WO2019146661A1 - Particules composites, poudre, composition de résine, et corps moulé - Google Patents

Particules composites, poudre, composition de résine, et corps moulé Download PDF

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Publication number
WO2019146661A1
WO2019146661A1 PCT/JP2019/002144 JP2019002144W WO2019146661A1 WO 2019146661 A1 WO2019146661 A1 WO 2019146661A1 JP 2019002144 W JP2019002144 W JP 2019002144W WO 2019146661 A1 WO2019146661 A1 WO 2019146661A1
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ferrite
particles
powder
mass
composite
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PCT/JP2019/002144
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English (en)
Japanese (ja)
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康二 安賀
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パウダーテック株式会社
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    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/34—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 soft-magnetic materials non-metallic substances, e.g. ferrites
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/34—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 soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—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 soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/34—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 soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—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 soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • H01F1/37—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 soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent

Definitions

  • the present invention relates to composite particles, powders, resin compositions and molded articles.
  • a metal detector can not detect a general plastic material or the like, it can not be detected even if foreign matter derived from a tool such as a packaging material used at the time of manufacture is mixed.
  • Patent Document 1 a working glove including a metal detection material made of metal such as iron has been proposed (see Patent Document 1).
  • metal may not be detected by a metal detector due to a change with time due to a chemical reaction such as an oxidation reaction.
  • the color tone of the working glove as a molded body containing the metal detection material is greatly affected, and it becomes difficult to adjust the molded body to a desired color tone.
  • An object of the present invention is to provide a molded product which can be stably detected by a metal detector and which is adjusted to a desired color tone, and a composite which can be suitably used for the production of the molded product. It is an object of the present invention to provide particles, powders and resin compositions.
  • the ferrite has a composition containing 47 mass% to 65 mass% of Fe, 10 mass% to 25 mass% of Mn, 0.1 mass% to 6 mass% of Mg, and 1 mass% or less of Sr.
  • a powder comprising a plurality of the composite particles according to any one of [1] to [8].
  • a resin composition comprising the powder according to any one of [9] to [12] and a resin material.
  • a molded product which can be stably detected by a metal detector and which is adjusted to a desired color tone, and a composite which can be suitably used for the production of the molded product. Particles, powders and resin compositions can be provided.
  • FIG. 3 is a cross-sectional FE-SEM image of the composite particle of Example 1.
  • 7 is a cross-sectional FE-SEM image of the composite particle of Example 2.
  • FIG. 7 is a cross-sectional FE-SEM image of the composite particle of Example 3.
  • 7 is a cross-sectional FE-SEM image of the composite particle of Example 4.
  • 7 is a cross-sectional EDX mapping image (Fe) of the composite particle of Example 4.
  • FIG. 7 is a cross-sectional EDX mapping image (Ag) of the composite particle of Example 4.
  • 7 is a cross-sectional EDX mapping image (Sr) of the composite particle of Example 4.
  • the composite particle of the present invention is a particle intended to be detected by a metal detector, and comprises base particles composed of ferrite and a coating layer composed of a metal material exhibiting white to silver color. . And the powder of the present invention contains a plurality of composite particles of the present invention.
  • ferrite generally exhibits a dark color such as black. Therefore, when ferrite is used as it is in the production of a molded product, it is difficult to suitably adjust the color tone of the molded product by color mixing, even if other colorants (eg, white colorant etc.) are used in combination. . In particular, it has been difficult to adjust the color tone to a high lightness such as white.
  • the mother particles composed of ferrite are coated with a white to silver coating layer, the color tone of ferrite is concealed. Therefore, for example, a color tone with high brightness such as white or silver can be suitably expressed. Moreover, it can adjust to various color tone by using together with another coloring agent.
  • weight reduction can be achieved as compared with the case of using particles made only of the above-mentioned metal material.
  • the amount of expensive metal used can be suppressed, and the cost can be reduced as a whole.
  • the particles according to the present invention can be oriented in an arbitrary state along the magnetic lines of force by molding while applying a magnetic field.
  • particles that do not have a coating layer as described above have the problem of low electrical conductivity and difficult to detect with metal detectors of the type that detects metal by eddy current.
  • the color tone of the particles is dark, such as black, which has a low lightness, it is difficult to adjust the color tone of the compact containing the powder.
  • the coating layer is provided on the surface of the ferrite particles, if the coating layer is made of a nonmetallic material, the electric conductivity is low as in the above, and the metal is detected by the eddy current.
  • Types of metal detectors have the problem of being difficult to detect.
  • a coating layer of another color tone is provided instead of the coating layer made of a metal material exhibiting white to silver, it is difficult to control the color tone of the powder-containing compact.
  • the elements constituting the metal particles may be eluted by being exposed to acid and alkali for a long time, or the magnetic field It causes a problem that it can not be detected by the type of metal detector that detects change.
  • the specific gravity of the particles as a whole is increased, which makes it difficult to reduce the weight of the powder or the compact.
  • the production cost of the powder or the molded body is increased.
  • the mother particles are composed of ferrite.
  • the base particles may be made of ferrite, and may contain, for example, hard ferrite or soft ferrite.
  • the ferrite may be hard ferrite or soft ferrite.
  • the particles according to the present invention can be oriented in any state along the magnetic lines of force by molding while applying a magnetic field.
  • the ferrite (soft ferrite) constituting the mother particle contains 47% by mass to 65% by mass of Fe, 10% by mass to 25% by mass of Mn, 0.1% to 6% by mass of Mg, Sr It is preferable to have a composition containing 1% by mass or less.
  • the Curie point of the ferrite (base particle) becomes higher, and the detection by the metal detector at high temperature can be performed more stably.
  • the soft ferrite itself has a high saturation magnetization, it can be suitably detected by a metal detector even when the content of the composite particles in the resin composition is smaller.
  • the crystal structure spinel structure exhibiting magnetic characteristics by relatively increasing the content of Mn and Mg.
  • the saturation magnetization may be lowered because the amount of formation of As a result, depending on the type of metal detector or the like, it may be difficult for the metal detector to detect a compact containing composite particles.
  • the Fe content in the ferrite (soft ferrite) exceeds the above upper limit, the amount of Fe becomes excessive, and the resin composition can be produced at a time of production (in particular, during mixing and kneading by heating) or in a molded article.
  • the oxidation reaction is likely to proceed at the time of manufacture (in particular, at the time of molding by heating) and the like, and as a result, the saturation magnetization of the finally obtained molded body may be lowered.
  • the content of Mn in the ferrite (soft ferrite) is less than the lower limit value, at the time of production of the resin composition (in particular, at the time of mixing and kneading by heating) and at the time of production of a molded body (particularly, The oxidation reaction is likely to proceed at the time of molding) and the like, and as a result, the saturation magnetization of the finally obtained molded body may be lowered. As a result, depending on the type of metal detector or the like, it may be difficult to detect the molded body by the metal detector.
  • the content of Mg in the ferrite (soft ferrite) is less than the lower limit, the contents of Fe and Mn relatively increase, and the particles generated upon thermal spraying easily become polyhedrons.
  • the BET specific surface area is larger than that of spherical particles. Therefore, when the coating layer of the same weight is formed, a portion where the thickness of the coating layer is thin tends to be generated.
  • the saturation magnetization is too low, and therefore, when a small amount of composite particles is added to the molded body, detection with a metal detector becomes difficult. In addition, when added in large amounts, the strength of the molded body may be inferior.
  • the saturation magnetization is too low, which makes detection with a metal detector difficult when a small amount of composite particles is added to a molded body.
  • the strength of the molded body may be inferior.
  • the Fe content is 47% by mass or more and 65% by mass or less, and more preferably 47.5% by mass or more and 63% by mass or less. Thereby, the above-mentioned effect is more remarkably exhibited.
  • the content of Mn is 10% by mass to 25% by mass, and more preferably 10% by mass to 20% by mass. Thereby, the above-mentioned effect is more remarkably exhibited.
  • the content rate of Mg is 0.1 to 6 mass%, it is more preferable that it is 0.2 to 2.8 mass%. Thereby, the above-mentioned effect is more remarkably exhibited.
  • the content of Sr is 1% by mass or less, but is more preferably 0.1% by mass or more and 0.75% by mass or less. Thereby, the above-mentioned effect is more remarkably exhibited.
  • the soft ferrite constituting the mother particles may contain components (elements) other than Fe, Mn, Mg, Sr, and O.
  • components (elements) other than Fe, Mn, Mg, Sr, and O As such a component, Ti, Si, Cl, Ca, Al etc. are mentioned, for example.
  • the content of the components (elements) other than Fe, Mn, Mg, Sr, and O contained in the soft ferrite constituting the mother particles is preferably 1.0% by mass or less.
  • the magnetic flux is always generated from the molded body by magnetizing treatment, so it is preferable to use a metal detector of the type that measures the magnetic flux directly with a magnetic sensor. It can be detected.
  • the ferrite (hard ferrite) constituting the mother particles has a composition containing 5.0% by mass or more and 9.0% by mass or less of Sr and 61.0% by mass or more and 67.8% by mass or less of Fe Is preferred.
  • the content of Fe in the ferrite (hard ferrite) is less than 61.0% by mass, the amount of Sr becomes excessive, and a relatively large amount of SrO is contained in the particles, or the Sr ferrite Other Sr-Fe oxides are contained, saturation magnetization decreases, and depending on the type of metal detector etc., detection by a metal detector of a compact containing composite particles may be difficult.
  • the metal detector when the content of Fe in the ferrite (hard ferrite) exceeds 67.8 mass%, the amount of Fe becomes excessive, and a relatively large amount of Fe 2 O 3 is contained in the particles, and the saturation magnetization Depending on the type of metal detector, etc., it may be difficult for the metal detector to detect molded articles containing composite particles.
  • the content of Sr in the ferrite (hard ferrite) is preferably 5.0% by mass or more and 9.0% by mass or less, but 5.5% by mass or more and 8.9% by mass or less Is more preferable, and it is more preferable that the content is 6.0% by mass or more and 8.8% by mass or less. As a result, the effects as described above are more significantly exhibited.
  • the Fe content in the ferrite (hard ferrite) is preferably 61.0% by mass to 67.8% by mass, but is 61.1% by mass to 67.3% by mass Is more preferable, and 61.2% by mass or more and 66.8% by mass or less is more preferable. As a result, the effects as described above are more significantly exhibited.
  • the hard ferrite constituting the mother particles may contain components (elements) other than Fe, Sr and O.
  • a component Ti, Si, Cl, Ca, Al etc. are mentioned, for example.
  • the content of components (elements) other than Fe, Sr and O contained in the hard ferrite constituting the mother particles is preferably 1.0% by mass or less.
  • the content of the metal element constituting the ferrite can be measured as follows.
  • ferrite particles base particles
  • a mixture of 20 ml of 1 N hydrochloric acid and 20 ml of 1 N nitric acid in 60 ml of pure water is heated to prepare an aqueous solution in which the ferrite particles are completely dissolved.
  • the content of the metal element can be determined by measurement using an ICP analyzer (ICPS-1000 IV, manufactured by Shimadzu Corporation).
  • the Curie point (also referred to as the Curie temperature) of the ferrite constituting the matrix particles is preferably 200 ° C. or more and 500 ° C. or less, and more preferably 200 ° C. or more and 450 ° C. or less.
  • the heat resistance of a composite particle or a molded product produced using the composite particle can be made excellent, and for example, it can be suitably applied to a molded product used under a high temperature environment.
  • the Curie point of the ferrite is determined by the composition, and the above-mentioned ferrite composition does not usually exceed 500 ° C.
  • the Curie point is determined as follows.
  • the above-mentioned Curie point is determined from measurement of change in magnetization of ferrite powder due to temperature change using a vibrating sample magnetometer (VSM) (VSM-5 manufactured by Toei Kogyo Co., Ltd.).
  • VSM vibrating sample magnetometer
  • the temperature at which the tangent of the curve from the low temperature side immediately before the magnetization becomes 0 crosses the line where the magnetization is 0 is the Curie point.
  • the shape of the mother particles is not particularly limited, but is preferably spherical.
  • the filling factor of powder can be made higher, and the ease of being detected by a metal detector can be improved. It becomes.
  • a true sphere means a true sphere or a shape that is sufficiently close to a true sphere, and specifically means that the spherical rate is 1 or more and 1.2 or less.
  • the spherical rate is determined as follows.
  • the magnification is preferably 100,000 to 200,000 when imaging particles with a Feret diameter (particle diameter) of 500 nm or less, and 10,000 when the Feret diameter (particle diameter) is 500 nm or more and 3 ⁇ m or less. It is preferable to shoot at double to 100,000 times, and when shooting particles larger than 3 ⁇ m, it is preferable to shoot at 1000 to 10,000 times.
  • a cross-sectional sample of the mother particles may be prepared using an ion milling apparatus, and the spherical ratio may be calculated by photographing with the above magnification .
  • the mean sphere of the base particles is preferably 1 or more and 1.14 or less, and more preferably 1 or more and 1.10 or less. Thereby, the above-mentioned effect is more remarkably exhibited.
  • the average globular ratio for example, an average value of the globular ratio determined for each base particle of 100 composite particles randomly extracted from the powder of the present invention can be adopted.
  • a value determined for 100 ferrite particles randomly extracted from ferrite powder aggregate of ferrite particles corresponding to base particles obtained in the production process of the composite particles (powder) of the present invention. it can.
  • the shape factor SF-1 of the base particles is preferably 100 or more and 120 or less, and more preferably 100 or more and 115 or less. If the shape factor SF-1 exceeds 120, it may be difficult to disperse when mixed with a resin, or the viscosity of the mixture with the resin may be easily increased, so that molding may not be performed well when producing a resin molded body.
  • SF-1 has a spherical shape at 100 and never falls below 100.
  • the filling factor of powder can be made higher, and the ease of being detected by a metal detector can be improved.
  • the shape factor SF-1 of the mother particles is determined as follows. First, particles are photographed in a 450 ⁇ field of view using a scanning electron microscope (FE-SEM (SU-8020, manufactured by Hitachi High-Technologies Corporation)).
  • the image information is introduced into an image analysis software (Image-Pro PLUS) manufactured by Media Cybernetics via an interface and analyzed to determine Area (projected area) and Feret diameter (maximum), and , SF-1 value is calculated. As the shape of the particles is closer to a sphere, the value is closer to 100.
  • Image-Pro PLUS image analysis software manufactured by Media Cybernetics via an interface and analyzed to determine Area (projected area) and Feret diameter (maximum), and , SF-1 value is calculated. As the shape of the particles is closer to a sphere, the value is closer to 100.
  • SF-1 can be calculated for each particle, and an average value of 100 particles can be adopted as SF-1 of ferrite powder.
  • the volume average particle diameter of the mother particles is preferably 1.0 ⁇ m to 19 ⁇ m, more preferably 1.5 ⁇ m to 15 ⁇ m, and still more preferably 2.0 ⁇ m to 12 ⁇ m.
  • the volume average particle size can be measured by the method described later.
  • magnetic characteristics such as saturation magnetization, residual magnetization, and coercivity can be measured using a vibrating sample magnetometer.
  • the above magnetic properties are determined as follows. That is, first, ferrite powder to be measured was packed in a cell with an inner diameter of 5 mm and a height of 2 mm, and set in a vibrating sample type magnetic measuring device (VSM-C7-10A manufactured by Toei Kogyo Co., Ltd.). Next, an applied magnetic field was applied and swept to 5 kOe (10 kOe in the case of hard ferrite), and then the applied magnetic field was decreased to create a hysteresis curve. Thereafter, saturation magnetization, remanent magnetization and coercivity of the ferrite powder were determined from the data of this curve. In addition, it calculated
  • the preferred range of saturation magnetization of ferrite when soft ferrite is used as ferrite is 30 to 95 emu / g
  • the preferred range of residual magnetization is 0.5 to 25 emu / g
  • the preferred range of coercivity is 1 to 80 Oe It is. Both are measured values of VSM @ 5 kOe.
  • the preferred range of saturation magnetization of ferrite is 20 to 60 emu / g
  • the preferred range of residual magnetization is 20 to 40 emu / g
  • the preferred range of coercivity is 500 to 3000 Oe.
  • Both are measured values of VSM @ 10 kOe.
  • the preferred range of saturation magnetization of powder (composite particles) as an aggregate of composite particles is 30 to 92 emu / g, and the preferred range of residual magnetization is 0.5 to 24 emu / g
  • the preferred range of coercivity is 1 to 80 Oe. Both are measured values of VSM @ 5 kOe.
  • the preferable range of powder (composite particle) saturation magnetization as an aggregate of composite particles is 20 to 59 emu / g, and the preferable range of residual magnetization is 20 to 39 emu / g.
  • the preferred range of the magnetic force is 500 to 3000 Oe. Both are measured values of VSM @ 10 kOe.
  • the preferred range of saturation magnetization of the powder (composite particles) as an aggregate of composite particles in which composite particles using soft ferrite and composite particles using hard ferrite are mixed is 30 to 92 emu / g, and preferable is residual magnetization.
  • the range is 0.5 to 38 emu / g, and the preferred range of coercivity is 1 to 2800 Oe. Both are measured values of VSM @ 5 kOe.
  • the preferred range of saturation magnetization of the powder (composite particle) as an aggregate of composite particles in which composite particles using soft ferrite and composite particles using hard ferrite are mixed is 30 to 94 emu / g, and preferable is residual magnetization.
  • the range is 0.5 to 39 emu / g, and the preferred range of coercivity is 1 to 3000 Oe. Both are measured values of VSM @ 10 kOe.
  • the BET specific surface area of the mother particles is preferably 0.1 to 2 m 2 / g.
  • the BET specific surface area was determined by measurement using a specific surface area measuring device (model: Macsorb HM model-1208 (manufactured by Mountech Co.)). More specifically, about 5 g of a measurement sample was placed in a standard sample cell dedicated to a specific surface area measuring device, accurately weighed with a precision balance, and a sample (ferrite powder) was set in the measurement port to start measurement. The measurement was performed by a one-point method, and when the weight of the sample was input at the end of the measurement, the BET specific surface area was automatically calculated.
  • the mother particles constituting a single composite particle may be, for example, those composed of a single particle, or may be a conjugate (including aggregates) of a plurality of fine particles.
  • the base particles may be made of a material containing ferrite, and may contain other components, for example.
  • the content of components other than ferrite in the matrix particles is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and still more preferably 0.5% by mass or less .
  • the coating layer covers at least a part of the mother particles.
  • the covering layer is made of a metallic material exhibiting white to silver.
  • the coating layer may be made of a metal material exhibiting white to silver color, but more specifically, for example, a metal material constituting the coating layer, that is, composite particles having the coating layer in the chromaticity diagram of the L * a * b * display defined by JIS Z8729, L * is 30 or more, a * is -2 to 1 or less, and, b * is 3 or more 15 satisfies the following conditions Is preferred.
  • a color difference meter Specification of L * a * b * of composite particles
  • the sample used for the measurement was prepared by mixing powder of a composite particle and fluorocarbon powder resin in a proportion of 90% by weight with a ball mill for 10 minutes, and charging it into a mold with an inner diameter of 32 mm It used what was pressure-molded.
  • the molding pressure at this time was 80 kN and the holding time was 10 seconds.
  • metal materials that satisfy such conditions include Al, Ti, V, Mn, Co, Ni, Zn, Nb, Mo, Ru, Rh, Pd, Ag, In, W, Os, Ir, Pt, and the like. And alloys (stainless steel etc.) containing at least one of these, and the like.
  • the covering layer is preferably made of a material containing at least one selected from the group consisting of Ag, Pt, Ni and Pd, and is more preferably made of a material containing Ag. .
  • the whiteness of the composite particles can be made higher, and the adjustment of the color tone of the resin composition and the molded body (adjustment of the color tone over a wider color range) can be performed more suitably.
  • the composite particles exhibit excellent antibacterial and bactericidal properties.
  • the content of the metal elements (Ag, Pt, Ni, and Pd) in the coating layer is preferably 80% by mass or more, 90 It is more preferable that the content is at least% by mass. As a result, the effects as described above are more significantly exhibited.
  • the thickness of the covering layer is not particularly limited, but is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 400 nm or less, and still more preferably 30 nm or more and 300 nm or less.
  • the thickness of the covering layer is determined by the following method. That is, after the particles were embedded in a resin, the cross section of the particles was processed using an ion milling apparatus, and the obtained sample for imaging was produced. The obtained sample for photography was photographed with FE-SEM, and the length (scaled value) in the image analysis software or image, and the measured value by the scale ruler in the SEM image and the covering layer Calculated using the actual value measured by the thickness ruler. As FE-SEM, SU-8020 manufactured by Hitachi High-Technologies Corporation was used. The ion milling apparatus used IM-4000 made by Hitachi High-Technologies. Epoxy resin was used for embedding resin.
  • the particle size of the above composite particles is a volume average particle size.
  • the volume average particle size can be measured by the method described later.
  • the covering layer may have, for example, a uniform composition at each site, or may have a plurality of sites of different compositions.
  • the covering layer may be a laminate having a plurality of layers made of different materials, or may be made of a graded material having a portion whose composition changes gradually in the thickness direction.
  • the covering layer may have a plurality of regions made of different materials.
  • the covering layer may have a region mainly composed of Ag (for example, an island-like region) and a region mainly composed of Pt (for example, an island-like region).
  • the coating layer may contain components (elements) other than those described above.
  • the content of components (elements) other than those described above in the coating layer is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, and 0.5% by mass or less Is more preferred. Thereby, the effects of the present invention as described above are more reliably exhibited.
  • the composite particle of the present invention may have any other configuration as long as it comprises the base particle and the coating layer as described above.
  • the composite particle may have at least one intermediate layer between the base particle and the coating layer.
  • or silver color may be provided in the surface of the coating layer mentioned above.
  • the surface treatment layer etc. by various coupling agents, such as a silane coupling agent, etc. are mentioned, for example.
  • first covering layer formed of a metallic material exhibiting white to silver color
  • second covering layer may be provided.
  • the powder of the present invention may contain a plurality of different composite particles. Thereby, the characteristics of the plurality of types of composite particles are exhibited, and the characteristics of the powder as a whole can be further improved. More specifically, the powder of the present invention may contain composite particles containing soft ferrite and composite particles containing hard ferrite.
  • the powder of this invention can be used suitably by manufacture of the molded object which can be stably detected by various metal detectors.
  • the volume average particle size of the composite particles is preferably 1.0 ⁇ m or more and 20 ⁇ m or less, more preferably 1.5 ⁇ m or more and 18 ⁇ m or less, and still more preferably 2.0 ⁇ m or more and 15 ⁇ m or less.
  • the volume average particle size is determined, for example, by the following measurement. First, 10 g of powder as a sample and 80 ml of water are placed in a 100 ml beaker, and 2 to 3 drops of a dispersant (sodium hexametaphosphate) are added. Then, dispersion is performed using an ultrasonic homogenizer (SMT. Co. LTD. UH-150 type). As an ultrasonic homogenizer, SMT. Co. LTD. Set the output level of UH-150 type manufactured to 4 and perform dispersion for 20 seconds. Thereafter, bubbles formed on the beaker surface can be removed, and introduced into a microtrack particle size analyzer (Model 9320-X100, manufactured by Nikkiso Co., Ltd.) for measurement.
  • a microtrack particle size analyzer Model 9320-X100, manufactured by Nikkiso Co., Ltd.
  • the volume resistivity of the composite particles is preferably 1.5 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 0 ( ⁇ ⁇ cm), and 1.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 2 More preferably, it is ( ⁇ ⁇ cm).
  • the volume resistivity (percentage) does not fall below 1.5 ⁇ 10 ⁇ 6 ( ⁇ ⁇ cm) which is the volume resistivity (percentage) of Ag.
  • the value of volume resistance is higher than 10 -0, it becomes difficult to be detected by a metal detector of a specific type, or the blackness is increased, and a member, a place, which can be applied when added to a resin molding, and There are restrictions in the field.
  • the value of volume resistance of composite particles was determined as follows. That is, first, powder, which is an aggregate of composite particles, is introduced into a Teflon cylinder having an electrode at the bottom of inner diameter 22.5 mm so that the height is 4 mm, and an electrode of the same size as the inner diameter is inserted from the top Connect the bottom and top electrodes to a measuring device (any of Model 2182, Model 2000, or Model 6517A made by Keithley) under a load of 1 kg from above, depending on the range of resistance to be measured, The resistance was measured. The volume resistance was calculated using the resistance value, the inner diameter and the thickness obtained by the measurement.
  • the powder of the present invention only needs to contain a plurality of the composite particles of the present invention, and may further include particles other than the composite particles of the present invention.
  • the content of particles other than the composite particles of the present invention in the powder of the present invention is preferably 10% by mass or less, more preferably 5.0% by mass or less, 1.0 It is more preferable that the content is not more than mass%. Thereby, the effects of the present invention as described above are more reliably exhibited.
  • the composite particle of the present invention can be produced by forming a coating layer on the surface of ferrite particles produced by a predetermined method by various plating methods.
  • Examples of plating methods for forming the covering layer include wet plating methods such as electrolytic plating and electroless plating, and dry plating methods such as vacuum deposition, sputtering and ion plating, but wet plating method is preferable. And electroless plating are more preferable.
  • the ferrite particles to be base particles may be produced by any method, but can be suitably produced, for example, by the method described below.
  • ferrite particles to be base particles can be suitably produced by spraying a ferrite raw material prepared to a predetermined composition in the atmosphere and then rapidly solidifying it.
  • a granulated material can be suitably used as a ferrite raw material.
  • the method for preparing the ferrite raw material is not particularly limited, and may be, for example, a dry method or a wet method.
  • a ferrite raw material (granulate) is given. That is, after weighing and mixing a plurality of types of raw materials containing metal elements so as to correspond to the composition of ferrite particles (base particles) to be produced, water is added and pulverized to prepare a slurry. The produced pulverized slurry is granulated with a spray drier and classified to prepare a granulated material having a predetermined particle size.
  • a ferrite raw material (granulated material)
  • the mixture is granulated with a granulator and provisionally prepared using a rotary kiln or the like.
  • dry pulverization and classification are performed to prepare a granulated material having a predetermined particle diameter. Pre-baking may be omitted depending on the composition of ferrite and the equipment used.
  • the granulated product prepared as described above is thermally sprayed and ferritized in the atmosphere.
  • a mixed gas of combustion gas and oxygen can be used as a flammable gas combustion flame.
  • the volume ratio of the combustion gas to oxygen is preferably 1: 3.5 or more and 1: 6.0 or less.
  • the volume ratio of the combustion gas to oxygen is preferably 1: 3.5 or more and 1: 6.0 or less.
  • propane gas propane gas, propylene gas, acetylene gas etc. are mentioned.
  • propane gas can be suitably used.
  • nitrogen, oxygen, air etc. can be used as granulated material carrier gas.
  • the flow velocity of the granulated material to be conveyed is 20 m / sec or more and 60 m / sec or less.
  • the thermal spraying is preferably performed at a temperature of 1000 ° C. or more and 3500 ° C. or less, more preferably 2000 ° C. or more and 3500 ° C. or less.
  • the formation of particles having a relatively small particle size by condensation of the volatilized material can be further preferably progressed.
  • shape of the ferrite particle (base particle) obtained can be adjusted more suitably.
  • processing such as classification in a later step can be omitted or simplified, and productivity of ferrite particles (base particles) can be further improved.
  • the ratio of particles to be removed by classification in a later step can be made smaller, and the yield of ferrite particles (base particles) can be made further excellent.
  • the thus thermally sprayed and ferrite-formed ferrite particles are quenched and solidified in water or air, and collected by a filter.
  • the ferrite particles collected by the collection filter are classified as required.
  • the particle size is adjusted to a desired particle size using an existing air classification, mesh filtration method, sedimentation method or the like.
  • the ferrite particles (base particles) can be suitably produced by the method (second method) as described below.
  • ferrite particles mother particles
  • ferrite particles are obtained, for example, by pelletizing a composition containing a ferrite raw material and calcining temporarily to obtain a calcined body, and calcining and classifying the calcined body to obtain calcined powder. It can manufacture by the method of having this baking process to bake.
  • ferrite particles used for the production of the composite particles having the shape and size as described above can be efficiently produced.
  • it can be effectively prevented that impurities derived from the acid or alkali or the like remain in ferrite particles (base particles),
  • the durability and reliability of a composite particle or a resin composition produced using the composite particle and a molded product can be further improved.
  • Pellet production can be suitably performed by using a pressure molding machine.
  • the heating temperature in the pre-baking step is not particularly limited, but is preferably 600 ° C. or more and 1200 ° C. or less, more preferably 650 ° C. or more and 1000 ° C. or less, and still more preferably 700 ° C. or more and 900 ° C. or less preferable.
  • pulverization of the pre-sintered body can be suitably performed, and ferrite particles used for the production of the composite particles having the shape and size as described above can be more suitably produced.
  • two or more steps of heat treatment may be performed.
  • the volume average particle diameter of the temporary fired body to be subjected to the main firing step is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 20 ⁇ m or less.
  • ferrite particles used for producing the composite particles of the shape and size as described above can be produced more efficiently.
  • processing such as classification in a later step can be omitted or simplified, and the productivity of ferrite particles can be further improved.
  • the proportion of particles to be removed by classification in a later step can be reduced, and the yield of ferrite particles can be further improved.
  • the main firing step is preferably performed, for example, on a granulated product obtained by granulating the powder of the calcined body (powder obtained by pulverization and classification).
  • ferrite particles used for producing the composite particles of the shape and size as described above can be produced more efficiently.
  • processing such as classification in a later step can be omitted or simplified, and the productivity of ferrite particles can be further enhanced.
  • the proportion of particles to be removed by classification in a later step can be made smaller, and the yield of ferrite particles can be made further excellent.
  • This firing can be suitably performed by spraying the powder of the temporary firing body in the air.
  • a mixed gas of combustion gas and oxygen can be used as a flammable gas combustion flame.
  • the volume ratio of the combustion gas to oxygen is preferably 1: 3.5 or more and 1: 6.0 or less.
  • propane gas propane gas, propylene gas, acetylene gas etc. are mentioned.
  • propane gas can be suitably used.
  • nitrogen, oxygen, air etc. can be used as granulated material carrier gas.
  • the flow velocity of the granulated material to be conveyed is 20 m / sec or more and 60 m / sec or less.
  • the thermal spraying is preferably performed at a temperature of 1000 ° C. or more and 3500 ° C. or less, more preferably 2000 ° C. or more and 3500 ° C. or less.
  • ferrite particles having a relatively small particle size by condensation of the volatilized material can be further preferably progressed.
  • shape of the ferrite particle obtained can be adjusted more suitably.
  • processing such as classification in a later step can be omitted or simplified, and the productivity of ferrite particles can be further enhanced.
  • proportion of particles to be removed by classification in a later step can be made smaller, and the yield of ferrite particles can be made further excellent.
  • the ferrite particles formed by the main firing by thermal spraying are rapidly solidified by being carried in an air flow by air supply in the atmosphere, and thereafter, the ferrite particles in a predetermined particle diameter range are collected and recovered.
  • the rapidly solidified ferrite particles are carried in an air flow by air supply, and the particles having a large particle diameter fall in the middle of the air flow conveyance, while the other particles are air conveyed to the downstream. It can be carried out by a method of using and collecting ferrite particles of a desired particle size range by a filter provided on the downstream side of the air flow.
  • the flow velocity at the time of air flow conveyance By setting the flow velocity at the time of air flow conveyance to 20 m / sec or more and 60 m / sec or less, particles having a large particle size can be dropped with particularly high selectivity, and ferrite particles in a predetermined particle size range can be recovered more efficiently. can do. If the flow velocity is too low, even particles having a relatively small particle diameter will fall on the way of air flow conveyance, so the average particle diameter of ferrite particles recovered downstream of the air flow may become too small, or As the absolute amount of ferrite particles recovered downstream of is decreased, the productivity is reduced. On the other hand, if the flow velocity is too high, even particles having a relatively large particle diameter are also transported downstream, so the average particle diameter of ferrite particles recovered downstream of the air flow tends to be too large. Thereafter, the recovered ferrite powder may be classified as required.
  • the resin composition of the present invention contains the above-described powder of the present invention and a resin material. Thereby, it is possible to provide a resin composition which can be stably detected by a metal detector and can be suitably used for the production of a molded article adjusted to a desired color tone.
  • the powder may be contained in any form, but is preferably dispersed and present in the resin material.
  • the content of the powder (composite particles) in the resin composition is not particularly limited, but is preferably 5.0% by mass or more and 90% by mass or less, and is 7.0% by mass or more and 88% by mass or less More preferable.
  • the formability of the formed body can be further improved, and the toughness, strength, reliability and the like of the formed body can be further improved, and the ease of detection of the formed body by the metal detector can be improved.
  • the stability can be further improved. Moreover, it can prevent effectively that specific gravity of a molded object becomes large too much.
  • the content ratio of the powder (composite particles) in the resin composition is less than the above lower limit, the ease of detection of the molded body by the metal detector and the stability of the detection may be insufficient. is there.
  • the content of the powder (composite particles) in the resin composition exceeds the above upper limit, the moldability of the molded product may be reduced, and the toughness, strength, reliability, etc. of the molded product may be reduced. .
  • thermoplastic resins various curable resins, etc.
  • curable resins etc.
  • polyolefins such as polyethylene, polypropylene, poly- (4-methylpentene-1), ethylene-propylene copolymer, cyclic polyolefin and the like; modified polyolefins; polystyrene; butadiene-styrene copolymer; acrylonitrile- Butadiene-Styrene copolymer (ABS resin); Acrylonitrile-Styrene copolymer (AS resin); Polyvinyl chloride; Polyvinylidene chloride; Ethylene-Vinyl acetate copolymer (EVA); Polyamides (eg Nylon 6, Nylon 46) , Nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66); polyimide; polyamide imide; acrylic resin such as polymethyl methacrylate; polycarbonate (PC); Nomer; polyvinyl alcohol (PVA); ethylene-vinyl alcohol copolymer (PVA); ethylene
  • Polyether Polyacetal (POM); Polyphenylene oxide; Modified polyphenylene oxide; Polyether ketone (PEK); Polyether ether ketone (PEEK); Polyether imide; Polysulfone; Polyether sulfone; Polyphenylene sulfide; Fluorine-based resins such as ethylene and polyvinylidene fluoride; silicone rubber, isoprene rubber, butadiene rubber, nitrile rubber, natural rubber, etc.
  • thermoplastic elastomers such as styrene type, polyolefin type, polyvinyl chloride type, polyurethane type, polyester type, polyamide type, polybutadiene type, trans polyisoprene type, fluoro rubber type, chlorinated polyethylene type; epoxy resin; phenol Resins; urea resins; melamine resins; unsaturated polyesters; silicone resins; polyurethanes, etc., copolymers thereof, blends, polymer alloys, etc., and combinations of one or more of these Can be used.
  • the resin material contained in the resin composition is polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol (PVA), fluorocarbon resin, 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 powder (composite particles) in the resin composition can be 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 the dispersion stability of the powder (composite particles) in the resin composition Can be further improved to further improve the moldability of the molded product.
  • the resin material contained in the resin composition may have a composition different from that of the resin material contained in a molded product produced using the resin composition.
  • the resin material contained in the resin composition may be a precursor (for example, monomer, dimer, trimer, oligomer, prepolymer, etc.) of the resin material contained in the final molded body.
  • the content rate of the resin material in a resin composition is not specifically limited, It is preferable that it is 8.0 to 95 mass%, and it is more preferable that it is 10 to 90 mass%.
  • the formability of the formed body can be further improved, and the toughness, strength, reliability and the like of the formed body can be further improved, and the ease of detection of the formed body by the metal detector can be improved.
  • the stability can be further improved.
  • the content of the resin material in the resin composition is less than the above lower limit, the moldability of the molded product may be reduced, and the toughness, strength, reliability, etc. of the molded product may be reduced. .
  • the content of the resin material in the resin composition exceeds the upper limit value, the content of the powder (composite particles) relatively decreases, and the ease of detection of the molded body by the metal detector, Stability may be inadequate.
  • the resin composition of the present invention only needs to contain a powder (composite particles) and a resin material, and may further contain other components (other components).
  • various colorants such as pigments and dyes; various fluorescent materials; various luminous materials; various phosphorescent materials; solvents; infrared absorbing materials; ultraviolet absorbers; Agents, polymerization initiators, polymerization accelerators, crosslinking agents, polymerization inhibitors, sensitizers, plasticizers, slip agents (leveling agents), penetration accelerators, wetting agents (humectants), antistatic agents, fixing agents, preservatives Anti-Fung agent; Antioxidant; Chelating agent; pH-adjusting agent; Alumina, Silica, Titanium oxide, Magnesium oxide, Antimony oxide, Calcium oxide, Zinc oxide, Aluminum hydroxide, Magnesium hydroxide, Calcium carbonate , Potassium titanate, glass fiber, carbon fiber, gypsum fiber, metal fiber, metal particle, graphite, talc, clay, mica, wollastonite, sonotolite, hydrotalcite , Fillers such as zeolite; aggregation inhibitor; defo
  • the color tone of the molded article can be suitably adjusted to a color tone other than white or silver.
  • the resin composition of the present invention may be in any form, and examples of the form of the resin composition include powders, pellets, dispersions, slurries, gels and the like, with preference given to pellets.
  • the ease of handling of the resin composition is further improved, and the production of a molded article using the resin composition can be performed more suitably.
  • the storage stability of the resin composition can be further improved, and deterioration or the like of components of the resin composition at the time of storage or the like 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 above-described powder and resin material.
  • the mixing of the powder and the resin material may be carried out, for example, with a mixer / kneader such as a planetary mixer, a twin-screw mixer, a kneader, a Banbury mixer, an oven roll, a stirring kneader such as an oven roll, a single-screw extruder, or a twin-screw extruder. It can carry out suitably by using.
  • a mixer / kneader such as a planetary mixer, a twin-screw mixer, a kneader, a Banbury mixer, an oven roll, a stirring kneader such as an oven roll, a single-screw extruder, or a twin-screw extruder. It can carry out suitably by using.
  • the molded article of the present invention is produced using a material containing the powder of the present invention and a resin material.
  • Such a molded article of the present invention can be suitably produced using the above-mentioned resin composition of the present invention.
  • the molded article of the present invention may contain at least a part of the composite particle according to the present invention at least in part, and may have, for example, a region not including the composite particle.
  • a base made of a material other than the resin composition of the present invention, and a surface layer provided on the surface of the base and formed using the resin composition of the present invention It may be
  • the composite particles contained in the molded body preferably satisfy the same conditions as those described in the description of the composite particles of the present invention.
  • the shaped body preferably contains at least the composite particles near the surface thereof. More specifically, the molded body preferably contains the composite particles in an area within 1.0 mm in the thickness direction from the surface, and the composite particles in an area within 0.5 mm from the surface in the thickness direction. Is more preferable.
  • the vicinity of the surface of the molded body is a portion which is particularly easy to be released among the molded bodies. Therefore, by including the composite particles in such a region, the effects of the present invention are more significantly exhibited.
  • such a molded object can be suitably manufactured by giving a magnetic field from the direction which should become the surface of a molded object, for example, at the time of molding of a molded object (state which resin material softened or melted). .
  • the above-described composite particles can be localized near the surface of the molded article, and the above-described effects can be more significantly exhibited.
  • the content of the powder (composite particles) in the molded article of the present invention varies depending on the application of the molded article, etc., but is preferably 2.0% by mass or more and 20% by mass or less, 2.5% by mass or more and 18% by mass It is more preferable that the content be less than or equal to%.
  • the toughness, strength, reliability and the like of the molded body can be further improved, and the ease of detection of the molded body by the metal detector and the stability of detection can be further improved. Moreover, it can prevent effectively that specific gravity of a molded object becomes large too much.
  • the content ratio as described above in the site containing the powder (composite particle) It is preferable to satisfy the conditions.
  • the formed body of the present invention may be applied to inspection by metal detection in whole or in part (for example, a section of the formed body), in other words, may be used for detection with a metal detector. If it is used, it may be used for any purpose, but applications of the molded article of the present invention include, for example, production, processing and packaging of food (including packing, the same applies hereinafter), cosmetics, quasi-drugs Manufacturing, processing, packaging field, pharmaceutical manufacturing, processing, packaging field, manufacturing of other products, processing, packaging field, medical field, cell culture, tissue culture, organ culture, genetic modification And the like, and those for chemical treatment such as synthesis of compounds. Among them, the molded article of the present invention is preferably used at food production, processing and packaging sites.
  • the form of food in addition to solid and semi-solid (gel, gel such as pudding, etc.), the form of food includes liquid, and food is a concept including drinks and the like.
  • Food additives and supplements are also included in the food concept.
  • Synthetic products are also included in the concept of food.
  • Examples of molded articles used in food manufacturing and processing sites include cooking equipment, cooking utensils, cooking utensils, dishes, clothes (articles used by being attached to the human body), packaging members used for packaging food And articles used concomitantly with these, and articles used for maintenance, repair, etc. of these.
  • a hot plate for example, a hot plate, a stove, a gas burner, an oven, a toaster, a microwave, a dishwasher, a tableware dryer, a scale, a kitchen timer, a thermometer, a water purifier, a water filter (cartridge) Cooking equipments, etc .; pots, pans, kettles, these lids, knives, scissors, tails (ladles), spatula, peelers, slicers, mixers, choppers, mashers, rolling pins, muddlers, whisks, bowls, bowls, drainers Bowls, cutting boards, mats, rice scoops, molds, dies, degreasers, grater (food graders), fly backs (turners), picks, drainers, sieves, mills, drop lids, ice trays, grills, tongs, egg cutters Utensils, measuring cups, measuring spoons and other utensils; cloths, kitchen paper, washcloths, towels, paper
  • the molded article of the present invention is preferably used for cooking utensils, cooking utensils, part or all of food packaging members.
  • Various molding methods can be used as a method for producing a molded body, and, for example, injection molding (insert molding, multicolor molding, sandwich molding, injection molding, etc.), extrusion molding, inflation molding, T-die film molding method, laminate molding method, blow molding method, hollow molding method, compression molding method, molding method such as calendar molding method, optical molding method, three-dimensional additive manufacturing method, etc. may be mentioned.
  • injection molding insert molding, multicolor molding, sandwich molding, injection molding, etc.
  • extrusion molding inflation molding
  • T-die film molding method laminate molding method
  • blow molding method hollow molding method
  • compression molding method molding method such as calendar molding method, optical molding method, three-dimensional additive manufacturing method, etc.
  • the curing 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 carried out by heating or irradiation of energy rays such as ultraviolet rays.
  • a molded body is a base formed using a composition not containing powder (composite particles), and a surface layer provided on the base and formed using a composition containing powder (composite particles) If it has, the coating method such as dipping or brushing, the inkjet method, etc. on the base manufactured by the method as described above, casting, forging, powder injection molding (PIM (Powder Injection Molding)), etc.
  • the surface layer may be formed and manufactured using various printing methods and the like.
  • it may be magnetized at the time of molding of the molded body. This makes it possible to further improve the ease of detection of the molded body by the metal detector and the stability of the detection.
  • the formed body may be produced by subjecting the formed body obtained by the above forming method to post-treatments such as grinding and polishing.
  • the powder (composite particles) according to the present invention is dispersed and present in the resin material in the resin composition
  • the powder (composite particles) according to the present invention is precipitated in a liquid, and may be dispersed by stirring or the like as needed.
  • the resin composition of the present invention may be a dispersion in which the powder (composite particles) according to the present invention and the resin particles are dispersed in a volatile liquid.
  • the resin composition of the present invention may have, for example, a configuration in which the powder (composite particles) according to the present invention and the resin powder are simply mixed.
  • the method for producing composite particles of the present invention may have other steps (pre-treatment step, intermediate step, post-treatment step), as necessary.
  • composite particles of the present invention are not limited to those produced by the method as described above, and may be produced by any method.
  • Example 1 First, Fe 2 O 3 , Mn 3 O 4 , Mg (OH) 2 and SrCO 3 as raw materials were mixed in a predetermined ratio and mixed for 15 minutes with a Henschel mixer. The pulverized material thus obtained was pelletized using a roller compactor, and then calcined using a rotary kiln at 900 ° C. for 5 hours in the atmosphere.
  • the mixture was pulverized with a ball mill to obtain a powdery calcined body (calcined powder) having a volume average particle diameter of 1.8 ⁇ m.
  • the volume average particle size of the powder was determined by the following measurement. That is, first, 10 g of powder as a sample and 80 ml of water were placed in a 100 ml beaker, and 2 drops of a dispersant (sodium hexametaphosphate) were added. Then, dispersion was performed using an ultrasonic homogenizer (SMT. Co. LTD. UH-150 type). At this time, the output level of the ultrasonic homogenizer was set to 4 and dispersion was performed for 20 seconds. Thereafter, bubbles formed on the surface of the beaker were removed, introduced into a microtrack particle size analyzer (Model 9320-X100, manufactured by Nikkiso Co., Ltd.), and measurement was performed. In addition, it calculated
  • the average value of SF-1 of the ferrite powder was 108.
  • the shape factor SF-1 was determined as follows.
  • the particles were photographed in a 450 ⁇ field of view using a scanning electron microscope (FE-SEM (SU-8020, manufactured by Hitachi High-Technologies Corporation)).
  • FE-SEM scanning electron microscope
  • the image information is introduced into an image analysis software (Image-Pro PLUS) manufactured by Media Cybernetics through an interface and analyzed to obtain Area (projected area) and Feret diameter (maximum), and the above equation , SF-1 values were calculated.
  • Image-Pro PLUS image analysis software manufactured by Media Cybernetics through an interface and analyzed to obtain Area (projected area) and Feret diameter (maximum), and the above equation , SF-1 values were calculated.
  • SF-1 was calculated for each particle, and the average value of 100 particles was taken as SF-1 of ferrite powder. In addition, it calculated
  • the BET specific surface area of the obtained ferrite powder was 0.74 m 2 / g.
  • the BET specific surface area was determined by measurement using a specific surface area measuring device (model: Macsorb HM model-1208 (manufactured by Mountech Co.)). More specifically, about 5 g of a measurement sample was placed in a standard sample cell dedicated to a specific surface area measuring device, accurately weighed with a precision balance, and a sample (ferrite powder) was set in the measurement port to start measurement. The measurement was performed by a one-point method, and when the weight of the sample was input at the end of the measurement, the BET specific surface area was automatically calculated.
  • the ferrite powder was measured using a vibrating sample type magnetic measuring device. As a result, saturation magnetization: 69.6 emu / g, residual magnetization: 2.7 emu / g, coercivity: 38 Oe.
  • the above magnetic properties were determined as follows. That is, first, ferrite powder to be measured was packed in a cell with an inner diameter of 5 mm and a height of 2 mm, and set in a vibrating sample type magnetic measuring device (VSM-C7-10A manufactured by Toei Kogyo Co., Ltd.). Next, an applied magnetic field was applied and swept to 5 kOe (10 kOe in the case of hard ferrite), and then the applied magnetic field was decreased to create a hysteresis curve. Thereafter, saturation magnetization, remanent magnetization and coercivity of the ferrite powder were determined from the data of this curve. In addition, it calculated
  • the obtained ferrite powder is subjected to electroless plating to obtain a powder containing a plurality of composite particles having a coating layer made of Ag on the surface of a base particle made of ferrite (soft ferrite). It was obtained.
  • Example 2 A powder (aggregate of a plurality of composite particles) was produced in the same manner as in Example 1 except that the thickness of the coating layer was changed.
  • Example 4 First prepared Fe 2 O 3 and SrCO 3, these, in a molar ratio, 3: 1 ratio, were charged into a Henschel mixer and dry mixing for 10 minutes, and granulated, the granules Obtained.
  • the obtained granulated product was calcined at 1150 ° C. for 4 hours (peak) in the atmosphere using a stationary electric furnace for 4 hours.
  • the fired product obtained by the above firing is wet-ground using a bead mill under the condition of solid content: 60% by mass for 30 minutes, washed, dehydrated, dried, and then sprayed in the same manner as in Example 1; Ferrite powder (volume average particle diameter: 9.0 ⁇ m) composed of individual ferrite particles (hard ferrite particles) was obtained.
  • the content of Sr in the hard ferrite particles obtained as described above was 6.10% by mass, and the content of Fe was 63.48% by mass.
  • the average value of SF-1 of the ferrite powder was 107. Further, the BET specific surface area of the obtained ferrite powder was 3.34 m 2 / g.
  • the obtained ferrite powder is subjected to electroless plating to obtain a powder containing a plurality of composite particles having a coating layer made of Ag on the surface of a base particle made of ferrite (hard ferrite). It was obtained.
  • a powder (aggregate of a plurality of composite particles) was produced in the same manner as in Example 1 except that hard ferrite particles produced as described above were used as the base particles. .
  • Example 1 A powder was manufactured in the same manner as in Example 1 except that the formation of the coating layer on the ferrite powder was omitted. That is, in the present comparative example, the ferrite powder was used as it was as a target powder.
  • Example 2 A powder was manufactured in the same manner as in Example 4 except that the formation of the coating layer on the ferrite powder was omitted. That is, in the present comparative example, the ferrite powder was used as it was as a target powder.
  • the composition of the powder of each said Example and each comparative example was put together in Table 1, Table 2, and was shown.
  • the color tone of the powder of each example was white to silver, while the color tone of the powder of each comparative example was black.
  • the value of the volume resistance shown in Table 2 was calculated
  • the resistance was measured by connecting the bottom and top electrodes to a measuring device (using either Model 2182, Model 2000, or Model 6517A made by Keithley) under load, according to the range of resistance to be measured. .
  • the volume resistance was calculated using the resistance value, the inner diameter and the thickness obtained by the measurement.
  • the true density was measured at a temperature of 25 ° C. according to JIS Z 8807: 2012 using a fully automatic closeness measuring apparatus Macpycno manufactured by Mountech Co., Ltd. Moreover, the measurement of the tap density was performed based on JIS1628. The measurement was performed using a powder tester PT-X manufactured by Hosokawa Micron Corporation. Further, the metal coating amount in the composite particles (proportion of the coating layer in the composite particles) was determined as follows using the true density obtained as described above.
  • the true density of the ferrite powder before forming the covering layer is g / cm 3 before the treatment D
  • the true density of the ferrite powder after forming the covering layer is g / cm 3 after the treatment
  • the true density of the metal that is the constituent material is D coat
  • the value obtained as (D after treatment-before D treatment ) / (D before coat- D treatment ) x 100 is the metal coating amount.
  • the true density of silver was 10.49 g / cm 3 .
  • the Curie temperature in Table 1 and the thickness T of the coating layer were each measured by the above method.
  • L * a * b * of the composite particles was measured by the method described above.
  • Examples 1 to 3 and Comparative Example 1 are measured values of the magnetic properties when 5 kOe is applied.
  • Example 4 and Comparative Example 2 are measured values of magnetic characteristics when 10 kOe is applied.
  • the content of components other than ferrite in the base particles was 0.1% by mass or less.
  • the content rate of components other than Ag in a coating layer was 0.1 mass% or less.
  • the content of the component outside the composite particle in the powder was 0.1% by mass or less.
  • FIG. 1 shows a cross-sectional FE-SEM image of the composite particle of Example 1
  • FIG. 2 shows a cross-sectional FE-SEM image of the composite particle of Example 2
  • FIG. 3 shows the composite particle of Example 3.
  • a cross-sectional FE-SEM image of the composite particle of Example 4 is shown in FIG.
  • FIG. 5 shows a cross-sectional EDX mapping image (Fe) of the composite particle of Example 4
  • FIG. 6 shows a cross-sectional EDX mapping image (Ag) of the composite particle of Example 4
  • FIG. 7 shows the composite particle of Example 4
  • a cross-sectional EDX mapping image (Sr) is shown.
  • the powder and polypropylene as a resin material were mixed and kneaded at a mass ratio of 7.5: 92.5 and granulated using a kneader and a pelletizer. Thus, a resin composition as pellets having a volume average particle size of 3 mm was obtained.
  • ⁇ 3 Production of Molded Product Using the resin compositions of the respective Examples and Comparative Examples prepared as described above, a molded product was produced as follows.
  • the resin compositions (pellets) of the respective Examples and Comparative Examples were melted and molded using a kneader and a T-die to obtain a sheet-like molded product having a thickness of 100 ⁇ m.
  • ⁇ 4 Evaluation of Molded Body >> [4-1] Detection by Metal Detector
  • the molded body produced in each of the above-described Examples and Comparative Examples was cut into a size of 80 mm ⁇ 60 mm to prepare a test piece.
  • the sensitivity (level meter, iron ball sensitivity) which can detect a molded object (test piece) was calculated
  • a belt conveyor type metal detector a fine metal detector NT2-K4B manufactured by Nikka Densei Co., Ltd.
  • a belt conveyor type metal detector (META-HAWKII manufactured by System Square Co., Ltd.) is used as the second metal detector.
  • the sensitivity (level meter, iron ball sensitivity) capable of detecting a molded body (test piece) was determined and evaluated according to the following criteria.
  • Ball sensitivity is 1.5 mm or more in diameter.
  • ⁇ 4-2 Tint of molded object About the molded object (sheet) manufactured by each Example mentioned above and each comparative example, using a color difference meter (Spectrodensiitometer X-Rite 938, X-rite company make), L * a * B * was measured.
  • Comparative Example 1 As apparent from Table 3, according to the present invention, it was possible to stably detect with various metal detectors, and to obtain a molded article adjusted to a desired color tone.
  • the powder used had high volume resistance, and not only low coercivity can not be detected by the first metal detector, but also difficult to detect by the second metal detector, and it becomes black. It became a resin molding with low versatility.
  • Comparative Example 2 has a high volume resistance of the powder used, is difficult to detect with any of the first metal detector and the second metal detector, and becomes a black one, resulting in a resin molding of low versatility.
  • powder, a resin composition, and a molded object are manufactured similarly to the above except having changed the constituent material of the coating layer into Pt, Ni, and Pd instead of Ag, and evaluation similar to the above is performed. The same results as described above were obtained.
  • the resin composition and the molded object were manufactured like the above except using various coloring agents with the resin material.
  • various coloring agents with the resin material.
  • the evaluation similar to the above was performed about these molded objects, the same result as the above was obtained.
  • the composite particle of the present invention is a particle intended to be detected by a metal detector, and includes base particles composed of ferrite, and a coating layer composed of a metal material exhibiting white to silver. Therefore, it can be stably detected by a metal detector, and can be suitably used for the production of a molded article adjusted to a desired color tone.
  • the composite particles of the present invention have industrial applicability.

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  • Medicinal Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention fournit : des particules composites qui sont équipées de particules de base configurées à base de ferrite, et d'une couche de revêtement configurée par un matériau métallique de couleur argentée ne blanchissant pas ; une poudre qui est caractéristique en ce qu'elle contient une pluralité desdites particules composites ; une composition de résine qui est caractéristique en ce qu'elle contient ladite poudre et un matériau de résine ; et un corps moulé qui est caractéristique en ce qu'il est fabriqué à l'aide d'un matériau contenant ladite poudre et ledit matériau de résine.
PCT/JP2019/002144 2018-01-23 2019-01-23 Particules composites, poudre, composition de résine, et corps moulé WO2019146661A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01223703A (ja) * 1988-03-02 1989-09-06 Hitachi Maxell Ltd 強磁性粉末とこれを用いた磁気記録媒体
JP2006286729A (ja) * 2005-03-31 2006-10-19 Kobe Steel Ltd 電磁波吸収性および導電性に優れた塗料組成物、並びに該塗料組成物で被覆されている塗装金属板
JP2018120921A (ja) * 2017-01-24 2018-08-02 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体
WO2019027023A1 (fr) * 2017-08-03 2019-02-07 パウダーテック株式会社 Particules composites, poudre, composition de résine et corps moulé

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190040226A1 (en) * 2016-03-31 2019-02-07 Powdertech Co., Ltd. Ferrite powder, resin composition, and molded article
JP2017201693A (ja) * 2017-05-12 2017-11-09 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01223703A (ja) * 1988-03-02 1989-09-06 Hitachi Maxell Ltd 強磁性粉末とこれを用いた磁気記録媒体
JP2006286729A (ja) * 2005-03-31 2006-10-19 Kobe Steel Ltd 電磁波吸収性および導電性に優れた塗料組成物、並びに該塗料組成物で被覆されている塗装金属板
JP2018120921A (ja) * 2017-01-24 2018-08-02 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体
WO2019027023A1 (fr) * 2017-08-03 2019-02-07 パウダーテック株式会社 Particules composites, poudre, composition de résine et corps moulé

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