはＴｉの他
に、Ａｕ、Ｔａ、Ｚｒ等の金属やそれらの酸化物等があ
る。この様にして作られた装身具と、前記従来技術で製
作した装身具とを人工汗浸漬２４時間の耐食試験を行な
い、その結果を示したのが第１表である。なお第１表に
おける従来技術は黄銅からなる装身具の表面に、下地層
としてニッケル層を形成し、イオンプレーティング法に
より前記下地層の上に窒化チタン層の有色被膜を形成
し、完成したものであり、この従来の装身具と、黄銅よ
りなる装身具の表面に、メッキ処理によりニッケル層を
形成し、更にニッケル層の上にメッキ処理により金層を
形成した装身具の２点の試験結果が示されている。Further, as the kind of gas, not only Ar—Ni mixed gas but also Hl as an inert gas, O 2 and C 2 as a reactive gas
There are H 2 , CH 3, etc. As the kind of metal, in addition to Ti, there are metals such as Au, Ta, and Zr, and oxides thereof. Table 1 shows the results of the corrosion resistance test of artificial jewelry soaked for 24 hours, which was performed on the jewelry made in this manner and the jewelry manufactured by the conventional technique. The prior art shown in Table 1 was completed by forming a nickel layer as an underlayer on the surface of an accessory made of brass and forming a colored film of a titanium nitride layer on the underlayer by an ion plating method. Yes, there are two test results of the conventional jewelry and the jewelry which has a nickel layer formed by plating on the surface of the brass jewelry and a gold layer formed on the nickel layer by plating. There is.
なお特公昭５９−４５７５４号の従来技術は、耐食性の
点はかなり改善されて実用としては差支えないので、耐
食試験の結果は第１表には試載しなかった。The conventional technique of Japanese Examined Patent Publication No. 59-45754 has a considerably improved corrosion resistance and can be practically used. Therefore, the results of the corrosion resistance test are not listed in Table 1.
第１表から明らかな様に、本発明により作られた装身具
は、耐食性があり、金メッキ仕様とほぼ同等の耐食性を
有することが判る。As is clear from Table 1, the jewelry made according to the present invention has corrosion resistance, and has corrosion resistance almost equal to the gold plating specification.
これに対し第１表に示す従来技術で作られた装身具は、
腐食が発生して耐食性が悪かった。On the other hand, the jewelry made by the conventional technique shown in Table 1 is
Corrosion occurred and the corrosion resistance was poor.
次に特公昭５９−４５７５４号の問題点があった作業性
や公害の点は、表を記載するのは省略したが、本発明の
装身具は前記実施例でのべた通り、クロムを使用しない
ので特公昭５９−４５７５４号の問題点も解決した。Regarding the workability and pollution of the Japanese Patent Publication No. 59-45754, the table is omitted, but since the jewelry of the present invention does not use chromium as described in the above examples. The problem of Japanese Patent Publication No. 59-45754 was also solved.
尚、実施例として装身具の材質を黄銅としたが洋白など
の銅合金ならばどれでも可能であり同様の結果が得られ
る。又スズコバルト合金層の上面に形成した窒化チタン
の有色被膜については他金属の組合せで多層にしても良
いものである。Although brass was used as the material of the accessory as an example, any copper alloy such as nickel silver can be used and the same result can be obtained. Further, the titanium nitride colored coating formed on the upper surface of the tin-cobalt alloy layer may be a multi-layer formed by combining other metals.
尚、ＧＰ３μ仕様は、１８ＫＡｕ／Ａｇ１μ＋２２ＫＡ
ｕ／Ｎｉ２μからなっている。また、それぞれの試験個
数ｎ＝１００、本発明及び従来技術の有色被膜は窒化チ
タン層0.3μである。 The GP3μ specification is 18KAu / Ag1μ + 22KA
It consists of u / Ni2μ. Further, each test number n = 100, and the colored coatings of the present invention and the prior art are titanium nitride layers of 0.3 μm.
以上の説明で明らかなように、本発明の装身具の表面に
ニッケル層、スズコバルト層、有色被膜の３層を形成す
ることにより金メッキ仕様と同等の耐食性が得られる。
その上、クロムを用いる必要がないために、作業性や公
害の問題も解消し、更に下地メッキと窒化チタン等の有
色被膜との密着も向上することが出来る。As is clear from the above description, by forming three layers of a nickel layer, a tin cobalt layer and a colored coating on the surface of the accessory of the present invention, corrosion resistance equivalent to that of gold plating specifications can be obtained.
In addition, since it is not necessary to use chromium, the problems of workability and pollution can be solved, and the adhesion between the undercoat and the colored film such as titanium nitride can be improved.
図面は本発明の実施例を示し、表面に有色を呈する装身
具の要部断面図である。 １……装身具、２……ニッケル層、 ３……スズコバルト合金層、 ４……窒化チタン層。The drawings show an embodiment of the present invention and are cross-sectional views of a main part of an accessory having a colored surface. 1 ... Jewelry, 2 ... Nickel layer, 3 ... Tin-cobalt alloy layer, 4 ... Titanium nitride layer.
Claims (1)
てニッケル層を形成した上にスズコバルト合金層を形成
し、更にイオンプレーティング法により前記スズコバル
ト合金層の上に窒化チタン等の有色被膜を形成したこと
を特徴とする表面に有色を呈する装身具。1. A tin-cobalt alloy layer is formed on a nickel alloy layer as a base layer on the surface of an accessory made of a copper alloy, and a tinted cobalt or other colored coating film is further formed on the tin-cobalt alloy layer by an ion plating method. An accessory that has a colored surface and is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6606885A JPH062934B2 (en) | 1985-03-29 | 1985-03-29 | Jewelry that has a colored surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6606885A JPH062934B2 (en) | 1985-03-29 | 1985-03-29 | Jewelry that has a colored surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61227162A JPS61227162A (en) | 1986-10-09 |
| JPH062934B2 true JPH062934B2 (en) | 1994-01-12 |
Family
ID=13305163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6606885A Expired - Lifetime JPH062934B2 (en) | 1985-03-29 | 1985-03-29 | Jewelry that has a colored surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062934B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989730A (en) * | 1997-04-30 | 1999-11-23 | Masco Corporation | Article having a decorative and protective multi-layer coating |
-
1985
- 1985-03-29 JP JP6606885A patent/JPH062934B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61227162A (en) | 1986-10-09 |
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