JP2022080817A - Method for manufacturing compound for bond magnet - Google Patents

Abstract

To provide a compound for a bond magnet that can be highly filled with magnetic powder by improving the fluidity of a compound for a bond magnet containing a thermoplastic resin, and a bond magnet having improved magnetic characteristics.SOLUTION: A method for manufacturing a compound for a bond magnet includes a step of thermally hardening a thermosetting resin and a curing agent to obtain an additive for a bond magnet, the ratio of the number of reactive groups of the curing gent to the number of reactive groups of the thermosetting resin being 2 or more and 11 or less, and a kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin. The magnetic powder contains SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.SELECTED DRAWING: None

Description

Application for application of Article 30, Paragraph 2 of the Patent Law [Meeting name] 2020BM Symposium Program "Development Trends of Cutting-edge Magnetic Materials and High-Performance and High-Efficiency Motor Technology" (held online on Webex) [Organizer Name] Japan Bond Magnetic Materials Association (JABM) [Date] December 4, 2nd year of Reiwa

The present invention relates to a method for producing a compound for a bonded magnet.

Patent Document 1 discloses a method for manufacturing a bonded magnet in which a thermoplastic resin and SmFeN particles are melt-kneaded, then compression-molded to produce a compound, and injection-molded.

On the other hand, Patent Document 2 discloses a bonded magnet using an amine-based curing agent as a curing agent for NdFeB magnetic powder, an epoxy resin, and an epoxy resin.

It is known that the coercive force of the SmFeN-based anisotropic magnetic powder is improved when the surface is coated with phosphate. For example, in Patent Document 3, SmFeN-based anisotropic magnetic powder is obtained by adding a phosphoric acid treatment solution containing pH-adjusted orthophosphoric acid to a slurry using water containing SmFeN-based anisotropic magnetic powder as a solvent. A method of coating the surface of a phosphate with a phosphate is disclosed.

In Patent Document 4, a pH-adjusted phosphoric acid treatment liquid is added to a slurry using an organic solvent containing an SmFeN-based anisotropic magnetic powder having a large particle size as a solvent, and then the SmFeN-based anisotropic magnetic powder is added. Disclosed is a method of adjusting the particle size of the SmFeN-based anisotropic magnetic powder by pulverizing the mixture and coating the surface with a phosphate.

In Patent Document 5, the coercive force of the phosphoric acid-coated SmFeN-based anisotropic magnetic powder is increased by performing an oxidation treatment on the phosphoric acid-coated SmFeN-based anisotropic magnetic powder. Is disclosed.

Japanese Unexamined Patent Publication No. 2017-43804 Japanese Unexamined Patent Publication No. 2010-232468 Japanese Unexamined Patent Publication No. 2020-056101 Japanese Unexamined Patent Publication No. 2017-210662 Japanese Unexamined Patent Publication No. 2014-160794

An object of the present invention is to provide a compound for a bond magnet that improves the fluidity of the compound for a bond magnet containing a thermoplastic resin and enables a high filling of magnetic powder, and a bond magnet with improved magnetic properties. do.

In the method for producing a compound for a bonded magnet according to one aspect of the present invention, a thermosetting resin and a curing agent in which the ratio of the reactive groups to the reactive groups of the thermosetting resin is 2 or more and 11 or less are thermally cured. The magnetic powder comprises a step of obtaining an additive for a bond magnet and a kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bond magnet, and the magnetic powder has phosphorus on the surface. Contains SmFeN-based anisotropic magnetic powder coated with an acid salt.

In the method for producing a compound for a bonded magnet according to one aspect of the present invention, a thermosetting resin and a curing agent in which the ratio of the reactive groups to the reactive groups of the thermosetting resin is 2 or more and 11 or less are thermally cured. The step of obtaining the bond magnet additive, the step of kneading the bond magnet additive and the thermoplastic resin to obtain the bond magnet resin composition, and the step of kneading the bond magnet resin composition and the magnetic powder are performed. The magnetic powder comprises a kneading step of obtaining a compound for a bond magnet, and the magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.

In the method for producing a bonded magnet according to one aspect of the present invention, a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less are thermally cured and bonded. A step of obtaining an additive for a magnet, a kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bond magnet, and an injection for injecting the obtained compound for a bond magnet. The magnetic powder includes a molding step, and the magnetic powder includes a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.

In the method for producing a bonded magnet according to one aspect of the present invention, a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less are thermally cured and bonded. A step of obtaining an additive for a magnet, a step of kneading the additive for a bond magnet and a thermoplastic resin to obtain a resin composition for a bond magnet, and a step of kneading the resin composition for a bond magnet and a magnetic powder to knead the bond magnet. The magnetic powder includes a kneading step for obtaining a compound for use and an injection molding step for injection molding the obtained compound for a bond magnet, and the magnetic powder includes a SmFeN-based anisotropic magnetic powder having a surface coated with a phosphate.

According to the above aspect, the fluidity of the compound for a bonded magnet containing a thermoplastic resin can be improved, the magnetic powder can be highly filled, and the bonded magnet having improved magnetic properties can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following. In this specification, the term "process" is used not only for an independent process but also for the term "process" if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. included.

The method for manufacturing the first bond magnet compound of the present embodiment is as follows.
A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
The magnetic powder comprises a kneading step of kneading the additive for a bonded magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bonded magnet, and the magnetic powder has a SmFeN-based anisotropic surface coated with a phosphate. It is characterized by containing magnetic powder.

When a bonded magnet containing a thermoplastic resin is manufactured by injection molding a kneaded thermoplastic resin and a thermocurable resin, the reactive group (for example, in the case of an epoxy resin, a glycisyl group) and heat of the thermoplastic resin are heat-molded. When the reactive group of the plastic resin (for example, the amide group in the case of nylon 12) reacts, the fluidity of the resin may decrease and the moldability may deteriorate. In the cured product of the thermosetting resin of the present embodiment in which the ratio of the equivalent to the equivalent of the thermosetting resin is 2 or more and 11 or less, the reactive group of the thermosetting resin is the reactive group of the curing agent ( For example, in the case of DDS (diaminodiphenyl sulfone), it is sufficiently deactivated by the amino group), so that the reaction with the reactive group of the thermoplastic resin is unlikely to occur and the decrease in the fluidity of the resin can be suppressed. Can be used as an additive for bonded magnets containing. Further, when the bond magnet is manufactured by injection molding using the bond magnet compound prepared by the additive for bond magnet containing the thermoplastic resin of the present embodiment, the injection pressure can be reduced, so that the obtained bond magnet can be obtained. The magnetic properties of the are improved.

The thermosetting resin is not particularly limited as long as it is thermosetting, and for example, epoxy resin, phenol resin, urea resin, melamine resin, guanamine resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, polyurethane resin, etc. Examples thereof include silicone resin, polyimide resin, alkyd resin, furan resin, dicyclopentadiene resin, acrylic resin, and allyl carbonate resin. Of these, epoxy resin is preferable in terms of mechanical properties and heat resistance. The thermosetting resin is preferably a liquid at room temperature or a solid that dissolves in a solvent and becomes liquid. Further, in the case of an epoxy resin, from the viewpoint of reactivity with a curing agent, it is preferable to select a resin having a rigid skeleton, a crystal structure with few steric hindrance, a small molecular weight and high fluidity, for example, biphenyl. Types, bisphenol A type, naphthalene type, anthracene type and the like can be mentioned. Examples of the epoxy resin include jER-YX4000, jER-828, jER-YX8800, jER-YL6121HA, jER-YL6677, (manufactured by Mitsubishi Chemical Corporation), EPICLON-HP-4032D, HP-7200L, HP-7200, HP- 7200H, HP-7200HH, HP-7200HHH, HP-4700, HP-4770, HP-5000, HP-6000, HP-4710 (manufactured by DIC Co., Ltd.), YDC-1312, YSLV-70XY, YSLV-80XY (Nittetsu) Chemical & Material Co., Ltd.) can be used.

The curing agent is not particularly limited as long as it heat-cures the selected thermosetting resin, and when the thermosetting resin is an epoxy resin, for example, an amine-based curing agent, an acid anhydride-based curing agent, or a polyamide-based curing agent. , Imidazole-based curing agent, phenol resin-based curing agent, polyvinylcaptan resin-based curing agent, polysulfide resin-based curing agent, organic acid hydrazide-based curing agent, and the like. Examples of the amine-based curing agent include diaminodiphenyl sulfone, meta-phenylenediamine, diaminodiphenylmethane, diethylenetriamine, and triethylenetetramine.

When a nylon resin is used as the thermoplastic resin and an epoxy resin is used as the thermosetting resin, it is preferable to use a diamine-based curing agent having an aromatic skeleton as the curing agent. Since the diamine-based curing agent having an aromatic skeleton has a chemical structure having a chemical structure with less steric damage around the amino group which is a reactive group due to having an aromatic skeleton, it reacts with a glycisyl group which is a reactive group of an epoxy resin. It is considered that the fluidity of the nylon resin is improved because the amino group has good properties and the amino group has a high affinity for the amide group which is the reactive group of the nylon resin. Examples of such a curing agent include 9,9-bis (4-amino-3-methylphenyl) fluorene, bisaniline P, bisaniline M, benzoguanamine, and 3 in addition to the above-mentioned diaminodiphenylsulfone, metaphenylenediamine, and diaminodiphenylmethane. , 3'-dinitrobenzidine, 4,4'-methylenebis (2-ethyl-6-methylaniline), o-tridine, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-amino) Phenoxy) phenyl] sulfone, 1,3-phenylenediamine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-diaminodiphenylmethane, 3,3'-sulfonyldianiline, 4,4'-diaminodiphenyl ether , 1,3-Bis (3-aminophenoxy) benzene.

The blending amount of the curing agent is adjusted by the ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin (the ratio of the equivalent amount of the curing agent to the equivalent amount of the thermosetting resin). The ratio of the number of reactive groups of the curing agent to the number of reactive groups of the thermosetting resin is 2 or more and 11 or less, preferably 2 or more and 10 or less, and more preferably 2 or more and 7 or less. The lower limit of the number of reactive groups is preferably more than 2.5, more preferably 3 or more. When the ratio exceeds 11, the mechanical properties of the bonded magnet deteriorate, and when it is less than 2, the ratio of the reactive group of the curing agent to the reactive group of the thermosetting resin is small, so that the reactive group of the thermosetting resin is small. Remains. When kneaded with the thermoplastic resin in the subsequent steps, the reactive group of the thermoplastic resin reacts with the reactive group of the residual thermosetting resin, which causes an increase in viscosity during injection molding and the formability of the bond magnet. The mechanical properties of the obtained molded product are worse than the moldability and mechanical properties of the thermoplastic resin alone. Here, the equivalent of the thermosetting resin type means the number of grams of the resin containing 1 gram equivalent of the reactive group, and the equivalent of the curing agent type means the equivalent of active hydrogen.

The cured product can be obtained by adding a curing agent to the above-mentioned thermosetting resin and heat-curing. The thermosetting temperature can be set according to the characteristics of the thermosetting resin to be used, but from the viewpoint of curability, it is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 180 ° C. or higher and 220 ° C. or lower.

The cured product can be pulverized if necessary. The method for pulverizing the cured product is not particularly limited, and a sample mill, a ball mill, a stamp mill, a mortar, a mixer pulverization, or the like can be used. If necessary, the crushed material can be classified by a sieve or the like. The average particle size of the pulverized product is preferably 1000 μm or less, more preferably 500 μm or less, from the viewpoint of compatibility with the thermoplastic resin.

The additive for a bonded magnet can also be obtained by blending a curing accelerator together with a thermosetting resin and a curing agent and curing the mixture. Examples of the curing accelerator include 1,8-diazabicyclo (5,4,0) -undecene-7, 1,5 diazabicyclo (4,3,0) -nonene-5, 1-cyanoethyl-2-ethyl-4. -Methylimidazole, 2-methyl-4methylimidazole, triphenylphosphine, sulfonium salt and the like can be mentioned. The content of the curing accelerator is not particularly limited, but in general, 0.01% by mass or more and 10% by mass or less is added to the total amount of the thermosetting resin and the curing agent.

In the kneading step, the additive for the bond magnet, the magnetic powder, and the thermoplastic resin are melt-kneaded to prepare a compound for the bond magnet used for injection molding. The melt kneader is not particularly limited, but a single-screw kneader, a twin-screw kneader, a mixing roll, a kneader, a Banbury mixer, a meshing twin-screw extruder, a non-meshing twin-screw extruder, etc. shall be used. Can be done. The melt-kneading temperature is not particularly limited and can be set according to the characteristics of the thermoplastic resin used, but is preferably 180 ° C. or higher and 250 ° C. or lower.

The thermoplastic resin is not particularly limited as long as it is an injection moldable resin, and is, for example, nylon resin (polyamide); polyolefins such as polypropylene (PP) and polyethylene (PE); polyester; polycarbonate (PC); polyphenylene sulfide (PPS). ; Polyetheretherketone (PEEK); Polyacetal (POM); Liquid crystal polymer (LCP) and the like. Nylon resins include polylactams such as 6 nylon, 11 nylon and 12 nylon, condensates of dicarboxylic acid and diamine such as 6,6 nylon, 6,10 nylon and 6,12 nylon, 6 nylon / 6, 6 Nylon, 6 Nylon / 6,10 Nylon, 6 Nylon / 12 Nylon, 6 Nylon / 6,12 Nylon, 6 Nylon / 6,10 Nylon / 6,10 Nylon, 6 Nylon / 6,6 Nylon / 6,12 Nylon , 6 Nylon / Polyether-like copolymerized polyamides, nylon 6T, nylon 9T, nylon MXD6, aromatic nylon, amorphous nylon and the like. Of these, nylon resin is preferable, and 12 nylon is particularly preferable, in view of the balance between low water absorption rate, moldability, and mechanical properties.

The magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate. The SmFeN-based anisotropic magnetic powder has a Th ₂ Zn ₁₇ -type crystal structure and is composed of a rare earth metal samarium Sm represented by the general formula Sm _x Fe _{100-xy Ny} , iron Fe, and nitrogen N. Examples include nitrides. Here, it is preferable that x is 8.1 atomic% or more and 10 atomic% or less, y is 13.5 atomic% or more and 13.9 atomic% or less, and the balance is mainly Fe, and the particle size distribution is demagnetized. From the viewpoint of the angularity of the characteristics, monodisperse is preferable. The method for forming a phosphate coating on the surface of the SmFeN-based anisotropic magnetic powder will be described later.

The magnetic powder may contain NdFeB-based or SmCo-based rare earth magnetic powder in addition to the SmFeN-based anisotropic magnetic powder.
The SmFeN-based anisotropic magnetic powder can be produced by the method disclosed in Japanese Patent Application Laid-Open No. 11-189811. The NdFeB-based magnetic powder can be produced by the HDDR method disclosed in International Publication No. 2003/85147. The SmCo-based magnetic powder can be produced by the method disclosed in JP-A-08-26083.

The magnetic powder may be treated with phosphoric acid, if necessary. The phosphoric acid treatment solution is basically dissolved in water or an organic solvent such as isopropanol, and if necessary, a reaction accelerator such as nitrate ion and a crystal micronizing agent such as V ion, Cr ion and Mo ion are added. The magnetic powder is put into the phosphoric acid bath, and an immobile film having a PO bond is formed on the surface of the rare earth magnetic powder. Examples of the phosphoric acid treatment agent include phosphates such as orthophosphoric acid, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, zinc phosphate and calcium phosphate, hypophosphite and hypophosphite. Examples thereof include inorganic phosphoric acid such as phosphate type, pyrophosphoric acid type and polyphosphoric acid type, and organic phosphoric acid.

[Silica treatment process]
The magnetic powder may be treated with silica if necessary. By forming a silica thin film on the magnetic powder, oxidation resistance can be improved. The silica thin film can be formed, for example, by mixing an alkyl silicate, a phosphate-coated magnetic powder, and an alkaline solution.

[Silane coupling treatment process]
The magnetic powder after the silica treatment may be further treated with a silane coupling agent. By silane coupling treatment of the magnetic powder on which the silica thin film is formed, a coupling agent film is formed on the silica thin film, improving the magnetic properties of the magnetic powder, as well as improving the wettability with the resin and the strength of the magnet. can do. The silane coupling agent may be selected according to the type of resin and is not particularly limited. For example, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-). Aminoethyl) Aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride , Γ-Glysidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethylene disilazane, γ-ani Renopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) ) Γ-Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, oleidopropyltriethoxysilane , Γ-Issipylpropyltriethoxysilane, polyethoxydimethylsiloxane, polyethoxymethylsiloxane, bis (trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) tetrasulfan, γ-isoxapropyltrimethoxysilane, vinyl Methyldimethoxysilane, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate, t-butylcarbamatetrialkoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) )-A silane coupling agent such as -1-propaneamine can be mentioned. Only one kind of these silane coupling agents may be used, or two or more kinds thereof may be used in combination. The amount of the silane coupling agent added is preferably 0.2% by mass or more and 0.8% by mass or less, and more preferably 0.25% by mass or more and 0.6% by mass or less with respect to 100 parts by weight of the magnetic powder. If it is less than 0.2% by mass, the effect of the silane coupling agent is small, and if it exceeds 0.8% by mass, the magnetic properties of the magnetic powder and the magnet tend to be deteriorated due to the aggregation of the magnetic powder.

The SmFeN-based anisotropic magnetic powder after the silica treatment or the silane coupling treatment can be filtered, dehydrated, and dried by a conventional method.

In the first method for producing a compound for a bonded magnet of the present embodiment, the filling rate of the magnetic powder in the compound for a bonded magnet is preferably 75% by mass or more and 96% by mass or less, and 90% by mass or more and 95.5% by mass or less. Is more preferable. If it exceeds 96% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates, and if it is less than 75% by mass, the residual magnetic flux density of the bonded magnet becomes low.

The content of the additive for the bond magnet in the first compound for the bond magnet of the present embodiment is preferably 0.1% by mass or more and 4.2% by mass or less, and 0.3% by mass or more and 3.5% by mass or less. Is more preferable, and 0.5% by mass or more and 1.2% by mass or less is further preferable. If the content of the additive for the bond magnet exceeds 4.2% by mass, the residual magnetic flux density of the bond magnet becomes low, and if it is less than 0.1% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates. Sometimes.

The content of the thermoplastic resin in the first compound for a bonded magnet of the present embodiment is preferably 2.5% by mass or more and 25% by mass or less, and more preferably 3.5% by mass or more and 10% by mass or less. If the content of the thermoplastic resin exceeds 25% by mass, the residual magnetic flux density of the bonded magnet becomes low, and if it is less than 2.5% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

In the first compound for bonded magnets of the present embodiment, the weight portion of the additive for bonded magnets with respect to 100 parts by weight of the magnetic powder is preferably 0.1 parts by weight or more and 5.6 parts by weight or less, preferably 0.31 parts by weight or more. 4.67 parts by weight or less is more preferable, and 0.52 parts by weight or more and 1.6 parts by weight or less is further preferable. If the amount of the additive for the bond magnet exceeds 5.6 parts by weight, the residual magnetic flux density of the bond magnet becomes low, and if it is less than 0.1 part by weight, the viscosity at the time of injection molding becomes high and the moldability may deteriorate. ..

In the first compound for a bonded magnet of the present embodiment, the weight portion of the thermoplastic resin with respect to 100 parts by weight of the magnetic powder is preferably 2.6 parts by weight or more and 33 parts by weight or less, preferably 3.6 parts by weight or more and 14 parts by weight or less. Is more preferable. If the weight portion of the thermoplastic resin exceeds 33 parts by weight, the residual magnetic flux density of the bonded magnet becomes low, and if it is less than 2.6 parts by weight, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

The method for manufacturing the second bond magnet compound of the present embodiment is as follows.
A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A step of kneading the additive for a bonded magnet and a thermoplastic resin to obtain a resin composition for a bonded magnet.
The process includes a kneading step of kneading the resin composition for a bonded magnet and a magnetic powder to obtain a compound for a bonded magnet.
The magnetic powder is characterized by containing a SmFeN-based anisotropic magnetic powder having a surface coated with a phosphate.

The step of obtaining the additive for the bond magnet, the thermosetting resin, the curing agent and the magnetic powder used in the step are as described above.

The kneading step for obtaining the resin composition for a bonded magnet, and the thermoplastic resin used in the step are as described above. The cured product of the thermosetting resin and the curing agent in which the ratio of the reactive groups to the reactive groups of the thermosetting resin is 2 or more and 11 or less, and the thermoplastic resin are melted in advance before being kneaded with the magnetic powder. A molten kneaded product is obtained by kneading. In the obtained kneaded product, the thermoplastic resin and the cured product may be completely compatible, partially compatible or incompatible as long as they are previously melt-kneaded, but complete compatibility is particularly preferable.

In the resin composition for a bonded magnet obtained by sufficiently kneading the cured product and the thermoplastic resin, when the thermoplastic resin is a crystalline resin, the melting point and the crystallization temperature are lowered. As a result, the injection pressure of the compound for the bond magnet is also reduced, the orientation ratio and magnetic characteristics of the obtained bond magnet are improved, and the coercive force is also improved. The melting point is preferably 3.0 ° C. or higher, more preferably 4.5 ° C. or higher, lower than the melting point of the thermoplastic resin. Further, the crystallization temperature is preferably 2.0 ° C. or higher, more preferably 3.0 ° C. or higher, lower than the crystallization temperature of the thermoplastic resin.

When the polyamide 12 is used as the thermoplastic resin, the melting point (peak top) of the resin composition for a bonded magnet is preferably 160 ° C. or higher and 177 ° C. or lower, more preferably 170 ° C. or higher and 175 ° C. or lower. Further, the difference between the peak top of the melting peak and the final melting point is preferably more than 5.0 ° C, more preferably more than 5.5 ° C. Further, the calorific value of the melting peak is preferably 50 mJ / mg or more, more preferably 55 mJ / mg or more.

The blending amount of the additive for the bond magnet is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 20% by mass or less in the resin composition composed of the additive for the bond magnet and the thermoplastic resin. If it exceeds 50% by mass, the filling rate of the magnetic powder is lowered, and if it is less than 5% by mass, the effect of lowering the melting point and the crystallization temperature of the melt-kneaded product is small, and the injection pressure at the time of forming the bond magnet is sufficiently lowered. Can't be done.

The step of obtaining the compound for the bond magnet and the magnetic powder used in the step are as described above.

In the second method for producing a compound for a bonded magnet of the present embodiment, the filling rate of the magnetic powder in the compound for a bonded magnet is preferably 75% by mass or more and 96% by mass or less, and 90% by mass or more and 95.5% by mass or less. Is more preferable. If it exceeds 96% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates, and if it is less than 75% by mass, the residual magnetic flux density of the bonded magnet becomes low.

The content of the resin composition for a bonded magnet in the second compound for a bonded magnet of the present embodiment is preferably 2.5% by mass or more and 25% by mass or less, and more preferably 3.5% by mass or more and 10% by mass or less. .. When the content of the resin composition for a bond magnet exceeds 25% by mass, the residual magnetic flux density of the bond magnet becomes low, and when it is less than 2.5% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

In the second compound for bonded magnets of the present embodiment, the weight portion of the resin composition for bonded magnets with respect to 100 parts by weight of the magnetic powder is preferably 2.6 parts by weight or more and 33 parts by weight or less, preferably 3.6 parts by weight or more and 14 parts by weight. More preferably, it is by weight or less. When the weight part of the resin composition for a bond magnet exceeds 33 parts by weight, the residual magnetic flux density of the bond magnet becomes low, and when it is less than 2.6 parts by weight, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

The compound for a bonded magnet of the present embodiment is obtained by the above-mentioned manufacturing method.

The method for manufacturing the first bonded magnet of the present embodiment is as follows.
A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bond magnet.
The magnetic powder includes an injection molding step of injection molding the obtained compound for a bonded magnet, and the magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.

The method for manufacturing the second bonded magnet of the present embodiment is as follows.
A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A step of kneading the additive for a bonded magnet and a thermoplastic resin to obtain a resin composition for a bonded magnet.
A kneading step of kneading the resin composition for a bonded magnet and a magnetic powder to obtain a compound for a bonded magnet.
The magnetic powder includes an injection molding step of injection molding the obtained compound for a bonded magnet, and the magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.

In the method for producing these two bonded magnets, the step of obtaining the additive for the bonded magnet and the kneading step of obtaining the compound for the bonded magnet are as described above.

In the injection molding step, a compound for a bond magnet is injection molded to obtain an injection molded product. The cylinder temperature of the injection molding machine may be in the temperature range in which the compound for the bond magnet melts, and is preferably 260 ° C. or lower from the viewpoint of suppressing magnetic deterioration due to heat of the magnetic powder. The injection pressure may be any pressure as long as the molten compound can be injected. For example, when the cylinder temperature of an injection molding machine is set to 230 ° C. and injection molding is performed into a cavity having a diameter of 10 mm and a thickness of 7 mm, the injection pressure is completely filled at less than 250 MPa from the viewpoint of moldability. It is preferable to be able to do it.

The first bonded magnet of the present embodiment is obtained by, for example, the above-mentioned method for producing the first bonded magnet of the present embodiment, and is characterized by containing an additive for a bonded magnet, a magnetic powder, and a thermoplastic resin. The first bond magnet is manufactured with a low injection pressure by using a highly fluid bond magnet compound containing an additive for the bond magnet, so that magnetic deterioration of the magnetic powder due to injection molding is suppressed. The magnetic properties of the bonded magnet are improved.

In the first bonded magnet of the present embodiment, the filling rate of the magnetic powder in the bonded magnet is preferably 75% by mass or more and 96% by mass or less, and more preferably 90% by mass or more and 95.5% by mass or less. If it exceeds 96% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates, and if it is less than 75% by mass, the residual magnetic flux density of the bonded magnet becomes low.

In the first bond magnet of the present embodiment, the content of the additive for the bond magnet in the bond magnet is preferably 0.1% by mass or more and 4.2% by mass or less, and 0.3% by mass or more and 3.5% by mass or less. % Or less is more preferable, and 0.5% by mass or more and 1.2% by mass or less is further preferable. If the content of the additive for the bond magnet exceeds 4.2% by mass, the residual magnetic flux density of the bond magnet becomes low, and if it is less than 0.1% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates. Sometimes.

In the first bonded magnet of the present embodiment, the content of the thermoplastic resin in the bonded magnet is preferably 2.5% by mass or more and 25% by mass or less, and more preferably 3.5% by mass or more and 10% by mass or less. If the content of the thermoplastic resin exceeds 25% by mass, the residual magnetic flux density of the bonded magnet becomes low, and if it is less than 2.5% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

In the first bonded magnet of the present embodiment, the weight part of the additive for the bonded magnet with respect to 100 parts by weight of the magnetic powder is preferably 0.1 part by weight or more and 5.6 parts by weight or less, and 0.31 part by weight or more and 4. 67 parts by weight or less is more preferable, and 0.52 parts by weight or more and 1.6 parts by weight or less is further preferable. If the amount of the additive for the bond magnet exceeds 5.6 parts by weight, the residual magnetic flux density of the bond magnet becomes low, and if it is less than 0.1 part by weight, the viscosity at the time of injection molding becomes high and the moldability may deteriorate. ..

In the first bonded magnet of the present embodiment, the weight portion of the thermoplastic resin with respect to 100 parts by weight of the magnetic powder is preferably 2.6 parts by weight or more and 33 parts by weight or less, preferably 3.6 parts by weight or more and 14 parts by weight or less. preferable. If the weight portion of the thermoplastic resin exceeds 33 parts by weight, the residual magnetic flux density of the bonded magnet becomes low, and if it is less than 2.6 parts by weight, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

The orientation ratio in the first bonded magnet of the present embodiment is not particularly limited, but is preferably 98% or more, and more preferably 99% or more.

The residual magnetic flux density in the first bonded magnet of the present embodiment is not particularly limited, but is preferably 0.75 T or more, and more preferably 0.8 T or more. A high residual magnetic flux density can be achieved by using the additive for the bonded magnet of the present embodiment.

The coercive force of the first bonded magnet of the present embodiment is not particularly limited, but is preferably 1100 kA / m or more, more preferably 1200 kA / m or more, and particularly preferably 1450 kA / m or more. .. A high coercive force can be achieved by using the additive for the bonded magnet of the present embodiment.

Since the first bond magnet of the present embodiment is manufactured by kneading the additive for the bond magnet, the magnetic powder and the thermoplastic resin, the additive for the bond magnet and the magnetic powder are present independently of each other. become.

The second bond magnet of the present embodiment is obtained by, for example, the above-mentioned method for producing the second bond magnet of the present embodiment, and is characterized by containing a resin composition for a bond magnet and a magnetic powder. The second bond magnet is produced by using a highly fluid bond magnet compound containing a resin composition for a bond magnet with a low injection pressure, so that magnetic deterioration of the magnetic powder due to injection molding is suppressed. , The magnetic properties of the bonded magnet are improved.

In the second bonded magnet of the present embodiment, the filling rate of the magnetic powder in the bonded magnet is preferably 75% by mass or more and 96% by mass or less, and more preferably 90% by mass or more and 95.5% by mass or less. If it exceeds 96% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates, and if it is less than 75% by mass, the residual magnetic flux density of the bonded magnet becomes low.

In the second bond magnet of the present embodiment, the content of the resin composition for the bond magnet in the bond magnet is preferably 2.5% by mass or more and 25% by mass or less, and 3.5% by mass or more and 10% by mass or less. More preferred. When the content of the resin composition for a bond magnet exceeds 25% by mass, the residual magnetic flux density of the bond magnet becomes low, and when it is less than 2.5% by mass, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

In the second bonded magnet of the present embodiment, the weight portion of the resin composition for a bonded magnet with respect to 100 parts by weight of the magnetic powder is preferably 2.6 parts by weight or more and 33 parts by weight or less, and 3.6 parts by weight or more and 14 parts by weight. The following are more preferable. When the weight part of the resin composition for a bond magnet exceeds 33 parts by weight, the residual magnetic flux density of the bond magnet becomes low, and when it is less than 2.6 parts by weight, the viscosity at the time of injection molding becomes high and the moldability deteriorates.

The orientation ratio in the second bonded magnet of the present embodiment is not particularly limited, but is preferably 98% or more, and more preferably 99% or more.

The residual magnetic flux density in the second bonded magnet of the present embodiment is not particularly limited, but is preferably 0.75 T or more, and more preferably 0.8 T or more. A high residual magnetic flux density can be achieved by using the resin composition for a bonded magnet of the present embodiment containing a cured product of a thermosetting resin and a curing agent and a melt-kneaded product of a thermoplastic resin. ..

The coercive force of the second bonded magnet of the present embodiment is not particularly limited, but is preferably 1150 kA / m or more, more preferably 1200 kA / m or more, and particularly preferably 1450 kA / m or more. A high coercive force can be achieved by using the resin composition for a bonded magnet of the present embodiment, which contains a cured product of a thermosetting resin and a curing agent, and a melt-kneaded product of a thermoplastic resin.

Since the second bond magnet of the present embodiment is produced by kneading the resin composition for the bond magnet and the magnetic powder, the resin composition for the bond magnet and the magnetic powder are present independently of each other. ..

<SmFeN-based anisotropic magnetic powder>
In the method for producing the first and second bonded magnet compounds of the present embodiment, the SmFeN-based anisotropic magnetic powder contained in the magnetic powder is not particularly limited, but for example, a solution containing Sm and Fe and a precipitant are mixed. Then, a step of obtaining a precipitate containing Sm and Fe (precipitation step),
Step of calcining the precipitate to obtain an oxide containing Sm and Fe (oxidation step),
A step of heat-treating the oxide in a reducing gas-containing atmosphere to obtain a partial oxide (pretreatment step).
A step of reducing the partial oxide (reduction step) and a step of nitriding the alloy particles obtained in the reduction step (nitriding step).
Those manufactured by a method including the above can be preferably used.

[Precipitation process]
In the precipitation step, the Sm raw material and the Fe raw material are dissolved in a strongly acidic solution to prepare a solution containing Sm and Fe. When Sm ₂ Fe ₁₇ N ₃ is obtained as the main phase, the molar ratio of Sm and Fe (Sm: Fe) is preferably 1.5:17 to 3.0:17, and 2.0:17 to 2.5:17. Is more preferable. Raw materials such as La, W, Co, Ti, Sc, Y, Pr, Nd, Pm, Gd, Tb, Dy, Ho, Er, Tm, and Lu may be added to the above-mentioned solution.

The Sm raw material and Fe raw material are not limited as long as they can be dissolved in a strongly acidic solution. For example, in terms of availability, samarium oxide can be mentioned as the Sm raw material, and FeSO ₄ can be mentioned as the Fe raw material. The concentration of the solution containing Sm and Fe can be appropriately adjusted within a range in which the Sm raw material and the Fe raw material are substantially dissolved in the acidic solution. Examples of the acidic solution include sulfuric acid in terms of solubility.

By reacting the solution containing Sm and Fe with the precipitating agent, an insoluble precipitate containing Sm and Fe is obtained. Here, the solution containing Sm and Fe may be a solution containing Sm and Fe at the time of reaction with the precipitating agent. For example, raw materials containing Sm and Fe are prepared as separate solutions, and each solution is dropped. And may react with the precipitating agent. Even when prepared as separate solutions, appropriate adjustments are made as long as each raw material is substantially dissolved in an acidic solution. The precipitating agent is not limited as long as it is an alkaline solution that reacts with a solution containing Sm and Fe to obtain a precipitate, and examples thereof include aqueous ammonia and caustic soda, and caustic soda is preferable.

In the precipitation reaction, a method of dropping a solution containing Sm and Fe and a precipitating agent into a solvent such as water is preferable because the properties of the particles of the precipitate can be easily adjusted. By appropriately controlling the supply rate of the solution containing Sm and Fe and the precipitant, the reaction temperature, the concentration of the reaction solution, the pH at the time of reaction, etc., the distribution of the constituent elements is uniform, the particle size distribution is sharp, and the powder shape is formed. A well-organized precipitate is obtained. By using such a precipitate, the magnetic properties of the final product, the magnetic powder, are improved. The reaction temperature can be 0 to 50 ° C, preferably 35 to 45 ° C. The concentration of the reaction solution is preferably 0.65 mol / L to 0.85 mol / L, more preferably 0.7 mol / L to 0.84 mol / L, as the total concentration of the metal ions. The reaction pH is preferably 5 to 9, more preferably 6.5 to 8.

The anisotropic magnetic powder particles obtained in the precipitation step roughly determine the powder particle size, powder shape, and particle size distribution of the finally obtained magnetic powder. When the particle size of the obtained particles is measured by a laser diffraction type wet particle size distribution meter, the total powder has a size and distribution within the range of 0.05 to 20 μm, preferably 0.1 to 10 μm. Is preferable. Further, the average particle size of the anisotropic magnetic powder particles is measured as a particle size corresponding to 50% of the cumulative volume from the small particle size side in the particle size distribution, and is preferably in the range of 0.1 to 10 μm.

After separating the precipitate, the precipitate is redissolved in the remaining solvent in the heat treatment of the subsequent oxidation step, and when the solvent evaporates, the precipitate aggregates and the particle size distribution, powder particle size, etc. change. It is preferable to desolvate the separated product in order to prevent the separation. Specific examples of the method for removing the solvent include, for example, when water is used as the solvent, a method of drying in an oven at 70 to 200 ° C. for 5 to 12 hours can be mentioned.

After the precipitation step, a step of separating and washing the obtained precipitate may be included. The washing step is appropriately performed until the conductivity of the supernatant solution becomes 5 mS / m ² or less. As a step of separating the precipitate, for example, a filtration method, a decantation method or the like can be used after adding a solvent (preferably water) to the obtained precipitate and mixing them.

[Oxidation process]
The oxidation step is a step of obtaining an oxide containing Sm and Fe by calcining the precipitate formed in the precipitation step. For example, the precipitate can be converted into an oxide by heat treatment. When the precipitate is heat-treated, it must be carried out in the presence of oxygen, for example, in the air atmosphere. Moreover, since it is necessary to carry out in the presence of oxygen, it is preferable that the non-metal portion in the precipitate contains an oxygen atom.

The heat treatment temperature (hereinafter referred to as the oxidation temperature) in the oxidation step is not particularly limited, but is preferably 700 to 1300 ° C, more preferably 900 to 1200 ° C. If the temperature is lower than 700 ° C., the oxidation becomes insufficient, and if the temperature exceeds 1300 ° C., the desired shape, average particle size and particle size distribution of the magnetic powder tend not to be obtained. The heat treatment time is not particularly limited, but 1 to 3 hours is preferable.

The obtained oxide is an oxide particle in which Sm and Fe are sufficiently microscopically mixed in the oxide particle, and the shape of the precipitate, the particle size distribution, and the like are reflected.

[Pretreatment process]
The pretreatment step is a step of heat-treating an oxide containing Sm and Fe in a reducing gas atmosphere to obtain a partially reduced oxide.

Here, the partial oxide means an oxide in which a part of the oxide is reduced. The oxygen concentration of the oxide is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less. If it exceeds 10% by mass, the reduction heat generation with Ca becomes large in the reduction step, and the firing temperature becomes high, so that particles with abnormal particle growth tend to be formed. Here, the oxygen concentration of the partial oxide can be measured by the non-dispersed infrared absorption method (ND-IR).

The reducing gas is appropriately selected from hydrocarbon gases such as hydrogen (H ₂ ), carbon monoxide (CO), and methane (CH ₄ ), but hydrogen gas is preferable in terms of cost, and the flow rate of the gas is oxidation. It is adjusted appropriately as long as the object does not scatter. The heat treatment temperature (hereinafter, pretreatment temperature) in the pretreatment step is in the range of 300 ° C. or higher and 950 ° C. or lower, preferably 400 ° C. or higher, more preferably 750 ° C. or higher, and preferably less than 900 ° C. When the pretreatment temperature is 300 ° C. or higher, the reduction of the oxide containing Sm and Fe proceeds efficiently. Further, when the temperature is 950 ° C. or lower, the oxide particles are suppressed from growing and segregating, and the desired particle size can be maintained. When hydrogen is used as the reducing gas, it is preferable to adjust the thickness of the oxide layer to be used to 20 mm or less, and further adjust the dew point in the reaction furnace to −10 ° C. or less.

[Reduction process]
The reduction step is a step of obtaining alloy particles by heat-treating the partial oxide at 920 ° C. or higher and 1200 ° C. or lower in the presence of a reducing agent. For example, the partial oxide is combined with a calcium melt or calcium vapor. Reduction is performed by contact. The heat treatment temperature is preferably 950 ° C. or higher and 1150 ° C. or lower, and more preferably 980 ° C. or higher and 1100 ° C. or lower from the viewpoint of magnetic characteristics. The heat treatment time is preferably less than 120 minutes, more preferably less than 90 minutes, and the lower limit of the heat treatment time is preferably 10 minutes or more, more preferably 30 minutes or more, from the viewpoint of more uniform reduction reaction.

Metallic calcium is used in the form of granules or powder, and the particle size thereof is preferably 10 mm or less. This makes it possible to more effectively suppress aggregation during the reduction reaction. In addition, metallic calcium is a reaction equivalent (a stoichiometric amount required to reduce Sm oxide, and if Fe is in the form of an oxide, it includes the amount required to reduce it). It can be added in an amount of 1.1 to 3.0 times, preferably 1.5 to 2.0 times.

In the reduction step, a disintegration accelerator can be used as needed together with the metallic calcium which is a reducing agent. This disintegration accelerator is appropriately used to promote disintegration and granulation of the product in the washing step described later. For example, alkaline earth metal salts such as calcium chloride and alkaline soil such as calcium oxide. Examples include similar oxides. These disintegration accelerators are used in a proportion of 1 to 30% by mass, preferably 5 to 28% by mass, per Sm oxide used as a Sm source.

[Nitriding process]
The nitriding step is a step of obtaining anisotropic magnetic particles by nitriding the alloy particles obtained in the reduction step. Since the particulate precipitate obtained in the above-mentioned precipitation step is used, porous lumpy alloy particles can be obtained in the reduction step. As a result, nitriding can be performed uniformly by heat treatment in a nitrogen atmosphere immediately without performing pulverization treatment.

The heat treatment temperature (hereinafter referred to as nitriding temperature) in the nitriding treatment of the alloy particles is preferably a temperature of 300 to 600 ° C., particularly preferably 400 to 550 ° C., and is carried out by replacing the atmosphere with a nitrogen atmosphere in this temperature range. The heat treatment time may be set so that the nitriding of the alloy particles is sufficiently uniform.

The product obtained after the nitriding step contains CaO by-produced, unreacted metallic calcium, and the like in addition to the magnetic particles, and may be in a sintered mass state in which these are combined. Therefore, in that case, this product can be put into cooling water to separate CaO and metallic calcium from the magnetic particles as a calcium hydroxide (Ca (OH) ₂ ) suspension. Further, the residual calcium hydroxide may be sufficiently removed by washing the magnetic particles with acetic acid or the like.

The SmFeN-based anisotropic magnetic powder obtained by the above-mentioned production method has a Th ₂ Zn ₁₇ -type crystal structure, and has a general formula of Sm _x Fe _{100-xy Ny} , which is a rare earth metal samarium Sm and iron. It is a nitride composed of Fe and nitrogen N. Here, it is preferable that x is 8.1 atomic% or more and 10 atomic% or less, y is 13.5 atomic% or more and 13.9 atomic% or less, and the balance is mainly Fe.

The average particle size of the SmFeN-based anisotropic magnetic powder is preferably 2 μm or more and 5 μm or less, and more preferably 2.5 μm or more and 4.8 μm or less. If it is less than 2 μm, the filling amount of the magnetic powder in the bonded magnet becomes small, so that the magnetization decreases, and if it exceeds 5 μm, the coercive force of the bonded magnet tends to decrease. Here, the average particle size is the particle size measured under dry conditions using a laser diffraction type particle size distribution measuring device.

The particle size D10 of the SmFeN-based anisotropic magnetic powder is preferably 1 μm or more and 3 μm or less, and more preferably 1.5 μm or more and 2.5 μm or less. If it is less than 1 μm, the filling amount of the magnetic powder in the bonded magnet becomes small, so that the magnetization decreases, while if it exceeds 3 μm, the coercive force of the bonded magnet tends to decrease. Here, D10 is a particle size corresponding to an integrated value of the particle size distribution based on the volume of the SmFeN-based anisotropic magnetic powder of 10%.

The particle size D50 of the SmFeN-based anisotropic magnetic powder is preferably 2.5 μm or more and 5 μm or less, and more preferably 2.7 μm or more and 4.8 μm or less. If it is less than 2.5 μm, the filling amount of the magnetic powder in the bonded magnet becomes small, so that the magnetization decreases, and if it exceeds 5 μm, the coercive force of the bonded magnet tends to decrease. Here, D50 is a particle size corresponding to an integrated value of the particle size distribution based on the volume of the SmFeN-based anisotropic magnetic powder of 50%.

The particle size D90 of the SmFeN-based anisotropic magnetic powder is preferably 3 μm or more and 7 μm or less, and more preferably 4 μm or more and 6 μm or less. If it is less than 3 μm, the filling amount of the magnetic powder in the bonded magnet becomes small, so that the magnetization decreases, and if it exceeds 7 μm, the coercive force of the bonded magnet tends to decrease. Here, D90 is a particle size corresponding to 90% of the integrated value of the particle size distribution based on the volume of the SmFeN-based anisotropic magnetic powder.

Span defined below for SmFeN-based anisotropic magnetic powders:
Span = (D90-D10) / D50
Is preferably 2 or less, more preferably 1.5 or less, from the viewpoint of coercive force.

The circularity of the SmFeN-based anisotropic magnetic powder is not particularly limited, but is preferably 0.5 or more, and more preferably 0.6 or more. If it is less than 0.5, the fluidity deteriorates and stress is applied between the particles during molding, so that the magnetic properties deteriorate. Here, in order to measure the circularity, the SEM image taken at 3000 times is binarized by image processing, and the circularity is obtained for one particle. The circularity defined in the present invention means an average value of circularity obtained by measuring about 1000 to 10000 particles. Generally, the larger the number of particles having a small particle size, the higher the circularity. Therefore, the circularity is measured for particles having a diameter of 1 μm or more. In the measurement of circularity, the definition formula: circularity = (4πS / L2) is used. However, S is the two-dimensional projected area of the particle, and L is the two-dimensional projected perimeter.

<Method for producing phosphate-coated SmFeN-based anisotropic magnetic powder>
The magnetic powder of the present embodiment contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate. The SmFeN-based anisotropic magnetic powder having a surface coated with a phosphate can be produced by adding a pH-adjusted phosphoric acid treatment solution to a slurry containing the SmFeN-based anisotropic magnetic powder.

[Phosphoric acid treatment process]
In the phosphoric acid treatment step, an SmFeN-based anisotropic magnetic powder, a solvent, and a phosphoric acid compound are mixed to obtain an SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate. The phosphate-coated SmFeN-based anisotropic magnetic powder is a phosphate obtained by reacting a metal component (for example, iron or samarium) contained in the SmFeN-based anisotropic magnetic powder with a phosphoric acid component contained in a phosphoric acid compound. (For example, iron phosphate, samarium phosphate) is formed by precipitating on the surface of the SmFeN-based anisotropic magnetic powder. Above all, when the solvent is water, a phosphate having a smaller particle size is precipitated as compared with the case where the solvent is an organic solvent, so that a phosphate-coated SmFeN-based anisotropic magnetic powder having a dense coating can be obtained. It is considered that the coercive force (iHc) is improved. The case where the solvent is water will be described below.

In the phosphoric acid treatment step, a slurry containing an SmFeN-based anisotropic magnetic powder, water, and a phosphoric acid compound is prepared. The method for producing the slurry is not particularly limited, but it can be obtained, for example, by mixing an SmFeN-based anisotropic magnetic powder and a phosphoric acid aqueous solution containing a phosphoric acid compound using water as a solvent. The content of the SmFeN-based anisotropic magnetic powder in the slurry is, for example, 1% by mass or more and 50% by mass or less, and preferably 5% by mass or more and 20% by mass or less from the viewpoint of productivity. The content of the phosphoric acid component ₍ PO ₄ ) in the slurry is, for example, 0.01% by mass or more and 10% by mass or less in terms of PO4, in terms of reactivity and productivity between the metal component and the phosphoric acid component. It is preferably 0.05% by mass or more and 5% by mass or less.

The phosphoric acid aqueous solution is obtained by mixing a phosphoric acid compound and water. Examples of the phosphoric acid compound include phosphates such as orthophosphoric acid, sodium dihydrogen phosphate, sodium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, zinc phosphate, and calcium phosphate, and hypophosphite. Examples thereof include organic phosphoric acid such as acid-based, hypophosphite-based, pyrophosphoric acid-based, and polyphosphoric acid-based inorganic phosphoric acid. Only one of these may be used, or two or more thereof may be used in combination. Further, for the purpose of improving the water resistance, corrosion resistance and magnetic properties of the magnetic powder of the coating portion, oxo acid salts such as molybdenate, tungstate, vanadinate and chromate, sodium nitrate, sodium nitrite, etc. An oxidizing agent or the like, a chelating agent such as EDTA can be used as an additive.

The concentration of phosphoric acid ₍ PO4 equivalent amount) in the aqueous phosphoric acid solution is, for example, 5% by mass or more and 50% by mass or less, and is 10% by mass in terms of solubility of the phosphoric acid compound, storage stability, and ease of chemical conversion treatment. It is preferably 30% by mass or less. The pH of the aqueous phosphoric acid solution is, for example, 1 or more and 4.5 or less, and preferably 1.5 or more and 4 or less from the viewpoint of easily controlling the precipitation rate of the phosphate. The pH can be adjusted with dilute hydrochloric acid, dilute sulfuric acid, or the like.

In the phosphoric acid treatment step, it is preferable to add an inorganic acid to adjust the pH of the slurry to 1 or more and 4.5 or less. When the pH is adjusted to 1 or more and 4.5 or less, the amount of phosphate precipitates can be increased as compared with the case where the pH is not adjusted, and the phosphate-coated SmFeN-based anisotropy with a thick coating portion. Since the magnetic powder is obtained, it is considered that the coercive force (iHc) is improved. The pH range to be adjusted is preferably pH 1 or more and 4.5 or less, more preferably pH 1.6 or more and 3.9 or less, and further preferably pH 2 or more and 3 or less. Examples of the inorganic acid to be added include hydrochloric acid, nitric acid, sulfuric acid, boric acid, and hydrofluoric acid. During the phosphoric acid treatment step, an inorganic acid is added at any time so as to be within the above pH range. Inorganic acids are used from the viewpoint of waste liquid treatment, but organic acids can be used in combination depending on the purpose. Examples of the organic acid include acetic acid, formic acid, tartaric acid and the like.

When the pH of the slurry is adjusted to 1 or more and 4.5 or less by adding an inorganic acid in the phosphoric acid treatment step, the adjustment is preferably performed for 10 minutes or more, and the viewpoint of reducing the portion where the thickness of the coating portion is thin is reduced. It is more preferable to carry out for 30 minutes or more. At the initial stage of pH maintenance, the pH control interval is short because the pH rises quickly, but as the coating progresses, the pH fluctuation gradually slows down and the inorganic acid input interval becomes longer, so the reaction end point is I can judge.

[Oxidation process after phosphoric acid treatment]
The phosphate-coated SmFeN-based anisotropic magnetic powder may be subjected to an oxidation treatment, if necessary. By oxidizing the phosphate-coated SmFeN-based anisotropic magnetic powder, the surface of the SmFeN-based anisotropic magnetic powder of the base material coated with the phosphate is oxidized to form an iron oxide layer, and phosphorus is formed. The oxidation resistance of the acid salt-coated SmFeN-based anisotropic magnetic powder is improved. Further, by oxidation, when the phosphate-coated SmFeN-based anisotropic magnetic powder is exposed to a high temperature during the production of the bonded magnet, an unfavorable redox reaction, decomposition reaction and alteration occur on the surface of the SmFeN particles. It can be suppressed, and as a result, a magnet having high magnetic properties, particularly high intrinsic coercive force (iHc), can be obtained.

The oxidation treatment is performed by heat-treating the SmFeN-based anisotropic magnetic powder after the phosphoric acid treatment in an oxygen-containing atmosphere. The reaction atmosphere preferably contains oxygen in an inert gas such as nitrogen or argon. The oxygen concentration is preferably 3% or more and 21% or less, and more preferably 3.5% or more and 10% or less. During the oxidation reaction, it is preferable to exchange the gas at a flow rate of 2 L / min or more and 10 L / min or less with respect to 1 kg of the magnetic powder.

The temperature during the oxidation treatment is preferably 150 ° C. or higher and 250 ° C. or lower, and more preferably 170 ° C. or higher and 230 ° C. or lower. Below 150 ° C., the formation of the iron oxide layer is insufficient, and the oxidation resistance tends to decrease. If the temperature exceeds 250 ° C., an iron oxide layer is excessively formed, and the coercive force tends to decrease. The reaction time is preferably 3 hours or more and 10 hours or less.

The SmFeN-based anisotropic magnetic powder after the phosphoric acid treatment may be subjected to the above-mentioned silica treatment or silane coupling treatment, if necessary.

The SmFeN-based anisotropic magnetic powder after the phosphoric acid treatment step, the oxidation step, the silica treatment, or the silane coupling treatment can be filtered, dehydrated, and dried by a conventional method.

<Phosphate-coated SmFeN-based anisotropic magnetic powder>
The lower limit of the phosphate content in the phosphate-coated SmFeN-based anisotropic magnetic powder may be 0.1% by mass or more, preferably 0.55% by mass or more, and 0.75% by mass or more. The upper limit of the phosphate content is preferably 4.5% by mass or less, more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less. When the phosphate content is less than 0.1% by mass, the effect of coating with the phosphate tends to be small, and when it exceeds 4.5% by mass, the phosphate-coated SmFeN-based anisotropic magnetism tends to be small. The powders tend to aggregate and the coercive force tends to decrease. The phosphate content of the magnetic powder is expressed as a PO4 molecule equivalent measured by ICP emission spectroscopic analysis (ICP _- AES).

The phosphate-coated SmFeN-based anisotropic magnetic powder may have a heat generation start temperature of 90 ° C. or higher, preferably 120 ° C. or higher, more preferably 170 ° C. or higher, and 200 ° C. or higher. Is particularly preferable. The heat generation start temperature in DSC is a comprehensive evaluation of the density, thickness, oxidation resistance, etc. of the phosphate coating, and a high coercive force can be obtained when the temperature is 90 ° C. or higher. The heat generation start temperature in the DSC is, for example, 20 mg of a phosphate-coated SmFeN-based anisotropic magnetic powder, and an air atmosphere (DSC6300, manufactured by Hitachi High-Tech Science Co., Ltd.) using a high-temperature differential scanning heat analyzer (DSC6300, manufactured by Hitachi High-Tech Science Co., Ltd.). It can be measured by performing DSC analysis under the measurement conditions of 200 mL / min), room temperature to 400 ° C. (heating rate: 20 ° C./min), and reference: alumina (20 mg). The high heat generation start temperature means that the phosphoric acid coating is formed more densely because heat generation due to oxidation is unlikely to occur.

The phosphate-coated SmFeN-based anisotropic magnetic powder has a diffraction peak intensity (I) on the (110) plane of αFe and a peak intensity (II) on the (300) plane of the SmFeN-based anisotropic magnetic powder in the XRD diffraction pattern. The ratio (I) / (II) to and to is preferably 3 × 10 ⁻² or less, more preferably 2.5 × 10 − ² or less, and preferably 1.0 × 10 − ² or less. Especially preferable. The diffraction peak intensity (I) on the (110) plane of αFe represents the abundance of the impurity αFe, and when the ratio (I) / (II) described above is 2.5 × 10 ⁻² or less. , High coercive force can be obtained. The diffraction peak intensity in the XRD diffraction pattern is determined by measuring the XRD pattern of a phosphate-coated SmFeN-based anisotropic magnetic powder with a powder X-ray crystal diffractometer (X-ray wavelength: CuKa1), and then α-. The value obtained by dividing the diffraction peak intensity of the (110) plane of Fe by the peak intensity of the (300) plane of Sm ₂ Fe ₁₇ N ₃ can be obtained as the α-Fe peak height ratio. A low α-Fe peak height ratio means that the content of the impurity α-Fe is low.

The phosphate-coated SmFeN-based anisotropic magnetic powder preferably has a carbon content of 1000 ppm or less, more preferably 800 ppm or less. The carbon content indicates the amount of organic impurities in the phosphate, and when the carbon content exceeds 1000 ppm, the phosphate-coated SmFeN-based anisotropic magnetic powder is exposed to a high temperature in the process of producing a bonded magnet. As a result, organic impurities are decomposed and defects are generated in the coating portion, so that the coercive force tends to decrease. Here, the carbon content can be measured by the TOC method.

The thickness of the phosphate-coated portion of the phosphate-coated SmFeN-based anisotropic magnetic powder is not particularly limited, but is preferably 10 nm or more and 200 nm or less from the viewpoint of the coercive force of the phosphate-coated SmFeN-based anisotropic magnetic powder. The thickness of the phosphate-coated portion can be measured by performing a composition analysis on the cross section of the phosphate-coated SmFeN-based anisotropic magnetic powder by line analysis using EDX.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

In the examples and comparative examples, the following materials were used.
Epoxy resin: Biphenyl type (epoxy equivalent 186 g / eq)
Curing agent: DDS (diaminodiphenyl sulfone) (active hydrogen equivalent 62.0 g / eq)
Curing accelerator: TPP (triphenylphosphine)
Thermoplastic resin: Polyamide 12 (ZZ3000P manufactured by Daicel Evonik)

Production Example 1
(Preparation of SmFeN-based anisotropic magnetic powder)
FeSO _{4.7H 2} O 5.0 kg was mixed and dissolved in 2.0 kg of pure water. Further, 0.49 kg of Sm ₂ O ₃ and 0.74 kg of 70% sulfuric acid were added and stirred well to completely dissolve them. Next, pure water was added to the obtained solution to adjust the Fe concentration to 0.726 mol / L and the Sm concentration to 0.112 mol / L to prepare a SmFe sulfuric acid solution.

[Precipitation process]
The entire amount of the prepared SmFe sulfuric acid solution was added dropwise to 20 kg of pure water maintained at a temperature of 40 ° C. with stirring for 70 minutes from the start of the reaction, and at the same time, a 15% ammonia solution was added dropwise to adjust the pH to 7-8. .. As a result, a slurry containing SmFe hydroxide was obtained. The obtained slurry was washed with pure water by decantation, and then the hydroxide was separated into solid and liquid. The separated hydroxide was dried in an oven at 100 ° C. for 10 hours.

[Oxidation process]
The hydroxide obtained in the precipitation step was calcined in the air at 1000 ° C. for 1 hour. After cooling, a red SmFe oxide was obtained as a raw material powder.

[Pretreatment process]
100 g of SmFe oxide was placed in a steel container so as to have a bulk thickness of 10 mm. The container was placed in a furnace, the pressure was reduced to 100 Pa, and then the temperature was raised to the pretreatment temperature of 850 ° C. while introducing hydrogen gas, and the mixture was kept as it was for 15 hours. The oxygen concentration was measured by the non-dispersed infrared absorption method (ND-IR) (EMGA-820 manufactured by HORIBA, Ltd.) and found to be 5% by mass. As a result, it was found that the oxygen bound to Sm was not reduced, and 95% of the oxygen bound to Fe was reduced to obtain a black partial oxide.

[Reduction process]
60 g of the partial oxide obtained in the pretreatment step and 19.2 g of metallic calcium having an average particle size of about 6 mm were mixed and placed in a furnace. After evacuating the inside of the furnace, argon gas (Ar gas) was introduced. Fe—Sm alloy particles were obtained by raising the temperature to 1045 ° C. and holding for 45 minutes.

[Nitriding process]
Subsequently, after cooling the temperature inside the furnace to 100 ° C., vacuum exhaust was performed, the temperature was raised to 450 ° C. while introducing nitrogen gas, and the temperature was maintained as it was for 23 hours to obtain a lump product containing magnetic particles. rice field.

[Washing process]
The lumpy product obtained in the nitriding step was put into 3 kg of pure water and stirred for 30 minutes. After standing still, the supernatant was drained by decantation. Addition to pure water, stirring and decantation were repeated 10 times. Then, 2.5 g of 99.9% acetic acid was added and stirred for 15 minutes. After standing still, the supernatant was drained by decantation. SmFeN-based anisotropic magnetic powder (average particle size 3 μm) was obtained by repeatedly adding water to pure water, stirring and decanting twice, followed by dehydration and drying, and then mechanically crushing the powder.

Manufacturing example 2
[Phosphoric acid treatment step 1]
As a phosphoric acid treatment solution, 85% orthophosphoric acid: sodium dihydrogen phosphate: sodium molybdate dihydrate = 1: 6: 1 was mixed in a weight ratio, and the pH was 2.5 and PO ₄ with pure water and dilute hydrochloric acid. A preparation having an adjusted concentration of 20% by mass was prepared. After removing 1000 g of the SmFeN-based anisotropic magnetic powder obtained in Production Example 1 in dilute hydrochloric acid of hydrogen chloride: 70 g for 1 minute to remove the surface oxide film and dirt components, the conductivity of the supernatant liquid is 100 μS / cm or less. Drainage and water injection were repeated until the amount became, and a slurry containing 10% by mass of SmFeN-based anisotropic magnetic powder was obtained. While stirring the obtained slurry, 100 g of the prepared phosphoric acid treatment liquid was put into the treatment tank in its entirety. The pH of the phosphoric acid treatment reaction slurry increased from 2.5 to 6 over 5 minutes. After stirring for 15 minutes, suction filtration, dehydration, and vacuum drying were performed to obtain a phosphate-coated SmFeN-based anisotropic magnetic powder.

[Silica treatment process]
Phosphate-coated SmFeN-based anisotropic magnetic powder, ethyl silicate 40, and 12.5% by weight of aqueous ammonia were mixed with a mixer at a weight ratio of 97.8: 1.8: 0.4, respectively. The mixture was heated in vacuum at 200 ° C. to obtain a SmFeN-based anisotropic magnetic powder having a silica thin film formed on the particle surface.

[Silane coupling treatment process]
After mixing SmFeN-based anisotropic magnetic powder on which a silica thin film is formed and 12.5% by weight of ammonia water in a mixer, 50% by weight of an ethanol solution of 3-aminopropyltriethoxysilane is mixed in the mixer. did. The weight ratio of the SmFeN-based anisotropic magnetic powder on which the silica thin film was formed, 12.5% by weight of ammonia water, and 50% by weight of the ethanol solution of 3-aminopropyltriethoxysilane was 99: 0.2: 0, respectively. It was 8.8. The mixture was dried in a nitrogen atmosphere at 100 ° C. for 10 hours to obtain a silane-coupled SmFeN-based anisotropic magnetic powder.

Production example 3
[Phosphoric acid treatment step 2]
As a phosphoric acid treatment solution, mix 85% orthophosphoric acid: sodium dihydrogen phosphate: sodium molybdenate dihydrate = 1: 6: 1, and use pure water and dilute hydrochloric acid to adjust the pH to ₂ and the PO4 concentration. The one adjusted to 20% by mass was prepared. After removing 1000 g of the SmFeN-based anisotropic magnetic powder obtained in Production Example 1 in dilute hydrochloric acid of hydrogen chloride: 70 g for 1 minute to remove the surface oxide film and dirt components, the conductivity of the supernatant liquid is 100 μS / cm or less. Drainage and water injection were repeated until the amount became, and a slurry containing 10% by mass of SmFeN-based anisotropic magnetic powder was obtained. While stirring the obtained slurry, 100 g of the prepared phosphoric acid treatment solution was put into the treatment tank in its entirety, and then 6% by weight of hydrochloric acid was added at any time to adjust the pH of the phosphoric acid treatment reaction slurry to 2.5 ± 0. It was controlled in the range of .1 and maintained for 30 minutes. Subsequently, suction filtration, dehydration, and vacuum drying were carried out to obtain a phosphate-coated SmFeN-based anisotropic magnetic powder.

[Oxidation process after phosphoric acid treatment]
1000 g of the obtained phosphate-coated SmFeN-based anisotropic magnetic powder was gradually heated from room temperature in an atmosphere of a mixed gas of nitrogen and air (oxygen concentration 4%, 5 L / min), and the maximum temperature was 170 ° C. for 8 hours. The heat treatment was carried out to obtain an oxidation-treated SmFeN-based anisotropic magnetic powder.

[Silica treatment process]
Oxidized SmFeN-based anisotropic magnetic powder, ethyl silicate 40, and 12.5% by weight of aqueous ammonia were mixed with a mixer at a weight ratio of 97.8: 1.8: 0.4, respectively. The mixture was heated in vacuum at 200 ° C. to obtain a SmFeN-based anisotropic magnetic powder having a silica thin film formed on the particle surface.

[Silane coupling treatment process]
The SmFeN-based anisotropic magnetic powder on which the silica thin film was formed was mixed with 12.5% by weight of aqueous ammonia in a mixer, and then an ethanol solution of 50% by weight 3-aminopropyltriethoxysilane was mixed with the mixer. .. The weight ratio of the SmFeN-based anisotropic magnetic powder on which the silica thin film was formed, 12.5% by weight of ammonia water, and 50% by weight of the ethanol solution of 3-aminopropyltriethoxysilane was 99: 0.2: 0, respectively. It was 8.8. 1 of the mixture
The mixture was dried in a nitrogen atmosphere at 00 ° C. for 10 hours to obtain a silane-coupled SmFeN-based anisotropic magnetic powder.

Production example 4
(Making additives for bonded magnets)
12 parts by weight of the epoxy resin, 8.8 parts by weight of the curing agent, and 0.4 parts by weight of the curing accelerator were dissolved and mixed with 100 parts by weight of acetone. After the acetone was volatilized, it was cured in a shelf dryer at 200 ° C. for 6 hours in a nitrogen atmosphere. The obtained cured product was pulverized with a mixer and classified with a sieve having an opening of 500 μm to prepare an additive for a bonded magnet.

Production Example 5
(Preparation of resin composition for bond magnet)
With respect to 100 parts by weight of the polyamide 12, the additive for a bonded magnet obtained in Production Example 4 of 17.4 parts by weight was melt-kneaded in a twin-screw kneader in an environment of 210 ° C. to obtain a resin composition for a bonded magnet. Got

Example 1
(Making a compound for bond magnets)
1.27 parts by weight of the additive for the bonded magnet prepared in Production Example 4 and 7.19 parts by weight with respect to 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder prepared in Production Example 2. The polyamide 12 was kneaded and melt-extruded and kneaded in a twin-screw kneader in an environment of 210 ° C. to obtain a compound for a bonded magnet.

(Making a bond magnet)
The obtained compound for a bond magnet was injection-molded at a cylinder temperature of 230 ° C., a mold temperature of 90 ° C., and an injection pressure of 186 MPa to obtain a bond magnet having a diameter of 10 mm and a thickness of 7 mm.

Example 2
(Making a compound for bond magnets)
8.46 parts by weight of the resin composition for a bonded magnet prepared in Production Example 5 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 2 and biaxially kneaded. It was melt-extruded and kneaded in a machine at 210 ° C. to obtain a compound for a bonded magnet.

(Making a bond magnet)
A bond magnet was obtained in the same manner as in Example 1 using the obtained compound for bond magnets. The injection pressure at the time of injection molding was 144 MPa.

Example 3
(Making a compound for bond magnets)
7.89 parts by weight of the resin composition for a bonded magnet prepared in Production Example 5 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 2 and biaxially kneaded. It was melt-extruded and kneaded in a machine at 210 ° C. to obtain a compound for a bonded magnet.

(Making a bond magnet)
A bond magnet was obtained in the same manner as in Example 1 using the obtained compound for bond magnets. The injection pressure during injection molding was 241 MPa.

Example 4
(Making a compound for bond magnets)
8.46 parts by weight of the resin composition for a bonded magnet prepared in Production Example 5 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 3 and biaxially kneaded. It was melt-extruded and kneaded in a machine at 210 ° C. to obtain a compound for a bonded magnet.

(Making a bond magnet)
A bond magnet was obtained in the same manner as in Example 1 using the obtained compound for bond magnets. The injection pressure during injection molding was 115 MPa.

Example 5
(Making a compound for bond magnets)
7.89 parts by weight of the resin composition for a bonded magnet prepared in Production Example 5 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 3 and biaxially kneaded. It was melt-extruded and kneaded in a machine at 210 ° C. to obtain a compound for a bonded magnet.

(Making a bond magnet)
A bond magnet was obtained in the same manner as in Example 1 using the obtained compound for bond magnets. The injection pressure during injection molding was 230 MPa.

Comparative Example 1
(Making a compound for bond magnets)
8.27 parts by weight of polyamide 12 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 2, and melt-extruded in a twin-screw kneader in an environment of 210 ° C. Kneading was performed to obtain a compound for a bonded magnet.

(Making a bond magnet)
A bond magnet was obtained in the same manner as in Example 1 using the obtained compound for bond magnets. The injection pressure during injection molding was 235 MPa.

Comparative Example 2
(Making a compound for bond magnets)
7.7 parts by weight of polyamide 12 is kneaded with 100 parts by weight of the silane-coupled SmFeN-based anisotropic magnetic powder produced in Production Example 2, and melt-extruded in a twin-screw kneader in an environment of 210 ° C. Kneading was performed to obtain a compound for a bonded magnet.

(Making a bond magnet)
When the same procedure as in Example 1 was carried out using the obtained compound for a bonded magnet, the injection die could not be completely filled and a molded product could not be obtained.

The residual magnetic flux density Br, coercive force iHc, and orientation rate of the bonded magnets obtained in Examples and Comparative Examples were evaluated by the following methods. The evaluation results are shown in Table 1.

(Residual magnetic flux density (Br) of magnetic powder, coercive force (iHc))
<Residual magnetic flux density, coercive force and orientation rate>
The silane-coupled SmFeN-based magnetic powder obtained in Production Example 2 and Production Example 3 is packed in a sample container together with paraffin wax, and the paraffin wax is melted by a dryer, and then easily magnetized by a 2T orientation magnetic field. Aligned magnetic domains. This magnetic field-oriented sample is pulse-magnetized with a magnetic field of 6T, and magnetic properties (residual magnetization σr, intrinsic maintenance) are used using VSM (vibrating sample magnetometer Riken Denshi; model: BHV-55) with a maximum magnetic field of 2T. The magnetic force iHc) was measured. The results are shown in Table 1. The residual magnetic flux density Br (unit: T) is calculated by using a calculation formula (Br = 4 × π × ρ × σr, ρ: density = 7.66 g / cm ³ ) for the residual magnetization σr (unit: emu / g). Calculated.

(PO ₄ adhesion amount)
The P concentration in the phosphate-coated SmFeN-based anisotropic magnetic powder obtained in Production Example 2 and Production Example 3 was measured by ICP emission spectroscopic analysis (ICP-AES) and converted into PO ₄ molecular weight. The amount of PO ₄ adhered was determined. The results are shown in Table 1.

(Residual magnetic flux density (Br) of bonded magnet, coercive force (iHc))
For the bonded magnets produced in Examples and Comparative Examples, the residual magnetic flux density Br (T) and the coercive force iHc (kA / m) were measured using a BH tracer. The orientation rate is calculated by the following formula:
Orientation rate (%) = Br (T) / (Volume filling rate of SmFeN-based magnetic powder (vol%) ÷ 100 × Silane coupling Residual magnetic flux density (T) of SmFeN-based magnetic powder) × 100
Calculated by

From Table 1, it was confirmed that in the examples, the injection pressure was lower and the fluidity of the compound for the bond magnet was improved when compared with each comparative example having the same volume filling factor of the magnetic powder. Further, as a result of improving the fluidity of the compound for the bond magnet, it was confirmed that the coercive force in the bond magnet was increased.

DSC measurement was carried out for a powder mixture in which the polyamide 12 and the polyamide 12 and the additive for a bond magnet prepared in Production Example 2 were mixed at the ratios shown in Table 2 below, and the resin composition for a bond magnet prepared in Production Example 3. The DSC measurement was performed by using a differential scanning calorimeter to raise the temperature to 210 ° C. at 10 ° C./min and then lower the temperature to 30 ° C. at 5 ° C./min. Table 2 shows the values of the melting peak and the crystallization peak.

In the resin composition for a bonded magnet in which the cured product and the polyamide 12 were melt-kneaded in advance, the melting point was about 5 ° C. and the crystallization temperature was about 3 ° C. lower than those of the polyamide 12 alone. It is presumed that the decrease in melting point and crystallization temperature slows the cooling and solidification of the resin in the mold during injection molding and improves the fluidity of the compound for bond magnets.

According to the method for producing a compound for a bond magnet of the present invention, a compound for a bond magnet having greatly improved fluidity can be obtained, and the coercive force of the obtained bond magnet can also be improved. The obtained bond magnet can be suitably applied to applications such as motors as a composite material and a bond magnet.

Claims (8)

A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bond magnet is included.
The magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.
How to manufacture a compound for bonded magnets. A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A step of kneading the additive for a bonded magnet and a thermoplastic resin to obtain a resin composition for a bonded magnet.
The process includes a kneading step of kneading the resin composition for a bonded magnet and a magnetic powder to obtain a compound for a bonded magnet.
The magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.
How to manufacture a compound for bonded magnets. The method for producing a compound for a bonded magnet according to claim 1 or 2, wherein the thermoplastic resin is a nylon resin. The method for producing a compound for a bonded magnet according to any one of claims 1 to 3, wherein the magnetic powder has a monodisperse particle size distribution. A compound for a bonded magnet obtained by the manufacturing method according to any one of claims 1 to 4. A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A kneading step of kneading the additive for a bond magnet, a magnetic powder, and a thermoplastic resin to obtain a compound for a bond magnet.
Including an injection molding step of injection molding the obtained compound for a bond magnet,
The magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.
How to manufacture a bond magnet. A step of thermally curing a thermosetting resin and a curing agent having a ratio of the number of reactive groups to the number of reactive groups of the thermosetting resin of 2 or more and 11 or less to obtain an additive for a bonded magnet.
A step of kneading the additive for a bonded magnet and a thermoplastic resin to obtain a resin composition for a bonded magnet.
A kneading step of kneading the resin composition for a bonded magnet and a magnetic powder to obtain a compound for a bonded magnet.
Including an injection molding step of injection molding the obtained compound for a bond magnet,
The magnetic powder contains a SmFeN-based anisotropic magnetic powder whose surface is coated with a phosphate.
How to manufacture a bond magnet. A bond magnet obtained by the manufacturing method according to claim 6 or 7.