JP2002120105A - Aluminum oxide coated tool and its manufacturing method - Google Patents

Aluminum oxide coated tool and its manufacturing method

Info

Publication number
JP2002120105A
JP2002120105A JP2001249788A JP2001249788A JP2002120105A JP 2002120105 A JP2002120105 A JP 2002120105A JP 2001249788 A JP2001249788 A JP 2001249788A JP 2001249788 A JP2001249788 A JP 2001249788A JP 2002120105 A JP2002120105 A JP 2002120105A
Authority
JP
Japan
Prior art keywords
oxide film
aluminum oxide
oxide
film
mainly composed
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.)
Granted
Application number
JP2001249788A
Other languages
Japanese (ja)
Other versions
JP3901477B2 (en
Inventor
Masayuki Gonda
正幸 権田
Toshio Ishii
敏夫 石井
Hiroshi Ueda
広志 植田
Nobuhiko Shima
順彦 島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Moldino Tool Engineering Ltd
Proterial Ltd
Original Assignee
Hitachi Metals Ltd
Hitachi Tool Engineering Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Metals Ltd, Hitachi Tool Engineering Ltd filed Critical Hitachi Metals Ltd
Priority to JP2001249788A priority Critical patent/JP3901477B2/en
Publication of JP2002120105A publication Critical patent/JP2002120105A/en
Application granted granted Critical
Publication of JP3901477B2 publication Critical patent/JP3901477B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum oxide coated tool having stable quality of a cutting characteristic by improving adhesiveness of both boundaries of a bonding layer disposed between an oxide film mainly composed of α type aluminum oxide and a non oxide film as the ground (a substrate-side film) and in directly contact with both films, mechanical strength of the bonding layer itself, and mechanical strength of the oxide film itself mainly composed of α type aluminum oxide. SOLUTION: In this aluminum oxide coated tool, a single layer film made of one of carbide, nitride, carbonitride, oxide, oxycarbide, oxynitride, and oxycarbonitride of metals of groups IVa, Va, and VIa in the periodic table or multi-layer film made of two or more of them, and at least a single layer of the oxide film mainly composed of α type aluminum oxide are formed on the surface of a substrate. The bonding layer containing oxygen is disposed between the non oxide film and the oxide film, and an X-ray diffraction highest peak face of the oxide film is (110) face.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、切削用及び耐摩耗
用の酸化アルミニウム被覆工具とその製造方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cutting and wear-resistant aluminum oxide-coated tool and a method for producing the same.

【０００２】[0002]

【従来の技術】一般に、被覆工具は超硬質合金、高速度
鋼、特殊鋼よりなる基体表面に硬質皮膜を化学蒸着法
や、物理蒸着法により成膜することにより作製される。
このような被覆工具は皮膜の耐摩耗性と基体の強靭性と
を兼ね備えており、広く実用に供されている。特に、高
硬度材を高速で切削する場合に、切削工具の刃先温度は
１０００℃前後まで上がるとともに、被削材との接触に
よる摩耗や断続切削等の機械的衝撃に耐える必要があ
り、耐摩耗性と強靭性とを兼ね備えた被覆工具が重宝さ
れている。2. Description of the Related Art In general, a coated tool is produced by forming a hard film on a substrate made of a super-hard alloy, high-speed steel or special steel by a chemical vapor deposition method or a physical vapor deposition method.
Such a coated tool has both the wear resistance of the film and the toughness of the substrate, and is widely used in practice. In particular, when cutting high-hardness materials at high speed, it is necessary to raise the cutting edge temperature of the cutting tool to around 1000 ° C. and to withstand mechanical shocks such as abrasion due to contact with a work material and intermittent cutting, and the like. Coated tools having both strength and toughness are useful.

【０００３】硬質皮膜には、耐摩耗性と靭性に優れた周
期律表IVａ、Ｖａ、VIａ族金属の炭化物、窒化物、炭窒
化物からなる非酸化膜や耐酸化性に優れた酸化膜が単層
あるいは多層膜として用いられる。非酸化膜では例えば
ＴｉＣ、ＴｉＮ、ＴｉＣＮが利用され、酸化膜では特に
α型酸化アルミニウムやκ型酸化アルミニウム等が利用
されている。炭化物、窒化物、炭窒化物等からなる非酸
化膜の欠点は酸化され易いことであり、この欠点を補う
ため、非酸化膜上に耐酸化性に優れた酸化アルミニウム
等の酸化膜を形成する多層膜構造を持たせることにより
非酸化膜の酸化を防止することが行われている。The hard coating includes a non-oxidized film made of carbides, nitrides and carbonitrides of Group IVa, Va and VIa metals excellent in wear resistance and toughness and an oxide film excellent in oxidation resistance. Used as a single-layer or multilayer film. For example, TiC, TiN, and TiCN are used for the non-oxide film, and α-type aluminum oxide and κ-type aluminum oxide are particularly used for the oxide film. The disadvantage of non-oxide films made of carbides, nitrides, carbonitrides, etc. is that they are easily oxidized. To compensate for this disadvantage, an oxide film such as aluminum oxide with excellent oxidation resistance is formed on the non-oxide film. It has been practiced to prevent a non-oxidized film from being oxidized by having a multilayer film structure.

【０００４】この非酸化膜／酸化膜の多層膜構造の欠点
は非酸化膜と酸化膜との間の密着性が低いこと、あるい
は高温で機械強度が安定しないことである。前記酸化膜
としてκ型酸化アルミニウム膜を用いた場合、このκ型
酸化アルミニウムは前記非酸化膜との密着性は比較的良
好でありしかも１０００〜１０２０℃と比較的低温で成
膜できる長所はあるものの、準安定状態のアルミナであ
るため高温での使用時にα型酸化アルミニウムに変態す
るため体積が変化し、膜中にクラックが入り、膜が剥が
れるという欠点がある。これに対して、前記酸化膜とし
てα型酸化アルミニウムを用いた場合、このα型酸化ア
ルミニウムは高温でも安定なアルミナ膜であり高温特性
に優れる長所があるものの、非酸化膜の上に直接成膜す
るためには高温で成膜する必要があり、α型酸化アルミ
ニウムの結晶粒径が大きくなり機械特性が低下する欠点
がある。The disadvantage of the non-oxide / oxide film multilayer structure is that the adhesion between the non-oxide film and the oxide film is low, or the mechanical strength is not stable at high temperatures. When a κ-type aluminum oxide film is used as the oxide film, the κ-type aluminum oxide has an advantage that it has relatively good adhesion to the non-oxide film and can be formed at a relatively low temperature of 1000 to 1020 ° C. However, since it is a metastable alumina, it is transformed into α-type aluminum oxide when used at a high temperature, so that its volume changes, cracks occur in the film, and the film peels off. In contrast, when α-type aluminum oxide is used as the oxide film, this α-type aluminum oxide is an alumina film that is stable even at high temperatures and has an advantage of excellent high-temperature characteristics, but is directly formed on a non-oxide film. In order to achieve this, it is necessary to form a film at a high temperature, and there is a disadvantage that the crystal grain size of the α-type aluminum oxide increases and the mechanical properties deteriorate.

【０００５】このため従来より、前記非酸化膜の表面を
酸化させ酸化膜生成の基点を形成した後に酸化アルミニ
ウムを形成することにより１０００〜１０２０℃と比較
的低温でα型酸化アルミニウムを得る手法が常用されて
いる。図４はこのような非酸化膜と酸化膜の界面近傍を
模式的に示したものであり、基体側に形成された非酸化
膜３とα型酸化アルミニウムを主とする酸化膜１との間
に結合層２が表記されている。上記のように結合層２は
一般に非酸化膜３の表面を酸化させることにより作製さ
れ、その厚さは１μｍ以下と薄い。このため、一見非酸
化膜３の上に直接酸化膜１が形成されているように見え
るが、本発明では非酸化膜３上に形成された酸化層をそ
の機能と特性を明確にするためその製法に関わらず全て
結合層２として表記する。For this reason, conventionally, a method of obtaining an α-type aluminum oxide at a relatively low temperature of 1000 to 1020 ° C. by oxidizing the surface of the non-oxide film to form a base point for forming an oxide film and then forming aluminum oxide. It is commonly used. FIG. 4 schematically shows the vicinity of the interface between such a non-oxide film and the oxide film, and shows the relationship between the non-oxide film 3 formed on the substrate side and the oxide film 1 mainly composed of α-type aluminum oxide. Indicates the bonding layer 2. As described above, the bonding layer 2 is generally produced by oxidizing the surface of the non-oxide film 3, and its thickness is as thin as 1 μm or less. For this reason, at first glance, it appears that the oxide film 1 is directly formed on the non-oxide film 3. However, in the present invention, the oxide layer formed on the non-oxide film 3 is used to clarify its function and characteristics. Regardless of the production method, they are all described as the bonding layer 2.

【０００６】上記のように結合層２を非酸化膜３表面の
酸化により形成した後成膜したα型酸化アルミニウムを
主とする酸化膜１は密着強度が充分ではなく、切削時に
酸化膜１がその下地である非酸化膜３から早期に剥がれ
る事故が発生することがある。このためα型酸化アルミ
ニウムを主とする酸化膜１と基体側に形成された非酸化
膜３との間の密着強度を高めるために結合層２の形成方
法に種々の工夫がなされてきた。例えば、特開平０６−
３１６７５８号では鋳鉄に対する切削性能を向上させる
ため、下地にＴｉＣＮ層（図４の３）を形成した後、酸
化ポテンシャルがＨ2Ｏの２０ｐｐｍ未満の濃度である
Ｈ2キャリアガスを用い、ＣＯ2、ＣＯ及びＡｌＣｌ3の
順序に反応ガスを順次供給することによりアルミナの核
形成を開始させ、核形成時の温度を約１０００℃にして
α−アルミナ膜を形成することにより、(０１２)面から
の等価Ｘ線強度ＴＣ（０１２）が１．３より大きいアル
ミナ層を提案している。この場合、ＴｉＣＮ層（図４の
３）の表面にまず酸化ポテンシャルがＨ2Ｏの２０ｐｐ
ｍ未満の濃度であるＨ2キャリアガスおよびＣＯ2ガス、
ＣＯガスを流すことによりＴｉＣＮ層表面が酸化される
ことにより結合層（図４中の２）が形成され、その後、
更にＡｌＣｌ3を加えて流すことによりα−アルミナ膜
が形成されているものと考えられる。As described above, the oxide film 1 mainly composed of α-type aluminum oxide formed after the bonding layer 2 is formed by oxidizing the surface of the non-oxide film 3 has insufficient adhesion strength. In some cases, an accident may occur in which the non-oxide film 3 serving as the base is peeled off at an early stage. Therefore, various methods have been devised for forming the bonding layer 2 in order to increase the adhesion strength between the oxide film 1 mainly composed of α-type aluminum oxide and the non-oxide film 3 formed on the substrate side. For example, Japanese Unexamined Patent Publication No.
In 316758, in order to improve the cutting performance for cast iron, after forming a TiCN layer (3 in FIG. 4) on the base, an H 2 carrier gas having an oxidation potential of less than 20 ppm of H 2 O is used, and CO 2 , The nucleation of alumina was started by sequentially supplying the reaction gas in the order of CO and AlCl 3 , the temperature at the time of nucleation was set to about 1000 ° C., and an α-alumina film was formed. An alumina layer having an equivalent X-ray intensity TC (012) of more than 1.3 has been proposed. In this case, the oxidation potential is first set to 20 pp of H 2 O on the surface of the TiCN layer (3 in FIG. 4).
H 2 carrier gas and CO 2 gas at a concentration of less than m,
By flowing CO gas, the surface of the TiCN layer is oxidized to form a bonding layer (2 in FIG. 4).
It is considered that an α-alumina film was formed by further adding AlCl 3 and flowing.

【０００７】また、酸化アルミニウム自体の耐摩耗性お
よび耐欠損性を高めるために、アルミナの成膜時にＨ2
ＳガスおよびＳＯ2ガスを添加した反応ガスを用いたり
（特開平０６−３１５０３号）あるいはＨ2Ｓガスおよ
びＳＯ2ガスに加えて更に２０〜３０ｖｏｌ％のＣＯ2を
用いることにより（特開平０７−１０８４０５号）、主
ピークである（０３０）面のＸ線回折ピーク強度Ｉ（０
３０）と（１０４）面のＸ線回折ピーク強度Ｉ（１０
４）との比がＩ（０３０）／Ｉ（１０４）＞１、あるい
はこれに加えて更に（０１２）面のＸ線回折ピーク強度
Ｉ（０１２）がＩ（０１２）／Ｉ（０３０）＞１なる関
係にあるα型結晶を主体にした結晶構造の酸化アルミニ
ウムを提案している。[0007] In order to improve the wear resistance and fracture resistance of aluminum oxide itself, H 2 during deposition of the alumina
By using a reaction gas to which S gas and SO 2 gas are added (JP-A-06-31503) or by further using 20 to 30% by volume of CO 2 in addition to H 2 S gas and SO 2 gas (Japanese Patent Laid-Open No. -108405), the X-ray diffraction peak intensity I (0) of the (030) plane which is the main peak.
X-ray diffraction peak intensities I (10) of (30) and (104) planes
4) and I (030) / I (104)> 1, or in addition, the X-ray diffraction peak intensity I (012) of the (012) plane is I (012) / I (030)> 1. An aluminum oxide having a crystal structure mainly composed of an α-type crystal having the following relationship has been proposed.

【０００８】[0008]

【発明が解決しようとする課題】本発明者等は超硬等の
基板上にα型酸化アルミニウムを主とする酸化膜を含む
多層膜を形成して作製した切削工具を切削テストし、そ
の破損部を詳細に評価した結果、上記のようにα型酸化
アルミニウムを主とする酸化膜１が下地である非酸化膜
３との界面の結合層部分（図４中の２）から剥がれた
り、酸化膜自体にクラックが入り結晶粒が脱落したりし
ていることがわかった。本発明が解決しようとする課題
はα型酸化アルミニウムを主とする酸化膜１とその下地
（基体側の膜）である非酸化膜３との間にあり両膜に直
接接触する結合層２の両界面の密着性あるいは結合層２
自体の機械強度やα型酸化アルミニウムを主とする酸化
膜１自体の機械強度を高めることにより、切削特性等の
品質が安定した酸化アルミニウム被覆工具を提供するこ
とである。SUMMARY OF THE INVENTION The present inventors conducted a cutting test on a cutting tool produced by forming a multilayer film containing an oxide film mainly composed of α-type aluminum oxide on a substrate such as a carbide substrate, and found that the cutting tool was damaged. As a result of detailed evaluation of the portion, as described above, the oxide film 1 mainly composed of α-type aluminum oxide was peeled off from the bonding layer portion (2 in FIG. 4) at the interface with the non-oxide film 3 as the base, It was found that the film itself had cracks and crystal grains were falling off. The problem to be solved by the present invention is that the bonding layer 2 which is between the oxide film 1 mainly composed of α-type aluminum oxide and the non-oxide film 3 which is the base (film on the substrate side) and is in direct contact with both films. Adhesion of both interfaces or bonding layer 2
An object of the present invention is to provide an aluminum oxide-coated tool with stable quality such as cutting characteristics by increasing the mechanical strength of itself and the mechanical strength of the oxide film 1 mainly composed of α-type aluminum oxide.

【０００９】一般に、前記結合層２はＴｉＣ、ＴｉＮ、
ＴｉＣＮ膜等より成る非酸化膜３の表面をＨ2ＯとＣＯ2
との混合ガスにより酸化することにより作製しているが
次のように品質の良いα型酸化アルミニウムを主とした
酸化膜被覆工具を安定して生産することは困難である。
即ち、結合層２成膜時に、ＣＯ2等による酸化性ガスの
濃度が高いと主にＴｉ2Ｏ3（Ｘ線パターンはＡＳＴＭ
Ｎｏ．１０−６３参照）やＴｉ3Ｏ5（ＡＳＴＭＮｏ．１
１−２１７）あるいはＴｉＯ2（ＡＳＴＭファイル Ｎ
ｏ．２１−１２７６）が形成され、下地との密着強度が
低く、酸化層（結合層）自体がもろく機械強度が低くな
る欠点が生じる。一方、ＣＯ2等による酸化性ガスの濃
度を下げてＴｉ2Ｏ3、Ｔｉ3Ｏ5、ＴｉＯ2が形成されな
いように非酸下膜３の酸化を行うと下地であるＴｉＣ、
ＴｉＮ、ＴｉＣＮ等の非酸化膜３表面の酸化が不十分に
なり、酸化アルミニウムの成膜温度が１０２０℃以下で
はκ型酸化アルミニウムが形成されα型酸化アルミニウ
ムが安定して形成されず、一方酸化アルミニウムの成膜
温度を１０３０℃以上にするとα型酸化アルミニウムを
主とする酸化膜１の粒径が粗大化するとともに、中心線
平均面粗さＲａや最大面粗さＲｍａｘも荒くなり被覆工
具の特性が低下する欠点が生じる。Generally, the bonding layer 2 is made of TiC, TiN,
The surface of the non-oxide film 3 made of a TiCN film or the like is made of H 2 O and CO 2
However, it is difficult to stably produce an oxide film-coated tool mainly composed of high-quality α-type aluminum oxide as described below.
That is, when the concentration of the oxidizing gas such as CO 2 is high during the formation of the bonding layer 2, Ti 2 O 3 (X-ray pattern
No. 10-63 reference) and Ti 3 O 5 (ASTMNo.1
1-217) or TiO 2 (ASTM file N
o. 21-1276), the adhesion strength to the base is low, the oxide layer (bonding layer) itself is brittle, and the mechanical strength is low. On the other hand, when the concentration of the oxidizing gas due to CO 2 or the like is reduced to oxidize the non-acidic lower film 3 so that Ti 2 O 3 , Ti 3 O 5 , and TiO 2 are not formed, the underlying TiC,
Oxidation of the surface of the non-oxidized film 3 such as TiN or TiCN becomes insufficient. When the film forming temperature of aluminum oxide is 1020 ° C. or less, κ-type aluminum oxide is formed and α-type aluminum oxide is not formed stably. When the film forming temperature of aluminum is set to 1030 ° C. or more, the grain size of the oxide film 1 mainly composed of α-type aluminum oxide becomes coarse, and the center line average surface roughness Ra and the maximum surface roughness Rmax also become rough, so that the coating tool becomes harder. A disadvantage occurs in that the characteristics are deteriorated.

【００１０】また、上記のように下地である非酸化膜３
を酸化させて結合層２を作製するのではなく、非酸化膜
３の上にＴｉＣＯ、ＴｉＮＯ、ＴｉＣＮＯ等の結合層２
を新たに成膜させる方法として次のものが提案されてい
る。特開昭６３−１９５２６８号ではアルミナ膜の内層
として０．５μｍ厚さのＴｉＣＮＯ膜を図４の結合層２
として１１００℃や１０３０℃で成膜し、その後アルミ
ナ膜１をそれぞれ９６０℃と１０００℃で成膜してお
り、特開平０２−３０４０６号では膜厚１μｍのＴｉＣ
Ｏ膜やＴｉＣＮＯ膜を図４の結合層２として成膜した後
にアルミナ膜１を形成している。また、特開平０５−３
４５９７６号では膜厚０．５μｍと３μｍで粒径０．２
〜１．５μｍのＴｉＣＮＯ膜やＴｉＣＯ膜をＴｉＣｌ4
やＣＯ、Ｈ2、Ｎ2ガスを用いて結合層２として１０００
℃で成膜した後、アルミナ膜１を１０００℃で成膜して
いる。これら結合層２を別個に成膜する従来例の特徴は
それぞれ結合層２の成膜温度がアルミナ膜の成膜温度よ
りも高いこと（特開昭６３−１９５２６８号）、結合層
２の膜厚が１μｍと厚いこと（特開平０２−３０４０６
号）、結合層２の成膜時にＣＯガスを用いていること
（特開平０５−３４５９７６号）である。結合層２の成
膜時に、ＣＯ2やＨ2Ｏ等の酸化性ガスが多すぎたり成膜
温度が高すぎたりすると結合層２中の酸素の含有量が多
くなりすぎ上記と同様に下地の非酸化膜３との密着性が
低下するとともに、結合層２自体の機械強度が低くなる
欠点が現れ、結合層２の膜厚が１μｍと厚いと結合層を
構成する酸化膜自体の機械強度が低いため結合層内で破
断する欠点が現れ、ＣＯ2ガスの代わりにＣＯガスを用
いると結合層２中の含有酸素量が不十分になりα型酸化
アルミニウムを主とする酸化膜１が安定して形成されな
くなる欠点が現れた。上記のように、本発明の課題は下
地の非酸化膜３と酸化膜１とを結合する膜厚の薄い結合
層２の密着性と機械強度特性とを改善することにより、
非酸化膜３との密着性が良いとともに、粒径が小さく機
械強度の優れたα型酸化アルミニウムを主とする酸化膜
１を持つ、長寿命の酸化アルミニウム被覆工具およびそ
の製造方法を提供することである。Further, as described above, the non-oxide film
Is not oxidized to form the bonding layer 2, but the bonding layer 2 of TiCO, TiNO, TiCNO, etc. is formed on the non-oxidized film 3.
The following has been proposed as a method for newly forming a film. In JP-A-63-195268, a 0.5 μm-thick TiCNO film is used as the inner layer of the alumina film as the bonding layer 2 shown in FIG.
A film is formed at 1100 ° C. or 1030 ° C., and then an alumina film 1 is formed at 960 ° C. and 1000 ° C., respectively.
After an O film or a TiCNO film is formed as the bonding layer 2 in FIG. 4, the alumina film 1 is formed. Also, Japanese Patent Application Laid-Open No. 05-3
No. 45976, a film thickness of 0.5 μm and 3 μm and a particle size of 0.2
TiCl the TiCNO film or TiCO film of ~1.5μm 4
And CO, H 2 , N 2 gas to form a bonding layer 2 of 1000
After the film formation at 1000 ° C., the alumina film 1 is formed at 1000 ° C. The features of the conventional example in which these bonding layers 2 are formed separately are that the film forming temperature of the bonding layer 2 is higher than the film forming temperature of the alumina film (Japanese Patent Laid-Open No. 63-195268). Is as thick as 1 μm (JP-A-02-30406)
) And the use of a CO gas at the time of forming the bonding layer 2 (Japanese Patent Application Laid-Open No. 05-345976). If the oxidizing gas such as CO 2 or H 2 O is too large or the film forming temperature is too high during the formation of the bonding layer 2, the oxygen content in the bonding layer 2 will be too large, and the base The adhesive strength with the non-oxide film 3 is reduced, and the mechanical strength of the bonding layer 2 itself is lowered. When the thickness of the bonding layer 2 is as thick as 1 μm, the mechanical strength of the oxide film itself constituting the bonding layer is reduced. When the CO gas is used instead of the CO 2 gas, the oxygen content in the bonding layer 2 becomes insufficient, and the oxide film 1 mainly composed of α-type aluminum oxide becomes stable. The disadvantage that it could not be formed appeared. As described above, an object of the present invention is to improve the adhesion and mechanical strength characteristics of the thin bonding layer 2 that bonds the underlying non-oxide film 3 and oxide film 1 to each other.
Provided is a long-life aluminum oxide-coated tool having an oxide film 1 mainly composed of α-type aluminum oxide having good adhesion to a non-oxide film 3 and having a small particle size and excellent mechanical strength, and a method for manufacturing the same. It is.

【００１１】[0011]

【課題を解決するための手段】本発明者らは、上記知見
に基づき鋭意検討した結果、下地であるＴｉＣ、Ｔｉ
Ｎ、ＴｉＣＮ等の非酸化膜３とα型酸化アルミニウムを
主とする酸化膜１との間に形成する薄い結合層２を改質
することで非酸化膜３およびα型酸化アルミニウムを主
とする酸化膜１との密着性を改善し、α型酸化アルミニ
ウムを主とする酸化膜１の（１１０）面のＸ線ピーク強
度を強くするとともに、α型酸化アルミニウムを主とす
る酸化膜１の結晶粒径を微細化することにより機械特性
が改善されて前記の問題点が解消することを見出し、本
発明に想到した。Means for Solving the Problems The inventors of the present invention have made intensive studies based on the above findings, and have found that TiC and Ti
By modifying the thin bonding layer 2 formed between the non-oxide film 3 of N, TiCN or the like and the oxide film 1 mainly containing α-type aluminum oxide, the non-oxide film 3 and α-type aluminum oxide are mainly used. The adhesiveness with the oxide film 1 is improved, the X-ray peak intensity of the (110) plane of the oxide film 1 mainly containing α-type aluminum oxide is increased, and the crystal of the oxide film 1 mainly containing α-type aluminum oxide is increased. The present inventors have found that by reducing the particle size, mechanical properties are improved and the above-mentioned problems are solved, and the present invention has been reached.

【００１２】すなわち本発明は、基体表面に周期律表の
IVａ、Ｖａ、VIａ族金属の炭化物、窒化物、炭窒化物、
酸化物、酸炭化物、酸窒化物および酸炭窒化物のいずれ
か一種の単層皮膜または二種以上からなる多層皮膜、並
びに少なくとも一層のα型酸化アルミニウムを主とする
酸化膜が形成されている酸化アルミニウム被覆工具にお
いて、該非酸化膜と該酸化膜との間に酸素を含有した結
合層を設けるとともに前記酸化膜のＸ線回析最強ピーク
面が（１１０）面であることを特徴とする酸化アルミニ
ウム被覆工具である。また、基体表面に周期律表のIV
ａ、Ｖａ、VIａ族金属の炭化物、窒化物、炭窒化物、酸
化物、酸炭化物、酸窒化物および酸炭窒化物のいずれか
一種の単層皮膜または二種以上からなる多層皮膜、並び
に少なくとも一層のα型酸化アルミニウムを主とする酸
化膜が形成されている酸化アルミニウム被覆工具におい
て、該非酸化膜と該酸化膜との間に酸素を含有した結合
層を設けるとともに前記酸化膜のＸ線回析の（１１０）
面による等価ピーク強度ＰＲ（１１０）が１以上好まし
くは１．５以上であることを特徴とする酸化アルミニウ
ム被覆工具である。また、前記α型酸化アルミニウムを
主とする酸化膜の膜厚が２．５μｍ未満のときの酸化膜
の平均粒径が２μｍ以下であり、その膜厚が２．５μｍ
以上のときの平均粒径が４μｍ以下であることを特徴と
するものである。また、前記α型酸化アルミニウムを主
とする酸化膜の中心線平均面粗さＲａが０．６μｍ以下
好ましくは０．５μｍ以下であることを特徴とするもの
であり、また、前記酸化膜の膜厚が２．５μｍ未満のと
きのその酸化膜の最大面粗さＲｍａｘが２μｍ以下であ
り、前記膜厚が２．５μｍ以上のときの最大面粗さＲｍ
ａｘが３μｍ以下であることを特徴とするものである。
また、前記各膜間の密着性が高まるように、α型酸化ア
ルミニウムを主とする酸化膜（図４中の１）の格子縞
と、α型酸化アルミニウムを主とする酸化膜と直接接触
する結合層（図４中の２）の格子縞とが界面において連
続していることを特徴とするものである。ここで、格子
縞とは、透過電子顕微鏡（ＴＥＭ）で結晶を高倍率で観
察したときに得られる格子像の縞模様の縞のことを云
う。二つ以上の相接する膜（結晶）の格子像を撮影しよ
うとした時、これらの膜の結晶方位が共に透過電子顕微
鏡の入射ビームと大略平行な時にのみ両者の結晶の格子
像が同時に観察される。α型酸化アルミニウムを主とす
る酸化膜１の格子縞と結合層２の各格子縞とが界面にお
いて連続しているということは即ち両結晶の結晶方位が
共に入射ビームに大略平行であり、α型酸化アルミニウ
ムを主とする酸化膜１と結合層２の両者がエピタキシャ
ルの関係にあることを示している。両膜の結晶方位が平
行でなく片一方の結晶方位のみが透過電子顕微鏡の入射
ビームに平行なときは、その結晶のみの格子像が得ら
れ、平行でないもう片一方の結晶の格子像は得られな
い。また、両結晶の結晶方位が平行であっても両結晶が
直接接触しておらず他の物質が介在している場合には、
両結晶の格子像は得られるものの間にある介在物により
格子縞が途中で中断し両者の格子縞は連続しない。ま
た、本発明はα型酸化アルミニウムを主とする酸化膜の
表面にチタンの窒化膜が形成されていることを特徴とす
るものである。また、本発明は周期律表のIVａ、Ｖａ、
VIａ族金属の炭化物、窒化物、炭窒化物の一種以上とＦ
ｅ、Ｎｉ、Ｃｏ、Ｗ、Ｍｏ、Ｃｒの一種以上とよりなる
超硬質合金を基体とすることを特徴とする酸化アルミニ
ウム被覆工具である。That is, according to the present invention, the surface of the base
Group IVa, Va, VIa group metal carbides, nitrides, carbonitrides,
Oxide, oxycarbide, oxynitride and oxycarbonitride are formed of any one type of single-layer film or a multi-layer film composed of two or more types thereof, and at least one oxide film mainly composed of α-type aluminum oxide. In the aluminum oxide coated tool, an oxygen-containing bonding layer is provided between the non-oxidized film and the oxide film, and the strongest X-ray diffraction peak plane of the oxide film is a (110) plane. It is an aluminum coated tool. In addition, IV of the periodic table
a, Va, VIa group metal carbide, nitride, carbonitride, oxide, oxycarbide, oxynitride and oxycarbonitride any one single-layer film or a multi-layer film consisting of two or more, and at least In an aluminum oxide-coated tool in which an oxide film mainly composed of α-type aluminum oxide is formed, a bonding layer containing oxygen is provided between the non-oxide film and the oxide film, and the X-ray diffraction of the oxide film is reduced. (110)
An aluminum oxide coated tool characterized in that the equivalent peak intensity PR (110) of the surface is 1 or more, preferably 1.5 or more. When the thickness of the oxide film mainly composed of the α-type aluminum oxide is less than 2.5 μm, the average particle size of the oxide film is 2 μm or less, and the thickness is 2.5 μm.
The average particle size at the time of the above is 4 μm or less. Further, the oxide film mainly composed of the α-type aluminum oxide has a center line average surface roughness Ra of 0.6 μm or less, preferably 0.5 μm or less, and a film of the oxide film. The maximum surface roughness Rmax of the oxide film when the thickness is less than 2.5 μm is 2 μm or less, and the maximum surface roughness Rm when the thickness is 2.5 μm or more.
ax is 3 μm or less.
Also, the lattice stripes of the oxide film mainly composed of α-type aluminum oxide (1 in FIG. 4) and the bonding directly contacting the oxide film mainly composed of α-type aluminum oxide so as to increase the adhesion between the respective films. It is characterized in that lattice fringes of the layer (2 in FIG. 4) are continuous at the interface. Here, the lattice fringes refer to fringes of a lattice pattern of a lattice image obtained when a crystal is observed at a high magnification with a transmission electron microscope (TEM). When trying to take a lattice image of two or more adjacent films (crystals), the lattice images of both crystals are simultaneously observed only when the crystal orientations of these films are almost parallel to the incident beam of the transmission electron microscope. Is done. The fact that the lattice fringes of the oxide film 1 mainly composed of α-type aluminum oxide and the lattice fringes of the coupling layer 2 are continuous at the interface means that the crystal orientations of both crystals are substantially parallel to the incident beam, This indicates that the oxide film 1 mainly composed of aluminum and the bonding layer 2 are in an epitaxial relationship. When the crystal orientations of both films are not parallel and only one crystal orientation is parallel to the incident beam of the transmission electron microscope, a lattice image of only that crystal is obtained, and a lattice image of the other non-parallel crystal is obtained. I can't. In addition, even if the crystal orientations of both crystals are parallel, if both crystals are not in direct contact and other substances are interposed,
In the lattice images of the two crystals, the lattice fringes are interrupted on the way due to inclusions between those obtained, and the lattice fringes of both crystals are not continuous. Further, the present invention is characterized in that a titanium nitride film is formed on the surface of an oxide film mainly composed of α-type aluminum oxide. Further, the present invention relates to IVa, Va,
One or more of group VIa metal carbides, nitrides, carbonitrides and F
An aluminum oxide coated tool characterized by using a super-hard alloy consisting of at least one of e, Ni, Co, W, Mo and Cr as a base.

【００１３】また、製造方法として、周期律表のIVａ、
Ｖａ、VIａ族金属の炭化物、窒化物、炭窒化物のいずれ
か一種または二種以上からなる非酸化膜層と、前記非酸
化膜層の成膜時に用いたガス構成を主として更に０．１
〜５ｖｏｌ％好ましくは０．５〜３ｖｏｌ％の酸化性ガ
スを加え成膜温度９５０〜１０２０℃で成膜した周期律
表のIVａ、Ｖａ、VIａ族金属の酸化物、酸炭化物、酸窒
化物および酸炭窒化物のいずれか一種または二種以上か
らなる薄層との組み合わせからなる結合層を成膜し、そ
の上にα型酸化アルミニウムを主とする酸化膜を成膜す
ることができる。[0013] Further, as a manufacturing method, IVa of the periodic table,
Further, a non-oxide film layer made of one or more of carbides, nitrides, and carbonitrides of Va and VIa group metals, and a gas composition used for forming the non-oxide film layer are further 0.1%.
And an oxide, oxycarbide, oxynitride and / or oxide of a Group IVa, Va, or VIa metal of the periodic table formed by adding an oxidizing gas of ５5 vol%, preferably 0.5 to 3 vol%, and forming a film at a film forming temperature of 950 to 1020 ° C. It is possible to form a bonding layer made of a combination of a thin layer made of any one or two or more of oxycarbonitrides, and to form an oxide film mainly composed of α-type aluminum oxide thereon.

【００１４】[0014]

【発明の実施の形態】図１は本発明品の酸化アルミニウ
ム被覆工具の皮膜部分を試料面にして２θ−θ走査法に
よりＸ線回析パターンを測定したときの一例を示したも
のである。Ｘ線源にはＣｕのＫα１（波長λ＝１．５４
０５Ａ）を用いた。本発明品は、従来品と同様に基体表
面にＴｉＮとＴｉＣＮを成膜した後、ＴｉＣ層を薄く成
膜しそのまま連続してＴｉＣの成膜に用いた構成ガスに
さらにＣＯ2ガスを追加して反応させてＴｉＣＯ層を成
膜することによりＴｉＣ層/ＴｉＣＯ層よりなる結合層
を作製した後、その表面上にα型酸化アルミニウムを成
膜したものである。図中にはα−Ａｌ2Ｏ3のＸ線ピーク
のみピーク面を表記し、他の形成化合物によるピーク
（例えばＴｉＣＮ等。）のピーク名は表記していない。
図１より、本発明品はα−Ａｌ2Ｏ3のＸ線ピークの（１
１０）面が他のピークに比べ強いピークを示し、（０１
２）ピークや（０３０）ピークの強度は弱く、（１１
０）のピーク強度を越えないことがわかる。α−Ａｌ2
Ｏ3の（ｈｋｌ）面からのＸ線ピーク強度を定量的に評
価するために次式により（ｈｋｌ）面による等価ピーク
強度ＰＲ（ｈｋｌ）とＴＣ（ｈｋｌ）とを定義した。こ
こでＩ（ｈｋｌ）は（ｈｋｌ）面による実測時のＸ線回
折強度を表し、I0（ｈｋｌ）はＡＳＴＭファイル Ｎ
ｏ．１０−１７３ （Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉ
ｏｎ Ｆｉｌｅ Ｐｕｂｌｉｓｈｅｄ ｂｙ ＪＣＰＤＳ
Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｅｎｔｅｒ ｆｏｒ Ｄ
ｉｆｆｒａｃｔｉｏｎ Ｄａｔａ）に記載されているＸ
線回折強度であり、配向が等方的である粉末粒子の（ｈ
ｋｌ）面からのＸ線回折強度を表している。ＴＣ（ｈｋ
ｌ）は特開平０６ー３１６７５８号中の定義と同一であ
り、ＰＲ（ｈｋｌ）は更に（１２４）、（０３０）のピ
ークまで含めて同様の定義を行ったものである。ＰＲ
（ｈｋｌ）、ＴＣ（ｈｋｌ）はともに、ＡＳＴＭのデー
タに記載された等方粒子のＸ線ピーク強度に対する、Ｘ
線回折で実測した皮膜の（ｈｋｌ）面からのＸ線回折ピ
ーク強度の相対強度を示しており、ＰＲ（ｈｋｌ）、Ｔ
Ｃ（ｈｋｌ）の値が大きい程（ｈｋｌ）面からのＸ線ピ
ーク強度が他のピーク強度よりも強く、（ｈｋｌ）方向
に測定サンプルが配向していることを示す。 ＰＲ（ｈｋｌ）＝｛Ｉ（ｈｋｌ）/I0（ｈｋｌ）｝／[Σ
｛Ｉ（ｈｋｌ）/I0（ｈｋｌ）｝/８]但し、（ｈｋｌ）
＝（０１２）、（１０４）、（１１０）、（１１３）、
（０２４）、（１１６）、（１２４）、（０３０） ＴＣ（ｈｋｌ）＝｛Ｉ（ｈｋｌ）/I0（ｈｋｌ）｝／[Σ
｛Ｉ（ｈｋｌ）/I0（ｈｋｌ）｝/６]但し、（ｈｋｌ）
＝（０１２）、（１０４）、（１１０）、（１１３）、
（０２４）、（１１６） 具体的には、図１のＰＲ（１１０）は５．０４であり、
図１の（１１０）のＸ線ピーク強度が粉末粒子が示す
（１１０）Ｘ線ピーク強度よりも５．０４倍強いことを
示している。なお、２θが２０〜８０°の範囲内には上
記の８ピーク以外に（００６）、（２０２）、（２１
１）、（１２２）、（０１８）ピークも存在するがこれ
らのピーク強度はI0が１０以下でありピーク強度Ｉの少
しの変化でＩ/I 0が大きく変動するためＰＲ（ｈｋ
ｌ）、ＴＣ（ｈｋｌ）の計算には含めなかった。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an aluminum oxide product of the present invention.
2θ-θ scanning method using the coating part of the
An example of the measurement of the X-ray diffraction pattern is shown below.
It is. The X-ray source is Cu Kα1 (wavelength λ = 1.54).
05A) was used. The product of the present invention has the same substrate surface as the conventional product.
After forming TiN and TiCN on the surface, a thin TiC layer is formed.
The constituent gas used for forming the TiC film is continuously formed as it is.
More COTwoA gas is added and reacted to form a TiCO layer.
Bonding layer consisting of TiC layer / TiCO layer
After the fabrication, α-type aluminum oxide is formed on the surface.
It is a film. In the figure, α-AlTwoOThreeX-ray peak of
Only the peak plane is indicated and peaks due to other forming compounds
The peak name (for example, TiCN or the like) is not shown.
From FIG. 1, the product of the present invention is α-AlTwoOThree(1)
10) The plane shows a stronger peak than the other peaks, and (01)
2) The intensity of the peak or (030) peak is weak, and (11)
It can be seen that the peak intensity does not exceed 0). α-AlTwo
OThreeX-ray peak intensity from (hkl) plane
Equivalent peak by (hkl) plane according to the following equation
The intensity PR (hkl) and TC (hkl) were defined. This
Here, I (hkl) is the X-ray number at the time of actual measurement by the (hkl) plane.
Fold strength0(Hkl) is the ASTM file N
o. 10-173 (Powder Diffraction
on File Published by JCPDS
International Center for D
X described in “fraction Data”
Line diffraction intensity and (h) of powder particles having isotropic orientation.
Kl) represents the X-ray diffraction intensity from the plane. TC (hk
l) is the same as the definition in JP-A-06-316758.
PR (hkl) is further divided into (124) and (030)
The same definition has been made including the work up to the end. PR
(Hkl) and TC (hkl) are both ASTM data.
X with respect to the X-ray peak intensity of isotropic particles described in
X-ray diffraction from the (hkl) plane of the film measured by X-ray diffraction
The relative intensity of the peak intensity, PR (hkl), T
As the value of C (hkl) increases, the X-ray peak from the (hkl) plane increases.
The peak intensity is stronger than the other peak intensity, and the (hkl) direction
Shows that the measurement sample is oriented. PR (hkl) = ｛I (hkl) / I0(Hkl)｝ / [Σ
｛I (hkl) / I0(Hkl)｝ / 8] where (hkl)
= (012), (104), (110), (113),
(024), (116), (124), (030) TC (hkl) = {I (hkl) / I0(Hkl)｝ / [Σ
｛I (hkl) / I0(Hkl)｝ / 6] where (hkl)
= (012), (104), (110), (113),
(024), (116) Specifically, PR (110) in FIG. 1 is 5.04,
The powder particle shows the X-ray peak intensity of (110) in FIG.
(110) It is 5.04 times stronger than the X-ray peak intensity.
Is shown. When 2θ is in the range of 20 to 80 °,
(006), (202), (21)
1), (122), and (018) peaks also exist.
Their peak intensity is I0Is 10 or less and the peak intensity I is small.
I / I with change 0Greatly fluctuates, PR (hk
l), not included in the calculation of TC (hkl).

【００１５】本発明品の酸化膜表面の平均結晶粒径は
（株）日立製作所製の走査電子顕微鏡（Ｓ−２３００）
の写真により測定し、膜厚が２．５μｍ未満のときは２
μｍ以下であり、膜厚が２．５μｍ以上のときは４μｍ
以下であった。また、中心線平均面粗さＲａは０．６μ
ｍ以下であり、また、最大面粗さＲｍａｘは酸化膜の膜
厚が２．５μｍ未満のときは２μｍ以下であり、膜厚が
２．５μｍ以上のときは３μｍ以下であった。The average crystal grain size on the surface of the oxide film of the product of the present invention was measured by a scanning electron microscope (S-2300) manufactured by Hitachi, Ltd.
Measured when the film thickness is less than 2.5 μm, 2
μm or less, and 4 μm when the film thickness is 2.5 μm or more.
It was below. The center line average surface roughness Ra is 0.6 μm.
m or less, and the maximum surface roughness Rmax was 2 μm or less when the thickness of the oxide film was less than 2.5 μm, and 3 μm or less when the thickness of the oxide film was 2.5 μm or more.

【００１６】また、本発明品の一例であるα型酸化アル
ミニウムを主とする酸化膜と本酸化膜に直接接触してい
るＴｉＣ／ＴｉＣＯ結合層及びその下のＴｉＣＮ膜との
界面近傍を（株）日立製作所製の透過電子顕微鏡（Ｈ−
９０００ＵＨＲ）により観測したところ、後述の図３の
ように膜間の各界面において格子縞が連続していること
が確認された。図５にこの格子縞の連続状況を模式的に
示す。図５はあくまで以下に述べる原子レベルでの膜の
成膜状況を説明するために示すものであり、各界面にお
ける格子縞の連続性は、格子縞間にわずかのずれ（不整
合性）が許容され、格子縞の連続状況、格子縞間隔、個
数等は図５に限定されるものでないことは言うまでもな
いことである。The vicinity of the interface between the oxide film mainly composed of α-type aluminum oxide, which is an example of the product of the present invention, the TiC / TiCO bonding layer which is in direct contact with the present oxide film, and the TiCN film thereunder is shown in FIG. ) Hitachi transmission electron microscope (H-
Observation by 9000 UHR) confirmed that lattice fringes were continuous at each interface between the films as shown in FIG. 3 described later. FIG. 5 schematically shows the continuity of the lattice fringes. FIG. 5 is provided only to explain the film formation state at the atomic level described below. Regarding the continuity of the lattice fringes at each interface, a slight shift (mismatch) between the lattice fringes is allowed. It goes without saying that the continuity of the lattice fringe, the lattice fringe interval, the number and the like are not limited to those shown in FIG.

【００１７】本発明品のα型酸化アルミニウムを主とす
る酸化膜の密着性や機械特性が優れる理由は明確ではな
いが次のことが考えられる。本発明品のα型酸化アルミ
ニウムを主とする酸化膜は図１のようにＸ線回析時の
（１１０）面ピーク強度が強く、α型酸化アルミニウム
の（１１０）面が母材と平行方向に強く配向しているも
のである。本発明の製造方法により作製すると、下地の
非酸化膜（図４中の３）や結合層（図４中の２）および
α型酸化アルミニウムを主とする酸化膜（図４中の１）
の間にエピタキシャルの関係が成立し、即ち各膜が界面
において連続的に形成（格子縞が連続的に形成）される
ため、α型酸化アルミニウムの（１１０）面が面内に強
く配向し、同時に、下地の非酸化膜３や結合層２と酸化
膜１との界面に空孔や、大きな欠陥が非常に生じにく
く、膜相互の密着性が高くなるものと考えられる。この
ような意味で、前記格子縞の連続性（エピタキシャルの
関係）はすべての界面で成立する必要はなく、透過電子
顕微鏡により結合層近傍を５万倍で観察したときに上記
格子縞の連続性（エピタキシャルの関係）が認められる
領域が存在すれば、本発明による優れた作用効果を獲得
することができる。本発明において下地に用いるＴｉ
Ｃ、ＴｉＮ、ＴｉＣＮ等の非酸化膜（図４中の３）及び
結合層（図４中の２に対応し、例えば、ＴｉＣ／ＴｉＣ
Ｏ、ＴｉＮ／ＴｉＮＯ、ＴｉＣＮ／ＴｉＣＮＯ等。）の
両者はｆｃｃ結晶構造を持っており、これらの膜がエピ
タキシャルに成長するとα型酸化アルミニウムを主とす
る酸化膜３は（１１０）方向に配向しやすくなるものと
考えられる。また、（１１０）面による等価Ｘ線ピーク
強度ＰＲ（１１０）が１以上好ましくは１．５以上であ
ることにより、通常は粉末状にして測定する等方的に配
向したα型酸化アルミニウムが示す（１１０）Ｘ線ピー
ク強度（即ち、ＡＳＴＭファイルＮｏ．１０−１７３に
記載されているＸ線強度）よりも本発明品の（１１０）
Ｘ線ピーク強度が１倍以上好ましくは１．５倍以上であ
り、（１１０）面が１倍以上好ましくは１．５倍以上配
向していることになり、上記の理由で密着性が優れるこ
とがわかる。本発明において、（１１０）ピーク強度が
強いときは（０１２）ピーク強度や（０３０）ピーク強
度は相対的に弱くなる傾向がみられる。ＰＲ（１１０）
の強度が大略１倍以上の時、ＴＣ（０１２）は１．３以
下であり、ＰＲ（１１０）の強度が大きくなるとともに
ＴＣ（０１２）値は小さくなり、ＰＲ（１１０）＝８付
近ではＴＣ（０１２）は約０．１になる。ＰＲ（１１
０）が１以上では、（０３０）ピークと（１０４）ピー
クの強度比Ｉ（０３０）/Ｉ（１０４）は０〜９．９７
と値がばらつき、（０１２）ピークと（０３０）ピーク
の強度比Ｉ（０１２）/Ｉ（０３０）は０．０８〜６
３．０６と値がばらつきＰＲ（１１０）とＩ（０３０）
/Ｉ（１０４）やＩ（０１２）/Ｉ（０３０）との相関は
見られなかった。本開発品は（１１０）ピークが特に強
く（０３０）ピークや（０１２）ピークは相対的に弱く
なっており、（０３０）ピークや（０１２）ピークの強
度が大きい特開平０６−３１５０３号や特開平０７−１
０８４０５号のアルミナ膜とは本質的に異なるものであ
ることがわかる。The reason why the oxide film mainly comprising α-type aluminum oxide of the present invention is excellent in adhesion and mechanical properties is not clear, but the following may be considered. As shown in FIG. 1, the oxide film mainly containing α-type aluminum oxide of the present invention has a strong peak intensity in the (110) plane at the time of X-ray diffraction, and the (110) plane of the α-type aluminum oxide is parallel to the base material. Are strongly oriented. When manufactured by the manufacturing method of the present invention, an underlying non-oxide film (3 in FIG. 4), a bonding layer (2 in FIG. 4), and an oxide film mainly composed of α-type aluminum oxide (1 in FIG. 4)
In other words, an epitaxial relationship is established between the films, that is, each film is continuously formed at the interface (lattice stripes are continuously formed), so that the (110) plane of the α-type aluminum oxide is strongly oriented in the plane, and It is considered that vacancies and large defects hardly occur at the interface between the underlying non-oxide film 3 and the bonding layer 2 and the oxide film 1, and the adhesion between the films is increased. In this sense, the continuity (epitaxial relationship) of the lattice fringes does not need to be established at all interfaces, and the continuity of the lattice fringes (epitaxial relation) is observed when the vicinity of the coupling layer is observed at a magnification of 50,000 with a transmission electron microscope. If there is a region in which the relationship (1) is recognized, the excellent operation and effect according to the present invention can be obtained. Ti used for the base in the present invention
Non-oxidized films (3 in FIG. 4) such as C, TiN, and TiCN, and a bonding layer (corresponding to 2 in FIG. 4, for example, TiC / TiC
O, TiN / TiNO, TiCN / TiCNO, etc. 2) have an fcc crystal structure, and it is considered that when these films grow epitaxially, the oxide film 3 mainly composed of α-type aluminum oxide is likely to be oriented in the (110) direction. Further, when the equivalent X-ray peak intensity PR (110) by the (110) plane is 1 or more, preferably 1.5 or more, it indicates an isotropically oriented α-type aluminum oxide which is usually measured in powder form. The (110) X-ray peak intensity (ie, the X-ray intensity described in ASTM file No. 10-173) of the product of the present invention is higher than that of (110).
The X-ray peak intensity is 1 or more times, preferably 1.5 times or more, and the (110) plane is oriented 1 time or more, preferably 1.5 times or more, and the adhesion is excellent for the above reason. I understand. In the present invention, when the (110) peak intensity is high, the (012) peak intensity and the (030) peak intensity tend to be relatively weak. PR (110)
When the intensity is approximately 1 or more, TC (012) is 1.3 or less, the intensity of PR (110) increases, the TC (012) value decreases, and near the PR (110) = 8, TC (012) decreases. (012) becomes about 0.1. PR (11
When (0) is 1 or more, the intensity ratio I (030) / I (104) between the (030) peak and the (104) peak is 0 to 9.97.
The intensity ratio I (012) / I (030) between the (012) peak and the (030) peak is 0.08 to 6
3.06 and the value fluctuated PR (110) and I (030)
No correlation with / I (104) or I (012) / I (030) was found. In this developed product, the (110) peak is particularly strong, the (030) peak and the (012) peak are relatively weak, and the intensity of the (030) peak and the (012) peak is large. Kaihei 07-1
It can be seen that this is essentially different from the alumina film of No. 08405.

【００１８】本発明方法で作製すると非酸化膜と結合層
およびα型酸化アルミニウムを主とする酸化膜とがエピ
タキシャルに成長するため、α型酸化アルミニウムを主
とする酸化膜を比較的低温度で密着性高く成膜出来る。
したがって、α型酸化アルミニウムを主とする酸化膜の
平均結晶粒径をこの酸化膜の膜厚が２．５μｍ未満のと
きは２μｍ以下、前記膜厚が２．５μｍ以上のときは４
μｍ以下に成膜出来、また、前記酸化膜の中心線平均面
粗さＲａを０．６μｍ以下、最大面粗さＲｍａｘを前記
酸化膜の膜厚が２．５μｍ未満のときは２μｍ以下でか
つその膜厚が２．５μｍ以上のときは３μｍ以下にする
事が出来る。上記のように、本発明ではα型酸化アルミ
ニウムを主とした酸化膜の粒径と中心線平均面粗さＲ
ａ、最大面粗さＲｍａｘが小さいため切削加工等の工具
として使用したときの摩擦が少なく、膜の磨耗や脱粒が
少なくなり、優れた機械特性が得られたものと考えられ
る。同様の理由で膜表面の中心線平均面粗さＲａは０．
５μｍ以下が望ましく、α型酸化アルミニウムを主とし
た酸化膜の磨耗や脱粒が更に少なくなり工具特性が更に
向上する。When the non-oxide film, the bonding layer and the oxide film mainly containing α-type aluminum oxide are grown epitaxially by the method of the present invention, the oxide film mainly containing α-type aluminum oxide is grown at a relatively low temperature. A film can be formed with high adhesion.
Therefore, the average crystal grain size of the oxide film mainly composed of α-type aluminum oxide is 2 μm or less when the thickness of the oxide film is less than 2.5 μm, and 4 when the thickness is 2.5 μm or more.
μm or less, and the center line average surface roughness Ra of the oxide film is 0.6 μm or less, and the maximum surface roughness Rmax is 2 μm or less when the thickness of the oxide film is less than 2.5 μm and When the film thickness is 2.5 μm or more, it can be reduced to 3 μm or less. As described above, in the present invention, the grain size and the center line average surface roughness R of the oxide film mainly composed of α-type aluminum oxide
a) Since the maximum surface roughness Rmax is small, friction when used as a tool for cutting or the like is small, and wear and shedding of the film are reduced, and it is considered that excellent mechanical properties are obtained. For the same reason, the center line average surface roughness Ra of the film surface is 0.1.
The thickness is preferably 5 μm or less, and the wear and shedding of the oxide film mainly composed of α-type aluminum oxide are further reduced, and the tool characteristics are further improved.

【００１９】次に、本発明による新規な酸化アルミニウ
ム被覆工具を得る製造方法について解説する。本発明
は、周期律表のIVａ、Ｖａ、VIａ族金属の炭化物、窒化
物、炭窒化物のいずれか一種または二種以上からなる非
酸化膜（図４中の３）を成膜した後、まず周期律表のIV
ａ、Ｖａ、VIａ族金属の炭化物、窒化物、炭窒化物のい
ずれか一種または二種以上からなる非酸化層を薄く成膜
し、そのまま連続してこの非酸化膜の成膜を構成したガ
スを主として更に０．１〜３．０ｖｏｌ％の酸化性ガス
を加えて成膜温度９５０〜１０２０℃で成膜することに
より結合層（図４中の２）を成膜した後、その上にα型
酸化アルミニウムを主とする酸化膜（図４中の１）を成
膜するものである。このように成膜する事により、非酸
化層（図４中の２−２）と下地である非酸化膜３との間
にエピタキシャル関係が得やすくなり非酸化膜３と結合
層２との間に高い密着性が得られ、更に連続して酸化性
ガスを加えて成膜した層（図４中の２−１）によりα型
酸化アルミニウムを主とする酸化膜１との間にエピタキ
シャル関係が得やすくなり結合層２と酸化膜１との間に
高い密着性が得られるのが本発明による製造方法の特徴
であり、膜剥がれを起こし難く、長寿命の酸化アルミニ
ウム被覆工具を製造することができる。この時、結合層
内を連続的に成膜するため途中で追加する酸化性ガス量
は全ガス流量の０．１〜５ｖｏｌ％である必要がある。
酸化性ガス量が０．１ｖｏｌ％未満では結合層表面の酸
素量が少ないため結合層上にκ型酸化アルミニウムが出
来やすくなり、安定してα型酸化アルミニウムを主とす
る酸化膜が成膜出来ず、５ｖｏｌ％を越えると結合層の
酸化が進みすぎＴｉ2Ｏ3、Ｔｉ3Ｏ5、ＴｉＯ2等が多く
成膜されるため結合層自体の機械的強度が低下しα型酸
化アルミニウムを主とする酸化膜が結合層内で剥離しや
すくなる欠点が生じる。また、成膜温度が９５０℃未満
の時は緻密な結合層を成膜出来ず膜剥がれを生じやす
く、１０２０℃を越える時は結合層の結晶粒が粗くしか
も酸化が進みすぎ膜剥がれを生じやすくなる。また、本
発明のα型酸化アルミニウムの成膜にはＡｌＣｌ3やＨ
2、ＣＯ2、Ｈ2Ｓ等のガスを用い酸化膜を成膜でき、毒
性や腐食性の高いＳＯ2ガスを用いる必要はなく、また
ＣＯ2ガス量も通常の流量である２０ｖｏｌ％以下で成
膜出来るため安定してα型酸化アルミニウムを主とする
酸化膜を成膜することができる。Next, a method for producing a novel aluminum oxide-coated tool according to the present invention will be described. The present invention forms a non-oxide film (3 in FIG. 4) formed of one or more of carbides, nitrides, and carbonitrides of metals of groups IVa, Va, and VIa of the periodic table, First, IV of the periodic table
a gas comprising a thin non-oxidized layer made of one or more of carbides, nitrides, and carbonitrides of a, Va, and VIa group metals, and continuously forming the non-oxidized film as it is Is formed at a film formation temperature of 950 to 1020 ° C. by adding an oxidizing gas of mainly 0.1 to 3.0 vol% to form a bonding layer (2 in FIG. 4). An oxide film (1 in FIG. 4) mainly composed of aluminum oxide is formed. By forming the film in this manner, an epitaxial relationship can be easily obtained between the non-oxide layer (2-2 in FIG. 4) and the non-oxide film 3 serving as a base, and the And a layer formed by continuously adding an oxidizing gas (2-1 in FIG. 4) has an epitaxial relationship with the oxide film 1 mainly composed of α-type aluminum oxide. It is a feature of the manufacturing method according to the present invention that it is easy to obtain and high adhesion between the bonding layer 2 and the oxide film 1 is obtained. it can. At this time, the amount of oxidizing gas to be added in the course of continuous formation in the bonding layer needs to be 0.1 to 5 vol% of the total gas flow rate.
When the amount of the oxidizing gas is less than 0.1 vol%, the amount of oxygen on the surface of the bonding layer is small, so that κ-type aluminum oxide is easily formed on the bonding layer, and an oxide film mainly composed of α-type aluminum oxide can be stably formed. On the other hand, if the content exceeds 5 vol%, the oxidation of the bonding layer proceeds too much, and a large amount of Ti2 O3, Ti3 O5, TiO2, etc. is formed. There is a disadvantage that the film is easily peeled off. When the film formation temperature is lower than 950 ° C., a dense bonding layer cannot be formed, and the film is easily peeled off. Become. In addition, AlCl3 or H
2. Oxide film can be formed using gases such as CO2, H2S, etc., and there is no need to use highly toxic or corrosive SO2 gas. CO2 gas can be formed at a normal flow rate of 20 vol% or less, so it is stable. Thus, an oxide film mainly composed of α-type aluminum oxide can be formed.

【００２０】本発明のα型酸化アルミニウムを主とする
酸化膜は、必ずしも最外層である必要はなく、α型酸化
アルミニウムを主とする酸化膜の上に更に少なくとも一
層のチタン化合物（例えばＴｉＮ層等。）を被覆しても
良い。The oxide film mainly composed of α-type aluminum oxide of the present invention is not necessarily required to be the outermost layer, and at least one titanium compound (for example, a TiN layer) is formed on the oxide film mainly composed of α-type aluminum oxide. Etc.).

【００２１】本発明における被覆方法には既知の成膜方
法を適用することが可能である。例えば、通常の化学蒸
着法（熱ＣＶＤ）、プラズマを付加した化学蒸着法（Ｐ
ＡＣＶＤ）等を用いることができる。用途は切削工具に
限るものではなく、α型酸化アルミニウムを主とする酸
化膜を含む単層あるいは多層の硬質皮膜により被覆され
た耐摩耗材や金型、溶湯部品等でも良い。酸化膜はα型
酸化アルミニウム単相に限るものではなく、α型酸化ア
ルミニウムが主であれば、他の酸化物、例えばα型酸化
アルミニウムとκ型酸化アルミニウムとの混合膜やγ型
酸化アルミニウム、θ型酸化アルミニウム、δ型酸化ア
ルミニウム、χ型酸化アルミニウム等、他の酸化アルミ
ニウムとの混合膜あるいはα型酸化アルミニウムと酸化
ジルコニウム等他の酸化物との混合膜であっても同様の
効果が得られる。なお、本発明のα型酸化アルミニウム
を主とする酸化膜とは、８０ｖｏｌ％以上のα型酸化ア
ルミニウムを含むものをいう。A known film forming method can be applied to the coating method in the present invention. For example, a normal chemical vapor deposition method (thermal CVD) or a chemical vapor deposition method (P
ACVD) can be used. The application is not limited to cutting tools, but may be a wear-resistant material, a mold, a molten metal part or the like coated with a single-layer or multilayer hard film containing an oxide film mainly composed of α-type aluminum oxide. The oxide film is not limited to α-type aluminum oxide single phase, and if α-type aluminum oxide is mainly used, other oxides such as a mixed film of α-type aluminum oxide and κ-type aluminum oxide or γ-type aluminum oxide, The same effect can be obtained even with a mixed film of other aluminum oxides such as θ-type aluminum oxide, δ-type aluminum oxide, and χ-type aluminum oxide, or a mixed film of α-type aluminum oxide and other oxides such as zirconium oxide. Can be Note that the oxide film mainly containing α-type aluminum oxide of the present invention means a film containing 80 vol% or more of α-type aluminum oxide.

【００２２】次に本発明による被覆工具を実施例によっ
て具体的に説明する。ただし、本発明はこれら実施例の
範囲に限定されるものでないことは言うまでもない。Next, the coated tool according to the present invention will be specifically described with reference to examples. However, it goes without saying that the present invention is not limited to the scope of these examples.

【００２３】（実施例１）ＷＣ７２％，ＴｉＣ８％，
（Ｔａ，Ｎｂ）Ｃ１１％，Ｃｏ９％（％はいずれも重量
％を示す。）の組成よりなる切削工具用超硬基板をＣＶ
Ｄ炉内にセットし、その表面に、化学蒸着法によりＨ2
キャリヤーガスとＴｉＣｌ4ガスとＮ2ガスとを原料ガス
に用い０．３μｍ厚さのＴｉＮを９００℃でまず形成
し、次に、Ｈ2キャリヤーガスとＴｉＣｌ4ガスとＣＨ3
ＣＮガスを原料ガスに用い６μｍ厚さのＴｉＣＮ膜を９
００℃で成膜することにより非酸化膜（図４中の３）を
形成した後、９５０〜１０２０℃でＨ2キャリヤーガス
とＴｉＣｌ4ガスとＣＨ4ガスとをトータル２，２００ｍ
ｌ／分を５〜３０分間流してまず成膜し、そのまま連続
して本構成ガスに更に２．２〜１１０ｍｌ／分のＣＯ2
ガスを追加して５〜３０分間成膜することによりＴｉＣ
層とＴｉＣＯ層とが薄く積層されたＴｉＣ/ＴｉＣＯ結
合層（図４中の２）を作製した。その後、続いてＡｌ金
属小片を詰め３５０℃に保温した小筒中にＨ2ガスを流
量３１０ｍｌ／分とＨＣｌガス１３０ｍｌ／分とを流す
ことにより発生させたＡｌＣｌ3ガスとＨ2ガス２ｌ／分
とＣＯ2ガス１００ｍｌ／分とをＣＶＤ炉内に流し１０
１０〜１０２０℃で反応させることにより所定の厚さの
酸化アルミニウム膜（図４中の１）を成膜し本発明品を
作製した。酸化アルミニウム膜の成膜時にＳＯ2ガスは
流さなかった。(Example 1) WC 72%, TiC 8%,
A carbide substrate for a cutting tool having a composition of (Ta, Nb) C11%, Co9% (% indicates weight%) is CV
D furnace, and the surface was coated with H 2 by chemical vapor deposition.
Using a carrier gas, a TiCl 4 gas, and a N 2 gas as source gases, a 0.3 μm thick TiN is first formed at 900 ° C., and then a H 2 carrier gas, a TiCl 4 gas, and a CH 3 gas are formed.
Using a CN gas as a source gas, a 6 μm thick TiCN film
After forming a non-oxidized film (3 in FIG. 4) by forming the film at 00 ° C., a H 2 carrier gas, a TiCl 4 gas and a CH 4 gas are added at 950 to 1020 ° C. for a total of 2,200 m.
1 / min for 5 to 30 minutes to form a film first, and then continuously and further add 2.2 to 110 ml / min of CO 2
By adding a gas and forming a film for 5 to 30 minutes, TiC
A TiC / TiCO bonding layer (2 in FIG. 4) in which the layer and the TiCO layer were thinly laminated was prepared. Thereafter, AlCl 3 gas and H 2 gas 2 l / min were generated by flowing a H 2 gas at a flow rate of 310 ml / min and a HCl gas at 130 ml / min into a small cylinder packed with small pieces of Al metal and kept at 350 ° C. Flow 100 ml / min of CO 2 gas into the CVD furnace and
By reacting at 10 to 1020 ° C., an aluminum oxide film (1 in FIG. 4) having a predetermined thickness was formed to produce a product of the present invention. No SO 2 gas was supplied during the formation of the aluminum oxide film.

【００２４】作製した膜のＸ線回折は理学電気（株）製
のＸ線回折装置（ＲＵ−３００Ｒ）を用いて２θ−θ法
により２θが２０〜９０°の範囲内で測定した。Ｘ線源
にはＫα１線のみを用い、装置に内蔵されたソフトによ
りＫα２線とノイズとを除去して測定した。The X-ray diffraction of the prepared film was measured using a X-ray diffractometer (RU-300R, manufactured by Rigaku Corporation) in the range of 20 to 90 ° by 2θ-θ method. Only the Kα1 ray was used as the X-ray source, and Kα2 ray and noise were removed by software built in the apparatus, and the measurement was performed.

【００２５】実施例１において、ＴｉＣ/ＴｉＣＯ結合
層まで成膜した後、ＡｌＣｌ3ガスとＨ2ガス２ｌ／分と
ＣＯ2ガス１００ｍｌ／分とを流し１０２０℃で酸化ア
ルミニウムを成膜したときの代表的な２つのＸ線回折測
定結果を図１、図２に示す。図中にはα−Ａｌ2Ｏ3のＸ
線ピークのみピーク面を表記し、他の形成化合物のピー
ク（例えばＴｉＣＮ等。）のピーク名は表記していな
い。図１、２よりα（１１０）ピークが強く、α（０１
２）やα（１０４）、α（０３０）等のピークは小さい
ことがわかる。図１の場合Ｉ（０３０）/Ｉ（１０４）
＜１、Ｉ（０１２）/Ｉ（０３０）＞１であり、図２の
場合Ｉ（０３０）/Ｉ（１０４）＞１、Ｉ（０１２）/Ｉ
（０３０）＞１となっている。同様に測定した実施例１
の本発明品のＰＲ（１１０）とＴＣ（０１２）およびＩ
（０３０）/Ｉ（１０４）、Ｉ（０１２）/Ｉ（０３０）
の評価結果を表１にまとめる。In Example 1, after the film was formed up to the TiC / TiCO bonding layer, the aluminum oxide film was formed at 1020 ° C. by flowing AlCl 3 gas, H 2 gas 2 l / min and CO 2 gas 100 ml / min. FIGS. 1 and 2 show the results of two representative X-ray diffraction measurements. In the figure, X of α-Al 2 O 3 is shown.
Only the line peak is shown as a peak plane, and the peak names of other forming compound peaks (eg, TiCN) are not shown. 1 and 2, the α (110) peak is stronger and α (01)
It can be seen that peaks such as 2), α (104) and α (030) are small. In the case of FIG. 1, I (030) / I (104)
<1, I (012) / I (030)> 1, and in the case of FIG. 2, I (030) / I (104)> 1, I (012) / I
(030)> 1. Example 1 measured similarly
PR (110) and TC (012) and I
(030) / I (104), I (012) / I (030)
Table 1 summarizes the evaluation results.

【００２６】[0026]

【表１】 [Table 1]

【００２７】酸化アルミニウム膜の平均粒径は酸化アル
ミニウム膜表面を図６（ａ）に示す通り倍率５０００倍
でＳＥＭ写真に撮り（写真上の倍率は５０００×０．８
＝４０００倍）、この図６（ａ）に対応した図６（ｂ）
の模式図に示すように寸法が７０ｍｍ×８５ｍｍのＳＥ
Ｍ写真上に上から１６．５ｍｍ,３５ｍｍ,５２．５ｍｍ
の各位置に横方向に引いた直線と写真の対角線を結んだ
直線二本、計五本を引き、各直線内にある結晶粒の数か
ら次式により平均粒径を求めた。平均粒径（μｍ）＝
（直線の総長さ（ｍｍ））／（直線内の結晶粒の総数
（ケ））×０．２５上記図６（ａ），図６（ｂ）は上記
平均粒径の測定の一例を示したもので、直線の総長さは
４７５ｍｍ、直線内の結晶粒の総数は８５ケであり、平
均結晶粒径は１．４μｍであった。酸化アルミニウム膜
表面の中心線平均面粗さＲａはＶｅｅｃｏ Ｉｎｓｔｒ
ｕｍｅｎｓ Ｉｎｃ．社製の触診型の表面粗さ計ＤＥＫ
ＴＡＫ８０００を用いて測定長０．２５ｍｍで測定し、
最大面粗さＲｍａｘはＬａｓｅｒｔｅｃ（株）社製のレ
ーザー顕微鏡１ＬＭ１１を用いて測定長１８μｍで測定
した。その時の酸化アルミニウム膜厚は表面粗さを測定
した試料の破断面を倍率５０００倍でＳＥＭ写真に撮り
測定した。上記測定長１８μｍでＲｍａｘを測定するこ
とにより異物等による測定誤差を抑えアルミナ膜本来の
Ｒｍａｘを測定できた。これらの評価結果を表１にまと
める。The average particle diameter of the aluminum oxide film was taken on a SEM photograph of the surface of the aluminum oxide film at a magnification of 5000 times as shown in FIG. 6A (magnification on the photograph was 5000 × 0.8).
= 4000 times), and FIG. 6B corresponding to FIG.
SE with dimensions of 70 mm x 85 mm as shown in the schematic diagram of
16.5mm, 35mm, 52.5mm from above on M-photo
A total of five lines were drawn by connecting a straight line drawn in the lateral direction to each position and a diagonal line of the photograph, and the average particle size was determined from the number of crystal grains in each straight line by the following formula. Average particle size (μm) =
(Total length of straight line (mm)) / (total number of crystal grains in straight line (q)) × 0.25 FIGS. 6A and 6B show an example of the measurement of the average particle size. The total length of the straight line was 475 mm, the total number of crystal grains in the straight line was 85, and the average crystal grain size was 1.4 μm. The center line average surface roughness Ra of the aluminum oxide film surface is Veeco Instr.
umens Inc. Palpable surface roughness meter DEK
Measure with a measurement length of 0.25 mm using TAK8000,
The maximum surface roughness Rmax was measured with a laser microscope 1LM11 manufactured by Lasertec Co., Ltd. at a measurement length of 18 μm. The aluminum oxide film thickness at that time was measured by taking a fractured surface of the sample whose surface roughness was measured in a SEM photograph at a magnification of 5000 times. By measuring Rmax at the above measurement length of 18 μm, measurement errors due to foreign substances and the like were suppressed, and the original Rmax of the alumina film could be measured. Table 1 summarizes the results of these evaluations.

【００２８】表１より本発明品はＰＲ（１１０）が１以
上でありＴＣ（０１２）は１．３以下であること、Ｉ
（０３０）/Ｉ（１０４）とＩ（０１２）/Ｉ（０３０）
とはＰＲ（１１０）と相関が無くそれぞれ０．１５４〜
４．３６９と０．０８２〜１１．６９３と値がばらつき
一貫性がないことがわかる。また、ＰＲ（１１０）が大
きくなるにつれて粒径/膜厚の比が若干大きくなってい
くことがわかる。また、表１より本発明品の平均粒径が
酸化膜の膜厚が２．５μｍ未満のときは２μｍ以下であ
り、膜厚が２．５μｍ以上のときは４μｍ以下であるこ
と、中心線平均面粗さＲａは０．６μｍ以下であり、最
大面粗さＲｍａｘは酸化膜の膜厚が２．５μｍ未満のと
きは２μｍ以下であり、膜厚が２．５μｍ以上のときの
Ｒｍａｘは３μｍ以下であることがわかる。According to Table 1, the product of the present invention has PR (110) of 1 or more and TC (012) of 1.3 or less.
(030) / I (104) and I (012) / I (030)
Means that there is no correlation with PR (110)
It can be seen that the values vary from 4.369 to 0.082 to 11.693 and are not consistent. Also, it can be seen that the ratio of particle size / film thickness slightly increases as PR (110) increases. Also, from Table 1, the average particle size of the product of the present invention is 2 μm or less when the thickness of the oxide film is less than 2.5 μm, and 4 μm or less when the thickness is 2.5 μm or more. The surface roughness Ra is 0.6 μm or less, and the maximum surface roughness Rmax is 2 μm or less when the thickness of the oxide film is less than 2.5 μm, and Rmax is 3 μm or less when the thickness of the oxide film is 2.5 μm or more. It can be seen that it is.

【００２９】（実施例２）上記実施例１の手順で、０．
３μｍ厚さのＴｉＮを９００℃で、６μｍ厚さのＴｉＣ
Ｎ膜を９００℃で形成した後、ＴｉＣ／ＴｉＣＯ結合層
を９５０〜１０１０℃で成膜した。次いで、ＡｌＣｌ3
ガスとＨ2ガス２ｌ／分とＣＯ 2ガス１００ｍｌ／分およ
びＨ2Ｓガス８ｍｌ／分とをＣＶＤ炉内に流し１０１０
℃で酸化アルミニウムを成膜し、その後、Ｈ2ガス４ｌ
／分とＴｉＣｌ4ガス５０ｍｌ／分とＮ2ガス１．３ｌ／
分を流し１０１０℃で窒化チタニウム膜を形成した時の
本発明品の代表的な３つのＸ線回折測定結果を図７、図
８、図９に示す。また、この実施例２による本発明品の
評価結果を表２にまとめる。(Embodiment 2) In the procedure of the above-mentioned embodiment 1, the same procedure as that of the embodiment of FIG.
3 μm thick TiN at 900 ° C., 6 μm thick TiC
After forming an N film at 900 ° C., a TiC / TiCO bonding layer is formed.
Was formed at 950 to 1010 ° C. Then, AlClThree
Gas and HTwoGas 2 l / min and CO TwoGas 100ml / min and
And HTwo10 ml of S gas was passed through the CVD furnace at a rate of 8 ml / min.
Film of aluminum oxide atTwo4 liters of gas
/ Min and TiClFourGas 50ml / min and NTwo1.3 l of gas
When a titanium nitride film is formed at 1010 ° C.
FIG. 7 and FIG. 7 show the results of three typical X-ray diffraction measurements of the product of the present invention.
8, shown in FIG. In addition, the product of the present invention
Table 2 summarizes the evaluation results.

【００３０】[0030]

【表２】 [Table 2]

【００３１】図７、８、９よりα（１１０）ピークが強
く、α（０１２）やα（１０４）、α（０３０）等のピ
ークは小さいことがわかる。この相対的に弱いα（０１
２）、α（１０４）、α（０３０）ピークに関し、図７
の場合Ｉ（０３０）/Ｉ（１０４）＜１、Ｉ（０１２）/
Ｉ（０３０）＞１であり、図８の場合Ｉ（０３０）/Ｉ
（１０４）＞１、Ｉ（０１２）/Ｉ（０３０）＜１であ
り、図９の場合Ｉ（０３０）/Ｉ（１０４）＞１、Ｉ
（０１２）/Ｉ（０３０）＞１となっていることがわか
る。7, 8, and 9, it can be seen that the peak of α (110) is strong and the peaks of α (012), α (104), α (030) are small. This relatively weak α (01
2), α (104) and α (030) peaks are shown in FIG.
In the case of I (030) / I (104) <1, I (012) /
I (030)> 1, and in the case of FIG. 8, I (030) / I
(104)> 1, I (012) / I (030) <1, and in the case of FIG. 9, I (030) / I (104)> 1, I
It can be seen that (012) / I (030)> 1.

【００３２】表２よりＨ2Ｓガスを用いて酸化アルミニ
ウム膜を成膜した本発明品はＰＲ（１１０）が１以上で
ありＴＣ（０１２）は１．３以下であること、Ｉ（０３
０）/Ｉ（１０４）とＩ（０１２）/Ｉ（０３０）とはＰ
Ｒ（１１０）と相関が無くそれぞれ０．０５９〜７．５
８０，０．０８２〜６３．０６０と値がばらつき一貫性
がないことがわかる。また、表２より本発明品の平均粒
径が酸化膜の膜厚が２．５μｍ未満のときは２μｍ以下
であり、かつ膜厚が２．５μｍ以上のときは４μｍ以下
であること、中心線平均面粗さＲａは０．６μｍ以下で
あり、最大面粗さＲｍａｘは酸化膜の膜厚が２．５μｍ
未満のときは２μｍ以下であり、かつ膜厚が２．５μｍ
以上のときは３μｍ以下であることがわかる。According to Table 2, the product of the present invention in which an aluminum oxide film was formed using H 2 S gas had PR (110) of 1 or more and TC (012) of 1.3 or less, and I (03)
0) / I (104) and I (012) / I (030) are P
No correlation with R (110), 0.059-7.5 respectively
It can be seen that the values vary from 80, 0.082 to 63.060 and are not consistent. From Table 2, the average particle size of the product of the present invention is 2 μm or less when the thickness of the oxide film is less than 2.5 μm, and 4 μm or less when the thickness is 2.5 μm or more. The average surface roughness Ra is 0.6 μm or less, and the maximum surface roughness Rmax is such that the thickness of the oxide film is 2.5 μm.
Is less than 2 μm and the film thickness is 2.5 μm
In the above case, it is understood that it is 3 μm or less.

【００３３】本発明品の表１中のα型酸化アルミニウム
を主とする酸化膜（図４中の１に対応。）及び結合層
（図４中の２に対応。）と非酸化膜（図４中の３に対
応。）近傍の破断面を電界放射型走査電子顕微鏡（ＦＥ
−ＳＥＭ）で観察した写真を図１０と図１１に示す。図
１０は倍率２万倍で、図１１は５万倍で結合層付近を撮
影したものである。図１０、図１１を始めとする本発明
品の破断面のＦＥ−ＳＥＭ写真より、本発明品は、α型
酸化アルミニウムを主とする酸化膜と下地である非酸化
膜との間に厚さが１００〜５００ｎｍで粒径が２０〜１
６０ｎｍの結合層が形成されていることがわかる。図１
２は上記本発明品の結合層近傍の透過電子顕微鏡（ＴＥ
Ｍ）写真である。図中、非酸化膜であるＴｉＣＮの結晶
粒（図１２中Ｂ４，Ｂ５はその一部）上に結合層（図１
２中Ｂ６，Ｂ７はその一部）が形成されその上にα型酸
化アルミニウムを主とする酸化膜が形成されている。図
３は図１２のａ部、即ち、α型酸化アルミニウムを主と
する酸化膜と結合層との界面近傍の格子像写真を示した
もので、写真の上方向から順に、α型酸化アルミニウム
を主とする酸化膜、α型酸化アルミニウムを主とする酸
化膜／結合層の界面、結合層が写っている。図３よりα
型酸化アルミニウムを主とする酸化膜と結合層との界面
において格子縞が連続していることがわかる。なお、図
３はα型酸化アルミニウムを主とする酸化膜／結合層の
界面がＴＥＭ写真面に垂直ではなく斜めに写っているも
のである。また、図１２における結合層と下地の非酸化
膜との界面（図１２中のｂ付近）を透過電子顕微鏡（Ｔ
ＥＭ）で同様に観測した結果、結合層と非酸化膜とは互
いにエピタキシャルの関係にあり、格子が連続的に成長
していることが確認された。図１３は本発明品の表２中
の試料２２について結合層とα型酸化アルミニウムを主
とする酸化膜との界面近傍を観察したものである。図１
３の上方向が酸化膜の上面方向で、図１３の中央部に結
合層の格子面が見られ、その両側にα型酸化アルミニウ
ムを主とする酸化膜の格子面が見られる。結合層と図中
右側のα型酸化アルミニウムを主とする酸化膜の粒子及
び結合層と図中左側のα型酸化アルミニウムを主とする
酸化膜の粒子との両界面において格子縞が連続している
ことがわかる。なお、図１３の左側の界面はα型酸化ア
ルミニウムを主とする酸化膜／結合層の界面がＴＥＭ写
真面に比較的垂直に写っているものである。An oxide film (corresponding to 1 in FIG. 4), a binding layer (corresponding to 2 in FIG. 4) and a non-oxide film (corresponding to 2 in FIG. 4) mainly containing α-type aluminum oxide in Table 1 of the product of the present invention. (Corresponding to 3 out of 4.) The fracture surface in the vicinity was examined by a field emission scanning electron microscope (FE
-SEM) are shown in FIGS. 10 and 11. FIG. 10 is an image of the vicinity of the binding layer at a magnification of 20,000, and FIG. From the FE-SEM photographs of the fracture surface of the product of the present invention including FIGS. 10 and 11, the product of the present invention has a thickness between the oxide film mainly composed of α-type aluminum oxide and the non-oxide film as the base. Is 100-500 nm and the particle size is 20-1.
It can be seen that a 60 nm bonding layer is formed. FIG.
2 is a transmission electron microscope (TE) near the bonding layer of the product of the present invention.
M) It is a photograph. In the figure, a bonding layer (FIG. 1) is formed on TiCN crystal grains (B4 and B5 in FIG.
2, B6 and B7 are partially formed), and an oxide film mainly composed of α-type aluminum oxide is formed thereon. FIG. 3 shows a lattice image photograph of the portion a in FIG. 12, that is, the vicinity of the interface between the oxide film mainly composed of α-type aluminum oxide and the bonding layer. The main oxide film, the interface of the oxide film / bonding layer mainly containing α-type aluminum oxide, and the bonding layer are shown. From FIG. 3, α
It can be seen that lattice fringes are continuous at the interface between the oxide film mainly composed of aluminum oxide and the bonding layer. In FIG. 3, the interface between the oxide film and the bonding layer mainly composed of α-type aluminum oxide is not perpendicular but obliquely shown on the TEM photograph surface. The interface between the bonding layer and the underlying non-oxide film (near b in FIG. 12) in FIG.
As a result of the same observation in (EM), it was confirmed that the bonding layer and the non-oxide film were in an epitaxial relationship with each other, and the lattice was continuously grown. FIG. 13 is an observation of the vicinity of the interface between the bonding layer and the oxide film mainly composed of α-type aluminum oxide for the sample 22 in Table 2 of the product of the present invention. FIG.
The upper direction of the oxide film 3 is the upper surface direction of the oxide film. The lattice plane of the coupling layer is seen in the center of FIG. 13, and the lattice plane of the oxide film mainly composed of α-type aluminum oxide is seen on both sides. The lattice fringes are continuous at both interfaces between the bonding layer and the particles of the oxide film mainly composed of α-type aluminum oxide on the right side of the figure and the interface between the bonding layer and the particles of oxide film mainly composed of α-type aluminum oxide on the left side of the figure. You can see that. The interface on the left side of FIG. 13 is an oxide film / bonding layer interface mainly composed of α-type aluminum oxide, which is relatively perpendicular to the TEM photograph surface.

【００３４】次に、実施例１および実施例２の条件で製
作した本発明品の切削工具各５個を用いて、鋳物の被削
材を以下の条件で１時間連続切削した後にアルミナ膜の
剥離状況を倍率２００倍の光学顕微鏡により観察し、評
価した。 被削材 ＦＣ２５（ＨＢ２３０） 切削速度 ３００ｍ／ｍｉｎ送り ０．３ｍｍ／ｒｅｖ切
り込み ２．０ｍｍ水溶性切削油使用この切削試験の結
果、上記本発明品はいずれも１時間連続切削後もアルミ
ナ膜の剥離が見られず切削工具として優れていること、
また、ＰＲ（１１０）が１．５以上の時は１．５時間連
続切削後もアルミナ膜の剥離が見られず更に優れている
ことが判明した。また、上記本発明品の切削工具各５個
を以下の条件で断続切削し、１，０００回衝撃切削後に
刃先先端の欠け状況を倍率５０倍の実体顕微鏡で観察
し、評価した。 被削材 ＳＣＭ材切削条件 １００ ｍ／ｍｉｎ送り ０．
３ ｍｍ／ｒｅｖ切り込み ２．０ ｍｍ切削試験後、上
記本発明品はいずれも刃先に欠損不良を発生すること無
く使用でき、長寿命であった。また、ＰＲ（１１０）が
２以上で、中心線平均面粗さＲａが０．５μｍ以下の時
は１，５００回衝撃切削後にも刃先に欠損不良を発生す
ること無く使用でき更に優れていることが判明した。Next, using a cutting tool of the present invention manufactured under the conditions of Examples 1 and 2, each of the five cutting tools of the present invention was used to continuously cut the cast workpiece for one hour under the following conditions. The state of peeling was observed and evaluated using an optical microscope with a magnification of 200 times. Work material FC25 (HB230) Cutting speed 300m / min Feeding 0.3mm / rev Cutting depth 2.0mm Water-soluble cutting oil used As a result of this cutting test, the above-mentioned present invention products have peeled off the alumina film even after continuous cutting for 1 hour. Is not seen and is excellent as a cutting tool,
When PR (110) was 1.5 or more, the alumina film was not peeled off even after continuous cutting for 1.5 hours, which proved to be more excellent. In addition, each of the five cutting tools of the present invention was intermittently cut under the following conditions, and after 1,000 times of impact cutting, the chipping state of the blade tip was observed and evaluated with a stereoscopic microscope at a magnification of 50 times. Work material SCM material cutting condition 100 m / min feed 0.
After a 2.0 mm cutting test with a cutting depth of 3 mm / rev, any of the above-described present invention products could be used without causing any chipping defects on the cutting edge, and had a long life. Further, when PR (110) is 2 or more and center line average surface roughness Ra is 0.5 μm or less, it can be used without causing chipping defects even after 1,500 times of impact cutting, and is more excellent. There was found.

【００３５】（従来例１）結合層の作製方法の差異によ
るα型酸化アルミニウムを主とする酸化膜の諸特性及び
切削特性への影響を明らかにするために、本発明品と同
様にＷＣ７２％、ＴｉＣ８％、（Ｔａ、Ｎｂ）Ｃ１１
％、Ｃｏ９％（％はいずれも重量％を示す。）の組成よ
りなる切削工具用超硬基板の表面に０．３μｍ厚さのＴ
ｉＮ膜と６μｍ厚さのＴｉＣＮ膜を形成した後、Ｈ2キ
ャリヤーガスとＴｉＣｌ4ガスとＣＨ4ガスを原料ガスに
用い１０１０℃で５〜３０分間反応させＴｉＣ膜を成膜
した後、ＴｉＣｌ4ガスとＣＨ4ガスとを止め、作製した
ＴｉＣ膜上にＨ2キャリヤーガスとＣＯ2ガスとを流して
１０１０℃で１５分間ＴｉＣ膜を酸化することにより結
合層を作製した。その後、実施例１と同一の条件で１０
２０℃でＨ2ガス、ＡｌＣｌ3ガスおよびＣＯ2ガスによ
り所定の厚さの酸化アルミニウム膜を成膜した従来品を
作製した。(Conventional Example 1) In order to clarify the influence on the various characteristics and the cutting characteristics of the oxide film mainly composed of α-type aluminum oxide due to the difference in the method of forming the bonding layer, WC 72% was used similarly to the product of the present invention. , TiC8%, (Ta, Nb) C11
%, Co 9% (% indicates weight%) on the surface of a carbide substrate for a cutting tool having a thickness of 0.3 μm.
After forming the iN film and 6μm thick TiCN film, after forming a TiC film of H 2 carrier gas and TiCl 4 gas and CH 4 gas are reacted for 5 to 30 minutes at 1010 ° C. using a raw material gas, TiCl 4 The gas and CH 4 gas were stopped, and a H 2 carrier gas and a CO 2 gas were allowed to flow on the produced TiC film to oxidize the TiC film at 1010 ° C. for 15 minutes to form a bonding layer. Then, 10 times under the same conditions as in Example 1.
A conventional product in which an aluminum oxide film having a predetermined thickness was formed at 20 ° C. using H 2 gas, AlCl 3 gas, and CO 2 gas.

【００３６】上記従来例１において、結合層を作製した
後、１０２０℃でＨ2ガス、ＡｌＣｌ3ガスおよびＣＯ2
ガスにより酸化アルミニウム膜を作製した従来品をＸ線
回析したところ、図１４に示されるＸ線回析パターンが
得られた。図１４の場合、α−Ａｌ2Ｏ3のＸ線回析ピー
ク強度は（１１６）、（１０４）、（０１２）、（１１
３）の順に強く、（１１０）ピークは弱いことがわか
る。作製したこの従来例品において、上記実施例と同様
に測定したＰＲ（１１０）、ＴＣ（０１２）、Ｉ（０３
０）/Ｉ（１０４）、Ｉ（０１２）/Ｉ（０３０）、結晶
の平均粒径、中心線平均面粗さＲａ、最大面粗さＲｍａ
ｘを表３にまとめる。In the above conventional example 1, after forming the bonding layer, H 2 gas, AlCl 3 gas and CO 2
X-ray diffraction of a conventional product in which an aluminum oxide film was produced with a gas yielded the X-ray diffraction pattern shown in FIG. In the case of FIG. 14, the X-ray diffraction peak intensities of α-Al 2 O 3 are (116), (104), (012), and (11).
It can be seen that the peak is stronger in the order of 3) and the (110) peak is weaker. In this manufactured conventional example, PR (110), TC (012), and I (03) were measured in the same manner as in the above example.
0) / I (104), I (012) / I (030), average grain size of crystal, center line average surface roughness Ra, maximum surface roughness Rma
x is summarized in Table 3.

【００３７】[0037]

【表３】 [Table 3]

【００３８】表３より、この従来例のものはＰＲ（１１
０）が１未満であり、Ｉ（０３０）/Ｉ（１０４）とＩ
（０１２）/Ｉ（０３０）とは０．１２２〜１．３０２
と０．２６８〜３．０４４と１前後でばらつき、その平
均粒径は酸化膜の膜厚が２．５μｍ未満のときも２μｍ
を越えることがあり、膜厚が２．５μｍ以上のときは４
μｍを越えることがあることがわかる。また、中心線平
均面粗さＲａは膜厚が２．５μｍ以上の領域で０．６μ
ｍを越えており、最大面粗さＲｍａｘも酸化膜の膜厚が
２．５μｍ未満でも２μｍを越え、かつ膜厚が２．５μ
ｍ以上では３μｍを越えることがあることがわかる。From Table 3, it can be seen that the conventional example has a PR (11
0) is less than 1 and I (030) / I (104) and I
(012) / I (030) means 0.122 to 1.302.
And 0.268 to 3.044, which is around 1, and the average particle size is 2 μm even when the thickness of the oxide film is less than 2.5 μm.
And when the film thickness is 2.5 μm or more, 4
It can be seen that it may exceed μm. The center line average surface roughness Ra is 0.6 μm in a region where the film thickness is 2.5 μm or more.
m, and the maximum surface roughness Rmax exceeds 2 μm even when the thickness of the oxide film is less than 2.5 μm, and the maximum thickness is 2.5 μm.
It can be seen that if m is more than m, it may exceed 3 μm.

【００３９】（従来例２）また、従来例１と同様にして
結合層を作製した後、１０１０℃でＡｌＣｌ3ガス、Ｈ2
ガス、ＣＯ2ガス、Ｈ2Ｓガスとにより所定の厚さの酸化
アルミニウム膜を成膜し、その後、Ｈ2ガス４ｌ／分と
ＴｉＣｌ4ガス５０ｍｌ／分とＮ2ガス１．３ｌ／分を流
し１０１０℃で窒化チタニウム膜を形成した従来品の代
表的なＸ線回折結果を図１５に示す。図１５のα−Ａｌ
2Ｏ3の場合、Ｘ線回析のピーク強度は（０１２）、（０
２４）、（１１６）、（０３０）の順に強く、（１１
０）ピークは弱いことがわかる。この作製した従来例品
を、上記実施例と同一条件で測定したＰＲ（１１０）、
ＴＣ（０１２）、Ｉ（０３０）/Ｉ（１０４）、Ｉ（０
１２）/Ｉ（０３０）、結晶の平均粒径、中心線平均面
粗さＲａ、最大面粗さＲｍａｘを表４にまとめる。(Conventional Example 2) Also, after forming a bonding layer in the same manner as in Conventional Example 1, AlCl 3 gas, H 2
An aluminum oxide film having a predetermined thickness is formed with a gas, a CO 2 gas, and a H 2 S gas. Thereafter, 4 l / min of H 2 gas, 50 ml / min of TiCl 4 gas, and 1.3 l / min of N 2 gas are formed. FIG. 15 shows a typical X-ray diffraction result of a conventional product in which a titanium nitride film is formed at a flow rate of 1010 ° C. Α-Al in FIG.
In the case of 2 O 3 , the peak intensity of X-ray diffraction is (012), (0
24), (116), and (030) in this order.
0) It can be seen that the peak is weak. PR (110), which was measured under the same conditions as the above example,
TC (012), I (030) / I (104), I (0
12) / I (030), the average grain size of the crystal, the center line average surface roughness Ra, and the maximum surface roughness Rmax are summarized in Table 4.

【００４０】[0040]

【表４】 [Table 4]

【００４１】表４より、Ｈ2ガス、ＡｌＣｌ3ガス、ＣＯ
2ガスおよびＨ2Ｓガスとを用いて１０１０℃で酸化アル
ミニウム膜を成膜した従来例２のものはいずれもＰＲ
（１１０）が１未満であり、Ｉ（０３０）/Ｉ（１０
４）、Ｉ（０１２）/Ｉ（０３０）はそれぞれ０．２８
９〜１．５４７と３．１８４〜７．８３６と１を越えて
いることもあることがわかる。According to Table 4, H 2 gas, AlCl 3 gas, CO
Conventional Example 2 in which an aluminum oxide film was formed at 1010 ° C. using 2 gas and H 2 S gas was PR
(110) is less than 1 and I (030) / I (10
4), I (012) / I (030) are each 0.28
9 to 1.547 and 3.184 to 7.836.

【００４２】上記従来例品の切削工具各５個を用いて上
記実施例と同一の連続切削テストを行った結果、従来例
品はいずれも１０分間連続切削後にアルミナ膜の剥離が
見られた。また、上記従来例品の切削工具各５個を上記
実施例と同一条件で断続切削し、１，０００回衝撃切削
後に刃先先端の欠け状況を倍率５０倍の実体顕微鏡で観
察した結果、いずれにも大きな欠けが発生しており、切
削工具として劣っていることが判明した。As a result of performing the same continuous cutting test as that of the above-mentioned embodiment using five cutting tools of the above-mentioned conventional example, the alumina film was peeled off after 10 minutes of continuous cutting. In addition, each of the five cutting tools of the conventional example was intermittently cut under the same conditions as in the above example, and after 1,000 times of impact cutting, the chipping state of the tip of the cutting edge was observed with a stereoscopic microscope with a magnification of 50 times. Also showed large chipping, which proved to be inferior as a cutting tool.

【００４３】以上より、酸化アルミニウム膜自体の成膜
方法は同一であっても結合層の作成方法を変化させるこ
とによりその上に成膜される酸化アルミニウム膜の諸特
性を制御出来ることがわかる。また、結合層はＴｉＣ／
ＴｉＣＯに限るものではなく、ＴｉＮ／ＴｉＮＯ、Ｔｉ
ＣＮ／ＴｉＣＮＯのいずれかまたはこれらを組み合わせ
た複数層でも上記実施例と同様の作用効果が得られた。
また、下地膜はＴｉＣＮに限るものではなく、結合層中
の非酸化膜（図４中の２ー２、例えばＴｉＣ／ＴｉＣＯ
結合層中のＴｉＣ）と同一物（ＴｉＣ）でも上記実施例
と同様の作用効果が得られた。From the above, it can be seen that even if the method of forming the aluminum oxide film itself is the same, various characteristics of the aluminum oxide film formed thereon can be controlled by changing the method of forming the bonding layer. The bonding layer is made of TiC /
Not limited to TiCO, TiN / TiNO, Ti
The same operation and effect as those of the above embodiment were obtained with any of CN / TiCNO or a plurality of layers in which these were combined.
The underlying film is not limited to TiCN, but may be a non-oxide film (2-2 in FIG. 4, for example, TiC / TiCO) in the bonding layer.
Even with the same material (TiC) as in the bonding layer (TiC), the same operation and effect as in the above-described embodiment were obtained.

【００４４】[0044]

【発明の効果】上述のように、本発明品によれば、基体
表面に周期律表のIVａ、Ｖａ、VIａ族金属の炭化物、窒
化物、炭窒化物、酸化物、酸炭化物、酸窒化物および酸
炭窒化物のいずれか一種の単層皮膜または二種以上から
なる多層皮膜上に、Ｘ線回析の（１１０）面ピーク強度
が強い、すなわち（１１０）面配向が強いα型酸化アル
ミニウムを主とする酸化膜が形成されていることにより
膜の密着性が良く、機械特性の優れた長寿命の酸化アル
ミニウム被覆工具が実現できる。As described above, according to the product of the present invention, carbides, nitrides, carbonitrides, oxides, oxycarbides, oxynitrides of metals belonging to groups IVa, Va and VIa of the periodic table are formed on the surface of the substrate. Α-type aluminum oxide having a strong (110) plane peak intensity of X-ray diffraction, that is, a strong (110) plane orientation, on a single-layer film of at least one of oxycarbonitride and oxycarbonitride. By forming an oxide film mainly composed of aluminum oxide, the adhesion of the film is good, and a long-life aluminum oxide-coated tool having excellent mechanical properties can be realized.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明に係わる酸化アルミニウム被覆工具のＸ
線回析パターンを示す図である。FIG. 1 shows the X of the aluminum oxide coated tool according to the present invention.
It is a figure which shows a line diffraction pattern.

【図２】本発明に係わる酸化アルミニウム被覆工具のＸ
線回析パターンを示す図である。FIG. 2 shows the X of the tool coated with aluminum oxide according to the present invention.
It is a figure which shows a line diffraction pattern.

【図３】本発明に係わる酸化アルミニウム被覆工具の結
晶の構造を示す写真である。FIG. 3 is a photograph showing a crystal structure of an aluminum oxide-coated tool according to the present invention.

【図４】酸化アルミニウム被覆工具の膜構成を説明する
ための模式図である。FIG. 4 is a schematic diagram for explaining a film configuration of an aluminum oxide-coated tool.

【図５】本発明に係わる酸化アルミニウム被覆工具の膜
界面の格子像を説明するための模式図である。FIG. 5 is a schematic diagram for explaining a lattice image of a film interface of the aluminum oxide-coated tool according to the present invention.

【図６】酸化アルミニウム表面の結晶粒径の測定方法に
係わるＳＥＭ写真（ａ）、および粒径測定方法を示す模
式図（ｂ）である。FIGS. 6A and 6B are an SEM photograph (a) relating to a method for measuring the crystal grain size on the surface of aluminum oxide, and a schematic diagram (b) showing the method for measuring the grain size.

【図７】本発明に係わる酸化アルミニウム被覆工具のＸ
線回析パターンを示す図である。FIG. 7 shows the X of the aluminum oxide coated tool according to the present invention.
It is a figure which shows a line diffraction pattern.

【図８】本発明に係わる酸化アルミニウム被覆工具のＸ
線回析パターンを示す図である。FIG. 8 shows the X of the aluminum oxide-coated tool according to the present invention.
It is a figure which shows a line diffraction pattern.

【図９】本発明に係わる酸化アルミニウム被覆工具のＸ
線回析パターンを示す図である。FIG. 9 shows X of the tool coated with aluminum oxide according to the present invention.
It is a figure which shows a line diffraction pattern.

【図１０】本発明に係わる酸化アルミニウム被覆工具の
セラミック材料の組織写真である。FIG. 10 is a structural photograph of the ceramic material of the aluminum oxide-coated tool according to the present invention.

【図１１】本発明に係わる酸化アルミニウム被覆工具の
セラミック材料の組織写真である。FIG. 11 is a structural photograph of a ceramic material of an aluminum oxide-coated tool according to the present invention.

【図１２】本発明に係わる酸化アルミニウム被覆工具の
セラミック材料の組織写真である。FIG. 12 is a structural photograph of a ceramic material of the aluminum oxide-coated tool according to the present invention.

【図１３】本発明に係わる酸化アルミニウム被覆工具の
結晶構造を示す写真である。FIG. 13 is a photograph showing a crystal structure of an aluminum oxide-coated tool according to the present invention.

【図１４】従来材に係わる酸化アルミニウム被覆工具の
Ｘ線回析パターンを示す図である。FIG. 14 is a diagram showing an X-ray diffraction pattern of a tool coated with aluminum oxide according to a conventional material.

【図１５】従来材に係わる酸化アルミニウム被覆工具の
Ｘ線回析パターンを示す図である。FIG. 15 is a view showing an X-ray diffraction pattern of a tool coated with aluminum oxide according to a conventional material.

【符号の簡単な説明】[Brief description of reference numerals]

１ 酸化膜、２ 結合層、３ 非酸化膜（下地膜）。 1 oxide film, 2 bonding layer, 3 non-oxide film (underlying film).

───────────────────────────────────────────────────── フロントページの続き (72)発明者 植田 広志 千葉県成田市新泉13番地の２日立ツール株 式会社成田工場内 (72)発明者 島 順彦 千葉県成田市新泉13番地の２日立ツール株 式会社成田工場内 Ｆターム(参考） 3C046 FF11 FF16 FF24 4K030 AA03 AA09 AA14 AA17 BA18 BA24 BA35 BA43 BB01 BB13 CA03 JA01 LA22  ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Ueda 13 Hitachi Tools Co., Ltd., 13-13 Shinsen, Narita City, Chiba Prefecture Inside the Narita Plant (72) Inventor Norihiko Shima 13 Hitachi Tools Co., Ltd., 13 Shinsen, Narita City, Chiba Prefecture F-term (reference) at Narita plant of formula company 3C046 FF11 FF16 FF24 4K030 AA03 AA09 AA14 AA17 BA18 BA24 BA35 BA43 BB01 BB13 CA03 JA01 LA22

Claims (9)

【特許請求の範囲】[Claims] 【請求項１】 基体表面に周期律表のIVａ、Ｖａ、VIａ
族金属の炭化物、窒化物、炭窒化物、酸化物、酸炭化
物、酸窒化物および酸炭窒化物のいずれか一種の単層皮
膜または二種以上からなる多層皮膜、並びに少なくとも
一層のα型酸化アルミニウムを主とする酸化膜が形成さ
れている酸化アルミニウム被覆工具において、該非酸化
膜と該酸化膜との間に酸素を含有した結合層を設けると
ともに前記酸化膜のＸ線回析最強ピーク面が（１１０）
面であることを特徴とする酸化アルミニウム被覆工具。1. The method according to claim 1, wherein the surface of the substrate is made of IVa, Va, VIa of the periodic table.
A single-layer coating or a multilayer coating composed of two or more of any one of a group III metal carbide, nitride, carbonitride, oxide, oxycarbide, oxynitride and oxycarbonitride, and at least one α-type oxidation In an aluminum oxide-coated tool in which an oxide film mainly composed of aluminum is formed, a bonding layer containing oxygen is provided between the non-oxide film and the oxide film, and the strongest X-ray diffraction peak surface of the oxide film is formed. (110)
An aluminum oxide coated tool characterized by being a surface. 【請求項２】 基体表面に周期律表のIVａ、Ｖａ、VIａ
族金属の炭化物、窒化物、炭窒化物、酸化物、酸炭化
物、酸窒化物および酸炭窒化物のいずれか１種の単層皮
膜または二種以上からなる多層皮膜、並びに少なくとも
一層のα型酸化アルミニウムを主とする酸化膜が形成さ
れている酸化アルミニウム被覆工具において、該非酸化
膜と該酸化膜との間に酸素を含有した結合層を設けると
ともに前記酸化膜のＸ線回析の（１１０）面による等価
ピーク強度ＰＲ（１１０）が１以上であることを特徴と
する酸化アルミニウム被覆工具。2. The substrate of the periodic table, IVa, Va, VIa,
Group 1 metal carbide, nitride, carbonitride, oxide, oxycarbide, oxynitride and oxycarbonitride any one single-layer coating or multilayer coating comprising two or more thereof, and at least one α-type coating In an aluminum oxide-coated tool on which an oxide film mainly composed of aluminum oxide is formed, a bonding layer containing oxygen is provided between the non-oxide film and the oxide film, and (110) of X-ray diffraction of the oxide film is performed. A) an aluminum oxide-coated tool, wherein the equivalent peak intensity PR (110) of the plane is 1 or more. 【請求項３】 前記α型酸化アルミニウムを主とする酸
化膜の膜厚が２．５μｍ未満のときの酸化膜の平均粒径
が２μｍ以下であり、前記膜厚が２．５μｍ以上のとき
の平均粒径が４μｍ以下であることを特徴とする請求項
１又は請求項２に記載の酸化アルミニウム被覆工具。3. The method according to claim 1, wherein when the thickness of the oxide film mainly composed of α-type aluminum oxide is less than 2.5 μm, the average particle size of the oxide film is 2 μm or less, and when the thickness is 2.5 μm or more. The aluminum oxide-coated tool according to claim 1 or 2, wherein the average particle size is 4 µm or less. 【請求項４】 前記α型酸化アルミニウムを主とする酸
化膜の中心線平均面粗さＲａが０．６μｍ以下であるこ
とを特徴とする請求項１乃至請求項３のいずれかに記載
の酸化アルミニウム被覆工具。4. The oxidation according to claim 1, wherein the oxide film mainly composed of α-type aluminum oxide has a center line average surface roughness Ra of 0.6 μm or less. Aluminum coated tool. 【請求項５】 前記α型酸化アルミニウムを主とする酸
化膜の膜厚が２．５μｍ未満のときのその酸化膜の最大
面粗さＲｍａｘが２μｍ以下であり、前記膜厚が２．５
μｍ以上のときの最大面粗さＲｍａｘが３μｍ以下であ
ることを特徴とする請求項１乃至請求項４のいずれかに
記載の酸化アルミニウム被覆工具。5. When the thickness of the oxide film mainly composed of α-type aluminum oxide is less than 2.5 μm, the maximum surface roughness Rmax of the oxide film is 2 μm or less, and the thickness is 2.5 μm or less.
The aluminum oxide-coated tool according to any one of claims 1 to 4, wherein the maximum surface roughness Rmax at 3 m or more is 3 m or less. 【請求項６】 前記各膜間の密着性が高まるように、前
記α型酸化アルミニウムを主とする酸化膜の格子縞と結
合層の格子縞とが界面において連続していることを特徴
とする請求項１乃至請求項５のいずれかに記載の酸化ア
ルミニウム被覆工具。6. The lattice fringes of the oxide film mainly composed of the α-type aluminum oxide and the lattice fringes of the coupling layer are continuous at the interface so that the adhesion between the films is enhanced. An aluminum oxide-coated tool according to any one of claims 1 to 5. 【請求項７】 前記α型酸化アルミニウムを主とする前
記酸化膜の表面にチタンの窒化膜が形成されていること
を特徴とする請求項１乃至請求項６のいずれかに記載の
酸化アルミニウム被覆工具。7. The aluminum oxide coating according to claim 1, wherein a titanium nitride film is formed on a surface of the oxide film mainly composed of the α-type aluminum oxide. tool. 【請求項８】 周期律表のIVａ、Ｖａ、VIａ族金属の炭
化物、窒化物、炭窒化物の一種以上とＦｅ、Ｎｉ、Ｃ
ｏ、Ｗ、Ｍｏ、Ｃｒの一種以上とよりなる超硬質合金を
基体とすることを特徴とする請求項１乃至請求項７のい
ずれかに記載の酸化アルミニウム被覆工具。8. A material selected from the group consisting of carbides, nitrides and carbonitrides of metals of groups IVa, Va and VIa of the periodic table and Fe, Ni, C
The aluminum oxide-coated tool according to any one of claims 1 to 7, wherein the base is a super-hard alloy comprising at least one of o, W, Mo, and Cr. 【請求項９】 周期律表のIVａ、Ｖａ、VIａ族金属の炭
化物、窒化物、炭窒化物のいずれか一種または二種以上
からなる非酸化膜層と、前記非酸化膜層の成膜時に用い
たガス構成を主として更に０．１〜５ｖｏｌ％の酸化性
ガスを加え成膜温度９５０〜１０２０℃で成膜した周期
律表のIVａ、Ｖａ、VIａ族金属の酸化物、酸炭化物、酸
窒化物および酸炭窒化物のいずれか一種または二種以上
からなる薄層との組み合わせからなる酸素を含有した結
合層を成膜し、その上にα型酸化アルミニウムを主とす
る酸化膜を成膜することを特徴とする酸化アルミニウム
被覆工具の製造方法。9. A non-oxide film layer made of one or more of carbides, nitrides, and carbonitrides of metals belonging to groups IVa, Va and VIa of the periodic table, and The gas composition used is mainly 0.1 to 5 vol% oxidizing gas, and oxides, oxycarbides, and oxynitrides of metals of Group IVa, Va, and VIa of the periodic table formed at a film formation temperature of 950 to 1020 ° C. Of a bonding layer containing oxygen consisting of one or two or more thin layers of oxides and oxycarbonitrides, and an oxide film mainly composed of α-type aluminum oxide formed thereon A method for producing an aluminum oxide-coated tool.
JP2001249788A 2001-08-21 2001-08-21 Aluminum oxide coated tool Expired - Fee Related JP3901477B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001249788A JP3901477B2 (en) 2001-08-21 2001-08-21 Aluminum oxide coated tool

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001249788A JP3901477B2 (en) 2001-08-21 2001-08-21 Aluminum oxide coated tool

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP33494896A Division JP3560303B2 (en) 1996-11-29 1996-11-29 Aluminum oxide coated tool and method of manufacturing the same

Publications (2)

Publication Number Publication Date
JP2002120105A true JP2002120105A (en) 2002-04-23
JP3901477B2 JP3901477B2 (en) 2007-04-04

Family

ID=19078733

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001249788A Expired - Fee Related JP3901477B2 (en) 2001-08-21 2001-08-21 Aluminum oxide coated tool

Country Status (1)

Country Link
JP (1) JP3901477B2 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009018405A (en) * 2007-06-12 2009-01-29 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009101463A (en) * 2007-10-23 2009-05-14 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009101462A (en) * 2007-10-23 2009-05-14 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009154235A (en) * 2007-12-26 2009-07-16 Mitsubishi Materials Corp Surface coated cutting tool
JP2009166216A (en) * 2008-01-21 2009-07-30 Hitachi Tool Engineering Ltd Coated tool
WO2012095994A1 (en) * 2011-01-14 2012-07-19 日立ツール株式会社 Hard film-coated tool and method for producing same
WO2012153438A1 (en) 2011-05-10 2012-11-15 住友電工ハードメタル株式会社 Surface-coated cutting tool
CN106856658A (en) * 2015-10-09 2017-06-16 住友电工硬质合金株式会社 Surface-coated cutting tool
JP2019126893A (en) * 2018-01-26 2019-08-01 株式会社タンガロイ Coated cutting tool
US11014169B2 (en) * 2016-08-25 2021-05-25 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool and method for manufacturing the same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009018405A (en) * 2007-06-12 2009-01-29 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009101463A (en) * 2007-10-23 2009-05-14 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009101462A (en) * 2007-10-23 2009-05-14 Mitsubishi Materials Corp Surface-coated cutting tool
JP2009154235A (en) * 2007-12-26 2009-07-16 Mitsubishi Materials Corp Surface coated cutting tool
JP2009166216A (en) * 2008-01-21 2009-07-30 Hitachi Tool Engineering Ltd Coated tool
JP5617933B2 (en) * 2011-01-14 2014-11-05 日立ツール株式会社 Hard film coated tool and manufacturing method thereof
WO2012095994A1 (en) * 2011-01-14 2012-07-19 日立ツール株式会社 Hard film-coated tool and method for producing same
JPWO2012095994A1 (en) * 2011-01-14 2014-06-09 日立ツール株式会社 Hard film coated tool and manufacturing method thereof
WO2012153438A1 (en) 2011-05-10 2012-11-15 住友電工ハードメタル株式会社 Surface-coated cutting tool
US8968866B2 (en) 2011-05-10 2015-03-03 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool
CN106856658A (en) * 2015-10-09 2017-06-16 住友电工硬质合金株式会社 Surface-coated cutting tool
CN106856658B (en) * 2015-10-09 2019-03-08 住友电工硬质合金株式会社 Surface-coated cutting tool
US11014169B2 (en) * 2016-08-25 2021-05-25 Sumitomo Electric Hardmetal Corp. Surface-coated cutting tool and method for manufacturing the same
JP2019126893A (en) * 2018-01-26 2019-08-01 株式会社タンガロイ Coated cutting tool

Also Published As

Publication number Publication date
JP3901477B2 (en) 2007-04-04

Similar Documents

Publication Publication Date Title
JP3418066B2 (en) Alumina-coated tool and manufacturing method thereof
JP3678924B2 (en) Aluminum oxide coated tool
JP5715570B2 (en) Coated tool
JP4004133B2 (en) Titanium carbonitride coated tool
JP3560303B2 (en) Aluminum oxide coated tool and method of manufacturing the same
KR20100135641A (en) Coating materials for a cutting tool or an abrasion resistance tool
JP2003025114A (en) Aluminium oxide coated cutting tool
JP3901477B2 (en) Aluminum oxide coated tool
JP3808648B2 (en) Titanium carbonitride film coating tool
JP3678945B2 (en) Titanium carbonitride coated tool
JP2001011632A (en) Zirconium-containing film-coated tool
JPH11335870A (en) Titanium carbonitride-aluminum oxide-coated tool
JP4107433B2 (en) α-type aluminum oxide coated member
JP2004148503A (en) Aluminum oxide coated tool
JP3544450B2 (en) Aluminum oxide coated tool
JP2002273607A (en) Multilayer coat tool
JPH11114704A (en) Titanium-carbide-covered tool
JP3818961B2 (en) Aluminum oxide coated tools
JPH10263903A (en) Titanium carbide coating tool
JP3347031B2 (en) Titanium carbide coated tool
JP2002205204A (en) Multilayer covering tool
JP2002192401A (en) Coated tool and method of manufacturing the same
JP2008173737A (en) Aluminum oxide coated tool
JP3781006B2 (en) Aluminum oxide coated tools
JP2004148502A (en) Aluminum oxide coated tool

Legal Events

Date Code Title Description
A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A711

Effective date: 20040913

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A132

Effective date: 20060728

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20060925

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A132

Effective date: 20061031

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20061130

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20061225

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20061226

R150 Certificate of patent (=grant) or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100112

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100112

Year of fee payment: 3

R360 Written notification for declining of transfer of rights

Free format text: JAPANESE INTERMEDIATE CODE: R360

R370 Written measure of declining of transfer procedure

Free format text: JAPANESE INTERMEDIATE CODE: R370

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100112

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110112

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120112

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120112

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130112

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140112

Year of fee payment: 7

LAPS Cancellation because of no payment of annual fees