Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
  • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
  • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
  • B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
  • B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
  • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
  • C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
  • C04B35/5831—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride based on cubic boron nitrides or Wurtzitic boron nitrides, including crystal structure transformation of powder
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/05—Mixtures of metal powder with non-metallic powder
  • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
  • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2200/00—Details of cutting inserts
  • B23B2200/28—Angles
  • B23B2200/283—Negative cutting angles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2200/00—Details of cutting inserts
  • B23B2200/28—Angles
  • B23B2200/286—Positive cutting angles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
  • B23B2222/04—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
  • B23B2222/28—Details of hard metal, i.e. cemented carbide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
  • B23B2222/88—Titanium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
  • B23B2222/92—Tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B2226/00—Materials of tools or workpieces not comprising a metal
  • B23B2226/12—Boron nitride
  • B23B2226/125—Boron nitride cubic [CBN]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23B—TURNING; BORING
  • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
  • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
  • B23B27/148—Composition of the cutting inserts
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
  • C22C2026/003—Cubic boron nitrides only
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
  • C22C2026/006—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being carbides

Definitions

• Cubic boron nitride (hereafter referred to as "cBN”) sintered bodies have extremely high hardness and excellent thermal and chemical stability, and are therefore used in cutting tools and wear-resistant tools.
• the cBN particle content and type of bonding phase of cubic boron nitride sintered bodies are being investigated to obtain characteristics suited to the application.
• Patent Document 1 discloses a technology for improving crater wear resistance and chipping resistance in a cubic boron nitride sintered body that contains cubic boron nitride particles and Ti compound particles as a binder phase by allowing the W-Co phase to exist uninterrupted between the cubic boron nitride particles.
• the cubic boron nitride sintered body of the present disclosure is A cubic boron nitride sintered body comprising cubic boron nitride particles, a binder phase, and a first phase, the content of the cubic boron nitride particles in the cubic boron nitride sintered body is 25 volume % or more and 80 volume % or less;
• the binder phase is one or more first compounds comprising at least one element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, and silicon, and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen; and,
• a solid solution derived from the first compound; including one or both of the first phase includes at least one first element selected from the group consisting of cobalt, tungsten, and elements included in the binder phase; The total content of cobalt and tungsten in the
• the cubic boron nitride sintered body of the present disclosure is A cubic boron nitride sintered body comprising cubic boron nitride particles, a binder phase, and a first phase, the content of the cubic boron nitride particles in the cubic boron nitride sintered body is 25% by volume or more and 80% by volume or less;
• the binder phase is one or more first compounds comprising at least one element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, and silicon, and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen; and,
• a solid solution derived from the first compound; including one or both of the first phase includes at least one first element selected from the group consisting of cobalt, tungsten, and elements included in the binder phase; The total content of cobalt and tungsten in the cubic
• the present disclosure therefore aims to provide a cubic boron nitride sintered body that, when used as a tool material, can provide a tool with a long tool life even in highly efficient machining of high-hardness steel, and a tool that includes the cubic boron nitride sintered body.
• the cubic boron nitride sintered body of the present disclosure has A cubic boron nitride sintered body comprising cubic boron nitride particles, a binder phase, and a first phase, the content of the cubic boron nitride particles in the cubic boron nitride sintered body is 25 volume % or more and 80 volume % or less;
• the binder phase is one or more first compounds comprising at least one element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, and silicon, and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen; and,
• a solid solution derived from the first compound; including one or both of the first phase includes at least one first element selected from the group consisting of cobalt, tungsten
• a cubic boron nitride sintered body that, when used as a tool material, can provide a tool with a long tool life even in highly efficient machining of high-hardness steel, and a tool that includes the cubic boron nitride sintered body.
• the plurality of binder phase particles contain second binder phase particles in an amount of 50% or more by number,
• the surface of the second binder phase particles may include 75% by area or more of the first region.
• the binder phase may contain at least one element selected from the group consisting of titanium, chromium, aluminum, carbon, nitrogen, and boron. This further improves the life of a tool having a cubic boron nitride sintered body.
• the first element may include at least one element selected from the group consisting of aluminum, carbon, nitrogen, boron, and silicon. This further improves the life of a tool having a cubic boron nitride sintered body.
• the first phase may not be present at the interface between the cubic boron nitride particles and the binder phase. This further improves the life of a tool having a cubic boron nitride sintered body, particularly in interrupted cutting under severe conditions.
• the thickness of the first phase may be 20 nm or less. This further improves the life of a tool having a cubic boron nitride sintered body, particularly in interrupted cutting under severe conditions.
• the tungsten content of the first phase may be greater than the cobalt content of the first phase. This further improves the life of a tool having a cubic boron nitride sintered body, particularly in interrupted cutting under severe conditions.
• the tool disclosed herein is a tool that includes any one of the cubic boron nitride sintered bodies described above in (1) to (7).
• the tool disclosed herein can have a long tool life even in high-efficiency machining of high-hardness steel.
• any one numerical value listed as the lower limit and any one numerical value listed as the upper limit is also considered to be disclosed.
• a1 or more, b1 or more, and c1 or more are listed as the lower limit and a2 or less, b2 or less, and c2 or less are listed as the upper limit, a1 or more and a2 or less, a1 or more and b2 or less, a1 or more and c2 or less, b1 or more and a2 or less, b1 or more and b2 or less, b1 or more and c2 or less, c1 or more and a2 or less, c1 or more and b2 or less, and c1 or more and c2 or less are considered to be disclosed.
• a cubic boron nitride sintered body comprises: A cubic boron nitride sintered body comprising cubic boron nitride particles, a binder phase, and a first phase, The content of cubic boron nitride particles in the cubic boron nitride sintered body is 25 volume % or more and 80 volume % or less,
• the bonded phase is one or more first compounds comprising at least one element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, and silicon, and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen; and,
• a solid solution derived from the first compound; including one or both of the first phase includes at least one first
• the cubic boron nitride sintered body disclosed herein can provide tools with long tool life, even in highly efficient machining of high-hardness steel. The reasons for this are believed to be as follows.
• the cubic boron nitride sintered body of the present disclosure contains 25% by volume or more and 80% by volume or less of cubic boron nitride particles that have excellent strength and toughness. Therefore, the cubic boron nitride sintered body can also have excellent strength and toughness. Therefore, a tool containing the cubic boron nitride sintered body can have excellent wear resistance and chipping resistance even in high-efficiency machining of high-hardness steel.
• the binder phase includes one or both of one or more first compounds consisting of at least one element selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, and silicon, and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen, and a solid solution derived from the first compound.
• the first compound itself has high strength and toughness, and improves the bonding force between cBN particles. Therefore, a tool including a cubic boron nitride sintered body containing the first compound as a binder phase can have excellent wear resistance and chipping resistance even in high-efficiency machining of high-hardness steel.
• the cubic boron nitride sintered body of the present disclosure contains a first phase that includes cobalt, tungsten, and at least one first element selected from the elements contained in the binder phase.
• the first phase can improve the bonding strength between binder phase particles.
• the percentage of the first binder phase particles that have 50% or more of their surfaces in contact with the first phase relative to the entire binder phase particles is 50% or more by number, and therefore the bonding strength between the binder phase particles is improved. Therefore, a tool including the cubic boron nitride sintered body of the present disclosure can have excellent wear resistance and chipping resistance even in high-efficiency machining of high-hardness steel.
• an example of high-hardness steel is chromium molybdenum steel (SCM415).
• SCM415 chromium molybdenum steel
• a tool containing the cubic boron nitride sintered body of the present disclosure has a long tool life in highly efficient machining of high-hardness steel, but the work material is not limited to this.
• work materials include high-strength cast iron (FCD700, etc.), carbon steel for machine construction (S50C, etc.), high-carbon chromium bearing steel (SUJ2, SUJ4, etc.), or alloy tool steel (SKD11, etc.).
• the cubic boron nitride sintered body of the first embodiment includes cubic boron nitride particles, a binder phase, and a first phase.
• the content of cubic boron nitride particles is 25 volume % or more and 80 volume % or less.
• the lower limit of the content of cubic boron nitride particles in the cubic boron nitride sintered body is 25 volume % or more, or may be 30 volume % or more, 35 volume % or more, or 40 volume % or more, from the viewpoint of improving hardness.
• the upper limit of the content of cubic boron nitride particles in the cubic boron nitride sintered body is 80 volume % or less, or may be 75 volume % or less, 70 volume % or less, or may be 65 volume % or less, from the viewpoint of improving toughness.
• the content of cubic boron nitride particles in the cubic boron nitride sintered body is 25% by volume or more and 80% by volume or less, or may be 25% by volume or more and 75% by volume or less, or 25% by volume or more and 70% by volume or less, or 30% by volume or more and 70% by volume or less, or 40% by volume or more and 65% by volume or less.
• the cubic boron nitride particle content of cubic boron nitride sintered bodies is measured using a scanning electron microscope (SEM) ("JSM-7800F” (trademark) manufactured by JEOL Ltd.) with an attached energy dispersive X-ray analyzer (EDX) ("Octane Elect EDS System” (trademark) manufactured by EDAX Corporation) (hereinafter also referred to as "SEM-EDX”) in the following manner.
• SEM scanning electron microscope
• a focused ion beam device, cross section polisher device, etc. can be used to cut the cubic boron nitride sintered body. If the cubic boron nitride sintered body is used as part of a tool, cut out a portion of the cubic boron nitride sintered body with a diamond grinding wheel, electroplated wire, etc. to expose a sample including the cross section of the cubic boron nitride sintered body.
• the cross section is observed at 5000x magnification using an SEM to obtain a backscattered electron image.
• the areas where the cBN particles are present appear as black areas, and the areas where the binder phase and first phase are present appear as gray or white areas.
• the backscattered electron image is binarized using image analysis software (Mitani Shoji Co., Ltd.'s "WinROOF 2018”) so that only cBN particles are extracted.
• image analysis software Mitsubishi Co., Ltd.'s "WinROOF 2018”
• the cBN particles are shown in the dark field (black), and the bonding phase and the first phase are shown in the bright field (white).
• area percentage of pixels originating from the dark field pixels originating from cBN particles
• area percentage of cBN particles is calculated.
• the above-mentioned cBN particle area percentage measurement is performed in five non-overlapping measurement fields, and the average of the cBN particle area percentages in the five measurement fields is calculated.
• the average of the cBN particle area percentages in the five measurement fields corresponds to the cubic boron nitride particle content (volume %) of the cubic boron nitride sintered body.
• the cubic boron nitride sintered body of the first embodiment can be composed of cubic boron nitride particles, a binder phase, and a first phase.
• the cubic boron nitride sintered body of the first embodiment can contain impurities resulting from raw materials, manufacturing conditions, and the like, in addition to the cubic boron nitride particles, binder phase, and first phase, as long as the effects of the present disclosure are not impaired.
• the cubic boron nitride sintered body of the first embodiment can be composed of cubic boron nitride particles, a binder phase, a first phase, and impurities. Examples of impurities include nickel.
• the impurity content of the cubic boron nitride sintered body can be 0.1 mass% or less.
• the impurity content of the cubic boron nitride sintered body can be measured by secondary ion mass spectrometry (SIMS).
• the cubic boron nitride particles are made of cubic boron nitride.
• the cubic boron nitride particles may contain impurities together with cubic boron nitride, as long as the effects of the present disclosure are not impaired.
• the impurity content of the cubic boron nitride particles may be 0.1 mass% or less.
• the impurity content of the cubic boron nitride particles may be measured by secondary ion mass spectrometry (SIMS).
• the average particle size of the cubic boron nitride particles is not particularly limited and may be a general average particle size used in conventional cubic boron nitride sintered bodies.
• the particle size of the cubic boron nitride particles may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
• the average particle size of cubic boron nitride particles is measured by the following procedure.
• a cross section of a cBN sintered body is exposed and polished using the same procedure as for measuring the cubic boron nitride particle content of a cubic boron nitride sintered body.
• the polished surface is then observed at 10,000x magnification with an SEM to obtain an SEM image.
• a rectangular measurement field of view of 12 ⁇ m x 15 ⁇ m is set in the SEM image.
• the SEM image is processed using image analysis software (Mitani Shoji Co., Ltd.'s "WinROOF ver. 7.4.5") to obtain the circular equivalent diameter of each cBN particle observed within the measurement field of view.
• the arithmetic mean of the circular equivalent diameters of all cBN particles within the measurement field of view is calculated. This arithmetic mean corresponds to the average particle size of the cBN particles in the measurement field of view.
• the above measurements are performed in five non-overlapping measurement fields.
• the arithmetic mean of the average particle size of the cBN particles in the five measurement fields is calculated.
• the arithmetic mean of the average particle size in the five measurement fields corresponds to the average particle size of the cubic boron nitride particles.
• the binder phase includes one or both of one or more first compounds consisting of at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum, chromium, molybdenum, aluminum, and silicon (hereinafter also referred to as "second element") and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen, and a solid solution derived from the first compound.
• first compounds consisting of at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum, chromium, molybdenum, aluminum, and silicon (hereinafter also referred to as "second element") and at least one element selected from the group consisting of nitrogen, carbon, boron, and oxygen, and a solid solution derived from the first compound.
• the bonded phase may be in any of the following forms: (i) The bonded phase comprises a first compound. (ii) The bonded phase comprises a first compound. (iii) the binder phase comprises a solid solution derived from the first compound; (iv) the binder phase comprises a solid solution derived from the first compound; (v) The bonded phase includes a first compound and a solid solution derived from the first compound. (vi) The binder phase comprises a first compound and a solid solution derived from the first compound.
• the bonded phase may contain impurities along with one or both of the first compound and the solid solution derived from the first compound, as long as the effects of the present disclosure are not impaired.
• the impurity content of the bonded phase may be 0.1 mass% or less.
• the impurity content of the bonded phase may be measured by secondary ion mass spectrometry (SIMS).
• Examples of the first compound (nitride) consisting of the second element and nitrogen include titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN), chromium nitride (Cr 2 N), molybdenum nitride (MoN), AlN (aluminum nitride), silicon nitride (Si 3 N 4 ), titanium zirconium nitride (TiZrN), titanium hafnium nitride (TiHfN), titanium vanadium nitride (TiVN), titanium niobium nitride (TiNbN), titanium tantalum nitride (TiTaN), titanium chromium nitride (TiCr
• Examples of the first compound (carbide) consisting of the second element and carbon include titanium carbide (TiC), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), and chromium carbide ( Cr2 C), molybdenum carbide (MoC), silicon carbide (SiC), titanium zirconium carbide (TiZrC), titanium hafnium carbide (TiHfC), titanium vanadium carbide (TiVC), titanium niobium carbide (TiNbC), titanium tantalum carbide (TiTaC), titanium chromium carbide (TiCrC), titanium molybdenum carbide (TiMoC), zirconium hafnium carbide (ZrHfC), zirconium vanadium carbide (ZrVC), zirconium niobium carbide (ZrNb
• Examples of the first compound (carbonitride) consisting of a second element, carbon, and nitrogen include titanium carbonitride (TiCN), zirconium carbonitride (ZrCN), hafnium carbonitride (HfCN), or titanium aluminum carbonitride (TiAlCN, Ti2AlCN , Ti3AlCN ).
• Examples of the first compound (boride) consisting of a second element and boron include titanium boride (TiB 2 ), zirconium boride (ZrB 2 ), hafnium boride (HfB 2 ), vanadium boride (VB 2 ), niobium boride (NbB 2 ), tantalum boride (TaB 2 ), chromium boride (CrB 2 ), molybdenum boride (MoB 2 ), and silicon boride (SiB 4 ).
• Examples of the first compound (oxide) consisting of the second element and oxygen include titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), hafnium oxide (HfO 2 ), vanadium oxide (V 2 O 5 ), niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), chromium oxide (Cr 2 O 3 ), molybdenum oxide (MoO 3 ), aluminum oxide (Al 2 O 3 ), and silicon oxide (SiO 2 ).
• Examples of the first compound (oxynitride) consisting of a second element, nitrogen, and oxygen include titanium oxynitride (TiON), zirconium oxynitride (ZrON), hafnium oxynitride (HfON), vanadium oxynitride (VON), niobium oxynitride (NbON), tantalum oxynitride (TaON), chromium oxynitride (CrON), molybdenum oxynitride (MoON), and SiAlON (sialon).
• TiON titanium oxynitride
• ZrON zirconium oxynitride
• HfON hafnium oxynitride
• VON vanadium oxynitride
• NbON niobium oxynitride
• TaON tantalum oxynitride
• CrON chromium oxynitride
• MoON mo
• the bonding phase may contain at least one element selected from the group consisting of titanium, chromium, aluminum, carbon, nitrogen and boron.
• the first compound may be at least one selected from the group consisting of TiN, TiCN, TiC, CrN, AlCrN, and Al 2 O 3.
• the first compound may be used alone or in combination of two or more.
• the bonding phase may contain a solid solution derived from the first compound.
• a solid solution derived from the first compound means a state in which two or more types of first compounds are dissolved in each other's crystal structure, and means an interstitial solid solution or a substitutional solid solution.
• composition of the binder phase is identified using X-ray diffraction in the following procedure: A cross section of the cBN sintered body is exposed and polished in the same manner as in the measurement of the cubic boron nitride particle content of a cubic boron nitride sintered body.
• An X-ray diffraction spectrum of the polished surface is obtained using an X-ray diffraction device (MiniFlex600 (trademark) manufactured by Rigaku Corporation).
• the conditions for the X-ray diffraction device are as follows.
• Characteristic X-ray Cu-K ⁇ (wavelength 1.54 ⁇ ) Tube voltage: 45 kV Tube current: 40mA Filter: Multilayer mirror Optical system: Focusing method X-ray diffraction method: ⁇ -2 ⁇ method.
• composition of the bonding phase is identified based on the obtained X-ray diffraction spectrum.
• the first phase contains cobalt, tungsten, and at least one first element selected from the group consisting of elements contained in the binder phase.
• the first element is an element other than tungsten among the elements contained in the binder phase.
• the first element is at least one element selected from the group consisting of the same elements as the elements contained in the binder phase among titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, aluminum, silicon, nitrogen, carbon, boron, and oxygen.
• the binder phase is made of TiCN
• the first element is at least one element selected from the group consisting of Ti, C, and N.
• the first phase contains at least one element identical to the elements contained in the binder phase in addition to cobalt and tungsten, thereby improving the bonding force between the binder phase particles.
• the first element may contain at least one element selected from the group consisting of aluminum, carbon, nitrogen, boron and silicon. This further improves the bonding strength between the binder phase particles.
• a sample is taken from the cubic boron nitride sintered body, and sliced to a thickness of 30 to 100 nm using an argon ion slicer to prepare slices. The slices are then observed at 10,000 times magnification using a transmission electron microscope (TEM) (JEOL Ltd.'s "JEM-2100F/Cs” (trademark)) to obtain TEM images.
• TEM transmission electron microscope
• an energy dispersive X-ray analyzer (EDX) attached to the TEM (“EDAX” (trademark) manufactured by AMETEK) is used to obtain an elemental mapping image of cobalt and an elemental mapping image of tungsten.
• image A in (A3) and image B in (A4) are superimposed.
• image C the superimposed image
• the total content of cobalt and tungsten in the cubic boron nitride sintered body is 1.0 mass% or more and 6.0 mass% or less.
• the lower limit of the total content of cobalt and tungsten in the cubic boron nitride sintered body is 1.0 mass% or more, or may be 1.4 mass% or more, 1.5 mass% or more, 1.8 mass% or more, 2.0 mass% or more, 2.5 mass% or more, or 3.0 mass% or more.
• the upper limit of the total content of cobalt and tungsten in the cubic boron nitride sintered body is 6.0 mass% or less, 5.8 mass% or less, 5.7 mass% or less, 5.5 mass% or less, 5.2 mass% or less, 5.0 mass% or less, 4.5 mass% or less, or 4.0 mass% or less, from the viewpoint of suppressing a decrease in wear resistance due to coarsening of the first phase.
• the total content of cobalt and tungsten in the cubic boron nitride sintered body may be 1.4 mass% or more and 5.8 mass% or less, 1.5 mass% or more and 5.7 mass% or less, 1.8 mass% or more and 5.5 mass% or less, 2.0 mass% or more and 5.2 mass% or less, 2.5 mass% or more and 5.0 mass% or less, or 3.0 mass% or more and 4.5 mass% or less.
• the combined mass content of cobalt and tungsten in cubic boron nitride sintered bodies is measured by ICP mass spectrometry.
• the thickness of the first phase may be 20 nm or less, 0.6 nm or more and 20 nm or less, or 5 nm or more and 10 nm or less.
• the thickness of the first phase is confirmed by the following procedure.
• the first phase is identified by the same procedures as (A1) to (A5) of the method for confirming that a cubic boron nitride sintered body contains a first phase, and line analysis is performed using EDX in a direction perpendicular to the extension direction of the first phase in the TEM image.
• the half-width of the tungsten peak is taken as the thickness of the first phase.
• the thickness of the first phase is measured at 10 different locations of the first phase and the average value is calculated. However, if the thickness of the first phase is less than 0.5 nm, it is excluded from the calculation of the average value as noise. In the present disclosure, this average value corresponds to the thickness of the first phase. It has been confirmed that, as long as the measurement is performed on the same cubic boron nitride sintered body, almost the same results can be obtained even if the measurement location is changed.
• the tungsten content of the first phase may be greater than the cobalt content of the first phase.
• the tungsten content and cobalt content of the first phase are measured by the following procedure.
• a line analysis of the first phase is performed using the same procedure as the method for measuring the thickness of the first phase.
• the content (atomic %) at the tungsten peak is regarded as the tungsten content of the first phase.
• the content (atomic %) at the cobalt peak is regarded as the cobalt content of the first phase.
• the tungsten content and cobalt content are measured at any 10 different locations in the first phase, and the average of each is calculated.
• the average tungsten content corresponds to the tungsten content of the first phase.
• the average cobalt content corresponds to the cobalt content of the first phase. It has been confirmed that as long as the same cubic boron nitride sintered body is measured, almost the same results can be obtained even if the measurement location is changed.
• the binder phase is composed of a plurality of binder phase particles.
• the plurality of binder phase particles contain first binder phase particles at 50% or more by number.
• the surfaces of the first binder phase particles contain first regions at 50% or more by area. The first regions are regions in contact with the first phase.
• the percentage of the first binder phase particles having 50% or more by area of the surfaces in contact with the first phase at 50% or more by number relative to the entire binder phase particles is 50% or more, and therefore the binding strength between the binder phase particles is improved.
• the lower limit of the percentage by number of the first binder phase particles to the total binder phase particles is 50% or more, or may be 55% or more, 60% or more, 70% or more, 75% or more, 80% or more, 95% or more, or may be 95% or more, from the viewpoint of improving the bonding strength between the binder phase particles.
• the percentage by number of the first binder phase particles to the total binder phase particles may be 100%.
• the plurality of binder phase particles may contain second binder phase particles at 50% or more by number, and the surface of the second binder phase particle may contain the first region at 75% or more by area. This further improves the bonding strength between the binder phase particles.
• the lower limit of the number-based percentage of the second binder phase particles to the total binder phase particles may be 50% or more, 55% or more, 60% or more, 70% or more, 75% or more, 80% or more, 95% or more, or 95% or more, from the viewpoint of improving the bonding strength between the binder phase particles.
• the number-based percentage of the second binder phase particles to the total binder phase particles may be 100%.
• the number-based content (percentage) of first binder phase particles in the multiple binder phase particles of a cubic boron nitride sintered body and the number-based content (percentage) of second binder phase particles in the multiple binder phase particles of a cubic boron nitride sintered body are measured using an energy dispersive X-ray analyzer (EDX) ("EDAX” (trademark) manufactured by AMETEK) attached to a transmission electron microscope (TEM) (“JEM-2100F/Cs” (trademark) manufactured by JEOL Ltd.) in the following manner.
• EDX energy dispersive X-ray analyzer
• TEM transmission electron microscope
• the grain boundaries between the binder phase particles can be identified by performing binarization and particle division processing using image analysis processing software (Mitani Shoji Co., Ltd.'s "WinROOF 2018").
• image analysis processing software Mitsubishi Shoji Co., Ltd.'s "WinROOF 2018”
• Image 1A the image obtained after binarization processing
• the pixel value of the grain boundary is 255
• the pixel value of the other areas is 0.
• an elemental mapping image of tungsten and an elemental mapping image of cobalt are obtained using EDX.
• the elemental mapping image of tungsten and the elemental mapping image of cobalt are each subjected to binarization processing using image analysis processing software.
• the image obtained by binarizing the elemental mapping image of tungsten hereinafter also referred to as the "second image”
• the pixel value of the area where tungsten is present is 255
• the pixel value of the other areas is 0.
• the pixel value of the area where cobalt is present is 255, and the pixel value of the other areas is 0.
• the second image and the third image are superimposed.
• the superimposed image hereinafter also referred to as the "fourth image”
• the area where the pixel value is 255 hereinafter also referred to as the "W-Co phase”
• the observation magnification of the slice of (B1) above can be set to 10 million times with a TEM. This makes it possible to obtain an image that identifies the W-Co phase (hereinafter also referred to as the "4th A image").
• a rectangular measurement field of view of 12 ⁇ m ⁇ 15 ⁇ m is set in the first image (or the first A image).
• the length L1 of the grain boundary that defines the outer edge of the binder phase particle is measured.
• the first image (or the first A image) and the fourth image (or the fourth A image with the magnification adjusted to that of the first image) are superimposed.
• a measurement field of the same area as above is set in the superimposed images.
• the length L2 of the W-Co phase that exists at a position that overlaps with the grain boundary that defines the outer edge of the binder phase particle is measured.
• the percentage (L2/L1) ⁇ 100 of L2 relative to L1 is calculated.
• the percentage (L2/L1) ⁇ 100 corresponds to the coverage rate of the surface of the binder phase particle by the first region.
• Binder phase particles with a percentage (L2/L1) ⁇ 100 of 50% or more correspond to first binder phase particles.
• Binder phase particles with a percentage (L2/L1) x 100 of 75% or more are classified as second binder phase particles. Note that in the vicinity of the outer edge of the measurement field, some of the binder phase particles may exist outside the measurement field. Only binder phase particles that exist entirely inside the measurement field are measured. If some of the binder phase particles exist outside the measurement field, those binder phase particles are excluded from the measurement.
• (B9) Calculate the percentage (N2/N1) x 100 of the number N2 of first binder phase particles relative to the number N1 of all binder phase particles in the measurement field of view.
• the percentage (N2/N1) x 100 is measured in three non-overlapping measurement fields of view.
• the arithmetic average of the percentages (N2/N1) x 100 of the three measurement fields of view corresponds to the number-based content (percentage) of first binder phase particles in the multiple binder phase particles of the cubic boron nitride sintered body.
• (B10) Calculate the percentage (N3/N1) x 100 of the number N3 of second binder phase particles relative to the number N1 of all binder phase particles in the measurement field of view.
• the percentage (N3/N1) x 100 is measured in three non-overlapping measurement fields of view.
• the arithmetic average of the percentages (N3/N1) x 100 of the three measurement fields of view corresponds to the number-based content (percentage) of second binder phase particles in the multiple binder phase particles of the cubic boron nitride sintered body.
• the average particle size of the binder phase particles is not particularly limited and may be a general average particle size used in conventional cubic boron nitride sintered bodies.
• the particle size of the binder phase particles may be, for example, 50 nm or more and 200 ⁇ m or less.
• the average particle size of the binder phase particles is measured by the following procedure.
• a first image in which the grain boundaries between the binder phase particles described above in (B5) are identified is obtained using the same method as the method for measuring the number-based content (percentage) of the first binder phase particles in the multiple binder phase particles of the cubic boron nitride sintered body.
• a rectangular measurement field of view of 12 ⁇ m x 15 ⁇ m is set in the first image.
• the first image is processed using image analysis software (Mitani Shoji Co., Ltd.'s "WinROOF ver. 7.4.5") to obtain the circular equivalent diameter of each binder phase particle observed in the measurement field of view.
• the arithmetic mean of the circular equivalent diameters of all binder phase particles in the measurement field of view is calculated. This arithmetic mean corresponds to the average particle size of the binder phase particles in the measurement field of view.
• the above measurements are performed in five non-overlapping measurement fields.
• the arithmetic mean of the average particle size of the binder phase particles in the five measurement fields is calculated.
• the arithmetic mean of the average particle size in the five measurement fields corresponds to the average particle size of the binder phase particles.
• the presence or absence of a first phase at the interface between cubic boron nitride particles and a binder phase is measured by the following procedure.
• the binder phase and the W-Co phase are identified in the TEM image using the same method as for measuring the number-based content (percentage) of first binder phase particles in multiple binder phase particles in cubic boron nitride sintered bodies.
• Elemental mapping of boron and nitrogen is performed on the same TEM image as above. Using the image analysis processing software mentioned above, the elemental mapping images of boron and nitrogen are superimposed, and the regions where each element overlap are extracted and regarded as cubic boron nitride particles. The elemental mapping images of each element that makes up the binder phase are superimposed on the extracted regions, and the regions where the cubic boron nitride particles and binder phase exist are identified.
• Line analysis is performed using EDX at 10 positions divided equally along the length of the interface in the direction perpendicular to the extension direction of the interface between any cubic boron nitride particle and an adjacent one binder phase particle. If a first phase with a thickness of 0.5 nm or more does not exist between the cubic boron nitride particle and the one binder phase particle at 8 or more of the 10 positions, it is determined that no first phase exists at the interface between the cubic boron nitride particle and the binder phase. It has been confirmed that, so long as measurements are taken on the same cubic boron nitride sintered body, nearly the same results are obtained even if the measurement location is changed.
• the method for producing the cubic boron nitride sintered body of the embodiment 1 can include, for example, a raw material preparation step, a mixing step, and a sintering step.
• cBN powder Cubic boron nitride powder
• binder phase raw material powder are prepared as raw materials for the cubic boron nitride sintered body.
• the cBN powder there are no particular limitations on the cBN powder, and any known cBN powder can be used.
• the average particle size of the cBN powder can be, for example, 0.1 to 12.0 ⁇ m.
• a binder phase raw material powder containing elements constituting the binder phase is prepared.
• the binder phase raw material powder, acetone or ethanol as a solvent, and cemented carbide balls are charged into a cemented carbide container and mixed (hereinafter also referred to as "first mixture").
• the cemented carbide contains tungsten carbide (WC) and cobalt (Co), for example, WC-6%Co.
• WC tungsten carbide
• Co cobalt
• a to C is adopted.
• A. The mixing time is from 120 hours to 240 hours.
• B. Use a cemented carbide ball with cobalt powder applied to its surface.
• C. Use a cemented carbide ball having a diameter larger than 3 mm and smaller than 10 mm.
• D. Use a cemented carbide ball having a smaller particle size than normal, ⁇ 0.5 mm or more and ⁇ 3 mm or less.
• F. Use of balls made of materials other than cemented carbide As balls made of materials other than cemented carbide, for example, balls made of silicon nitride or aluminum oxide can be mentioned.
• the solvent is removed by natural drying. Then, heat treatment is performed to volatilize impurities such as moisture adsorbed on the surface of the mixed powder, and the surface of the mixed powder is cleaned.
• the first mixing may be performed under the following condition G, and then a coating treatment may be performed to form a coating of the target composition on the powder after the first mixing under the conditions described in the coating treatment below.
• G Use a 2.0 mm diameter cemented carbide ball.
• the mixing time is 24 to 90 hours.
• Coating treatment Coating device Nanoparticle formation device APD-P manufactured by Advance Riko Co., Ltd.
• ⁇ Mixing process (2)> Following the above-mentioned raw material preparation step (2), a second mixing is carried out under the following condition H, instead of the above-mentioned mixing step (1).
• H. Use a 2.0 mm diameter cemented carbide ball. The mixing time is 6 to 12 hours.
• ⁇ Sintering process> The mixed powder is placed in contact with a WC-6%Co cemented carbide disk and then filled into a Ta (tantalum) container and vacuum sealed.
• the vacuum sealed mixed powder is sintered by holding it for 5 to 30 minutes under conditions of 3 GPa to 12 GPa and 1100°C to 2200°C using a belt-type ultra-high pressure and high temperature generator. This produces the cubic boron nitride sintered body of the first embodiment.
• nano W powder with an average particle size of 500 nm to 900 nm and nano Co powder with an average particle size of 20 nm to 40 nm are added to cBN powder and Ti compound particle powder in the manufacturing process, and then the mixed powder is sintered to produce a cubic boron nitride sintered body.
• Patent Document 1 when conditions are adopted such that the total content of cobalt and tungsten in the cubic boron nitride sintered body is a small amount of 1.0 mass% or more and 6.0 mass% or less, the area where the surfaces of the binder phase particles contact the W-Co phase is small, and the content by number of binder phase particles in the cubic boron nitride sintered body in which 50 area% or more of the surface is in contact with the first phase is less than 50%. It has also been confirmed that in the manufacturing method of Patent Document 1, the W-Co phase does not contain elements contained in the binder phase.
• the inventors have found that by adopting at least one of the above conditions A through C, and at least one of the above conditions D through F, or the above conditions G and coating treatment, and H, it is possible to increase the area in which the surfaces of the binder phase particles come into contact with the first phase, and that the content by number of binder phase particles in a cubic boron nitride sintered body in which 50% or more of the surface area is in contact with the first phase can be made 50% or more, and that the first phase contains elements contained in the binder phase along with tungsten and cobalt.
• the tungsten and cobalt contained in the cemented carbide container and cemented carbide balls will be more likely to come into contact with the surfaces of the binder phase particles, and the surfaces of the binder phase particles will be more likely to react with the first phase.
• a tool according to one embodiment of the present disclosure is a tool including the cubic boron nitride sintered body of embodiment 1.
• Each tool may be entirely made of a cubic boron nitride sintered body, or only a part of the tool (for example, the cutting edge in the case of a cutting tool) may be made of a cubic boron nitride sintered body.
• a coating film may be formed on the surface of each tool.
• Cutting tools include drills, end mills, indexable cutting tips for drills, indexable cutting tips for end mills, indexable cutting tips for milling, indexable cutting tips for turning, metal saws, gear cutting tools, reamers, taps, cutting bits, etc.
• wear-resistant tools include dies, scribers, scribing wheels, dressers, etc.
• grinding tools include grinding wheels, etc.
• Cubic boron nitride sintered bodies for each sample were prepared according to the following procedure.
• the binder phase raw material powder, acetone or ethanol as a solvent, and cemented carbide balls were placed in a cemented carbide container and mixed under one of the following conditions A to C and G.
• the conditions used for each sample are shown in the "First Mix" column of Table 1.
• A. The mixing time is from 120 hours to 240 hours. A 2.0 mm diameter cemented carbide ball is used.
• B. Use a cemented carbide ball ( ⁇ 2.0 mm) with cobalt powder applied to its surface. The mixing time is 96 hours.
• C. Use carbide balls with a diameter of 3 mm to 10 mm. The mixing time is 96 hours.
• G. Use a 2.0 mm diameter cemented carbide ball. The mixing time is 24 to 90 hours.
• Treatment I Coating device Nanoparticle forming device APD-P manufactured by Advance Riko Co., Ltd.
• Target W 60 atomic %, Co 40 atomic % Introduced gas: Ar Film formation pressure: 0.88 Pa Discharge voltage: 150V Discharge frequency: 6Hz
• Capacitor capacity 1080 ⁇ F Number of shots: 1000 to 10000
• Powder container rotation speed 50 rpm Processing powder amount: 30g Processing J In treatment J, only the targets of treatment I were changed as follows: Target: 30 atomic % W, 70 atomic % Co
• ⁇ Mixing process> The cBN powder, the binder raw material powder after mixing with the ball mill, acetone or ethanol, and balls were placed in a container made of cemented carbide, and mixed under one of the following conditions D to F and H.
• the conditions used for each sample are as shown in the "Second Mix" column in Table 1.
• D. Use carbide balls with a diameter of 0.5 mm to 3 mm. The mixing time is 6 to 24 hours.
• E. The cBN powder with a small particle size and the binder raw material powder are mixed first, and after 12 hours, the cBN powder with a large particle size is added and mixed. A 2.0 mm diameter cemented carbide ball is used.
• F. Use a ball of ⁇ 2.0 mm other than that made of cemented carbide. The mixing time is 6 to 24 hours.
• H. Use a 2.0 mm diameter cemented carbide ball. The mixing time is 6 to 12 hours.
• the mixing ratio of each raw material powder was adjusted so that the cubic boron nitride particle content (volume %) of the cubic boron nitride sintered compact of each sample, and the total tungsten and cobalt content (mass %) of the cubic boron nitride sintered compact were as shown in the "cBN particle content” and "W + Co content” columns of "Cubic boron nitride sintered compact" in Table 2.
• the mixed powder was naturally dried and then heat-treated to volatilize impurities such as moisture adsorbed on the surface of the mixed powder, cleaning the surface of the mixed powder.
• ⁇ Sintering process> The mixed powder was placed in contact with a WC-6%Co cemented carbide disk and then loaded into a Ta (tantalum) container and vacuum sealed.
• the vacuum sealed mixed powder was sintered using a belt-type ultra-high pressure and high temperature generator under conditions of 3 GPa to 12 GPa and 1100°C to 2200°C for 5 minutes to 30 minutes. In this way, cubic boron nitride sintered bodies of each sample were produced.
• the tool shape of the cubic boron nitride sintered body was DNGA150408.
• composition of the binder phase in each sample of cubic boron nitride sintered body was identified by X-ray diffraction. The specific identification method is as described in embodiment 1. The results of the elements contained in the binder phase are shown in the "Binder Phase Composition" column of Table 2.
• ⁇ Total content of cobalt and tungsten in cubic boron nitride sintered body The total content of cobalt and tungsten was measured for each sample of the cubic boron nitride sintered body. The specific measurement method is as described in embodiment 1. The results are shown in the "W+Co content" column in Table 2.
• ⁇ Tool evaluation> ⁇ Samples 1 to 6, Sample 103, and Sample 104>
• the following cutting test 1 and cutting test 2 were carried out using tools (shape: DNGA150408) made of cubic boron nitride sintered bodies of Samples 1 to 6, 103, and 104, in which the content of cubic boron nitride particles in the cubic boron nitride sintered bodies is 25 volume % or more and 45 volume % or less.
• the conditions for cutting test 1 and cutting test 2 correspond to high-efficiency machining of high-hardness steel.
• the cubic boron nitride sintered body and tools of Samples 1 to 6 correspond to the examples, while the cubic boron nitride sintered body and tools of Samples 103 and 104 correspond to the comparative examples. It was confirmed that the tools of Samples 1 to 6 have excellent chipping resistance and wear resistance, and have long tool life. It was confirmed that the tools of Samples 103 and 104 are insufficient in either chipping resistance or wear resistance, and have insufficient tool life.
• the cubic boron nitride sintered bodies and tools of Samples 7 to 19 correspond to the examples, while the cubic boron nitride sintered bodies and tools of Samples 101, 102, and 105 correspond to the comparative examples. It was confirmed that the tools of Samples 7 to 19 have excellent chipping resistance and wear resistance, and have long tool life. It was confirmed that the tools of Samples 101, 102, and 105 have insufficient chipping resistance or wear resistance, and have insufficient tool life.
• the cubic boron nitride sintered body and tools of Samples 20 to 25 correspond to the working examples, while the cubic boron nitride sintered body and tools of Samples 106 and 107 correspond to the comparative examples. It was confirmed that the tools of Samples 20 to 25 have excellent chipping resistance and wear resistance, and have long tool life. It was confirmed that the tools of Samples 106 and 107 have insufficient chipping resistance or wear resistance, and have insufficient tool life.
• Cutting test 6 was carried out under the following conditions using tools (shape: DNGA150408) made of cubic boron nitride sintered bodies of samples 11, 101, 26, 30, 31, and 32.
• Cutting test 7 was carried out under the following conditions using tools (shape: DNGA150408) made of the cubic boron nitride sintered bodies of sample 22, sample 106, and sample 29.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Ceramic Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Structural Engineering (AREA)
• Ceramic Products (AREA)
• Cutting Tools, Boring Holders, And Turrets (AREA)
• Powder Metallurgy (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=93256916

Family Applications (1)

Country Status (5)

Citations (7)

Family Cites Families (4)

• 2024
  • 2024-04-26 CN CN202480002781.XA patent/CN119212964A/zh active Pending
  • 2024-04-26 WO PCT/JP2024/016539 patent/WO2024225465A1/ja not_active Ceased
  • 2024-04-26 EP EP24797208.6A patent/EP4707260A1/en active Pending
  • 2024-04-26 US US18/878,748 patent/US12571079B2/en active Active
  • 2024-04-26 JP JP2024555961A patent/JP7685683B2/ja active Active

Patent Citations (7)

Also Published As

Similar Documents

Legal Events