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JP4331384B2 - Coated hard tool - Google Patents
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JP4331384B2 - Coated hard tool - Google Patents

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Publication number
JP4331384B2
JP4331384B2 JP2000164938A JP2000164938A JP4331384B2 JP 4331384 B2 JP4331384 B2 JP 4331384B2 JP 2000164938 A JP2000164938 A JP 2000164938A JP 2000164938 A JP2000164938 A JP 2000164938A JP 4331384 B2 JP4331384 B2 JP 4331384B2
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base material
mass
coating film
coated hard
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JP2001341005A (en
Inventor
泰久 橋本
晋也 今村
治世 福井
明彦 池ヶ谷
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Sumitomo Electric Hardmetal Corp
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Sumitomo Electric Hardmetal Corp
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Description

【0001】
【発明の属する技術分野】
本発明は、被覆硬質工具に関し、具体的には、耐摩耗性の要求される切削工具やその他の耐摩工具として利用される被覆硬質合金工具の中で耐摩耗性、耐溶着性に優れる被覆硬質合金工具に関するものである。
【0002】
【従来の技術】
従来、切削用の工具としては、超硬合金(WC−Co合金にTi(チタン)やTa(タンタル)、Nb(ニオブ)の炭窒化物を添加した合金)が用いられてきた。しかし、近年の切削の高速化に伴い、超硬合金、サーメット、あるいはアルミナ系や窒化珪素系のセラミックを母材として、その表面にPVD(Physical Vapor Deposition)法で元素周期律表のIVa、Va、VIa族金属やAl(アルミニウム)などの炭化物、窒化物、炭窒化物、ホウ窒化物、酸化物からなる膜を3〜20μmの厚さに被覆した硬質合金工具の使用割合が増大している。
【0003】
特にPVD法による被覆は、母材強度の劣化を招かずに耐摩耗性を高め得るということから、ドリル、エンドミル、フライス用スローアウェイチップなどの強度の要求される切削工具に多用されている。
【0004】
【発明が解決しようとする課題】
近年、加工能率を一層向上させるため、切削速度がより高速になってきており、そのことに伴い工具には一層の耐摩耗性、耐酸化性が要求されるようになってきている。特に高速切削においては高温になることから母材の耐摩耗性があまり期待できなくなるため、被覆膜の耐摩耗性が非常に重要になってきている。
【0005】
それゆえ本発明の目的は、高速切削においても良好な耐摩耗性を有する被覆硬質工具を提供することである。
【0006】
【課題を解決するための手段】
本願発明者らは、被覆膜の耐摩耗性の向上を達成するため、応力歪について研究した。一般に格子欠陥や転位が多く入った材料は転位の動きが制約されるため硬くなる。そこで、被覆膜に欠陥を導入すれば耐摩耗性が向上するのではないかと考えた。
【0007】
そして、超硬合金に種々のTiCN(炭窒化チタン)を被覆し、その被覆膜に転位や格子欠陥を導入して耐摩耗性を調べた。その結果、転位や格子欠陥が導入されると、耐摩耗性が向上することが判明した。また非常に興味深いことであるが、転位や格子欠陥が増えると被覆膜の色調も変ることが判明した。
【0008】
TiCNでは、一般にC(炭素)とN(窒素)との含有比が変ると色調が変化することが知られているが、本願発明者らは、切削性能の向上が見られるほど転位や格子欠陥が十分に入った場合のみ、色度a*(赤方向)が0以上10以下、色度b*(黄方向)が0以上20以下、明度L*が0以上100以下となることを見出した。そのうち、特に色度a*(赤方向)が0以上5以下、色度b*(黄方向)が0以上10以下、明度L*が10以上50以下のものは性能が著しく良くなることがわかった。
【0009】
それゆえ本発明の被覆硬質工具は、母材と、母材上の最表面に形成されたTiCNからなる被覆膜とを備え、被覆膜の色調において、色度a*が0以上10以下、色度b*が0以上20以下、明度L*が0以上100以下である。
【0010】
これにより、被覆膜に十分に転位や格子欠陥が導入され、高速切削においても良好な耐摩耗性が得られる。
【0011】
なお、色度a*、色度b*および明度L*による色の表示方法は、JIS Z 8730に準拠するものであり、分光測色方法により測定する場合には、JISZ 8722の4.(分光測色方法)の規定により、刺激値直読方法により測定する場合には、JIS Z 8722の5.(刺激値直読方法)の規定による。ただし、測定に用いる光電色彩計は、計器の指示から直接L***を求めるものでもよい。
【0012】
上記の被覆硬質工具において好ましくは、被覆膜の色調において、色度a*が0以上5以下、色度b*が0以上10以下、明度L*が10以上50以下である。
【0013】
これにより、高速切削においてより良好な耐摩耗性を得ることができる。
上記の被覆硬質工具において好ましくは、被覆膜の厚みは0.5μm以上10μm以下である。
【0014】
これは被覆膜の厚みが5μm未満では被覆の効果が少なく、10μmを超えると被覆膜が剥離しやすくなるからである。
【0015】
上記の被覆硬質工具において好ましくは、母材と被覆膜との間に、TiN(窒化チタン)、TiC(炭化チタン)、ZrN(窒化ジルコニウム)、ZrC(炭化ジルコニウム)、CrN(窒化クロム)およびCrC(炭化クロム)よりなる群から選ばれる1種以上からなる付着強化層がさらに備えられている。
【0016】
これにより、被覆膜と母材との付着強度が向上するため、より高性能が期待される。
【0017】
上記の被覆硬質工具において好ましくは、母材の材質は、Co(コバルト)を8質量%以上12質量%以下有している。
【0018】
このように超硬合金として母材のCo含有量を適切に選択することにより、耐摩耗性が著しく向上する。Coの含有量が8質量%未満であると、超硬合金自体の耐摩耗性が良いため、被覆の効果があまり発揮されない。一方、Coの含有量が12質量%を超えると、母材自体が軟らかくなりすぎ、本発明のような硬い被覆膜とのヤング率が違いすぎることから膜剥離が発生し、被覆の効果が発揮されない。
【0019】
上記の被覆硬質工具において好ましくは、母材の材質は、0.05質量%以上1質量%以下のCr(クロム)および/または0.05質量%以上0.5質量%以下のV(バナジウム)を有している。
【0020】
このように母材としての超硬合金にさらにCrやVを加えることにより、性能改善の効果が顕著となる。
【0021】
【発明の実施の形態】
以下、本発明の実施の形態について図に基づいて説明する。
【0022】
図1は、本発明の一実施の形態における被覆硬質工具の部分断面図である。図1を参照して、TiCNよりなる被覆膜1は、超硬合金よりなる母材2の表面上に形成されている。この母材2には、たとえばWC−Co合金や、この合金にCrやVを添加した合金が用いられる。被覆膜1の色調において、色度a*(赤方向)が0以上10以下、色度b*(黄方向)が0以上20以下、明度L*が0以上100以下である。特に色度a*(赤方向)が0以上5以下、色度b*(黄方向)が0以上10以下、明度L*が10以上50以下であることが好ましい。
【0023】
また被覆膜1の厚みは、被覆の効果および剥離防止を考慮すると、0.5μm以上10μm以下であることが好ましい。
【0024】
また被覆膜1と母材2との間には、図2に示すように付着強化層3が形成されていることが好ましく、この付着強化層3は、TiN、TiC、ZrN、ZrC、CrNおよびCrCのいずれかの材質よりなっていてもよく、またこれらの任意の組合せの材質よりなっていてもよい。
【0025】
母材2の材質は、8質量%以上12質量%以下のCoを有していることが好ましく、さらに0.05質量%以上1質量%以下のCrおよび/または0.05質量%以上0.5質量%以下のVを有していることが好ましい。
【0026】
【実施例】
以下、本発明の実施例について詳細に述べる。
【0027】
(実験例1)
型番SDKN42の形状のISO P30超硬合金母材(Coを11質量%含み、残部がWCである)に表2に示す各種のTiCNの被覆を施した。また、その被覆を施した各サンプルを使って合金鋼のブロックを表1の条件で切削し、切削後の各サンプルの摩耗量を測定した。その摩耗量の結果を表2に併せて示す。
【0028】
【表1】

Figure 0004331384
【0029】
【表2】
Figure 0004331384
【0030】
表2の結果から、色度a*(赤方向)が0以上10以下、色度b*(黄方向)が0以上20以下、明度L*が0以上100以下の範囲内の色調を有する本発明品のサンプル1〜5では、その範囲外の色調を有するサンプル6〜8よりも逃げ面摩耗量が少なく、耐摩耗性が高いことがわかる。さらに、色度a*(赤方向)が0以上5以下、色度b*(黄方向)が0以上10以下、明度L*が10以上50以下の範囲内の色調を有するサンプル1、2および5では、その範囲外の色調を有するサンプル3および4よりもさらに高い耐摩耗性の得られることがわかる。
【0031】
(実験例2)
次に母材と被覆膜の界面に付着強化層としてTiN、TiC、ZrN、ZrC、CrN、CrC薄膜を配したことの効果を確かめる実験を行なった。その実験として、実験例1のサンプル2と同じ被覆膜と母材との界面の間に上記各付着強化層を形成したサンプル11〜16を作製し、実験例1と同じ条件で切削し耐摩耗性を評価した。その結果を表3に示す。
【0032】
【表3】
Figure 0004331384
【0033】
表3の結果より、付着強化層を配置することにより、さらに逃げ面摩耗量が少なくなり、耐摩耗性が向上していることがわかる。
【0034】
(実験例3)
次に母材の組成が違う場合の効果を確かめる実験として実験例1と同じ方法で作成したサンプルを準備し、実験例1と同じ条件で切削し耐摩耗性を評価した。その結果を表4に示す。
【0035】
【表4】
Figure 0004331384
【0036】
なお、表4の結果には明示していないが、サンプル22および23は、摩耗が少ないものの、チッピングが発生しワークに傷をつけてしまうため工具として使用不能であった。
【0037】
この結果より、母材に含有されるCo量が8質量%以上12質量%以下であれば、色調が本発明範囲内になるとともに優れた切削性能の得られることがわかる。
【0038】
また、母材にCo以外に0.05質量%以上1質量%以下のCrおよび/または0.05質量%以上0.5質量%以下のVを添加することにより、さらに切削性能が向上することがわかる。
【0039】
今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
【0040】
【発明の効果】
以上説明したように本発明の被覆硬質工具では、被覆膜の色調において、色度a*が0以上10以下、色度b*が0以上20以下、明度L*が0以上100以下であるため、被覆膜に十分に転位や格子欠陥が導入され、高速切削においても良好な耐摩耗性が得られる。これにより、本発明の被覆硬質工具は、ドリル、エンドミル、フライス用スローアウェイチップ、切削用刃先交換型チップ、メタルソー、刃切り工具、リーマー、タップなどの切削工具、その表面に耐摩耗性被覆膜を形成した金属プレス加工用、金属鍛造用、ダイキャスト用、プラスチック成形用金型などに良好に適用することが可能である。
【図面の簡単な説明】
【図1】 本発明の一実施の形態における被覆硬質工具の部分断面図を示す図である。
【図2】 本発明の一実施の形態における被覆硬質工具において被覆膜と母材との間に付着強化層を備えた構成を示す部分断面図である。
【符号の説明】
1 被覆膜、2 母材、3 付着強化層。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a coated hard tool, specifically, a coated hard alloy having excellent wear resistance and welding resistance among coated hard alloy tools used as cutting tools and other wear resistant tools that require wear resistance. It relates to alloy tools.
[0002]
[Prior art]
Conventionally, cemented carbide (alloy obtained by adding carbonitride of Ti (titanium), Ta (tantalum), or Nb (niobium) to a WC-Co alloy) has been used as a cutting tool. However, with the recent increase in cutting speed, cemented carbide, cermet, or alumina-based or silicon nitride-based ceramic is used as a base material, and its surface is subjected to PVD (Physical Vapor Deposition) method IVa, Va of the periodic table of elements. The use ratio of hard alloy tools in which a film made of carbide, nitride, carbonitride, boronitride, oxide such as VIa group metal or Al (aluminum) is coated to a thickness of 3 to 20 μm is increasing. .
[0003]
In particular, the coating by the PVD method is often used for cutting tools that require strength, such as drills, end mills, and throw-away tips for milling mills, because wear resistance can be improved without causing deterioration of the base material strength.
[0004]
[Problems to be solved by the invention]
In recent years, in order to further improve the machining efficiency, the cutting speed has been increased, and accordingly, further wear resistance and oxidation resistance have been required for tools. Particularly in high-speed cutting, the wear resistance of the base material cannot be expected so much because the temperature becomes high, so the wear resistance of the coating film has become very important.
[0005]
Therefore, an object of the present invention is to provide a coated hard tool having good wear resistance even in high-speed cutting.
[0006]
[Means for Solving the Problems]
The inventors of the present invention studied stress strain in order to achieve an improvement in the wear resistance of the coating film. In general, a material containing many lattice defects and dislocations becomes hard because the movement of dislocations is restricted. Therefore, it was thought that wear resistance could be improved by introducing defects in the coating film.
[0007]
Then, the cemented carbide was coated with various TiCN (titanium carbonitride), and dislocations and lattice defects were introduced into the coating film to examine the wear resistance. As a result, it was found that the wear resistance is improved when dislocations and lattice defects are introduced. It is also very interesting that the color tone of the coating film changes as the number of dislocations and lattice defects increases.
[0008]
In TiCN, it is generally known that the color tone changes when the content ratio of C (carbon) and N (nitrogen) changes. However, the inventors of the present application have found that dislocation and lattice defects are improved as the cutting performance is improved. Was found that chromaticity a * (red direction) was 0 or more and 10 or less, chromaticity b * (yellow direction) was 0 or more and 20 or less, and lightness L * was 0 or more and 100 or less . Among them, in particular, when the chromaticity a * (red direction) is 0 or more and 5 or less, the chromaticity b * (yellow direction) is 0 or more and 10 or less, and the lightness L * is 10 or more and 50 or less, the performance is remarkably improved. It was.
[0009]
The coated hard tool therefore present invention, the base material, and a coating film made of TiCN formed on the outermost surface on the base material, the color tone of the coating film, chromaticity a * 0 to 10 The chromaticity b * is 0 or more and 20 or less, and the lightness L * is 0 or more and 100 or less.
[0010]
Thereby, dislocations and lattice defects are sufficiently introduced into the coating film, and good wear resistance is obtained even in high-speed cutting.
[0011]
The color display method based on chromaticity a * , chromaticity b *, and lightness L * is based on JIS Z 8730. In the case of measuring by the stimulus value direct reading method according to the provision of (spectral colorimetry method), JIS Z 8722 5. According to (stimulation value direct reading method) regulations. However, the photoelectric colorimeter used for the measurement may directly obtain L * a * b * from the instruction of the instrument.
[0012]
In the coated hard tool described above, preferably, in the color tone of the coating film, the chromaticity a * is 0 or more and 5 or less, the chromaticity b * is 0 or more and 10 or less, and the lightness L * is 10 or more and 50 or less.
[0013]
Thereby, better wear resistance can be obtained in high-speed cutting.
In the above-mentioned coated hard tool, the thickness of the coating film is preferably 0.5 μm or more and 10 μm or less.
[0014]
This is because when the thickness of the coating film is less than 5 μm, the coating effect is small, and when the thickness exceeds 10 μm, the coating film is easily peeled off.
[0015]
In the above-mentioned coated hard tool, preferably, TiN (titanium nitride), TiC (titanium carbide), ZrN (zirconium nitride), ZrC (zirconium carbide), CrN (chromium nitride) and An adhesion reinforcing layer made of at least one selected from the group consisting of CrC (chromium carbide) is further provided.
[0016]
Thereby, since the adhesion strength between the coating film and the base material is improved, higher performance is expected.
[0017]
In the above-mentioned coated hard tool, the material of the base material preferably has Co (cobalt) in an amount of 8% by mass to 12% by mass.
[0018]
Thus, wear resistance is remarkably improved by appropriately selecting the Co content of the base material as a cemented carbide. If the Co content is less than 8% by mass, the wear resistance of the cemented carbide itself is good, so that the coating effect is not exhibited so much. On the other hand, if the Co content exceeds 12% by mass, the base material itself becomes too soft, and the Young's modulus is too different from that of the hard coating film as in the present invention. It is not demonstrated.
[0019]
In the above-mentioned coated hard tool, preferably, the material of the base material is 0.05 mass% or more and 1 mass% or less of Cr (chromium) and / or 0.05 mass% or more and 0.5 mass% or less of V (vanadium). have.
[0020]
Thus, the effect of performance improvement becomes remarkable by adding Cr and V further to the cemented carbide as a base material.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0022]
FIG. 1 is a partial cross-sectional view of a coated hard tool according to an embodiment of the present invention. Referring to FIG. 1, coating film 1 made of TiCN is formed on the surface of base material 2 made of cemented carbide. As the base material 2, for example, a WC-Co alloy or an alloy obtained by adding Cr or V to the alloy is used. In the color tone of the coating film 1, the chromaticity a * (red direction) is 0 or more and 10 or less, the chromaticity b * (yellow direction) is 0 or more and 20 or less, and the lightness L * is 0 or more and 100 or less. In particular, the chromaticity a * (red direction) is preferably 0 or more and 5 or less, the chromaticity b * (yellow direction) is preferably 0 or more and 10 or less, and the lightness L * is preferably 10 or more and 50 or less.
[0023]
The thickness of the coating film 1 is preferably 0.5 μm or more and 10 μm or less in consideration of the effect of coating and prevention of peeling.
[0024]
Further, an adhesion strengthening layer 3 is preferably formed between the coating film 1 and the base material 2 as shown in FIG. 2, and this adhesion strengthening layer 3 is composed of TiN, TiC, ZrN, ZrC, CrN. And any material of CrC, or any combination of these materials.
[0025]
The material of the base material 2 preferably has 8% by mass or more and 12% by mass or less of Co, and further 0.05% by mass or more and 1% by mass or less of Cr and / or 0.05% by mass or more and 0.0. It is preferable to have V of 5% by mass or less.
[0026]
【Example】
Examples of the present invention will be described in detail below.
[0027]
(Experimental example 1)
Various types of TiCN coatings shown in Table 2 were applied to an ISO P30 cemented carbide base material having a shape of model number SDKN42 (containing 11 mass% Co and the balance being WC). Moreover, the block of alloy steel was cut on the conditions of Table 1 using each sample which gave the coating, and the amount of wear of each sample after cutting was measured. The results of the amount of wear are also shown in Table 2.
[0028]
[Table 1]
Figure 0004331384
[0029]
[Table 2]
Figure 0004331384
[0030]
From the results shown in Table 2, the chromaticity a * (red direction) is 0 or more and 10 or less, the chromaticity b * (yellow direction) is 0 or more and 20 or less, and the lightness L * is 0 or more and 100 or less. It can be seen that Samples 1 to 5 of the invention have less flank wear and higher wear resistance than Samples 6 to 8 having a color tone outside the range. Furthermore, Samples 1 and 2 having a color tone in the range of chromaticity a * (red direction) of 0 or more and 5 or less, chromaticity b * (yellow direction) of 0 or more and 10 or less, and lightness L * of 10 or more and 50 or less, and 5 shows that higher abrasion resistance can be obtained than Samples 3 and 4 having a color tone outside the range.
[0031]
(Experimental example 2)
Next, an experiment was conducted to confirm the effect of disposing a TiN, TiC, ZrN, ZrC, CrN, CrC thin film as an adhesion strengthening layer at the interface between the base material and the coating film. As the experiment, Samples 11 to 16 in which each of the adhesion reinforcing layers is formed between the same coating film and the base material as Sample 2 of Experimental Example 1 are manufactured, and cut under the same conditions as in Experimental Example 1 Abrasion was evaluated. The results are shown in Table 3.
[0032]
[Table 3]
Figure 0004331384
[0033]
From the results in Table 3, it can be seen that the amount of flank wear is further reduced and the wear resistance is improved by arranging the adhesion reinforcing layer.
[0034]
(Experimental example 3)
Next, as an experiment to confirm the effect when the composition of the base material is different, a sample prepared by the same method as in Experimental Example 1 was prepared, and was cut under the same conditions as in Experimental Example 1 to evaluate the wear resistance. The results are shown in Table 4.
[0035]
[Table 4]
Figure 0004331384
[0036]
Although not clearly shown in the results of Table 4, Samples 22 and 23 were unusable as tools because chipping occurred and scratched the workpiece, although there was little wear.
[0037]
From this result, it is understood that when the amount of Co contained in the base material is 8% by mass or more and 12% by mass or less, the color tone is within the range of the present invention and excellent cutting performance is obtained.
[0038]
In addition to Co, 0.05% by mass or more and 1% by mass or less Cr and / or 0.05% by mass or more and 0.5% by mass or less V may be added to the base material to further improve cutting performance. I understand.
[0039]
It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
[0040]
【The invention's effect】
As described above, in the coated hard tool of the present invention, in the color tone of the coating film, the chromaticity a * is 0 or more and 10 or less, the chromaticity b * is 0 or more and 20 or less, and the lightness L * is 0 or more and 100 or less. Therefore, dislocations and lattice defects are sufficiently introduced into the coating film, and good wear resistance is obtained even in high-speed cutting. As a result, the coated hard tool of the present invention is a drill, an end mill, a throw-away tip for milling, a cutting edge replaceable tip for cutting, a metal saw, a cutting tool, a reamer, a tap and other cutting tools, and a wear-resistant coating on the surface thereof. It can be favorably applied to metal press working, metal forging, die casting, plastic molding dies and the like on which a film is formed.
[Brief description of the drawings]
FIG. 1 is a partial sectional view of a coated hard tool according to an embodiment of the present invention.
FIG. 2 is a partial cross-sectional view showing a configuration in which an adhesion reinforcing layer is provided between a coating film and a base material in the coated hard tool according to the embodiment of the present invention.
[Explanation of symbols]
1 coating film, 2 base material, 3 adhesion strengthening layer.

Claims (7)

母材と、
前記母材上の最表面に形成されたTiCNからなる被覆膜とを備え、
前記被覆膜の色調において、色度a*が0以上10以下、色度b*が0以上20以下、明度L*が0以上100以下である、被覆硬質工具。
With the base material,
And a coating film made of TiCN formed on the outermost surface on the base material,
A coated hard tool having a chromaticity a * of 0 or more and 10 or less, a chromaticity b * of 0 or more and 20 or less, and a lightness L * of 0 or more and 100 or less in the color tone of the coating film.
前記被覆膜の色調において、色度a*が0以上5以下、色度b*が0以上10以下、明度L*が10以上50以下である、請求項1に記載の被覆硬質工具。The coated hard tool according to claim 1, wherein in the color tone of the coating film, chromaticity a * is 0 or more and 5 or less, chromaticity b * is 0 or more and 10 or less, and lightness L * is 10 or more and 50 or less. 前記被覆膜の厚みが0.5μm以上10μm以下である、請求項1または2に記載の被覆硬質工具。The coated hard tool according to claim 1 or 2, wherein the thickness of the coating film is 0.5 µm or more and 10 µm or less. 前記母材と前記被覆膜との間に、TiN、TiC、ZrN、ZrC、CrNおよびCrCよりなる群から選ばれる1種以上からなる付着強化層をさらに備えた、請求項1〜3のいずれかに記載の被覆硬質工具。Any one of Claims 1-3 further equipped with the adhesion reinforcement layer which consists of 1 or more types chosen from the group which consists of TiN, TiC, ZrN, ZrC, CrN, and CrC between the said base material and the said coating film. The coated hard tool according to crab. 前記母材の材質は、Coを8質量%以上12質量%以下有している、請求項1〜4のいずれかに記載の被覆硬質工具。The coated hard tool according to any one of claims 1 to 4, wherein a material of the base material includes 8 mass% to 12 mass% of Co. 前記母材の材質は、Crを0.05質量%以上1質量%以下有している、請求項5に記載の被覆硬質工具。The coated hard tool according to claim 5, wherein a material of the base material includes 0.05 mass% or more and 1 mass% or less of Cr. 前記母材の材質は、Vを0.05質量%以上0.5質量%以下有している、請求項5または6に記載の被覆硬質工具。The coated hard tool according to claim 5 or 6, wherein a material of the base material has V of 0.05 mass% or more and 0.5 mass% or less.
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