JP2019104954A - Metal element-containing powder, and molded body - Google Patents

Abstract

To provide a metal element-containing powder suitable for the production of a molded body having a reduced magnetic loss, and a molded body containing the metal element-containing powder.SOLUTION: Provided is a metal element-containing powder comprising: metal element-containing particles; and a coating compound covering the metal element-containing particles, and the coating compound includes at least one kind of a silanol group-compound and an organic phosphoric compound.SELECTED DRAWING: None

Description

  The present invention relates to a metal element-containing powder and a molded body.

  The metal element-containing powder containing a metal powder is used as a raw material of various industrial products such as an inductor, an electromagnetic wave shield, or a bond magnet according to various physical properties of the metal powder (see Patent Document 1 below).

Unexamined-Japanese-Patent No. 10-154613 gazette

  Magnetic powder is used for a magnetic core with which high frequency coils, such as a high frequency transformer, a reactor, a thyristor valve, a noise filter, and a choke coil, are provided, for example. The energy lost in the magnetic material in which alternating current magnetic flux is flowing is called magnetic loss. The magnetic core of the high frequency coil is required to have a small magnetic loss and a high magnetic flux density even in a high frequency region.

  The magnetic loss mainly consists of eddy current loss and hysteresis loss. Eddy current loss is closely related to the specific resistance of the magnetic core. The hysteresis loss is greatly affected by the distortion in the magnetic powder produced in the manufacturing process and subsequent processes of the magnetic powder. Eddy current loss is proportional to the square of the frequency of the AC electrical signal. Therefore, in order to reduce the magnetic loss in the high frequency region, it is important to reduce the eddy current loss. In order to reduce the eddy current loss, it is necessary to confine the eddy current to a small area. In order to confine the eddy current in a small area, it is necessary to form a magnetic core by compressing fine magnetic powder, and to isolate individual particles constituting the magnetic powder from one another.

  If the insulation between the individual particles making up the magnetic powder is insufficient, the eddy current losses are large. In order to improve the insulation, it is conceivable to coat individual particles constituting the magnetic powder with an insulation layer. However, when the insulating layer is thick, the ratio of the magnetic powder to the magnetic core decreases. As a result, the magnetic flux density of the core decreases. In addition, if the ratio of magnetic powder in the magnetic core is increased by compression molding of magnetic powder under high pressure in order to increase the magnetic flux density, distortion generated in the magnetic powder at the time of molding becomes large. As a result, hysteresis loss increases and magnetic loss increases.

  As described above, it is important to increase the specific resistance of the magnetic core without reducing the ratio of the magnetic powder to the magnetic core in the production of the magnetic core having a small magnetic loss. In order to increase the specific resistance of the magnetic core, it is necessary to cover the magnetic powder with an insulating layer which is thin and excellent in insulation.

  An object of the present invention is to provide a metal element-containing powder suitable for producing a compact having a small magnetic loss, and a molded body provided with the metal element-containing powder.

  The metal element-containing powder according to one aspect of the present invention comprises a metal element-containing particle and a coating compound covering the metal element-containing particle, wherein the coating compound is a compound having a silanol group, and an organic phosphoric acid compound Includes at least one.

  In the metal element-containing powder according to one aspect of the present invention, the compound having a silanol group may be a hydrolyzate of alkoxysilane.

  In the metal element-containing powder according to one aspect of the present invention, the organic phosphoric acid compound may have an alkyl group.

  In the metal element-containing powder according to one aspect of the present invention, the compound having a silanol group may have a glycidyl group.

  In the metal element-containing powder according to one aspect of the present invention, the compound having a silanol group may have an alkyl group.

  In the metal element-containing powder according to one aspect of the present invention, the compound having a silanol group may have a methacryloyl group.

  In the metal element-containing powder according to one aspect of the present invention, the compound having a silanol group may have an amino group.

  In the metal element-containing powder according to one aspect of the present invention, the content of the coating compound may be 0.001% by mass or more and 1.00% by mass or less.

  The metal element-containing powder according to one aspect of the present invention may be used for a magnetic core.

  The molded object concerning one side of the present invention is provided with the above-mentioned metallic element content powder.

  ADVANTAGE OF THE INVENTION According to this invention, the metal element containing powder suitable for preparation of the molded object with a small magnetic loss, and the molded object provided with the said metal element containing powder are provided.

  Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiment.

<Overview of powder containing metal element>
The metal element-containing powder according to the present embodiment includes a plurality (multiple) of metal element-containing particles and a coating compound covering individual metal element-containing particles. That is, each of the plurality of particles constituting the metal element-containing powder has the metal element-containing particles and the coating compound covering the surface of the metal element-containing particles. For example, a layer containing a coating compound (such as a layer consisting of a coating compound) may cover the surface of the metal element-containing particle. The coating compound contains at least one of a compound having a silanol group and an organic phosphoric acid compound. The coating compound may be chemically adsorbed or bound to the surface of the metal element-containing particle.

  Both compounds having silanol groups and organic phosphoric acid compounds are superior in insulation to general surface treatment agents for metals (for example, inorganic phosphates and the like), and thus coating compounds containing these are also insulating Excellent in quality. By covering the metal element-containing particles with the coating compound, individual metal element-containing particles constituting the metal element-containing powder are mutually insulated by the coating compound. As a result, the eddy current loss of the compact formed of the metal element-containing powder is small, and the magnetic loss of the compact is small. In addition, since the coating compound is excellent in insulation, even when the thickness of the layer of the coating compound is thin, the metal element-containing particles can be sufficiently insulated with each other by the thin layer of the coating compound. As a result, the content of the metal element-containing particles in the compact can be increased by reducing the ratio of the coating compound to the compact, and the magnetic flux density of the compact can be increased.

  The coating compound may cover at least a part or the whole of the surface of the metal element-containing particle. The content of the coating compound in the metal element-containing powder may be 0.001% by mass or more and 1.00% by mass or less. When the content of the coating compound is within the above range, the content of the metal element-containing particles in the molded body tends to be large, and the magnetic flux density of the molded body tends to be high.

  The average particle size of the metal element-containing particles may be, for example, 1 μm or more and 300 μm or less. The mean particle size may, for example, be measured by means of a particle size distribution meter. Although the shape of each particle which comprises metal element containing powder is not limited, For example, it may be spherical shape, flat shape, prismatic shape, or needle shape. Since the thickness of the coating compound is very small compared to the particle size of the metal element-containing particle, the average particle size of the entire metal element-containing particle covered with the coating compound is the metal element-containing particle not covered with the coating compound Approximately equal to the average particle size.

  Depending on the composition or combination of the metal element-containing particles contained in the metal element-containing powder, various physical properties such as electromagnetic properties or thermal conductivity of the metal element-containing powder can be freely controlled, and the metal element-containing powder can be various industrial products Or it can be used for those raw materials. Industrial products manufactured using the metal element-containing powder may be, for example, automobiles, medical devices, electronic devices, electric devices, information communication devices, home appliances, audio devices, and general industrial devices. The metal element-containing powder may be used, for example, in a magnetic core. When the metal element-containing powder contains soft magnetic powder such as an Fe-Si-Cr alloy or ferrite as the metal element-containing particle, the metal element-containing powder is the above-mentioned inductor (for example, EMI filter) or transformer material (for example, magnetic core) May be used as When the metal element-containing powder contains a permanent magnet as the metal element-containing particle, the metal element-containing powder may be used as a raw material of a bonded magnet. When the metal element-containing powder contains iron and copper as the metal element-containing particles, a compact (for example, a sheet) formed of the metal element-containing powder may be used as an electromagnetic wave shield.

<Composition of Metal Element Containing Powder>
(Coating compound)
The coating compound may include a compound having a silanol group. The coating compound may comprise an organophosphate compound. The coating compound may include a compound having a silanol group, and an organic phosphoric acid compound.

[Compound having a silanol group]
Examples of compounds having a silanol group include alkylsilane compounds, epoxysilane compounds, aminosilane compounds, cationic silane compounds, vinylsilane compounds, acrylsilane compounds, mercaptosilane compounds, and composite compounds of these compounds. And at least one selected from the group consisting of The compound having a silanol group may be a hydrolyzate of alkoxysilane.

  The compound having a silanol group may have at least one functional group selected from the group consisting of glycidyl group, alkyl group, methacryloyl group, and amino group at the end of the compound (molecule). The end of a compound may be the end of a molecular chain or the end of a side chain possessed by a molecule.

  When the compound having a silanol group has a glycidyl group, the compound having a silanol group is contained in the formed body via the glycidyl group when forming a formed body from a mixture (compound) of a metal element-containing powder and a resin. And easy to bond with resin. As a result, the mechanical strength of the molded body tends to be high.

  When the compound having a silanol group has an alkyl group, the individual particles constituting the metal element-containing powder are difficult to bond with each other, and the metal element-containing powder and the resin constituting the molded body are difficult to bond with each other. That is, the individual particles constituting the metal element-containing powder are easily slipped with each other, and the metal element-containing powder and the resin constituting the molded body are easily slipped with each other. Therefore, when forming a molded product, the metal element-containing powder is likely to be densely filled in the molded product, and the content of the metal element-containing powder in the molded product tends to be large. As a result, the magnetic flux density of the molded body tends to be high. In addition, since the individual particles constituting the metal element-containing powder are difficult to bond with each other, the flowability of the paste prepared using the metal element-containing powder tends to be high. When individual particles constituting the metal element-containing powder do not easily bond to each other, and the metal element-containing powder and the resin forming the molded product do not easily bond to each other, in a mixture (compound) of the metal element-containing powder and the resin, Since individual metal element-containing particles are easily oriented along the external magnetic field, a bonded magnet having excellent magnetic properties can be easily manufactured from a compound.

  When the compound having a silanol group has a methacryloyl group, when forming a formed body, the compound having a silanol group easily bonds to the resin contained in the formed body via the methacryloyl group. As a result, the mechanical strength of the molded body tends to be high.

  When the compound having a silanol group has an amino group, when forming a molded article, the compound having a silanol group easily bonds to the resin contained in the molded article via the amino group. As a result, the mechanical strength of the molded body tends to be high.

  The compound having a silanol group is, for example, vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3 Glycidoxypropylmethyldimethoxysilane (KBM-402), 3-glycidoxypropyltrimethoxysilane (KBM-403), p-styryltrimethoxysilane (KBM-1403), 3-methacryloxypropylmethyldimethoxysilane KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropyltriethoxysilane (KBE-503), 3- Akri Xypropyltrimethoxysilane (KBM-5103), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane KBM-603), 3-aminopropyltrimethoxysilane (KBM-903), 3-aminopropyltriethoxysilane (KBE-903), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573), hydrochloride of N-vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane (KBM-575), Tris- (trimethoxysilylpropyl) isocyanurate (KBM 9659), 3-ureidopropyltrialkoxysilane (KBE-585), 3-mercaptopropylmethyldimethoxysilane (KBM-802), 3-mercaptopropyltrimethoxysilane (KBM-803), 3-isocyanatopropyltriethoxysilane (KBD) KBM-9007), octenyltrimethoxysilane (KBM-1083), glycidoxyoctyltrimethoxysilane (KBM-4803), methacryloxyoctyltrimethoxysilane (KBM-5803), methyltrimethoxysilane (KBM-13) Methyltriethoxysilane (KBE-13), dimethyldimethoxysilane (KBM-22), dimethyldiethoxysilane (KBE-22), phenyltrimethoxysilane (KBM-103), phenyltrietoxy Sisilane (KBE-103), n-propyltrimethoxysilane (KBM-3033), n-propyltriethoxysilane (KBE-3033), hexyltrimethoxysilane (KBM-3063), hexyltriethoxysilane (KBE-3063) , Octyltriethoxysilane (KBE-3083), decyltrimethoxysilane (KBM-3103C), 1,6- (trimethoxysilyl) hexane (KBM-3066), trifluoropropyltrimethoxysilane (KBM-7103), hexa It may be at least one selected from the group consisting of methyldisilazane (SZ-31) and hydrolyzable group-containing siloxane (KPN-3504) (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.). The compound having a silanol group may be a silicone alkoxy oligomer (silicone oligomer having an alkoxy group). The silicone alkoxy oligomer may have at least one alkoxy group of methoxy group and ethoxy group. The silicone alkoxy oligomer may have at least one organic substituent selected from the group consisting of an epoxy group, a methyl group, a mercapto group, an acryloyl group, a methacryloyl group, a vinyl group, and a phenyl group. Examples of silicone alkoxy oligomers include, for example, KR-517, X-41-1059A, X-24-9590, KR-516, X-41-1805, X-41-1818, X-41-1810, KR-513, X -40-9296, KR-511, KC-89S, KR-515, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, KR It may be at least one selected from the group consisting of -510, KR-9218, and KR-213 (all trade names of Shin-Etsu Chemical Co., Ltd.).

  The coating compound may contain one of the above-mentioned compounds as a compound having a silanol group. The coating compound may contain two or more of the above-mentioned compounds as a compound having a silanol group.

[Organic phosphoric acid compound]
The organic phosphoric acid compound may be, for example, an acidic phosphoric acid ester. The organic phosphoric acid compound may have an alkyl group. When the organic phosphoric acid compound has an alkyl group, the individual particles constituting the metal element-containing powder are difficult to bond to each other, and the metal element-containing powder to form a molded product and the resin do not easily bond to each other. That is, the individual particles constituting the metal element-containing powder are easily slipped with each other, and the metal element-containing powder and the resin constituting the molded body are easily slipped with each other. Therefore, when forming a molded product, the metal element-containing powder is likely to be densely filled in the molded product, and the content of the metal element-containing powder in the molded product tends to be large. As a result, the magnetic flux density of the molded body tends to be high. When individual particles constituting the metal element-containing powder do not easily bond to each other, and the metal element-containing powder and the resin forming the molded product do not easily bond to each other, in a mixture (compound) of the metal element-containing powder and the resin, Since individual metal element-containing particles are easily oriented along the external magnetic field, a bonded magnet having excellent magnetic properties can be easily manufactured from a compound.

  The organic phosphoric acid compounds are, for example, ethyl acid phosphate (JP-502), butyl acid phosphate (JP-504), dibutyl pyrophosphate (JP-504A), butoxyethyl acid phosphate (JP-506AH), 2-ethylhexyl acid phosphate (JP-508), alkyl (C12, C14, C16, C18) acid phosphate (JP-512), isotridecyl acid phosphate (JP-513), oleyl acid phosphate (JP-518-O), tetracosyl acid Phosphate (JP-524R), ethylene glycol acid phosphate (EGAP), 2-hydroxyethyl methacrylate acid phosphate (JPA-514), dibutyl phosphate (DBP), and Bis (2-ethylhexyl) phosphate (LB-58) (or, Johoku Chemical Co., Ltd.) may be at least one selected from the group consisting of.

  The coating compound may contain one of the above-mentioned organic phosphoric acid compounds. The coating compound may contain two or more of the above-mentioned organic phosphoric acid compounds.

(Metal element containing particles)
The metal element-containing particle may contain, for example, at least one selected from the group consisting of a single metal, an alloy and a metal compound. The metal element-containing particles may be made of, for example, at least one selected from the group consisting of simple metals, alloys, and metal compounds. The alloy may include at least one selected from the group consisting of solid solution, eutectic and intermetallic compounds. The alloy may be, for example, stainless steel (Fe-Cr based alloy, Fe-Ni-Cr based alloy, etc.). The metal compound may be, for example, an oxide such as ferrite. The metal element-containing particles may contain one or more metal elements. The metal element contained in the metal element-containing particle may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element. The metal element contained in the metal element-containing powder is, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), praseodymium (Pr), neodymium (Nd), samarium (Sm) and dysprosium ( It may be at least one selected from the group consisting of Dy). The metal element-containing particle may contain an element other than the metal element. The metal element-containing particles may contain, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The metal element-containing particles may be magnetic powder. The metal element-containing particles may be a soft magnetic alloy or a ferromagnetic alloy. The metal element-containing particles are, for example, Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Cu-Ni alloys (Permalloy), Fe-Co alloys (Permendur), Fe-Cr-Si alloy (electromagnetic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), Al-Ni-Co alloy It may be at least one selected from the group consisting of (alnico magnet) and ferrite. The ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite. The metal element-containing particles may be a copper alloy such as a Cu-Sn alloy, a Cu-Sn-P alloy, a Cu-Ni alloy, or a Cu-Be alloy. The metal element-containing particle may contain one of the above elements and compositions, and may contain a plurality of the above elements and compositions.

  The metal element-containing particles may be Fe alone. The metal element-containing particles may be an iron-containing alloy (Fe-based alloy). The Fe-based alloy may be, for example, an Fe-Si-Cr-based alloy or an Nd-Fe-B-based alloy. When the metal element-containing powder contains at least one of Fe and Fe-based alloy as metal element-containing particles, it is easy to produce a molded body having a high space factor and excellent in magnetic characteristics from the metal element-containing powder . The metal element-containing particles may be Fe amorphous alloy. Commercial products of Fe amorphous alloy powder include, for example, AW2-08, KUAMET-6B2 (all trade names of Epson Atomics Co., Ltd., DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV 49). , DAP 410L, DAP 430L, DAP HYB series (all trade names of Daido Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (all trade names of Kobe Steel, Ltd.) Or at least one of them may be used.

  The shape of the metal element-containing particle is not particularly limited. The individual metal element-containing particles may be, for example, spherical, flat or needle-like. The metal element-containing powder may contain plural types of metal element-containing particles having different average particle sizes.

<Method of producing metal element-containing powder>
The method for producing the metal element-containing powder is not particularly limited as long as at least a part or the whole of the surface of the metal element-containing particle can be covered with the coating compound. The metal element-containing powder may be produced, for example, by the following method.

  First, a surface treatment liquid is obtained by dissolving a coating compound in a solvent. The solvent is not particularly limited as long as it is a liquid that dissolves the coating compound. The solvent may be at least one of water and ethanol.

  Subsequently, a mixture is obtained by mixing the metal element-containing particles with the surface treatment liquid. The content of the surface treatment liquid in the mixture may be 5 parts by mass or more and 10 parts by mass or less with respect to the total mass (100 parts by mass) of the metal element-containing particles contained in the mixture. When the content of the surface treatment liquid is less than 5 parts by mass, the surface of the metal element-containing particle is hardly covered with the coating compound. When the content of the surface treatment liquid exceeds 10 parts by mass, when the metal element-containing particles and the surface treatment liquid are mixed, aggregates of the metal element-containing particles are easily generated. As a result, it is difficult for the surface of the metal element-containing particles to be uniformly covered with the coating compound. When the content of the surface treatment liquid is within the above range, the surface of the metal element-containing particle is likely to be sufficiently and uniformly covered with the coating compound. As a result, the insulation of the metal element-containing powder can be easily improved.

  The metal element-containing powder is obtained by sufficiently removing the solvent from the above mixture. With the removal of the solvent, the coating compound contained in the surface treatment liquid adheres to the surface of the metal element-containing particles. The coating compound may be attached to the entire surface of the metal element-containing particle, or may be attached to only a part of the surface of the metal element-containing particle. The method of removing the solvent from the mixture is not particularly limited. For example, the solvent can be removed from the mixture by drying the mixture. The drying temperature may be 50 ° C. or more and 200 ° C. or less. If the drying temperature is less than 50 ° C., drying tends to be insufficient, and the coating compound is less likely to adhere to the surface of the metal element-containing particles. When the drying temperature exceeds 200 ° C., the metal element-containing powder is easily oxidized. When the drying temperature is in the above range, the coating compound easily adheres to the surface of the metal element-containing particles, and the metal element-containing powder is not easily oxidized. As a result, the insulation of the metal element-containing powder can be easily improved. When the coating compound contains an organic phosphoric acid compound, the organic phosphoric acid compound attached to the surface of the metal element-containing particles becomes an inorganic film by drying the mixture at a drying temperature of 150 ° C. or higher. As a result, the insulation of the metal element-containing powder is likely to be improved, and the voltage resistance of the molded article is likely to be improved.

  The metal-element-containing powder may be produced by directly mixing the metal-element-containing particles and the coating compound to adhere the coating compound to the surface of the metal-element-containing particles.

<Compound>
The compound according to the present embodiment includes the metal element-containing powder and a resin composition. The resin composition may cover at least a part or the whole of the individual particles constituting the metal element-containing powder. The resin composition may adhere to the surface of the individual particles that make up the metal element-containing powder. The resin composition may be attached to the entire surface of the particle or may be attached to only a part of the surface of the particle. The compound may comprise an uncured resin composition and a metal element-containing powder. The compound may comprise a semi-cured product of the resin composition (for example, a B-stage resin composition) and a metal element-containing powder. The compound may be a powder (compound powder).

(Resin composition)
The resin composition contains at least a resin. The resin composition is a component that may include a resin, a curing agent, a curing accelerator, and an additive, and the remaining components (nonvolatile) excluding the organic solvent and the metal element-containing powder (metal element-containing particles and coating compound) Component). The additive is a component of the resin composition except the resin, the curing agent and the curing accelerator. The additive is, for example, a coupling agent or a flame retardant. The resin composition may contain a wax as an additive. As described below, the compound may be formed from the metal element-containing powder and the resin composition.

  The resin composition has a function of a metal element-containing powder as a binder and imparts mechanical strength to a molded body formed from a compound. For example, when the compound is molded at a high pressure using a mold, the resin composition contained in the compound is filled in between the particles constituting the metal element-containing powder to bind the particles to one another. By curing the resin composition in the molded body, the cured product of the resin composition binds particles forming the metal element-containing powder more firmly, and the mechanical strength of the molded body is improved.

  The resin composition may contain a thermosetting resin. The thermosetting resin may be, for example, at least one selected from the group consisting of an epoxy resin, a phenol resin, and a polyamideimide resin. If the resin composition comprises both an epoxy resin and a phenolic resin, the phenolic resin may function as a curing agent for the epoxy resin. The resin composition may contain a thermoplastic resin. The thermoplastic resin may be, for example, at least one selected from the group consisting of acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin composition may contain both a thermosetting resin and a thermoplastic resin. The resin composition may contain a silicone resin.

  The content of the resin composition in the compound may be 0.2 to 10% by mass, more preferably 4 to 6 based on the mass of the entire compound (the total of the mass of the metal element-containing powder and the resin composition). It may be mass%.

  It is preferable that the resin composition contains an epoxy resin, since the epoxy resin is excellent in fluidity among thermosetting resins. The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. Among epoxy resins, crystalline epoxy resins are preferred. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity.

  The epoxy resin is, for example, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenol Copolymerized epoxy resin, epoxy compound of aralkyl type phenol resin, bisphenol type epoxy resin, glycidyl ether type epoxy resin of alcohols, glycidyl ether type epoxy resin of paraxylylene and / or metaxylylene modified phenolic resin, terpene modified phenolic resin Of glycidyl ether type epoxy resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenolic resin, naphthalene Containing phenolic resin glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic type epoxy resin, halogenated phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, hydroquinone type epoxy It may be at least one selected from the group consisting of a resin, a trimethylolpropane type epoxy resin, and a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid.

  The crystalline epoxy resin (highly crystalline epoxy resin) may be, for example, at least one selected from the group consisting of a hydroquinone epoxy resin, a bisphenol epoxy resin, a thioether epoxy resin, and a biphenyl epoxy resin. Commercial products of crystalline epoxy resin include, for example, Epiclon 860, Epiclon 1050, Epiclon 1055, Epiclon 2050, Epiclon 3050, Epiclon 4050, Epiclon 7050, Epiclon HM-091, Epiclon HM-101, Epiclon N-730A, Epiclon N -740, epiclone N-770, epiclone N-775, epiclone N-865, epiclone HP-4032D, epiclone HP-7200L, epiclone HP-7200, epiclone HP-7200 H, epiclone HP-7200 HH, epiclone HP-7200 HHH, epiclone HP -4700, Epiclon HP-4710, Epiclon HP-4770, Epiclon HP-5000, Epiclon HP-6000, and N500P-2 (above, Trade name of IC Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000-L , NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (Above, trade name of Nippon Kayaku Co., Ltd.), YX-4000, YX-4000H, YL4121H, and YX-8800 (above, trade name of Mitsubishi Chemical Co., Ltd.) You may

  The resin composition may contain one of the above epoxy resins. The resin composition may contain a plurality of epoxy resins among the above. It is preferable that a resin composition contains both a biphenyl type epoxy resin (YX-4000H) and an ortho cresol novolak type epoxy resin (N500P-2) among said epoxy resins.

  The curing agent is classified into a curing agent which cures an epoxy resin in a range from low temperature to room temperature, and a heat curing type curing agent which cures an epoxy resin with heating. Examples of curing agents that cure epoxy resins in the range from low temperature to room temperature include aliphatic polyamines, polyaminoamides, polymercaptans and the like. The heat-curable curing agent is, for example, an aromatic polyamine, an acid anhydride, a phenol novolac resin, and dicyandiamide (DICY).

  When a curing agent for curing the epoxy resin in the range from low temperature to room temperature is used, the glass transition point of the cured product of the epoxy resin is low, and the cured product of the epoxy resin tends to be soft. As a result, the molded body formed from the compound also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the molded product, the curing agent may preferably be a heat-curing type curing agent, more preferably a phenol resin, and still more preferably a phenol novolac resin. In particular, by using a phenol novolac resin as a curing agent, a cured product of an epoxy resin having a high glass transition temperature can be easily obtained. As a result, the heat resistance and mechanical strength of the molded body can be easily improved.

  The phenolic resin is, for example, an aralkyl type phenolic resin, a dicyclopentadiene type phenolic resin, a salicylaldehyde type phenolic resin, a novolak type phenolic resin, a copolymer type phenolic resin of benzaldehyde type phenol and an aralkyl type phenol, paraxylylene and / or metaxylylene modified From the group consisting of phenolic resin, melamine modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified phenolic resin, biphenyl type phenolic resin, and triphenylmethane type phenolic resin It may be at least one selected. The phenolic resin may be a copolymer composed of two or more of the above. As a commercial item of a phenol resin, for example, Tamanor 758 manufactured by Arakawa Chemical Industries, Ltd., or HP-850N manufactured by Hitachi Chemical Co., Ltd. may be used.

  The phenol novolac resin may be, for example, a resin obtained by condensation or cocondensation of phenols and / or naphthols with aldehydes under an acidic catalyst. The phenols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol. The naphthols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of α-naphthol, β-naphthol and dihydroxynaphthalene. The aldehydes constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.

  The curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may be, for example, at least one selected from the group consisting of resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.

  The resin composition may contain one of the above phenolic resins. The resin composition may comprise a plurality of phenolic resins of the above. The resin composition may contain one of the above curing agents. The resin composition may contain a plurality of curing agents among the above.

  The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably one equivalent to the epoxy group in the epoxy resin. May be 0.9 to 1.4 equivalents, more preferably 1.0 to 1.2 equivalents. When the ratio of active groups in the curing agent is less than 0.5 equivalent, the amount of OH per unit weight of the epoxy resin after curing decreases, and the curing rate of the resin composition (epoxy resin) decreases. If the ratio of active groups in the curing agent is less than 0.5 equivalent, the glass transition temperature of the resulting cured product may be lowered, or a sufficient elastic modulus of the cured product may not be obtained. On the other hand, when the ratio of active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength after curing of the molded body formed from the compound tends to decrease. However, even when the ratio of active groups in the curing agent is out of the above range, the effects according to the present invention can be obtained.

  The curing accelerator is not limited as long as it is, for example, a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin. The curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole. The resin composition may comprise one type of curing accelerator. The resin composition may be provided with a plurality of curing accelerators. By containing a curing accelerator as a component of the resin composition, the moldability and releasability of the compound can be easily improved. Further, by containing a curing accelerator as a component of the resin composition, the mechanical strength of a molded article (for example, an electronic component) manufactured using the compound is improved, or the compound in a high temperature / high humidity environment is used. Storage stability is improved.

  The compounding quantity of a hardening accelerator should just be an quantity which the hardening acceleration effect is acquired, and is not specifically limited. However, from the viewpoint of improving the curability and fluidity of the resin composition during moisture absorption, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. Preferably, it may be 1 to 15 parts by mass. It is preferable that content of a hardening accelerator is 0.001 mass part or more and 5 mass parts or less with respect to the sum total of the mass of an epoxy resin and a hardening agent (for example, phenol resin). When the compounding quantity of a hardening accelerator is less than 0.1 mass part, sufficient hardening acceleration effect is hard to be acquired. If the amount of the curing accelerator exceeds 30 parts by mass, the storage stability of the compound tends to be reduced. However, even when the compounding amount and the content of the curing accelerator are out of the above range, the effect according to the present invention can be obtained.

  The coupling agent improves the adhesion between the resin composition and the particles constituting the metal element-containing powder, and improves the flexibility and mechanical strength of the molded body formed from the compound. The coupling agent may be, for example, at least one selected from the group consisting of silane compounds (silane coupling agents), titanium compounds, aluminum compounds (aluminum chelates), and aluminum / zirconium compounds. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride silane and vinylsilane. In particular, aminophenyl-based silane coupling agents are preferred. The compound may include one of the above coupling agents, and may include more than one of the above coupling agents.

  The compounds may contain flame retardants because of their environmental safety, recyclability, moldability and low cost. The flame retardant is, for example, at least one selected from the group consisting of bromine flame retardants, stalk flame retardants, hydrated metal compound flame retardants, silicone flame retardants, nitrogen containing compounds, hindered amine compounds, organic metal compounds and aromatic engineering plastics It may be. The compound may include one of the above-described flame retardants, and may include more than one of the above-described flame retardants.

  The wax may be at least one of fatty acids such as higher fatty acids and fatty acid esters. The compound may comprise more than one wax. The wax preferably contains a fatty acid from the viewpoint of easily improving the flowability of the compound.

  Waxes are, for example, fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, lauric acid or esters thereof; zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, Fatty acid salts such as zinc linoleate, calcium ricinoleate and zinc 2-ethylhexoate; stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylene bis stearin Acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, distearyl adipic acid amide, ethylene bis oleic acid amide, dioleyl adipic acid amide, N-stearyl Fatty acid amides such as stearic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide, methylol behenic acid amide; fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; Polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polyethers comprising these modified products; silicone oils, polysiloxanes such as silicone grease; fluorine compounds such as fluorine oil, fluorine grease, fluorine resin powder, etc .; Selected from the group consisting of waxes such as paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba, micro wax, etc. It may be at least one material.

  As a commercial product of montanic acid wax, at least one selected from the group consisting of Licowax E, Licowax OP, Recolube E and Recoleve WE 40 (all trade names manufactured by Clariant Chemicals, Inc.) may be used. As a commercially available product of stearic acid wax, at least one of Lunak S-50V (titer: 56 ° C.) and Lunack S-90 V (melting point: 68 ° C.) manufactured by Kao Corporation may be used. As a commercially available product of polyethylene wax, at least one selected from the group consisting of Recolub H12, Licowax PE 520, and Licowax PED 191 (all trade names manufactured by Clariant Chemicals, Inc.) may be used. As a commercially available product of an amide wax, at least one of Recolbe FA1 (trade name of Clariant Chemicals Co., Ltd.) and DISPARLON 6650 (trade name of Enomoto Kasei Co., Ltd.) may be used. The wax contained in the compound is appropriately selected according to the requirements of the compound design, such as the fluidity, releasability of the compound, temperature and pressure at molding, and melting point, dropping point and melt viscosity of the wax. Good. It is particularly preferable that the compound contains at least one of Lucac S-50V and Lucac S-90V in terms of flowability of the compound, releasability, temperature and pressure at molding, and melting point of the wax.

<Method of manufacturing compound>
Although the manufacturing method of a compound is not specifically limited, For example, it may be as follows. First, a resin solution is prepared by uniformly stirring and mixing a resin, metal element-containing powder and an organic solvent. In other words, the resin solution, the metal element-containing powder and the organic solvent are mixed to prepare a resin solution. The resin solution may contain a curing agent. The resin solution may contain a curing accelerator. The resin solution may contain additives such as coupling agents, flow aids, flame retardants, and lubricants. The organic solvent is not particularly limited as long as it is a liquid that dissolves the resin composition. The organic solvent is, for example, at least one selected from the group consisting of acetone, N-methyl pyrrolidinone (N-methyl-2-pyrrolidone), γ-butyrolactone, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene. May be there. Subsequently, the compound is obtained by sufficiently removing the organic solvent from the resin solution. With the removal of the organic solvent, the resin composition adheres to the surface of the individual particles constituting the metal element-containing powder. The resin composition may be attached to the entire surface of the particle or may be attached to only a part of the surface of the particle. The method for removing the organic solvent from the resin solution is not particularly limited. For example, the organic solvent can be removed from the resin solution by drying the resin solution. The method of drying the resin solution may be, for example, vacuum drying. A lubricant may be added to the compound obtained above in order to reduce mold damage in the second step described later. The lubricant is not particularly limited. The lubricant may be, for example, at least one selected from the group consisting of metal soaps and wax-based lubricants. Also, in order to reduce damage to the mold in the second step, a lubricant is dispersed in a suitable dispersion medium to prepare a dispersion, and the dispersion is used as a wall in the mold die (wall in contact with the punch) And the applied dispersion may be dried. A powdery compound is obtained by the above method.

<Molded body>
The molded object which concerns on this embodiment is equipped with the said metal element containing powder. The molded body may consist of only the metal element-containing powder, and may have other components in addition to the metal element-containing powder. The molded body may include the metal element-containing powder and the resin composition. The molded body is at least one selected from the group consisting of an uncured resin composition, a semi-cured product of the resin composition (B-stage resin composition), and a cured product of the resin composition (C-stage resin composition) May be included. The molded body may be a cured product of the above compound. The molded object comprised from the hardened | cured material of a compound may be equipped with the hardened | cured material of the metal element containing powder and the resin composition which mutually bonds a metal element containing powder.

<Method of manufacturing molded body>
The method for producing a molded article provided with the metal element-containing powder according to the present embodiment may include the step of pressing the metal element-containing powder in a mold. The method for producing a molded body may include only the step of pressing the metal element-containing powder in a mold, and may include other steps in addition to the step. The manufacturing method of the molded object comprised from the hardened | cured material of the said compound may be equipped with a 1st process, a 2nd process, and a 3rd process. Below, the detail of each process is demonstrated.

  In the first step, a compound is produced by the method described above.

  In the second step, the compound is pressurized in a mold to obtain a molded body (a molded body of B-stage). Here, the resin composition is filled between the individual particles constituting the metal element-containing powder. And a resin composition functions as a binder (binder), and mutually ties the particle | grains which comprise metal element containing powder | flour. The higher the pressure exerted on the compound, the higher the density of the molded body, and the higher the mechanical strength of the molded body. When manufacturing a bonded magnet, the higher the pressure exerted on the compound, the higher the magnetic flux density of the bonded magnet tends to be, and the higher the mechanical strength of the bonded magnet. The pressure exerted on the compound may be, for example, preferably 500 MPa or more and 2500 MPa or less, more preferably 1400 MPa or more and 2000 MPa or less. When the pressure exerted on the compound is within the above range, the mass productivity of the molded product is likely to be improved and the life of the mold is likely to be extended.

  In the third step, the compact is cured by heat treatment to obtain a C-staged compact. The temperature of the heat treatment may be a temperature at which the resin composition in the molded body is sufficiently cured. The temperature of the heat treatment may be, for example, preferably 150 ° C. or more and 300 ° C. or less, more preferably 175 ° C. or more and 250 ° C. or less. In order to suppress the oxidation of the metal element-containing powder (the metal element-containing particles) in the molded body, the heat treatment is preferably performed in an inert atmosphere. When the heat treatment temperature exceeds 300 ° C., the metal element-containing powder is oxidized or the cured resin product is degraded by a trace amount of oxygen inevitably contained in the atmosphere of the heat treatment. In order to cure the resin composition sufficiently while suppressing the oxidation of the metal element-containing powder and the deterioration of the cured resin, the holding time of the heat treatment temperature is preferably several minutes to 4 hours, more preferably 5 minutes. It may be one hour or less.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by these examples.

(Preparation of surface treatment solution)
[Surface treatment solution 1]
19.4 g of pure water and 19.4 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in 50 mL of polybin (polyethylene bottle). The polybin was shaken to mix the liquid in the polybin. While stirring the liquid in the polybin with a syringe, 1.20 g of 3-glycidoxypropyltrimethoxysilane as a coating compound was dropped to the liquid in the polybin. As 3-glycidoxypropyl trimethoxysilane, KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. was used. The coating compound solution was obtained by the above method.

  In a 50 mL polycup (polypropylene cup), 1.0 g of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 4.5 g of pure water, and 4.5 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) were placed. The diluted acetic acid solution was obtained by mixing the liquids in the polycup.

  30 g of the above coating compound solution was placed in 50 mL of poly bottles. The diluted acetic acid solution was added dropwise to the coating compound solution in the polybin to adjust the pH of the coating compound solution to 4.5. The polybin was shaken to mix the solution in the polybin. Thereafter, the polybin was allowed to stand for 30 minutes. The surface treatment liquid 1 was obtained by the above method. The coating compound contained in the surface treatment solution 1, the mass (unit: g) of pure water and ethanol, the pH of the surface treatment solution 1, and the content (unit: mass%) of the coating compound in the surface treatment solution 1 , Table 1 below. In Table 1, "solution concentration" means the content of the coating compound in the surface treatment liquid.

[Surface treatment solution 2 to 11]
In the preparation of the surface treatment solutions 2 to 6 and 10, the coating compounds shown in Table 1 below were used. In the preparation of the surface treatment solutions 2 to 6 and 10, the mass of each of pure water, ethanol and coating compound contained in the surface treatment solution was adjusted to a value (unit: g) shown in Table 1 below. Surface treatment solutions 2 to 6 and 10 were individually prepared by the same method as the surface treatment solution 1 except for the above matters.
The coating compounds shown in Table 1 below were used in the preparation of the surface treatment solutions 7 to 9 and 11 respectively. In the preparation of each of the surface treatment solutions 7 to 9 and 11, the mass of each of pure water, ethanol and the coating compound contained in the surface treatment solution was adjusted to a value (unit: g) shown in Table 1 below. No dilute acetic acid solution was used in the preparation of surface treatment solutions 7-9 and 11 respectively. That is, the pH of the coating compound solution was not adjusted in the preparation of the surface treatment solutions 7 to 9 and 11 respectively. The surface treatment solutions 7 to 9 and 11 were individually prepared by the same method as the surface treatment solution 1 except for the above matters.

KBM-503 in the following Table 1 is 3-methacryloxypropyl trimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-5803 in the following Table 1 is methacryloxyoctyl trimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-13 in the following Table 1 is methyltrimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-3063 in the following Table 1 is hexyltrimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-7103 in the following Table 1 is trifluoropropyltrimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-903 in the following Table 1 is 3-aminopropyltrimethoxysilane (compound having a silanol group) manufactured by Shin-Etsu Chemical Co., Ltd.
JP-504 in the following Table 1 is butyl acid phosphate (organic phosphoric acid compound) manufactured by Johoku Chemical Industry Co., Ltd.
JP-513 in the following Table 1 is isotridecyl acid phosphate (organic phosphoric acid compound) manufactured by Johoku Chemical Industry Co., Ltd.

Example 1
[Preparation of metal element-containing powder]
400.0 g of carbonyl iron powder (pure iron powder) was placed in 50 mL of polyvin as metal element-containing particles. As carbonyl iron powder, SQ made by BASF Japan Ltd. was used. 20.0 g of the surface treatment solution 1 was placed in a polybin. The polybin was shaken for 10 minutes, and the metal element-containing particles and the surface treatment solution 1 were mixed to obtain a mixture. The mixture in the polybin was transferred to a metal vat and placed in an oven preheated to 100 ° C. The mixture was dried by heating the mixture in an oven. The drying temperature was 100.degree. The drying time was 1 hour. The metal element containing powder was obtained by the above method. The metal element-containing powder was provided with the metal element-containing particles and the coating compound covering the surfaces of the individual metal element-containing particles.

[Measurement of repose angle]
The repose angle of the metal element-containing powder of Example 1 was measured using a repose angle measurement device. As a repose angle measuring device, FSA-100 manufactured by Tsutsui Rikakai Kaisha, Ltd. was used. The angle of repose (unit: °) of Example 1 is shown in Table 2 below.

[Measurement of content of coating compound]
The mass m ₁ of carbon contained in the metal element-containing powder was measured using a carbon / sulfur analyzer. As carbon / sulfur analyzer, CS744 manufactured by LECO Japan Ltd. was used. In the same manner as described above, the mass m ₀ of the carbon contained in the metal element-containing particles prior to mixing with the surface treatment solution was measured. It was calculated difference _m 1 -m ₀ of m ₁ and _{m 0.} m ₁ -m ₀ corresponds to the mass m _A of carbon contained in the coating compound attached to the surface of the metal element-containing particle. The m _A, divided by the mass M of the entire metal-element-containing powder used in the measurement, the content of carbon in the entire metal-element-containing powder M _{A (unit:} mass%) was calculated. M _A equals 100 × m _A / M. When the molecular weight of the coating compound is described as M 2 _C , the ratio M _B of mass m 2 _C of carbon in one molecule of the coating compound was determined based on the molecular structure of the coating compound. M _B is equal to m _C / M _C. The content [C] (unit: mass%) of the coating compound contained in the metal element-containing powder was calculated by dividing M _A by M _B. [C] is equal to M _A / M _B. [C] of Example 1 is shown in Table 2 below.

[Preparation of toroidal]
The metal element-containing powder of Example 1 was loaded into a mold. The metal element-containing powder in the mold was pressurized using a hydraulic press to obtain a toroidal (molded body). The pressure applied to the metal element-containing powder was 300 MPa (3 ton / cm ² ). The toroidal shape had an outer diameter of 20 mm, an inner diameter of 12 mm, and a length of 2 mm.

[Measurement of magnetic loss]
The toroidal magnetic loss of Example 1 was measured using a B-H analyzer. As B-H analyzer, SY-8258 manufactured by Iwasaki Tsushinki Co., Ltd. was used. In the toroidal, a copper wire with a diameter of 0.4 mm was wound 5 turns on the excitation side, and a 0.26 mm copper wire was wound 5 turns on the detection side. The magnetic loss at a frequency of 1000 kHz was measured at an excitation magnetic flux density of 10 mT. The magnetic loss Pcv (unit: kW / m ³ ) of Example 1 is shown in Table 2 below.

[Measurement of toroidal density]
The toroidal density of Example 1 was measured by the Archimedes method. The density (unit: Mg / m ³ = 10 ⁶ g / m ³ ) of Example 1 is shown in Table 2 below.

[Preparation of paste]
In a 650 mL ointment container, 9.9 g of epoxy resin, 17.4 g of phenol resin, and 22.7 g of acetic acid diethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were placed. As epoxy resin, EPICLON 860 manufactured by DIC Corporation was used. The epoxy equivalent of the epoxy resin was 240 g / eq. As a phenol resin, TD-2090 manufactured by DIC Corporation was used. The hydroxyl equivalent of the phenol resin was 105 g / eq, and the softening point of the phenol resin was 120 ° C. The raw material in the ointment container was stirred for 5 minutes at a revolution speed of 1000 rpm using a revolution stirrer, to obtain an epoxy resin solution. As a revolution-revolution stirrer, ARE-500 made by Shinky Co., Ltd. was used.

  In a 650 mL ointment container, 50.0 g of the metal element-containing powder of Example 1, 5.3 g of the above epoxy resin solution, and 2.0 g of acetic acid diethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) were placed. A paste was obtained by stirring the raw material in the ointment container for 40 seconds at a revolution speed of 1000 rpm using the above-mentioned revolution stirrer.

[Measurement of viscosity]
The viscosity at 25 ° C. of the paste of Example 1 was measured using a viscometer. As the viscometer, a TV-33 viscometer (TV-33 viscometer cone plate type, rotor code: 04 (3 ° × R14)) manufactured by Toki Sangyo Co., Ltd. was used. The rotational speed of the rotor was 0.5 rpm. The viscosity (unit: Pa · s) of Example 1 is shown in Table 2 below.

(Examples 2 to 9)
In preparation of the metal element containing powder of Examples 2-9, the surface treatment liquid shown by following Table 2 was used. The metal element-containing powders of Examples 2 to 9 were individually produced by the same method as Example 1 except for the above matters.

  The repose angle and [C] of each of Examples 2 to 9 were measured in the same manner as Example 1. In the same manner as in Example 1, toroids of Examples 2 to 9 were individually produced. In the same manner as in Example 1, the magnetic loss and toroidal density in each of Examples 2 to 9 were measured. The pastes of Examples 2 to 9 were prepared in the same manner as Example 1. The viscosity of each of Examples 2 to 9 was measured in the same manner as Example 1. The measurement results are shown in Table 2 below.

(Comparative example 1)
As the metal element-containing powder of Comparative Example 1, the same metal element-containing particles as those used in Example 1 were prepared. That is, the metal element-containing powder of Comparative Example 1 consisted of only the metal element-containing particles, and was not provided with the coating compound.

  The repose angle and [C] of Comparative Example 1 were measured in the same manner as in Example 1. A toroidal of Comparative Example 1 was produced in the same manner as in Example 1. The magnetic loss and toroidal density of Comparative Example 1 were measured in the same manner as in Example 1. In the same manner as in Example 1, a paste of Comparative Example 1 was produced. The viscosity of Comparative Example 1 was measured in the same manner as Example 1. The measurement results are shown in Table 2 below.

(Example 10)
In preparation of the metal element containing powder | flour of Example 10, the surface treatment liquid shown by following Table 3 was used. In addition, in the preparation of the metal element-containing powder of Example 10, a Sm-Fe-N alloy manufactured by Nichia Corporation was used as the metal element-containing particles. In preparation of the metal element-containing powder of Example 10, the mass of the metal element-containing particles and the surface treatment liquid contained in the mixture in the polybin was adjusted to a value (unit: g) shown in Table 3 below. The metal element-containing powder of Example 10 was produced in the same manner as in Example 1 except for the above matters.

  [C] of Example 10 was measured by the same method as Example 1. [C] of Example 10 is shown in Table 3 below.

[Preparation of compound]
In a 50 mL polycup, 2.8 g of an epoxy resin, 1.8 g of a phenol resin, 0.1 g of a curing accelerator, and 14.0 g of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) were placed. As the epoxy resin, EPPN-502H manufactured by Nippon Kayaku Co., Ltd. was used. The epoxy equivalent of the epoxy resin was 180 g / eq, and the softening point of the epoxy resin was 90 ° C. As phenolic resin, HP-850N made by Hitachi Chemical Co., Ltd. was used. As a curing accelerator, Hishikorin PX-4PB manufactured by Nippon Chemical Industrial Co., Ltd. was used. The raw material in the polycup was stirred for 10 minutes to obtain an epoxy resin solution.

  In 50 mL of poly bottles, 10.7 g of the metal element-containing powder of Example 10 and 1.4 g of the above epoxy resin solution were placed. The polybin was shaken for 10 minutes to mix the ingredients in the polybin to obtain a mixture. The mixture in the polybin was transferred to a metal vat and allowed to dry for 30 minutes. The drying method was air drying. Thereafter, the dried mixture was placed in a vacuum furnace and dried at room temperature under reduced pressure for 3 hours to obtain a compound.

[Preparation of toroidal]
The compound of Example 10 was loaded into a mold preheated to 200 ° C. The compound in the mold was pressed using a hydraulic press for 3 minutes to obtain a toroidal. The pressure applied to the compound was 300 MPa (3 ton / cm ² ). The toroidal shape had an outer diameter of 20 mm, an inner diameter of 12 mm, and a length of 2 mm.

[Measurement of magnetic loss]
The toroidal magnetic loss of Example 10 was measured using the B-H analyzer. In the toroidal, a copper wire with a diameter of 0.4 mm was wound 5 turns on the excitation side, and a 0.26 mm copper wire was wound 5 turns on the detection side. The magnetic loss at a frequency of 1000 kHz was measured at an excitation magnetic flux density of 10 mT. The magnetic loss Pcv (unit: kW / m ³ ) of Example 10 is shown in Table 3 below.

[Production of molded body]
The compound of Example 10 was filled in a mold. The dimensions of the mold were 7 mm wide × 7 mm deep. A compression molded body was obtained by applying pressure from a height direction to the compound in the mold using a hydraulic press. The pressure applied to the compound was 100 MPa (1 ton / cm ² ). The compact was placed in a dryer. The temperature in the dryer was raised from normal temperature at 5 ° C./min. It hold | maintained for 10 minutes, after the temperature in a dryer reached 200 degreeC. Thereafter, the compact was removed from the drier and the temperature of the compact was returned to room temperature. A molded body was obtained by the above method.

[Measurement of density of molded body]
The dimensions (width, depth, height) of the compact of Example 10 were measured using a micrometer to determine the volume V of the compact. The mass W of the molded article of Example 10 was measured using an electronic balance. The density W / V of the compact of Example 10 was calculated by dividing W by V. The density (unit: Mg / m ³ ) of Example 10 is shown in Table 3 below.

[Crushing strength test]
Using a universal compression tester, the compact of Example 10 was subjected to compressive pressure from the height direction. As a universal compression tester, AG-10TBR manufactured by Shimadzu Corporation was used. The maximum value of the compression pressure when the compact was broken by the compression pressure was calculated as the crush strength (unit: MPa). The crushing strength (unit: MPa) of the molded body of Example 10 is shown in Table 3 below.

(Examples 11 to 23)
In preparation of the metal element containing powder of each Example 11-23, the surface treatment liquid shown by following Table 4 was used. The metal element-containing powders of Examples 11 to 23 were individually manufactured by the same method as Example 10 except for the above matters.

[C] in each of Examples 11 to 23 was measured in the same manner as in Example 10. The compounds of Examples 11 to 23 were individually prepared in the same manner as in Example 10. In the same manner as in Example 10, the toroidal elements of Examples 11 to 23 were individually produced.
The magnetic loss of each of Examples 11 to 16 was measured in the same manner as in Example 10.
In the same manner as in Example 10, molded articles in Examples 11 to 16 were produced.
The pressure applied to the compound was 2500 MPa (25 ton / cm ² ) in the preparation of each of the molded articles of Examples 17-23. Molded articles of Examples 17 to 23 were individually produced in the same manner as in Example 10 except for the matters described above.
The density and crushing strength of each of Examples 11 to 23 were measured in the same manner as in Example 10.
The respective measurement results are shown in Tables 3 and 4 below.

(Comparative Examples 2 and 3)
The same metal element-containing particles as used in Example 10 were prepared as the metal element-containing powders of Comparative Examples 2 and 3, respectively. That is, Comparative Example 2 and 3 metal element-containing powders consisted only of the metal element-containing particles and did not have the coating compound.

[C] of Comparative Examples 2 and 3 was measured in the same manner as in Example 10. The compounds of Comparative Example 2 and 3 were separately prepared in the same manner as in Example 10. In the same manner as in Example 10, Comparative Examples 2 and 3 were individually produced.
The magnetic loss of Comparative Example 2 was measured in the same manner as in Example 10.
A molded body of Comparative Example 2 was produced in the same manner as in Example 10.
A molded body of Comparative Example 3 was produced in the same manner as in Example 17.
The density and crushing strength of each of Comparative Examples 2 and 3 were measured in the same manner as in Example 10.
The respective measurement results are shown in Tables 3 and 4 below.

  As shown in Table 2, the density of toroids of Examples 1 to 9 was higher than that of Comparative Example 1, and the magnetic loss of each of Examples 1 to 9 was smaller than that of Comparative Example 1. The angle of repose of Examples 1, 2 and 4 to 9 was smaller than that of Comparative Example 1. On the other hand, the repose angle of Example 3 was larger than that of Comparative Example 1. The viscosity of each of Examples 2, 3, 5, 6, 8, and 9 was lower than that of Comparative Example 1. On the other hand, the viscosity of each of Examples 1, 4 and 7 was higher than that of Comparative Example 1.

  As shown in Tables 3 and 4, the density of each of the molded articles of Examples 10 to 16 is equal to or higher than the density of Comparative Example 2, and the magnetic loss of each of Examples 10 to 16 is smaller than that of Comparative Example 2. Was small. The density of the molded articles of Examples 12 to 16 was higher than that of Comparative Example 2. The crushing strength of each of Examples 17, 18, 20, 22 and 23 was higher than that of Comparative Example 3.

  The metal element-containing powder according to the present invention has high industrial value because it is suitable as a material for producing a compact having a small magnetic loss.

Claims (10)

Metal element-containing particles,
A coating compound covering the metal element-containing particles;
Equipped with
The coating compound contains at least one of a compound having a silanol group and an organic phosphoric acid compound.
Metal element containing powder. The compound having a silanol group is a hydrolyzate of alkoxysilane,
The metal element-containing powder according to claim 1. The organic phosphoric acid compound has an alkyl group,
The metal element-containing powder according to claim 1 or 2. The compound having a silanol group has a glycidyl group,
The metal element containing powder as described in any one of Claims 1-3. The compound having a silanol group has an alkyl group,
The metal element containing powder as described in any one of Claims 1-4. The compound having a silanol group has a methacryloyl group,
The metal element containing powder as described in any one of Claims 1-5. The compound having a silanol group has an amino group,
The metal element containing powder as described in any one of Claims 1-6. The content of the coating compound is 0.001% by mass or more and 1.00% by mass or less.
The metal element containing powder as described in any one of Claims 1-7. Used for magnetic core,
The metal element containing powder as described in any one of Claims 1-8. A powder containing the metal element according to any one of claims 1 to 9.
Molded body.