WO2018182021A1 - フェライト粉末、樹脂組成物および成形体 - Google Patents
フェライト粉末、樹脂組成物および成形体 Download PDFInfo
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- WO2018182021A1 WO2018182021A1 PCT/JP2018/013991 JP2018013991W WO2018182021A1 WO 2018182021 A1 WO2018182021 A1 WO 2018182021A1 JP 2018013991 W JP2018013991 W JP 2018013991W WO 2018182021 A1 WO2018182021 A1 WO 2018182021A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/08—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/706—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/706—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material
- G11B5/70626—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances
- G11B5/70642—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances iron oxides
- G11B5/70678—Ferrites
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/714—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the dimension of the magnetic particles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
- H01F1/113—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles in a bonding agent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Definitions
- the present invention relates to a ferrite powder, a resin composition, and a molded body.
- a dispersion liquid in which magnetic powder is dispersed is generally used (see, for example, Patent Documents 1 and 2).
- Patent Documents 1 and 2 a dispersion liquid in which magnetic powder is dispersed.
- the magnetic ink in which magnetic powder is dispersed has the same problem.
- An object of the present invention is to provide a ferrite powder having a small particle size, a high coercive force, and excellent dispersibility in a resin and a solvent, to provide a resin composition containing the ferrite powder, and It is providing the molded object which has a site
- a ferrite powder containing a plurality of ferrite particles The ferrite particle is a single crystal having an average particle diameter of 1 nm or more and 2000 nm or less, and has a polyhedral shape, The ferrite particles contain 2.0 mass% to 10.0 mass% of Sr and ferrite powder containing 55.0 mass% to 70.0 mass% of Fe.
- part comprised with the resin composition as described in [2].
- part manufactured using the resin composition can be provided.
- FIG. 4 is a TEM image (magnification of 400,000 times) of ferrite particles according to Example 4. 6 is an image of an electron beam diffraction pattern of a ferrite particle according to Example 4. 4 is a SEM image of ferrite powder according to Example 4.
- the ferrite powder according to the present invention is a ferrite powder containing a plurality of ferrite particles.
- the ferrite particles are single crystals having an average particle diameter of 1 nm or more and 2000 nm or less, have a polyhedral shape, contain 2.0 mass% or more and 10.0 mass% or less of Sr, and contain 55 of Fe. 0.0 mass% or more and 70.0 mass% or less.
- the ferrite powder of such a structure can be suitably detected by a metal detector. Therefore, it can be suitably applied to a molded body that may be applied to inspection by a metal detector (a molded body that may be used for the purpose of detection by a metal detector) and magnetic ink. . Further, it can be suitably applied to the production of a high-density magnetic recording medium, a thin film, etc. utilizing the nano size.
- the ferrite particles are likely to aggregate, and the dispersibility of the ferrite powder in the resin or solvent is significantly reduced.
- the average particle diameter of the ferrite particles exceeds the upper limit, the dispersibility of the ferrite powder in the resin and the solvent decreases, and the resin composition and the unintentional in the molded body produced using the resin composition are undesired. Variations in composition are likely to occur.
- a dispersion liquid for example, magnetic ink
- ferrite particles are likely to precipitate, and long-term storage becomes difficult.
- the average particle diameter of the ferrite particles exceeds the upper limit, in the molded body manufactured using the ferrite powder, unintentional irregularities may occur on the surface of the molded body due to the presence of the ferrite particles.
- the metal wiring formed on the surface may be damaged by the unevenness.
- the ferrite particles according to the present invention are single crystal. If the ferrite particles are polycrystalline, for example, when used as a magnetic recording medium, there is a possibility that when the magnetic moment is aligned by magnetization, a place where the coercive force is locally weak and strong may be created. This may cause problems in terms of storage stability. In addition, for example, when the domain wall generated by the alternating magnetic field passes through the grain interface, the domain wall is stopped at the crystal grain boundary, so that the frequency characteristics may be inferior.
- the ferrite particles do not have a polyhedral particle shape (polyhedral shape) (for example, in the case of a hexagonal plate shape), the anisotropy of the particles is strong and the dispersibility in an organic solvent or a resin solution is poor. there is a possibility.
- the polyhedron shape is not particularly limited as long as it is a 10-hedron or more, but is preferably a 10-hedron or more and a 100-hedron or less, more preferably a 12-hedron or more and a 72-hedron or less, and further preferably a 14-hedron or more and a 24-hedron or less.
- the shape of the ferrite particles can be observed using, for example, a transmission electron microscope HF-2100 Cold-FE-TEM (manufactured by Hitachi High-Technology Corporation).
- the Sr content in the ferrite particles is less than the lower limit, the amount of Fe becomes excessive, and a relatively large amount of Fe 2 O 3 is contained in the particles, so that the coercive force is lowered. Moreover, it becomes difficult to make ferrite particles into a single crystal.
- the Sr content in the ferrite particles exceeds the upper limit, the amount of Sr becomes excessive and the particles contain a relatively large amount of SrO, or Sr—Fe oxide other than Sr ferrite. Is excessively contained, and various magnetic properties are deteriorated.
- Fe content in the ferrite particles is less than the lower limit, Sr—Fe oxide other than Sr ferrite is excessively contained, and various magnetic properties are deteriorated.
- the ferrite powder (ferrite particles) is likely to be oxidized in the production process, and various magnetic properties are deteriorated.
- the particle diameter of the ferrite particles is a horizontal ferret diameter determined from an SEM image taken using a scanning electron microscope, and the average particle diameter of the ferrite particles is determined for 100 or more ferrite particles. It means the average value of the particle diameter (horizontal ferret diameter).
- the scanning electron microscope for example, SU-8020 manufactured by Hitachi High-Technologies Corporation can be used. Further, the magnification at the time of photographing the SEM image can be set to 100,000 to 200,000 times.
- image analysis software such as Image-Pro PLUS manufactured by MEDIA CYBERNETICS can be used.
- the content of the metal element constituting the ferrite particles can be measured as follows.
- ferrite powder was weighed and a mixture of pure water: 60 ml with 1N hydrochloric acid: 20 ml and 1N nitric acid: 20 ml was heated to prepare an aqueous solution in which ferrite powder (ferrite particles) was completely dissolved.
- the content of the metal element can be determined by performing measurement using an ICP analyzer (for example, ICPS-1000IV manufactured by Shimadzu Corporation).
- the average particle size of the ferrite particles may be 1 nm or more and 2000 nm or less, but is preferably 1 nm or more and 800 nm or less, and more preferably 1 nm or more and 300 nm or less. Thereby, the effect mentioned above is exhibited more notably.
- the ferrite particles constituting the ferrite powder of the present invention may have a polyhedral particle shape, but the spherical ratio (average spherical ratio) of the ferrite particles is 1.02 or more and 1.43 or less. Is more preferably 1.05 or more and 1.42 or less, and further preferably 1.11 or more and 1.33 or less.
- the polyhedral ferrite particles are considered to be generated by acting as a flux when the Sr component contained in the raw material volatilizes at a high temperature during thermal spray firing. Therefore, even if the same operation is performed using a raw material that does not contain Sr, polyhedral ferrite particles are not generated or very little generated. Further, when the firing temperature is low, Sr does not easily function as a flux, so that it is difficult to form a polyhedral shape.
- the sphericity can be determined as follows. First, ferrite particles are photographed at a magnification of 200,000 times using a scanning electron microscope (FE-SEM (for example, SU-8020 manufactured by Hitachi High-Technology Corporation)). Then, the circumscribed circle diameter and the inscribed circle diameter are determined for the ferrite particles from the photographed SEM image, and the ratio (circumscribed circle diameter / inscribed circle diameter) is obtained as a spherical ratio. If the two diameters are the same, i.e. a true sphere, this ratio is 1. As the average sphericity, for example, an average value of the sphericity obtained for 100 ferrite particles randomly extracted from the ferrite powder can be adopted.
- FE-SEM for example, SU-8020 manufactured by Hitachi High-Technology Corporation
- the Sr content in the ferrite particles may be 2.0% by mass or more and 10.0% by mass or less, preferably 2.5% by mass or more and 9.5% by mass or less, and 4.0% by mass. % Or more and 9.0 mass% or less is more preferable.
- the Fe content in the ferrite particles may be 55.0 mass% or more and 70.0 mass% or less, but is preferably 57.0 mass% or more and 69.0 mass% or less, and 58.0 mass%. % Or more and 68.0% by mass or less is more preferable. Thereby, the effect mentioned above is exhibited more notably.
- the ferrite particles may contain components (elements) other than Fe, Sr, and O.
- components include Mn, Mg, Ti, Si, Cl, Ca, Al and the like.
- the content of components (elements) other than Fe, Sr, and O contained in the ferrite particles as described above is preferably 2.0% by mass or less, and 1.5% by mass or less. More preferably, it is 0.8 mass% or less.
- Sr is unevenly distributed on the surface of the ferrite particle.
- the surface treatment for the ferrite particles with a surface treatment agent particularly, a silane coupling agent as described in detail later can be more suitably performed, and the aggregation of the ferrite particles can be more effectively prevented.
- the fluidity and ease of handling of the ferrite particles and the resin composition containing the ferrite particles can be further improved.
- the dispersibility of the ferrite particles in the molded body in the resin composition can be further improved.
- the surface treatment with the surface treatment agent can be more uniformly performed on each part of the ferrite particle as the mother particle. Such an effect is more prominent when Sr is unevenly distributed on the surface of the ferrite particle in the state of an oxide (for example, SrO).
- the distribution of the constituent elements in the ferrite particles is determined from the outer surface of the ferrite particles to the inside by performing energy dispersive X-ray analysis (EDX) on the image (STEM image) of the ferrite particles observed with a scanning transmission electron microscope. It can be determined as the intensity of the constituent element with respect to the moving distance of the electron beam swept toward the surface.
- EDX energy dispersive X-ray analysis
- STEM image image of the ferrite particles observed with a scanning transmission electron microscope.
- EDAX Octane T Ultra W manufactured by AMETEK
- the ferrite particles may be subjected to a surface treatment.
- the surface treatment agent used for the particle surface treatment include a silane coupling agent, a phosphoric acid compound, a carboxylic acid, a fluorine compound, a titanate coupling agent, and an aluminate coupling agent.
- the aggregation of ferrite particles can be more effectively prevented, and the flowability and handling of ferrite powder and resin compositions containing the ferrite powder can be prevented. It is possible to further improve ease of handling. Moreover, the dispersibility of the ferrite powder in the molded body in the resin composition can be further improved.
- the electrical resistance of the ferrite powder (ferrite particles) can be further increased. Further, from the relationship between the affinity between the silane coupling agent and the above-described ferrite particles, the surface treatment with the silane coupling agent can be performed more uniformly on each part of the ferrite particles as the mother particles.
- the silane coupling agent for example, a silane compound having a silyl group and a hydrocarbon group can be used.
- the silane coupling agent has an alkyl group having 8 to 10 carbon atoms as the alkyl group. It is preferable.
- the surface treatment with the silane coupling agent can be performed more uniformly on each part of the ferrite particles as the mother particles.
- the silane coupling agent having an alkyl group having 8 to 10 carbon atoms include decyltrimethyoxysilane and n-octyltriethoxysilane.
- the affinity with the epoxy resin can be further improved, and the dispersion stability of the ferrite particles in the resin composition containing the epoxy resin can be further improved.
- Examples of the phosphoric acid compound include lauryl phosphate, lauryl-2-phosphate, steareth-2 phosphate, phosphate ester of 2- (perfluorohexyl) ethylphosphonic acid, and the like.
- carboxylic acid for example, a compound having a hydrocarbon group and a carboxyl group (fatty acid) can be used. Specific examples of such compounds include decanoic acid, tetradecanoic acid, octadecanoic acid, cis-9-octadecenoic acid and the like.
- fluorine compound examples include a silane coupling agent as described above, a phosphoric acid compound, and a compound having a structure in which at least a part of hydrogen atoms of the carboxylic acid is substituted with a fluorine atom (fluorine silane compound, fluorine A phosphoric acid compound and a fluorine-substituted fatty acid).
- the ferrite powder of the present invention can obtain an appropriate saturation magnetization by having the above-described configuration.
- the saturation magnetization of the ferrite powder of the present invention by VSM measurement when a magnetic field of 10K ⁇ 1000 / 4 ⁇ A / m is applied is preferably 15 Am 2 / kg or more and 80 Am 2 / kg or less, and 20 Am 2 / Kg or more and 70 Am 2 / kg or less is more preferable, and 25 Am 2 / kg or more and 65 Am 2 / kg or less is more preferable.
- the ferrite powder satisfying such conditions is preferably used by adding to a magnetic metal powder used as a magnetic core material, for example.
- a magnetic field at the time of manufacturing the molded body so that ferrite particles are unevenly distributed in a desired portion of the molded body, or to apply a magnetic field to the manufactured molded body and attract it by magnetic force. it can.
- the saturation magnetic flux density after molding is unlikely to decrease.
- the saturation magnetization when the saturation magnetization is less than the lower limit value, it becomes difficult to suitably distribute the ferrite particles in a desired portion of the molded body and to attract the manufactured molded body by applying a magnetic field. there is a possibility. In the configuration as described above, it is difficult for the saturation magnetization to exceed the upper limit.
- the remanent magnetization of the ferrite powder according to the present invention by VSM measurement when a magnetic field of 10 K ⁇ 1000 / 4 ⁇ A / m is applied is preferably 2.0 Am 2 / kg or more and 35 Am 2 / kg or less, and 3.0 Am 2. / Kg or more and 30 Am 2 / kg or less is more preferable, and 5.0 Am 2 / kg or more and 25 Am 2 / kg or less is more preferable.
- the coercive force of the ferrite powder by VSM measurement when a magnetic field of 10 K ⁇ 1000 / 4 ⁇ A / m is applied is preferably 30 kA / m to 400 kA / m, and more preferably 50 kA / m to 350 kA / m. More preferably, it is 80 kA / m or more and 300 kA / m or less.
- the properties as a magnetic recording medium can be further improved.
- the coercive force is less than the lower limit, there is a possibility that the recording cannot be read well when used as a magnetic recording medium.
- the coercive force exceeds the upper limit.
- the saturation magnetization, residual magnetization, and coercive force can be obtained, for example, as follows. That is, first, a ferrite powder (ferrite particles) of interest is packed in a cell having an inner diameter of 5 mm and a height of 2 mm, and the cell is set in a vibrating sample type magnetic measuring device. Next, an applied magnetic field is applied, sweeping to 10K ⁇ 1000 / 4 ⁇ ⁇ A / m, and then the applied magnetic field is reduced to create a hysteresis curve. Saturation magnetization, residual magnetization, and coercive force can be obtained from the data of this curve. As the vibration sample type magnetometer, for example, VSM-C7-10A (manufactured by Toei Kogyo Co., Ltd.) can be used.
- VSM-C7-10A manufactured by Toei Kogyo Co., Ltd.
- the ferrite powder of the present invention has the above-described configuration, a sufficiently high powder resistance (electric resistance) can be obtained. This makes it possible to reduce eddy current loss when used by being mixed with metal powder and using it even at higher frequencies. In addition, for example, when the ferrite powder is applied to a printed wiring board, it is possible to prevent current leakage and ensure durability.
- the electrical resistance of the ferrite powder can be evaluated by, for example, the volume resistivity when the electric field strength is 5000 V / cm (650 V when the height is 1.3 mm).
- the volume resistivity of the ferrite powder of the present invention is preferably 1 ⁇ 10 7 ⁇ ⁇ cm or more, more preferably 1 ⁇ 10 8 ⁇ ⁇ cm or more, More preferably, it is 1 ⁇ 10 9 ⁇ ⁇ cm or more.
- the electrical resistivity of the ferrite powder can be determined as follows, for example. That is, after filling a sample (ferrite powder) to a fluororesin cylinder with a cross-sectional area of 1.77 cm 2 to a height of 1.3 mm, attach electrodes to both ends, and place a weight of 1 kg from above. In this state, using a Keithley 6517A type insulation resistance measuring instrument, a measurement voltage was applied to the electrode stepwise from 50 V to 1000 V in increments of 50 V every 5 seconds, and the current value 5 seconds after each step. The volume resistivity can be calculated from the obtained current value and the applied voltage.
- the BET specific surface area of the constituent particles (ferrite particles) of the ferrite powder of the present invention is preferably 9.0 m 2 / g or more and 28 m 2 / g or less, and preferably 10 m 2 / g or more and 20 m 2 / g or less. More preferably, it is more preferably 11 m 2 / g or more and 14 m 2 / g or less.
- the BET specific surface area can be determined by measurement using a specific surface area measuring device (for example, model: Macsorb HM model-1208 (manufactured by Mountec)).
- a specific surface area measuring device for example, model: Macsorb HM model-1208 (manufactured by Mountec)
- the ferrite powder of the present invention only needs to include a plurality of ferrite particles that satisfy the above-described conditions, and may further include other particles (particles that do not satisfy the above-described conditions). Good.
- the content of the other particles in the ferrite powder is preferably 10% by mass or less, more preferably 3.0% by mass or less, and 0.5% by mass or less. Is more preferable. Thereby, the effects as described above are more remarkably exhibited.
- the ferrite powder of the present invention may be produced by any method, but can be suitably produced, for example, by the method described below.
- the ferrite powder of the present invention is, for example, selectively spraying particles (ferrite particles) having a particle size within a predetermined range after spraying a ferrite raw material containing Fe and Sr in the atmosphere to form a ferrite, followed by rapid solidification. It can manufacture suitably by collect
- the method for preparing the ferrite raw material is not particularly limited, and a conventionally known method can be employed. For example, a dry method or a wet method may be used.
- Examples of the method for preparing the ferrite raw material (granulated product) include the following methods. That is, first, an appropriate amount of Fe raw material and Sr raw material is weighed so as to have a desired ferrite composition, and then water is added and pulverized to prepare a slurry. Then, the produced slurry is granulated with a spray dryer, and pulverized and classified as necessary to prepare a granulated product having a predetermined particle size.
- Examples of the classification method include wind classification, mesh filtration method, sedimentation method, classification using various sieves, and the like.
- the average particle size of the granulated product is not particularly limited, but is preferably 0.5 ⁇ m or more and 30 ⁇ m or less.
- the average particle diameter can be obtained, for example, by measuring the particle diameter D50 at which the accumulation of the volume-based particle size distribution is 50% using a laser diffraction particle size distribution analyzer (LA-950, Horiba, Ltd.). it can.
- the formation of single crystal particles having a relatively small particle size can be more suitably progressed during thermal spraying, and a ferrite powder satisfying the above-described conditions can be more efficiently produced.
- the pore volume, average pore diameter, BET specific surface area and the like of the finally obtained ferrite particles can be adjusted more suitably.
- the proportion of particles to be removed by classification in a later step can be further reduced, and the yield of ferrite powder can be further improved.
- the viscosity means a value measured at 25 ° C. using a B-type viscometer (for example, a visco tester manufactured by Rion Co., Ltd.).
- a method for preparing a ferrite raw material for example, a ferrite raw material having a composition prepared is mixed, dry pulverized, each raw material is pulverized and dispersed, and the mixture is mixed with a granulator.
- the method of granulating and classifying and preparing the granulated material of a predetermined particle diameter is mentioned.
- the granulated material prepared as described above is sprayed in the atmosphere to be ferritized.
- a mixed gas of combustion gas and oxygen can be used.
- the mixing ratio of the combustion gas and oxygen in the mixed gas is preferably 1: 3.5 or more and 1: 6.0 or less in terms of volume ratio. If the ratio of oxygen in the mixed gas is less than the lower limit, melting may be insufficient. Moreover, when the ratio of oxygen in the mixed gas exceeds the upper limit value, it becomes difficult to form ferrite.
- propane gas for example, propane gas, propylene gas, acetylene gas or the like can be used, and propane gas can be particularly preferably used.
- the granulated material transport gas may be used.
- nitrogen, oxygen, air, or the like can be used as the granule carrier gas.
- the flow rate of the granulated material to be conveyed is preferably 20 m / second or more and 60 m / second or less.
- the thermal spraying is preferably performed at a temperature of 1000 ° C. or higher and 3500 ° C. or lower, more preferably at a temperature of 1500 ° C. or higher and 3500 ° C. or lower.
- the formation of single crystal particles having a relatively small particle size can be advanced more suitably, and it is possible to more efficiently produce a ferrite powder that satisfies the above-described conditions. it can.
- the pore volume, average pore diameter, BET specific surface area, etc. of the ferrite particles constituting the finally obtained ferrite powder can be adjusted more suitably.
- the proportion of particles to be removed by classification in a later step can be further reduced, and the yield of ferrite powder can be further improved.
- the ferrite particles formed by the main firing by thermal spraying are rapidly cooled and solidified by being carried in an air stream by air supply, and then ferrite particles having a predetermined particle size range are collected and recovered.
- the collection is performed by transporting rapidly solidified ferrite particles in an air flow by air supply, and particles having a large particle size fall in the middle of the air flow while other particles are carried downstream.
- the ferrite particles having the average particle diameter in the above range can be collected by a filter provided on the downstream side of the airflow.
- the collected ferrite particles may be classified as necessary. Thereby, the ferrite particle which satisfies the preferable conditions as mentioned above can be obtained more suitably.
- a classification method an existing air classification, mesh filtration method, sedimentation method, or the like can be used. It is possible to remove particles having a large particle diameter with a cyclone or the like.
- the ferrite particles may be subjected to a surface treatment after the main firing treatment.
- ferrite particles having a surface layer can be suitably formed.
- the amount of the surface treatment agent used depends on the BET specific surface area of the ferrite particles as the mother particles, but is 0.05 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the ferrite particles (mother particles). preferable.
- the application of the ferrite powder according to the present invention is not particularly limited, but for example, for magnetic recording medium tapes, flexible printed wiring boards, electromagnetic shielding materials, pigments, power generation members (for example, magnetic core materials), fillers ( In particular, magnetic filler), for articles applied to metal detectors (for example, articles used in manufacturing sites for foods, pharmaceuticals, etc. and should be prevented from being mixed as foreign substances), dust magnets Examples include a core additive.
- the ferrite powder of the present invention may be used by being incorporated in a cloth (for example, a woven fabric, a non-woven fabric, etc.) or inside or on the surface of a fiber.
- the resin composition of the present invention contains the ferrite powder of the present invention.
- a resin composition of the present invention can be suitably used for the production of a molded article described in detail later. More specifically, it can be suitably used for the production of a molded article having high saturation magnetization, coercive force and electrical resistance.
- the ferrite powder can be well dispersed in the resin composition, and it is possible to effectively prevent the aggregation of the ferrite particles and the unintentional variation of the composition. Therefore, it can be suitably used for the production of a molded product prevented.
- the ferrite powder may be contained in any form, but is preferably present dispersed in the resin material.
- the content of the ferrite powder in the resin composition is not particularly limited, but is preferably 5.0% by mass or more and 90% by mass or less, and more preferably 7.0% by mass or more and 88% by mass or less.
- the moldability of the molded body can be further improved, the toughness, strength, reliability, etc. of the molded body can be further improved, and the magnetic properties, electrical insulation, etc. of the molded body can be further improved. Can do.
- resin material contained in the resin composition for example, various thermoplastic resins, various curable resins, and the like can be used.
- polyolefin such as polyethylene, polypropylene, poly- (4-methylpentene-1), ethylene-propylene copolymer, cyclic polyolefin; modified polyolefin; polystyrene; butadiene-styrene copolymer; acrylonitrile— Butadiene-styrene copolymer (ABS resin); acrylonitrile-styrene copolymer (AS resin); polyvinyl chloride; polyvinylidene chloride; ethylene-vinyl acetate copolymer (EVA); polyamide (eg, nylon 6, nylon 46) , Nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66); polyimide; polyamideimide; acrylic resin such as polymethyl methacrylate; polycarbonate (PC); eye Polymer alcohol (PVA); ethylene-vinyl alcohol copolymer (EVOH); polyethylene terephthalate (PET),
- Polyether Polyacetal (POM); Polyphenylene oxide; Modified polyphenylene oxide; Polyetherketone (PEK); Polyetheretherketone (PEEK); Polyetherimide; Polysulfone; Polyethersulfone; Polyphenylenesulfide; Polytetrafluoro Fluorine resins such as ethylene and polyvinylidene fluoride; silicone rubber, isoprene rubber, butadiene rubber, nitrile rubber, natural rubber, etc.
- Rubber materials Various thermoplastic elastomers such as styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene; epoxy resin; phenol Resins; Urea resins; Melamine resins; Unsaturated polyesters; Silicone resins; Polyurethanes, etc., and copolymers, blends, polymer alloys, etc. mainly composed of these, and combinations of one or more of these Can be used.
- thermoplastic elastomers such as styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene; epoxy resin; phenol Resins; Urea resins; Melamine resins; Unsaturated polyesters; Silicone resins; Polyurethanes, etc., and copoly
- the resin materials contained in the resin composition are polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), fluororesin, silicone rubber, butadiene rubber, thermoplastic elastomer, epoxy resin, and silicone resin. It is preferable to include one or more selected from the group consisting of:
- the dispersion stability of the ferrite powder in the resin composition is further improved, and the moldability of the molded body can be further improved.
- the toughness, strength, reliability and the like of the molded body can be further improved.
- the adhesion with various resins is improved, so that the dispersion stability of the ferrite powder in the resin composition is further improved, and the molded body The moldability of can be further improved.
- the resin material contained in the resin composition may have a composition different from that of the resin material contained in the molded body produced using the resin composition.
- the resin material contained in the resin composition may be a precursor (for example, a monomer, dimer, trimer, oligomer, prepolymer, etc.) of the resin material contained in the final molded body.
- the content of the resin material in the resin composition is not particularly limited, but is preferably 8.0% by mass to 95% by mass, and more preferably 10% by mass to 90% by mass.
- the moldability of the molded body can be further improved, the toughness, strength, reliability, etc. of the molded body can be further improved, and the content of ferrite powder can be sufficiently increased, The magnetic characteristics, electrical insulation, etc. of the body can be further improved.
- the content of the resin material in the resin composition is less than the lower limit, the moldability of the molded body is lowered, and the toughness, strength, reliability, etc. of the molded body may be lowered. .
- the content of the resin material in the resin composition exceeds the upper limit, the content of the ferrite powder is relatively lowered, and depending on the composition of the ferrite powder, the magnetic properties of the molded body, electrical insulation, etc. It may be difficult to sufficiently improve
- the resin composition of the present invention only needs to contain the ferrite powder and resin material of the present invention, and may further contain other components (other components).
- Such components include various colorants such as pigments and dyes, various fluorescent materials, various phosphorescent materials, various phosphorescent materials, solvents, infrared absorbing materials, ultraviolet absorbers, dispersants, and surfactants.
- the resin composition of the present invention may be in any form, and examples of the resin composition include powders, pellets, dispersions, slurries, gels, etc., but pellets are preferred.
- the ease of handling of the resin composition is further improved, and a molded article using the resin composition can be more suitably produced.
- the storage stability of the resin composition can be further improved, and deterioration of the constituent components of the resin composition during storage can be more effectively prevented.
- the volume average particle size is preferably 1 mm or more and 10 mm or less, and more preferably 2 mm or more and 7 mm or less.
- the resin composition of the present invention can be produced, for example, by mixing the ferrite powder of the present invention and a resin material.
- the mixing of the ferrite powder and the resin material is, for example, a mixing device (kneading device) such as a planetary mixer, a twin screw mixer, a kneader, a Banbury mixer, a stirring kneader such as an oven roll, a single screw extruder, a twin screw extruder, etc. It can carry out suitably by using.
- a mixing device such as a planetary mixer, a twin screw mixer, a kneader, a Banbury mixer, a stirring kneader such as an oven roll, a single screw extruder, a twin screw extruder, etc. It can carry out suitably by using.
- the molded product of the present invention has a portion composed of the resin composition of the present invention.
- a molded body having high saturation magnetization, coercive force and electrical resistance can be obtained.
- the ferrite powder of the present invention it is possible to further improve the strength, durability, etc. of the molded body, for example, when an external force such as tension or bending is applied, particularly when a large external force is applied or Even when an external force is repeatedly applied, it is more effectively prevented that a part of the molded body is detached due to cutting or the like.
- the molded body of the present invention only needs to contain ferrite powder in at least a part thereof, and may have, for example, a region not containing ferrite powder.
- a first region as a region including the ferrite powder of the present invention (region formed using the resin composition of the present invention) and a region not including the ferrite powder of the present invention (for example, And a second region as a region composed of a material other than the resin composition of the present invention.
- the molded body preferably contains the ferrite powder of the present invention at least near the surface thereof.
- the molded body preferably contains the ferrite powder of the present invention in a region within 1.0 mm in the thickness direction from the surface, and a region within 0.5 mm in the thickness direction from the surface. It is more preferable that the ferrite powder of the present invention is included.
- the properties (for example, magnetic properties, electrical properties, etc.) of the ferrite powder can be more effectively exhibited in the molded body.
- such a molded body can be preferably manufactured by applying a magnetic field from the direction to be the surface of the molded body, for example, when the molded body is molded (the resin material is softened or melted). .
- the above-described ferrite can be unevenly distributed in the vicinity of the surface of the molded body, and the effects as described above can be exhibited more remarkably.
- the content of the ferrite powder of the present invention in the molded product of the present invention varies depending on the usage of the molded product, but is preferably 2.0% by mass or more and 20% by mass or less, and is preferably 2.5% by mass or more and 18% by mass. % Or less is more preferable.
- the toughness, strength, reliability and the like of the molded body can be further improved, and the magnetic properties, electrical insulation and the like of the molded body can be further improved.
- Various molding methods can be used as a method for producing a molded body, such as an injection molding method (insert molding method, multicolor molding method, sandwich molding method, injection molding method, etc.), compression molding method, extrusion molding method, Examples include inflation molding methods, T-die film molding methods, laminate molding methods, blow molding methods, hollow molding methods, compression molding methods, calender molding methods, various coating methods, stereolithography, three-dimensional additive manufacturing methods, etc. It is done.
- injection molding method insert molding method, multicolor molding method, sandwich molding method, injection molding method, etc.
- compression molding method extrusion molding method
- examples include inflation molding methods, T-die film molding methods, laminate molding methods, blow molding methods, hollow molding methods, compression molding methods, calender molding methods, various coating methods, stereolithography, three-dimensional additive manufacturing methods, etc. It is done.
- a resin composition contains curable resin
- the hardening reaction of the said curable resin is performed.
- the curing reaction varies depending on the type of the curable resin and the like, but can be performed by heating or irradiation with energy rays such as ultraviolet rays.
- a molded body is formed using a composition that does not include the ferrite powder of the present invention, and a surface layer that is provided on the base and is formed using the composition that includes the ferrite powder of the present invention.
- a base manufactured by methods such as the above, casting, forging, powder injection molding (PIM (Powder Injection Molding)), such as coating methods such as dipping and brushing, ink jet methods, etc.
- PIM Powder injection molding
- coating methods such as dipping and brushing, ink jet methods, etc. You may manufacture by forming a surface layer using various printing methods.
- ferrite powder can be suitably unevenly distributed in the area
- the molded body may be manufactured by subjecting the molded body obtained by the above-described molding method to post-treatment such as grinding and polishing.
- the ferrite powder is dispersed in the resin material in the resin composition.
- the resin composition for example, the ferrite powder is in the liquid. It has settled and may be used after being dispersed by stirring or the like, if necessary.
- the resin composition of the present invention may be a dispersion in which ferrite powder and resin particles are dispersed in a volatile liquid.
- the resin composition of the present invention may have a configuration in which, for example, ferrite powder and resin powder are simply mixed.
- the ferrite powder of the present invention may be manufactured by any method, and the manufacturing method is not limited to the method described above.
- Fe 2 O 3 iron oxide
- SrCO 3 strontium carbonate
- the cooled particles were collected by a filter provided on the downstream side of the airflow.
- the particles having a large particle diameter were not collected by the filter because they dropped in the middle of the air flow and were collected by the cyclone.
- Example 2 Ferrite powder was produced in the same manner as in Example 1 except that the mixing ratio of iron oxide and strontium carbonate was changed as shown in Table 1 below.
- Example 4 Ferrite powder was produced in the same manner as in Example 3 except that carbon black was added as an additive (combustion aid) at the time of thermal spraying so that the content in the entire thermal spray raw material was 0.5% by mass. did.
- the particle size of the granulated product is a value within the range of 0.5 ⁇ m or more and 30 ⁇ m or less, and the viscosity of the slurry (B-type viscometer (Bisco Tester manufactured by Rion Co., Ltd.))
- the values measured at 25 ° C.) are values within the range of 0.5 poise or more and 4 poises or less, and the mixing ratio of the combustion gas and oxygen in the mixed gas is the combustion gas.
- the flow rate of granules to be conveyed are both fall within a range of less than 20 m / sec 60 m / sec Yes, the temperature during thermal spraying was 2000 ° C. in all cases.
- the obtained granulated material is housed in a mortar and fired in an electric furnace at 1100 ° C. for 4 hours in an air atmosphere to be ferritized to form a lump that conforms to the shape of the mortar. I got a thing.
- the obtained fired product was pulverized by grinding in a mortar to produce a ferrite powder.
- Table 1 summarizes the configurations of the ferrite powders of the above Examples and Comparative Examples.
- chemical analysis evaluation of surface uneven distribution elements, crystal morphology, particle shape observation, average particle diameter, and BET specific surface area measurement for the ferrite powders (ferrite particles) of the respective Examples and Comparative Examples are as follows. This was done as follows.
- the content of the metal component in the ferrite powder was measured as follows. First, 0.2 g of ferrite powder was weighed, and a mixture obtained by adding 20 mL of 1N hydrochloric acid and 20 mL of 1N nitric acid to 60 mL of pure water was heated to prepare an aqueous solution in which the ferrite powder was completely dissolved. The obtained aqueous solution was set in an ICP analyzer (manufactured by Shimadzu Corporation, ICPS-1000IV), and the content of metal components in the ferrite powder was measured. In addition, the description of “ ⁇ 0.01” in the column of chemical analysis in Table 1 means that it is a measurement error or exists as an inevitable impurity derived from raw materials, manufacturing processes, and the like. .
- FIG. 1 is an analysis result of Fe of ferrite particles according to Example 4, FIG.
- FIG. 2 is an analysis result of Sr of ferrite particles according to Example 4, and FIG. 4 is a diagram in which the analysis results of Fe and Sr are superimposed on the ferrite particles according to No. 4.
- Sr is present inside the particle, it is clear that Sr is also present in the vicinity of the particle surface (it is unevenly distributed on the surface).
- FIGS. 1 to 3 were obtained for the ferrite particles according to other examples.
- FIG. 5 shows an image of an electron diffraction pattern of the ferrite particles according to Example 4.
- the horizontal ferret diameter was taken as the average particle diameter.
- the volume average particle diameter was made into the average particle diameter.
- the horizontal ferret diameter was determined as follows. That is, the ferrite particles were photographed at a magnification of 100,000 using a scanning electron microscope FE-SEM (manufactured by Hitachi High-Technologies Corporation, SU-8020). At this time, the ferrite particles were photographed in a visual field capable of counting 100 particles or more. The photographed SEM image was read with a scanner, and image analysis was performed using image analysis software (Image-Pro PLUS, MEDIA CYBERNETICS). With respect to the obtained image of each particle, the horizontal ferret diameter of each particle was measured by manual measurement. In FIG. 6, the SEM image of the ferrite powder which concerns on Example 4 is shown.
- the volume average particle diameter was determined as follows. That is, 10 g of ferrite powder was placed in a beaker with 80 mL of water as a dispersion medium, and 2 to 3 drops of sodium hexametaphosphate as a dispersant were added. Next, the obtained solution was oscillated with an ultrasonic homogenizer (manufactured by SMT Co., UH-150) for 20 seconds at an output level of 4 to disperse ferrite powder in the solution. Next, after removing bubbles generated on the surface of the beaker, solid-liquid separation was performed to collect ferrite powder. The volume average particle size of the recovered ferrite powder was measured using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd., Model 9320-X100).
- BET specific surface area The BET specific surface area was measured using a specific surface area measuring device (Macsorb HM model-1208, manufactured by Mountec Co., Ltd.). First, about 10 g of the obtained ferrite powder was placed on a medicine wrapping paper, deaerated with a vacuum dryer, and after confirming that the degree of vacuum was ⁇ 0.1 MPa or less, the ferrite particles were heated at 200 ° C. for 2 hours. The water adhering to the surface of was removed. Subsequently, about 0.5 to 4 g of ferrite powder (ferrite particles) from which moisture was removed was placed in a standard sample cell dedicated to the apparatus and accurately weighed with a precision balance.
- Macsorb HM model-1208 manufactured by Mountec Co., Ltd.
- the weighed ferrite powder was set in the measurement port of the apparatus and measured.
- the measurement was performed by a one-point method.
- the measurement atmosphere was a temperature of 10 to 30 ° C. and a relative humidity of 20 to 80% (no condensation).
- ⁇ 2 >> Evaluation of ferrite particles (saturation magnetization, residual magnetization and coercivity)
- ferrite powder was packed into a cell having an inner diameter of 5 mm and a height of 2 mm, and set in a vibration sample type magnetic measuring device (VSM-C7-10A manufactured by Toei Kogyo Co., Ltd.).
- VSM-C7-10A vibration sample type magnetic measuring device manufactured by Toei Kogyo Co., Ltd.
- an applied magnetic field was applied, sweeping was performed to 10K ⁇ 1000 / 4 ⁇ ⁇ A / m, and then the applied magnetic field was decreased to prepare a hysteresis curve. Thereafter, saturation magnetization, residual magnetization, and coercive force were obtained from the data of this curve.
- ⁇ 4 Manufacture of Molded Body Using the resin compositions according to the respective Examples and Comparative Examples obtained as described above, PET as a base material using a baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) A coating film was formed on the film. The thickness of the coating film was 1 mil (25.4 ⁇ m), and the width of the coating film was 10 cm. Thereafter, the solvent was dried and the resin was cured to obtain a resin film as a molded body.
- SA-201 baker type applicator
- the coating films (including PET film) according to each of the examples and comparative examples were cut out to 20 mm ⁇ 20 mm, and a belt conveyor type metal detector (META-HAWKII, manufactured by System Square Co., Ltd.) was used for each of the obtained samples.
- Sensitivity iron ball sensitivity (F value), SUS ball sensitivity (S value) capable of passing through and detecting the sample was determined.
- Table 2 summarizes the results of evaluation of the above ferrite particles and evaluation of the coating film.
- the ferrite powder of the present invention includes a plurality of ferrite particles, and the ferrite particles are a single crystal having an average particle diameter of 1 nm to 2000 nm and have a polyhedral shape, and the ferrite particles include Sr. 2.0 mass% or more and 10.0 mass% or less are contained, and Fe is contained 55.0 mass% or more and 70.0 mass% or less. Therefore, it is possible to provide a ferrite powder having a small particle size, a high coercive force, and excellent dispersibility in resins and solvents. Therefore, the ferrite powder of the present invention has industrial applicability.
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Abstract
Description
しかしながら、従来においては、分散液中における磁性粉末の分散性を優れたものとすることが困難であった。また、分散液中における磁性粉末の分散性を向上させようとすると、磁性粉末の磁気特性の低下(特に、保磁力の低下)の問題を生じていた。
また、磁性粉末が分散してなる磁性インクにおいても、同様の問題があった。
複数個のフェライト粒子を含むフェライト粉末であって、
前記フェライト粒子は、平均粒径が1nm以上2000nm以下の単結晶体で、かつ、多面体状の形状を備え、
前記フェライト粒子は、Srを2.0質量%以上10.0質量%以下含有し、Feを55.0質量%以上70.0質量%以下含有するフェライト粉末。
[2]
[1]に記載のフェライト粉末を含有する樹脂組成物。
[3]
[2]に記載の樹脂組成物で構成された部位を有する成形体。
《フェライト粉末》
まず、本発明のフェライト粉末について説明する。
また、フェライト粒子の平均粒径が前記上限値を超えると、フェライト粉末の樹脂や溶媒に対する分散性が低下し、樹脂組成物や当該樹脂組成物を用いて製造される成形体中における不本意な組成のばらつきを生じやすくなる。また、フェライト粒子が分散した分散液(例えば、磁性インク等)として用いる際に、フェライト粒子が沈殿しやすく長期保存が難しくなる。また、フェライト粒子の平均粒径が前記上限値を超えると、フェライト粉末を用いて製造される成形体において、フェライト粒子の存在によって成形体の表面に不本意な凹凸が生じることがある。特に、電子機器への配線、ケーブル等に用いられるフレキシブルプリント配線基板に適用される場合に、その表面に形成される金属配線が上記凹凸によって損傷するおそれがある。
多面体形状とは、10面体以上であれば特に限定されないが、10面体以上100面体以下が好ましく、12面体以上72面体以下がより好ましく、14面体以上24面体以下がさらに好ましい。
フェライト粒子の形状は、例えば、透過型電子顕微鏡HF-2100 Cold-FE-TEM(日立ハイテクノロジー社製)を用いて観察することができる。
これにより、前述した効果がより顕著に発揮される。
まず、走査型電子顕微鏡(FE-SEM(例えば、日立ハイテクノロジー社製、SU-8020等))を用いて、倍率20万倍でフェライト粒子を撮影する。そして、撮影したSEM画像から、フェライト粒子について、外接円直径、内接円直径を求め、その比(外接円直径/内接円直径)を球状率として求める。2つの直径が同一である場合、すなわち、真球である場合、この比が1となる。平均球状率は、例えば、フェライト粉末から無作為に抽出した100個のフェライト粒子について求めた球状率の平均値を採用することができる。
これにより、前述した効果がより顕著に発揮される。
これにより、例えば、後に詳述するような表面処理剤(特に、シランカップリング剤)によるフェライト粒子に対する表面処理をより好適に行うことができ、フェライト粒子の凝集をより効果的に防止することができ、フェライト粒子や当該フェライト粒子を含む樹脂組成物の流動性、取り扱いのし易さをより向上させることができる。また、樹脂組成物中、成形体中におけるフェライト粒子の分散性をより向上させることができる。また、母粒子としてのフェライト粒子の各部位に対しより均一に表面処理剤による表面処理を施すことができる。このような効果は、Srが、酸化物(例えば、SrO)の状態でフェライト粒子の表面に偏在している場合に、より顕著に発揮される。
粒子の表面処理に用いる表面処理剤としては、例えば、シランカップリング剤、リン酸系化合物、カルボン酸、フッ素系化合物、チタネート系カップリング剤、アルミネート系カップリング剤等が挙げられる。
次に、本発明に係るフェライト粉末の製造方法について説明する。
本発明のフェライト粉末は、いかなる方法で製造してもよいが、例えば、以下に述べるような方法により、好適に製造することができる。
分級方法としては、例えば、風力分級、メッシュ濾過法、沈降法、各種篩を使った分級等が挙げられる。
上記平均粒径は、例えば、レーザー回折式粒度分布測定装置(LA-950、株式会社堀場製作所)によって、体積基準の粒度分布の累積が50%となる粒子径D50を測定することにより得ることができる。
また、前記溶射は、温度1000℃以上3500℃以下で行うのが好ましく、温度1500℃以上3500℃以下で行うのがより好ましい。
これにより、前述したような好ましい条件を満足するフェライト粒子をより好適に得ることができる。
分級方法としては、既存の風力分級、メッシュ濾過法、沈降法等を用いることができる。なお、サイクロン等で、粒径の大きい粒子を除去することも可能である。
本発明に係るフェライト粉末の用途は、特に限定されないが、例えば、磁気記録媒体用テープ用、フレキシブルプリント配線基板用、電磁波シールド材用、顔料、発電部材(例えば、磁心材料等)用、フィラー(特に、磁性フィラー)、金属探知機に適用される物品用(例えば、食品、医薬品等の製造現場で用いられる物品であって、異物としての混入が防止されるべき物品用等)、圧粉磁芯の添加剤等が挙げられる。また、本発明のフェライト粉末は、布(例えば、織布、不織布等)や、繊維の内部や表面に含有させて用いられてもよい。
次に、本発明の樹脂組成物について説明する。
このような本発明の樹脂組成物は、後に詳述する成形体の製造に好適に用いることができる。より具体的には、飽和磁化、保磁力および電気抵抗が高い成形体の製造に好適に用いることができる。また、樹脂組成物中においてフェライト粉末を良好に分散させることができ、フェライト粒子の凝集や不本意な組成のばらつきを効果的に防止することができるため、不本意な組成のばらつき等が効果的に防止された成形体の製造に好適に用いることができる。
また、混合の処理は、例えば、複数の工程に分けて行ってもよい。
次に、本発明の成形体について説明する。
また、成形体の製造時には、複数種の樹脂組成物(例えば、複数種の本発明の樹脂組成物)を組み合わせて用いてもよい。
(実施例1)
まず、酸化鉄(Fe2O3)および炭酸ストロンチウム(SrCO3)をモル比でFe2O3/SrCO3=5.75の割合で計量し、混合し、そこに、水を加えて粉砕し固形分50質量%のスラリーを作製した。次に、作製されたスラリーをスプレードライヤーで造粒し、ジャイロシフター、及びターボクラシファイアにて分級して平均粒径15μmの造粒物を作製した。
酸化鉄および炭酸ストロンチウムの混合比率をそれぞれ下記表1に記載の通りに変更した以外は、前記実施例1と同様にしてフェライト粉末を製造した。
溶射の際に、添加剤(燃焼助剤)としてカーボンブラックを溶射原料全体中における含有率が0.5質量%となるように添加した以外は、前記実施例3と同様にしてフェライト粉末を製造した。
酸化鉄および炭酸ストロンチウムの使用量をそれぞれ下記表1に記載の通りに変更した以外は、前記実施例1と同様にしてフェライト粉末を製造した。
まず、酸化鉄(Fe2O3)および炭酸ストロンチウムをモル比で、Fe2O3/SrCO3=5.75の割合で計量し、ヘンシェルミキサーで混合し、原料混合物を作製した。
フェライト粉末における金属成分の含有量は、次のようにして測定した。まず、フェライト粉末0.2gを秤量し、純水60mLに1Nの塩酸20mLおよび1Nの硝酸20mLを加えた混合物を加熱し、フェライト粉末を完全溶解させた水溶液を調製した。得られた水溶液をICP分析装置(島津製作所社製、ICPS-1000IV)にセットし、フェライト粉末における金属成分の含有量を測定した。なお、表1中の化学分析の欄での「<0.01」という記載は、測定誤差であるか、または、原料や製造工程等に由来する不可避的不純物として存在することを意味している。
フェライト粒子を走査透過電子顕微鏡(HD-2700 Cs-corrected STEM(日立ハイテクノロジー社製))によって観察した像(STEM像)に対し、エネルギー分散型X線分析(EDX)を行った。分析には、EDAX Octane T Ultra W(AMETEK社製)を用いた。その結果、前記各実施例では、フェライト粒子の表面にSrが偏在していることが確認された。
図1~図3に、実施例4に係るフェライト粒子のEDX分析結果を示す。より具体的には、図1は、実施例4に係るフェライト粒子のFeの分析結果であり、図2は、実施例4に係るフェライト粒子のSrの分析結果であり、図3は、実施例4に係るフェライト粒子について、FeとSrの分析結果を重ね合わせた図である。これらの図からも明らかなように、粒子内部にもSrは存在するものの、粒子表面付近にもSrが存在していること(表面に偏在していること)は明らかである。また、他の実施例に係るフェライト粒子についても、図1~図3と同様の結果が得られた。
フェライト粒子の形状は、透過型電子顕微鏡HF-2100 Cold-FE-TEM(日立ハイテクノロジー社製)を用いて観察した。加速電圧は200kVとした。図4に、実施例4に係るフェライト粒子のTEM像(倍率40万倍)の画像を示す。なお、前記各実施例では、いずれも、フェライト粒子の平均球状率が1.11以上1.33以下の範囲内の値であった。
フェライト粒子の結晶形態は、走査透過電子顕微鏡HD-2700 Cs-corrected STEM(日立ハイテクノロジー社製)を用いて観察した。加速電圧は200kVとした。図5に実施例4に係るフェライト粒子の電子線回折パターンの画像を示す。
前記各実施例および比較例1、2のフェライト粒子については、水平フェレ径を平均粒径とした。また、比較例3のフェライト粒子については、体積平均粒径を平均粒径とした。
BET比表面積の測定は、比表面積測定装置(マウンテック社製、Macsorb HM model-1208)を用いて行った。まず、得られたフェライト粉末約10gを薬包紙に載せ、真空乾燥機で脱気して真空度が-0.1MPa以下であることを確認した後に、200℃で2時間加熱することにより、フェライト粒子の表面に付着している水分を除去した。続いて、水分が除去されたフェライト粉末(フェライト粒子)を当該装置専用の標準サンプルセルに約0.5~4g入れ、精密天秤で正確に秤量した。続いて、秤量したフェライト粉末を当該装置の測定ポートにセットして測定した。測定は1点法で行った。測定雰囲気は、温度10~30℃、相対湿度20~80%(結露なし)であった。
(飽和磁化、残留磁化および保磁力)
まず、内径5mm、高さ2mmのセルにフェライト粉を詰めて振動試料型磁気測定装置(東英工業社製 VSM-C7-10A)にセットした。次に、印加磁場を加え、10K・1000/4π・A/mまで掃引し、次いで、印加磁場を減少させ、ヒステリシスカーブを作製した。その後、このカーブのデータより飽和磁化、残留磁化および保磁力を求めた。
まず、断面積が1.77cm2のフッ素樹脂製のシリンダーに高さ1.3mmとなるように試料(フェライト粉末)を充填した後、両端に電極を取り付け、さらにその上から1kgの分銅を乗せた状態とした。続いて、ケースレー社製6517A型絶縁抵抗測定器を用いて、上記電極に測定電圧を5秒ごとに50V刻みで50Vから1000Vまで階段状に印加し、各ステップの5秒後の電流値を測定し、得られた電流値と印加電圧から体積抵抗率を算出した。
前記各実施例および各比較例のフェライト粉末を用いて、以下のようにして樹脂組成物を調製した。
上記のようにして得られた各実施例および各比較例に係る樹脂組成物を用い、ベーカー式アプリケーター(テスター産業社製、SA-201)によって、基材としてのPETフィルム上に塗膜を形成した。塗膜の厚さは1mil(25.4μm)とし、塗膜の幅は10cmとした。その後、溶媒を乾燥させ樹脂を硬化させることにより、成形体としての樹脂フィルムを得た。
前記各実施例および各比較例に係る樹脂組成物および成形体について、以下のような評価を行った。
前記各実施例および各比較例に係る樹脂組成物について、目視による観察で、フェライト粉末が塗工出来たかどうか、下記基準に従い評価した。
A:得られた塗膜(PETフィルム含む)に背面から光を当てて光が透過しない。(均一に塗工出来ている)
B:得られた塗膜(PETフィルム含む)に背面から光を当てて部分的に明るいところがある。(厚さにむらが生じる)
C:得られた塗膜(PETフィルム含む)に背面から光を当てて透過する。
前記各実施例および各比較例に係る塗膜(PETフィルム含む)を、20mm×20mmに切り抜き、得られた各サンプルについて、ベルトコンベア式の金属探知機(システムスクエア社製、META-HAWKII)を通過させ、前記サンプルを検出することができる感度(鉄球感度(F値)、SUS球感度(S値))を求めた。
本出願は、2017年3月31日出願の日本特許出願(特願2017-073209)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (3)
- 複数個のフェライト粒子を含むフェライト粉末であって、
前記フェライト粒子は、平均粒径が1nm以上2000nm以下の単結晶体で、かつ、多面体状の形状を備え、
前記フェライト粒子は、Srを2.0質量%以上10.0質量%以下含有し、Feを55.0質量%以上70.0質量%以下含有するフェライト粉末。 - 請求項1に記載のフェライト粉末を含有する樹脂組成物。
- 請求項2に記載の樹脂組成物で構成された部位を有する成形体。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5574107A (en) * | 1978-11-18 | 1980-06-04 | Dornier System Gmbh | Hard ferrite powder and method of fabricating same |
JPS621149A (ja) * | 1985-06-27 | 1987-01-07 | Toshiba Corp | 光磁気記録媒体 |
US4765920A (en) * | 1986-07-14 | 1988-08-23 | Cabot Corporation | High temperature process for producing fine magnetic particles of M-phase structure |
JPH05258932A (ja) * | 1992-03-12 | 1993-10-08 | Showa Denko Kk | 磁気記録用磁性粉 |
JPH0948618A (ja) * | 1995-07-31 | 1997-02-18 | Sumitomo Chem Co Ltd | 鉄含有複合酸化物粉末の製造方法 |
JP2002025816A (ja) * | 2000-07-07 | 2002-01-25 | Shoei Chem Ind Co | 単結晶フェライト微粉末 |
JP2003104790A (ja) * | 2001-05-31 | 2003-04-09 | Tdk Corp | 単結晶セラミックス粉末の製造方法、単結晶セラミックス粉末、複合材料および電子部品 |
JP2013211316A (ja) | 2012-03-30 | 2013-10-10 | Fujifilm Corp | 六方晶ストロンチウムフェライト磁性粉末およびその製造方法、ならびに磁気記録媒体およびその製造方法 |
JP2016139451A (ja) | 2015-01-22 | 2016-08-04 | Dowaエレクトロニクス株式会社 | 磁気記録媒体用磁性粉 |
WO2016136701A1 (ja) * | 2015-02-23 | 2016-09-01 | Dowaエレクトロニクス株式会社 | ボンド磁石用フェライト粉末とその製造方法並びにフェライト系ボンド磁石 |
JP2017073209A (ja) | 2015-10-05 | 2017-04-13 | 昭和電工株式会社 | 蓄電デバイス |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4042516A (en) | 1974-03-01 | 1977-08-16 | Sakai Chemical Industry Co., Ltd. | Bonded magnets containing single crystalline ferrite particles |
JPS5820890B2 (ja) | 1974-03-01 | 1983-04-26 | サカイカガクコウギヨウ カブシキガイシヤ | フエライト粒子の製造法 |
JPS566411A (en) | 1979-06-27 | 1981-01-23 | Sumitomo Special Metals Co Ltd | Manufacture of anisotropic resin bonded magnet |
TWI291936B (ja) | 2001-05-31 | 2008-01-01 | Tdk Corp | |
EP2983178B1 (en) | 2013-04-03 | 2019-06-19 | Toda Kogyo Corp. | Ferrite particle powder for bonded magnet, resin composition for bonded magnet, and molded body using same |
US20160217892A1 (en) | 2013-10-02 | 2016-07-28 | Toda Kogyo Corp. | Ferrite particles for bonded magnets, resin composition for bonded magnets, and molded product using the same |
JP5978201B2 (ja) * | 2013-12-27 | 2016-08-24 | 富士フイルム株式会社 | 磁気記録用磁性粉、磁気記録媒体、および磁気記録用磁性粉の製造方法 |
JP6947490B2 (ja) * | 2015-02-23 | 2021-10-13 | Dowaエレクトロニクス株式会社 | ボンド磁石用フェライト粉末とその製造方法並びにフェライト系ボンド磁石 |
JP6393944B2 (ja) * | 2016-09-30 | 2018-09-26 | パウダーテック株式会社 | Ni−Zn−Cu系フェライト粒子、樹脂組成物及び樹脂成形体 |
JP6787840B2 (ja) * | 2017-06-14 | 2020-11-18 | 富士フイルム株式会社 | 磁気記録用六方晶ストロンチウムフェライト粉末および磁気記録媒体 |
JP7338161B2 (ja) * | 2019-02-05 | 2023-09-05 | Tdk株式会社 | フェライト焼結磁石 |
-
2018
- 2018-03-30 US US16/496,357 patent/US11521768B2/en active Active
- 2018-03-30 CN CN201880018157.3A patent/CN110402238B/zh active Active
- 2018-03-30 JP JP2019509434A patent/JP7126267B2/ja active Active
- 2018-03-30 WO PCT/JP2018/013991 patent/WO2018182021A1/ja active Application Filing
- 2018-03-30 EP EP18778294.1A patent/EP3604227A4/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5574107A (en) * | 1978-11-18 | 1980-06-04 | Dornier System Gmbh | Hard ferrite powder and method of fabricating same |
JPS621149A (ja) * | 1985-06-27 | 1987-01-07 | Toshiba Corp | 光磁気記録媒体 |
US4765920A (en) * | 1986-07-14 | 1988-08-23 | Cabot Corporation | High temperature process for producing fine magnetic particles of M-phase structure |
JPH05258932A (ja) * | 1992-03-12 | 1993-10-08 | Showa Denko Kk | 磁気記録用磁性粉 |
JPH0948618A (ja) * | 1995-07-31 | 1997-02-18 | Sumitomo Chem Co Ltd | 鉄含有複合酸化物粉末の製造方法 |
JP2002025816A (ja) * | 2000-07-07 | 2002-01-25 | Shoei Chem Ind Co | 単結晶フェライト微粉末 |
JP2003104790A (ja) * | 2001-05-31 | 2003-04-09 | Tdk Corp | 単結晶セラミックス粉末の製造方法、単結晶セラミックス粉末、複合材料および電子部品 |
JP2013211316A (ja) | 2012-03-30 | 2013-10-10 | Fujifilm Corp | 六方晶ストロンチウムフェライト磁性粉末およびその製造方法、ならびに磁気記録媒体およびその製造方法 |
JP2016139451A (ja) | 2015-01-22 | 2016-08-04 | Dowaエレクトロニクス株式会社 | 磁気記録媒体用磁性粉 |
WO2016136701A1 (ja) * | 2015-02-23 | 2016-09-01 | Dowaエレクトロニクス株式会社 | ボンド磁石用フェライト粉末とその製造方法並びにフェライト系ボンド磁石 |
JP2017073209A (ja) | 2015-10-05 | 2017-04-13 | 昭和電工株式会社 | 蓄電デバイス |
Non-Patent Citations (1)
Title |
---|
See also references of EP3604227A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2021153612A1 (ja) * | 2020-01-27 | 2021-08-05 | ||
WO2021153612A1 (ja) * | 2020-01-27 | 2021-08-05 | パウダーテック株式会社 | フェライト粉末及びその製造方法 |
JP7278001B2 (ja) | 2020-01-27 | 2023-05-19 | パウダーテック株式会社 | フェライト粉末及びその製造方法 |
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