[go: up one dir, main page]

WO2006068136A1 - OXIDE FILM COATED Fe-Ni-Mo BASED FLAT METAL SOFT MAGNETIC POWDER HAVING HIGH SURFACE ROUGHNESS AND METHOD FOR PRODUCTION THEREOF - Google Patents

OXIDE FILM COATED Fe-Ni-Mo BASED FLAT METAL SOFT MAGNETIC POWDER HAVING HIGH SURFACE ROUGHNESS AND METHOD FOR PRODUCTION THEREOF Download PDF

Info

Publication number
WO2006068136A1
WO2006068136A1 PCT/JP2005/023359 JP2005023359W WO2006068136A1 WO 2006068136 A1 WO2006068136 A1 WO 2006068136A1 JP 2005023359 W JP2005023359 W JP 2005023359W WO 2006068136 A1 WO2006068136 A1 WO 2006068136A1
Authority
WO
WIPO (PCT)
Prior art keywords
soft magnetic
magnetic powder
flat metal
metal soft
based flat
Prior art date
Application number
PCT/JP2005/023359
Other languages
French (fr)
Japanese (ja)
Inventor
Gakuji Uozumi
Ryoji Nakayama
Original Assignee
Mitsubishi Materials Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corporation filed Critical Mitsubishi Materials Corporation
Publication of WO2006068136A1 publication Critical patent/WO2006068136A1/en

Links

Classifications

    • 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
    • H01F1/14—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 metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14708—Fe-Ni based alloys
    • H01F1/14733—Fe-Ni based alloys in the form of particles
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • 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
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • H01F1/33—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 mixtures of metallic and non-metallic particles; metallic particles having oxide skin

Definitions

  • Fe-Ni-Mo-based flat metal soft magnetic powder with high surface roughness and its production method Fe-Ni-Mo-based flat metal soft magnetic powder with high surface roughness and its production method
  • the present invention relates to an oxide having a high surface roughness used for a high frequency magnetic material such as a radio wave absorber having excellent radio wave absorption characteristics and an antenna core for radio communication having excellent magnetic characteristics.
  • the present invention relates to a film-coated Fe—Ni—Mo-based flat metal soft magnetic powder and a method for producing the same.
  • the present invention also provides a magnetic film having a high resistivity and a low coercive force, in which the acid-coating-coated Fe—Ni—Mo flat metal soft magnetic powder having a high surface roughness is oriented and dispersed in a resin. Relates to a composite sheet.
  • Mo permalloy Fe—79% Ni—4% Mo
  • Mo—Fe—Ni—Mo based soft such as single permalloy (Fe—79% Ni—5% Mo).
  • Magnetic powders are known. Even if these materials are gradually cooled after heat treatment with Mo additive, the formation of FeNi ordered phase
  • the crystal magnetic anisotropy constant ⁇ is around zero even without quenching after heat treatment, and it exhibits excellent permeability even in polycrystalline materials that are isotropic in terms of crystal orientation.
  • High permeability soft magnetic materials are also known in which Cu, Cr and Mn are added in addition to Mo in order to further improve the permeability.
  • the Fe-Ni-Mo soft magnetic powder is often used in a flat shape.
  • Patent Document 1 describes the composition of Fe—70 to 83% Ni—2 to 6% Mo—3 to 6% Cu—1 to 2% ⁇ in terms of mass% (hereinafter, “%” represents mass%).
  • a flat metal soft magnetic powder having an average particle size of 0.1 to 30 m and an average thickness of 2 m or less is described, and the flat metal soft magnetic powder is used for a magnetic shield. Is described.
  • Patent Document 2 has a composition of Fe-40 to 80% Ni—2 to 6% Mo, a thickness of 1 to 5 ⁇ m, and a ratio of thickness to length of 1: 5 to 200.
  • Flat flaky soft magnetic powder is described In addition, it is described that this flat flake-like soft magnetic powder is used for a marking body such as a road surface.
  • Patent Document 3 has a composition of Fe-60 to 80% N or Fe-60 to 80% Ni— 5% or less, and has a flake thickness of 30 ⁇ m or less and a flake diameter of 50 to 50%.
  • a flat metal soft magnetic powder having 2000 ⁇ m is described, and this flat metal soft magnetic powder is described as being used as a magnetic material for high frequency.
  • These conventional Fe-Ni-Mo-based flat metal soft magnetic powders are all made by adding ethanol or water as a solvent to Fe-Ni-Mo-based powders obtained by ordinary pulverization or atomization. According to this, it is manufactured by adding a grinding aid and subjecting them to a flat wrinkle treatment using an attritor or a ball mill.
  • the Fe-Ni-Mo-based flat metal soft magnetic powder produced in this way is dispersed in the resin so that the flat surface is oriented in a direction perpendicular to the thickness direction of the magnetic composite sheet.
  • a high-frequency magnetic material such as a radio wave absorber having radio wave absorption characteristics at several tens of MHz to several GHz, or an antenna core for wireless communication having magnetic characteristics at several tens of kHz to several ⁇ . Is also known.
  • Patent Document 1 Japanese Patent Laid-Open No. 3-223401
  • Patent Document 2 JP-A-3-232574
  • Patent Document 3 Japanese Patent Laid-Open No. 4-78112
  • Patent Document 4 Japanese Patent Laid-Open No. 4-213803
  • Fe-Ni-Mo-based flat metal soft magnetic powders have relatively good corrosion resistance, they must be heated in an oxidizing atmosphere and at a relatively high temperature of 300 to 400 ° C! /.
  • Fe—Ni—Mo flat metal soft magnetic powder is heated at a high temperature, NiO with a low resistivity is formed as an acid film. Therefore, it is necessary to increase the thickness of the NiO oxide film necessary to maintain the insulation, and the Fe—Ni—Mo flat metal soft magnetic powder formed with this thick NiO has a coercive force. Increase significantly.
  • a composite magnetic sheet prepared by using an Fe—Ni—Mo-based flat metal soft magnetic powder having a high coercive force is not preferable because the characteristics as a radio wave absorber and a magnetic material for high frequency are greatly deteriorated.
  • the present invention has been made in view of the above circumstances, and is used for a high-frequency magnetic material such as a radio wave absorber having excellent radio wave absorption characteristics and an antenna core for wireless communication having excellent magnetic characteristics.
  • An object of the present invention is to provide an Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness.
  • the present inventors produced an Fe-Ni-Mo-based flat metal soft magnetic powder in which an Fe-Ni-Mo-based flat metal soft magnetic powder was coated with an acid-coating film on the surface. And this acid coating We conducted research to obtain high-resistivity and low-coercivity magnetic composite sheets with excellent characteristics as radio wave absorbers or high-frequency magnetic materials using coated Fe-Ni-Mo-based flat metal soft magnetic powders. As a result, the following (A) to (D) were discovered for the first time.
  • an ordinary Fe-Ni-Mo-based flat metal soft magnetic powder is boiled in water (more preferably distilled water)
  • an oxide film having a high resistivity is formed on the surface of the Fe-Ni-Mo-based flat metal soft magnetic powder.
  • the specific surface area obtained by calculation of Ni—Mo-based flat metal soft magnetic powder is SI and the proportionality coefficient obtained by dividing SR by SI is k
  • the proportionality factor k which is obtained by dividing the specific surface area of the Fe-Ni-Mo flat metal soft magnetic powder coated with an oxide film by heating in a normal oxidizing atmosphere such as the atmosphere by SI, must exceed 8. Hana was strong. Therefore, the proportional coefficient k of the acid-coating-coated Fe-Ni-Mo-based flat metal soft magnetic powder obtained by boiling in water (more preferably distilled water) must be heated in the atmosphere. Oxide-coated Fe-Ni-Mo-based flattened by the conventional method The surface roughness of the metal soft magnetic powder is the same as the surface of the normal acid film-coated Fe—Ni — Mo flat metal soft magnetic powder obtained by heating in a normal acid atmosphere such as the atmosphere.
  • the oxide film formed on the surface of the Fe—Ni—Mo-based flat metal soft magnetic powder obtained by boiling is represented by the composition formula: Ni Fe O (where 0 ⁇ x ⁇ 3), This oxide film
  • Fe-Ni-Mo-based flat metal soft magnetic powders with an oxidized film are heated at a relatively low temperature because the boiling temperature is around 100 ° C. ⁇
  • the thickness of the film can be made smaller than that of the NiO oxide film, so that the coercivity of the Fe-Ni-Mo-based flat metal soft magnetic powder is not increased during the manufacturing process.
  • the Fe-Ni-Mo-based flat metal soft magnetic powder for producing an acid-coating-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness obtained by boiling is , Ni: 60-90%, Mo: 0.05-: L 95% contained, the remainder: more preferably having a component composition consisting of Fe and inevitable impurities, etc. .
  • Average particle size 30 to 150 ⁇ m and aspect ratio (average particle size Z average thickness): High surface roughness on the surface of Fe-Ni-Mo based flat metal soft magnetic powder of 5 to 500 An oxide film coated Fe-Ni-Mo flat metal soft magnetic powder with high surface roughness formed with an oxide film coating,
  • the ratio table area of the above-mentioned Fe-Ni-Mo-based flat metal soft magnetic powder coated with an oxide film having a high surface roughness is SR
  • the acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder is in% by mass (hereinafter,% indicates% by mass), Ni: 60 to 90%, Mo: 0.05 to The above (1), wherein the powder is formed by forming an oxide film on the surface of a Fe-Ni-Mo-based flat metal soft magnetic powder containing 95% L and the balance: Fe and an inevitable impurity component composition.
  • the acid film formed on the surface of the Fe-Ni-Mo-based flat metal soft magnetic powder is: Ni Fe O (where 0 ⁇ x ⁇ 3), which has the high surface roughness described in (1) or (2) 3 4
  • Average particle diameter 30 to 150 ⁇ m and aspect ratio (average particle diameter Z average thickness): 5 to 500, and in mass% (hereinafter,% represents mass%) Ni: 60 to 90%, Mo: 0.05-: L 95%, the remainder: Fe and Ni—Mo-based flat metal soft magnetic powder having a component composition that also has inevitable impurity power is boiled in water (1) or The method for producing an oxide film-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness described in (2) or (3) is preferred.
  • the time for boiling the Fe—Ni—Mo-based flat metal soft magnetic powder in water is preferably in the range of 10 minutes to 10 hours.
  • the flat surface of the acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having the high surface roughness described in (1), (2) or (3) is the thickness direction of the magnetic composite sheet
  • the magnetic composite sheet is oriented and dispersed in the direction intersecting with respect to.
  • the flat surface of the acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having the high surface roughness described in (1), (2) or (3) is the thickness direction of the magnetic composite sheet
  • the magnetic composite sheet is oriented and dispersed in a direction perpendicular to the magnetic field.
  • the Fe—Ni—Mo flat metal soft magnetic powder is boiled.
  • the time is preferably in the range of 10 minutes to 10 hours. If the boiling time is less than 10 minutes, a sufficiently thick oxide film is not formed, which is not preferable. On the other hand, if the boiling time is longer than 10 hours, the formed oxide film becomes too thick and the oxide film becomes thick. This is because it is preferable that the coercive force is increased if it becomes too large.
  • the resistivity of the composite magnetic sheet obtained by solidifying the oxide-coated Fe—Ni—Mo flat metal soft magnetic powder having a high surface roughness of this invention by mixing the resin with high density is that the surface roughness is Rise because it is coarse.
  • the reason for this is that the contact area between the adjacent oxide-coated Fe-Ni-Mo flat metal soft magnetic powders is reduced due to the unevenness formed on the surface of the powder, and the gap between the powders is reduced. It is considered that fat spreads evenly and increases the resistivity of the obtained composite magnetic sheet.
  • an ordinary commercially available Fe—Ni—Mo based flat metal soft magnetic powder is immersed in water, In particular, it may be dried after boiling in distilled water.
  • the resin used in the magnetic composite sheet of the present invention includes chlorinated polyethylene, silicone, polyurethane, poly (acetic acid butyl), ethylene-acetic acid butyl copolymer, acrylonitrile butadiene-styrene resin (ABS resin), poly salt
  • ABS resin acrylonitrile butadiene-styrene resin
  • poly salt such as rubber, polybutyl butyral, thermoplastic elastomer, EPDM copolymer rubber (ethylene 'propylene copolymer rubber), styrene-butadiene rubber, acrylonitrile butadiene rubber, and blended or blended It may be denatured.
  • denatured this resin may be sufficient.
  • the Ni content in the Fe-Ni-Mo-based flat metal soft magnetic powder constituting the oxide-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is reduced to 60 to 90%.
  • the reason for the limitation is that the magnetic properties are deteriorated when it is less than 60% or more than 90%, and this range is a generally known range.
  • the Ni content in the film-coated Fe—Ni—Mo-based flat metal soft magnetic powder is in the range of 70 to 85%.
  • FeNi ordered phase is excessively formed by slow cooling after heat treatment.
  • the magnetic anisotropy constant is negative and its absolute value becomes too large, resulting in a decrease in magnetic properties.
  • it exceeds 1.95% the formation of FeNi ordered phase becomes insufficient and the crystal
  • the magnetic anisotropy constant ⁇ is negative and its absolute value is too small or positive, the effect of making the flat surface easier to magnetize due to crystal magnetic anisotropy becomes insufficient. Since the in-plane magnetic permeability decreases, it is preferable to limit the amount of Mo added to 0.05-1.95%.
  • the more preferable range of the Mo content in the Fe-Ni-Mo-based flat metal soft magnetic powder having high surface roughness according to the present invention is 0.5 to 1.95%, more preferably. Is between 0.8 and 1.9%.
  • the content of the remaining Fe and inevitable impurities is preferably 8.05% to 39.95%, more preferably 13.05% to 29.5%.
  • the average particle diameter of the Fe-Ni-Mo-based flat metal soft magnetic powder used for the acid-coated film Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is It was set to 30 to 150 ⁇ m. A more preferable range of the average particle diameter is 35 to 140 ⁇ m.
  • the aspect ratio of the Fe—Ni—Mo-based flat metal soft magnetic powder in the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is less than 5, the demagnetizing field of the powder
  • the aspect ratio is greater than 500, distortion is significantly introduced during flattening treatment, and sufficient magnetic properties are obtained. It is not preferable because it is not possible. Therefore, the aspect ratio of the Fe-Ni-Mo-based flat metal soft magnetic powder used for the oxide film-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is 5 to 500. Determined.
  • the specific surface area of the metal soft magnetic powder is SI
  • the oxide film-covered Fe-Ni-Mo-based flat metal soft magnetic powder having a proportionality coefficient k of less than 10 is not preferable because a composite magnetic sheet having a sufficiently high resistivity cannot be produced. This is because, in order to produce an Fe-Ni-Mo-based flat metal soft magnetic powder with an oxide film with a proportionality coefficient k exceeding 200, boiling for a considerable time must be performed, which is not practical.
  • the oxide film-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention has an average particle size of about 30 to 150, preferably about 35 to 140 111, and an aspect ratio of 500 to 500. It may be within the range.
  • the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness can provide a high-frequency magnetic material having a high resistivity for an antenna and an inductor. It is possible to provide a radio wave absorber having a resistivity, which provides excellent effects in the electrical and electronic industries.
  • the alloy raw material was melted at high frequency to prepare a molten metal having a composition of Ni: 79% by mass, M 0 : 1% by mass, the balance being Fe and inevitable impurities. Then, these molten metal is used as water atom.
  • Fe—Ni—Mo-based metal soft magnetic atomized powder After classifying the Fe-Ni-Mo-based metal soft magnetic atomized powder, it is subjected to flattening with an ordinary attritor, and the resulting flat powder is classified with an air classifier to obtain an average particle size d
  • a raw material powder of an Fe—Ni—Mo based flat metal soft magnetic powder having an average thickness t: l. 96 ⁇ m and an aspect ratio (dZt): 42.3 was prepared.
  • the raw material powder of the Fe—Ni—Mo-based flat metal soft magnetic powder obtained in this way is boiled in distilled water for the time shown in Table 1 so that the acid-coating-coated Fe—Ni—Mo-based powder of the present invention is obtained.
  • Flat metal soft magnetic powder hereinafter referred to as oxide-coated flat soft magnetic powder of the present invention
  • comparative oxide-coated Fe-Ni-Mo series flat metal soft magnetic powder hereinafter referred to as comparative oxide-coated flat soft magnetic powder
  • the Fe-Ni-Mo-based flat metal soft magnetic powder material powder is heated in the atmosphere at a temperature of 375 ° C for 1 hour or 6 minutes.
  • Flat metal soft magnetic powders (hereinafter referred to as conventional oxide film-coated flat soft magnetic powders) 1 to 2 were produced.
  • the oxide film-coated flat soft magnetic powders 1 to 9 were further compared by the gas adsorption method specified in JIS Z 8830.
  • the surface area SR was measured and the results are shown in Table 1.
  • the oxide film-coated flat soft magnetic powders 1 to 9 of the present invention, and a comparative oxide film-coated flat soft magnetic powder 1 In addition, 15% by mass of chlorinated polyethylene: 1 to 2 is mixed with kneaded and soft oxide film-coated flat soft magnetic powder 1-2, and then the flat surface of the oxide film-coated flat metal soft magnetic powder is formed into a sheet by roll forming.
  • the present invention having a thickness of 0.5 mm arranged parallel to the surface (in other words, the flat surfaces of the oxide-coated flat metal soft magnetic powder are arranged in a direction perpendicular to the thickness direction of the sheet)
  • Magnetic composite sheets 1 to 9 comparative magnetic composite sheet 1 and conventional magnetic composite sheets 1 to 2 were prepared, and the resistivity ( ⁇ cm) and coercive force (Oe) of these magnetic composite sheets were measured. It was shown to. LOe is about 80AZm.
  • the present invention oxide film having a proportional coefficient k in the range of 10 200 obtained by boiling Fe-Ni-Mo-based flat metal soft magnetic powder in distilled water.
  • the coated flat soft magnetic powder 19 has a higher resistivity than the conventional oxide-coated flat soft magnetic powder 2 and has a high specific surface area and a high proportionality coefficient k.
  • the oxide film-coated flat soft magnet It can be seen that all of the conductive powders 1 to 9 have a low 1S coercive force with the same resistivity as that of the conventional oxide-coated flat soft magnetic powder 1.
  • the magnetic composite sheets 1 to 9 of the present invention prepared with the oxide film-coated flat soft magnetic powders 1 to 9 have higher resistivity than the conventional magnetic composite sheet 2 of the conventional oxide film-coated flat soft magnetic powder 2 Have
  • the magnetic composite sheets 1 to 9 of the present invention prepared with the oxide film-coated flat soft magnetic powders 1 to 9 of the present invention are the same as the conventional magnetic composite sheet 1 prepared with the conventional oxide film-coated flat soft magnetic powder 1 of V. It can be seen that the resistivity is comparable but the coercive force is low.
  • the comparative magnetic composite sheet 1 produced from the comparative oxide-coated flat soft magnetic powder 1 having a proportional coefficient k that deviates from the conditions of the present invention has a low coercive force but a low resistivity of less than 10 3 ⁇ cm. I understand.
  • Fe-Ni-Mo system with high surface roughness used for high frequency magnetic materials such as radio wave absorbers with excellent radio wave absorption characteristics and antenna cores for radio communications with excellent magnetic characteristics
  • a flat metal soft magnetic powder can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Soft Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

An oxide film coated Fe-Ni-Mo based flat metal soft magnetic powder having high surface roughness, which is composed of an Fe-Ni-Mo based flat metal soft magnetic powder having an average particle diameter of 30 to 150 µm and an aspect ratio (average particle diameter/average thickness) of 5 to 500 and, formed on the surface thereof, an oxide film having a high surface roughness, wherein the above oxide film coated Fe-Ni-Mo based flat metal soft magnetic powder having high surface roughness has a specific surface area satisfying SR = k·SI, wherein SR represents a specific surface area of the above Fe-Ni-Mo based flat metal soft magnetic powder, SI represents a calculated specific surface area for an oxide film coated Fe-Ni-Mo based flat metal soft magnetic powder of a smooth surface having no unevenness, and k is a proportionality constant and k ­= 10 to 200.

Description

明 細 書  Specification
高表面粗さを有する酸ィ匕膜被覆 Fe— Ni—Mo系扁平金属軟磁性粉末お よびその製造方法  Fe-Ni-Mo-based flat metal soft magnetic powder with high surface roughness and its production method
技術分野  Technical field
[0001] この発明は、優れた電波吸収特性を有する電波吸収体や優れた磁気特性を有す る無線通信用アンテナコアなどの高周波用磁性材料に使用される高表面粗さを有す る酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末およびその製造方法に関する。 また、この発明は、前記高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属 軟磁性粉末を榭脂中に配向させて分散させた高抵抗率および低保磁力を有する磁 性複合シートに関する。  [0001] The present invention relates to an oxide having a high surface roughness used for a high frequency magnetic material such as a radio wave absorber having excellent radio wave absorption characteristics and an antenna core for radio communication having excellent magnetic characteristics. The present invention relates to a film-coated Fe—Ni—Mo-based flat metal soft magnetic powder and a method for producing the same. The present invention also provides a magnetic film having a high resistivity and a low coercive force, in which the acid-coating-coated Fe—Ni—Mo flat metal soft magnetic powder having a high surface roughness is oriented and dispersed in a resin. Relates to a composite sheet.
本願は、 2004年 12月 21日に日本国特許庁に出願された特願 2004— 369372 号に基づく優先権を主張し、その内容をここに援用する。  This application claims priority based on Japanese Patent Application No. 2004-369372 filed with the Japan Patent Office on December 21, 2004, the contents of which are incorporated herein by reference.
背景技術  Background art
[0002] 一般に、パーマロイに Moを添カ卩した Moパーマロイ（Fe— 79%Ni—4%Mo)ゃス 一パーマロイ（Fe— 79%Ni— 5%Mo)などの Fe— Ni— Mo系軟磁性粉末は知られ ている。これら材料は Moの添カ卩により熱処理後に徐冷しても、 FeNi規則相の生成  [0002] In general, Mo permalloy (Fe—79% Ni—4% Mo) with permalloy added with Mo—Fe—Ni—Mo based soft such as single permalloy (Fe—79% Ni—5% Mo). Magnetic powders are known. Even if these materials are gradually cooled after heat treatment with Mo additive, the formation of FeNi ordered phase
3  Three
が抑制され、熱処理後の急冷を施さなくても結晶磁気異方性定数 κが零前後となり 、結晶方位の上で等方的な多結晶体においても優れた透磁率を示すため、工業的 にも広く使用されている。また、さらに透磁率を改善するために Moのほかにさらに Cu 、 Cr、 Mnを添加した高透磁率軟磁性材料も知られている。  The crystal magnetic anisotropy constant κ is around zero even without quenching after heat treatment, and it exhibits excellent permeability even in polycrystalline materials that are isotropic in terms of crystal orientation. Are also widely used. High permeability soft magnetic materials are also known in which Cu, Cr and Mn are added in addition to Mo in order to further improve the permeability.
[0003] 前記 Fe— Ni— Mo系軟磁性粉末は、一般に、扁平ィ匕して使用されることが多い。 [0003] In general, the Fe-Ni-Mo soft magnetic powder is often used in a flat shape.
例えば、特許文献 1には、質量％で (以下、％は質量％を示す。）、 Fe— 70〜83% Ni— 2〜6%Mo— 3〜6%Cu— 1〜2%Μηの組成を有し、平均粒径： 0. 1〜30 m、平均厚さ： 2 m以下を有する扁平金属軟磁性粉末が記載されており、この扁平 金属軟磁性粉末は磁気シールド用に使用されることが記載されて 、る。  For example, Patent Document 1 describes the composition of Fe—70 to 83% Ni—2 to 6% Mo—3 to 6% Cu—1 to 2% Μη in terms of mass% (hereinafter, “%” represents mass%). A flat metal soft magnetic powder having an average particle size of 0.1 to 30 m and an average thickness of 2 m or less is described, and the flat metal soft magnetic powder is used for a magnetic shield. Is described.
また、特許文献 2には、 Fe— 40〜80%Ni— 2〜6%Moの組成を有し、厚さ： 1〜5 μ m、厚さと長さの比が 1： 5〜200を有する扁平フレーク状軟磁性粉末が記載されて おり、この扁平フレーク状軟磁性粉末は路面などの標識体に使用されることが記載さ れている。 Patent Document 2 has a composition of Fe-40 to 80% Ni—2 to 6% Mo, a thickness of 1 to 5 μm, and a ratio of thickness to length of 1: 5 to 200. Flat flaky soft magnetic powder is described In addition, it is described that this flat flake-like soft magnetic powder is used for a marking body such as a road surface.
さらに、特許文献 3には、 Fe— 60〜80%Nほたは Fe— 60〜80%Ni— 5%以下 Moの組成を有し、フレーク厚さ： 30 μ m以下、フレーク径： 50〜2000 μ mを有する 扁平金属軟磁性粉末が記載されており、この扁平金属軟磁性粉末は高周波用磁性 材料として使用することが記載されている。  Furthermore, Patent Document 3 has a composition of Fe-60 to 80% N or Fe-60 to 80% Ni— 5% or less, and has a flake thickness of 30 μm or less and a flake diameter of 50 to 50%. A flat metal soft magnetic powder having 2000 μm is described, and this flat metal soft magnetic powder is described as being used as a magnetic material for high frequency.
これら従来の Fe— Ni— Mo系扁平金属軟磁性粉末は、いずれも通常の粉砕また はアトマイズして得られた Fe— Ni— Mo系粉末にエタノールや水を溶媒として添カロし 、さらに必要に応じて粉砕助剤を添加し、これらをアトライターやボールミルを使用し て扁平ィ匕処理することにより製造されている。  These conventional Fe-Ni-Mo-based flat metal soft magnetic powders are all made by adding ethanol or water as a solvent to Fe-Ni-Mo-based powders obtained by ordinary pulverization or atomization. According to this, it is manufactured by adding a grinding aid and subjecting them to a flat wrinkle treatment using an attritor or a ball mill.
このようにして製造した Fe— Ni— Mo系扁平金属軟磁性粉末は、榭脂中に扁平面 が磁性複合シートの厚さ方向に対して直角方向に配向するように分散させて磁性複 合シートを作製し、数 10MHz〜数 GHzにて電波吸収特性を有する電波吸収体、ま たは数 10kHz〜数 ΙΟΜΗζで磁気特性を有する無線通信用アンテナコアなどの高 周波用磁性材料として使用されることも知られている。  The Fe-Ni-Mo-based flat metal soft magnetic powder produced in this way is dispersed in the resin so that the flat surface is oriented in a direction perpendicular to the thickness direction of the magnetic composite sheet. And used as a high-frequency magnetic material such as a radio wave absorber having radio wave absorption characteristics at several tens of MHz to several GHz, or an antenna core for wireless communication having magnetic characteristics at several tens of kHz to several ΙΟΜΗζ. Is also known.
カゝかる従来の Fe— Ni— Mo系扁平金属軟磁性粉末を榭脂中に扁平面が磁性複 合シートの厚さ方向に対して直角方向に配向するように分散させた磁性複合シートを 電波吸収体または無線通信用アンテナコアなどの高周波用磁性材料として使用し、 その特性を高めようとすると、磁性複合シートに含まれる Fe— Ni— Mo系扁平金属軟 磁性粉末の充填密度を上げる必要がある。しかし、 Fe— Ni— Mo系扁平金属軟磁性 粉末の充填密度を上げると、隣接する Fe— Ni— Mo系扁平金属軟磁性粉末が接触 し、 Fe— Ni— Mo系扁平金属軟磁性粉末相互の絶縁を保つことが難しくなつて磁性 複合シートの抵抗率が 103 Ω cm未満に低下し、電波吸収体および高周波用磁性材 料としての特性が低下するので好ましくない。このような場合には、 Fe— Ni— Mo系 扁平金属軟磁性粉末を予め絶縁体でコーティングしておくことが好ましいことも知ら れている (特許文献 4参照)。 A magnetic composite sheet in which a conventional Fe-Ni-Mo-based flat metal soft magnetic powder is dispersed in a resin so that the flat plane is oriented in a direction perpendicular to the thickness direction of the magnetic composite sheet. If it is used as a magnetic material for high frequency such as an absorber or antenna core for wireless communication and its characteristics are to be improved, it is necessary to increase the packing density of the Fe-Ni-Mo flat metal soft magnetic powder contained in the magnetic composite sheet. is there. However, when the packing density of Fe-Ni-Mo-based flat metal soft magnetic powder is increased, adjacent Fe-Ni-Mo-based flat metal soft magnetic powders come into contact with each other, and Fe-Ni-Mo-based flat metal soft magnetic powders are in contact with each other. Since it is difficult to maintain insulation, the resistivity of the magnetic composite sheet is lowered to less than 10 3 Ωcm, and the characteristics as a radio wave absorber and a magnetic material for high frequency are deteriorated. In such a case, it is also known that it is preferable to coat the Fe—Ni—Mo flat metal soft magnetic powder with an insulator in advance (see Patent Document 4).
特許文献 1：特開平 3 - 223401号公報 Patent Document 1: Japanese Patent Laid-Open No. 3-223401
特許文献 2：特開平 3 - 232574号公報 特許文献 3：特開平 4— 78112号公報 Patent Document 2: JP-A-3-232574 Patent Document 3: Japanese Patent Laid-Open No. 4-78112
特許文献 4：特開平 4— 213803号公報  Patent Document 4: Japanese Patent Laid-Open No. 4-213803
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 一般に、金属軟磁性粉末の表面に予め絶縁体でコーティングする方法の一つとし て、金属軟磁性粉末の表面に酸化膜を形成することが知られていることから、 Fe-N i Mo系扁平金属軟磁性粉末を酸化雰囲気中で加熱することにより Fe— Ni— Mo 系扁平金属軟磁性粉末の表面に前記絶縁を保っために一定以上の厚さの酸化膜 を形成した酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末を作製することが考え られる。この場合、前記絶縁を保っために必要な酸ィ匕膜の厚みは酸ィ匕膜の抵抗率に 反比例する。しかし、 Fe— Ni— Mo系扁平金属軟磁性粉末を酸化雰囲気中で加熱 して Fe— Ni— Mo系扁平金属軟磁性粉末の表面に前記絶縁を保っために必要な 酸化膜を形成するには、 Fe— Ni— Mo系扁平金属軟磁性粉末が比較的優れた耐 食性を有することから、酸化雰囲気中でしかも比較的高温度の 300〜400°Cで加熱 しなければならな!/、。力かる高温で上記 Fe— Ni— Mo系扁平金属軟磁性粉末を加 熱すると、酸ィ匕膜として抵抗率の低い NiOが形成される。このため前記絶縁を保った めに必要な NiO酸ィ匕膜の厚みは大きくする必要があり、この厚みの大きな NiOが形 成された Fe— Ni— Mo系扁平金属軟磁性粉末は保磁力が大幅に上昇する。かかる 高保磁力を有する Fe— Ni— Mo系扁平金属軟磁性粉末を用 Vヽて作製した複合磁 性シートは電波吸収体および高周波用磁性材料としての特性は大幅に低下するの で好ましくない。 [0005] In general, as one method of coating the surface of the metal soft magnetic powder with an insulator in advance, it is known to form an oxide film on the surface of the metal soft magnetic powder. An oxide coating with a certain thickness of oxide film formed on the surface of the Fe-Ni-Mo flat metal soft magnetic powder by heating the Mo-based flat metal soft magnetic powder in an oxidizing atmosphere to maintain the insulation. It is conceivable to produce Fe-Ni-Mo-based flat metal soft magnetic powders. In this case, the thickness of the oxide film necessary for maintaining the insulation is inversely proportional to the resistivity of the oxide film. However, to heat the Fe-Ni-Mo-based flat metal soft magnetic powder in an oxidizing atmosphere to form the oxide film necessary for maintaining the insulation on the surface of the Fe-Ni-Mo-based flat metal soft magnetic powder. Because Fe-Ni-Mo-based flat metal soft magnetic powders have relatively good corrosion resistance, they must be heated in an oxidizing atmosphere and at a relatively high temperature of 300 to 400 ° C! /. When the Fe—Ni—Mo flat metal soft magnetic powder is heated at a high temperature, NiO with a low resistivity is formed as an acid film. Therefore, it is necessary to increase the thickness of the NiO oxide film necessary to maintain the insulation, and the Fe—Ni—Mo flat metal soft magnetic powder formed with this thick NiO has a coercive force. Increase significantly. A composite magnetic sheet prepared by using an Fe—Ni—Mo-based flat metal soft magnetic powder having a high coercive force is not preferable because the characteristics as a radio wave absorber and a magnetic material for high frequency are greatly deteriorated.
本発明は、上記事情に鑑みてなされたものであって、優れた電波吸収特性を有す る電波吸収体や優れた磁気特性を有する無線通信用アンテナコアなどの高周波用 磁性材料に使用される高い表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属 軟磁性粉末を提供することを目的とする。  The present invention has been made in view of the above circumstances, and is used for a high-frequency magnetic material such as a radio wave absorber having excellent radio wave absorption characteristics and an antenna core for wireless communication having excellent magnetic characteristics. An object of the present invention is to provide an Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness.
課題を解決するための手段  Means for solving the problem
[0006] そこで、本発明者らは、 Fe— Ni— Mo系扁平金属軟磁性粉末の表面に酸ィ匕膜を 被覆した酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末を作製し、この酸ィ匕膜被 覆 Fe— Ni— Mo系扁平金属軟磁性粉末を用いて電波吸収体または高周波用磁性 材料として優れた特性を有する高抵抗率および低保磁力の磁性複合シートを得るベ く研究を行った。その結果、以下の (A)から（D)のことを初めて知見した。 [0006] Therefore, the present inventors produced an Fe-Ni-Mo-based flat metal soft magnetic powder in which an Fe-Ni-Mo-based flat metal soft magnetic powder was coated with an acid-coating film on the surface. And this acid coating We conducted research to obtain high-resistivity and low-coercivity magnetic composite sheets with excellent characteristics as radio wave absorbers or high-frequency magnetic materials using coated Fe-Ni-Mo-based flat metal soft magnetic powders. As a result, the following (A) to (D) were discovered for the first time.
(A) Fe— Ni— Mo系金属軟磁性粉末を溶媒とともにアトライタやボールミルを使用 し扁平化処理して得られた平均粒径： 30〜 150 μ m、アスペクト比： 5〜500の範囲 内にある通常の Fe— Ni— Mo系扁平金属軟磁性粉末を水（一層好ましくは蒸留水） 中で煮沸すると、 Fe— Ni— Mo系扁平金属軟磁性粉末の表面に高抵抗率を有する 酸化膜が形成され、この煮沸により形成された酸ィ匕膜被覆 Fe— Ni— Mo系扁平金 属軟磁性粉末の比表面積を SRとし、表面に凹凸のない平滑な表面を有する酸ィ匕膜 被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の計算で求めた比表面積を SIとし、 SR を SIで除した比例係数を kとすると、前記煮沸により形成された高表面粗さを有する 酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末は、 SRZSI = k (ただし、 kは比例 係数であって、 k= 10〜200)の条件を満たす比表面積を有することがわかった。 一方、大気中などの通常の酸化性雰囲気中で加熱することにより作製した酸化膜 被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の比表面積を上記 SIで除した比例係数 kは 8を越えることはな力つた。これらのことから、水（一層好ましくは蒸留水）中で煮沸 することにより得られた酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の比例係 数 kは大気中で加熱することにより作製した通常の酸ィ匕膜被覆 Fe— Ni— Mo系扁平 金属軟磁性粉末の比例係数に比べて格段に大きぐしたがって、煮沸することにより 得られた酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の表面粗さは、大気中な どの通常の酸ィ匕雰囲気中で加熱することにより得られた通常の酸ィ匕膜被覆 Fe— Ni — Mo系扁平金属軟磁性粉末の表面粗さに比べて格段に大きいことがわ力つた。 (B)この煮沸することにより得られた Fe— Ni— Mo系扁平金属軟磁性粉末の表面に 形成された酸化膜は組成式： Ni Fe O (ただし、 0< x< 3)で表され、この酸化膜  (A) Average particle size obtained by flattening Fe-Ni-Mo based metal soft magnetic powder with a solvent using an attritor or ball mill: 30 to 150 μm, aspect ratio: within the range of 5 to 500 When an ordinary Fe-Ni-Mo-based flat metal soft magnetic powder is boiled in water (more preferably distilled water), an oxide film having a high resistivity is formed on the surface of the Fe-Ni-Mo-based flat metal soft magnetic powder. Oxidized film coated Fe-Ni-Mo-based flat metal soft magnetic powder formed by boiling and having a smooth surface with no irregularities on the surface with SR as the specific surface area When the specific surface area obtained by calculation of Ni—Mo-based flat metal soft magnetic powder is SI and the proportionality coefficient obtained by dividing SR by SI is k, the oxide film coated Fe— Ni—Mo-based flat metal soft magnetic powder has SRZSI = k (where k is a proportional coefficient and k = 10-2 It was found to have a specific surface area that satisfies the condition of 00). On the other hand, the proportionality factor k, which is obtained by dividing the specific surface area of the Fe-Ni-Mo flat metal soft magnetic powder coated with an oxide film by heating in a normal oxidizing atmosphere such as the atmosphere by SI, must exceed 8. Hana was strong. Therefore, the proportional coefficient k of the acid-coating-coated Fe-Ni-Mo-based flat metal soft magnetic powder obtained by boiling in water (more preferably distilled water) must be heated in the atmosphere. Oxide-coated Fe-Ni-Mo-based flattened by the conventional method The surface roughness of the metal soft magnetic powder is the same as the surface of the normal acid film-coated Fe—Ni — Mo flat metal soft magnetic powder obtained by heating in a normal acid atmosphere such as the atmosphere. Compared to that, it was much bigger than that. (B) The oxide film formed on the surface of the Fe—Ni—Mo-based flat metal soft magnetic powder obtained by boiling is represented by the composition formula: Ni Fe O (where 0 <x <3), This oxide film
3 4  3 4
は従来の酸化雰囲気中で加熱することにより Fe— Ni— Mo系扁平金属軟磁性粉末 の表面に形成された同じ厚さの NiO酸ィ匕膜と比べて抵抗率が高 、ところから、一層 抵抗率の高い酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末が得られ、この酸化 膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末に榭脂を混合し固化して得られた複合 磁性シートの抵抗率は一層向上する。 Has a higher resistivity than the NiO oxide film of the same thickness formed on the surface of Fe-Ni-Mo flat metal soft magnetic powder by heating in a conventional oxidizing atmosphere. High-rate oxide-coated Fe-Ni-Mo-based flat metal soft magnetic powder is obtained, and this oxide-coated Fe-Ni-Mo-based flat metal soft magnetic powder is a composite obtained by mixing and solidifying grease The resistivity of the magnetic sheet is further improved.
(C)また、この発明の煮沸することにより表面に Ni Fe O (ただし、 0く Xく 3)の酸  (C) In addition, by boiling the present invention, Ni Fe O (however, 0 to X 3) acid is formed on the surface.
3 4  3 4
化膜が形成された Fe— Ni— Mo系扁平金属軟磁性粉末は、煮沸温度が 100°C前 後であるから比較的低温で加熱されることから、前記絶縁を保っために必要な酸ィ匕 膜の厚みを NiO酸ィ匕膜と比べて小さくすることができ、このためにその製造過程で Fe — Ni— Mo系扁平金属軟磁性粉末の保磁力を上昇させることがない。 Fe-Ni-Mo-based flat metal soft magnetic powders with an oxidized film are heated at a relatively low temperature because the boiling temperature is around 100 ° C.匕 The thickness of the film can be made smaller than that of the NiO oxide film, so that the coercivity of the Fe-Ni-Mo-based flat metal soft magnetic powder is not increased during the manufacturing process.
(D)前記煮沸することにより得られた高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo 系扁平金属軟磁性粉末を作製するための Fe— Ni— Mo系扁平金属軟磁性粉末は 、 Ni: 60〜90%、 Mo : 0. 05〜： L 95%を含有し、残部： Feおよび不可避不純物か らなる成分組成を有することが一層好まし 、、などの知見を得たのである。  (D) The Fe-Ni-Mo-based flat metal soft magnetic powder for producing an acid-coating-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness obtained by boiling is , Ni: 60-90%, Mo: 0.05-: L 95% contained, the remainder: more preferably having a component composition consisting of Fe and inevitable impurities, etc. .
この発明は、力かる知見に基づいて成されたものであって、  This invention was made on the basis of strong knowledge,
(1)平均粒径： 30〜150 μ mおよびアスペクト比（平均粒径 Z平均厚さ）： 5〜500の Fe— Ni— Mo系扁平金属軟磁性粉末の表面に、高表面粗さを有する酸化膜被覆を 形成した高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末であ つて、  (1) Average particle size: 30 to 150 μm and aspect ratio (average particle size Z average thickness): High surface roughness on the surface of Fe-Ni-Mo based flat metal soft magnetic powder of 5 to 500 An oxide film coated Fe-Ni-Mo flat metal soft magnetic powder with high surface roughness formed with an oxide film coating,
前記高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の比表 面積を SR、  The ratio table area of the above-mentioned Fe-Ni-Mo-based flat metal soft magnetic powder coated with an oxide film having a high surface roughness is SR,
表面に凹凸のない平滑な表面を有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁 性粉末の計算で求めた比表面積を SIとすると、  When the specific surface area obtained by calculation of the Fe-Ni-Mo-based flat metal soft magnetic powder having a smooth surface with no irregularities on the surface is defined as SI,
前記 SRと SIの比力 SRZSI = k (ただし、 kは表面粗さを表現する比例係数であつ て、 k= 10〜200)の条件を満たす範囲内の比表面積を有する高表面粗さを有する 酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末である。  Specific surface force of SR and SI SRZSI = k (where k is a proportional coefficient expressing surface roughness, k = 10 to 200), and has a high surface roughness having a specific surface area within a range that satisfies the condition of This is an Fe-Ni-Mo-based flat metal soft magnetic powder coated with an acid film.
(2)前記酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末は、質量％で (以下、 % は質量％を示す）、 Ni: 60〜90%、Mo : 0. 05〜： L 95%を含有し、残部： Feおよび 不可避不純物からなる成分組成を有する Fe— Ni— Mo系扁平金属軟磁性粉末の表 面に酸化膜が形成されて ヽる粉末である前記（1)記載の高表面粗さを有する酸ィ匕膜 被覆 Fe - Ni- Mo系扁平金属軟磁性粉末であることが好ま U、。  (2) The acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder is in% by mass (hereinafter,% indicates% by mass), Ni: 60 to 90%, Mo: 0.05 to The above (1), wherein the powder is formed by forming an oxide film on the surface of a Fe-Ni-Mo-based flat metal soft magnetic powder containing 95% L and the balance: Fe and an inevitable impurity component composition. U-preferred to be a Fe-Ni-Mo-based flat metal soft magnetic powder coated with an acid film having a high surface roughness of U.
(3)前記 Fe— Ni— Mo系扁平金属軟磁性粉末の表面に形成されている酸ィ匕膜は、 Ni Fe O (ただし、 0<x< 3)である前記（1)または（2)記載の高表面粗さを有す 3 4 (3) The acid film formed on the surface of the Fe-Ni-Mo-based flat metal soft magnetic powder is: Ni Fe O (where 0 <x <3), which has the high surface roughness described in (1) or (2) 3 4
る酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末であることが好ましい。 It is preferable to use an Fe-Ni-Mo-based flat metal soft magnetic powder.
(4)平均粒径： 30〜150 μ mおよびアスペクト比（平均粒径 Z平均厚さ）： 5〜500を 有する Fe— Ni— Mo系扁平金属軟磁性粉末を水中で煮沸する前記（1)または（2) または（3)記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性 粉末の製造方法である。  (4) Boiling Fe-Ni-Mo flat metal soft magnetic powder having an average particle size of 30 to 150 μm and an aspect ratio (average particle size Z average thickness) of 5 to 500 (1) Or (2) A method for producing an acid-coating-coated Fe—Ni—Mo based flat metal soft magnetic powder having a high surface roughness according to (2) or (3).
(5)平均粒径： 30〜150 μ mおよびアスペクト比（平均粒径 Z平均厚さ）： 5〜500を 有し、かつ質量％で（以下、％は質量％を示す） Ni: 60〜90%、 Mo : 0. 05〜： L 95 %を含有し、残部: Feおよび不可避不純物力もなる成分組成を有する Fe— Ni— Mo 系扁平金属軟磁性粉末を水中で煮沸する前記（1)または (2)または (3)記載の高表 面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の製造方法である ことが好ましい。  (5) Average particle diameter: 30 to 150 μm and aspect ratio (average particle diameter Z average thickness): 5 to 500, and in mass% (hereinafter,% represents mass%) Ni: 60 to 90%, Mo: 0.05-: L 95%, the remainder: Fe and Ni—Mo-based flat metal soft magnetic powder having a component composition that also has inevitable impurity power is boiled in water (1) or The method for producing an oxide film-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness described in (2) or (3) is preferred.
(6)前記煮沸するための水は蒸留水である前記 (4)または（5)記載の高表面粗さを 有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の製造方法である。  (6) The method for producing an oxide film-coated Fe—Ni—Mo based flat metal soft magnetic powder having a high surface roughness according to the above (4) or (5), wherein the water for boiling is distilled water.
(7)前記 Fe— Ni— Mo系扁平金属軟磁性粉末を水中で煮沸する時間は、 10分から 10時間の範囲内であることが好ましい。  (7) The time for boiling the Fe—Ni—Mo-based flat metal soft magnetic powder in water is preferably in the range of 10 minutes to 10 hours.
(8)前記（1)または（2)または（3)記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の扁平面が磁性複合シートの厚さ方向に対して交差す る方向に配向して分散して 、る磁性複合シートである。  (8) The flat surface of the acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having the high surface roughness described in (1), (2) or (3) is the thickness direction of the magnetic composite sheet The magnetic composite sheet is oriented and dispersed in the direction intersecting with respect to.
(9)前記（1)または（2)または（3)記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の扁平面が磁性複合シートの厚さ方向に対して直角方 向に配向して分散して 、る磁性複合シートである。  (9) The flat surface of the acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having the high surface roughness described in (1), (2) or (3) is the thickness direction of the magnetic composite sheet The magnetic composite sheet is oriented and dispersed in a direction perpendicular to the magnetic field.
前記 (4)〜（7)記載の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属 軟磁性粉末の製造方法において、 Fe— Ni— Mo系扁平金属軟磁性粉末を煮沸す る時間は 10分から 10時間の範囲内であることが好まし 、。煮沸時間が 10分未満で あると十分な厚さの酸ィ匕膜が形成されないので好ましくなぐ一方、 10時間を越えて 煮沸すると、形成される酸化膜が厚くなり過ぎ、酸ィ匕膜が厚くなり過ぎると保磁力が増 加するようになるので好ましくな 、と 、う理由によるものである。 この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 を高密度に榭脂を混合し固化して得られた複合磁性シートの抵抗率はその表面粗さ が粗いために上昇する。その理由としては、粉末の表面に形成されている凹凸によつ て隣接する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末相互の接触面積が小 さくなり、粉末と粉末の隙間に榭脂がまんべんなく行き渡り、得られた複合磁性シート の抵抗率を上昇させるものと考えられる。 In the method for producing an oxide film-coated Fe—Ni—Mo flat metal soft magnetic powder having a high surface roughness described in (4) to (7), the Fe—Ni—Mo flat metal soft magnetic powder is boiled. The time is preferably in the range of 10 minutes to 10 hours. If the boiling time is less than 10 minutes, a sufficiently thick oxide film is not formed, which is not preferable. On the other hand, if the boiling time is longer than 10 hours, the formed oxide film becomes too thick and the oxide film becomes thick. This is because it is preferable that the coercive force is increased if it becomes too large. The resistivity of the composite magnetic sheet obtained by solidifying the oxide-coated Fe—Ni—Mo flat metal soft magnetic powder having a high surface roughness of this invention by mixing the resin with high density is that the surface roughness is Rise because it is coarse. The reason for this is that the contact area between the adjacent oxide-coated Fe-Ni-Mo flat metal soft magnetic powders is reduced due to the unevenness formed on the surface of the powder, and the gap between the powders is reduced. It is considered that fat spreads evenly and increases the resistivity of the obtained composite magnetic sheet.
[0009] この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 を製造するには、通常の市販の Fe— Ni— Mo系扁平金属軟磁性粉末を水中、特に 蒸留水中で煮沸したのち乾燥すれば良い。  In order to produce an oxide film-coated Fe—Ni—Mo based flat metal soft magnetic powder having a high surface roughness according to the present invention, an ordinary commercially available Fe—Ni—Mo based flat metal soft magnetic powder is immersed in water, In particular, it may be dried after boiling in distilled water.
また、この発明の磁性複合シートで使用する榭脂は、塩素化ポリエチレン、シリコー ン、ポリウレタン、ポリ酢酸ビュル、エチレン-酢酸ビュル共重合体、アクリロニトリル ブタジエン—スチレン榭脂 (ABS榭脂）、ポリ塩ィ匕ビュル、ポリビュルブチラール、熱 可塑性エラストマ一、 EPDM共重合ゴム（エチレン 'プロピレン共重合ゴム）、スチレン -ブタジエン系ゴム、アクリロニトリル ブタジエン系ゴムなどであり、さらにこれらをブ レンドしたものまたはブレンドし変性したものであってもよい。また、上記のいずれかの 榭脂を構成する繰り返し単位のうちから選択された二種以上の繰り返し単位を有する 榭脂又はさらにこの榭脂を変性したものであってもよい。  In addition, the resin used in the magnetic composite sheet of the present invention includes chlorinated polyethylene, silicone, polyurethane, poly (acetic acid butyl), ethylene-acetic acid butyl copolymer, acrylonitrile butadiene-styrene resin (ABS resin), poly salt Such as rubber, polybutyl butyral, thermoplastic elastomer, EPDM copolymer rubber (ethylene 'propylene copolymer rubber), styrene-butadiene rubber, acrylonitrile butadiene rubber, and blended or blended It may be denatured. Moreover, the resin which has 2 or more types of repeating units selected from the repeating unit which comprises one of the above-mentioned resin, or what modified | denatured this resin may be sufficient.
[0010] この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 において、成分組成、平均粒径、アスペクト比および比表面積を前述の如く限定した 理由を説明する。  [0010] The reason why the composition, average particle diameter, aspect ratio, and specific surface area of the oxide film-coated Fe-Ni-Mo-based flat metal soft magnetic powder having high surface roughness according to the present invention are limited as described above will be described. .
[0011] 成分組成：  [0011] Ingredient composition:
この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 を構成する Fe— Ni— Mo系扁平金属軟磁性粉末に含まれる Niの含有量を 60〜90 %に限定した理由は、 60%より少なくても 90%より多くても磁気特性が低下するから であり、この範囲は通常知られている範囲である力 この発明の高表面粗さを有する 酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末における Niの含有量は、 70〜85 %の範囲内にあることが一層好ましい。  The Ni content in the Fe-Ni-Mo-based flat metal soft magnetic powder constituting the oxide-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is reduced to 60 to 90%. The reason for the limitation is that the magnetic properties are deteriorated when it is less than 60% or more than 90%, and this range is a generally known range. More preferably, the Ni content in the film-coated Fe—Ni—Mo-based flat metal soft magnetic powder is in the range of 70 to 85%.
また、 Moが 0. 05%未満では熱処理後の徐冷により FeNi規則相の生成が過剰に なり、結晶磁気異方性定数 が負でその絶対値が大きくなり過ぎて磁気特性が低下 し、一方、 1. 95%よりも多く含有すると、 FeNi規則相の生成が不十分となり、結晶 Also, if Mo is less than 0.05%, FeNi ordered phase is excessively formed by slow cooling after heat treatment. The magnetic anisotropy constant is negative and its absolute value becomes too large, resulting in a decrease in magnetic properties. On the other hand, if it exceeds 1.95%, the formation of FeNi ordered phase becomes insufficient and the crystal
3  Three
磁気異方性定数 κが負でその絶対値力 、さくなり過ぎたり、正になつたりして、結晶 磁気異方性により扁平面内をより一層磁化容易面とする効果が不十分となり、扁平 面内の透磁率が低下するので Moの添加量を 0. 05-1. 95%に限定することが好 ましい。この発明の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁 性粉末において Moの含有量の一層好ましい範囲は 0. 5〜1. 95%であり、さらに好 ましくは 0. 8〜1. 9%である。  When the magnetic anisotropy constant κ is negative and its absolute value is too small or positive, the effect of making the flat surface easier to magnetize due to crystal magnetic anisotropy becomes insufficient. Since the in-plane magnetic permeability decreases, it is preferable to limit the amount of Mo added to 0.05-1.95%. The more preferable range of the Mo content in the Fe-Ni-Mo-based flat metal soft magnetic powder having high surface roughness according to the present invention is 0.5 to 1.95%, more preferably. Is between 0.8 and 1.9%.
残部の Feおよび不可避不純物の含有量は、 8. 05%〜39. 95%であることが好ま しく、さらに好ましくは 13. 05%〜29. 5%である。  The content of the remaining Fe and inevitable impurities is preferably 8.05% to 39.95%, more preferably 13.05% to 29.5%.
[0012] 平均粒径： [0012] Average particle size:
この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 において、 Fe— Ni— Mo系扁平金属軟磁性粉末の平均粒径が 30 mよりも小さい と、扁平ィ匕処理時の歪の導入が著しくなり、十分な磁気特性が得られないので好まし くなぐ一方、 150 /z mを超えると、シート等を作製する際の榭脂等との混練において 、粉末が折れ曲がったり、ちぎれたりして磁気特性が低下するので好ましくない。した がって、この発明の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁 性粉末に用 ヽられる Fe— Ni— Mo系扁平金属軟磁性粉末の平均粒径は 30〜 150 μ mに定めた。平均粒径の一層好ましい範囲は 35〜140 μ mである。  In the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to the present invention, when the average particle size of the Fe—Ni—Mo-based flat metal soft magnetic powder is smaller than 30 m, The introduction of strain during the glazing process becomes significant, and it is not preferable because sufficient magnetic properties cannot be obtained. It is not preferable because the magnetic properties deteriorate due to bending or tearing. Therefore, the average particle diameter of the Fe-Ni-Mo-based flat metal soft magnetic powder used for the acid-coated film Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is It was set to 30 to 150 μm. A more preferable range of the average particle diameter is 35 to 140 μm.
[0013] アスペクト比： [0013] Aspect ratio:
この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 において、 Fe— Ni— Mo系扁平金属軟磁性粉末のアスペクト比が 5より小さいと、粉 末の反磁界が大きくなり、扁平面内の透磁率が低下するので好ましくなぐ一方、ァス ぺクト比が 500よりも大きくなると、扁平ィ匕処理時の歪の導入が著しくなり、十分な磁 気特性が得られなくなるので好ましくない。したがって、この発明の高表面粗さを有す る酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末に用 ヽられる Fe— Ni— Mo系 扁平金属軟磁性粉末のアスペクト比は 5〜500に定めた。  When the aspect ratio of the Fe—Ni—Mo-based flat metal soft magnetic powder in the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is less than 5, the demagnetizing field of the powder However, when the aspect ratio is greater than 500, distortion is significantly introduced during flattening treatment, and sufficient magnetic properties are obtained. It is not preferable because it is not possible. Therefore, the aspect ratio of the Fe-Ni-Mo-based flat metal soft magnetic powder used for the oxide film-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention is 5 to 500. Determined.
比表面積： この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 の比表面積 SR、表面に凹凸のない平滑な表面を有する酸ィ匕膜被覆 Fe— Ni— Mo 系扁平金属軟磁性粉末の比表面積を SIとすると、 SR=k' SI (ただし、 kは表面粗さ を表現する比例係数であって、 k= 10〜200)の条件を満たす範囲内の比表面積を 有する。すなわち、比例係数 kは k = SRZSIで定義される係数である力 比例係数 k が大きくなるほど表面粗さが大きくなる。しかし、比例係数 kが 10未満の酸化膜被覆 F e— Ni— Mo系扁平金属軟磁性粉末では従来と比べて十分な高抵抗率を有する複 合磁性シートを作製することができないので好ましくなぐ一方、比例係数 kが 200を 越える酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末を作製するには相当時間 の煮沸を行わなければならず、現実的でな 、からである。 Specific surface area: The specific surface area SR of the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention, and the oxide film-coated Fe—Ni—Mo-based flat having a smooth surface with no irregularities on the surface If the specific surface area of the metal soft magnetic powder is SI, the specific surface area within the range that satisfies the condition of SR = k'SI (where k is a proportional coefficient expressing the surface roughness and k = 10 to 200). Have. In other words, the proportionality coefficient k increases as the force proportionality coefficient k, which is a coefficient defined by k = SRZSI, increases as the surface roughness increases. However, the oxide film-covered Fe-Ni-Mo-based flat metal soft magnetic powder having a proportionality coefficient k of less than 10 is not preferable because a composite magnetic sheet having a sufficiently high resistivity cannot be produced. This is because, in order to produce an Fe-Ni-Mo-based flat metal soft magnetic powder with an oxide film with a proportionality coefficient k exceeding 200, boiling for a considerable time must be performed, which is not practical.
この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 の比表面積を、 SR = k' SIで表現したのは、粉末の比表面積は一般に同じ表面粗さ を有する粉末であっても、粒径が小さくなるほど大きな比表面積値を示すためであり 、粒径の大小にかかわらず正確な比表面積を得るためには、粉末の比表面積を SR =k' SIと 、う式で定義することが必要であり、この定義を用いれば粉末の粒径の大 小に関係なく正確な比表面積を得られるからである。  The specific surface area of the oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to the present invention is expressed by SR = k′SI because the specific surface area of the powder generally has the same surface roughness. This is because the specific surface area of the powder is larger as the particle size is smaller, and in order to obtain an accurate specific surface area regardless of the size of the particle size, the specific surface area of the powder is set to SR = k'SI. This is because it is necessary to define by the formula, and if this definition is used, an accurate specific surface area can be obtained regardless of the particle size of the powder.
本発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末は 、平均粒径：30〜150 程度、好ましくは35〜140 111程度、アスペクト比： 5〜5 00の範囲内であってもよい。  The oxide film-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness of the present invention has an average particle size of about 30 to 150, preferably about 35 to 140 111, and an aspect ratio of 500 to 500. It may be within the range.
発明の効果  The invention's effect
[0014] この発明の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 は、アンテナ、インダクタ用として高抵抗率を有する高周波磁性材料を提供すること ができ、さらに高抵抗率を有する電波吸収体を提供することができ、電気および電子 産業にお ヽて優れた効果をもたらすものである。  [0014] The oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to the present invention can provide a high-frequency magnetic material having a high resistivity for an antenna and an inductor. It is possible to provide a radio wave absorber having a resistivity, which provides excellent effects in the electrical and electronic industries.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0015] (実施例） [0015] (Example)
合金原料を高周波溶解して Ni: 79質量％、 M0 : l質量％を含有し、残部が Feおよ び不可避不純物からなる成分組成の溶湯を作製した。ついで、これら溶湯を水アトマ ィズして Fe— Ni— Mo系金属軟磁性ァトマイズ粉末を作製した。その Fe— Ni— Mo 系金属軟磁性アトマイズ粉末を分級処理したのち、通常のアトライターにて扁平ィ匕処 理し、得られた扁平粉末を風力分級機により分級することにより、平均粒径 d: 82. 9 ^ m,平均厚さ t: l. 96 ^ m,アスペクト比（dZt) :42. 3を有する Fe— Ni— Mo系扁 平金属軟磁性粉末の原料粉末を作製した。 The alloy raw material was melted at high frequency to prepare a molten metal having a composition of Ni: 79% by mass, M 0 : 1% by mass, the balance being Fe and inevitable impurities. Then, these molten metal is used as water atom. To prepare Fe—Ni—Mo-based metal soft magnetic atomized powder. After classifying the Fe-Ni-Mo-based metal soft magnetic atomized powder, it is subjected to flattening with an ordinary attritor, and the resulting flat powder is classified with an air classifier to obtain an average particle size d A raw material powder of an Fe—Ni—Mo based flat metal soft magnetic powder having an average thickness t: l. 96 ^ m and an aspect ratio (dZt): 42.3 was prepared.
このようにして得られた Fe— Ni— Mo系扁平金属軟磁性粉末の原料粉末を蒸留水 中で表 1に示される時間煮沸することにより本発明の酸ィ匕膜被覆 Fe— Ni— Mo系扁 平金属軟磁性粉末 (以下、本発明酸化膜被覆扁平軟磁性粉末という） 1〜9および 比較酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 (以下、比較酸化膜被覆扁 平軟磁性粉末という） 1を作製した。  The raw material powder of the Fe—Ni—Mo-based flat metal soft magnetic powder obtained in this way is boiled in distilled water for the time shown in Table 1 so that the acid-coating-coated Fe—Ni—Mo-based powder of the present invention is obtained. Flat metal soft magnetic powder (hereinafter referred to as oxide-coated flat soft magnetic powder of the present invention) 1 to 9 and comparative oxide-coated Fe-Ni-Mo series flat metal soft magnetic powder (hereinafter referred to as comparative oxide-coated flat soft magnetic powder) 1) was prepared.
さらに比較のために前記 Fe— Ni— Mo系扁平金属軟磁性粉末の原料粉末を大気 中、温度： 375°Cで 1時間あるいは 6分間加熱することにより従来酸ィ匕膜被覆 Fe—Ni Mo系扁平金属軟磁性粉末 (以下、従来酸化膜被覆扁平軟磁性粉末という） 1〜2 を作製した。  For further comparison, the Fe-Ni-Mo-based flat metal soft magnetic powder material powder is heated in the atmosphere at a temperature of 375 ° C for 1 hour or 6 minutes. Flat metal soft magnetic powders (hereinafter referred to as conventional oxide film-coated flat soft magnetic powders) 1 to 2 were produced.
これら本発明酸化膜被覆扁平軟磁性粉末 1〜9、比較酸化膜被覆扁平軟磁性粉 末 1および従来酸ィ匕膜被覆扁平軟磁性粉末 1〜2についてその表面に形成されてい る酸化膜の成分組成およびその厚さを測定し、その結果を表 1に示した。  Components of oxide films formed on the surface of these oxide film-coated flat soft magnetic powders 1 to 9, the comparative oxide film-coated flat soft magnetic powder 1 and the conventional oxide film-coated flat soft magnetic powders 1-2 The composition and thickness were measured and the results are shown in Table 1.
[0016] これら本発明酸化膜被覆扁平軟磁性粉末 1〜9、比較酸化膜被覆扁平軟磁性粉 末 1および従来酸化膜被覆扁平軟磁性粉末 1〜2について粉体抵抗率および保磁 力を測定し、その結果を表 1に示した。 [0016] Measured powder resistivity and coercive force of these oxide-coated flat soft magnetic powders 1 to 9, comparative oxide-coated flat soft magnetic powder 1 and conventional oxide-coated flat soft magnetic powders 1 to 2 of the present invention The results are shown in Table 1.
その後、さらに本発明酸化膜被覆扁平軟磁性粉末 1〜9、比較酸化膜被覆扁平軟 磁性粉末 1および従来酸化膜被覆扁平軟磁性粉末 1〜2について JIS Z 8830で 規定される気体吸着法により比表面積 SRを測定し、その結果を表 1に示した。  Thereafter, the oxide film-coated flat soft magnetic powders 1 to 9, the comparative oxide film-coated flat soft magnetic powder 1 and the conventional oxide film-coated flat soft magnetic powders 1 to 2 were further compared by the gas adsorption method specified in JIS Z 8830. The surface area SR was measured and the results are shown in Table 1.
さらに、平均粒径 d: 82. 9 111、平均厚さ1;: 1. 96 ^ m,アスペクト比（dZt) :42. 3 を有する表面に凹凸のない平滑な表面を有する仮想の Fe— Ni— Mo系扁平金属軟 磁性粉末の比表面積 SIを計算で求めると、 SI = 0. 12398m2Zgとなるから、 SR/ SI=kから kの値を計算により求め、その結果を表 1に示した。 Furthermore, a hypothetical Fe—Ni having a smooth surface without unevenness on the surface having an average particle diameter d: 82.9 9 111, an average thickness 1 ;: 1. 96 ^ m, and an aspect ratio (dZt): 42.3 — When the specific surface area SI of Mo-based flat metal soft magnetic powder is calculated, SI = 0. 12398m 2 Zg. Therefore, the value of k is calculated from SR / SI = k. The results are shown in Table 1. It was.
[0017] この本発明酸化膜被覆扁平軟磁性粉末 1〜9、比較酸化膜被覆扁平軟磁性粉末 1 および従来酸ィ匕膜被覆扁平軟磁性粉末 1〜2に塩素化ポリエチレン： 15質量％を混 合し混練したのち、ロール成形することにより酸ィ匕膜被覆扁平金属軟磁性粉末の扁 平面がシート面に平行に配列した (言 、換えれば、酸化膜被覆扁平金属軟磁性粉 末の扁平面がシートの厚さ方向に対して直角方向に配列した)厚み： 0. 5mmを有す る本発明磁性複合シート 1〜9、比較磁性複合シート 1および従来磁性複合シート 1 〜2を作製し、これら磁性複合シートの抵抗率（ Ω cm)および保磁力（Oe)を測定し、 その結果を表 2に示した。なお、 lOeは約 80AZmである。 [0017] The oxide film-coated flat soft magnetic powders 1 to 9 of the present invention, and a comparative oxide film-coated flat soft magnetic powder 1 In addition, 15% by mass of chlorinated polyethylene: 1 to 2 is mixed with kneaded and soft oxide film-coated flat soft magnetic powder 1-2, and then the flat surface of the oxide film-coated flat metal soft magnetic powder is formed into a sheet by roll forming. The present invention having a thickness of 0.5 mm arranged parallel to the surface (in other words, the flat surfaces of the oxide-coated flat metal soft magnetic powder are arranged in a direction perpendicular to the thickness direction of the sheet) Magnetic composite sheets 1 to 9, comparative magnetic composite sheet 1 and conventional magnetic composite sheets 1 to 2 were prepared, and the resistivity (Ωcm) and coercive force (Oe) of these magnetic composite sheets were measured. It was shown to. LOe is about 80AZm.
[表 1] [table 1]
Figure imgf000013_0001
Figure imgf000013_0001
[0019] [表 2] [0019] [Table 2]
Figure imgf000014_0001
Figure imgf000014_0001
[0020] 表 1 2に示される結果から、 Fe— Ni— Mo系扁平金属軟磁性粉末を蒸留水中で 煮沸して得られた比例係数 kが 10 200の範囲内にある本発明酸ィ匕膜被覆扁平軟 磁性粉末 1 9はいずれも従来酸化膜被覆扁平軟磁性粉末 2よりも高抵抗率を有し かつ高比表面積および高比例係数 kを有する。また、本発明酸化膜被覆扁平軟磁 性粉末 1〜9はいずれも従来酸化膜被覆扁平軟磁性粉末 1と抵抗率が同程度である 1S 保磁力が低いことが分かる。 [0020] From the results shown in Table 12, the present invention oxide film having a proportional coefficient k in the range of 10 200 obtained by boiling Fe-Ni-Mo-based flat metal soft magnetic powder in distilled water. The coated flat soft magnetic powder 19 has a higher resistivity than the conventional oxide-coated flat soft magnetic powder 2 and has a high specific surface area and a high proportionality coefficient k. In addition, the oxide film-coated flat soft magnet It can be seen that all of the conductive powders 1 to 9 have a low 1S coercive force with the same resistivity as that of the conventional oxide-coated flat soft magnetic powder 1.
本発明酸ィ匕膜被覆扁平軟磁性粉末 1〜9で作製した本発明磁性複合シート 1〜9 は、従来酸化膜被覆扁平軟磁性粉末 2で作製した従来磁性複合シート 2に比べて高 抵抗率を有する。また、本発明酸化膜被覆扁平軟磁性粉末 1〜9で作製した本発明 磁性複合シート 1〜9は、 V、ずれも従来酸化膜被覆扁平軟磁性粉末 1で作製した従 来磁性複合シート 1に比べて抵抗率が同程度であるが、保磁力が低いことが分かる。 しかし、この発明の条件から外れた比例係数 kを有する比較酸化物被覆扁平軟磁 性粉末 1で作製した比較磁性複合シート 1は保磁力が低 、が抵抗率も 103 Ω cm未満 と低いことが分かる。 The magnetic composite sheets 1 to 9 of the present invention prepared with the oxide film-coated flat soft magnetic powders 1 to 9 have higher resistivity than the conventional magnetic composite sheet 2 of the conventional oxide film-coated flat soft magnetic powder 2 Have In addition, the magnetic composite sheets 1 to 9 of the present invention prepared with the oxide film-coated flat soft magnetic powders 1 to 9 of the present invention are the same as the conventional magnetic composite sheet 1 prepared with the conventional oxide film-coated flat soft magnetic powder 1 of V. It can be seen that the resistivity is comparable but the coercive force is low. However, the comparative magnetic composite sheet 1 produced from the comparative oxide-coated flat soft magnetic powder 1 having a proportional coefficient k that deviates from the conditions of the present invention has a low coercive force but a low resistivity of less than 10 3 Ωcm. I understand.
産業上の利用可能性 Industrial applicability
優れた電波吸収特性を有する電波吸収体や優れた磁気特性を有する無線通信用 アンテナコアなどの高周波用磁性材料に使用される高い表面粗さを有する酸ィ匕膜被 覆 Fe— Ni— Mo系扁平金属軟磁性粉末を提供できる。  Fe-Ni-Mo system with high surface roughness used for high frequency magnetic materials such as radio wave absorbers with excellent radio wave absorption characteristics and antenna cores for radio communications with excellent magnetic characteristics A flat metal soft magnetic powder can be provided.

Claims

請求の範囲 The scope of the claims
[1] 平均粒径：30〜150 111ぉょびァスぺクト比（平均粒径7平均厚さ）：5〜500を有 する Fe— Ni— Mo系扁平金属軟磁性粉末の表面に、高表面粗さを有する酸化膜被 覆が形成された高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉 末であって、  [1] Average particle size: 30-150 111-n-h-light aspect ratio (average particle size: 7 average thickness): 5-500 on the surface of Fe-Ni-Mo based flat metal soft magnetic powder, An oxide-coated Fe-Ni-Mo-based flat metal soft magnetic powder having a high surface roughness formed with an oxide film covering having a high surface roughness,
前記高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の比表 面積を SR、  The ratio table area of the above-mentioned Fe-Ni-Mo-based flat metal soft magnetic powder coated with an oxide film having a high surface roughness is SR,
表面に凹凸のない平滑な表面を有する酸ィ匕膜被覆 Fe— Ni— Mo系扁平金属軟磁 性粉末の計算で求めた比表面積を SIとすると、  When the specific surface area obtained by calculation of the Fe-Ni-Mo-based flat metal soft magnetic powder having a smooth surface with no irregularities on the surface is defined as SI,
前記 SRと SIと力 SR=k' SI (ただし、 kは表面粗さを表現する比例係数であって、 k= 10〜200)の関係を満たす範囲内の比表面積を有する高表面粗さを有する酸ィ匕 膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末。  SR, SI, and force SR = k 'SI (where k is a proportional coefficient expressing surface roughness, k = 10 to 200), and high surface roughness having a specific surface area within a range satisfying the relationship of Oxide film coating Fe-Ni-Mo-based flat metal soft magnetic powder.
[2] 前記酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末は、質量％で (以下、％は 質量0 /0を示す。）、 Ni: 60〜90%、 Mo : 0. 05〜： L 95%を含有し、残部： Feおよび 不可避不純物からなる成分組成を有する Fe— Ni— Mo系扁平金属軟磁性粉末の表 面に酸化膜が形成されている粉末である請求項 1記載の高表面粗さを有する酸化膜 被覆 Fe— Ni— Mo系扁平金属軟磁性粉末。 [2] The oxide film-coated Fe- Ni- Mo-based flat soft magnetic metal powder is a mass% (hereinafter,% represents mass 0/0.), Ni: 60~90%, Mo: 0. 05~ The powder according to claim 1, wherein the oxide film is formed on the surface of a Fe-Ni-Mo-based flat metal soft magnetic powder having a component composition comprising L: 95% L and the balance: Fe and inevitable impurities. Oxide film coated Fe-Ni-Mo based flat metal soft magnetic powder with high surface roughness.
[3] 前記 Fe— Ni— Mo系扁平金属軟磁性粉末の表面に形成されている酸ィ匕膜は、 Ni [3] The acid film formed on the surface of the Fe—Ni—Mo-based flat metal soft magnetic powder is Ni
Fe O (ただし、 0<x< 3)である請求項 1記載の高表面粗さを有する酸ィ匕膜被覆 3 4  The acid oxide film coating having high surface roughness according to claim 1, wherein Fe O (where 0 <x <3) 3 4
Fe Ni— Mo系扁平金属軟磁性粉末。  Fe Ni—Mo-based flat metal soft magnetic powder.
[4] 平均粒径： 30〜150 μ mおよびアスペクト比（平均粒径 Z平均厚さ）： 5〜500を有 する Fe— Ni— Mo系扁平金属軟磁性粉末を水中で煮沸する請求項 1記載の高表面 粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の製造方法。  [4] A Fe—Ni—Mo flat metal soft magnetic powder having an average particle size of 30 to 150 μm and an aspect ratio (average particle size Z average thickness) of 5 to 500 is boiled in water. The manufacturing method of the oxide film coating Fe-Ni-Mo type flat metal soft magnetic powder which has the high surface roughness of description.
[5] 前記 Fe— Ni— Mo系扁平金属軟磁性粉末は、質量％で (以下、％は質量％を示 す。）Ni: 60〜90%、 Mo : 0. 05〜： L 95%を含有し、残部： Feおよび不可避不純物 からなる成分組成を有する請求項 4記載の高表面粗さを有する酸化膜被覆 Fe Ni Mo系扁平金属軟磁性粉末の製造方法。  [5] The Fe—Ni—Mo-based flat metal soft magnetic powder is in mass% (hereinafter, “%” represents mass%) Ni: 60 to 90%, Mo: 0.05 to L: 95% L 5. The method for producing an oxide film-coated Fe Ni Mo-based flat metal soft magnetic powder having a high surface roughness according to claim 4, comprising: a component composition comprising: Fe and inevitable impurities.
[6] 前記 Fe— Ni— Mo系扁平金属軟磁性粉末を煮沸するための水は蒸留水である請 求項 4記載の高表面粗さを有する酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末 の製造方法。 [6] The water for boiling the Fe—Ni—Mo flat metal soft magnetic powder is distilled water. A method for producing an oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to claim 4.
[7] 前記 Fe— Ni— Mo系扁平金属軟磁性粉末を水中で煮沸する時間は、 10分から 1 0時間の範囲内である請求項 4記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— M o系扁平金属軟磁性粉末の製造方法。  7. The time required for boiling the Fe—Ni—Mo-based flat metal soft magnetic powder in water is in the range of 10 minutes to 10 hours. — Ni—Mo-based flat metal soft magnetic powder manufacturing method.
[8] 前記請求項 1、 2または 3に記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo 系扁平金属軟磁性粉末と榭脂とかなる磁性複合シートであって、前記酸化膜被覆 F e— Ni— Mo系扁平金属軟磁性粉末の扁平面が前記磁性複合シートの厚さ方向に 対して交差するように配向して分散して 、る磁性複合シート。  [8] A magnetic composite sheet comprising an acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to claim 1, 2 or 3, and a resin, wherein the oxidation Film-coated Fe-Ni-Mo-based flat metal soft magnetic powder is a magnetic composite sheet that is oriented and dispersed so that the flat surface intersects the thickness direction of the magnetic composite sheet.
[9] 前記請求項 1、 2または 3に記載の高表面粗さを有する酸ィ匕膜被覆 Fe— Ni— Mo 系扁平金属軟磁性粉末と榭脂とからなる磁性複合シートであって、前記酸化膜被覆 Fe— Ni— Mo系扁平金属軟磁性粉末の扁平面が磁性複合シートの厚さ方向に対し て直角方向に配向して分散して 、る磁性複合シート。  [9] A magnetic composite sheet comprising an acid-coating-coated Fe—Ni—Mo-based flat metal soft magnetic powder having a high surface roughness according to claim 1, 2 or 3, and a resin. A magnetic composite sheet in which a flat surface of an oxide-coated Fe—Ni—Mo-based flat metal soft magnetic powder is oriented and dispersed in a direction perpendicular to the thickness direction of the magnetic composite sheet.
PCT/JP2005/023359 2004-12-21 2005-12-20 OXIDE FILM COATED Fe-Ni-Mo BASED FLAT METAL SOFT MAGNETIC POWDER HAVING HIGH SURFACE ROUGHNESS AND METHOD FOR PRODUCTION THEREOF WO2006068136A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004369372A JP2006179576A (en) 2004-12-21 2004-12-21 OXIDE FILM-COVERED Fe-Ni-Mo FLAT METAL SOFT MAGNETIC POWDER AND ITS MANUFACTURING METHOD HAVING HIGH SURFACE FINISH.
JP2004-369372 2004-12-21

Publications (1)

Publication Number Publication Date
WO2006068136A1 true WO2006068136A1 (en) 2006-06-29

Family

ID=36601736

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/023359 WO2006068136A1 (en) 2004-12-21 2005-12-20 OXIDE FILM COATED Fe-Ni-Mo BASED FLAT METAL SOFT MAGNETIC POWDER HAVING HIGH SURFACE ROUGHNESS AND METHOD FOR PRODUCTION THEREOF

Country Status (2)

Country Link
JP (1) JP2006179576A (en)
WO (1) WO2006068136A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105436498B (en) * 2015-11-18 2017-12-01 山东大学 A kind of porous nickel carbon composite nano-microsphere electromagnetic wave absorbent material and preparation method and application
JP2023079827A (en) * 2021-11-29 2023-06-08 Tdk株式会社 Soft-magnetic metal powder, magnetic powder core, magnetic component and electronic appliance

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5638402A (en) * 1979-09-05 1981-04-13 Tdk Corp High density sintered magnetic body and its manufacture
WO2002008129A1 (en) * 2000-07-26 2002-01-31 Heraeus Tenevo Ag Method for the vitrification of a porous soot body
WO2003015109A1 (en) * 2001-08-09 2003-02-20 The Circle For The Promotion Of Science And Engineering Composite magnetic material prepared by compression forming of ferrite-coated metal particles and method for preparation thereof
JP2003086415A (en) * 2001-09-12 2003-03-20 Aisin Seiki Co Ltd Soft magnetic particles for motor or electromagnetic actuator, method for producing soft magnetic particles for motor or electromagnetic actuator, soft magnetic molded article for motor or electromagnetic actuator, method for producing soft magnetic molded article for motor or electromagnetic actuator
JP2003332114A (en) * 2002-05-09 2003-11-21 Mitsubishi Materials Corp Bonded soft magnetic body with excellent mechanical strength and cavitation damage resistance at room temperature and high temperature and its fabricating method
JP2004039703A (en) * 2002-06-28 2004-02-05 Tdk Corp Electromagnetic wave absorption sheet and its manufacturing metod
JP2005264317A (en) * 2003-08-05 2005-09-29 Mitsubishi Materials Corp Fe-Ni-Mo-based flat metal soft magnetic powder and magnetic composite material including the soft magnetic powder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5638402A (en) * 1979-09-05 1981-04-13 Tdk Corp High density sintered magnetic body and its manufacture
WO2002008129A1 (en) * 2000-07-26 2002-01-31 Heraeus Tenevo Ag Method for the vitrification of a porous soot body
WO2003015109A1 (en) * 2001-08-09 2003-02-20 The Circle For The Promotion Of Science And Engineering Composite magnetic material prepared by compression forming of ferrite-coated metal particles and method for preparation thereof
JP2003086415A (en) * 2001-09-12 2003-03-20 Aisin Seiki Co Ltd Soft magnetic particles for motor or electromagnetic actuator, method for producing soft magnetic particles for motor or electromagnetic actuator, soft magnetic molded article for motor or electromagnetic actuator, method for producing soft magnetic molded article for motor or electromagnetic actuator
JP2003332114A (en) * 2002-05-09 2003-11-21 Mitsubishi Materials Corp Bonded soft magnetic body with excellent mechanical strength and cavitation damage resistance at room temperature and high temperature and its fabricating method
JP2004039703A (en) * 2002-06-28 2004-02-05 Tdk Corp Electromagnetic wave absorption sheet and its manufacturing metod
JP2005264317A (en) * 2003-08-05 2005-09-29 Mitsubishi Materials Corp Fe-Ni-Mo-based flat metal soft magnetic powder and magnetic composite material including the soft magnetic powder

Also Published As

Publication number Publication date
JP2006179576A (en) 2006-07-06

Similar Documents

Publication Publication Date Title
EP4001449B1 (en) Fe-based nanocrystalline alloy powder, magnetic component, and dust core
TWI535861B (en) Alloy composition, fe-based nano-crystalline alloy and forming method of the same and magnetic component
CN101636515B (en) Soft magnetic alloy, magnetic parts using the soft magnetic alloy, and their manufacturing method
TWI626666B (en) Soft magnetic alloy and magnetic parts
EP2482291B1 (en) Magnetic powder material and low-loss composite magnetic material containing same
TWI697571B (en) Soft magnetic alloys and magnetic parts
CN108376598B (en) Soft magnetic alloy and magnetic component
CN110225801A (en) Soft magnetic powder, Fe Based Nanocrystalline Alloys powder, magnetic part and compressed-core
JP2004349585A (en) Method of manufacturing dust core and nanocrystalline magnetic powder
CN111801752B (en) Magnetic core, method for manufacturing the same, and coil component
TWI636143B (en) Soft magnetic alloy and magnetic parts
US7622012B2 (en) Flat soft magnetic metal powder and composite magnetic material including the soft magnetic metal powder
CN108461245B (en) Soft magnetic alloy and magnetic component
TW201817896A (en) Soft magnetic alloy and magnetic device
TWI685004B (en) Soft magnetic alloy and magnetic parts
TW202000945A (en) Soft magnetic alloy and magnetic device
CN105702410A (en) Method for preparing soft magnetic powder core
WO2005011899A1 (en) Fe-Ni-Mo FLAKY METAL SOFT MAGNETIC POWDER AND MAGNETIC COMPOSITE MATERIAL CONTAINING SOFT MAGNETIC POWDER
TWI683011B (en) Soft magnetic alloy and magnetic parts
TW201925493A (en) Soft magnetic alloy and magnetic component
WO2006068136A1 (en) OXIDE FILM COATED Fe-Ni-Mo BASED FLAT METAL SOFT MAGNETIC POWDER HAVING HIGH SURFACE ROUGHNESS AND METHOD FOR PRODUCTION THEREOF
JP2625485B2 (en) Electromagnetic shielding material
JP2006219714A (en) Fe-Ni-(Nb, V, Ta) BASED FLAT METAL SOFT MAGNETIC POWDER AND MAGNETIC COMPOSITE MATERIAL COMPRISING THE SOFT MAGNETIC POWDER
JPH03125404A (en) Treatment of magnetic ribbon or magnetic core
JP2006219700A (en) Fe-Ni-Mo-(Nb, V, Ta) BASED FLAT METAL SOFT MAGNETIC POWDER AND MAGNETIC COMPOSITE MATERIAL COMPRISING THE SOFT MAGNETIC POWDER

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05819812

Country of ref document: EP

Kind code of ref document: A1

WWW Wipo information: withdrawn in national office

Ref document number: 5819812

Country of ref document: EP