JP3150712B2 - Member covered with carbon film - Google Patents
Member covered with carbon filmInfo
- Publication number
- JP3150712B2 JP3150712B2 JP41869390A JP41869390A JP3150712B2 JP 3150712 B2 JP3150712 B2 JP 3150712B2 JP 41869390 A JP41869390 A JP 41869390A JP 41869390 A JP41869390 A JP 41869390A JP 3150712 B2 JP3150712 B2 JP 3150712B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- film
- main component
- covering
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、風雨に曝され得る
と共に、風切りがなされる自動車、オ−トバイ、自転
車、船舶、航空機等の輸送手段のフロントウインド等の
窓、ビル、家屋等の採光用窓、厳しい自然条件下で使用
されるヘルメットバイザー、スキー用ゴーグルその他に
対し、透光性の有機物の部材の表面を、炭素または炭素
を主成分とする保護用被膜で覆ったものである。そして
表面において耐摩耗性を向上させ、裏面において静電気
の発生を防ぎ、ほこりの付着を防いだものである。本発
明はかかる薄膜として、可視領域で透光性を有するとと
もに、硬度が十分な炭素または炭素を主成分とする被膜
を摩耗防止用保護膜としたものである。特にこの保護膜
は、有機物上に密着させ得るとともに、その電気的固有
抵抗として１×106 〜５×1012Ωcmを有せしめて、静電
気の発生を防ぐとともに、表面に平滑性を有せしめ、ほ
こりの付着を防がんとしたものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to daylighting of windows, buildings, houses and the like of vehicles such as automobiles, motorcycles, bicycles, ships, aircraft, etc., which can be exposed to wind and rain, and which are cut off. For a window, a helmet visor used under severe natural conditions, ski goggles, and the like, the surface of a member made of a transparent organic material is covered with carbon or a protective coating containing carbon as a main component. Further, the abrasion resistance is improved on the front surface, the generation of static electricity on the back surface is prevented, and the adhesion of dust is prevented. According to the present invention, as such a thin film, carbon or a film containing carbon as a main component having sufficient hardness while having a light-transmitting property in a visible region is used as a protective film for preventing wear. In particular, this protective film can be brought into close contact with an organic material, and has an electric resistivity of 1 × 10 6 to 5 × 10 12 Ωcm, thereby preventing the generation of static electricity and having a smooth surface. This is to prevent the adhesion of dust to cancer.
【０００２】また、本発明は、かかるフロントガラス、
サイドガラス、リアウインド等の窓の表裏両面にプラズ
マＣＶＤ法で炭素膜または炭素を主成分とする被膜を形
成せんとしたものであり、この時片面を成膜したのち真
空破壊することなく同一反応室にて連続的に処理できる
ようにしたものである。[0002] The present invention also relates to such a windshield,
A carbon film or a film containing carbon as a main component is formed on both sides of windows such as side glass and rear window by plasma CVD method. The process can be performed continuously.
【０００３】[0003]
【従来の技術】一般にプラズマＣＶＤ法においては、平
坦面を有する導電性基板上に平面状に成膜する方法が工
業的に有効であるとされている。さらに、プラズマＣＶ
Ｄ法でありながら、スパッタ効果を伴わせつつ成膜させ
る方法も知られている。その代表例である炭素膜のコ−
ティングに関しては、本発明人の出願になる特許願『炭
素被膜を有する複合体およびその作製方法』（特願昭56
−146936 昭和56年９月17日出願) が知られている。し
かし、これらは一対の電極のみを用いる平行平板型の一
方の電極（カソ−ド側）に基板を配設し、導体基板であ
るため、自ら発生するセルフバイアスを用いて平坦面の
上面に炭素膜を成膜する方法である。2. Description of the Related Art In general, in a plasma CVD method, a method of forming a film in a plane on a conductive substrate having a flat surface is considered to be industrially effective. Furthermore, plasma CV
There is also known a method of forming a film with a sputtering effect while using the D method. A typical example is a carbon film core.
The patent application filed by the present inventor, entitled “Composite Having Carbon Coating and Method for Producing the Same” (Japanese Patent Application No.
−146936 (filed on Sep. 17, 1981). However, since these are a conductor substrate in which a substrate is provided on one parallel plate type electrode (cathode side) using only a pair of electrodes, a self-bias generated by itself is used to apply carbon to a flat surface. This is a method for forming a film.
【０００４】[0004]
【発明が解決しようとする課題】しかし、かかるスパッ
タ効果を伴わせつつ成膜させる従来例は、フロントウイ
ンド、特に自動車またはオ−トバイ等の曲面を有する基
体上または家の窓上に膜を作ることができない。また、
有機物等容易に傷のつくものではその両面に膜を作る必
要があるが、従来の方法ではできない。このため、大容
量空間で一度に多数の部材に対し両面に膜を形成する方
法が求められていた。本発明はかかる目的のためになさ
れたものである。However, in the prior art in which a film is formed with such a sputtering effect, a film is formed on a front window, particularly on a substrate having a curved surface such as an automobile or a motorcycle, or on a window of a house. Can not do. Also,
It is necessary to form a film on both sides of an easily scratched organic material or the like, but this cannot be done by a conventional method. For this reason, there has been a demand for a method of forming films on both surfaces of a large number of members at once in a large-capacity space. The present invention has been made for such a purpose.
【０００５】[0005]
【課題を解決するための手段】本発明は、風雨に曝され
得るとともに、風切りがなされる自動車、オ−トバイ、
自転車、船舶、航空機等のフロントウインドその他の透
光性を有する有機物の表面を有する部材の表面に、保護
膜として、炭素または炭素を主成分とする被膜を設け、
かつ、前記部材の裏面に保護膜としての機能以外に静電
気の発生防止の機能を有した炭素または炭素を主成分と
する被膜を設けたものである。この被膜の裏面には固有
抵抗として１×106 〜５×1012Ωcmを有せしめ、ほこり
（一般に絶縁性または鉱物性）を伴う摩擦による静電気
の発生を防ぎ、ひいてはほこりの付着、ほこりによる透
光性表面の微小傷の発生による失透または「にごり」を
防ぎ、常に鮮やかな透光性の面を保存せしめたものであ
る。SUMMARY OF THE INVENTION The present invention is directed to an automobile, an motorcycle, and a vehicle that can be exposed to the elements of the wind and can be exposed to the elements.
Bicycles, ships, aircraft, etc., the surface of a member having a surface of a translucent organic material such as a front window, as a protective film, as a protective film, provided with a coating mainly composed of carbon or carbon,
Further, carbon or a coating mainly composed of carbon having a function of preventing generation of static electricity in addition to a function as a protective film is provided on the back surface of the member. The back surface of this film has a specific resistance of 1 × 10 6 to 5 × 10 12 Ωcm to prevent the generation of static electricity due to friction accompanied by dust (generally insulating or mineral), and furthermore, adhesion of dust and transmission by dust. Prevents devitrification or "smearing" due to the occurrence of microscopic scratches on the optical surface, and preserves a bright transparent surface at all times.
【０００６】 本発明は、かかる目的の保護膜としてビッ
カ−ス硬度として600 〜6000Kg/cm2の値を有するプラズ
マ重合またはＣＶＤ法による炭素または炭素を主成分と
する膜を有機物上に密着せしめ得ることの発見に基づ
く。 The present invention, Vickers hardness as a protective film for this purpose - may the film mainly containing carbon or a carbon by plasma polymerization or CVD having a 600 value of ~6000Kg / cm 2 as scan hardness in close contact on organics Based on that discovery.
【０００７】 本発明は、かかるプラズマ重合即ちプラズ
マＣＶＤ用として、反応空間の一端側および他端側に互
いに離間して第１の一対の電極( 第１および第２の電
極）を配設する。さらにこの空間内に交流バイアスを加
えるためのもう１つの電極（第３の電極）を設け、その
第３の電極に被形成面を有する基体、部材の裏面を接す
るように配設する。反応性気体のプラズマ化のため、一
対の電極間に第１の交番電圧を印加する。このそれぞれ
の電極には、接地に対して互いに位相が180 °または０
°異なった高周波電圧をそれぞれの高周波電源より印加
し、互いに対称または同相の交番電圧を印加する。そし
て結果として合わせて実質的に１つの高周波の交番電圧
として枠構造内に印加し、反応性気体を完全に分解、電
離させるための高周波プラズマを誘起させる。さらにそ
のそれぞれの高周波電源の他端を接地せしめる。また基
体または部材の裏面に接して第３の電極を具備せしめ、
ここに第２の交番電圧を印加する。すると第２の交番電
圧で加速されたイオンが部材の被形成面上をスパッタし
つつ、被形成面上に強く被膜化させる。この時、第２の
交番電圧を発生させる電源と第３の電極の間にはブロッ
キングコンデンサが挿入され、第３の電極には負の直流
バイアスが自己発生的に印加される。よって、第３の電
極に接する基体または部材の表面には陽イオンのボンバ
ードメントが加えられることとなる。 In the present invention, a first pair of electrodes (first and second electrodes) are provided at one end and the other end of the reaction space so as to be separated from each other for such plasma polymerization, that is, for plasma CVD. Further, another electrode (third electrode) for applying an AC bias is provided in this space, and the third electrode is arranged so that the back surface of the base member having the surface to be formed and the back surface of the member are in contact with the third electrode. A first alternating voltage is applied between the pair of electrodes to convert the reactive gas into plasma. The respective electrodes are 180 ° or 0 ° out of phase with respect to ground.
° Apply different high-frequency voltages from the respective high-frequency power supplies, and apply alternating voltages that are symmetric or in phase with each other. Then, as a result, a high frequency alternating voltage is applied to the frame structure as substantially one high frequency alternating voltage to induce high frequency plasma for completely decomposing and ionizing the reactive gas. Further, the other end of each high-frequency power supply is grounded. In addition, a third electrode is provided in contact with the back surface of the base or the member,
Here, a second alternating voltage is applied. Then, ions accelerated by the second alternating voltage sputter on the surface of the member on which the member is formed, and strongly form a film on the surface of the member. At this time, a blocking capacitor is inserted between the power supply for generating the second alternating voltage and the third electrode, and a negative DC bias is self-generated to the third electrode. Therefore, cation bombardment is applied to the surface of the base or the member in contact with the third electrode.
【０００８】 前記基体または部材の表面に所定の膜が形
成されれば、次に第３の電極若しくは基体または部材を
並行移動させ、今度は基体または部材の表面に第３の電
極が接するように配置する。この時部材が曲面を有して
いるものであっても、第３の電極の各々の面が部材の表
面及び裏面の形状と同じものであればよい。この後、表
面を形成したと同様に裏面を形成する。かくして、部材
の両面に膜が形成される。 When a predetermined film is formed on the surface of the base or the member, the third electrode or the base or the member is then moved in parallel so that the third electrode comes into contact with the surface of the base or the member. Deploy. At this time, even if the member has a curved surface, it suffices that each surface of the third electrode has the same shape as the front and back surfaces of the member. Thereafter, the back surface is formed in the same manner as the front surface. Thus, a film is formed on both surfaces of the member.
【０００９】 この薄膜の形成の１例として、エチレン(C
2H4), メタン(CH4),アセチレン(C2H2)のような炭化水素
気体またはこれと弗化窒素の混合気体またはC2F6, C
3F8,CF4,CH2F2等の弗化炭素の如き炭素弗化物気体を導
入し、分解せしめることによりSP3 軌道を有するダイヤ
モンドと類似のC-C 結合をつくり、比抵抗( 固有抵抗)1
×106 〜５×1012Ωcm代表的には１×108 〜５×1011Ω
cmを有するとともに、光学的エネルギバンド巾(Eg とい
う）が1.0eV 以上、好ましくは1.5 〜5.5eV を有する可
視領域で透光性のダイヤモンドと類似の特性を有する炭
素膜または炭素を主成分( 副成分の主たるものは水素、
弗素、窒素である）とする被膜を形成した。 As one example of the formation of this thin film, ethylene (C
2 H 4), methane (CH 4), acetylene (C 2 H 2) hydrocarbon gas or its gas mixture or C 2 F 6, C of nitrogen fluoride such as
Introduce and decompose a carbon fluoride gas such as carbon fluoride such as 3 F 8 , CF 4 , CH 2 F 2 to create a CC bond similar to diamond with SP 3 orbit, and specific resistance (specific resistance) 1
× 10 6 to 5 × 10 12 Ωcm typically 1 × 10 8 to 5 × 10 11 Ωcm
and a carbon film or carbon having a property similar to that of diamond that is transparent in a visible region having an optical energy bandwidth (referred to as Eg) of 1.0 eV or more, preferably 1.5 to 5.5 eV. The main component is hydrogen,
A film of fluorine and nitrogen).
【００１０】 尚、前記炭素膜または炭素を主成分とする
被膜の副成分の内、とくに窒素濃度が高くなると固有抵
抗が小さくなるという実験結果は本発明人らの研究で明
らかとなっている。また、窒素濃度が高いほど、即ち、
固有抵抗が小さいほど膜の硬度は小さくなる傾向も判明
しているため、通常より硬度の要求される表面には窒素
濃度が低く硬い膜を、裏面には窒素濃度が高く固有抵抗
の低い膜を形成して静電気の対策とするのが有効であ
る。 [0010] Note that the carbon film or among subcomponents of a coating containing carbon as a main component, the experimental result that in particular the nitrogen concentration of the specific resistance decreases increases are found in the present study have found. Also, the higher the nitrogen concentration, that is,
It is also known that the lower the specific resistance, the lower the hardness of the film.Therefore, a hard film with a low nitrogen concentration is used on the surface that requires higher hardness than usual, and a film with a high nitrogen concentration and a low specific resistance is used on the back surface. It is effective to form it as a measure against static electricity.
【００１１】 本発明を用いた透光性有機物は、固有抵抗
１×1015Ωcm以上の絶縁性部材であり、材料は、ポリエ
ステル樹脂、アルキド樹脂、オイルフリ−アルキド樹
脂、不飽和ポリエステル樹脂、アクリル樹脂、アミノ樹
脂、ポリカーボネート、塩化ビニールが用いられる。特
に自動車ライン用にはアクリルラッカ−、アクリルメラ
ミン、ブロックアクリルウレタンの有機溶融型の有機物
とした。 The translucent organic substance using the present invention is an insulating member having a specific resistance of 1 × 10 15 Ωcm or more, and is made of polyester resin, alkyd resin, oil-free alkyd resin, unsaturated polyester resin, acrylic resin. , Amino resin, polycarbonate, and vinyl chloride are used. Particularly, for an automobile line, an organic melting type organic material of acrylic lacquer, acrylic melamine and block acrylic urethane was used.
【００１２】 本発明方法での成膜に際し、弗素の如きハ
ロゲン元素と窒素とを、プラズマＣＶＤ中に炭化物気体
に加えて同時に混入させて、厚さ方向に均一な濃度勾配
を設けた炭素を主成分とする被膜または添加物の有無を
制御した多層の複合膜を作ってもよい。 In forming a film by the method of the present invention, a halogen element such as fluorine and nitrogen are added to a carbide gas and simultaneously mixed during plasma CVD, and carbon having a uniform concentration gradient in a thickness direction is mainly formed. A multilayer composite film in which the presence or absence of a coating or an additive as a component is controlled may be produced.
【００１３】 以下に図面に従って本発明の作製方法を記
す。 [0013] referred to as a manufacturing method of the present invention with reference to the accompanying drawings below.
【００１４】[0014]
【実施例１】第２図は、自動車のフロントウインド等の
基体または部材上に薄膜形成方法を実施するためのプラ
ズマＣＶＤ装置の概要を示す。Embodiment 1 FIG. 2 shows an outline of a plasma CVD apparatus for carrying out a method for forming a thin film on a substrate or member such as a front window of an automobile.
【００１５】 図面において、プラズマＣＶＤ装置の反応
容器(7) はゲ−ト弁(9) で外部と仕切られている。ガス
系(30)において、キャリアガスであるアルゴンを(31)よ
り、反応性気体である炭化水素気体、例えばメタン、エ
チレンを(32)より、添加物気体である弗化炭素(C2F6,C3
F8) を(33)より、反応容器のエッチング用気体である酸
素を(34)より、バルブ(28)、流量計(29)をへて反応系(5
0)中にノズル(25)より導入する。エチレンと二弗化炭素
とを導入すると、水素と弗素が添加されたSP3結合を多
数有するダイヤモンド状炭素膜( ＤＬＣともいうが、添
加物が添加されたＤＬＣを含めて本発明は炭素または炭
素を主成分とする被膜という) を成膜できる。 In the drawing, a reaction vessel (7) of a plasma CVD apparatus is separated from the outside by a gate valve (9). In the gas system (30), the carrier gas, argon, is converted from (31) to a reactive gas, such as methane and ethylene, from (32) to the additive gas, carbon fluoride (C 2 F 6). , C 3
F 8 ) from (33), oxygen as the etching gas for the reaction vessel from (34) through valve (28) and flow meter (29) to the reaction system (5).
0) is introduced through the nozzle (25). When ethylene and carbon difluoride are introduced, a diamond-like carbon film having a large number of SP 3 bonds to which hydrogen and fluorine are added (also referred to as DLC, including DLC to which additives are added, the present invention relates to carbon or carbon ).
【００１６】 これと同一主成分の被膜を作るため、C
2F6,C3F8 を(32)より、またNH3 を(33)より導入して形
成してもよい。 In order to form a film of the same main component, C
It may be formed by introducing 2 F 6 and C 3 F 8 from (32) and NH 3 from (33).
【００１７】 この反応容器(7) の上下に第１の一対の電
極を同一形状を有せしめて第１および第２の電極(3-1),
(3-2) をアルミニウムの金属メッシュで構成せしめる。
反応性気体はノズル(25)より下方向に放出される。さら
に第３の電極(13-1),(13-2),・・・(13-ｎ) （集合させ
て第３の電極という）を先ず、基体または部材の裏面に
接触させて配置する。基体または部材(1-),(1-2)・・・
(1-n) は絶縁材料であるが、ここに第２の交番電圧を加
え、交流的には実質的に導体化してバイアスを印加し
た。第２の交番電圧源と基体または部材間にはブロッキ
ングコンデンサ(61)を挿入した。基体または部材(1) 上
の有機物の被形成面(1')には、プラズマ雰囲気またはポ
ジティブシ−スができ、負の自己バイアスが印加され
る。この負の自己バイアスが積極的に発生するよう、第
２の交番電圧の周波数を10kHz〜100KHzと電子が電界に
追随するがイオンは電界の変化に追随できない周波数と
した。基体または部材(1) は有機物の被形成面(1')を有
し、第１の高周波の交番電圧によりグロ−放電のプラズ
マ化した反応性気体は、反応空間(8) で均一に分散し、
反応空間でのプラズマ電位を均質にした。 [0017] The first and second electrodes of the first pair of electrodes brought have the same shape above and below the reaction vessel (7) (3-1),
(3-2) is made of aluminum metal mesh.
The reactive gas is discharged downward from the nozzle (25). Further, third electrodes (13-1), (13-2),... (13-n) (collectively referred to as third electrodes) are first placed in contact with the back surface of the base or member. Substrate or member (1-), (1-2) ...
(1-n) is an insulating material, to which a second alternating voltage was applied, and in terms of alternating current, the conductor was substantially made conductive and a bias was applied. A blocking capacitor (61) was inserted between the second alternating voltage source and the substrate or member. A plasma atmosphere or a positive sheet is formed on the organic substance forming surface (1 ') on the substrate or member (1), and a negative self-bias is applied. In order to positively generate the negative self-bias, the frequency of the second alternating voltage is set to 10 kHz to 100 KHz, which is a frequency at which electrons follow the electric field but ions cannot follow the change of the electric field. The substrate or member (1) has a surface (1 ') on which an organic substance is formed, and the reactive gas that has been turned into a glow discharge plasma by the first high-frequency alternating voltage is uniformly dispersed in the reaction space (8). ,
The plasma potential in the reaction space was made uniform.
【００１８】 さらにプラズマ反応空間での電位分布をよ
り等しくさせるため、電源系(40)には独立した二種類の
周波数の交番電圧が印加できるようになっている。第１
の交番電圧は１〜100MHz例えば13.56MHzの高周波であ
り、一対をなす２つの電源(15-1), (15-2)即ち(15)より
LCR 回路でできたマッチングボックス(16-1),(16-2) に
至る。このマッチングボックスでの互いの位相は位相調
整器(26)により調整し、互いに180 °または0 °ずれて
供給できるようにしている。そして対称型または同相型
の出力を有し、電源(15-1),(15-2) のそれぞれの一端(4
-1),(4-2) は一対の第１および第２の電極(3-1),(3-2)
にそれぞれ連結されている。また、それぞれの電源(15-
1),(15-2) の他端は接地(5-1),(5-2) されている。第２
の10kHz〜100KHz例えば50kHzの交番電圧が電源(17)即ち
より第３の電極(13-1), ・・・(13-n)に連結されてお
り、印加されている [0018] To further more equal potential distribution in the plasma reaction space, the alternating voltage independent two kinds of frequencies is adapted to be applied to the power supply system (40). First
The alternating voltage is a high frequency of 1 to 100 MHz, for example, 13.56 MHz, and is obtained from a pair of two power supplies (15-1), (15-2), that is, (15).
It reaches the matching boxes (16-1) and (16-2) made of LCR circuits. The phases of the matching boxes are adjusted by a phase adjuster (26) so that they can be supplied at 180 ° or 0 ° from each other. It has a symmetric or in-phase output, and has one end (4) of each of the power supplies (15-1) and (15-2).
-1) and (4-2) are a pair of first and second electrodes (3-1) and (3-2)
Respectively. In addition, each power supply (15-
The other ends of 1) and (15-2) are grounded (5-1) and (5-2). Second
10 kHz to 100 KHz, for example, an alternating voltage of 50 kHz is connected to the power supply (17), that is, the third electrodes (13-1),... (13-n), and is applied.
【００１９】 かくして：反応空間にプラズマ(8) が発生
する。排気系(25)は、圧力調整バルブ(21), タ−ボ分子
ポンプ(22), ロ−タリ−ポンプ(23)を経て不要気体を排
気する。 [0019] Thus: plasma (8) is generated in the reaction space. The exhaust system (25) exhausts unnecessary gas through a pressure adjusting valve (21), a turbo molecular pump (22), and a rotary pump (23).
【００２０】 これらの反応性気体は、反応空間(60)で0.
001 〜1.0torr 例えば0.05torrとした。 [0020] These reactive gases are added to the reaction space (60) in an amount of 0.1 mm.
001 to 1.0 torr For example, 0.05 torr.
【００２１】 かかる空間において、13.56MHzの周波数の
0.5 〜5KW(単位面積あたり0.03〜3W/cm2) 例えば1KW (
単位面積あたり0.6W/cm2の高エネルギ) の第１の高周波
電圧を加える。さらに第２の交番電圧による交流バイア
スの印加により、被形成面上には-200〜-600V(例えばそ
の出力は1KW)の負の自己バイアス電圧が印加されてお
り、この負の自己バイアス電圧により加速された反応性
気体を基体または部材表面上にスパッタしつつ成膜し、
かつ緻密な膜とすることができた。 In such a space, a frequency of 13.56 MHz
0.5 to 5KW (0.03 to 3W / cm 2 per unit area) 1KW (
A first high-frequency voltage of 0.6 W / cm 2 per unit area) is applied. Further, by applying an AC bias by the second alternating voltage, a negative self-bias voltage of -200 to -600 V (for example, the output is 1 KW) is applied on the surface to be formed. Forming a film while sputtering the accelerated reactive gas on the substrate or member surface,
In addition, a dense film could be obtained.
【００２２】 反応性気体は、例えばエチレンと水素の混
合気体とした。その割合はH2/C2H4＝1/4 〜4/1 とし、
代表的には1/1 である。また、C2F6等によりフッ素を添
加してもよい。 The reactive gas is, for example, a mixed gas of ethylene and hydrogen. The ratio is set to H 2 / C 2 H 4 = 1/4 ~4 / 1,
Typically, it is 1/1. Further, fluorine may be added by C 2 F 6 or the like.
【００２３】 次に回転導入端子(62)と適当な歯車（図示
せず）とを介してモーター(60)と連結された基体移動機
構(20)を用いて基体を横方向に移動させ、先に膜を形成
した表面が今度は第三の電極と接するようにした。これ
は、真空破壊をせずに行なったため不純物の混入が少な
くまた、スループットも高くできた。この後、表面を形
成したと同様に裏面も形成した。但し、裏面形成時は原
料ガス中にNF3 を混合して膜中に窒素を添加し、比抵抗
を下げた。エチレンに対するNF3 の比は1/1 である。本
実施例では窒素源としてNF3 を用いたがアンモニアでも
比抵抗に対する効果は同じである。但し、アンモニアの
場合は成膜速度がNF3 に比べて５〜１０分の１となる。 [0023] and then move the substrate using rotary introducing a suitable gear pin (62) through (not shown) and connected to the motor (60) a substrate transfer mechanism (20) laterally above The surface on which the film was formed was in contact with the third electrode. Since this was carried out without breaking in vacuum, the contamination with impurities was small and the throughput could be increased. Thereafter, the back surface was formed in the same manner as the front surface. However, when forming the back surface, NF 3 was mixed in the source gas and nitrogen was added to the film to lower the specific resistance. The ratio of NF 3 to ethylene is 1/1. In this example, NF 3 was used as the nitrogen source, but the effect on the specific resistance was the same for ammonia. However, if ammonia deposition rate is 1 5 to 10 minutes compared to NF 3.
【００２４】 基体または部材(1) の温度は〜150 ℃、代
表的には外部加熱をすることなく室温に保持させる。か
くして被形成面上の比抵抗は表面において１×1010Ωc
m、裏面において１×106 Ωcmを有し、有機樹脂上にも
密着させて成膜させ得る。可視光に対し、透光性のアモ
ルファス構造または結晶構造を有する水素と窒素が添加
された炭素または炭素を主成分とする被膜を0.1 〜８μ
ｍ例えば0.5 μｍ（平面部),１〜３μｍ（凸部）に生成
させた。成膜速度は100 〜1000Å／分を有していた。 The temperature to 150 DEG ° C. of substrate or member (1), typically is maintained at room temperature without external heating. Thus, the specific resistance on the surface to be formed is 1 × 10 10 Ωc
m, having 1 × 10 6 Ωcm on the back surface, and can be formed in close contact with the organic resin to form a film. Hydrogen and nitrogen-added carbon having a transparent or amorphous structure or a crystal structure with respect to visible light, or a coating containing carbon as a main component is 0.1 to 8 μm.
m, for example, 0.5 μm (flat portion) and 1-3 μm (convex portion). The deposition rate was 100-1000 ° / min.
【００２５】 かくして部材であるフロントウインド、そ
の他の部材に炭素を主成分とする被膜、特に炭素中に水
素を30原子％以下含有するとともに、0.1 〜10原子% の
窒素が混入した炭素を形成させることができた。有機物
上に100 〜2000Åの厚さにエチレンのみによる第１の炭
素を設け、さらにその上に弗素と水素とが添加された炭
素を主成分とする被膜をも多層に形成させることができ
た。 [0025] Thus the windshield a member, other members in the film containing carbon as a main component, in particular with a hydrogen-containing 30 atomic% in the carbon to form a carbon 0.1-10 atomic% of nitrogen is mixed I was able to. A first carbon consisting of only ethylene was formed on the organic material to a thickness of 100 to 2000 mm, and a multilayer film mainly composed of carbon to which fluorine and hydrogen were added could be formed thereon.
【００２６】[0026]
【実施例２】この実施例は実施例１で用いた装置によ
り、第１図に示す如く、透光性有機物の部材要部上に炭
素を主成分とする膜を作製した例である。Embodiment 2 In this embodiment, as shown in FIG. 1, a film containing carbon as a main component is formed on a main part of a translucent organic material by the apparatus used in Embodiment 1.
【００２７】 第１図(A) において、自動車のフロントウ
インド(1) の縦断面図を示す。その横断面部を第１図
(B) に示す。 FIG . 1 (A) is a longitudinal sectional view of a front window (1) of an automobile. Fig. 1 shows the cross section.
See (B).
【００２８】 第１図(A),(B) において、この透光性プラ
スチックス(1) は軽量であり、例えばアクリル樹脂で設
けられている。その被形成面を有する基体または部材
(1) 上に炭素または炭素を主成分とする耐摩耗性の保護
膜(45)を0.1 〜８μｍの厚さに設けた。 In FIGS. 1 (A) and 1 (B), this translucent plastics (1) is lightweight, and is made of, for example, acrylic resin. Substrate or member having the surface to be formed
(1) An abrasion-resistant protective film (45) containing carbon or carbon as a main component was provided thereon with a thickness of 0.1 to 8 μm.
【００２９】 本発明において、特にこの炭素または窒素
が添加された炭素を主成分とする被膜は静電気の発生に
よるゴミの付着を防ぐため、その比抵抗は表面において
１×1010Ωcm、裏面において１×106 Ωcmを有したもの
である。 In the present invention, in particular, the coating mainly composed of carbon to which carbon or nitrogen is added has a specific resistance of 1 × 10 10 Ωcm on the front surface and 1 on the rear surface in order to prevent adhesion of dust due to generation of static electricity. × 10 6 Ωcm.
【００３０】[0030]
【発明の効果】本発明は無機ガラス、有機物のいずれの
透光性材料に対しても有効であり、特にその上面を水は
けのよい弗素が添加されたビッカ−ス硬度600 〜3000Kg
/cm2の炭素を主成分とする被膜、またはビッカ−ス硬度
が1000〜7000Kg/cm2の炭素( 水素も添加されている) の
多層膜を有機物上に密着させてコ−トした。その結果、
風雨に曝され、またほこりを伴う風切りの多い凸部によ
り厚く耐摩耗性膜として形成することができた。The present invention is effective for both inorganic glass and organic light-transmitting materials, and particularly has a Vickers hardness of 600 to 3000 Kg to which the upper surface is added with well-drainable fluorine.
A coating containing carbon / cm 2 as a main component or a multilayer film of carbon (to which hydrogen is also added) having a Vickers hardness of 1000 to 7000 kg / cm 2 was adhered onto an organic material and coated. as a result,
It was exposed to the wind and rain, and it was possible to form a thick and wear-resistant film due to the protruding portions with many dusts accompanied by dust.
【００３１】 これまでの自動車、ビル等のフロントウイ
ンドは晴天時ほこりがきわめてつきやすかった。しかし
本発明により、その表面に絶縁性のほこりの衝突によっ
て生ずる静電気の発生およびそれに伴うほこりの付着を
軽減することができた。 Conventionally , the front windows of automobiles, buildings, and the like have been extremely susceptible to dust in fine weather. However, according to the present invention, it was possible to reduce the generation of static electricity caused by the impact of insulating dust on the surface and the accompanying dust adhesion.
【００３２】 以上に示す如く、透光性の風切りまたほこ
りの付着を防ぐ窓に特に透光の遮光もＤＬＣの光学的エ
ネルギバンド巾を制御することにより可能であり、無機
ガラスまたは有機物において耐熱性を有さない有機物上
にも密着させ得ることはこれまで柔らかいためまったく
使えなかったプラスチック製ウインドを作ることの可能
性を実現したことで有効である。 As described above, a light-transmitting window, especially for preventing dust from adhering, can be shielded from light by controlling the optical energy bandwidth of the DLC. It is effective to be able to adhere to an organic material that does not have a plastic window by realizing the possibility of making a plastic window that could not be used at all because of its softness.
【００３３】 以上の説明より明らかな如く、本発明は有
機樹脂またはこれらの多層膜をコ−ティングして設けた
ものに特に有効である。この複合体は、他の多くの実施
例にみられる如く、その応用ははかりしれないものであ
り、特にこの炭素が150 ℃以下の低温で形成でき、この
ため下地の塗装面の有機物の変成による色調も変わら
ず、その硬度また基体または部材に対する密着性がきわ
めて優れているのが特徴である。 As is apparent from the above description, the present invention is particularly effective for those provided with a coating of an organic resin or a multilayer film thereof. This composite, as seen in many other embodiments, is of immeasurable application, especially when the carbon can be formed at low temperatures below 150 ° C., and therefore, due to the transformation of organic matter on the underlying painted surface. The feature is that the color tone does not change, and its hardness and adhesion to a substrate or a member are extremely excellent.
【第１図】本発明のフロントウインド等の部材上への炭
素膜または炭素を主成分とした保護膜をコートした例お
よびその要部を示す。FIG. 1 shows an example in which a carbon film or a protective film containing carbon as a main component is coated on a member such as a front window of the present invention, and an essential part thereof.
【第２図】本発明のプラズマＣＶＤ 装置の製造装置の
概要を示す。FIG. 2 shows an outline of an apparatus for manufacturing a plasma CVD apparatus of the present invention.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/00 - 31/36 C23C 14/00 - 14/58 C23C 16/00 - 16/56 C30B 29/04 ──────────────────────────────────────────────────の Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) C01B 31/00-31/36 C23C 14/00-14/58 C23C 16/00-16/56 C30B 29 / 04
Claims (7)
膜で覆われた絶縁性を有する部材であって、前記部材の
一方の面を覆う炭素膜または炭素を主成分とする膜の窒
素濃度は、前記部材の他方の面を覆う炭素膜または炭素
を主成分とする膜の窒素濃度より低いことを特徴とする
部材。 An insulating member covered on both sides with a carbon film or a film containing carbon as a main component.
Nitrogen on a carbon film or a carbon-based film covering one surface
The elemental concentration is determined by a carbon film or carbon covering the other surface of the member.
It is characterized by being lower than the nitrogen concentration of the film containing
Element.
膜で覆われた絶縁性を有する部材であって、前記部材の
一方の面を覆う炭素膜または炭素を主成分とする膜は、
前記部材の他方の面を覆う炭素膜または炭素を主成分と
する膜より硬いことを特徴とする部材。 2. An insulating member having both surfaces covered with a carbon film or a film containing carbon as a main component, the member having an insulating property .
A carbon film covering one surface or a film containing carbon as a main component is
A carbon film or carbon covering the other surface of the member as a main component
A member characterized by being harder than a film to be formed.
膜で覆われた絶縁性を有する部材であって、前記部材の
一方の面を覆う炭素膜または炭素を主成分とする膜は、
前記部材の他方の面を覆う炭素膜または炭素を主成分と
する膜より固有抵抗が大きいことを特徴とする部材。 3. An insulating member covered on both sides with a carbon film or a film containing carbon as a main component.
A carbon film covering one surface or a film containing carbon as a main component is
A carbon film or carbon covering the other surface of the member as a main component
A member characterized by having a higher specific resistance than a film to be formed.
一方の面を覆う炭素膜または炭素を主成分とする膜の窒
素濃度は、前記部材の他方の面を覆う炭素膜または炭素
を主成分とする膜の窒素濃度より低いことを特徴とする
部材。 4. The member according to claim 2, wherein
Nitrogen on a carbon film or a carbon-based film covering one surface
The elemental concentration is determined by a carbon film or carbon covering the other surface of the member.
It is characterized by being lower than the nitrogen concentration of the film containing
Element.
前記他方の面を覆う炭素膜または炭素を主成分とする膜
の窒素の濃度は０．１原子％以上であることを特徴とす
る炭素膜で覆われた部材。 5. according to any one of claims 1 to 4,
A member covered with a carbon film, wherein the concentration of nitrogen in the carbon film or the film containing carbon as a main component covering the other surface is 0.1 atomic% or more.
前記部材の両面の少なくとも一方が曲面であることを特
徴とする部材。6. The method according to claim 1, wherein
A member characterized in that at least one of both surfaces of the member is a curved surface.
前記部材は風雨に曝され得る自動車、オ−トバイ、自転
車、船舶、電車、航空機のフロントウインド、リアウイ
ンド、サイドミラ−、もしくはサイドウインド、ヘルメ
ットバイザー、スキー用ゴーグル、ブラウン管用ビデオ
フィルター、又はビルもしくは家屋等の採光用窓に用い
られていることを特徴とする部材。 7. A any one of claims 1 to 6,
The member may be exposed to the weather, such as automobiles, motorcycles, bicycles, ships, trains, aircraft front windows, rear windows, side mirrors, or side windows, helmet visors, ski goggles, video filters for cathode ray tubes, or buildings or Used for lighting windows in houses
A member characterized by being made .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41869390A JP3150712B2 (en) | 1990-12-31 | 1990-12-31 | Member covered with carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41869390A JP3150712B2 (en) | 1990-12-31 | 1990-12-31 | Member covered with carbon film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000166852A Division JP3165423B2 (en) | 1990-12-31 | 2000-06-02 | Member covered with carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04272178A JPH04272178A (en) | 1992-09-28 |
| JP3150712B2 true JP3150712B2 (en) | 2001-03-26 |
Family
ID=18526487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41869390A Expired - Fee Related JP3150712B2 (en) | 1990-12-31 | 1990-12-31 | Member covered with carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3150712B2 (en) |
-
1990
- 1990-12-31 JP JP41869390A patent/JP3150712B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04272178A (en) | 1992-09-28 |
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