JPH04341582A - Carbon head film excellent in peeling property - Google Patents
Carbon head film excellent in peeling propertyInfo
- Publication number
- JPH04341582A JPH04341582A JP14098691A JP14098691A JPH04341582A JP H04341582 A JPH04341582 A JP H04341582A JP 14098691 A JP14098691 A JP 14098691A JP 14098691 A JP14098691 A JP 14098691A JP H04341582 A JPH04341582 A JP H04341582A
- Authority
- JP
- Japan
- Prior art keywords
- intermediate layer
- carbon
- film
- base material
- hard film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000004767 nitrides Chemical class 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 3
- 229910001369 Brass Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010951 brass Substances 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ULAUBQTVYAVTFT-UHFFFAOYSA-N dinitro carbonate Chemical compound [O-][N+](=O)OC(=O)O[N+]([O-])=O ULAUBQTVYAVTFT-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 2
- 238000005121 nitriding Methods 0.000 abstract 2
- 238000011084 recovery Methods 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- -1 nitride carbonate Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】 本発明は、被覆膜として剥離
性が良く、再生可能なカ−ボン硬質膜に関するものであ
る。TECHNICAL FIELD The present invention relates to a hard carbon film that has good removability as a coating film and is recyclable.
【０００２】0002
【従来の技術】カ−ボン硬質膜は、プラズマＣＶＤ法で
得られる水素を結合したダイヤモンド状カ−ボンとかｉ
カ−ボンとも言われている非晶質のカ−ボン膜で、ダイ
ヤモンドにつぐ硬度（約５０００Ｈｖ）と、高い熱伝導
性、化学的安定性をもつため、近年注目され広く応用さ
れている素材であつて、たとえば抗張力が大きく内部摩
擦が小さい点からスピ−カ−等の音響製品に使用されて
いる。[Prior Art] Carbon hard films are made of hydrogen-bonded diamond-like carbon or i
An amorphous carbon film, also known as carbon, that has attracted attention in recent years and has been widely applied because it has a hardness second only to diamond (approximately 5000 Hv), high thermal conductivity, and chemical stability. For example, it is used in acoustic products such as speakers because of its high tensile strength and low internal friction.
【０００３】0003
【発明が解決しようとする課題】しかしながら、カ−ボ
ン硬質膜で被覆した製品は不良品が発生すると再生がで
きないため、廃棄するほかなくリスクが大きかった。ま
た再生のために真空中で被覆膜にイオンボンバ−ドを行
なう場合は、効率を考慮すると専用の装置が必要で、セ
ット時間、排気時間等の処理にも時間を要するため、均
一な膜の剥離はほとんど不可能であった。[Problems to be Solved by the Invention] However, if a product coated with a hard carbon film is found to be defective, it cannot be recycled, so there is a great risk that the product must be discarded. In addition, when performing ion bombardment on the coated film in vacuum for regeneration, special equipment is required in consideration of efficiency, and processing time such as setting time and exhaust time is also required. was almost impossible to remove.
【０００４】また、約５００℃以上の高温でカ−ボン硬
質膜を昇華させて除去させる方法もあるが、これは基材
に対する影響が大きく、硬度が低下するので低融点の部
材には適しない。物理的研摩で除去するのは、非常に時
間がかかるため実際上不可能である。[0004]Also, there is a method of sublimating and removing the carbon hard film at a high temperature of about 500°C or higher, but this has a large effect on the base material and reduces the hardness, so it is not suitable for low melting point parts. . Removal by physical polishing is very time consuming and is practically impossible.
【０００５】[0005]
【課題を解決するための手段】本発明は、前記課題を解
決するため、基材とカ−ボン硬質膜との間に特定の層を
介在させる方法を提案するもので、これによって部品の
再生利用が可能になった。本発明は、基材面を、Ｓｉ，
Ｇｅ，Ｔｉ，Ｚｒ，Ｈｆ，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃ
ｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｐｔ，Ａｕの金属、合金、炭化
物、窒化物、窒炭化物、窒炭酸化物のいずれかの組成の
、少くとも１μｍの厚さの中間層を介して被覆してなる
ことを特徴とする剥離性の良いカ−ボン硬質膜を要旨と
するものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention proposes a method of interposing a specific layer between the base material and the carbon hard film. Now available. In the present invention, the base material surface is made of Si,
Ge, Ti, Zr, Hf, Cr, Fe, Co, Ni, C
Coated with an intermediate layer having a thickness of at least 1 μm and having a composition of u, Rh, Pd, Ag, Pt, or Au, metal, alloy, carbide, nitride, nitride carbide, or nitride carbonate. The object of the present invention is to provide a carbon hard film with good releasability.
【０００６】従来のカ−ボン硬質層は、一般に基材との
接着性がないため、特定の基材以外は出来るだけ薄い中
間層を介して基材を被覆するようにされていた。この場
合、薬品で中間層を溶解してカ−ボン硬質層を剥離させ
ようとしてもムラなく層を溶解できない。[0006] Conventional carbon hard layers generally do not have adhesive properties with base materials, and therefore, except for specific base materials, the base materials are coated with an intermediate layer as thin as possible. In this case, even if an attempt is made to remove the hard carbon layer by dissolving the intermediate layer with a chemical, the layer cannot be dissolved evenly.
【０００７】本発明は、この中間層を少なくとも１μｍ
の厚さとすることによって薬品による均一な除去を可能
としたのである。本発明では、ステンレス鋼、アルミニ
ウム、鉄、黄銅を基材とし、中間層としては、Ｓｉ，Ｇ
ｅ，Ｔｉ，Ｚｒ，Ｈｆ，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ
，Ｒｈ，Ｐｄ，Ａｇ，Ｐｔ，Ａｕの金属、合金、炭化物
、窒化物、窒炭化物、窒炭酸化物のいずれかに属し、上
記基材に適するものが使用される。[0007] The present invention provides that the intermediate layer has a thickness of at least 1 μm.
This thickness made it possible to remove the particles uniformly using chemicals. In the present invention, stainless steel, aluminum, iron, and brass are used as base materials, and the intermediate layer is made of Si, G
e, Ti, Zr, Hf, Cr, Fe, Co, Ni, Cu
, Rh, Pd, Ag, Pt, and Au, metals, alloys, carbides, nitrides, nitrides, and nitrocarbonates, and are suitable for the above-mentioned base material.
【０００８】[0008]
実施例１
ステンレス鋼からなる基材上に、厚さ１．５μｍのシリ
コン層を中間層として乾式メッキのスパッタリング法に
よって形成させた。この場合次の条件で 実施した。
真空度 １×１０‐３ 〜７×１０‐３ Ｔｏｒ
ｒガス種 アルゴン
基材温度 １００〜３００℃
バイアス電圧 −１０〜１００Ｖ
タ−ゲット シリコンExample 1 A silicon layer having a thickness of 1.5 μm was formed as an intermediate layer on a base material made of stainless steel by a dry plating sputtering method. In this case, the test was conducted under the following conditions. Vacuum degree 1×10-3 ~ 7×10-3 Tor
r Gas type Argon base temperature 100~300℃ Bias voltage -10~100V Target Silicon
【０００９】この中間層上にプラズマＣＶＤ法により、
次ぎの条件でカ−ボン硬質膜（膜厚１μｍ）を形成させ
た。
原料ガス： メタンガス
励起法： 高周波（１３．５６ＭＨｚ）高周
波電力： ３００Ｗ
ガス圧力： ０．１Ｔｏｒｒ[0009] On this intermediate layer, by plasma CVD method,
A carbon hard film (film thickness: 1 μm) was formed under the following conditions. Raw material gas: Methane gas excitation method: High frequency (13.56 MHz) high frequency power: 300 W Gas pressure: 0.1 Torr
【００１０】この被覆膜をフッ化水素酸と硝酸の混酸中
に１時間放置したところ、カ−ボン硬質膜は完全に剥離
された。
実施例２
ステンレス鋼からなる基材上に、厚さ３μｍの窒化チタ
ン層をイオンプレ−テイング法によって中間層として形
成させた。この中間層上にプラズマＣＶＤ法により、実
施例１と同じ条件でカ−ボン硬質膜（約膜厚１μｍ）を
形成させた。こ被覆膜をフッ化水素酸、過酸化水素、水
酸化ナトリウムの混合液中に常温で２時間放置したとこ
ろ硬質膜は完全に剥離された。When this coating film was left in a mixed acid of hydrofluoric acid and nitric acid for one hour, the hard carbon film was completely peeled off. Example 2 A titanium nitride layer having a thickness of 3 μm was formed as an intermediate layer on a base material made of stainless steel by ion plating. A hard carbon film (about 1 μm thick) was formed on this intermediate layer by plasma CVD under the same conditions as in Example 1. When this coated film was left in a mixed solution of hydrofluoric acid, hydrogen peroxide, and sodium hydroxide at room temperature for 2 hours, the hard film was completely peeled off.
【００１１】実施例３
実施例２と同じ方法で厚さ３μｍの炭化チタンの中間層
を形成し、その上にカ−ボン硬質膜（約膜厚１μｍ）を
形成させ、８０℃で５０％硝酸の剥離液中に置したとこ
ろ３０分で膜が剥離した。尚、中間層の形成方法として
スパッタリング法、イオンプレ−テイング法に代えてア
−ク蒸気着法等の他のＰＶＤ法、湿式メッキ法の適用な
ど種々適用できる。またカ−ボン硬質膜の形成方法とし
ても前記以外にスパッタリング法、イオンプレテイン法
でも同様な膜が得られる。Example 3 An intermediate layer of titanium carbide with a thickness of 3 μm was formed by the same method as in Example 2, and a hard carbon film (approximately 1 μm in thickness) was formed on it, and the layer was heated with 50% nitric acid at 80°C. When placed in a stripping solution, the film peeled off in 30 minutes. In addition, as a method for forming the intermediate layer, various methods such as other PVD methods such as arc vapor deposition method, wet plating method, etc. can be applied instead of sputtering method and ion plating method. Furthermore, as a method for forming the carbon hard film, in addition to the above-mentioned method, a similar film can be obtained by sputtering method or ion pretaining method.
【００１２】0012
【発明の効果】本発明によりカ−ボン硬質膜を短時間で
大量の剥離処理ができるので製品不良のときのリスクが
少なくなくなり、ランニングコストを安くできる。According to the present invention, a large amount of carbon hard film can be removed in a short period of time, so the risk of product defects is reduced and running costs can be reduced.
Claims (2)
，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｒｈ，Ｐｄ，Ａｇ，
Ｐｔ，Ａｕの金属、合金、炭化物、窒化物、窒炭化物、
窒炭酸化物のいずれかの組成の、少くとも１μｍの厚さ
の中間層を介して被覆してなることを特徴とする剥離性
の良いカ−ボン硬質膜。[Claim 1] The base material surface is made of Si, Ge, Ti, Zr, Hf.
, Cr, Fe, Co, Ni, Cu, Rh, Pd, Ag,
Pt, Au metals, alloys, carbides, nitrides, nitrides,
1. A carbon hard film with good releasability, characterized in that it is coated with an intermediate layer of at least 1 μm thick, which is made of any one of nitrocarbonate compositions.
鉄、黄銅の面である請求項１に記載のカ−ボン硬質膜。[Claim 2] The base material surface is stainless steel, aluminum,
The carbon hard film according to claim 1, which has an iron or brass surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14098691A JPH04341582A (en) | 1991-05-16 | 1991-05-16 | Carbon head film excellent in peeling property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14098691A JPH04341582A (en) | 1991-05-16 | 1991-05-16 | Carbon head film excellent in peeling property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04341582A true JPH04341582A (en) | 1992-11-27 |
Family
ID=15281481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14098691A Pending JPH04341582A (en) | 1991-05-16 | 1991-05-16 | Carbon head film excellent in peeling property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04341582A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5691010A (en) * | 1993-10-19 | 1997-11-25 | Sanyo Electric Co., Ltd. | Arc discharge plasma CVD method for forming diamond-like carbon films |
| US5695832A (en) * | 1993-07-07 | 1997-12-09 | Sanyo Electric Co., Ltd. | Method of forming a hard-carbon-film-coated substrate |
| JPH10130865A (en) * | 1996-09-06 | 1998-05-19 | Sanyo Electric Co Ltd | Substrate with hard carbon film and its forming method |
| US5955196A (en) * | 1996-06-28 | 1999-09-21 | Bp Amoco Corporation | Polyester fibers containing naphthalate units |
| US6572936B1 (en) | 1996-06-09 | 2003-06-03 | Sanyo Electric Co., Ltd. | Hard carbon film-coated substrate and method for fabricating the same |
| JP2011241420A (en) * | 2010-05-17 | 2011-12-01 | Showa Denko Kk | Method for manufacturing copper material with carbon thin film |
-
1991
- 1991-05-16 JP JP14098691A patent/JPH04341582A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695832A (en) * | 1993-07-07 | 1997-12-09 | Sanyo Electric Co., Ltd. | Method of forming a hard-carbon-film-coated substrate |
| US5691010A (en) * | 1993-10-19 | 1997-11-25 | Sanyo Electric Co., Ltd. | Arc discharge plasma CVD method for forming diamond-like carbon films |
| US6572936B1 (en) | 1996-06-09 | 2003-06-03 | Sanyo Electric Co., Ltd. | Hard carbon film-coated substrate and method for fabricating the same |
| US5955196A (en) * | 1996-06-28 | 1999-09-21 | Bp Amoco Corporation | Polyester fibers containing naphthalate units |
| JPH10130865A (en) * | 1996-09-06 | 1998-05-19 | Sanyo Electric Co Ltd | Substrate with hard carbon film and its forming method |
| JP2011241420A (en) * | 2010-05-17 | 2011-12-01 | Showa Denko Kk | Method for manufacturing copper material with carbon thin film |
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