JPH0558067B2 - - Google Patents
Info
- Publication number
- JPH0558067B2 JPH0558067B2 JP60272252A JP27225285A JPH0558067B2 JP H0558067 B2 JPH0558067 B2 JP H0558067B2 JP 60272252 A JP60272252 A JP 60272252A JP 27225285 A JP27225285 A JP 27225285A JP H0558067 B2 JPH0558067 B2 JP H0558067B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- diamond
- adhesion
- outer layer
- substrate
- 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 - Lifetime
Links
- 239000010432 diamond Substances 0.000 claims description 64
- 229910003460 diamond Inorganic materials 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 230000003014 reinforcing effect Effects 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 230000000737 periodic effect Effects 0.000 claims description 16
- 150000004767 nitrides Chemical class 0.000 claims description 10
- 239000006104 solid solution Substances 0.000 claims description 10
- 150000001247 metal acetylides Chemical class 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 120
- 239000011247 coating layer Substances 0.000 description 36
- 239000000758 substrate Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- -1 iron group metals Chemical class 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011817 metal compound particle Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、切削工具、耐摩耗工具又は研削工具
などの工具部材並びに半導体レーザ又はダイオー
ドなどのヒートシンク及びスピーカ用振動板に代
表されるエレクトロニクス用部材に応用できるダ
イヤモンド被覆部材に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention is applicable to tool members such as cutting tools, wear-resistant tools, or grinding tools, and to electronics such as heat sinks such as semiconductor lasers or diodes, and diaphragms for speakers. The present invention relates to a diamond-coated member that can be applied to members.
（従来の技術）
気相からダイヤモンドを合成する方法が多数提
案されており、これらの方法によつて、各種の基
体の表面にダイヤモンドの被覆層を形成してなる
ダイヤモンド被覆部材も提案されている。(Prior Art) Many methods have been proposed for synthesizing diamond from a gas phase, and diamond-coated members formed by forming diamond coating layers on the surfaces of various substrates using these methods have also been proposed. .
ダイヤモンドの被覆層を基体の表面に形成する
場合、特に、気相合成法では、被覆層の形成と同
時にカーボンも析出して、被覆層中に軟質なアモ
ルフアス状カーボン又はグラフアイトが混在する
傾向にある。このために、例えば、超硬合金やサ
ーメツトのような鉄族金属を含む基体の表面にダ
イヤモンドの被覆層を形成すると被覆層中に混在
するカーボンが基体の鉄族金属と反応して、基体
内部に固溶拡散し遊離カーボンを生じさせるため
に、基体の強度低下及び基体と被覆層との密着性
を低下させるという問題がある。また、基体の表
面に鉄族金属が存在すると、この鉄族金属が気相
合成法のための供給炭化水素ガスの分解の触媒と
して作用するのと、又は、ダイヤモンド合成法の
ための供給水素ガスを吸収するために被覆層の質
を低下させるという問題がある。 When forming a diamond coating layer on the surface of a substrate, especially in the vapor phase synthesis method, carbon also precipitates at the same time as the coating layer is formed, and soft amorphous carbon or graphite tends to be mixed in the coating layer. be. For this reason, for example, when a diamond coating layer is formed on the surface of a substrate containing an iron group metal such as cemented carbide or cermet, the carbon mixed in the coating layer reacts with the iron group metal of the substrate, causing the inside of the substrate to Since free carbon is produced by solid solution diffusion into the carbon, there are problems in that the strength of the substrate and the adhesion between the substrate and the coating layer are reduced. In addition, when iron group metals are present on the surface of the substrate, this iron group metal acts as a catalyst for the decomposition of the hydrocarbon gas supplied for the vapor phase synthesis method, or the hydrogen gas supplied for the diamond synthesis method. There is a problem that the quality of the coating layer is deteriorated due to the absorption of .
このような問題点を解決しようと試みたものに
特開昭58−126972号公報がある。この特開昭58−
126972号公報は、超硬合金の表面に4a、5a、6a
族元素の炭化物、窒化物、ホウ化物、酸化物及び
これらの化合物、混合物並びにAl2O3、AlN、
B4C、SiC、Si3N4、SiO2から選ばれた１種以上
の内層を形成した後、更に内層の表面にダイヤモ
ンドの外層を形成するダイヤモンド被覆超硬合金
である。この特開昭58−126972号公報は、超硬合
金と外層との間に内層を形成することによつて、
超硬合金の表面に存在する鉄族金属の影響を除去
したものである。しかしながら、共有結合で、他
の物質と殆んど反応しないダイヤモンドからなる
外層が内層の表面に形成されているために、内層
と外層との密着性が悪く、非常に低い応力でもつ
て外層が剥離し、実用化できないという問題があ
る。 Japanese Unexamined Patent Application Publication No. 126972/1983 is an attempt to solve these problems. This JP-A-58-
Publication No. 126972 discloses 4a, 5a, 6a on the surface of cemented carbide.
Group element carbides, nitrides, borides, oxides, and compounds and mixtures thereof, as well as Al 2 O 3 , AlN,
This is a diamond-coated cemented carbide in which an inner layer of one or more selected from B 4 C, SiC, Si 3 N 4 and SiO 2 is formed, and then an outer layer of diamond is formed on the surface of the inner layer. This Japanese Patent Application Laid-open No. 58-126972 discloses that by forming an inner layer between the cemented carbide and the outer layer,
This removes the effects of iron group metals present on the surface of cemented carbide. However, because an outer layer made of diamond, which is covalently bonded and hardly reacts with other substances, is formed on the surface of the inner layer, the adhesion between the inner layer and the outer layer is poor, and the outer layer peels off even with very low stress. However, there is a problem that it cannot be put into practical use.
このような、問題点を、更に解決しようと試み
たものに特開昭59−93869号公報がある。 Japanese Patent Laid-Open No. 59-93869 is an attempt to further solve these problems.
（発明が解決しようとする問題点）
特開昭59−93869号公報は、被膜の30体積％〜
95体積％をダイヤモンドもしくはダイヤモンド状
の相が占め、残部を鉄族金属又は無機硬質金属化
合物が占めたダイヤモンドを含有する硬質被膜で
母材表面を被覆した構造物である。この特開昭59
−93869号公報に開示の構造物は、他の物質と殆
んど反応しないダイヤモンドを鉄族金属又は無機
硬質金属化合物と混合又は分散させてなる被覆層
にすることにより、ダイヤモンド粒子を保持する
面積が増大して被覆層中のダイヤモンド粒子と母
材との密着性を高めているものと思われる。しか
しながら、鉄族金属を含有したダイヤモンド被覆
層は、前述したように、鉄族金属の影響で被覆層
中にアモルフアス状カーボンが混在して被覆層の
強度及び硬度などの諸特性を低下させるという問
題がある。また、無機硬質金属化合物とダイヤモ
ンドとの被覆層は、無機硬質金属化合物粒子とダ
イヤモンド粒子との混合物であつて、これらの各
粒子間の密着性が悪いのと、又は無機硬質金属化
合物粒子とダイヤモンド粒子との間に気孔が生じ
るために被覆層内強度が低いという問題がある。(Problems to be solved by the invention) JP-A-59-93869 discloses that 30% by volume of the coating
It is a structure in which the surface of the base material is coated with a diamond-containing hard coating in which 95% by volume is diamond or a diamond-like phase and the remainder is an iron group metal or an inorganic hard metal compound. This JP-A-59
The structure disclosed in Publication No. 93869 has an area that holds diamond particles by forming a coating layer in which diamond, which hardly reacts with other substances, is mixed or dispersed with an iron group metal or an inorganic hard metal compound. It is thought that this increases the adhesion between the diamond particles in the coating layer and the base material. However, as mentioned above, diamond coating layers containing iron group metals have the problem that amorphous carbon is mixed in the coating layer due to the influence of iron group metals, reducing various properties such as strength and hardness of the coating layer. There is. In addition, the coating layer of an inorganic hard metal compound and diamond is a mixture of inorganic hard metal compound particles and diamond particles, and the adhesion between these particles is poor, or the inorganic hard metal compound particles and diamond are a mixture of inorganic hard metal compound particles and diamond particles. There is a problem in that the strength within the coating layer is low due to the formation of pores between the particles.
本発明は、上述のような問題点を解決したもの
で、具体的には、基体とダイヤモンドの外層との
間に、ダイヤモンドの外層を形成しやすく、しか
も、外層との密着性がすぐれる中間層を介在させ
てなるダイヤモンド被覆部材の提供を目的とする
ものである。 The present invention solves the above-mentioned problems. Specifically, the present invention provides an intermediate layer that is easy to form an outer layer of diamond between the substrate and the outer layer of diamond, and has excellent adhesion to the outer layer. The object of the present invention is to provide a diamond-coated member having a layer interposed therebetween.
（問題点を解決するための手段）
一般に、ダイヤモンドは、他の物質との濡れ性
が著しく悪いこと、熱膨張率が小さいこと、及び
ダイヤモンド中への他原子の拡散が少ないことか
ら基体の表面に密着性の高いダイヤモンド及び／
又はダイヤモンド状カーボンからなる被覆層を形
成するのが非常に困難である。そこで、本発明者
は、ダイヤモンド及び／又はダイヤモンド状カー
ボンからなる被覆層の形成しやすい物質並びにダ
イヤモンド及び／又はダイヤモンド状カーボンか
らなる被覆層の密着性を高める物質について検討
していた所、周期律表4a、5a、6a族の金属又は
Siの中の少なくとも１種と周期律表4a、5a、6a
族の金属又はSiの炭化物、窒化物及びこれらの相
互固溶体の中の少なくとも１種とダイヤモンド及
び／又はダイヤモンド状カーボンからなる物質の
表面には、ダイヤモンド及び／又はダイヤモンド
状カーボンからなる被覆層が形成しやすくなるこ
と並びに密着性もすぐれているという知見を得
て、本発明を完成するに至つたものである。(Means for solving the problem) In general, diamond has extremely poor wettability with other substances, has a small coefficient of thermal expansion, and has low diffusion of other atoms into diamond, so it is difficult to Diamonds with high adhesion to
Alternatively, it is very difficult to form a coating layer made of diamond-like carbon. Therefore, the inventor of the present invention was considering a substance that facilitates the formation of a coating layer made of diamond and/or diamond-like carbon, and a substance that enhances the adhesion of a coating layer made of diamond and/or diamond-like carbon. Table 4a, 5a, 6a metals or
At least one type of Si and periodic table 4a, 5a, 6a
A coating layer made of diamond and/or diamond-like carbon is formed on the surface of a substance made of diamond and/or diamond-like carbon and at least one of group metals or Si carbides, nitrides, and mutual solid solutions thereof. The present invention was completed based on the knowledge that it is easier to apply and has excellent adhesion.
すなわち、本発明のダイヤモンド被覆部材は、
基体の表面にダイヤモンド及び／又はダイヤモン
ド状カーボンでなる外層を形成する被覆部材にお
いて、前記基体と前記外層との間に１層又は多層
で構成される中間層を介在させ、前記外層に隣接
する該中間層が周期律表4a、5a、6a族の金属又
はSiの中の少なくとも１種と周期律表4a、5a、
6a族の金属又はSiの炭化物、窒化物及びこれらの
相互固溶体の中の少なくとも１種とダイヤモンド
及び／又はダイヤモンド状カーボンでなる密着強
化層によつて形成されていることを特徴とする。 That is, the diamond-coated member of the present invention is
In a coating member in which an outer layer made of diamond and/or diamond-like carbon is formed on the surface of a substrate, an intermediate layer composed of one layer or multiple layers is interposed between the substrate and the outer layer, and a layer adjacent to the outer layer is provided. The intermediate layer is at least one metal of group 4a, 5a, 6a of the periodic table or Si and 4a, 5a of the periodic table,
It is characterized by being formed by an adhesion-enhancing layer made of at least one of group 6a metals or Si carbides, nitrides, and mutual solid solutions thereof, and diamond and/or diamond-like carbon.
ここで用いる基体は、後述する製造条件に耐え
ることが可能な材質ならば特別に制限されるもの
でなく、例えば、各種の金属、合金、焼結ハイ
ス、超硬合金、サーメツト又はセラミツクスなど
を用途によつて使い分けることができる。 The substrate used here is not particularly limited as long as it can withstand the manufacturing conditions described below, and examples include various metals, alloys, sintered high speed steel, cemented carbide, cermets, and ceramics. Can be used depending on.
これらの基体と外層との間に介在させる中間層
は、外層に隣接する中間層が密着強化層により形
成されていることを特徴とするもので、使用する
基体の材質又は本発明のダイヤモンド被覆部材の
用途もしくは形状により各種の構成にすることが
できる。 The intermediate layer interposed between these substrates and the outer layer is characterized in that the intermediate layer adjacent to the outer layer is formed of an adhesion reinforcing layer, and is characterized by the fact that the intermediate layer adjacent to the outer layer is formed of an adhesion reinforcing layer, and the intermediate layer is formed by the material of the substrate used or the diamond-coated member of the present invention. Various configurations can be made depending on the purpose or shape.
例えば、第１の構成としては、外層に隣接する
中間層が周期律表4a、5a、6a族の金属又はSiの
中の少なくとも１種と周期律表4a、5a、6a族の
金属又はSiの炭化物、窒化物及びこれらの相互固
溶体の中の少なくとも１種とダイヤモンド及び／
又はダイヤモンド状カーボンとでなる密着強化層
により形成されているものである。この場合は、
基体と外層との間に密着強化層が介在しているも
のである。この密着強化層は、周期律表4a、5a、
6a族の金属又はSiの中の少なくとも１種と周期律
表4a、5a、6a族の金属又はSiの炭化物、窒化物
及びこれらの相互固溶体の中の少なくとも１種と
ダイヤモンド及び／又はダイヤモンド状カーボン
とでなる混合物であつても、密着強化層と外層と
の密着性の効果及び外層の合成を促進する効果に
すぐれているが、特に、密着強化層中にダイヤモ
ンド型構造を含有している場合には、それらの効
果が一層すぐれると共に密着強化層の強度を高め
るので好ましいものである。この第１の構成でな
る中間層の場合は、密着強化層との密着性にすぐ
れる基体、例えば、各種のセラミツクスでなる基
体に適用することができる。 For example, in the first configuration, the intermediate layer adjacent to the outer layer is made of at least one metal of groups 4a, 5a, or 6a of the periodic table or Si and a metal of groups 4a, 5a, or 6a of the periodic table or Si. At least one of carbides, nitrides and mutual solid solutions thereof, diamond and/or
Alternatively, it is formed by an adhesion reinforcing layer made of diamond-like carbon. in this case,
An adhesion reinforcing layer is interposed between the base and the outer layer. This adhesion reinforcing layer is based on periodic table 4a, 5a,
At least one metal of Group 6a or Si, at least one of carbides, nitrides of metals of Groups 4a, 5a, or 6a of the periodic table or Si, and mutual solid solutions thereof, and diamond and/or diamond-like carbon. Even if it is a mixture of This is preferable because these effects are even better and the strength of the adhesion reinforcing layer is increased. The intermediate layer having the first configuration can be applied to a substrate having excellent adhesion to the adhesion reinforcing layer, for example, a substrate made of various ceramics.
第２の構成としては、中間層が外層に隣接する
密着強化層と密着強化層に隣接する密着補助層と
からななり、この密着強化層が周期律表4a、5a、
6a族の金属又はSiの炭化物、窒化物、ホウ化物及
びこれらの相互固溶体の中の少なくとも１種から
なるものである。この場合は、基体と外層との間
に密着強化層と密着補助層が介在し、基体に密着
補助層が隣接し、外層に密着強化層が隣接してい
るもので、密着補助層との密着性にすぐれている
基体、例えば、SiC系セラミツクス、Si3N4系セ
ラミツクス、TiC系セラミツクス、超硬合金、サ
ーメツト又は各種の工具鋼もしくは非鉄金属材料
などの基体に適用すると、外層のすぐれた特性を
発揮することができる。特に、密着強化層と密着
補助層とに同一元素を含有している場合、例え
ば、密着強化層中にTiを含有し、密着補助層中
にTiC、TiN、TiCN又はTiB2を含有している
と、更に、密着性から好ましいものである。 In the second configuration, the intermediate layer is composed of an adhesion reinforcing layer adjacent to the outer layer and an adhesion auxiliary layer adjacent to the adhesion reinforcing layer, and this adhesion reinforcing layer is composed of the periodic table 4a, 5a,
It is made of at least one of carbides, nitrides, borides, and mutual solid solutions of metals of Group 6a or Si. In this case, an adhesion reinforcing layer and an adhesion auxiliary layer are interposed between the base and the outer layer, the adhesion auxiliary layer is adjacent to the base, and the adhesion reinforcement layer is adjacent to the outer layer. When applied to substrates with excellent properties, such as SiC ceramics, Si 3 N 4 ceramics, TiC ceramics, cemented carbide, cermets, or various tool steels or non-ferrous metal materials, the outer layer has excellent properties. can demonstrate. In particular, when the adhesion-strengthening layer and the adhesion-assisting layer contain the same element, for example, the adhesion-strengthening layer contains Ti, and the adhesion-assisting layer contains TiC, TiN, TiCN, or TiB2 . Furthermore, it is preferable from the viewpoint of adhesion.
その他の中間層の構成としては、中間層が密着
強化層と金属層とでなる場合又は密着強化層と密
着補助層との金属層とからなる場合など各種の構
成にすることができる。この場合は、ガラス、鉄
族金属材料又は非鉄金属材料などの基体の表面
に、例えば、Fe、Ni、Co、Cu、Ti、Taなどの
金属層を形成して、この金属層の表面に密着強化
層又は密着補助層を形成することができる。 Other configurations of the intermediate layer may include various configurations, such as a case where the intermediate layer is composed of an adhesion reinforcing layer and a metal layer, or a case where the intermediate layer is composed of a metal layer of an adhesion reinforcing layer and an adhesion auxiliary layer. In this case, a metal layer such as Fe, Ni, Co, Cu, Ti, Ta, etc. is formed on the surface of the substrate such as glass, ferrous metal material or non-ferrous metal material, and the layer is tightly adhered to the surface of this metal layer. A reinforcing layer or adhesion auxiliary layer can be formed.
これらの中間層の厚さは、外層の合成の促進性
及び外層と基体との密着性の媒介的作用が可能
で、しかも強度低下の生じない50Å〜10μｍ厚さ
が好ましく、特に、密着強化層の厚さは50Å〜
5μｍが好ましい。 The thickness of these intermediate layers is preferably 50 Å to 10 μm, which is capable of promoting the synthesis of the outer layer and mediating the adhesion between the outer layer and the substrate, and does not cause a decrease in strength. The thickness is 50Å~
5 μm is preferred.
これらの中間層の表面に形成する外層は、ダイ
ヤモンド及び／又はダイヤモンド状カーボンから
なり、その厚さは、ダイヤモンド被覆部材の用途
及び形状によつて異なり、特に、切削工具として
のドリルのように鋭角な刃先を有する部材には
0.1μｍ〜5μｍ厚さが好ましく、耐摩耗工具又はエ
レクトロニクス用部材には用途及び形状によつて
0.1μｍ〜50μｍとすることができる。 The outer layer formed on the surface of these intermediate layers is made of diamond and/or diamond-like carbon, and its thickness varies depending on the use and shape of the diamond-coated member. For parts with sharp cutting edges,
The thickness is preferably 0.1 μm to 5 μm, depending on the use and shape for wear-resistant tools or electronics parts.
It can be 0.1 μm to 50 μm.
本発明のダイヤモンド被覆部材は、次のような
方法により製造することができる。まず、各種の
基体の表面を必要に応じて研摩、洗浄した後、密
着補助層を形成する必要がある場合は、化学蒸着
法（CVD法）又は物理蒸着法（PVD法）により
形成し、次いで、密着強化層を形成する場合は、
膜状のダイヤモンド及び／又はダイヤモンド状カ
ーボンを形成することができる。例えば、熱フイ
ラメントCVD法、マイクロ波プラズマCVD法、
高周波プラズマCVD法又は磁界分離によるイオ
ンビーム蒸着法などによるダイヤモンド及び／又
はダイヤモンド状カーボンの合成と同時に周期律
表4a、5a、6a族の金属又はSiの中の少なくとも
１種と周期律表4a、5a、6a族の金属又はSiの炭
化物、窒化物、ホウ化物及びこれらの相互固溶体
の中の少なくとも１種とが形成されるようにした
後、周期律表4a、5a、6a族の金属又はSiの中の
少なくとも１種と周期律表4a、5a、6a族の金属
又はSiの炭化物、窒化物、ホウ化物及びこれらの
相互固溶体の中の少なくとも１種との形成を中止
して、例えば、周期律表4a、5a、6a族の元素又
はSiを含む水素化物もしくはハロゲン化物などの
ガスの供給を中止して、ダイヤモンド及び／又は
ダイヤモンド状カーボンの合成のみを継続するこ
とにより外層が形成される。 The diamond-coated member of the present invention can be manufactured by the following method. First, after polishing and cleaning the surfaces of various substrates as necessary, if it is necessary to form an adhesion auxiliary layer, it is formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD), and then , when forming an adhesion reinforcing layer,
A film of diamond and/or diamond-like carbon can be formed. For example, thermal filament CVD method, microwave plasma CVD method,
Simultaneously with the synthesis of diamond and/or diamond-like carbon by a high-frequency plasma CVD method or an ion beam evaporation method using magnetic field separation, at least one of the metals of Groups 4a, 5a, and 6a of the Periodic Table or Si and 4a of the Periodic Table, 5a, 6a or Si with at least one of carbides, nitrides, borides, and mutual solid solutions thereof, and then the metal of Group 4a, 5a, 6a of the periodic table or Si. By ceasing the formation of at least one of carbides, nitrides, borides, and mutual solid solutions of metals of groups 4a, 5a, and 6a of the periodic table and Si, for example, periodic The outer layer is formed by stopping the supply of a gas such as a hydride or halide containing an element of Groups 4a, 5a, or 6a of the Table of Contents, and continuing only the synthesis of diamond and/or diamond-like carbon.
基体の材質又は形状の関係から基体と中間層と
の密着性を、更に、補助する目的で、例えば、基
体の表面に金属層を形成する必要がある場合は、
メツキ法、蒸着法又はPVD法により行なうこと
ができる。 For example, if it is necessary to form a metal layer on the surface of the substrate in order to further enhance the adhesion between the substrate and the intermediate layer due to the material or shape of the substrate,
This can be done by a plating method, a vapor deposition method, or a PVD method.
（作用）
本発明の被覆部材は、中間層としての密着強化
層が外層の合成を促進し、外層の形成後には、中
間層と外層との密着性を著しく高めることができ
るものである。また、基体の材質又は形状によ
り、基体と密着強化層との密着性が劣る場合は、
基体と密着強化層との間に密着補助層や金属層な
どの中間層を介在させることにより、基体と密着
強化層との密着性を高めることができるものであ
る。(Function) In the coated member of the present invention, the adhesion reinforcing layer as an intermediate layer promotes synthesis of the outer layer, and after the formation of the outer layer, the adhesion between the intermediate layer and the outer layer can be significantly improved. In addition, if the adhesion between the substrate and the adhesion reinforcing layer is poor due to the material or shape of the substrate,
By interposing an intermediate layer such as an adhesion auxiliary layer or a metal layer between the base and the adhesion-enhancing layer, the adhesion between the base and the adhesion-enhancing layer can be improved.
（実施例）
実施例 １
ISO分類のK10相当の超硬合金からなる基体を
研摩、洗浄及び乾燥後、マイクロ波プラズマ
CVDの反応容器内に設置し、8vol％TiCl4−5vol
％CH4−87vol％H2雰囲気中、圧力20Torr、温度
1000℃、保持時間30分にて基体の表面にTiC層を
被覆した。次いで、反応容器内を真空排気した
後、５ml／minTiCl4−２ml／minCH4−300ml／
minH2雰囲気中、外部加熱900℃、フイラメント
温度2000℃、保持時間35分にて被覆層を形成し、
次に、２ml／minCH4−300ml／minH2雰囲気中、
外部加熱900℃、フイラメント温度2000℃、保持
時間145分にて、更に被覆層を形成することによ
り本発明品１を得た。(Example) Example 1 After polishing, cleaning and drying a substrate made of cemented carbide equivalent to ISO classification K10, microwave plasma was applied.
Installed in the CVD reaction vessel, 8vol% TiCl 4 -5vol
% CH4−87vol % H2 atmosphere, pressure 20Torr, temperature
A TiC layer was coated on the surface of the substrate at 1000°C for 30 minutes. Next, after evacuating the inside of the reaction container, the reaction volume was 5 ml/minTiCl 4 -2 ml/minCH 4 -300 ml/
A coating layer was formed in a minH 2 atmosphere with external heating at 900°C, filament temperature at 2000°C, and holding time for 35 minutes.
Next, in a 2ml/minCH 4 -300ml/minH 2 atmosphere,
Inventive product 1 was obtained by further forming a coating layer under external heating at 900°C, filament temperature at 2000°C, and holding time for 145 minutes.
比較として、上記超硬合金の基体を上記反応容
器内に設置し、8vol％TiCl4−5vol％CH4−87vol
％H2雰囲気中、圧力20Torr、温度1000℃、保持
時間30分にて基体の表面にTiC層を被覆した後、
反応容器内を２ml／minCH4−300ml／minH2雰
囲気にして、外部加熱900℃、フイラメント温度
2000℃、保持時間145分にて被覆層を形成するこ
とにより比較品１を得た。 For comparison, the above cemented carbide substrate was placed in the above reaction vessel, and 8vol% TiCl4-5vol % CH4-87vol
After coating the surface of the substrate with a TiC layer at a pressure of 20 Torr, a temperature of 1000℃, and a holding time of 30 minutes in a % H2 atmosphere,
The inside of the reaction vessel was set to an atmosphere of 2 ml/minCH 4 -300 ml/minH 2 , external heating at 900°C, and filament temperature.
Comparative product 1 was obtained by forming a coating layer at 2000° C. for 145 minutes.
この本発明品１と比較品１の各被覆層を走査型
電子顕微鏡、ラマン分光分析及び電子線マイクロ
アナライザーにて調べた所、本発明品１は外層が
2μｍ厚さのダイヤモンド層で、中間層が0.5μｍ厚
さのダイヤモンドとTiと炭化チタンとのダイヤ
モンド型構造を主とする密着強化層と0.5μｍ厚さ
のTiCの密着補助層とからなつており、比較品１
は外層が1.6μｍ厚さのダイヤモンド層で、中間層
が0.5μｍ厚さのTiC層であつた。 When each coating layer of Inventive Product 1 and Comparative Product 1 was examined using a scanning electron microscope, Raman spectroscopy, and an electron beam microanalyzer, it was found that Inventive Product 1 had an outer layer that
The diamond layer is 2μm thick, and the middle layer is composed of a 0.5μm thick adhesion reinforcement layer mainly having a diamond-shaped structure of diamond, Ti and titanium carbide, and a 0.5μm thick TiC adhesion auxiliary layer. , comparison product 1
The outer layer was a 1.6 μm thick diamond layer, and the middle layer was a 0.5 μm thick TiC layer.
この本発明品１と比較品１をダイヤモンド圧子
による引掻き試験を行なつて被覆層の耐剥離性を
比較した結果、比較品１は1.7Kg荷重にて被覆層
の剥離が生じたのに対して、本発明品１は5.2Kg
荷重まで被覆層の剥離が生じなかつた。 A scratch test was conducted using a diamond indenter to compare the peeling resistance of the coating layer between Product 1 of the present invention and Comparative Product 1. As a result, the coating layer of Comparative Product 1 peeled off under a load of 1.7 kg. , Invention product 1 is 5.2Kg
No peeling of the coating layer occurred up to the load.
実施例 ２
実施例１で用いたと同様の基体の表面に、1.3
×10-3TorrN2−1.5×10-4TorrC2H2雰囲気中、
基体に20Vのバイアス電圧を印加したホローカソ
ード型電子ビームによりTiを蒸発させた後、５
ml／minTiCl4−５ml／minCH4−500ml／minH2、
圧力40Torr、出力350W、温度920℃、保持時間
15分によるマイクロ波プラズマCVD法で、被覆
層を形成し、次に、５ml／minCH4−500ml／
minH2、圧力40Torr、出力350W、温度920℃、
保持時間180分によるマイクロ波プラズマCVD法
で、更に被覆層を形成することにより本発明品２
を得た。Example 2 On the surface of the same substrate as used in Example 1, 1.3
×10 -3 TorrN 2 −1.5×10 -4 TorrC 2 H 2 atmosphere,
After evaporating Ti using a hollow cathode electron beam with a bias voltage of 20 V applied to the substrate,
ml/ minTiCl4-5ml / minCH4-500ml / minH2 ,
Pressure 40Torr, output 350W, temperature 920℃, holding time
A coating layer was formed by microwave plasma CVD method for 15 minutes, and then 5 ml/min CH 4 -500 ml/
minH 2 , pressure 40Torr, output 350W, temperature 920℃,
Inventive product 2 was obtained by further forming a coating layer using a microwave plasma CVD method with a holding time of 180 minutes.
I got it.
比較として、上述の本発明品の製造行程の内、
５ml／minTiCl4−５ml／minCH4−500ml／
minH2雰囲気中で行なつた被覆層の形成のみ省
略して、比較品２を得た。 For comparison, in the manufacturing process of the above-mentioned product of the present invention,
5ml/minTiCl 4 -5ml/minCH 4 -500ml/
Comparative product 2 was obtained by omitting only the formation of the coating layer, which was performed in a minH 2 atmosphere.
この本発明品２と比較品２の各被覆層を実施例
１と同様にして調べた所、本発明品２は外層が
2μｍ厚さのダイヤモンド層で、中間層がダイヤ
モンドとTiと炭化チタンとのダイヤモンド型構
造を主とする1μｍ厚さの密着強化層と2.0μｍ厚さ
のTiCNからなるの密着補助層とからなつてお
り、比較品２は外層が1.5μｍ厚さのダイヤモンド
層で、中間層が2μｍ厚さのTiCN層であつた。 When each coating layer of the present invention product 2 and comparative product 2 was examined in the same manner as in Example 1, it was found that the present invention product 2 has an outer layer.
The diamond layer is 2μm thick, and the middle layer is composed of a 1μm thick adhesion reinforcement layer mainly having a diamond-shaped structure of diamond, Ti, and titanium carbide, and a 2.0μm thick adhesion auxiliary layer made of TiCN. In Comparative Product 2, the outer layer was a diamond layer with a thickness of 1.5 μm, and the intermediate layer was a TiCN layer with a thickness of 2 μm.
この本発明品２と比較品２を被削材Al−18％
Si、切削速度250ｍ／min、送り速度0.1mm／rev、
切込み量0.5mmの条件で旋削試験を行なつた結果、
比較品２は切削初期に被覆層の剥離が生じたのに
対して、本発明品２は30分間切削後も摩耗が殆ん
ど生じていなかつた。 This invention product 2 and comparison product 2 were used as work material Al-18%.
Si, cutting speed 250m/min, feed rate 0.1mm/rev,
As a result of a turning test with a depth of cut of 0.5mm,
In comparison product 2, the coating layer peeled off at the initial stage of cutting, whereas inventive product 2 showed almost no wear even after 30 minutes of cutting.
実施例 ３
Si3N4−５％AlN−5wt％Y2O3組成のセラミツ
クスからなる基体を研摩、洗浄、乾燥後、プラズ
マCVDの反応容器内に設置し、10vol％Si3N4−
5vol％CH4−400vol％H2、圧力30Torr、温度900
℃、保持時間30分にて基体の表面に被覆層を形成
した後、反応容器内へのSiCl4の供給を中止し、
5vol％CH4−400vol％H2雰囲気中、保持時間200
分、他は同条件にて被覆層を形成させることによ
り本発明品３を得た。Example 3 After polishing, cleaning, and drying a substrate made of ceramics having a composition of Si 3 N 4 −5% AlN − 5wt% Y 2 O 3 , it was placed in a plasma CVD reaction vessel, and 10 vol% Si 3 N 4 −
5vol%CH 4 −400vol%H 2 , pressure 30Torr, temperature 900
After forming a coating layer on the surface of the substrate at ℃ and holding time for 30 minutes, the supply of SiCl 4 into the reaction vessel was stopped.
5vol% CH4−400vol % H2 atmosphere, retention time 200
Inventive product 3 was obtained by forming a coating layer under the same conditions as above.
比較として、上記と同じ基体を上記と同反応容
器内に設置し、5vol％CH4−400vol％H2、圧力
30Torr、温度900℃、保持時間200分にて被覆層
を形成させることにより比較品３を得た。 For comparison, the same substrate as above was placed in the same reaction vessel as above, and 5vol% CH4 - 400vol% H2 , pressure
Comparative product 3 was obtained by forming a coating layer at 30 Torr, a temperature of 900° C., and a holding time of 200 minutes.
この本発明品３と比較品３を実施例１と同様に
して調べた所、本発明品３は外層が厚さ3μｍの
ダイヤモンド層で、中間層がダイヤモンドとSiと
炭化ケイ素とでなるのダイヤモンド型構造を主と
する1.0μｍ厚さの密着強化層からなつており、比
較品３は厚さ2.3μｍのダイヤモンド層からなつて
いた。 Inventive Product 3 and Comparative Product 3 were examined in the same manner as in Example 1, and it was found that Inventive Product 3 had a diamond layer with a thickness of 3 μm as the outer layer, and a diamond layer with an intermediate layer of diamond, Si, and silicon carbide. It consisted of a 1.0 μm thick adhesion reinforcing layer mainly having a mold structure, and Comparative Product 3 consisted of a 2.3 μm thick diamond layer.
この本発明品３と比較品３を被削材Al−８％
Si合金、切削速度400ｍ／min、切込み量１mm、
送り速度0.15mm／revの条件で旋削試験を行なつ
た結果、比較品３は30分切削後に被覆層が剥離し
たのに対し、本発明品３は60分切削後も被覆層の
剥離が生じなく正常摩耗で摩耗量も非常に少なか
つた。 This invention product 3 and comparison product 3 were used as work material Al-8%.
Si alloy, cutting speed 400m/min, depth of cut 1mm,
As a result of a turning test conducted at a feed rate of 0.15 mm/rev, the coating layer of Comparative Product 3 peeled off after 30 minutes of cutting, whereas the coating layer of Invention Product 3 peeled off even after 60 minutes of cutting. There was no normal wear and the amount of wear was very small.
（発明の効果）
以上の結果から、本発明のダイヤモンド被覆部
材は、ダイヤモンド及び／又はダイヤモンド状カ
ーボンからなる外層と基体との密着性が著しくす
ぐれていて、従来のダイヤモンド被覆部材の３倍
以上の耐剥離性があり、それに伴つて寿命も向上
しているものである。このために、苛酷な重負荷
の作用する切削工具として、例えば、旋削工具は
勿論のこと、フライス工具、ドリル、エンドミル
及びミクロンドリルなどの回転用工具にも応用で
き、又印字ピンの先端もしくは紙、テープなどの
切断用スリツターを含めた耐摩耗用工具にも応用
できる。さらに、ダイヤモンド自体が有している
高電気絶縁性及び高熱伝導性を利用してヒートシ
ンクをはじめとするエレクトロニクス用部材にも
応用できる産業上有用な材料である。(Effects of the Invention) From the above results, the diamond-coated member of the present invention has extremely excellent adhesion between the outer layer made of diamond and/or diamond-like carbon and the substrate, which is more than three times that of the conventional diamond-coated member. It has peeling resistance and has a correspondingly improved lifespan. For this reason, it can be applied to cutting tools that are subject to severe heavy loads, such as turning tools, milling tools, drills, end mills, micron drills, and other rotating tools. It can also be applied to wear-resistant tools, including slitters for cutting tape, etc. Furthermore, it is an industrially useful material that can be applied to electronic components such as heat sinks by utilizing the high electrical insulation and high thermal conductivity that diamond itself has.
Claims (1)
モンド状カーボンでなる外層を形成する被覆部材
において、前記基体と前記外層との間に１層又は
多層で構成される中間層を介在させ、前記外層に
隣接する該中間層が周期律表4a、5a、6a族金属
又はSiの中の少なくとも１種と周期律表4a、5a、
6a族の金属又はSiの炭化物、窒化物及びこれらの
相互固溶体の中の少なくとも１種とダイヤモンド
及び／又はダイヤモンド状カーボンとでなる密着
強化層によつて形成されていることを特徴とする
ダイヤモンド被覆部材。 ２ 上記中間層は、上記外層に隣接する上記密着
強化層と該密着強化層に隣接する密着補助層とか
らなり、該密着補助層が周期律表4a、5a、6a族
の金属又はSiの炭化物、窒化物及びホウ化物及び
これらの相互固溶体の中の少なくとも１種からな
ることを特徴とする特許請求の範囲第１項記載の
ダイヤモンド被覆部材。 ３ 上記密着強化層は、50Å〜5μｍ厚さである
ことを特徴とする特許請求の範囲第１項又は第２
項記載のダイヤモンド被覆部材。 ３ 上記外層は、0.1μｍ〜50μｍ厚さであること
を特徴とする特許請求の範囲第１項又は第２項記
載のダイヤモンド被覆部材。[Scope of Claims] 1. A covering member in which an outer layer made of diamond and/or diamond-like carbon is formed on the surface of a base, in which an intermediate layer composed of one layer or multiple layers is interposed between the base and the outer layer. , the intermediate layer adjacent to the outer layer is made of at least one metal of group 4a, 5a, or 6a of the periodic table or Si and 4a, 5a of the periodic table,
A diamond coating characterized by being formed of an adhesion-enhancing layer made of at least one of group 6a metals or Si carbides, nitrides, and mutual solid solutions thereof and diamond and/or diamond-like carbon. Element. 2 The intermediate layer is composed of the adhesion reinforcing layer adjacent to the outer layer and the adhesion auxiliary layer adjacent to the adhesion reinforcing layer, and the adhesion auxiliary layer is made of a metal of group 4a, 5a, or 6a of the periodic table or a carbide of Si. The diamond-coated member according to claim 1, characterized in that the diamond-coated member is made of at least one of , nitride, boride, and a mutual solid solution thereof. 3. Claim 1 or 2, wherein the adhesion reinforcing layer has a thickness of 50 Å to 5 μm.
The diamond-coated member described in Section 1. 3. The diamond-coated member according to claim 1 or 2, wherein the outer layer has a thickness of 0.1 μm to 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27225285A JPS62133068A (en) | 1985-12-03 | 1985-12-03 | Diamond coated member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27225285A JPS62133068A (en) | 1985-12-03 | 1985-12-03 | Diamond coated member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62133068A JPS62133068A (en) | 1987-06-16 |
| JPH0558067B2 true JPH0558067B2 (en) | 1993-08-25 |
Family
ID=17511253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27225285A Granted JPS62133068A (en) | 1985-12-03 | 1985-12-03 | Diamond coated member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62133068A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2543132B2 (en) * | 1988-04-26 | 1996-10-16 | 出光石油化学株式会社 | Cemented carbide with diamond thin film and method for producing the same |
| JPH01246118A (en) * | 1988-03-26 | 1989-10-02 | Semiconductor Energy Lab Co Ltd | Composite carbon coating film having high heat-resistance and production thereof |
| DE4111238A1 (en) * | 1991-04-08 | 1992-10-15 | Hilti Ag | TOOL FOR MACHINING MATERIALS |
| GB9226568D0 (en) * | 1992-12-21 | 1993-02-17 | Univ Hull | Atomic beam coating of polymers |
| BE1008229A3 (en) * | 1993-10-29 | 1996-02-20 | Vito | METHOD FOR APPLYING A WEAR PROTECTIVE LAYER TO A SUBSTRATE |
| JP5212416B2 (en) * | 2000-02-25 | 2013-06-19 | 住友電気工業株式会社 | Amorphous carbon coated member |
| JP4815065B2 (en) * | 2001-05-30 | 2011-11-16 | 株式会社トクヤマ | Heat sink and manufacturing method thereof |
| DE10149588B4 (en) * | 2001-10-08 | 2017-09-07 | Oerlikon Trading Ag, Trübbach | Process for diamond coating of substrates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106494A (en) * | 1984-10-29 | 1986-05-24 | Kyocera Corp | Member coated with diamond and its production |
-
1985
- 1985-12-03 JP JP27225285A patent/JPS62133068A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106494A (en) * | 1984-10-29 | 1986-05-24 | Kyocera Corp | Member coated with diamond and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62133068A (en) | 1987-06-16 |
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