JPS6217190A - Method for removing hard film - Google Patents
Method for removing hard filmInfo
- Publication number
- JPS6217190A JPS6217190A JP15663985A JP15663985A JPS6217190A JP S6217190 A JPS6217190 A JP S6217190A JP 15663985 A JP15663985 A JP 15663985A JP 15663985 A JP15663985 A JP 15663985A JP S6217190 A JPS6217190 A JP S6217190A
- Authority
- JP
- Japan
- Prior art keywords
- brass
- hard coating
- titanium nitride
- watch case
- hydrogen peroxide
- 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.)
- Granted
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
耐食性材料よりなる装身具の表面に形成された硬質被膜
を化学的に溶解除去する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 chemically dissolving and removing a hard coating formed on the surface of an accessory made of a corrosion-resistant material.
従来、Ｎ１−（’ｒ−ｋ１合金、ステライト、ステンレ
スからなる装身具の表面に形成された窒化チタン等の硬
質被膜の溶解除去方法は、特開昭５９−４２７４４号、
特開昭５９−４１４７９号の公報で開示されている様に
、表面に窒化チタン等の硬質被膜が形成された装身具を
、加温硝酸液弛浸漬し溶解除去していた。また、黄銅、
洋白等の銅合金からなる装身具の表面にニッケル層とク
ロム層の２層からなる下地層を形成した上に窒化チタン
等の硬質被膜が形成゛された装身具の硬質被膜を溶解除
去する方法は、非常にむずかしく、はとんど行なわれて
いなかった。Conventionally, a method for dissolving and removing a hard film such as titanium nitride formed on the surface of jewelry made of N1-('r-k1 alloy, stellite, or stainless steel) is disclosed in Japanese Patent Application Laid-Open No. 59-42744,
As disclosed in Japanese Unexamined Patent Publication No. 59-41479, jewelry on which a hard coating of titanium nitride or the like was formed was dissolved and removed by soaking in a heated nitric acid solution. Also, brass,
A method for dissolving and removing the hard coating of an accessory made of a copper alloy such as nickel silver, in which a base layer consisting of two layers, a nickel layer and a chromium layer, is formed on the surface, and then a hard coating of titanium nitride, etc. is formed on the surface of the jewelry. , was extremely difficult and rarely practiced.
この従来の装身具の表面に形成された窒化チタン等の硬
質被膜の溶解除去方法のうち、Ｎ１−Ｃｒ−ＡＪ金合金
ステライト、ステンレスからなる装身具においては、加
温硝酸液に浸漬し、装身具の表面に形成された硬質被膜
を溶解除去してい □たが、溶解除去するための最
適条件の範囲が狭く、 ゛硝酸液の濃度等の管理がき
びしく条件が少しズレただけでも溶解除去の時間が長く
なったり、装身具の素材表面を荒したり、液管理が大変
で作業性が悪かった。また黄銅、洋白等の銅合金からな
る装身具の表面にニッケル層とクロム層からなる下地層
を形成した上に窒化チタン等の硬質被膜が形成された装
身具の硬質被膜を加温硝酸液に浸漬し溶解除去すると、
硬質被膜及び下地層だけでなく黄銅、洋白等の銅合金の
素材表面まで腐食されてしまい、装身具としての外観品
質が失われてしまう。Among these conventional methods for dissolving and removing hard coatings such as titanium nitride formed on the surface of jewelry, jewelry made of N1-Cr-AJ gold alloy stellite and stainless steel is immersed in a heated nitric acid solution. However, the range of optimal conditions for dissolving and removing is narrow, and the concentration of the nitric acid solution must be controlled so that even a slight deviation in the conditions will result in a long dissolution and removal time. It also roughened the surface of the jewelry material, making it difficult to manage the liquid and resulting in poor workability. Additionally, a base layer consisting of a nickel layer and a chromium layer is formed on the surface of an accessory made of a copper alloy such as brass or nickel silver, and then a hard coating such as titanium nitride is formed on the surface of the accessory, and the hard coating is immersed in a heated nitric acid solution. When it is dissolved and removed,
Not only the hard coating and base layer but also the surface of copper alloy materials such as brass and nickel silver are corroded, and the appearance quality as jewelry is lost.
また、硬質被膜の溶解除去に使用する硝酸液は高温で使
用しているため酸化窒素が多量に発生し、環境衛生面か
らも好ましくない。Furthermore, since the nitric acid solution used to dissolve and remove the hard coating is used at high temperatures, a large amount of nitrogen oxide is generated, which is unfavorable from an environmental hygiene perspective.
本発明は、上記従来方法の欠点を解消し、溶解除去の作
業性を向上させ、耐食性素材の表面に被覆された窒化チ
タン被膜を、表面品質を何等損なわずに溶解除去すると
ともに再被覆を可能とし、さらに溶解除去の作業時に環
境衛生面で問題が生ずることをなくし、作業性、表面品
質、衛生面のすぐれた硬質被膜の除去方法を提供する事
を目的としたものである。The present invention eliminates the drawbacks of the conventional methods described above, improves the workability of dissolving and removing, and enables the titanium nitride coating coated on the surface of a corrosion-resistant material to be dissolved and removed and re-coated without any loss of surface quality. Furthermore, the purpose of the present invention is to provide a method for removing hard coatings that is superior in terms of workability, surface quality, and hygiene, and eliminates environmental sanitation problems during dissolution and removal work.
本発明は黄銅、洋白やＮ ｉ −Ｃｒ −Ａ １合金、
ステライト、ステンレス等の耐食性材料よりなる装身具
の表面に被覆された硬質被膜を除去する方法において、
苛性アルカリを主成分とし、過酸化水素水を含有させた
液と接触させる事により、硬質被膜を溶解除去する事を
特徴としている。The present invention uses brass, nickel silver, Ni-Cr-A1 alloy,
In a method for removing a hard film coated on the surface of an accessory made of a corrosion-resistant material such as stellite or stainless steel,
It is characterized by dissolving and removing hard coatings by bringing it into contact with a solution containing caustic alkali as its main component and hydrogen peroxide.
以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.
第１実施例においては、湿式メッキにより下地層が形成
された黄銅からなる時計ケースに被覆された窒化チタン
の硬質被膜の一部にシミがある等の理由により、窒化チ
タン被膜を全部溶解除去する場合の方法について説明す
る。In the first embodiment, the titanium nitride coating was completely dissolved and removed due to some stains on the hard coating of titanium nitride coated on a watch case made of brass with a base layer formed by wet plating. We will explain the method in this case.
先ず、黄銅材料を時計ケースに機械成形し、公知の加工
手法により表面を仕上げる。次に該表面に、ニッケルメ
ッキを施し、その直上にクロムメッキを湿式メッキ法に
より形成する。そして、イオンブレーティング法によっ
て窒化チタンの硬質被膜を被覆する。この様にして完成
した黄銅よりなる時計ケースの表面に形成した窒化チタ
ンの硬質被膜を溶解除去する方法は、下記に示す条件で
、前記時計ケースを苛性アルカリ水溶液中に浸漬し、窒
化チタンの硬質被膜を溶解除去する。次に硬質被膜を溶
解除去した時計ケースを十分に水洗し、乾燥を行なう。First, a brass material is mechanically formed into a watch case, and the surface is finished using a known processing method. Next, nickel plating is applied to the surface, and chromium plating is formed directly above the nickel plating using a wet plating method. Then, a hard film of titanium nitride is coated using the ion blasting method. The method for dissolving and removing the hard coating of titanium nitride formed on the surface of the finished brass watch case is to immerse the watch case in a caustic alkaline aqueous solution under the conditions shown below. Dissolve and remove the film. Next, the watch case from which the hard coating has been dissolved and removed is thoroughly washed with water and dried.
苛性アルカリ水溶液組成
水酸化ナトリウム １００９／１
過酸化水素水 ５０ｍ１／１溶解除去条件
温度 ８０°Ｃ
時 間 ７分
本実施例による硬質被膜の溶解除去方法をもちいること
により、仮にイオンブレーティング法で時計ケース表面
に形成した窒化チタンの硬質被膜にシミが有り、外観品
質上満足のいく状態でなかった時でも、再びイオンブレ
ーティングにより窒化チタンの硬質被膜を形成する事が
できる。この結果完成状態になっている時計ケースを廃
棄せずに再使用でき、コストアップを抑える事が出来る
。Caustic alkali aqueous solution composition Sodium hydroxide 1009/1 Hydrogen peroxide solution 50ml 1/1 Dissolution and removal conditions Temperature 80°C Time 7 minutes By using the method for dissolving and removing a hard coating according to this example, it is possible to remove the hard film by using the ion blating method. Even when the hard titanium nitride film formed on the surface of a watch case has stains and is not satisfactory in terms of appearance quality, the hard titanium nitride film can be re-formed by ion blating. As a result, the completed watch case can be reused without being discarded, and cost increases can be suppressed.
また、本実施例によれば加温硝酸液を使用しないので酸
化窒素が発生せず、環境衛生面で問題がなく、その上装
身具表面の素地を腐食されることがないので作業性が良
くなった。In addition, according to this embodiment, since no heated nitric acid solution is used, no nitrogen oxide is generated, and there is no problem in terms of environmental hygiene.Furthermore, the material on the surface of the jewelry is not corroded, resulting in improved workability. Ta.
なお本実施例は、時計ケースが黄銅の代りに洋白であっ
たり、Ｎ１−Ｃｒ−Ａｚ金合金ステライト、ステンレス
等の時計ケースの表面に硬質被膜を被覆した場合にも同
様に実施できる。Note that this embodiment can be similarly carried out when the watch case is made of nickel silver instead of brass, or when the surface of the watch case is made of N1-Cr-Az gold alloy stellite, stainless steel, etc. and coated with a hard coating.
次に第２実施例として、Ｎｉ−Ｃｒ−Ａｌ合金からなる
時計ケースの表面に被覆された窒化チタンＱ硬質被膜の
一部を溶解除去し、２トーンからなる時計ケースを作る
場合の方法を説明する。Next, as a second example, a method will be explained in which a part of the titanium nitride Q hard coating coated on the surface of a watch case made of Ni-Cr-Al alloy is dissolved and removed to create a two-tone watch case. do.
先ず、Ｎｉ−Ｃｒ−Ａｌ合金を時計ケースに機械成形し
、公知の加工手法により表面を仕上げる。First, a Ni-Cr-Al alloy is mechanically formed into a watch case, and the surface is finished using a known processing method.
次に該表面に、イオンブレーティング法によって、窒化
チタンの硬質被膜を被覆する。Next, a hard film of titanium nitride is coated on the surface by an ion blasting method.
次に、耐アールカリ性で熱硬化性のエポキシ系樹脂から
なる保護塗料を前記時計ケースの表面にデザイン仕様に
基づいて硬質被膜を残したい部分にマスク処理をする。Next, a protective paint made of alkali-resistant and thermosetting epoxy resin is applied to the surface of the watch case to mask the portions where a hard film is to be left based on the design specifications.
マスク処理は、刷毛又は印刷で行う。保護塗料が加熱乾
燥により固化した後、前記の時計ケースを苛性アルカリ
水溶液中に浸漬し、マスク処理されていない部分の窒化
チタンの硬質被膜を溶解除去する。窒化チタンの硬質被
膜を溶解除去する条件及び苛性アルカリ水溶液の液組成
は、前記第１実施例と同じである。Mask processing is performed using a brush or printing. After the protective paint is solidified by heating and drying, the watch case is immersed in an aqueous caustic solution to dissolve and remove the hard titanium nitride film on the areas that are not masked. The conditions for dissolving and removing the hard coating of titanium nitride and the liquid composition of the aqueous caustic solution are the same as in the first embodiment.
次に、硬質被膜の一部を溶解除去した前記時計ケースの
表面に残った保護塗料を剥離剤で取除き、十分に水洗し
、乾燥を行ない、２トーンからなる時計ケースを完成さ
せる。Next, the protective paint remaining on the surface of the watch case from which part of the hard coating has been dissolved and removed is removed using a remover, thoroughly washed with water, and dried to complete a two-tone watch case.
第１図は、上記方法で完成した時計ケースの斜視図を示
し、１は時計ケース、２は金色を呈する窒化チタンの硬
質被膜、３は白色を呈する時計ケースの素地である。本
実施例による硬質被膜の溶解除去方法をもちいることに
より窒化チタンの硬質被膜２の一部を除去しても、Ｎ１
−Ｃｒ−Ａ／金合金らなる時計ケース１表面の素地乙の
腐食や変色等が起こらず、被覆前の表面品質を保持して
おり、金色を呈する窒化チタンの硬質被膜２と白色を呈
するＮ ｉ −Ｃｒ −Ａ １合金の素地６との組合せ
による２トーンの時計ケースを作る事が出来る。また、
第１実施例でも述べた様に、加温硝酸を使用しないので
酸化窒素の発生がな（環境衛生面で問題がなく、その上
硬質被膜２を溶解除去するための最適条件の範囲が従来
に比べ広（なり作業性が良くなった。なお本実施例は、
時計ケースがステライト、ステンレス等である場合は勿
論、黄銅又は洋白の表面に下地層を形成し、その上に硬
質被膜を形成した場合にも同様に実施できる。FIG. 1 shows a perspective view of a watch case completed by the above method, where 1 is the watch case, 2 is a gold-colored hard coating of titanium nitride, and 3 is a white base for the watch case. Even if a part of the titanium nitride hard coating 2 is removed by using the method for dissolving and removing the hard coating according to this embodiment, the N1
- The base material B on the surface of the watch case 1 made of Cr-A/gold alloy does not undergo corrosion or discoloration, and maintains the surface quality before coating, with the hard coating 2 of titanium nitride exhibiting a golden color and the N coating exhibiting a white color. A two-tone watch case can be made by combining the base material 6 of i-Cr-A1 alloy. Also,
As mentioned in the first embodiment, since heated nitric acid is not used, no nitrogen oxide is generated (there is no problem in terms of environmental hygiene), and the range of optimal conditions for dissolving and removing the hard coating 2 is lower than that of conventional methods. Comparatively, it is wider (and the workability is improved.In this example,
The same method can be applied not only when the watch case is made of Stellite, stainless steel, etc., but also when a base layer is formed on the surface of brass or nickel silver, and a hard coating is formed on the base layer.
尚、第２図は、本発明において使用する苛性アルカリ液
中に含まれる酸化剤である過酸化水素水の濃度と装身具
の表面に形成された窒化チタンの硬質被膜が溶解除去出
来るまでの浸漬時間との関係を示すグラフである。この
グラフからも判るように、過酸化水素水の濃度が５％以
上で使用すると硬質被膜の溶解除去が早（出来、しかも
溶解除去の時間は殆ど変化が見られない。Furthermore, Figure 2 shows the concentration of hydrogen peroxide, which is an oxidizing agent contained in the caustic alkaline solution used in the present invention, and the immersion time until the hard coating of titanium nitride formed on the surface of the jewelry can be dissolved and removed. It is a graph showing the relationship between As can be seen from this graph, when the hydrogen peroxide solution is used at a concentration of 5% or more, the hard coating can be dissolved and removed quickly (and the time for dissolution and removal hardly changes).
この結果過酸化水素水の濃度が５％以上となるようにす
ればよ（、従来技術のように濃度管理を厳密にする必要
がない。そのため、従来技術の溶解除去方法と比べ、溶
解除去するための液管理が容易で、作業性も良くなる。As a result, as long as the concentration of hydrogen peroxide solution is 5% or more, there is no need to strictly control the concentration as in the conventional technology. Easy liquid management and improved workability.
さらに本発明によれば装身具の表面荒れなどという不良
がなくなった。Furthermore, according to the present invention, defects such as surface roughness of jewelry are eliminated.
以上の説明で明らかなように、本発明の過酸化水素を含
有する苛性アルカリ水溶液を使用することにより、Ｎｉ
−Ｃｒ−Ａｌ合金、ステライト、ステンレスはもとより
、黄銅、洋白等の銅合金からなる装身具の表面に形成さ
れた硬質被膜を簡単に溶解除去することが出来、装身具
の素材表面を犯される事なく、満足のいく表面状態を得
る事が出来る。As is clear from the above explanation, by using the caustic alkaline aqueous solution containing hydrogen peroxide of the present invention, Ni
- Hard coatings formed on the surface of jewelry made of copper alloys such as brass, nickel silver, etc. as well as Cr-Al alloy, stellite, and stainless steel can be easily dissolved and removed without damaging the material surface of the jewelry. , it is possible to obtain a satisfactory surface condition.
また、硬質被膜を溶解除去するための水溶液の管理が特
開昭５９−４２７４４号、特開昭５９−４１４７９号に
くらべ、容易であるので作業性が良く、また加温硝酸液
を使用しないので環境衛生面からも好ましい。In addition, the control of the aqueous solution for dissolving and removing the hard coating is easier than in JP-A-59-42744 and JP-A-59-41479, which improves workability, and since no heated nitric acid solution is used. It is also preferable from the standpoint of environmental hygiene.
第１図は本発明の実施例を示す２ト一ン時計ケースの斜
視図、第２図は本発明における過酸化水素水の濃度と硬
質被膜の溶解除去の関係を示すグラフである。
１・・・・・・時計ケース、２・・・・・・硬質被膜、
３・・・・・・素地。FIG. 1 is a perspective view of a two-tone watch case showing an embodiment of the present invention, and FIG. 2 is a graph showing the relationship between the concentration of hydrogen peroxide and the dissolution and removal of a hard coating in the present invention. 1... Watch case, 2... Hard coating,
3...Material.
Claims (2)
、ステンレス等の耐食性材料よりなる装身具の表面に被
覆された硬質被膜を除去する方法において、苛性アルカ
リを主成分とし、過酸化水素水を含有させた液と接触さ
せ溶解除去する事を特徴とする硬質被膜の除去方法。(1) In a method for removing the hard film coated on the surface of jewelry made of corrosion-resistant materials such as brass, nickel silver, Ni-Cr-Al alloy, stellite, stainless steel, etc., the main component is caustic alkali, and hydrogen peroxide solution is used. A method for removing a hard film, which is characterized by contacting with a liquid containing a liquid to dissolve and remove it.
層にニッケル、第二層にクロムがメッキ処理により形成
されていることを特徴とする特許請求の範囲第一項記載
の硬質被膜の除去方法。(2) Among the corrosion-resistant materials, the surface of brass or nickel silver is plated with nickel in the first layer and chromium in the second layer, as described in claim 1. How to remove the film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60156639A JPH0689461B2 (en) | 1985-07-16 | 1985-07-16 | Method for removing titanium nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60156639A JPH0689461B2 (en) | 1985-07-16 | 1985-07-16 | Method for removing titanium nitride film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6217190A true JPS6217190A (en) | 1987-01-26 |
| JPH0689461B2 JPH0689461B2 (en) | 1994-11-09 |
Family
ID=15632061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60156639A Expired - Lifetime JPH0689461B2 (en) | 1985-07-16 | 1985-07-16 | Method for removing titanium nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689461B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0661736A1 (en) * | 1993-12-28 | 1995-07-05 | Nec Corporation | Method for fabricating multilayer semiconductor device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021065804A (en) * | 2019-10-17 | 2021-04-30 | 株式会社平和カーボン | Method for removing titanium nitride-containing lump |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124425A (en) * | 1976-04-13 | 1977-10-19 | Tokyo Shibaura Electric Co | Solution for exfoliating nickellphosphor alloy film |
-
1985
- 1985-07-16 JP JP60156639A patent/JPH0689461B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124425A (en) * | 1976-04-13 | 1977-10-19 | Tokyo Shibaura Electric Co | Solution for exfoliating nickellphosphor alloy film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0661736A1 (en) * | 1993-12-28 | 1995-07-05 | Nec Corporation | Method for fabricating multilayer semiconductor device |
| US5668053A (en) * | 1993-12-28 | 1997-09-16 | Nec Corporation | Method for fabricating multilayer semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689461B2 (en) | 1994-11-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |