JP3205363B2 - Mold with diamond-like protective film - Google Patents
Mold with diamond-like protective filmInfo
- Publication number
- JP3205363B2 JP3205363B2 JP30826191A JP30826191A JP3205363B2 JP 3205363 B2 JP3205363 B2 JP 3205363B2 JP 30826191 A JP30826191 A JP 30826191A JP 30826191 A JP30826191 A JP 30826191A JP 3205363 B2 JP3205363 B2 JP 3205363B2
- Authority
- JP
- Japan
- Prior art keywords
- mold
- diamond
- intermediate layer
- thin film
- hardness
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/37—Mould cavity walls, i.e. the inner surface forming the mould cavity, e.g. linings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2883/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as mould material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2907/00—Use of elements other than metals as mould material
- B29K2907/04—Carbon
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ダイヤモンド様薄膜で
保護した金型に関し、安価な鋼鉄を使用した高性能金型
とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold protected by a diamond-like thin film, and more particularly to a high-performance mold using inexpensive steel and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】従来、ガラスやプラスチックの射出成
形、押出成形、圧縮成形等の成形用または加工用金型
は、超硬質材料から製造されている。しかしこのような
材料は高価であり、手配及び製造に時間と費用が掛か
る。また靭性に欠けるため割れ易い欠点がある。超硬質
材料の脆さと耐摩耗性を補うために金型表面のうち摩擦
面又は摺動面をダイヤモンド様薄膜被覆して保護膜を作
ることが特開平２−１５１６９、同２−２２０１２、同
２−１５１７０等により提案されているが、ダイヤモン
ド様薄膜は金型基体の表面への結合力が弱く、微結晶の
集まりであるため、外力の作用で金型表面から剥離し易
い問題があった。そのため保護被覆として耐食性、耐摩
耗性等が必要な用途において充分に効果を発揮出来な
い。2. Description of the Related Art Conventionally, molds for molding or processing such as injection molding, extrusion molding, compression molding and the like of glass and plastic have been manufactured from ultra-hard materials. However, such materials are expensive and require time and expense to arrange and manufacture. In addition, there is a disadvantage that it is easily broken due to lack of toughness. To compensate for the brittleness and wear resistance of super-hard materials, it is known to form a protective film by coating a frictional surface or a sliding surface of a mold surface with a diamond-like thin film. However, the diamond-like thin film has a problem in that the diamond-like thin film has a weak bonding force to the surface of the mold base and is a collection of microcrystals, and is easily peeled off from the mold surface by the action of an external force. Therefore, the effect cannot be sufficiently exerted in applications requiring corrosion resistance, wear resistance, etc. as a protective coating.
【０００３】一方焼入れ鋼は安価に入手出来、加工にも
手間と費用が余りかからないが、金型表面が摩耗し易く
寿命が短い欠点がある。この欠点を改良するには上記特
開平２−１５１６９、同２−２２０１２、同２−１５１
７０等に示されているような気相法によりダイヤモンド
様薄膜を被覆すると良いが、同じ理由から結合力が不十
分である。他の方法によるダイヤモンド様薄膜製造方法
には各種の形式がある（例えば「表面化学」第５巻第１
０８号（１９８４年）第１０８−１１５頁の各種の方法
参照）が、一般に、６００℃以上の高温度の基質温度が
必要であり、焼入れ鋼の焼鈍が生じて金型の硬度を損な
う問題がある。[0003] On the other hand, hardened steel is available at low cost and requires little labor and cost for processing, but has the disadvantage that the mold surface is easily worn and the life is short. In order to remedy this drawback, JP-A-2-15169, JP-A-2-22012, and JP-A-2-151
It is preferable to coat the diamond-like thin film by a gas phase method as shown in No. 70, etc., but the bonding force is insufficient for the same reason. There are various types of diamond-like thin film production methods by other methods (for example, “Surface Chemistry” Vol. 5, No. 1).
No. 08 (1984) pp. 108-115) generally requires a high substrate temperature of 600 ° C. or more, which causes the problem that the quenched steel is annealed and the hardness of the mold is impaired. is there.
【０００４】[0004]
【発明が解決すべき課題】本発明は安価な焼入れ鋼を使
用して、耐摩耗性の高い金型を製造することを目的とす
る。しかしこの焼入れ鋼は耐熱性が低く、又ダイヤモン
ド様薄膜に対する接着性に乏しいので工業的に耐摩耗性
のダイヤモンド様薄膜被覆金型を構成することが出来な
かった。特願平１−２１４９１３号には金属やセラミッ
ク等の保護のためにＡｒイオン等による基板ボンバード
とそれに続くイオン化蒸着法によるダイヤモンド成膜を
使用する技術が記載されているが、焼入れ鋼による金型
の製造への応用は開示していない。SUMMARY OF THE INVENTION An object of the present invention is to manufacture a mold having high wear resistance by using inexpensive hardened steel. However, this quenched steel has low heat resistance and poor adhesion to a diamond-like thin film, so that it was not possible to industrially form a wear-resistant diamond-like thin film-coated mold. Japanese Patent Application No. 1-214913 describes a technique of using a substrate bombard by Ar ions or the like and a subsequent diamond film formation by an ionization vapor deposition method to protect metals and ceramics. It does not disclose any application to the manufacture of.
【０００５】[0005]
【課題を解決するための手段】本発明は、ダイヤモンド
様薄膜との親和性の悪い金型表面に保護膜を有効に形成
することができる。すなわち、本発明は、炭化水素プラ
ズマから、金型の摩耗を受ける表面に、炭化水素プラズ
マに対して第１の負バイアス条件下に蒸着して得た、前
記表面よりも硬度が大きく且つ後記ダイヤモンド様薄膜
よりは硬度が小さい硬度Ｈｖ＝１０００〜５０００ｋｇ
／ｍｍ 2 の炭素膜中間層と、その上に炭化水素プラズマ
から、炭化水素プラズマに対してより大きい第２の負バ
イアス条件下に蒸着して得た硬度が前記中間層よりも大
きいダイヤモンド様薄膜とよりなる保護膜を有する金型
を提供する。 ここに、中間層はバイアス印加プラズマＣ
ＶＤ方またはイオンか蒸着法により形成することができ
る。好ましくは、本発明の中間層は金型からダイヤモン
ド様薄膜に向かって段階的または連続的に硬度が大きく
なる。本発明はまた、炭化水素ガスをプラズマ化し、金
型の摩耗を受ける表面に、前記表面よりも硬度が大きく
且つ後記ダイヤモンド様薄膜よりは硬度が小さい硬度Ｈ
ｖ＝１０００〜５０００ｋｇ／ｍｍ 2 の炭素膜中間層が
得られるように第１の負バイアス条件下に蒸着させ、次
いで前記中間層の上に前記負バイアス条件をより大きい
第２の負バイアス条件に変えて、より硬質であるダイヤ
モンド様薄膜を形成することを特徴とする金型の保護膜
形成方法を提供する。 本発明では、成膜時に負バイアス
蒸着条件を制御することによりプラズマ中の水素及び炭
素の正イオンを金型表面に蒸着して、前記金型表面より
も硬度が大きく且つ後記ダイヤモンド様薄膜よりは硬度
が小さい炭素中間層を成膜し、次いで原料炭化水素を変
更することなく且つ同じイオン化蒸着法を使用して負バ
イアス蒸着条件を変更しダイヤモンド様薄膜を成膜す
る。特に中間層は硬度が金型表面からダイヤモンド様薄
膜に向かって大きくなる様に中間層自体の成膜時にも階
段的または連続的な成膜条件の変更を実施することが好
ましい。 SUMMARY OF THE INVENTION The present invention can effectively form a protective film on affinity poor die table surface of a diamond-like carbon film. That is, the present invention
The surface that is subject to mold wear from the
Obtained by vapor deposition under the first negative bias condition for
Hardness greater than the surface and diamond-like thin film described later
Hardness Hv = 1000-5000 kg
/ Mm 2 carbon film intermediate layer and hydrocarbon plasma on it
From the larger second negative
Hardness obtained by evaporation under ias conditions is greater than that of the intermediate layer.
Mold with protective film consisting of diamond-like thin film
I will provide a. Here, the intermediate layer is a bias-applied plasma C
It can be formed by VD method or ion or vapor deposition method.
You. Preferably, the hardness of the intermediate layer of the present invention increases stepwise or continuously from the mold toward the diamond-like thin film. The present invention also provides a method for converting hydrocarbon gas into plasma,
The surface subjected to mold wear has a higher hardness than the surface
And hardness H which is lower than that of the diamond-like thin film described later
v = 1000-5000 kg / mm 2 carbon film intermediate layer
Deposited under a first negative bias condition to obtain
Then, the negative bias condition is increased on the intermediate layer.
In place of the second negative bias condition, a harder diamond
Mold protective film characterized by forming Monde-like thin film
A method of forming is provided. In the present invention, a negative bias is applied during film formation.
Hydrogen and carbon in plasma by controlling deposition conditions
Elemental positive ions are deposited on the mold surface,
Hardness is higher than that of diamond-like thin film
To form a carbon intermediate layer with small
Without any modification and using the same ionized deposition method.
Changing diamond deposition conditions to form diamond-like thin films
You. In particular, the intermediate layer has a diamond-like hardness from the mold surface.
During the deposition of the intermediate layer itself,
It is preferable to change the deposition conditions stepwise or continuously.
Good.
【０００６】本発明は、イオン化蒸着法の蒸着条件を制
御することにより、金型の表面に、前記金型よりも硬度
が大きく且つ後記ダイヤモンド様薄膜よりは硬度が小さ
い炭素中間層を成膜し、次いで原料炭化水素を変更する
ことなく且つ同じイオン化蒸着法を使用して成膜条件を
変更しダイヤモンド様薄膜を成膜することにより、保護
膜付き金型を提供する。特に中間層は硬度が金型表面か
らダイヤモンド様薄膜に向かって大きくなる様に中間層
自体の成膜時にも階段的または連続的な成膜条件の変更
を実施することが好ましい。According to the present invention, a carbon intermediate layer having a hardness higher than that of the mold and a hardness lower than that of a diamond-like thin film described later is formed on the surface of the mold by controlling the deposition conditions of the ionization vapor deposition method. Then, a metal mold with a protective film is provided by changing the film forming conditions without changing the raw material hydrocarbon and using the same ionization vapor deposition method to form a diamond-like thin film. In particular, it is preferable to change the film forming conditions stepwise or continuously even when forming the intermediate layer itself so that the hardness of the intermediate layer increases from the mold surface toward the diamond-like thin film.
【０００７】中間層を形成するための方法は、特開昭５
８−１７４５０７号及び特開平１−２３４３９６号に記
載されたイオン化蒸着法を使用する。この方法によれ
ば、中間層の成膜後に、その層を空気にさらすことな
く、あるいは作業自体を中断することなく条件をダイヤ
モンド様薄膜の成膜条件に変更することにより、次のダ
イヤモンド様薄膜の形成工程に移行することができる。
このため本発明の方法は作業性が極めてよい。なお、好
ましくはこの工程に先立って、成膜装置の真空室内に前
記金型を配置し、Ａｒ等のボンバード用ガスを前記真空
室内に導入し、熱陰極フィラメントとその周りに設けら
れた対陰極とよりなるイオン化手段により電離してイオ
ンの流れを形成し、これを前記対陰極よりも低電位にあ
るグリッドにより加速して金型の表面をボンバードして
活性化する前工程を採用してもよい。A method for forming an intermediate layer is disclosed in
The ionization deposition method described in JP-A-8-174507 and JP-A-1-234396 is used. According to this method, after the formation of the intermediate layer, the next diamond-like thin film can be formed by changing the conditions to the diamond-like thin film formation conditions without exposing the layer to air or without interrupting the operation itself. Can be shifted to the forming process.
For this reason, the method of the present invention has extremely good workability. Preferably, prior to this step, the mold is arranged in a vacuum chamber of a film forming apparatus, a bombarding gas such as Ar is introduced into the vacuum chamber, and a hot cathode filament and a cathode provided around the hot cathode filament are provided. The ionization means consisting of ionizing means to form a flow of ions, accelerated by a grid at a lower potential than the counter cathode, accelerated by bombarding the surface of the mold, and activated. Good.
【０００８】中間層は金型の硬度よりは大きく且つダイ
ヤモンド様薄膜の硬度よりは小さい一定の組成の膜でも
良いが、好ましくは金型表面側で低硬度、ダイヤモンド
側で高硬度にする。これにより結合性を改善することが
できる。中間層とダイヤモンド様薄膜の成膜は同一のイ
オン化蒸着装置を使用し、同一の原料を使用し、単に蒸
着条件を連続的または段階的に変化させるだけで良い。
中間層の膜厚は０．０２〜３μｍが好適であり、更に好
ましくは０．０５〜０．５μｍである。余り薄いと効果
がなく、余り厚過ぎても効果が飽和する。The intermediate layer may be a film having a constant composition larger than the hardness of the mold and smaller than the hardness of the diamond-like thin film. Preferably, the intermediate layer has a low hardness on the mold surface side and a high hardness on the diamond side. This can improve the connectivity. For forming the intermediate layer and the diamond-like thin film, the same ionized vapor deposition apparatus is used, the same raw material is used, and the vapor deposition conditions may be simply changed continuously or stepwise.
The thickness of the intermediate layer is preferably 0.02 to 3 μm, more preferably 0.05 to 0.5 μm. If it is too thin, there is no effect, and if it is too thick, the effect is saturated.
【０００９】ダイヤモンド様薄膜の硬度はイオン化蒸着
法によるとき約６０００ｋｇ／ｍｍ2 以上である。一方
基板になる金型の硬度は材質によって異なるが、通常は
２００〜３０００ｋｇ／ｍｍ2 である。したがって、中
間層の硬度を基板の材料とダイヤモンド様薄膜の中間の
硬度である１０００〜５０００ｋｇ／ｍｍ2 の範囲で選
択すれば良い。[0009] The hardness of the diamond-like thin film is about 6000 kg / mm 2 or more as measured by ionization vapor deposition. On the other hand, the hardness of the mold as the substrate varies depending on the material, but is usually 200 to 3000 kg / mm 2 . Therefore, the hardness of the intermediate layer may be selected in the range of 1000 to 5000 kg / mm 2 which is the intermediate hardness between the substrate material and the diamond-like thin film.
【００１０】イオン化蒸着法による中間層及びダイヤモ
ンド様薄膜の形成にあっては、炭化水素原料ガス又は分
解又は反応により炭化水素を生成し得る原料ガス（ここ
に炭化水素とはメタン、エタン、プロパン等の飽和炭化
水素、エチレン、プロピレン、アセチレン等の不飽和炭
化水素等があり、分解して炭化水素を生成し得る原料ガ
スはメチルアルコール、エチルアルコール等のアルコー
ル類、アセトン、メチルエチルケトン等のケトン類など
があり、又反応して炭化水素ガスを生成する原料ガスに
は一酸化炭素、二酸化炭素と水素との混合ガス等があ
る。また前記原料にはヘリウム、ネオン、アルゴン等の
希ガスあるいは水素、酸素、窒素、水、一酸化炭素、二
酸化炭素、等の少なくとも一種を含ませることができ
る）を熱陰極フィラメント−対陰極間のアーク放電、陰
極熱フィラメント−対陰極間の熱電子放出によるイオン
化等の手段でイオン化してイオン流とし、この流れを電
場で加速して金型に差し向けることにより中間層及びダ
イヤモンド様薄膜を成膜する方法であり、詳細は特開昭
５８−１７４５０７号及び特開平１−２３４３９６号に
記載されている。中間層はダイヤモンド様薄膜の成膜エ
ネルギーを下げることにより形成できる。In the formation of the intermediate layer and the diamond-like thin film by the ionization vapor deposition method, a hydrocarbon raw material gas or a raw material gas capable of generating hydrocarbon by decomposition or reaction (here, hydrocarbon means methane, ethane, propane, etc.) There are unsaturated hydrocarbons such as saturated hydrocarbons, ethylene, propylene, and acetylene, etc., and raw material gases that can be decomposed to produce hydrocarbons include alcohols such as methyl alcohol and ethyl alcohol, and ketones such as acetone and methyl ethyl ketone. The raw material gas which reacts to generate a hydrocarbon gas includes carbon monoxide, a mixed gas of carbon dioxide and hydrogen, etc. The raw material includes a rare gas such as helium, neon, argon or hydrogen, At least one of oxygen, nitrogen, water, carbon monoxide, carbon dioxide, etc.). (I) ionization by means such as arc discharge between the cathode and the cathode, ionization by thermionic emission between the cathode hot filament and the cathode, and the like, and the ion stream is accelerated by an electric field and directed to the mold to form an intermediate layer. And a method of forming a diamond-like thin film, the details of which are described in JP-A-58-174507 and JP-A-1-234396. The intermediate layer can be formed by lowering the film formation energy of the diamond-like thin film.
【００１１】第１図に特開昭５８−１７４５０７号に従
った成膜装置の好ましい例を示す。その他の公知のイオ
ン化蒸着装置を使用してもよいことはもちろんである。
図中３０は真空容器、３１はチャンバーであり、排気系
３８に接続されて１０-6Ｔｏｒｒ程度までの高真空に引
かれる。３２は金型Ｓの裏面に設けられ負の電位Ｖａに
保たれた基板電極である。金型Ｓの表面に近接又は接触
してダイヤモンド様薄膜の形状を規制する窓を有するマ
スク４２が設けられる。このマスクは金型に接していて
も良いが膜の周部の厚みを薄くして割れ（クラック）を
減じるためにはなるべくは離間させる。３３は金型と同
一の電位Ｖａを与えられたグリッドで成膜工程で炭化水
素イオンの加速を行なうのに使用される。このグリッド
３３は膜の連続性を高め且つ表面を平滑にするため適正
に定めた空間率（単位面積あたりの穴の面積）と穴密度
（単位長さあたりの穴の数）のグリッドを使用し、或い
はその面内方向に振動するための手段を有していても良
い。３４は負の電位Ｖｄに維持された熱陰極フィラメン
トであり、交流電源からの電流Ｉｆによって加熱されて
熱電子を発生する。３５は原料でガスの供給口であり、
３７はガス供給通路、３７’はプラズマ励起室である。
フィラメント３４を取囲んで陽極３６が配置されてい
る。この陽極はこの場合接地されているが、フィラメン
トに対しては正の電圧Ｖｄを有し、電極３２及びグリッ
ド３３に対しては正の電位Ｖａを与えられている。フィ
ラメント３４、陽極３６及び供給口３５の周りを取り囲
んでイオン化ガスの閉じ込め用の磁界を発生するために
電源Ｖｃからの電流Ｉｃで励磁される電磁コイル３９が
配置されている。従って、Ｉｆ、Ｖａ、Ｖｄ、コイルの
電流Ｉｃを調整することにより膜質を変えることができ
る。特にＶａ（基体電圧）及びＶｄ（熱陰極ー陽極間の
電位差）の制御が好ましい。このような成膜条件の制御
は、コンピュータによるプログラム制御により容易に実
行することができる。FIG. 1 shows a preferred example of a film forming apparatus according to JP-A-58-174507. Of course, other known ionized vapor deposition devices may be used.
In the figure, reference numeral 30 denotes a vacuum container, and 31 denotes a chamber, which is connected to an exhaust system 38 and is evacuated to a high vacuum of about 10 -6 Torr. Reference numeral 32 denotes a substrate electrode provided on the back surface of the mold S and maintained at a negative potential Va. A mask 42 having a window which regulates the shape of the diamond-like thin film in proximity to or in contact with the surface of the mold S is provided. This mask may be in contact with the mold, but should be separated as much as possible in order to reduce the thickness of the peripheral part of the film and reduce cracks. Reference numeral 33 denotes a grid to which the same potential Va as that of the mold is applied, which is used for accelerating hydrocarbon ions in a film forming process. This grid 33 uses a grid with an appropriately determined void ratio (area of holes per unit area) and hole density (number of holes per unit length) to increase the continuity of the film and smooth the surface. Alternatively, a means for vibrating in the in-plane direction may be provided. Numeral 34 denotes a hot cathode filament maintained at a negative potential Vd, which is heated by a current If from an AC power supply to generate thermoelectrons. 35 is a raw material gas supply port,
37 is a gas supply passage, and 37 'is a plasma excitation chamber.
An anode 36 is arranged around the filament 34. This anode is grounded in this case, but has a positive voltage Vd for the filament and a positive potential Va for the electrode 32 and the grid 33. An electromagnetic coil 39 energized by a current Ic from a power supply Vc is provided to surround the filament 34, the anode 36, and the supply port 35 to generate a magnetic field for confining the ionized gas. Therefore, the film quality can be changed by adjusting If, Va, Vd, and the current Ic of the coil. In particular, control of Va (substrate voltage) and Vd (potential difference between hot cathode and anode) is preferable. Such control of the film forming conditions can be easily performed by program control by a computer.
【００１２】成膜にあたり、チャンバー３１内を１０-6
Ｔｏｒｒまで高真空とし、ガス供給通路３７のバルブを
操作して所定流量の中間層成膜用のガス、またはダイヤ
モンド成膜用のガス、場合によりそれと水素との混合ガ
ス、或いはそれとＡｒ、Ｈｅ、Ｎｅ等のキャリアガス等
を各供給口３５から導入しながら排気系３８を調整して
所定のガス圧例えば１０-1Ｔｏｒｒとする。一方、複数
の熱陰極フイラメント３４には交流電流Ｉｆを流して加
熱し、フイラメント３４と陽極３６の間には電位差Ｖｄ
を印加して放電を形成する。供給口３５から供給された
原料ガスは熱分解されるとともにフィラメントからの熱
電子と衝突してプラスのイオンと電子を生じる。この電
子は別の熱分解粒子と衝突する。電磁コイルの磁界によ
る閉じ込め作用の下に、このような現象を繰り返すこと
によりメタンガスは熱分解物質のプラスイオンとなる。
プラスイオンは電極３２、グリッド３６に印加された負
電位Ｖａにより引き寄せられ、金型Ｓの方へ向けて加速
され、金型に衝突して成膜反応を行ない、ダイヤモンド
様薄膜を形成する。なお、各部の電位、電流、温度等の
条件については上に述べた条件の他、先に引用した特許
公報を参照されたい。In forming a film, the inside of the chamber 31 is 10 −6.
A high vacuum was applied to Torr, and a valve for the gas supply passage 37 was operated to operate a predetermined flow rate of a gas for forming an intermediate layer, a gas for forming a diamond, a mixed gas of hydrogen and gas, or Ar, He, The exhaust system 38 is adjusted while introducing a carrier gas such as Ne from each supply port 35 to a predetermined gas pressure, for example, 10 -1 Torr. On the other hand, the plurality of hot cathode filaments 34 are heated by passing an alternating current If, and a potential difference Vd is applied between the filaments 34 and the anode 36.
Is applied to form a discharge. The raw material gas supplied from the supply port 35 is thermally decomposed and collides with thermoelectrons from the filament to generate positive ions and electrons. This electron collides with another pyrolysis particle. By repeating such a phenomenon under the confinement effect of the magnetic field of the electromagnetic coil, methane gas becomes a positive ion of a pyrolysis substance.
The positive ions are attracted by the negative potential Va applied to the electrode 32 and the grid 36, accelerated toward the mold S, collide with the mold and perform a film forming reaction, thereby forming a diamond-like thin film. For the conditions such as the potential, current, and temperature of each part, refer to the above-mentioned patent publications in addition to the above-mentioned conditions.
【００１３】以下に本発明を例示する。Hereinafter, the present invention will be exemplified.
【実施例の説明】イオン化蒸着法を用い、ＳＫＤ１１及
びＳＫＳ２よりなる焼入れ鋼金型上に表１に示す条件で
中間層を成膜し、次いで表１の条件でダイヤモンド様薄
膜を成膜した。フィラメント３４はコイル状としその幅
３ｍｍ、その周りを取り囲む電極３６との隙間８ｍｍと
した。グリッド３３は５ｍｍ／分の速度で振動させた。
フィラメント電流Ｉｆ＝２５Ａ、フィラメント電圧Ｖｄ
可変、基体電圧Ｖａ可変、電磁コイルの磁束密度３００
Ｇの条件で、ＣＨ4 を導入し、各種膜厚の中間層、次い
で膜厚３．０μｍのダイヤモンド様薄膜を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS An intermediate layer was formed on a hardened steel mold made of SKD11 and SKS2 under the conditions shown in Table 1, and then a diamond-like thin film was formed under the conditions shown in Table 1 by ionization deposition. The filament 34 was coil-shaped and had a width of 3 mm and a gap of 8 mm with the electrode 36 surrounding the filament. The grid 33 was vibrated at a speed of 5 mm / min.
Filament current If = 25A, filament voltage Vd
Variable, variable substrate voltage Va, magnetic flux density of electromagnetic coil 300
Under the conditions of G, CH 4 was introduced to obtain intermediate layers having various thicknesses, and then a diamond-like thin film having a thickness of 3.0 μm.
【００１４】[0014]
【表１】 [Table 1]
【００１５】得られた保護膜付き金型の保護膜の特性は
表２に示す通りであった。ただし密着力とスクラッチ力
の評価は次の通りであった。密着力は１ｃｍ角、長さ１
０ｃｍの角材をダイヤモンド様薄膜にエポキシ樹脂で接
着し、引張試験機（テンシロン−商品名）で引っ張って
剥離し測定を行なった。又スクラッチ力はＲｈｅｓｃａ
社製のＣＳＲ−０２試験機で測定した。いずれの値も表
２の第１行の値を基準とした相対値である。The characteristics of the protective film of the obtained mold with a protective film are as shown in Table 2. However, the evaluation of adhesion and scratching power was as follows. Adhesion is 1cm square, length 1
A square material of 0 cm was adhered to the diamond-like thin film with an epoxy resin, and pulled and peeled off by a tensile tester (Tensilon-trade name) to measure. The scratch force is Rhesca
It was measured with a CSR-02 tester manufactured by the company. Each value is a relative value based on the value in the first row of Table 2.
【００１６】[0016]
【表２】 [Table 2]
【００１７】更にＳＫＤ１１の焼入れ鋼を用いた金型の
直径２０ｍｍのフェライトコア成形時の耐用ショット数
を測定して表３の結果を得た。Further, the number of durable shots at the time of molding a ferrite core having a diameter of 20 mm in a mold using hardened steel of SKD11 was measured, and the results shown in Table 3 were obtained.
【００１８】[0018]
【表３】 [Table 3]
【００１９】[0019]
【発明の効果】本発明によると中間層を介在することに
よりダイヤモンド様薄膜を、通常では結合が困難な金型
に施すことが可能になり、かつ金型の耐摩耗性及び耐久
性を大幅に向上させることができる。According to the present invention, it is possible to apply a diamond-like thin film to a mold which is usually difficult to bond by interposing an intermediate layer, and to greatly improve the wear resistance and durability of the mold. Can be improved.
【図１】本発明に使用するイオン化蒸着装置の概要を示
す。FIG. 1 shows an outline of an ionization vapor deposition apparatus used in the present invention.
３０ 真空容器 ３１ チャンバー ３２ 負電極 ４２ マスク ３３ グリッド ３４ 熱陰極フィラメント ３５ 原料ガスの供給口 ３６ 陽極 ３７ ガス供給通路 ３７’ プラズマ励起室 Reference Signs List 30 vacuum vessel 31 chamber 32 negative electrode 42 mask 33 grid 34 hot cathode filament 35 source gas supply port 36 anode 37 gas supply passage 37 ′ plasma excitation chamber
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−201095（ＪＰ，Ａ) 特開 平２−15169（ＪＰ，Ａ) 特開 平２−22012（ＪＰ，Ａ) 特開 平２−15170（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-201095 (JP, A) JP-A-2-15169 (JP, A) JP-A-2-22012 (JP, A) JP-A-2-2 15170 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C30B 1/00-35/00
Claims (5)
ける表面に、炭化水素プラズマに対して第１の負バイア
ス条件下に蒸着して得た、前記表面よりも硬度が大きく
且つ後記ダイヤモンド様薄膜よりは硬度が小さい硬度Ｈ
ｖ＝１０００〜５０００ｋｇ／ｍｍ2 の炭素膜中間層
と、その上に炭化水素プラズマから、炭化水素プラズマ
に対してより大きい第２の負バイアス条件下に蒸着して
得た硬度が前記中間層よりも大きいダイヤモンド様薄膜
とよりなる保護膜を有する金型。 From 1. A hydrocarbon plasma to a surface subject to wear of the mold, a first negative bias with respect to hydrocarbon plasma
Hardness H, which is higher than the surface and lower than the diamond-like thin film described later , obtained by vapor deposition under
v = 1000 kg / mm 2 of carbon film intermediate layer, and a hydrocarbon plasma
Deposited under a second larger negative bias condition
Large diamond-like carbon film obtained hardness than the intermediate layer
Mold having become more protective film when.
またはイオンか蒸着法により形成されている請求項１に
記載の保護膜を有する金型。2. The mold having a protective film according to claim 1, wherein the intermediate layer is formed by a bias-applied plasma CVD method or an ion or vapor deposition method.
向かって段階的または連続的に硬度が大きくなる請求項
１または２に記載の保護膜を有する金型。3. The mold having a protective film according to claim 1, wherein the hardness of the intermediate layer increases stepwise or continuously from the mold toward the diamond-like thin film.
る請求項１〜３のいずれかに記載の保護膜を有する金
型。4. The gold having a protective film according to claim 1, wherein the thickness of the intermediate layer is 0.2 to 3.0 μm.
Type .
耗を受ける表面に、前記表面よりも硬度が大きく且つ後
記ダイヤモンド様薄膜よりは硬度が小さい硬度Ｈｖ＝１
０００〜５０００ｋｇ／ｍｍ 2 の炭素膜中間層が得られ
るように第１の負バイアス条件下に蒸着させ、次いで前
記中間層の上に前記負バイアス条件をより大きい第２の
負バイアス条件に変えて、より硬質であるダイヤモンド
様薄膜を形成することを特徴とする金型の保護膜形成方
法。 5. The method according to claim 5, wherein the hydrocarbon gas is converted into plasma and the mold is polished.
The surface subjected to wear has a higher hardness and
Hardness Hv = 1, which is smaller than the diamond-like thin film
000-5000 kg / mm 2 carbon film intermediate layer is obtained
Deposited under a first negative bias condition such that
On said intermediate layer, said negative bias condition is
Harder diamonds with negative bias
Of forming a protective film on a mold characterized by forming a uniform thin film
Law.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30826191A JP3205363B2 (en) | 1991-10-29 | 1991-10-29 | Mold with diamond-like protective film |
| US08/209,573 US5707717A (en) | 1991-10-29 | 1994-03-10 | Articles having diamond-like protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30826191A JP3205363B2 (en) | 1991-10-29 | 1991-10-29 | Mold with diamond-like protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05117856A JPH05117856A (en) | 1993-05-14 |
| JP3205363B2 true JP3205363B2 (en) | 2001-09-04 |
Family
ID=17978883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30826191A Expired - Fee Related JP3205363B2 (en) | 1991-10-29 | 1991-10-29 | Mold with diamond-like protective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3205363B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6541406B1 (en) | 1999-11-15 | 2003-04-01 | Ngk Insulators, Ltd. | Silicon nitride sintered material and process for production thereof |
| US11286858B2 (en) | 2017-03-21 | 2022-03-29 | Toshiba Energy Systems & Solutions Corporation | Gas turbine combustor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60040365D1 (en) | 1999-07-08 | 2008-11-13 | Sumitomo Electric Industries | Hard coating and coated component |
| JP2001277251A (en) * | 2000-03-29 | 2001-10-09 | Bridgestone Corp | Thin film for molding mold, and mold |
| TWI230119B (en) * | 2002-10-17 | 2005-04-01 | Sumitomo Heavy Industries | Mold device and manufacturing method thereof, molding method, molded product and molding machine |
| JP4918656B2 (en) | 2005-12-21 | 2012-04-18 | 株式会社リケン | Amorphous hard carbon film |
-
1991
- 1991-10-29 JP JP30826191A patent/JP3205363B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6541406B1 (en) | 1999-11-15 | 2003-04-01 | Ngk Insulators, Ltd. | Silicon nitride sintered material and process for production thereof |
| US6667264B2 (en) | 1999-11-15 | 2003-12-23 | Kiyoshi Araki | Silicon nitride sintered material and process for production thereof |
| US11286858B2 (en) | 2017-03-21 | 2022-03-29 | Toshiba Energy Systems & Solutions Corporation | Gas turbine combustor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05117856A (en) | 1993-05-14 |
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