JP4036105B2 - Method for removing diamond-like carbon film - Google Patents

Description

【０１６２】
２．装飾品の外観評価
上記各実施例および各比較例で製造した装飾品について、目視および顕微鏡による観察を行い、これらの外観を以下の４段階の基準に従い、評価した。
◎：外観優良（表面の荒れが認められない）。
○：外観良（表面の荒れがほとんど認められない）。
△：外観やや不良（表面の荒れがはっきりと認められる）。
×：外観不良（表面の荒れが顕著に認められる）。
【０１６３】
３．ダイヤモンド様炭素膜の耐擦傷性評価
上記各実施例および各比較例で製造した装飾品について、以下に示すような試験を行い、耐擦傷性を評価した。
ステンレス製のブラシを、各装飾品のダイヤモンド様炭素膜が形成された部位に押し付け、５０往復摺動させた。このときの押し付け荷重は、０．２ｋｇｆであった。
【０１６４】
その後、装飾品の表面を目視により観察し、これらの外観を以下の４段階の基準に従い、評価した。
◎：ダイヤモンド様炭素膜の表面に、傷の発生が全く認められない。
○：ダイヤモンド様炭素膜の表面に、傷の発生がほとんど認められない。
△：ダイヤモンド様炭素膜の表面に、傷の発生がわずかに認められる。
×：ダイヤモンド様炭素膜の表面に、傷の発生が顕著に認められる。
【０１６５】
４．装飾品の耐摩耗性評価
上記各実施例および各比較例で製造した各装飾品のダイヤモンド様炭素膜が形成された部位について、摩耗係数（耐鋼）の測定を行い、以下の３段階の基準に従い、評価した。
◎：摩耗係数が０．７未満。
○：摩耗係数が０．７以上０．８未満。
×：摩耗係数が０．８以上。
これらの結果を、ダイヤモンド様炭素膜のビッカース硬度Ｈｖ、ボールオンディスク法により測定されるダイヤモンド様炭素膜の摩擦係数μとともに表２に示す。なお、ビッカース硬度Ｈｖとしては、各装飾品のダイヤモンド様炭素膜表面について、測定荷重２５ｇｆにて測定した値を示す。
【０１６６】
【表２】

【０１６７】
表２から明らかなように、本発明の装飾品は、いずれも優れた美的外観を有しており、耐擦傷性、耐摩耗性にも優れていた。
また、本発明の装飾品は、いずれも、ザラツキ感のない、優れた触感を有していた。
これに対し、比較例の装飾品は、美的外観に劣っていた。
【０１６８】
５．回転ベゼルの回転トルク
上記実施例３および比較例３で製造した装飾品（腕時計ケースおよび回転ベゼル）を用いて、時計を製造した。得られた各時計について、３００ｇｆの荷重を掛ける条件で、回転ベゼルの回転トルクの測定を行った。また、回転ベゼルを１００００回回転させた後、同様の条件で回転トルクを測定した。
その結果を表３に示す。
【０１６９】
【表３】

【０１７０】
表３から明らかなように、実施例３の装飾品（腕時計ケースおよび回転ベゼル）を備えた時計では、製造直後、および、回転ベゼルの回転操作を繰り返し行った後のいずれにおいても、比較的高い回転トルクを安定して有していた。これに対し、比較例３の装飾品（腕時計ケースおよび回転ベゼル）を備えた時計では、回転トルクは小さかった。また、回転操作を繰り返し行うことにより、回転トルクはさらに低下した。
【０１７１】
６．ネジロック式りゅうずの着脱操作性評価
上記実施例４および比較例４で製造した装飾品（腕時計ケースおよびネジロック式りゅうず）を用いて、時計を製造した。得られた各時計について、ケースからネジロック式りゅうずを回転着脱する、回転着脱操作を行ったときの操作のし易さ（着脱操作性）を以下の４段階の基準に従い、評価した。
◎：回転着脱操作を非常にスムーズに行うことができる。
○：回転着脱操作を十分にスムーズに行うことができる。
△：回転着脱操作を行う際に、若干のゴリ感がある。
×：回転着脱操作を行う際に、顕著なゴリ感がある。
また、ネジロック式りゅうずの回転着脱操作を１００００回行った後、上記と同様の基準に従い、着脱操作性を評価した。
その結果を表４に示す。
【０１７２】
【表４】

【０１７３】
表４から明らかなように、実施例４の装飾品（腕時計ケースおよびネジロック式りゅうず）を備えた時計では、製造直後、回転着脱操作を繰り返し行った後のいずれにおいても、優れた着脱操作性を示した。これに対し、比較例４の装飾品（腕時計ケースおよびネジロック式りゅうず）を備えた時計では、着脱操作性に劣っていた。また、回転着脱操作を繰り返し行うことにより、着脱操作性はさらに低下した。
【０１７４】
７．バンド中留の着脱性評価
上記実施例５および比較例５で製造した装飾品（バンド中留）を用いて、時計を製造した。得られた各時計について、バンド中留の着脱操作を行ったときの操作のし易さ（着脱操作性）を以下の４段階の基準に従い、評価した。
◎：着脱操作を非常にスムーズに行うことができる。
○：着脱操作を十分にスムーズに行うことができる。
△：着脱操作を行う際に、若干の引っかかりが認められる。
×：着脱操作を行う際に、顕著な引っかかりが認められる。
また、バンド中留の着脱操作を１００００回行った後、上記と同様の基準に従い、着脱操作性を評価した。
その結果を表５に示す。
【０１７５】
【表５】

【０１７６】
表５から明らかなように、実施例５の装飾品（バンド中留）を備えた時計では、製造直後、着脱操作を繰り返し行った後のいずれにおいても、優れた着脱操作性を示した。これに対し、比較例５の装飾品（バンド中留）を備えた時計では、着脱操作性に劣っていた。また、回転着脱操作を繰り返し行うことにより、着脱操作性はさらに低下した。
【図面の簡単な説明】
【図１】 本発明のダイヤモンド様炭素膜の除去方法に適用される部材の製造方法の一例を模式的に示す断面図である。
【図２】 本発明のダイヤモンド様炭素膜の除去方法の第１実施形態を模式的に示す断面図である。
【図３】 本発明のダイヤモンド様炭素膜の除去方法に適用される部材の製造方法の一例を模式的に示す断面図である。
【図４】 本発明のダイヤモンド様炭素膜の除去方法の第２実施形態を模式的に示す断面図である。
【図５】 本発明のダイヤモンド様炭素膜の除去方法の他の実施形態を模式的に示す断面図である。
【符号の説明】
１Ａ、１Ｂ、１Ｂ’……装飾品 ２……基材 ３……ダイヤモンド様炭素膜 ４０……下地層 ４１……第１の下地層 ４２……第２の下地層 ４３……第３の下地層 ５……マスキング １０Ａ、１０Ｂ……部材[0001]
BACKGROUND OF THE INVENTION
  The present inventionMethod for removing diamond-like carbon filmAbout.
[0002]
[Prior art]
Diamond-like carbon (DLC) has high hardness, excellent wear resistance, a small coefficient of friction, and excellent corrosion resistance. For this reason, it attracts attention as a coating material for various members. On the other hand, since diamond-like carbon has the characteristics as described above, it has been difficult to remove the film from a member on which a diamond-like carbon film is formed by a mechanical method such as polishing.
[0003]
In order to solve such a problem, a method of removing a diamond-like carbon film by glow discharge or arc discharge has been proposed (for example, see Patent Document 1). However, in such a method, when removing the diamond-like carbon film, it is extremely difficult to avoid damage to the base material on which the film is formed. There was a problem of ruining. Such a tendency becomes more prominent in a material whose base material is relatively soft (for example, Cu, Al, or an alloy containing at least one of them), and is particularly substantial in a decorative article that requires an aesthetic appearance. Could not be applied. Further, with such a method, it has been substantially impossible to selectively remove only a part of the diamond-like carbon film. In addition, such a method requires a special device, is complicated in setting the conditions of the device, and is disadvantageous in terms of production cost.
[0004]
[Patent Document 1]
JP-A-5-339758 (Claims)
[0005]
[Problems to be solved by the invention]
  An object of the present invention is a method for removing at least a part of a diamond-like carbon film without substantially damaging a substrate on which the diamond-like carbon film is formed.To provideIt is in.
[0006]
[Means for Solving the Problems]
  Such an object is achieved by the present invention described below.
  The method for removing a diamond-like carbon film of the present invention comprises a base material,
  At least one underlayer formed on at least a portion of the substrate;
  A method of removing at least a part of the diamond-like carbon film from a member having a diamond-like carbon film mainly formed of diamond-like carbon (DLC) formed on at least a part of the underlayer,
The diamond-like carbon film is formed at a film formation speed of 0.05 to 30 μm / h,
The underlayer can be peeled offImmerse the member in a liquid release agentBy doing so, the release agent penetrates into the diamond-like carbon film, and at least a part of the diamond-like carbon film is removed together with at least a part of the underlayer.Is,
  When the member is immersed in the release agent, the atmospheric pressure is set to 8 × 10. ⁴ Then, the pressure of the atmosphere is 1.1 × 10. ⁵ Set to Pa or higherIt is characterized by that.
  Thereby, at least a part of the diamond-like carbon film can be removed without substantially damaging the base material on which the diamond-like carbon film is formed.
[0007]
The method for removing a diamond-like carbon film of the present invention comprises a base material,
An underlayer formed on at least a part of the substrate;
A method of removing a part of the diamond-like carbon film from a member having a diamond-like carbon film formed on at least a part of the underlayer and mainly composed of diamond-like carbon (DLC),
The member includes, as the base layer, a first base layer provided on at least a part of the surface of the base material and a second base layer provided on at least a part of the surface of the first base layer. And a third underlayer provided on a part of the surface of the second underlayer, and provided so that at least a part of the second underlayer is in contact with the diamond-like carbon film. And at least a part of the third underlayer is provided so as to contact the diamond-like carbon film,
By applying a release agent capable of peeling the second underlayer or the third underlayer from the base material from above the diamond-like carbon film, the release agent penetrates into the diamond-like carbon film. A part of the diamond-like carbon film is removed together with at least a part of the second underlayer or the third underlayer..
Thereby, at least a part of the diamond-like carbon film can be removed without substantially damaging the base material on which the diamond-like carbon film is formed.
[0008]
In the method for removing a diamond-like carbon film of the present invention, the application of the release agent is performed by immersing the member in the liquid release agent,
When the member is immersed in the release agent, the atmospheric pressure is set to 8 × 10. ⁴ Then, the pressure of the atmosphere is 1.1 × 10. ⁵ It is preferable to set it to Pa or more.
  Thereby, the diamond-like carbon film can be removed more reliably in a relatively short time.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of a method for removing a diamond-like carbon film, a decorative article, and a timepiece of the present invention will be described with reference to the accompanying drawings.
First, a method for removing a diamond-like carbon film, a decorative article, and a watch according to a first embodiment of the present invention will be described.
FIG. 1 is a cross-sectional view showing an example of a member manufacturing method applied to the method for removing a diamond-like carbon film of the present invention, and FIG. 2 shows a first embodiment of the method for removing a diamond-like carbon film of the present invention. It is sectional drawing.
[0022]
First, prior to the description of the method for removing the diamond-like carbon film, the member 10A and the method for manufacturing the member 10A will be described.
As shown in FIG. 1, the member 10 </ b> A includes a step (1 b) of forming a base layer 40 on at least a part (1 a) of the surface of the substrate 2 and a diamond mainly on at least a part of the surface of the base layer 40. And a step (1c) of forming a diamond-like carbon film 3 made of like carbon (DLC).
[0023]
[Base material]
The base material 2 may be composed of any material, and may be composed of a metal material or a non-metal material.
When the base material 2 is comprised with a metal material, the member 10A (decoration 1A) which has the especially outstanding intensity | strength characteristic can be provided. Moreover, when the base material 2 is comprised with a metal material, even if it is a case where the surface roughness of the base material 2 is comparatively large, by the leveling effect at the time of forming the base layer 40 and the diamond-like carbon film 3 which are mentioned later The surface roughness of the obtained member 10A (decorative item 1A) can be reduced. For example, it is possible to perform mirror finishing even if machining by grinding, polishing, or the like on the surface of the substrate 2 is omitted, or the substrate 2 is formed by the MIM method, and the surface is Even when the surface is pear ground, it can be easily mirror-finished. As a result, a decorative article having excellent gloss can be obtained.
[0024]
When the base material 2 is made of a non-metallic material, it is possible to provide the member 10A (decoration 1A) that is relatively light and easy to carry and has a heavy appearance. Moreover, when the base material 2 is comprised with a nonmetallic material, it can shape | mold to a desired shape comparatively easily. Moreover, when the base material 2 is comprised with a nonmetallic material, the effect which shields electromagnetic noise is also acquired.
[0025]
Examples of the metal material constituting the substrate 2 include various metals such as Fe, Cu, Zn, Ni, Mg, Cr, Mn, Mo, Nb, Al, V, Zr, Sn, Au, Pd, Pt, and Ag. And alloys containing at least one of these. Among these, in particular, the material mainly includes at least one metal selected from the group consisting of Fe, Cu, Zn, Ni, Ti, Al, Mg, Si, Zr, and W or an alloy containing the metal. preferable. When the base material 2 is made of the material as described above, the adhesion between the base material 2 and a base layer 40 described later is particularly excellent. Further, when the base material 2 is composed of at least one metal selected from the group consisting of Cu, Zn, and Ni or an alloy containing the metal, the base material 2 and a base layer 40 described later The adhesion of the substrate 2 is particularly excellent, the workability of the substrate 2 is improved, and the degree of freedom of molding of the substrate 2 is further increased.
[0026]
Moreover, as a nonmetallic material which comprises the base material 2, plastics, ceramics, a stone material, wood, etc. are mentioned, for example.
Examples of the plastic include various thermoplastic resins and various thermosetting resins.
When the base material 2 is comprised with a plastic, the ornament 1A (member 10A) which is comparatively light and easy to carry, and has a heavy external appearance can be obtained. Moreover, when the base material 2 is comprised with a plastic, it can shape | mold to a desired shape comparatively easily. For this reason, even if it is member 10A (decoration 1A) which has a complicated shape, it can be manufactured comparatively easily. Moreover, when the base material 2 is comprised with a plastic, the effect which shields electromagnetic noise is acquired.
[0027]
As ceramics, for example, Al₂O_Three, SiO₂TiO₂, Ti₂O_Three, ZrO₂, Y₂O_Three, Oxide ceramics such as barium titanate and strontium titanate, AlN, Si_ThreeN_Four, SiN, TiN, BN, ZrN, HfN, VN, TaN, NbN, CrN, Cr₂Nitride ceramics such as N, graphite, SiC, ZrC, Al_FourC_Three, CaC₂, WC, TiC, HfC, VC, TaC, NbC and other carbide-based ceramics, ZrB₂, BoB-based ceramics such as MoB, or composite ceramics in which two or more of these are arbitrarily combined.
When the base material 2 is comprised with the above ceramics, the high-strength, high-hardness ornament 1A (member 10A) can be obtained.
[0028]
The manufacturing method of the base material 2 is not specifically limited.
When the base material 2 is made of a metal material, examples of the manufacturing method include press working, cutting, forging, casting, powder metallurgy sintering, metal powder injection molding (MIM), and lost wax method. Among these, casting or metal powder injection molding (MIM) is particularly preferable. Casting and metal powder injection molding (MIM) are particularly excellent in workability. For this reason, when these methods are used, the base material 2 having a complicated shape can be obtained relatively easily.
[0029]
Metal powder injection molding (MIM) is usually performed as follows.
First, a material containing metal powder and an organic binder is mixed and kneaded to obtain a kneaded product.
Next, the kneaded product is injection molded to form a molded body.
Thereafter, the molded body is subjected to a degreasing process (debinding process) to obtain a degreased body. This degreasing treatment is usually performed by heating under reduced pressure conditions. Furthermore, a sintered body is obtained by sintering the obtained degreased body. This sintering process is usually performed by heating at a higher temperature than the degreasing process.
In the present invention, the sintered body obtained as described above can be used as a base material.
[0030]
Moreover, when the base material 2 is comprised with the above plastics, as the manufacturing method, compression molding, extrusion molding, injection molding, stereolithography, etc. are mentioned, for example.
Moreover, when the base material 2 is comprised with the above ceramics, the manufacturing method is not specifically limited, However, It is preferable that it is metal powder injection molding (MIM). Since metal powder injection molding (MIM) is particularly excellent in processability, the base material 2 having a complicated shape can be obtained relatively easily.
[0031]
The surface of the substrate 2 is preferably subjected to surface processing such as mirror surface processing, streak processing, and satin processing. Thereby, it becomes possible to give a variation in the glossiness of the surface of the member 10A (decoration article 1A) to be obtained, and the decorativeness of the decoration article 1A (member 10A) can be further improved.
Further, the decorative article 1A (member 10A) manufactured using the base material 2 subjected to such surface processing is compared with that obtained by directly performing the surface processing on the diamond-like carbon film 3. The glare of the diamond-like carbon film 3 is suppressed, and the aesthetic appearance is particularly excellent.
[0032]
In addition, for the purpose of improving the adhesion between the base material 2 and the base layer 40, the base material 2 may be pretreated prior to the formation of the base layer 40 described later. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, bombarding and other cleaning treatment, etching treatment, etc., among which cleaning treatment is particularly preferable. By subjecting the surface of the base material 2 to a cleaning treatment, the adhesion between the base material 2 and the base layer 40 is particularly excellent.
[0033]
[Formation of underlayer]
An underlayer 40 is formed on the surface of the substrate 2 (1b).
At least a part of the foundation layer 40 is removed by a release agent described later. By providing such an underlayer 40, the diamond-like carbon film 3 can be easily and reliably removed.
The underlayer 40 has, for example, a function of improving the adhesion between the base material 2 and the diamond-like carbon film 3, a function of repairing holes, scratches, etc. of the base material 2 by leveling (leveling), during storage ( It may have a function of preventing the occurrence of corrosion during the process until the diamond-like carbon film 3 is formed).
[0034]
As a method for forming the underlayer 40, for example, wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, sputtering, and ion plating are used. Examples thereof include dry plating methods such as coating, thermal spraying, joining of metal foils, etc. Among these, wet plating methods or dry plating methods are particularly preferable.
By using a wet plating method or a dry plating method as a method for forming the underlayer 40, the formed underlayer 40 is particularly excellent in adhesion to the base material 2. As a result, the long-term durability of the resulting decorative article 1A (member 10A) is particularly excellent.
The underlayer 40 is subjected to chemical treatment such as oxidation treatment, nitriding treatment, chromate treatment, carbonization treatment, acid dipping, acid electrolytic treatment, alkali dipping treatment, alkaline electrolytic treatment, etc. on the surface of the base material 2. It may be a formed film, in particular a passive film.
[0035]
As a constituent material of the underlayer 40, for example, a metal material such as Cu, Co, Pd, Au, Ag, In, Sn, Ni, Ti, Zn, Cr, Al, Fe, W, Si, Ge, or the metal Alloys containing at least one of the materials, metal compounds (for example, metal oxides, metal nitrides, metal carbides, etc.) based on at least one of the metal materials, various resin materials, or combinations of two or more of these Is mentioned.
In addition, the constituent material of the underlayer 40 preferably includes at least one of the material constituting the substrate 2 or the material constituting the diamond-like carbon film 3. Thereby, adhesiveness with the base material 2 and the diamond-like carbon film 3 further improves.
[0036]
The average thickness of the underlayer 40 is not particularly limited, but is preferably 0.1 to 20.0 μm, and more preferably 0.5 to 10.0 μm, for example. If the average thickness of the underlayer 40 is less than the lower limit, the effect of the underlayer 40 may not be sufficiently exhibited. On the other hand, when the average thickness of the foundation layer 40 exceeds the upper limit, the variation in film thickness at each portion of the foundation layer 40 tends to increase. Further, the internal stress of the underlayer 40 is increased, and cracks are easily generated.
[0037]
As described above, by forming the base layer 40 on the surface of the base material 2, the adhesion between the base material 2 and the diamond-like carbon film 3 and the corrosion resistance of the decorative article 1A (member 10A) are further improved. It becomes. As a result, the decorative article 1A (member 10A) is particularly excellent in durability.
The underlayer 40 is formed on the entire surface of the base material 2 in the illustrated configuration, but may be formed on at least a part of the surface of the base material 2. Moreover, the composition in each part of the foundation layer 40 may be constant or not constant. For example, the underlayer 40 may be one whose composition changes sequentially along the thickness direction (gradient material).
[0038]
Further, for the purpose of improving the adhesion between the underlayer 40 and the diamond-like carbon film 3, the underlayer 40 may be pretreated prior to the formation of the diamond-like carbon film 3 described later. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, bombarding and other cleaning treatment, etching treatment, etc., among which cleaning treatment is particularly preferable. By subjecting the surface of the underlayer 40 to a cleaning treatment, the adhesion between the underlayer 40 and the diamond-like carbon film 3 is particularly excellent.
[0039]
[Formation of diamond-like carbon film]
A diamond-like carbon film 3 mainly composed of diamond-like carbon (DLC) is formed on the surface of the underlayer 40 (1c).
The diamond-like carbon film 3 has an excellent gloss. For this reason, the aesthetic appearance as the decoration 1A (member 10A) as a whole can be made particularly excellent.
The diamond-like carbon film 3 has high hardness and excellent wear resistance and scratch resistance. For this reason, by having the diamond-like carbon film 3, breakage, damage, etc. of the member 10A (decoration 1A) can be effectively prevented.
[0040]
The diamond-like carbon film 3 has excellent lubricity. For this reason, the friction in the site | part in which the diamond-like carbon film 3 was formed can be reduced effectively. As a result, for example, the decorative article 1A (member 10A) is used by being slid (for example, having a threaded portion, a rotating bezel, a button, a screw-locking crown, a gear, In the case of a train wheel receiver or the like having the diamond-like carbon film 3 at its sliding portion, the sliding operation can be performed smoothly. Moreover, damage, failure, etc. of the decorative article 1A (member 10A) due to friction can be effectively prevented.
[0041]
Examples of the index indicating lubricity include the friction coefficient μ in the ball-on-disk method measured according to JIS R 1613. The friction coefficient μ of the diamond-like carbon film 3 measured by the ball-on-disk method is preferably about 0.05 to 0.7, more preferably about 0.1 to 0.5, and More preferably, it is about 1 to 0.35. When the friction coefficient μ of the diamond-like carbon film 3 is in such a range, the friction at the portion where the diamond-like carbon film 3 is formed can be more effectively reduced, and the sliding operation of the decorative article 1A can be performed. It can be performed more smoothly. Further, when the friction coefficient μ of the diamond-like carbon film 3 is in such a range, the slipperiness of the decorative article 1A (member 10A) can be improved, and the feeling of roughness can be reduced or prevented. It is possible to reduce or prevent discomfort and discomfort when (member 10A) contacts the skin or the like.
[0042]
The diamond-like carbon film 3 has high hardness and excellent wear resistance and scratch resistance. For this reason, even if it is provided in a site where repeated friction occurs, the above-described effects can be maintained over a long period of time. Therefore, the decorative article 1A (member 10A) having the diamond-like carbon film 3 has excellent durability. Further, since the diamond-like carbon film 3 has excellent scratch resistance, the decorative article 1A (member 10A) can maintain an excellent aesthetic appearance for a longer period of time.
[0043]
The Vickers hardness Hv of the diamond-like carbon film 3 is preferably 700 or more, more preferably 800 to 5000, and further preferably 2000 to 5000. When the Vickers hardness Hv of the diamond-like carbon film 3 is a value in such a range, the above-described effect becomes more remarkable.
The diamond-like carbon film 3 has a property that dirt is difficult to adhere, that is, an excellent antifouling property. Further, even when dirt is attached, the dirt can be easily removed. Therefore, the decorative article 1A (member 10A) having the diamond-like carbon film 3 can maintain an excellent aesthetic appearance over a long period of time.
[0044]
The diamond-like carbon film 3 may be formed by any method, but is preferably formed by a vapor deposition method, and among them, thermal CVD, plasma CVD (RF plasma CVD) is particularly preferable. , ECR plasma CVD, etc.), chemical vapor deposition (CVD) such as laser CVD, sputtering such as chemical sputtering and physical sputtering, vacuum deposition, and ion plating are preferred. By using such a method, a homogeneous diamond-like carbon film 3 with little unevenness can be obtained relatively easily. Moreover, according to such a method, the diamond-like carbon film 3 excellent in adhesiveness with the base material 2 and the base layer 40 can be formed. As a result, the resulting decorative article 1A is excellent in corrosion resistance and durability.
[0045]
Moreover, the following effects can be obtained by forming the diamond-like carbon film 3 using the dry plating method as described above.
That is, as represented by the description of sputtering described later, the diamond-like carbon film 3 having a desired composition can be easily formed by appropriately selecting the composition of the atmospheric gas. Thus, by easily adjusting the composition of the diamond-like carbon film 3, the characteristics (for example, color, glossiness, hardness, etc.) of the diamond-like carbon film 3 can be adjusted.
[0046]
Hereinafter, an example of a method for forming the masking 5 by sputtering will be described.
Sputtering is usually performed in an atmospheric gas mainly composed of an inert gas such as argon gas or helium gas. The atmospheric gas contains hydrocarbon gas such as methane gas or ethane gas, hydrogen gas, or the like. Is preferred. Thereby, the diamond-like carbon film 3 to be formed can be composed of hydrogenated DLC. If the diamond-like carbon film 3 is composed of hydrogenated DLC, the friction coefficient of the diamond-like carbon film 3 is lowered and the lubricity is further improved.
[0047]
The total content of hydrocarbon gas and hydrogen gas in the atmospheric gas is preferably 10 vol% or more. Thereby, it becomes possible to perform hydrogen addition to DLC more effectively.
Note that, in the atmospheric gas, for example, O₂, N₂, NH₃A reactive gas such as may be contained. By performing sputtering in an atmospheric gas containing such a reactive gas, the diamond-like carbon film 3 to which elements other than C and H are added can be formed. Thereby, the adhesion between the diamond-like carbon film 3 and the underlayer 40 can be improved, and the hardness of the diamond-like carbon film 3 can be adjusted.
[0048]
Moreover, graphite etc. are normally used as a target.
Note that a material containing an element other than C and H (for example, N, O, Ti, Al, Cr, Si, Zr, Mo, W, B, P, F, etc.) is used as the target, or such a material. A mixture of graphite and graphite may be used. Thereby, the diamond-like carbon film 3 to which elements other than C and H are added can be formed. As a result, the adhesion between the diamond-like carbon film 3 and the underlayer 40 can be improved, and the hardness of the diamond-like carbon film 3 can be adjusted.
Such sputtering is preferably performed by radio frequency (RF) discharge. Thereby, the plasma density can be increased and arc discharge can be effectively prevented.
[0049]
The deposition rate of the diamond-like carbon film 3 is not particularly limited, but is preferably 0.05 to 30 μm / h, and more preferably 0.1 to 20 μm / h. If the deposition rate of the diamond-like carbon film 3 is less than the lower limit, the porosity in the diamond-like carbon film 3 to be formed becomes too low (the diamond-like carbon film 3 becomes dense), which will be described later. In the process, it may be difficult to efficiently remove the diamond-like carbon film 3. Moreover, when the film-forming speed | rate of the diamond-like carbon film 3 is less than the said lower limit, it takes time for film-forming and the productivity of member 10A (decoration article 1A) falls. On the other hand, when the deposition rate of the diamond-like carbon film 3 exceeds the upper limit, the variation in the thickness of the diamond-like carbon film 3 tends to increase.
[0050]
The average thickness of the diamond-like carbon film 3 is not particularly limited, but is preferably 0.1 to 5.0 μm, and more preferably 0.5 to 2.0 μm. By setting the average thickness of the diamond-like carbon film 3 to a value in such a range, the effect of the diamond-like carbon film 3 described above can be exhibited more remarkably.
On the other hand, if the average thickness of the diamond-like carbon film 3 is less than the lower limit value, the effect of the diamond-like carbon film 3 described above may be sufficient depending on the constituent material, thickness, etc. of the base material 2 and the underlayer 40. It may be difficult to make it appear. Further, if the average thickness of the diamond-like carbon film 3 exceeds the upper limit, the internal stress of the diamond-like carbon film 3 increases, the adhesion between the diamond-like carbon film 3 and the underlayer 40 decreases, and cracks occur. Is likely to occur. As a result, the durability of the decorative article 1A is reduced, and a stable aesthetic appearance cannot be obtained. If the average thickness of the diamond-like carbon film 3 exceeds the upper limit, it may be difficult to efficiently remove the diamond-like carbon film 3 in a process described later.
[0051]
In addition, the composition in each part of the diamond-like carbon film 3 may be constant or may not be constant. For example, the diamond-like carbon film 3 may be one whose composition changes sequentially along the thickness direction (graded material). In addition, the diamond-like carbon film 3 is formed on the entire surface of the base layer 40 in the illustrated configuration, but may be formed on a part of the surface of the base layer 40. The diamond-like carbon film 3 only needs to be at least partially formed on the surface of the underlayer 40. For example, the diamond-like carbon film 3 may be partially formed without the underlayer 40 interposed therebetween. It may be formed directly on the surface of the material 2.
[0052]
Next, a method for removing at least a part of the diamond-like carbon film 3 from the member 10A described above will be described.
As shown in FIG. 2, the method for removing the diamond-like carbon film of the present embodiment uses a step (1d) of forming a masking 5 on at least a part (1c) of the surface of the member 10A, and a release agent. It has the process (1e) of removing the base layer 40 and the diamond-like carbon film 3 of the site | part which is not coat | covered with the masking 5, and the process (1f) of removing the masking 5.
[0053]
[Mask coating]
First, a part of the surface (1c) of the diamond-like carbon film 3 is covered with a masking 5 (1d). This masking 5 functions as a mask for protecting the underlying layer 40 and the diamond-like carbon film 3 at the covered portion in the step of removing the underlying layer 40 and the diamond-like carbon film 3 described later.
[0054]
By forming the masking 5 as in the present embodiment, selective removal of the underlayer 40 and the diamond-like carbon film 3 can be easily and reliably performed in the steps described later. Thereby, the ornament 1A which has the diamond-like carbon film 3 of a fine pattern can be obtained easily. Thereby, the characteristics of the diamond-like carbon film as described above can be sufficiently exhibited even in the finally obtained decorative article 1A. In addition, by selectively removing the underlayer 40 and the diamond-like carbon film 3, the finally obtained member 10A (decoration 1A) can sufficiently exhibit the functions required in each part. And operability and aesthetics are further improved. For example, the diamond-like carbon film 3 is allowed to remain on the sliding portion or the like of the finally obtained member 10A (decoration 1A), and the diamond-like carbon film 3 is not allowed to remain on other portions. Thus, the sliding operation of the member 10A (the decorative article 1A) can be easily performed while sufficiently preventing the hand from slipping during the operation. Further, by leaving a part of the diamond-like carbon film 3, for example, an uneven pattern is formed in a portion where the diamond-like carbon film 3 remains and a portion where the diamond-like carbon film 3 is removed, The difference in color becomes remarkable. As a result, the aesthetic appearance of the decorative article 1A can be further improved.
[0055]
Any masking 5 may be used as long as it has a function of protecting the underlying layer 40 and the diamond-like carbon film 3 in the coated portion in the step of removing the underlying layer 40 and the diamond-like carbon film 3. In the step of removing the masking 5 to be performed, it is preferable that it can be easily removed.
As a material constituting such a masking 5, for example, an acrylic resin, a polyimide resin, a polysulfone resin, an epoxy resin, a fluorine resin, etc., Au, Ni, Pd, Cu, Ag, Ti, Cr, etc. The metal material can be used.
[0056]
The method for forming the masking 5 is not particularly limited, and examples thereof include dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating and the like, wet plating methods such as electrolytic plating, immersion plating and electroless plating, and thermal CVD. Examples thereof include chemical vapor deposition (CVD) such as plasma CVD and laser CVD, dry plating such as vacuum deposition, sputtering and ion plating, and thermal spraying.
[0057]
Although the average thickness of the masking 5 is not specifically limited, For example, it is preferable that it is 100-2000 micrometers, and it is more preferable that it is 500-1000 micrometers. If the average thickness of the masking 5 is less than the lower limit value, pinholes tend to occur in the masking 5. Therefore, in the process of removing the diamond-like carbon film 3 and the underlayer 40 described later, the function as the masking 5 (function as a mask for protecting the underlayer 40 and the diamond-like carbon film 3) is sufficiently exhibited. It becomes difficult and the aesthetic appearance of the resulting decorative article 1A may be reduced. On the other hand, when the average thickness of the masking 5 exceeds the upper limit value, the variation in film thickness at each portion of the masking 5 tends to increase. Further, the internal stress of the masking 5 is increased, and as a result, the adhesion between the masking 5 and the diamond-like carbon film 3 is lowered or cracks are likely to occur.
[0058]
The masking 5 is preferably transparent. This makes it possible to visually recognize the close contact state with the diamond-like carbon film 3 from the outside.
The masking 5 is not limited to that formed directly on the surface of the diamond-like carbon film 3 so as to have a desired shape. For example, the masking 5 having a desired pattern may be obtained by covering almost the entire surface of the diamond-like carbon film 3 with the constituent material of the masking 5 and then removing a part thereof.
[0059]
Examples of a method for removing a part of the masking 5 covered on almost the entire surface of the diamond-like carbon film 3 include a method of irradiating the masking 5 at a site to be removed with a laser beam. Examples of the laser used at this time include Ne-He laser, Ar laser, and CO.₂Gas laser such as laser, ruby laser, semiconductor laser, YAG laser, glass laser, YVO₄A laser, an excimer laser, etc. are mentioned.
[0060]
Prior to the formation of the masking 5 as described above, the diamond-like carbon film 3 may be subjected to a base treatment. The purpose of the ground treatment may be any, but for example, the adhesion between the diamond-like carbon film 3 and the masking 5 can be improved by the ground treatment. Examples of the pretreatment include blast treatment, alkali washing, acid washing, water washing, organic solvent washing, bombarding and other cleaning treatment, etching treatment, etc., among which cleaning treatment is particularly preferable. By subjecting the surface of the underlayer 40 to a cleaning treatment, the adhesion between the underlayer 40 and the diamond-like carbon film 3 is particularly excellent.
[0061]
[Removal of underlayer and diamond-like carbon film]
Next, the diamond-like carbon film 3 and the base layer 40 in a portion not covered with the masking 5 are removed (1e).
The present invention is characterized in that the diamond-like carbon film is removed (peeled) together with the underlying layer where the diamond-like carbon film is formed. More specifically, it is characterized in that by applying a release agent from the diamond-like carbon film, the release agent penetrates into the diamond-like carbon film, and the diamond-like carbon film is removed together with the underlayer. In this specification, peeling of the underlayer refers to removing at least part of the underlayer from the substrate. In the present specification, “peeling of the underlayer” means, for example, separating the underlayer from the surface of the substrate by reducing the adhesion between the substrate and the underlayer, or the thickness of the underlayer. It is assumed that at least part of the direction is dissolved in a release agent (release liquid).
The release agent is not particularly limited, but is preferably a fluid such as a liquid or a gas, and among them, a liquid is particularly preferable. Thereby, the diamond-like carbon film 3 and the underlayer 40 can be removed more easily and reliably.
[0062]
As a method for applying the release agent to the member 10A (the member 10A on which the masking 5 is formed), for example, an immersion method (a method in which the member 10A is immersed in a liquid release agent, which is immersed in a liquid release agent) A method of electrolyzing in a state), a spray method, a brush coating, an inkjet method, an octopus printing method, a screen printing method and the like. Among these, the dipping method is excellent in that the diamond-like carbon film 3 can be easily and reliably removed in a relatively short time. In the dipping method, the temperature, composition, etc. of the release agent applied to the member 10A can be easily managed, and the contact time between the member 10A and the release agent (immersion time of the member 10A in the release agent). ) Is also easy to control.
[0063]
When the release agent is applied to the member 10A by the dipping method, the immersion time of the member 10A in the release agent varies depending on the composition of the release agent, the composition of the underlayer 40, the thickness of the diamond-like carbon film 3, etc. It is preferably ˜60 minutes, and more preferably 20 to 30 minutes. When the immersion time of the member 10A in the release agent is in such a range, the diamond-like carbon film 3 and the underlayer 40 can be formed in a relatively short time while sufficiently preventing damage to the substrate 2. It can be removed more reliably.
[0064]
Further, when the member 10A is immersed in the release agent, the temperature, pressure, etc. of the atmosphere can be adjusted as necessary.
For example, when the member 10 </ b> A is immersed in the release agent (while being immersed), the pores of the diamond-like carbon film 3 are adjusted by reducing the pressure of the atmosphere to a pressure lower than atmospheric pressure (reducing pressure). The gas existing in the inside, the gas dissolved in the release agent, and the like can be efficiently removed. Thereby, the penetration of the release agent into the diamond-like carbon film 3 is promoted, and the removal efficiency of the diamond-like carbon film 3 and the underlayer 40 can be increased.
In such a case, the pressure of the atmosphere during immersion (during immersion) is 8 × 10⁴Preferably it is Pa or less, 1 × 10²~ 5x10⁴More preferably, it is Pa. When the atmospheric pressure is in such a range, the above-described effect becomes more remarkable.
[0065]
Further, when the member 10A is immersed in the release agent (while being immersed), the pressure of the atmosphere can be made higher than the atmospheric pressure (pressurization). Thereby, the release agent can be forcibly fed into the pores of the diamond-like carbon film 3. As a result, the penetration of the release agent into the diamond-like carbon film 3 is promoted, and the removal efficiency of the diamond-like carbon film 3 and the underlayer 40 can be increased.
In such a case, the pressure of the atmosphere during immersion (during immersion) is 1.1 × 10⁵Preferably it is Pa or higher, 1.5 × 10⁵~ 5x10⁷More preferably, it is Pa. When the atmospheric pressure is in such a range, the above-described effect becomes more remarkable.
[0066]
In addition, the pressure of the atmosphere when the member 10A is immersed in the release agent may be changed continuously or intermittently (discontinuously) in the middle thereof. For example, in the initial stage of immersion, the pressure of the atmosphere may be lowered (reduced pressure) below atmospheric pressure, and then the pressure of the atmosphere may be increased to a pressure substantially equal to or higher than the atmospheric pressure. Thus, the effect mentioned above becomes still more remarkable by adjusting the pressure of atmosphere.
[0067]
Further, the temperature of the release agent applied to the member 10A varies depending on the application method, the composition of the release agent, the composition of the underlayer 40, the thickness of the diamond-like carbon film 3, and the like, but is 20 to 60 ° C. Preferably, it is 25-40 degreeC. When the temperature of the release agent is within such a range, the diamond-like carbon film 3 and the underlayer 40 are more reliably removed in a relatively short time while sufficiently preventing damage to the substrate 2. Can do.
The release agent may be, for example, a mist (mist) when applied to the member 10A, or a gas (gas) vaporized by heating or the like. Good.
[0068]
The release agent used in this step can selectively remove only the underlying layer 40 and the diamond-like carbon film 3 in a portion not covered with the masking 5 without substantially dissolving and peeling off the masking 5. It is preferable to use one.
The specific composition of the release agent varies depending on the composition of the underlayer, but the release agent is generally composed mainly of an inorganic material (specifically, the proportion of the inorganic material in the release agent is 80 wt% or more). Thereby, the diamond-like carbon film 3 can be removed more reliably in a relatively short time. In addition, since the inorganic material is excellent in affinity with diamond-like carbon, even if the condition for applying the release agent to the member 10A (the member 10A on which the masking 5 is formed) is relatively mild, it takes a relatively short time. The diamond-like carbon film 3 can be removed more reliably.
As described above, the composition of the release agent varies depending on the composition of the underlayer 40 and the like, but examples of specific combinations of the composition of the underlayer 40 and the composition of the release agent are shown below. Needless to say, the release agent used in the present invention is not limited to these.
[0069]
When the underlayer 40 is mainly composed of Cu (including a Cu-based alloy), the release agent preferably includes nitric acid. The concentration of nitric acid in the release agent is preferably 30 to 90 wt%, and more preferably 40 to 60 wt%. In particular, when the diamond-like carbon film 3 is removed by the dipping method, the dipping time of the member 10A is preferably 20 to 120 minutes, and more preferably 40 to 60 minutes. Moreover, it is preferable that the temperature of a peeling agent is 15-50 degreeC, and it is more preferable that it is 20-30 degreeC.
[0070]
In the case where the underlayer 40 is mainly composed of Cr (including a Cr-based alloy or the like), the release agent preferably includes sodium carbonate. The concentration of sodium carbonate in the release agent is preferably 1 to 20 wt%, more preferably 5 to 10 wt%. When a release agent containing sodium carbonate is used, the diamond-like carbon film 3 is usually removed by performing anodic electrolysis with the member 10A immersed in the release agent. Current density during anodic electrolysis is 1 to 10 A / dm²Preferably, 3-7 A / dm²It is more preferable that Further, the immersion time of the member 10A is preferably 10 to 60 minutes, and more preferably 20 to 30 minutes. Moreover, it is preferable that the temperature of a peeling agent is 20-60 degreeC, and it is more preferable that it is 25-40 degreeC.
[0071]
In the case where the underlayer 40 is mainly composed of TiN, the release agent preferably contains hydrofluoric acid (hydrogen fluoride) and nitric acid. The hydrogen fluoride concentration in the release agent is preferably 10 to 40 wt%, and more preferably 20 to 30 wt%. The nitric acid concentration in the release agent is preferably 30 to 60 wt%, more preferably 40 to 50 wt%. In particular, when the diamond-like carbon film 3 is removed by the dipping method, the dipping time of the member 10A is preferably 1 to 60 minutes, and more preferably 10 to 20 minutes. Moreover, it is preferable that the temperature of a peeling agent is 15-50 degreeC, and it is more preferable that it is 20-30 degreeC.
[0072]
When the underlayer 40 is mainly composed of Si (including Si-based alloys and the like), it is preferable that the release agent includes hydrofluoric acid (hydrogen fluoride) and nitric acid. The hydrogen fluoride concentration in the release agent is preferably 10 to 40 wt%, and more preferably 20 to 30 wt%. The nitric acid concentration in the release agent is preferably 30 to 60 wt%, more preferably 40 to 50 wt%. In particular, when the diamond-like carbon film 3 is removed by the dipping method, the dipping time of the member 10A is preferably 1 to 60 minutes, and more preferably 10 to 20 minutes. Moreover, it is preferable that the temperature of a peeling agent is 15-50 degreeC, and it is more preferable that it is 20-30 degreeC.
[0073]
When the underlayer 40 is mainly composed of Au (including an Au-based alloy or the like), a cyan-based release agent can be suitably used as the release agent. In particular, when the diamond-like carbon film 3 is removed by the dipping method, the dipping time of the member 10A is preferably 5 to 60 minutes, and more preferably 20 to 30 minutes. Moreover, it is preferable that the temperature of a peeling agent is 15-50 degreeC, and it is more preferable that it is 20-30 degreeC.
[0074]
When the underlayer 40 is mainly composed of Ag (including an Ag-based alloy or the like), a cyan-based release agent can be suitably used as the release agent. In particular, when the diamond-like carbon film 3 is removed by the dipping method, the dipping time of the member 10A is preferably 5 to 60 minutes, and more preferably 20 to 30 minutes. Moreover, it is preferable that the temperature of a peeling agent is 15-50 degreeC, and it is more preferable that it is 20-30 degreeC.
[0075]
In the configuration shown in the figure, the base layer 40 in the portion where the diamond-like carbon film 3 to be removed in this step is formed is completely removed. For example, the base layer 40 has one thickness direction. Only the portion (near the surface side in contact with the diamond-like carbon film 3) may be removed. Thereby, the decorativeness of 1 A of obtained ornaments can further be improved. The removal amount in the thickness direction of the underlayer 40 can be controlled by controlling conditions for applying the immersion liquid to the member 10A, for example.
[0076]
[Removing masking]
Thereafter, by removing the masking 5, the decorative article 1A is obtained (1f).
The masking 5 may be removed by any method, but the masking 5 can be removed and is applied to the substrate 2 and the diamond-like carbon film 3 (more preferably to the underlayer 40). Also, it is preferable to use a masking remover that does not substantially damage.
By using such a mask remover, the masking 5 can be easily and reliably removed.
[0077]
The mask remover used for removing the masking 5 is not particularly limited, but is preferably a fluid such as a liquid or a gas. Among them, a liquid is particularly preferable. As a result, the masking 5 can be removed more easily and reliably.
Examples of the masking remover include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl teton (MIBK), Ketone solvents such as methyl isopropyl ketone (MIPK) and cyclohexanone, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG) and glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME) 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, ether solvents such as diethylene glycol dimethyl ether (diglyme), methyl cellosolve, ethyl acetate Cellosolve solvents such as sorb, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, aromatic hydrocarbon solvents such as toluene, xylene, benzene, pyridine, pyrazine, furan, pyrrole, thiophene, etc. Aromatic heterocyclic compound solvents, amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane, Ester solvents such as ethyl acetate, methyl acetate and ethyl formate, sulfur compound solvents such as dimethyl sulfoxide (DMSO) and sulfolane, nitrile solvents such as acetonitrile and propionitrile, formic acid, acetic acid, trichloroacetic acid and trifluoroacetic acid Organic acids such as organic solvents 1 type selected from a medium or a mixture of 2 or more types, acidic substances such as nitric acid, sulfuric acid, hydrogen chloride, hydrogen fluoride, phosphoric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide , Alkaline substances such as calcium hydroxide, magnesium hydroxide, ammonia, potassium permanganate (KMnO₄), Manganese dioxide (MnO₂), Potassium dichromate (K₂Cr₂O₇), Oxidants such as ozone, concentrated sulfuric acid, nitric acid, white powder, hydrogen peroxide, quinones, sodium thiosulfate (Na₂S₂O₃), A mixture of reducing agents such as hydrogen sulfide, hydrogen peroxide, and hydroquinones.
[0078]
As a method for removing the masking 5, for example, a method of spraying a masking remover (spray method), a method of immersing in a masking remover in a liquid state (a method of electrolyzing in a state immersed in a masking remover in a liquid state, etc.) Inkjet method, and the like. Among these, the method of immersing in a liquid masking remover is particularly preferable. As a result, the masking 5 can be removed more easily and reliably.
[0079]
When removing the masking 5 by immersing it in a liquid masking removal agent, the temperature of the masking removal agent is not particularly limited, but is preferably 15 to 100 ° C, for example, 30 to 50 ° C. Is more preferable. If the temperature of the masking remover is less than the lower limit, depending on the thickness of the masking 5 and the like, the time required to sufficiently remove the masking 5 may become long, and the productivity of the decorative article 1A may be reduced. . On the other hand, when the temperature of the masking remover exceeds the upper limit, the amount of volatilization of the masking remover increases depending on the vapor pressure, boiling point, etc. of the masking remover, and the amount of the masking remover necessary for removing the masking 5 increases. It shows a tendency to increase.
[0080]
Moreover, the immersion time in a masking removal agent is not specifically limited, For example, it is preferable that it is 5 to 60 minutes, and it is more preferable that it is 5 to 30 minutes. If the immersion time in the masking remover is less than the lower limit, depending on the thickness of the masking 5, the temperature of the masking remover, etc., it may be difficult to sufficiently remove the masking 5. On the other hand, when the immersion time in the masking remover exceeds the upper limit, the productivity of the decorative article 1A is lowered.
[0081]
As described above, in the present invention, the diamond-like carbon film can be removed without substantially damaging the substrate.
Thereby, for example, when a diamond-like carbon film is formed on a base material (decoration article) having an underlayer, a coating defect (for example, uneven film thickness, color tone variation, etc.) occurs. Even in such a case, the diamond-like carbon film can be easily and reliably removed from the base material, and the base material can be reused. As a result, the yield of decorative articles (members) is improved.
[0082]
According to the present invention, the diamond-like carbon film can be removed at low cost without using a special apparatus. The present invention is also advantageous from the viewpoint of production cost.
Further, as described above, the diamond-like carbon film 3 has excellent gloss. For this reason, the aesthetic appearance as the decoration 1A (member 10A) as a whole can be made particularly excellent.
The diamond-like carbon film 3 has high hardness and excellent wear resistance and scratch resistance. For this reason, by having the diamond-like carbon film 3, breakage, damage, etc. of the member 10A (decoration 1A) can be effectively prevented.
[0083]
The diamond-like carbon film 3 has excellent lubricity. For this reason, the friction in the site | part in which the diamond-like carbon film 3 was formed can be reduced effectively. As a result, for example, the decorative article 1A (member 10A) is used by being slid (for example, having a threaded portion, a rotating bezel, a button, a screw-locking crown, a gear, In the case of a train wheel receiver or the like having the diamond-like carbon film 3 at its sliding portion, the sliding operation can be performed smoothly. Moreover, damage, failure, etc. of the decorative article 1A (member 10A) due to friction can be effectively prevented.
[0084]
In addition, a diamond-like carbon film having a desired composition and characteristics can be easily formed by appropriately selecting the composition of the atmospheric gas when forming the diamond-like carbon film.
In addition, by selecting a constituent material of the base material, it is possible to easily manufacture a decorative article having a complicated shape, and it is possible to reduce the weight of the decorative article and reduce the manufacturing cost. .
[0085]
In the present embodiment, the configuration in which the member 5A is coated with the masking 5 and then the diamond-like carbon film 3 is removed using a release agent has been described. However, the masking 5 may not be formed. For example, all of the diamond-like carbon film 3 of the member 10 </ b> A can be removed by applying a release agent to almost the entire surface of the diamond-like carbon film 3 without forming the masking 5. As described above, in the present invention, a part of the diamond-like carbon film 3 may be removed or a part of the diamond-like carbon film 3 may be removed.
[0086]
Further, as described above, in the present invention, the method for applying the release agent is not particularly limited. For example, the release agent may be applied to the member 10A by an inkjet method or the like. According to the ink jet method, the portion to which the release agent (release solution) is applied can be easily and reliably controlled, and thus the step of forming a mask as described above can be omitted or simplified.
[0087]
Next, the decorative article 1A will be described.
The decorative item 1A may be any item as long as it has a decorative property. For example, an interior such as an ornament, an exterior article, a jewelry, a watch case (a trunk, a back cover, etc.), a watch band (a band Nakadome, (Including band and bangle attachment / detachment mechanism), dial, clock hands, bezel (for example, rotating bezel), crown (for example, screw lock type crown), watch exterior parts such as buttons, movement base plate, Interior parts for watches such as gears, train wheels, rotating weights, glasses, tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings and other accessories, lighters or their cases, automobile wheels Sports equipment such as golf clubs, nameplates, panels, prize cups, other equipment parts including housings, various containers, etc. It is. Among these, in particular, those which are used in contact with at least a part of the skin are preferred, and watch exterior parts are more preferred. A watch exterior part is required to have a beautiful appearance as a decorative product, and as a practical product, durability, corrosion resistance, wear resistance, excellent tactile sensation, etc. are required. All requirements can be satisfied.
[0088]
In particular, when the present invention is applied to a rotating bezel, sliding of the click portion is improved and the rotation of the bezel becomes smooth. As a result, the practicality of the rotating bezel is improved and the sense of quality as a decorative product is also improved. In addition, the groove of the rotation mechanism portion of the bezel and the wear of the projection portion are preferably prevented and suppressed. In addition, when the rotating bezel is mass-produced, variations in the rotating torque value of the bezel among individuals can be suppressed, and the overall quality is stabilized.
[0089]
Further, when the present invention is applied to a screw lock type crown, it is possible to suitably prevent a so-called crunch feeling (feeling that a screw bites) when turning a screw. In addition, when the screw lock-type crown is mass-produced, variation in the rotational torque value of the screw among the individual members can be suppressed, and the quality as a whole is stabilized.
In addition, when the present invention is applied to a band middle piece band end piece, a band / bangle attachment / detachment mechanism, a back cover, etc., a stable fastening force can be secured over a long period of time. In particular, when the present invention is applied to the case back, the water resistance of the timepiece can be more reliably exhibited.
In addition, when the present invention is applied to a button, the feeling of pushing the button becomes smooth. As a result, the practicality of the button is improved and the sense of quality as a decorative product is also improved.
[0090]
Moreover, the timepiece of the present invention has the ornament of the present invention as described above. As described above, the decorative article of the present invention has high hardness, excellent scratch resistance (abrasion resistance) and corrosion resistance, and can maintain an excellent aesthetic appearance over a long period of time. For this reason, the timepiece of the present invention provided with such a decorative article can sufficiently satisfy the required requirements as a timepiece. That is, the timepiece of the present invention can maintain a particularly excellent aesthetic property over a long period of time. Moreover, since it is hard to produce discoloration, the state which is easy to visually recognize can be maintained over a long period of time. In particular, the present invention is characterized in that the above-described effects can be obtained without requiring a special airtight structure. In addition, well-known things can be used as parts other than the said ornaments which comprise the timepiece of this invention.
In the present embodiment, the method for obtaining a decorative article by the method for removing a diamond-like carbon film of the present invention has been described. However, the present invention is, for example, a decorative property such as a mold (tool), a tool, and an electronic component. Needless to say, the present invention can also be applied to articles (members) for which is not required.
[0091]
Next, a diamond-like carbon film removing method, a decorative article, and a second embodiment of the present invention will be described.
FIG. 3 is a cross-sectional view showing an example of a member manufacturing method applied to the diamond-like carbon film removal method of the present invention, and FIG. 4 shows a second embodiment of the diamond-like carbon film removal method of the present invention. It is sectional drawing.
[0092]
Hereinafter, the method for removing the diamond-like carbon film of the second embodiment and the decorative article of the second embodiment manufactured by using the method will be described focusing on the differences from the first embodiment, and similar matters will be described. The description of is omitted.
As shown in FIG. 3, the member 10 </ b> B is formed on at least a part (2 a) of the surface of the base material 2 with a base layer (first base layer 41, second base layer 42, and third layer in order from the base material side). Forming a base layer 43) (2b, 2c, 2d) and forming a diamond-like carbon film 3 mainly composed of diamond-like carbon (DLC) on at least a part of the surface of the base layer ( 2e).
Hereinafter, the first base layer 41, the second base layer 42, and the third base layer 43 will be described in order.
[0093]
[First underlayer]
A first base layer 41 is formed on the surface of the substrate 2.
The first base layer 41 has, for example, a function of improving the adhesion between the base material 2 and the second base layer 42, a function of repairing holes, scratches, and the like of the base material 2 by leveling. Have.
[0094]
Examples of the method for forming the first underlayer 41 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, and sputtering. , Dry plating methods such as ion plating, thermal spraying, joining of metal foil, chemical treatment (for example, oxidation treatment, nitriding treatment) on the surface of the substrate 2, etc., among others, wet plating method or dry plating The method is preferred.
[0095]
By using a wet plating method or a dry plating method as a method of forming the first underlayer 41, the formed first underlayer 41 has particularly excellent adhesion to the substrate 2. As a result, the long-term durability of the resulting decorative article 1B is particularly excellent.
The first underlayer 41 is subjected to chemical treatment such as oxidation treatment, nitriding treatment, chromate treatment, carbonization treatment, acid dipping, acid electrolytic treatment, alkaline dipping treatment, alkaline electrolytic treatment, etc. on the surface of the substrate 2. It may be a film formed by application, particularly a passive film.
[0096]
Examples of the constituent material of the first underlayer 41 include metal materials such as Cu, Sn, Ni, Zn, Fe, In, Co, and Al, alloys containing at least one of the metal materials, and the metal materials. Among them, at least one kind of metal compound (for example, metal oxide, metal nitride, metal carbide, etc.) or a combination of two or more of these may be used.
In addition, the constituent material of the first underlayer 41 preferably includes at least one of the material constituting the base material 2 or the material constituting the second underlayer 42. Thereby, adhesiveness with the base material 2 and the 2nd base layer 42 further improves.
[0097]
Although the average thickness of the 1st foundation | substrate layer 41 is not specifically limited, For example, it is preferable that it is 0.1-20.0 micrometers, and it is more preferable that it is 0.5-10.0 micrometers. If the average thickness of the first foundation layer 41 is less than the lower limit, the effect of the first foundation layer 41 may not be sufficiently exhibited. On the other hand, when the average thickness of the first foundation layer 41 exceeds the upper limit, the variation in film thickness at each portion of the first foundation layer 41 tends to increase. In addition, the internal stress of the first underlayer 41 is increased, and cracks are likely to occur.
[0098]
In the illustrated configuration, the first base layer 41 is formed on the entire surface of the base material 2, but it may be formed on at least a part of the surface of the base material 2. In addition, the composition of each part of the first base layer 41 may or may not be constant. For example, the first underlayer 41 may be one whose composition changes sequentially along the thickness direction (gradient material).
[0099]
[Second base layer]
Next, the second underlayer 42 is formed on the surface of the first underlayer 41.
The second underlayer 42 functions as, for example, a buffer layer that alleviates a potential difference between one surface side (first underlayer 41) and the other surface side (third underlayer 43). As a result, the occurrence of corrosion (dissimilar metal contact corrosion) due to a potential difference between one surface side (first ground layer 41) and the other surface side (third ground layer 43) of the second ground layer 42 is further increased. It can be effectively prevented.
[0100]
Examples of the method for forming the second underlayer 42 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, and sputtering. , Dry plating methods such as ion plating, thermal spraying, joining of metal foil, chemical treatment (for example, oxidation treatment, nitriding treatment) on the surface of the first underlayer 41, etc., among these, wet plating methods are particularly preferable. Alternatively, dry plating is preferable.
[0101]
By using a wet plating method or a dry plating method as a method of forming the second underlayer 42, the second underlayer 42 to be formed is particularly excellent in adhesion with the first underlayer 41. Become. As a result, the long-term durability of the resulting decorative article 1B is particularly excellent.
The second underlayer 42 is formed on the surface of the first underlayer 41 by, for example, oxidation treatment, nitriding treatment, chromate treatment, carbonization treatment, acid dipping, acid electrolysis treatment, alkali dipping treatment, alkaline electrolysis treatment or the like. It may be a film formed by chemical treatment, particularly a passive film.
[0102]
The standard potential of the second base layer 42 is preferably a value between the standard potential of the first base layer 41 and the standard potential of the third base layer 43. That is, the second base layer 42 is a material whose standard potential is a value between the standard potential of the constituent material of the first base layer 41 and the standard potential of the constituent material of the third base layer 43. It is preferred that it is constructed. As a result, the occurrence of corrosion (dissimilar metal contact corrosion) due to a potential difference between one surface side (first ground layer 41) and the other surface side (third ground layer 43) of the second ground layer 42 is further increased. It can be effectively prevented.
[0103]
Examples of the constituent material of the second underlayer 42 include metal materials such as Cu, Sn, Zn, Fe, In, Ag, Au, Pd, Ti, and Cr, and alloys containing at least one of the metal materials. In addition, a metal compound (for example, metal oxide, metal nitride, metal carbide, etc.) of at least one of the metal materials, or a combination of two or more of these may be used.
[0104]
The constituent material of the second base layer 42 preferably includes at least one of the material forming the first base layer 41 and the material forming the third base layer 43. In other words, the adjacent two underlayers are preferably made of a material containing a common element. Thereby, adhesiveness with an adjacent foundation layer (the 1st foundation layer 41, the 3rd foundation layer 43) further improves. In particular, when the common element is Cu, the adhesion with the adjacent base layer is particularly excellent.
[0105]
Although the average thickness of the 2nd foundation | substrate layer 42 is not specifically limited, For example, it is preferable that it is 0.1-20.0 micrometers, and it is more preferable that it is 0.5-10.0 micrometers. If the average thickness of the second underlayer 42 is less than the lower limit, the effect of the second underlayer 42 may not be sufficiently exhibited. On the other hand, when the average thickness of the second underlayer 42 exceeds the upper limit, the variation in film thickness at each portion of the second underlayer 42 tends to increase. Further, the internal stress of the second underlayer 42 is increased, and cracks are easily generated.
[0106]
In the configuration shown in the figure, the second underlayer 42 is formed on the entire surface of the first underlayer 41, as long as it is formed on at least a part of the surface of the first underlayer 41. Good. Further, the composition in each part of the second underlayer 42 may or may not be constant. For example, the second underlayer 42 may be one whose composition changes sequentially along the thickness direction (gradient material).
[0107]
[Third underlayer]
Further, a third underlayer 43 is formed on the surface of the second underlayer 42.
At least a part of the third base layer 43 is removed by a release agent described later. By providing such a third underlayer 43, the diamond-like carbon film 3 can be easily and reliably removed.
The third underlayer 43 is, for example, a function for improving the adhesion between the second underlayer 42 and the diamond-like carbon film 3 or during storage (until the step of forming the diamond-like carbon film 3). For example, it may have a function of preventing the occurrence of corrosion.
[0108]
Examples of the method for forming the third underlayer 43 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD, vacuum deposition, and sputtering. , Dry plating methods such as ion plating, thermal spraying, joining of metal foil, chemical treatment (for example, oxidation treatment, nitriding treatment) on the surface of the second underlayer 42, etc., among these, wet plating methods are particularly preferable. Alternatively, dry plating is preferable.
[0109]
By using a wet plating method or a dry plating method as a method of forming the third underlayer 43, the third underlayer 43 to be formed is particularly excellent in adhesion with the second underlayer 42. Become. As a result, the long-term durability of the resulting decorative article 1B is particularly excellent.
The third underlayer 43 is formed on the surface of the second underlayer 42 by, for example, oxidation treatment, nitriding treatment, chromate treatment, carbonization treatment, acid dipping, acid electrolysis treatment, alkali dipping treatment, alkaline electrolysis treatment, etc. It may be a film formed by chemical treatment, particularly a passive film.
[0110]
As the constituent material of the third underlayer 43, the constituent material of the underlayer 40 in the above-described embodiment can be used.
Further, the constituent material of the third underlayer 43 preferably includes at least one of the material constituting the second underlayer 42 or the material constituting the diamond-like carbon film 3. As a result, the adhesion between the second underlayer 42 and the diamond-like carbon film 3 is further improved.
[0111]
Although the average thickness of the 3rd foundation | substrate layer 43 is not specifically limited, For example, it is preferable that it is 0.1-20.0 micrometers, and it is more preferable that it is 1.0-3.0 micrometers. If the average thickness of the third underlayer 43 is less than the lower limit, the effect of the third underlayer 43 may not be sufficiently exhibited. On the other hand, when the average thickness of the third foundation layer 43 exceeds the upper limit, the variation in film thickness at each portion of the third foundation layer 43 tends to increase. Further, the internal stress of the third underlayer 43 is increased, and cracks are easily generated.
[0112]
As shown in FIG. 3, in the present embodiment, the third foundation layer 43 is formed only on a part of the surface of the second foundation layer 42. With such a configuration, the diamond-like carbon film 3 can be suitably removed without using masking in the steps described later.
The third underlayer 43 is not limited to the one formed directly on the surface of the second underlayer 42 so as to have a desired shape. For example, the third base layer 43 having a desired pattern is obtained by covering almost the entire surface of the second base layer 42 with the constituent material of the third base layer 43 and then removing a part thereof. Also good. Alternatively, a mask (resist) having a desired shape may be formed by a photolithography method or the like to form the third base layer 43 having a desired pattern, and then the mask (resist) may be removed.
Note that the third underlayer 43 may be formed on substantially the entire surface of the second underlayer 42.
In addition, the composition of each part of the third base layer 43 may or may not be constant. For example, the third underlayer 43 may be a material whose composition changes sequentially along the thickness direction (gradient material).
[0113]
As described above, the first base layer 41, the second base layer 42, and the third base layer 43 are laminated on the surface of the base material 2 in this order, so that the base material 2 and the diamond are laminated. The adhesion to the carbon film 3 and the corrosion resistance of the decorative article 1B are further improved. As a result, the decorative article 1B is particularly excellent in durability.
The first underlayer 41, the second underlayer 42, and the third underlayer 43 are not limited to those having the functions described above, and may have other effects.
[0114]
Next, a method for removing at least a part of the diamond-like carbon film 3 from the member 10B described above will be described focusing on differences from the above-described embodiment.
As shown in FIG. 4, the method for removing the diamond-like carbon film of the present embodiment applies the release agent to the surface (2e) of the member 10B as described above, so that the third underlayer 43 and the diamond-like carbon film are removed. A step (2f) for removing the carbon film 3 is included. In other words, unlike the embodiment described above, there is no step of forming a mask on the member and no step of removing the mask.
[0115]
As described above, in the member 10 </ b> B, the third foundation layer 43 is formed only on a part of the surface of the second foundation layer 42. For this reason, for example, by using a release agent that can remove the third underlayer 43 and is substantially impossible to remove the second underlayer 42, Even without using masking as described above, only the portion of the diamond-like carbon film 3 formed on the third underlayer 43 can be removed.
[0116]
Further, as the release agent, a material that can remove the second underlayer 42 and that is substantially impossible to remove the third underlayer 43 is used in FIG. As shown, it is possible to remove only the portion directly formed on the surface of the second underlayer 42 of the diamond-like carbon film 3 without using the masking as described above.
[0117]
The preferred embodiments of the method for removing a diamond-like carbon film, the decorative article, and the timepiece of the present invention have been described above, but the present invention is not limited thereto.
For example, in the first embodiment described above, the member has one base layer, and in the second embodiment, the member has three layers (first base layer, second base layer). , A third underlayer), but the underlayer may be two layers or four or more layers. In this case, it is preferable that at least one layer of the underlayer has a function of relaxing a potential difference between one side and the other side.
[0118]
Even when the underlayer is composed of two layers or four or more layers, as described above, the two adjacent underlayers are preferably made of a material containing a common element. Thereby, the adhesiveness of adjacent base layers improves further. In addition, when the common element is Cu, the adhesion between adjacent base layers is particularly excellent.
In addition, at least a part of the surface of the decorative article is given corrosion resistance, weather resistance, water resistance, oil resistance, abrasion resistance, discoloration resistance, etc., and effects such as rust prevention, antifouling, antifogging, and scratch resistance A protective layer or the like may be formed.
[0119]
【Example】
Next, specific examples of the present invention will be described.
1. Manufacture of ornaments
Example 1
A decorative article (watch case (back cover)) was manufactured by the method as described below.
[0120]
[A1] First, a base material having the shape of a watch case (back cover) was produced by casting using stainless steel (SUS304), and then necessary portions were cut and polished.
[A2] Next, this base material was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0121]
[A3] An underlayer composed of Cr was formed on the surface of the base material thus cleaned.
The underlayer is formed by wet plating, bath temperature: 45 ° C., current density: 4 A / dm.², Time: Performed under conditions of 5 minutes.
The average thickness of the underlying layer thus formed was 1.0 μm.
[A4] Next, the substrate on which the underlayer was laminated was washed. As this cleaning, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0122]
[A5] A diamond-like carbon film mainly composed of diamond-like carbon was formed on the surface of the ground layer cleaned in this manner, thereby obtaining a member.
The diamond-like carbon film was formed by sputtering.
This sputtering was performed using a vacuum apparatus as follows.
First, the inside of the vacuum apparatus was replaced with a mixed gas of argon gas: 60 vol% and methane gas: 40 vol%. Thereafter, the atmospheric pressure was adjusted to 0.6 Pa by adjusting the flow rate of the mixed gas and the exhaust amount.
After adjusting the atmospheric pressure in the vacuum apparatus, a diamond-like carbon film was formed by performing high frequency discharge using graphite as a target.
Note that the flow rate of the mixed gas during sputtering was 60 SCCM, and the atmospheric pressure was 0.6 Pa. The high frequency power was 500W. The film formation rate was 0.4 μm / h.
The diamond-like carbon film thus formed had an average thickness of 0.5 μm.
[0123]
[A6] The member obtained in the step [A5] was immersed in a stripping solution in an atmosphere at atmospheric pressure, and anodic electrolysis was performed to remove the diamond-like carbon film together with the base layer. As the stripping solution, a 7 wt% sodium carbonate aqueous solution was used. The immersion time of the member in the stripping solution was 25 minutes. The temperature of the stripping solution during immersion is 30 ° C., and the current density is 5 A / dm.²Met.
[0124]
[A7] Thereafter, the series of steps [A2] to [A6] was repeated three times to obtain a decorative article. That is, the diamond-like carbon film formation-removal process was repeated four times.
Moreover, about the base material used for manufacture of an ornament, and the obtained ornament, JIS B
Surface roughness R defined by 0601_maxWas measured.
Surface roughness R where the substrate is polished_maxWas 0.2 to 0.4 μm. In the finally obtained decorative article, the surface roughness R of the location corresponding to this_maxWas 0.2 to 0.45 μm. From this, it can be seen that in this example, the surface of the substrate is hardly roughened even if the diamond-like carbon film formation-removal process is repeated.
[0125]
(Example 2)
A decorative article (watch dial) was manufactured by the following method.
[B1] First, a base material having the shape of a watch dial was produced by casting using stainless steel (SUS304), and then necessary portions were cut and polished.
[B2] About the base material obtained as described above, the necessary portion was cut and polished, and then the base material was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0126]
[B3] An underlayer composed of TiN was formed on the surface of the base material thus cleaned.
The underlayer was formed by ion plating as described below.
First, the base material on which the underlayer is formed is attached in the ion plating apparatus, and then the inside of the ion plating apparatus is 3 × 10 3 while preheating the apparatus.^-3Exhaust (reduced pressure) to Pa.
[0127]
Next, bombarding was performed for 3 minutes at an argon gas flow rate of 100 ml / min. The pressure in the ion plating apparatus in the bombard process is 9 × 10.^-2Pa.
Next, inside the ion plating apparatus, 2 × 10^-3After exhausting (reducing pressure) to Pa, nitrogen gas is introduced, and the pressure in the ion plating apparatus is 3 × 10^-1Pa. In such a state, Ti was used as a target and an ionization voltage was set to 30 V and an ionization current was set to 140 A, thereby forming an underlayer composed of TiN.
The average thickness of the underlying layer thus formed was 5 μm.
[0128]
[B4] Next, the base material on which the underlayer was formed was washed. As this cleaning, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[B5] A diamond-like carbon film mainly composed of diamond-like carbon was formed on the surface of the ground layer cleaned in this manner, to obtain a member.
The diamond-like carbon film was formed by sputtering under the same conditions as in Example 1.
[0129]
[B6] Next, masking was formed in a predetermined shape on part of the surface of the diamond-like carbon film of the member obtained in the step [B5].
Masking was formed as follows.
First, the entire surface of the diamond-like carbon film was coated by brushing a rubber-based resin, and then dried at 180 to 200 ° C. for 30 minutes.
Thereafter, a predetermined pattern was formed by irradiating a laser beam (YAG laser) and removing a part of the masking. The average thickness of the mask formed in this way was 500 μm.
[0130]
[B7] Next, the diamond-like carbon film at a portion not covered with the masking was removed.
[B8] The member covered with the masking was immersed in a stripping solution to remove the diamond-like carbon film together with the underlayer. As the stripping solution, a solution containing hydrogen fluoride: 30 wt%, nitric acid: 40 wt%, and water: 30 wt% was used. The immersion time of the member in the stripping solution was 15 minutes. The temperature of the stripping solution at the time of immersion was 25 ° C. In addition, the atmosphere (air) pressure when the member is immersed in the stripping solution is 1 × 10 at the initial stage.³After 5 minutes have passed since the member was immersed in the stripping solution, the atmospheric pressure was increased, and after 2 minutes, 1 × 10⁷It was set to Pa.
[0131]
[B9] Then, by immersing in a masking removal agent comprising a halogen compound solvent and a ketone solvent, the masking was removed to obtain a decorative product. Moreover, the temperature of the masking removal agent and the immersion time in the masking removal agent in this step were 30 ° C. and 30 minutes, respectively.
Moreover, about the base material used for manufacture of an ornament, and the obtained ornament, JIS B
Surface roughness R defined by 0601_maxWas measured.
[0132]
Surface roughness R of the part where the base material of the decorative article is exposed_maxWas 0.2 to 0.4 μm. Moreover, in the base material used for manufacture of the ornament, the surface roughness R of the location corresponding to this_maxWas 0.2 to 0.45 μm. From this, it can be seen that in this example, the surface of the substrate is hardly roughened even when the diamond-like carbon film is formed and removed.
[0133]
(Example 3)
Decorative articles (watch case and rotating bezel) were manufactured by the following method.
[0134]
[C1] First, using a Cu—Zn alloy (alloy composition: Cu 60 wt% —Zn 40 wt%), a base material having the shape of a wristwatch case (body) and a base material having the shape of a rotating bezel are produced by casting. After that, necessary portions were cut and polished.
[C2] Next, the substrate was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0135]
[C3] A first underlayer composed of Cu was formed on the surface of the base material thus cleaned.
The first underlayer is formed by wet plating, bath temperature: 60 ° C., current density: 3 A / dm², Time: 1 minute.
The average thickness of the first underlayer formed in this way was 1 μm.
[0136]
[C4] Thereafter, a second underlayer composed of a Cu—Sn alloy was formed on the surface of the first underlayer.
The second underlayer is formed by wet plating, bath temperature: 60 ° C., current density: 3 A / dm.², Time: Performed under the condition of 2 minutes.
The average thickness of the second underlayer formed in this way was 3 μm.
[0137]
[C5] Furthermore, a third base layer made of Au was formed on a part of the surface of the second base layer (a part other than the part to be the sliding portion of the rotating bezel).
In this step, first, a mask (resist) having a predetermined pattern is formed by a photolithography method, a third underlayer composed of Au is formed in the opening by wet plating, and then the mask (resist) is formed. This was done by removing.
For wet plating, bath temperature: 60 ° C., current density: 3 A / dm²And time: 10 minutes.
The average thickness of the third underlayer thus formed was 3 μm.
[0138]
[C6] Next, the substrate on which the first to third base layers were laminated was washed. As this cleaning, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[C7] A diamond-like carbon film mainly composed of diamond-like carbon was formed on the surfaces of the third and second underlayers cleaned in this manner, thereby obtaining a member.
The diamond-like carbon film was formed by sputtering under the same conditions as in Example 1.
[0139]
[C8] Next, by immersing the member obtained in the step [C7] in a stripping solution, a part of the diamond-like carbon film is removed together with the third underlayer, and a decorative article (watch Case and rotating bezel). As the stripping solution, a cyan stripping agent was used. The immersion time of the member in the stripping solution was 15 minutes. The temperature of the stripping solution at the time of immersion was 25 ° C. In addition, the atmosphere (air) pressure when the member is immersed in the stripping solution is 1 × 10 at the initial stage.³After 5 minutes have passed since the member was immersed in the stripping solution, the atmospheric pressure was increased, and after 2 minutes, 1 × 10⁷It was set to Pa.
[C9] Then, each decorative article (watch case and rotating bezel) was assembled.
[0140]
Example 4
Decorative articles (watch case and screw lock type crown) were manufactured by the method as described below.
[D1] First, a base material having the shape of a wristwatch case (body) and a base material having a shape of a screw lock-type crown are produced by forging using brass (Cu 65 wt%, Zn 35 wt%), and then necessary. The part was cut and polished.
[0141]
[D2] Next, these base materials were washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0142]
[D3] A first base layer made of Cu was formed on the surface of the base material thus cleaned.
The first underlayer is formed by wet plating, bath temperature: 60 ° C., current density: 3 A / dm², Time: 1 minute.
The average thickness of the first underlayer formed in this way was 1 μm.
[0143]
[D4] Thereafter, a second underlayer composed of Ni was formed on the surface of the first underlayer.
The second underlayer is formed by wet plating, bath temperature: 40 ° C., current density: 3 A / dm.², Time: Performed under conditions of 5 minutes.
The average thickness of the second underlayer formed in this way was 2 μm.
[0144]
[D5] Furthermore, a third base layer made of Au was formed on a part of the surface of the second base layer (a portion to be a screw portion of a screw lock type crown).
In this step, first, a mask (resist) having a predetermined pattern is formed by a photolithography method, a third underlayer composed of Au is formed in the opening by wet plating, and then the mask (resist) is formed. This was done by removing.
For wet plating, bath temperature: 60 ° C., current density: 3 A / dm²And time: 10 minutes.
The average thickness of the third underlayer thus formed was 3 μm.
[0145]
[D6] Next, the base material on which the first to third base layers were laminated was washed. As this cleaning, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[D7] A diamond-like carbon film mainly composed of diamond-like carbon was formed on the surfaces of the third underlayer and the second underlayer that were cleaned in this manner, to obtain a member.
The diamond-like carbon film was formed by sputtering under the same conditions as in Example 1.
[0146]
[D8] Next, the member obtained in the step [D7] is dipped in a stripping solution, whereby the second underlayer (the second underlayer where the third underlayer is not laminated) is obtained. A part of the diamond-like carbon film was removed together with the strata) to obtain decorative articles (watch case and screw lock type crown). As the stripping solution, a cyan stripping agent was used. The immersion time of the member in the stripping solution was 15 minutes. The temperature of the stripping solution at the time of immersion was 25 ° C. In addition, the atmosphere (air) pressure when the member is immersed in the stripping solution is 1 × 10 at the initial stage.³After 5 minutes have passed since the member was immersed in the stripping solution, the atmospheric pressure was increased, and 2 minutes later, 1 × 10⁷It was set to Pa.
[D9] Thereafter, each decorative article (watch case and screw lock type crown) was assembled.
[0147]
(Example 5)
A decorative article (a tri-fold band band) was manufactured by the following method.
[E1] First, using stainless steel (SUS316L), a base material having the shape of each component of the band middle end of the three-fold structure was produced by forging, and then necessary portions were cut and polished.
[E2] Next, the substrate was washed. As the cleaning of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0148]
[E3] An underlayer composed of Cr was formed on the surface of the base material thus cleaned.
The underlayer is formed by wet plating, bath temperature: 45 ° C., current density: 4 A / dm.², Time: Performed under conditions of 5 minutes.
The average thickness of the underlying layer thus formed was 1 μm.
[E4] Next, the base material on which the underlayer was laminated was washed. As this cleaning, first, alkaline electrolytic degreasing was performed for 30 seconds, and then alkaline immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds.
[0149]
[E5] A diamond-like carbon film mainly composed of diamond-like carbon was formed on the surface of the ground layer washed in this manner, thereby obtaining a member.
The diamond-like carbon film was formed by sputtering.
This sputtering was performed using a vacuum apparatus as follows.
First, the inside of the vacuum apparatus was replaced with a mixed gas of argon gas: 60 vol% and methane gas: 40 vol%. Thereafter, the atmospheric pressure was adjusted to 0.6 Pa by adjusting the flow rate of the mixed gas and the exhaust amount.
[0150]
After adjusting the atmospheric pressure in the vacuum apparatus, a diamond-like carbon film was formed by performing high frequency discharge using graphite as a target.
Note that the flow rate of the mixed gas during sputtering was 60 SCCM, and the atmospheric pressure was 0.6 Pa. The high frequency power was 500W. The film formation rate was 0.4 μm / h.
The diamond-like carbon film thus formed had an average thickness of 0.5 μm.
[0151]
[E6] The member obtained in the step [E5] was immersed in a stripping solution in an atmospheric pressure atmosphere, and anodic electrolysis was performed to remove the diamond-like carbon film together with the base layer. As the stripping solution, a 7 wt% sodium carbonate aqueous solution was used. The immersion time of the member in the stripping solution was 25 minutes. The temperature of the stripping solution during immersion is 30 ° C., and the current density is 5 A / dm.²Met.
[E7] Furthermore, a series of steps [E2] to [E5] were performed, and then each part was assembled to obtain a decorative product (a band tie having a tri-fold structure).
[0152]
(Comparative Example 1)
A decorative article (watch case (back cover)) was manufactured by the method as described below.
[F1] First, in the same manner as in Example 1 (steps [A1] to [A5]), a member having the shape of a watch case (back cover) was formed.
[F2] Next, the diamond-like carbon film was removed from the obtained member by glow discharge to obtain a decorative article. Specifically, a member having a diamond-like carbon film is held at the same potential as the cathode, and a discharge current of 500 mA is passed under a pressure of 50 Pa in a mixed gas atmosphere in which the volume ratio of hydrogen to oxygen is 5: 1. Then, glow discharge was generated and the treatment was performed for 2 hours.
As a result, in the resulting decorative article, the diamond-like carbon film remained partially (mottled). Moreover, in the site | part from which the diamond-like carbon film was removed, the base layer was removed partially, and the site | part where the base material was exposed, and the site | part where a base layer remain | survived were mixed.
[0153]
(Comparative Example 2)
A decorative article (watch case (back cover)) was manufactured by the method as described below.
[G1] First, in the same manner as in Example 1 (steps [A1] to [A5]), a member having the shape of a watch case (back cover) was formed.
[G2] Next, the diamond-like carbon film was removed from the obtained member by arc discharge to obtain a decorative article. Specifically, a member having a diamond-like carbon film was held in an arc discharge plasma generated in a mixed gas having a volume ratio of hydrogen to oxygen of 5: 1 in a stationary potential state for 2 hours.
As a result, in the resulting decorative article, the diamond-like carbon film remained partially (mottled). Moreover, in the site | part from which the diamond-like carbon film was removed, the base layer was removed partially, and the site | part where the base material was exposed, and the site | part where a base layer remain | survived were mixed.
[0154]
(Comparative Example 3)
Decorative articles (watch case and rotating bezel) were manufactured by the following method.
[H1] First, in the same manner as in Example 3 (steps [C1] to [C7]), members having the shape of a watch case and a rotating bezel were formed.
[0155]
[H2] Next, the diamond-like carbon film was removed from the obtained member by glow discharge to obtain a decorative article. Specifically, a member having a diamond-like carbon film is held at the same potential as the cathode, and a discharge current of 500 mA is passed under a pressure of 50 Pa in a mixed gas atmosphere in which the volume ratio of hydrogen to oxygen is 5: 1. Then, glow discharge was generated and the treatment was performed for 2 hours. The glow discharge tried to remove the diamond-like carbon film from only the part other than the part to be the sliding portion of the rotating bezel, but the diamond-like carbon film was removed almost uniformly from each part of the member.
Further, in the ornament obtained as described above, the diamond-like carbon film remained partially (mottled). Further, in the portion where the diamond-like carbon film has been removed, the foundation layer (third foundation layer, second foundation layer, first foundation layer) is partially removed, and the second foundation layer, The first base layer, the portion where the base material is exposed, and the portion where the third base layer remains are mixed.
[H3] Thereafter, each decorative article (watch case and rotating bezel) was assembled.
[0156]
(Comparative Example 4)
Decorative articles (watch case and screw lock type crown) were manufactured by the method as described below.
[I1] First, in the same manner as in Example 4 (steps [D1] to [D7]), members having the shape of a wristwatch case and a screw lock type crown were formed.
[0157]
[I2] Next, the diamond-like carbon film was removed from the obtained member by glow discharge to obtain a decorative article. Specifically, a member having a diamond-like carbon film is held at the same potential as the cathode, and a discharge current of 500 mA is passed under a pressure of 50 Pa in a mixed gas atmosphere in which the volume ratio of hydrogen to oxygen is 5: 1. Then, glow discharge was generated and the treatment was performed for 2 hours. Glow discharge tried to remove the diamond-like carbon film only from the part other than the part to be the screw part of the screw lock type crown, but the diamond-like carbon film was removed almost uniformly from each part of the member. .
Further, in the ornament obtained as described above, the diamond-like carbon film remained partially (mottled). Further, in the portion where the diamond-like carbon film has been removed, the foundation layer (third foundation layer, second foundation layer, first foundation layer) is partially removed, and the second foundation layer, The first base layer, the portion where the base material is exposed, and the portion where the third base layer remains are mixed.
[I3] Then, each decorative article (watch case and screw lock type crown) was assembled.
[0158]
(Comparative Example 5)
A decorative article (a tri-fold band band) was manufactured by the following method.
[J1] First, in the same manner as in Example 5 (steps [E1] to [E5]), a member having the shape of each component of the band middle ring having a trifold structure was formed.
[0159]
[J2] Next, the diamond-like carbon film was removed from the obtained member by glow discharge to obtain a decorative article. Specifically, a member having a diamond-like carbon film is held at the same potential as the cathode, and a discharge current of 500 mA is passed under a pressure of 50 Pa in a mixed gas atmosphere in which the volume ratio of hydrogen to oxygen is 5: 1. Then, glow discharge was generated and the treatment was performed for 2 hours.
As a result, in the resulting decorative article, the diamond-like carbon film remained partially (mottled). Moreover, in the site | part from which the diamond-like carbon film was removed, the base layer was removed partially, and the site | part where the base material was exposed, and the site | part where a base layer remain | survived were mixed.
[0160]
[J3] Further, a series of steps of [E2] to [E5] of Example 5 were performed, and thereafter, each part was assembled to obtain a decorative article (a tri-fold band middle ring).
Table 1 summarizes the structure of the members and the conditions for removing the diamond-like carbon film in each example and each comparative example.
[0161]
[Table 1]

[0162]
2. Appearance evaluation of ornaments
About the ornament manufactured by each said Example and each comparative example, visual observation and observation with a microscope were performed, and these external appearances were evaluated in accordance with the following four-stage criteria.
A: Appearance is excellent (roughness of the surface is not recognized).
○: Appearance is good (the surface is hardly roughened).
Δ: Slightly poor appearance (roughness of the surface is clearly recognized)
X: Appearance defect (surface roughness is recognized remarkably).
[0163]
3. Evaluation of scratch resistance of diamond-like carbon films
The decorative articles manufactured in the above Examples and Comparative Examples were subjected to the following tests to evaluate the scratch resistance.
A stainless steel brush was pressed against the portion of each decorative article where the diamond-like carbon film was formed and slid 50 times. The pressing load at this time was 0.2 kgf.
[0164]
Thereafter, the surface of the decorative article was visually observed, and the appearance was evaluated according to the following four criteria.
A: Scratches are not observed at all on the surface of the diamond-like carbon film.
○: Scratches are hardly observed on the surface of the diamond-like carbon film.
Δ: Slight scratches are observed on the surface of the diamond-like carbon film.
X: Scratches are significantly observed on the surface of the diamond-like carbon film.
[0165]
4). Wear resistance evaluation of decorative products
The wear coefficient (steel resistance) was measured for the site where the diamond-like carbon film of each ornament manufactured in each of the above Examples and Comparative Examples was formed, and was evaluated according to the following three criteria.
A: Wear coefficient is less than 0.7.
○: Wear coefficient is 0.7 or more and less than 0.8.
X: Abrasion coefficient is 0.8 or more.
These results are shown in Table 2 together with the Vickers hardness Hv of the diamond-like carbon film and the friction coefficient μ of the diamond-like carbon film measured by the ball-on-disk method. In addition, as Vickers hardness Hv, the value measured with the measurement load 25gf about the diamond-like carbon film surface of each ornament is shown.
[0166]
[Table 2]

[0167]
As is apparent from Table 2, all the decorative articles of the present invention had an excellent aesthetic appearance, and were excellent in scratch resistance and abrasion resistance.
Moreover, all the decorative articles of the present invention had an excellent tactile sensation without a rough feeling.
On the other hand, the decorative article of the comparative example was inferior in aesthetic appearance.
[0168]
5. Rotational torque of rotating bezel
A watch was manufactured using the decorative articles (watch case and rotating bezel) manufactured in Example 3 and Comparative Example 3 above. For each of the obtained timepieces, the rotational torque of the rotating bezel was measured under a condition where a load of 300 gf was applied. Further, after rotating the rotating bezel 10,000 times, the rotational torque was measured under the same conditions.
The results are shown in Table 3.
[0169]
[Table 3]

[0170]
As is apparent from Table 3, in the timepiece provided with the decorative article (watch case and rotating bezel) of Example 3, it is relatively high both immediately after manufacture and after repeated rotation of the rotating bezel. It had a stable rotational torque. On the other hand, in the watch provided with the decorative article (watch case and rotating bezel) of Comparative Example 3, the rotational torque was small. Further, the rotational torque was further reduced by repeatedly performing the rotation operation.
[0171]
6). Detachment operability evaluation of screw lock type crown
A watch was manufactured using the decorative articles (watch case and screw lock type crown) manufactured in Example 4 and Comparative Example 4 above. About each obtained timepiece, the ease of operation (detachment operability) when performing the rotation attachment / detachment operation in which the screw lock type crown was attached / detached from the case was evaluated according to the following four criteria.
A: The rotation attachment / detachment operation can be performed very smoothly.
○: The rotation attachment / detachment operation can be performed sufficiently smoothly.
Δ: There is a slight sensation when performing the rotation attachment / detachment operation.
X: When performing rotation attachment / detachment operation, there is a noticeable sensation.
Moreover, after performing the rotation attachment / detachment operation of the screw-lock type crown 10,000 times, the attachment / detachment operability was evaluated according to the same criteria as described above.
The results are shown in Table 4.
[0172]
[Table 4]

[0173]
As is apparent from Table 4, in the watch provided with the decorative article of Example 4 (watch case and screw lock type crown), excellent attachment / detachment operability immediately after manufacture and after repeated rotation attachment / detachment operations were performed. showed that. On the other hand, the timepiece provided with the decorative article of Comparative Example 4 (watch case and screw lock-type crown) was inferior in detachability. Moreover, the detachability operability was further reduced by repeatedly performing the rotation detachment operation.
[0174]
7. Removability evaluation of band Nakadome
A watch was manufactured using the decorative article (band Nakadome) manufactured in Example 5 and Comparative Example 5 above. About each obtained timepiece, the ease of operation (attachment / detachment operability) when performing the attachment / detachment operation of the band clasp was evaluated according to the following four-stage criteria.
A: The attachment / detachment operation can be performed very smoothly.
○: The attachment / detachment operation can be performed sufficiently smoothly.
(Triangle | delta): A slight catch is recognized when performing attachment / detachment operation.
X: Remarkable catch is recognized when performing attachment / detachment operation.
Moreover, after performing attachment and detachment operation of the band Nakadome, detachability operability was evaluated according to the same criteria as described above.
The results are shown in Table 5.
[0175]
[Table 5]

[0176]
As can be seen from Table 5, the timepiece provided with the decorative article (band clasp) of Example 5 showed excellent attachment / detachment operability both immediately after production and after repeated attachment / detachment operations. On the other hand, the timepiece provided with the decorative article (band Nakadome) of Comparative Example 5 was inferior in attaching / detaching operability. Moreover, the detachability operability was further reduced by repeatedly performing the rotation detachment operation.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an example of a member manufacturing method applied to a method for removing a diamond-like carbon film of the present invention.
FIG. 2 is a cross-sectional view schematically showing a first embodiment of a method for removing a diamond-like carbon film of the present invention.
FIG. 3 is a cross-sectional view schematically showing an example of a member manufacturing method applied to the method for removing a diamond-like carbon film of the present invention.
FIG. 4 is a cross-sectional view schematically showing a second embodiment of the method for removing a diamond-like carbon film of the present invention.
FIG. 5 is a cross-sectional view schematically showing another embodiment of the method for removing a diamond-like carbon film of the present invention.
[Explanation of symbols]
1A, 1B, 1B '... Decorative product 2 ... Base material 3 ... Diamond-like carbon film 40 ... Underlayer 41 ... First underlayer 42 ... Second underlayer 43 ... Under the third Formation 5 ... Masking 10A, 10B ... Members

Claims (3)

A substrate;
At least one underlayer formed on at least a portion of the substrate;
A method of removing at least a part of the diamond-like carbon film from a member having a diamond-like carbon film mainly formed of diamond-like carbon (DLC) formed on at least a part of the underlayer,
The diamond-like carbon film is formed at a film formation speed of 0.05 to 30 μm / h,
By immersing the member in a liquid release agent capable of peeling the underlayer, the release agent penetrates into the diamond-like carbon film, and together with at least a part of the underlayer, the diamond-like carbon film To remove at least part of it,
When immersing the member in the release agent, the atmospheric pressure is set to 8 × 10 ⁴ Pa or less, and then the atmospheric pressure is set to 1.1 × 10 ⁵ Pa or more. A method for removing a diamond-like carbon film. A substrate;
An underlayer formed on at least a part of the substrate ;
A method of removing a part of the diamond-like carbon film from a member having a diamond-like carbon film formed on at least a part of the underlayer and mainly composed of diamond-like carbon (DLC),
The member includes, as the base layer, a first base layer provided on at least a part of the surface of the base material and a second base layer provided on at least a part of the surface of the first base layer. And a third underlayer provided on a part of the surface of the second underlayer, and provided so that at least a part of the second underlayer is in contact with the diamond-like carbon film. And at least a part of the third underlayer is provided so as to contact the diamond-like carbon film,
By applying a release agent that can peel off the second underlayer or the third underlayer from the base material from above the diamond-like carbon film, the release agent penetrates into the diamond-like carbon film. , at least with a portion of the second base layer or the third base layer, the method of removing the diamond-like carbon film and removing a portion of the diamond-like carbon film. The application of the release agent is performed by immersing the member in the liquid release agent,
  When the member is immersed in the release agent, the atmospheric pressure is set to 8 × 10. ⁴ Then, the pressure of the atmosphere is 1.1 × 10. ⁵ The method for removing a diamond-like carbon film according to claim 2, wherein the state is set to Pa or higher.

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