JP2007307652A - Coated tool and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coated tool excellent in surface smoothness, which is improved in peeling resistance by exhibiting high hardness and heat resistance of a film including Si and enhancing its toughness. <P>SOLUTION: In the coated tool with the film coated on the surface of a base material, at least one layer of the film is a hard nitride film including Si, and the hard film includes Kr. Preferably, the Kr content of the hard film is not less than 0.01 and not more than 0.6 by atomic%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coated tool that requires a wear resistance coated with a hard coating, and a method for manufacturing the same.

  For the purpose of improving the hardness and heat resistance of the coating, Patent Documents 1 to 3 below describe Si-containing coated tools, and Patent Document 4 discloses a coating containing Kr.

JP-A-8-118106 JP 2002-337006 A JP-A-2005-344148 JP 2000-80473 A

Patent Document 1 discloses a hard layer-coated cutting tool in which a hard layer of Ti and Si is coated as a hard layer-coated cutting tool that exhibits excellent cutting performance for high-speed continuous cutting. However, this hard layer has a drawback that the compressive residual stress becomes large due to the Si content, and the coating is extremely brittle. Patent Documents 2 and 3 disclose a coated cutting tool that further improves the high hardness and oxidation resistance unique to a Si-containing film, has high toughness and excellent chipping resistance, and is optimal for high-speed cutting. However, although the brittleness of the Si-containing film is greatly improved, the peel resistance is not sufficient. Patent Document 4 discloses a carbon-based film in which at least one atom selected from He, Ne, Ar, Kr, and Xe is contained in the film. However, no specific study has been conducted on the hard nitride film. Moreover, since it is a carbon-type film, oxidation resistance is scarce and oxidation resistance is not examined at all.
Accordingly, an object of the present invention is to provide a coated tool that improves the peel resistance by increasing the toughness by utilizing the high hardness of a coating film containing Si, and further provides a coated tool excellent in oxidation resistance and surface smoothness, and a method for producing the same. That is.

  The coated tool of the present invention is a coated tool in which a film is coated on the surface of a base material, wherein at least one layer of the film is a hard film of nitride containing Si, and the hard film contains Kr. This is a coated tool. By adopting this configuration, taking advantage of the high hardness of the coating film containing Si, improving the toughness, improving the peel resistance, further excellent in oxidation resistance and surface smoothness, in the wear environment, chipping and It is possible to realize a coated tool having an excellent life that does not easily cause film peeling and can be used stably for a long time.

  In the coated tool of the present invention, the Kr content of the hard coating is preferably at least 0.01 and not more than 0.6 in atomic%. In the hard coating, 1 part of Si is replaced with one or more metal elements selected from Ti, Cr, Nb, Al, Zr, Y, V, W, and Mo, and 1 part of N is replaced with C, O Substitution with one or more non-metallic elements selected from B, S is preferable. Of the diffraction peaks in X-ray diffraction of the hard coating, the half width calculated from (200) of the face-centered cubic structure is preferably 1 ° or more at 2θ.

  The coating method of the present invention is a physical vapor deposition method using a solid evaporation source containing at least Si, and a method for producing a coated tool for coating a hard nitride film in a reduced pressure atmosphere containing Kr and N as gas components And it is preferable that the flow volume ratio R of Kr gas with respect to nitrogen gas is 0.2 <= R <= 4.

  According to the present invention, it was possible to provide a coated tool that improves the peel resistance by increasing the toughness by utilizing the high hardness of the coating film containing Si, and further has excellent oxidation resistance and surface smoothness, and a method for producing the same. . As a result, it was possible to realize a coated tool having excellent life that can be used stably for a long period of time without causing chipping or film peeling even in a wear environment.

The hard film to be coated on the coated tool of the present invention is that Kr is contained in a nitride film containing Si, so that the toughness of the Si-containing film is remarkably improved and the oxidation resistance is further improved without reducing the film hardness. , And surface smoothness can be improved. The reason why the toughness of the hard coating of the present invention is improved is that Kr is mainly present at the grain boundaries, and in addition to suppressing the progress of cracks, the residual compressive stress of the Si-containing coating can be reduced. The reason why the oxidation resistance of the hard coating is improved is mainly due to the effect of Kr inhibiting the progress of oxygen diffusing through the grain boundaries. The reason why the surface smoothness of the hard coating is improved is that, compared to the case of adding Ar or the like, the ionization of the components constituting the hard coating is promoted during coating, and the macro particles are greatly reduced, and the surface of the hard coating is improved. This is because the implantation efficiency is improved and the crystal grains on the surface grow smoothly. The preferable Kr content of the hard coating is at least 0.01 and not more than 0.6 in atomic%. If it is less than 0.01, the effect of containing Kr is weakened, the residual compressive stress tends to increase, and the peel resistance tends to decrease. On the other hand, if it exceeds 0.6, the hardness tends to decrease and the wear resistance becomes poor.
The hard film of the present invention is a hard film of nitride containing Si. A nitride containing Si has high hardness and excellent oxidation resistance, and is effective in improving the wear resistance of the tool, but on the other hand, it has extremely brittle characteristics. Therefore, in consideration of peeling resistance, the Si content is practically less than 25% in terms of atomic% concentration ratio with respect to the total metal elements. Here, by containing Kr, the brittleness of the Si-containing film can be greatly improved, and the Si content can be contained in an atomic% concentration ratio of less than 50% with respect to the total metal elements. It is possible to improve the properties.

  The metal element of the hard coating of the present invention replaces a part of Si with one or more metal elements selected from Ti, Cr, Nb, Al, Zr, Y, V, W, and Mo, and 1 of N By replacing the part with one or more non-metallic elements selected from C, O, B, and S, high hardness, high oxidation resistance, high lubricity, and low friction resistance are obtained, and an excellent coated tool is obtained. Realized and preferred. For example, replacing one part of Si with one or more elements selected from Ti, Nb, Cr, and Al has an effect that contributes particularly to increasing the hardness of the film. Replacing with one or more of W, Y, Al, Mo, etc. particularly improves the heat resistance, and substituting with one or more of Nb, Al, Y, Cr, etc. particularly improves the oxidation resistance. Substitution with one or more of Cr, Cr, etc. is particularly effective for improving strength and plastic deformation resistance, and substitution with one or more of V, Zr, Mo, W, etc. is particularly effective for improving slidability. And preferred. Examples of additive elements that are remarkably improved in film hardness and oxidation resistance include Ti, Al, Cr, and Nb. From the viewpoint of wear resistance, preferred metal element components include TiSi, TiAlSi, AlCrSi, AlSi, AlNbCrSi, and TiSiNbAl. Moreover, it is more preferable to substitute less than 40 atomic% of N with nonmetallic elements of C, B, O, and S among nonmetallic components. By containing B, heat resistance and lubricity are particularly excellent, and by containing C and S, welding resistance and sliding characteristics can be significantly improved, which is preferable. Preferred non-metallic element components are NC, NB, NCB, NCOB.

  The hard film of the present invention preferably has a half width calculated from (200) of the face-centered cubic structure of diffraction peaks in X-ray diffraction being 2 degrees or more at 2θ. The crystal structure of the hard coating is preferably a structure having at least a diffraction peak from the face-centered cubic structure of the cubic B1 structure, and may include a close-packed hexagonal structure of the hexagonal B4 structure or an amorphous phase. By containing a close-packed hexagonal structure, oxidation resistance is particularly improved, which is preferable. In addition, a mixed structure of a face-centered cubic structure and an amorphous phase is preferable because the hardness of the film is improved and the wear resistance is improved. The half-value width calculated from (200) of the face-centered cubic structure is preferably 1 ° or more at 2θ. Accordingly, the effect of improving the hardness of the film and increasing the toughness due to Kr is remarkably exhibited, and the wear resistance of the tool can be greatly improved, which is preferable. From the balance between improving the hardness of the film and increasing the toughness, the half width is preferably 2 ° or more and 2 ° or less at 2θ, and most preferably 1.3 ° or more and 2.5 ° or less. The hardness of the hard coating is preferably 30 GPa or more and 60 GPa or less because the wear resistance of the tool can be improved. Examples of means for quantifying and qualifying Kr in the hard coating include X-ray photoelectron spectroscopy, secondary ion mass spectrometry, or electron beam probe microanalyzer.

  The coating method of the present invention is a physical vapor deposition method using a solid evaporation source containing at least Si, and a manufacturing method for coating a hard nitride film in a reduced-pressure atmosphere containing Kr and N as gas components is preferable. When Si, which is a metal component of the hard film, is added to the hard film by a physical vapor deposition method using a solid evaporation source, the effect of adding Kr appears remarkably, and a hard film having high hardness and high toughness is obtained. It is done. By covering the Si-containing film in a reduced-pressure atmosphere containing Kr and N as gas components, the compressive residual stress can be reduced, the toughness of the film can be increased, and the peel resistance is greatly improved. In the production method, by setting the flow volume ratio R of Kr gas to nitrogen gas in the range of 0.2 ≦ R ≦ 4, the Si-containing hard film has high hardness and excellent toughness, and also has excellent smoothness. preferable. When the R value is less than 0.2, the effect of Kr addition is not sufficient, brittle characteristics appear, and the peel resistance tends to decrease. Further, it was confirmed that Kr was not detected in the hard coating. When the R value exceeds 4 and the film hardness tends to decrease, the wear resistance decreases. In order to contain Kr more effectively in the Si-containing hard film, the grain boundary becomes clearer by making the bias voltage applied at the time of coating a pulsed bias voltage, and Kr can be effectively used as a crystal grain. It can be taken into the field, which is preferable. A bipolar-pulse-like pulse bias voltage is more preferable, and the inversion time is preferably set long. Ar can be used in addition to Kr and N. In this case, a flow volume ratio R of Kr gas to nitrogen gas of 1.2 or more and 4 or less is suitable from the viewpoint of wear resistance.

The hard coating of the present invention exhibits excellent wear resistance even in a single layer, but in order to improve wear resistance and peel resistance and extend the tool life, as an intermediate layer between the substrate and the hard coating. One or more nitride films selected from Ti, Cr, Al, Nb, and Y can be coated, which is preferable. The components of the intermediate layer exhibiting excellent wear resistance are particularly preferably (TiAl) N, (AlCr) N, (AlNb) N, (AlCrTi) N, and (AlCrY) N. By laminating the thickness of each layer of the intermediate layer and the hard coating in the range of 2 nm or more and 20 nm or less with 500 layers or more and 8000 layers or less, the residual compressive stress of the entire coating can be reduced, and the tool life is further increased. It can be extended and is preferable.
The coated tool of the present invention is used for wear-resistant tools such as molds and cutting tools, particularly end mills, drills, reamers, cutters, broaches, hobbs, micro drills, routers, milling inserts, turning inserts, etc. An excellent cutting life is obtained, which is preferable. The coated tool of the present invention is preferable because the base material is a cubic boron nitride sintered body, and thus further excellent wear resistance and plastic deformation resistance can be obtained. The cubic boron nitride sintered body has a cBN content of 55% by volume or more, an average particle size of cBN of less than 3 μm, and the main binder is any one of TiN, Ti (CN), and TiC. The strength is well balanced and the adhesiveness is excellent, which is preferable. Moreover, since the base material is a WC-Co based cemented carbide, a film having excellent adhesion strength and chipping resistance can be obtained, which is preferable. The WC-Co cemented carbide has the most excellent mechanical strength in addition to wear resistance because it has a WC average particle size of 0.6 μm or less, a Co binder of 8 wt% or less, and V and / or Cr. ,preferable. Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to the following Example, It is contained in the range of this invention to change suitably.

  In order to evaluate the tool life of the coated tool of the present invention, as a base material, Co: 6% by mass, WC average particle size is 0.2 μm, VN: 0.3% by mass, Cr: 0.5% by mass, hardness Used a 2 flute ball end mill with a diameter of 1 mm made of ultra-fine cemented carbide of HRA 94.3. This base material was degreased and washed, set in a sputtering apparatus, and a nitride-based hard film containing Si and Kr of the present invention was formed. For film formation, a sputtering apparatus equipped with four sputtering evaporation sources and equipped with a sample holder that revolves at a predetermined rotation speed was used, and Si targets were installed in two of these sputtering evaporation sources. As the target, a hot-water isostatic sintered material stuck on a backing plate was used. The substrate after degreasing and cleaning was mounted on a sample holder in a sputtering apparatus and subjected to heat degassing at 500 ° C. After evacuating the vacuum in the apparatus to 4 × 10 −4 Pa or less, Ar is introduced into the apparatus, the pressure is set to 8 × 10 −1 Pa, a bias voltage of −200 V is applied to the base, and the base The cleaning treatment with Ar ions was performed for about 60 minutes. Thereafter, Ar gas was continuously introduced into the apparatus at a flow rate of 300 ml / min, Kr gas at 200 ml / min, and N 2 gas at a flow rate of 100 ml / min, and the R value was set to 2.0. The pressure in the apparatus was 5 × 10 −1 Pa, the film formation temperature was 480 ° C., and a pulsed bias voltage having a frequency of 2 kHz and an inversion time of 1600 ns was applied to the substrate between −100 V and +0 V. Electric power of 2 kW was supplied to each of the two Si targets, and a hard coating containing Si and Kr was coated with a thickness of about 3 μm. During the film formation, the sample holder was rotated at a revolution speed of 2 revolutions per minute to produce Invention Example 1. Table 1 shows the film configurations and details of the inventive examples and comparative examples produced.

For Invention Examples 2 to 33, the conditions according to Invention Example 1 were used unless otherwise specified. In Invention Example 4, a composite target made of Ti and AlSi was used. The composite target was prepared so that the area ratio of Si was 10 to 20%. Unless otherwise specified, other composite targets were produced in the same manner. Invention Examples 5 to 6 were formed by adding a small amount of oxygen gas or acetylene gas as a reaction gas. In Invention Examples 25 to 29, an intermediate layer was used. Of the four sputtering evaporation sources, two TiSi targets were used, and the remaining two were targets with different compositions. The film forming conditions were the same as those in Example 1 of the present invention, and a cleaning process using Ar ions was performed. The pressure inside the apparatus is 5 × 10 −1 Pa, the film forming temperature is 480 ° C., a bias voltage of −100 V is applied to the substrate, 4 kW power is supplied to the target for forming the intermediate layer, and the intermediate layer is substantially The coating was about 3 μm thick. Thereafter, a (TiSi) N film was coated with a thickness of about 1 μm under substantially the same film formation conditions as Example 11 of the present invention. Inventive Examples 30, 31, and 32 have substantially the same film forming conditions as Inventive Example 13, but samples with different TiB2 area ratios on the target surface were prepared. Inventive Example 33 has substantially the same film forming conditions as Inventive Example 13, but the bias voltage during film formation was changed to −50 V to prepare a sample.
For comparison, although substantially the same film forming conditions as in Example 1 of the present invention were used, the gas introduced continuously into the apparatus was changed and coated. In Comparative Example 34, N2 gas was introduced at 100 ml / min and residual Ar gas was introduced, and the film was formed at a pressure of 5 × 10 −1 Pa in the apparatus. Comparative Example 35 uses substantially the same film formation conditions as Example 2 of the present invention. The gas continuously introduced into the apparatus is N2 gas at 100 ml / min, the remaining Ar gas is introduced, and the pressure in the apparatus is 5 × 10. The film was formed at −1 Pa. Comparative Example 36 uses substantially the same film formation conditions as Example 3 of the present invention. The gas continuously introduced into the apparatus is 100 ml / min of N2 gas, the remaining Ar gas is introduced, and the pressure in the apparatus is 5 ×. The film was formed at 10-1 Pa. Comparative Example 37 used substantially the same film forming conditions as Example 23 of the present invention, and used a composite target composed of Al and Ti. Comparative Example 38 uses substantially the same film forming conditions as Comparative Example 37. The gas continuously introduced into the apparatus is N 2 gas at 100 ml / min, the remaining Ar gas is introduced, and the pressure in the apparatus is 5 × 10 −. The film was formed at 1 Pa.

The qualitative analysis of Kr of the present invention example and the comparative example was evaluated by the following method. HORIBA, Ltd. EMAX-7000, SPECTRUM, Rel. Attached to Hitachi S-4200 Field Emission Scanning Electron Microscope (hereinafter referred to as FE-SEM). M905313E, Ver. 1.20, ROM, Ver. 1.0, EDX equipment was used. Hereinafter, this is referred to as EDX analysis. Measurement with acceleration voltage of 20 kV, emission current of approximately 10 μA, X-ray capture time of 100 seconds, X-ray extraction angle of 30 degrees, electron beam incident angle of 90 degrees, pulse processing time of P5, and probe current of 0.2 nA Under the conditions, the presence or absence of a peak attributed to Kr was confirmed. The analysis sample used was a ball end mill used for the evaluation of tool life, and was subjected to ultrasonic cleaning in acetone for 10 minutes after coating.
The quantitative analysis of Kr in the inventive examples was evaluated by the following method. Using a Quantum 2000 scanning X-ray photoelectron spectroscopic analyzer manufactured by PHI, AlKα (monochrome) was used as the X-ray source, the analysis area was 100 μm in diameter, and an electron neutralizing gun was used. An analysis was performed after etching the sample surface for 1 minute using an Ar ion gun immediately before the measurement. The etching rate at this time was 6.5 nm per minute in terms of SiO2. Using these measurement methods, the elements present on the extreme surface of the sample were analyzed, and the surface atomic concentration was estimated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI. As the analysis sample, a 1 mm-thick cemented carbide specimen subjected to mirror finishing was used, and after the coating, ultrasonic cleaning in acetone was performed for 10 minutes. Table 2 shows the details of the quantitative analysis results by X-ray photoelectron spectroscopic analysis of the manufactured example of the present invention. C and O in Table 2 are not intentionally added during film formation. The Kr content of the sample measured in the same manner is also shown in Table 1.

  Of the diffraction peaks in X-ray diffraction of the film, the half width of the (200) peak of the face-centered cubic structure was measured. The measurement was performed by an X-ray diffractometer with a tube voltage of 120 kV, a current of 40 μA, an X-ray source of Cukα, an incident angle of 5 degrees, an incident slit of 0.4 mm, and 2θ of 30 to 70 degrees. Of the X-ray diffraction profile from the obtained film, the half-value width of the peak showing the maximum peak intensity in the range of 38 to 45 degrees at 2θ of the cubic B1 structure, that is, the peak corresponding to the (200) plane is measured. did. The evaluation results are also shown in Table 1. In order to evaluate the smoothness of the film, FE-SEM was used, the film surface was observed at a magnification of 10,000 times, and surface irregularities were observed.

The tool lifes of the manufactured inventive examples and comparative examples were evaluated under the following conditions. Cutting evaluation is performed under the following conditions, cutting length when the flank wear width has reached 0.1 mm, or extremely unstable machining state, such as sparking, abnormal noise, flaking of the machining surface, burning, etc. The cutting length when reached was judged as the tool life. Less than 10m was rounded down. The evaluation results are also shown in Table 1.
(Cutting conditions)
Tool: 2-flute ball end mill, 1 mm diameter
Cutting method: Super high speed finishing Work material: SUS420J2, hardness HRC50
Cutting: axial direction, 0.01 mm, radial direction, 0.01 mm
Spindle speed: 20000 min-1
Table feed: 4m / min
Cutting oil: None, dry cutting

  Invention Example 1 and Comparative Example 34 were compared. Comparative Example 34 is a film that does not contain Kr, and the film peeled off at the beginning of cutting and reached the tool life at 20 m, while Example 1 of the present invention had a tool life of 70 m and improved the tool life by 3.5 times. did. FIG. 1 shows the EDX result of Inventive Example 1, and FIG. 2 shows the EDX result of Comparative Example 34. FIG. 1 shows the Kr peak intensity, but FIG. 2 shows no Kr peak detected. The result of having observed the film | membrane surface of this invention example 1 and the comparative example 34 by FE-SEM is shown in FIG. 3, FIG. In FIG. 3, a particulate interface was observed, and Example 1 of the present invention containing Si and Kr was excellent in smoothness. However, in FIG. 4, the particulate interface was not clearly observed. Invention Example 2 and Comparative Example 35 were compared. Comparative Example 35 was a film containing no Kr, and the film peeled off at the initial stage of cutting and reached the tool life at 20 m. However, Example 1 of the present invention had a tool life of 120 m, and the tool life improved 6 times. Invention Example 3 and Comparative Example 36 were compared. Comparative Example 36 is a film containing no Kr, and the film peeled off at the initial stage of cutting and reached the tool life at 50 m. In Invention Example 3, the tool life was 250 m, and the tool life was improved 5 times. FIG. 5 shows the EDX results of Example 3 of the present invention. In Example 3 of the present invention, a peak of Kr was clearly recognized. Invention Example 4 and Comparative Example 37 were compared. In Comparative Example 37, Kr was used at the time of coating, and the peak of Kr was detected from the film, but the film did not contain Si. The flank wear width reached 0.1 mm at 80 m, and the tool life was reached. Invention Example 4 containing Si had a tool life of 360 m, and improved the tool life by 4.5 times. Therefore, although a film containing only Si has high hardness and excellent heat resistance, the film is extremely brittle, so that film peeling is likely to occur and the characteristics are not sufficiently exhibited. By making it a coating film, the high hardness and heat resistance of the coating film containing Si can be utilized, and by increasing the toughness, it is possible to provide a coated tool with markedly improved peel resistance and excellent surface smoothness. became. Even when Comparative Examples 37 and 38 were seen, the tool life was improved by containing Kr in the coating.

  Invention Example 1 and Invention Examples 5 to 9 are compared. Invention Examples 5 to 9 contain B, O, S, and C as nonmetallic elements in addition to N. While the tool life of Invention Example 1 is 70 m, Invention Examples 5 to 9 contain B, O, S, and C together with Si and Kr, and the tool life is twice or more that of Invention Example 1. It was long and excellent. Therefore, in the present invention, the coating containing Si and Kr preferably contains at least one element selected from B, O, S, and C as a nonmetallic element. This is because the film containing Si and Kr contains at least one element selected from B, O, S, and C, so that high hardness, adhesion resistance, high lubricity, This is because the low frictional resistance is achieved. Inventive Examples 12, 15 to 20, and 22 to 24, which were formed by adding other metal elements, were compared to Inventive Example 1 having substantially the same base material and composed of Si and nitrogen. While the tool life of the inventive example 1 is 70 m, the inventive examples 12, 15 to 20 and 22 to 24 formed by adding other metal elements together with Si and Kr have a tool life more than twice as long. Was long and excellent. For example, Invention Example 2 and Invention Example 10 are compared. Invention Example 2 contains Si, nitrogen, and carbon, and Invention Example 10 was formed by adding a Ti metal element. While the tool life of Invention Example 2 is 120 m, Invention Example 10 is excellent because the tool life is twice or more. Invention Example 3 and Invention Examples 11, 13, 14, and 21 are compared. Invention Example 3 contains TiSi and nitrogen, and Invention Examples 11, 13, 14, and 21 were formed by adding boron or boron and carbon. FIG. 6 shows the EDX result of Example 11 of the present invention, and FIG. In Invention Example 11, Kr and Ar peaks were detected. The EDX result of Example 21 of the present invention is shown in FIG. 8, and a Kr peak was detected. In contrast to the tool life of Invention Example 3, which is 250 m, Invention Examples 11, 13, 14, and 21 formed by adding boron or boron and carbon have a longer tool life of 1.4 times or more and are excellent. It was. Therefore, in the present invention, the coating containing Si and Kr contains at least one selected from Ti, Cr, Nb, Al, Zr, Y, V, W, and Mo as a metallic element, and as a nonmetallic element It is preferable to contain 1 or more types selected from N, C, O, B, and S. Invention Example 3 is compared with Invention Examples 25-29. In Examples 25 to 29 of the present invention, the tool life was improved twice or more by using the intermediate layer. Therefore, it is more preferable to use an intermediate layer. From Table 2, the Kr contents of Invention Examples 13, 31, 32, and 33 were atomic%, which were 0.31, 0.23, 0.22, and 0.61, respectively. Inventive Example 33 having a Kr content of 0.61 has decreased wear resistance. From this, it is more preferable that the Kr content of the hard coating is 0.01% or more and 0.6 or less in atomic%. The Si2p spectra of Invention Examples 13, 30, and 31 are shown in FIG. 9 to FIG. 11. The peak in the range of 85 to 90 eV is attributed to Kr, and the peak in the range of 95 to 105 eV is attributed to Si. It is a peak. From the figure, it was confirmed that Kr was present in the hard coating also in the X-ray photoelectron spectroscopic analysis. The content of Kr depends particularly on the crystal particle morphology of the coating. That is, in the case of a columnar structure, a relatively large number of detected and smooth surface structures are relatively few. The present invention example 33 having a half width calculated from (200) of 2θ of 0.7 degrees and the present invention example 13 of 1.4 degrees are compared. Invention Example 13 had a tool life that was 1.5 times longer than Invention Example 33. Moreover, after maintaining at 1000 degreeC in air | atmosphere for 1 hour, as a result of observing the film | membrane surface by FE-SEM, the direction of this invention example 13 is finer than the example 33 of this invention, and oxidation is also in cross-sectional structure | tissue. The layer was thin and excellent in oxidation resistance. Therefore, it is more preferable that the half width calculated from (200) of the face-centered cubic structure among the diffraction peaks in the X-ray diffraction of the hard film is 1 degree or more at 2θ.

FIG. 1 shows an EDX result of Example 1 of the present invention. FIG. 2 shows the EDX result of Comparative Example 34. FIG. 3 shows the observation results of the coating surface of Example 1 of the present invention. FIG. 4 shows the observation results of the coating surface of Comparative Example 34. FIG. 5 shows the EDX result of Example 3 of the present invention. FIG. 6 shows the EDX result of Example 11 of the present invention. FIG. 7 shows an enlarged view of FIG. FIG. 8 shows the EDX result of Example 21 of the present invention. FIG. 9 shows the results of X-ray photoelectron spectroscopy analysis of Example 13 of the present invention. FIG. 10 shows the results of X-ray photoelectron spectroscopy analysis of Example 30 of the present invention. FIG. 11 shows the results of X-ray photoelectron spectroscopy analysis of Example 31 of the present invention.

Claims (6)

A coated tool in which a surface of a substrate is coated with a film, wherein at least one layer of the film is a hard film of nitride containing Si, and the hard film contains Kr. The coated tool according to claim 1, wherein the hard coating has a Kr content of 0.01% or more and 0.6 or less in atomic%. 3. The coated tool according to claim 1, wherein the hard coating is configured such that one part of Si is selected from Ti, Cr, Nb, Al, Zr, Y, V, W, and Mo. A coated tool, wherein one or more metal elements are substituted, and one part of N is substituted with one or more nonmetallic elements selected from C, O, B, and S. 4. The coated tool according to claim 3, wherein a half-value width calculated from (200) of a face-centered cubic structure among diffraction peaks in X-ray diffraction of the hard film is 1 ° or more at 2θ. Coated tool. 2. The coated tool according to claim 1, wherein the method of coating the hard film is a physical vapor deposition method using a solid evaporation source containing at least Si, and nitride in a reduced pressure atmosphere containing Kr and nitrogen as gas components. A method for producing a coated tool, characterized in that a hard film is coated. 6. The method for manufacturing a coated tool according to claim 5, wherein a flow volume ratio R of Kr gas to nitrogen gas is 0.2 ≦ R ≦ 4.