JPH05308007A - Thermosetting magnetic material resin composite material - Google Patents

Abstract

PURPOSE:To provide a magnetic material resin composite material which has high density, and which is excellent in the magnetic field orientation and the oxide resistance by using a rare-earth-iron-nitrogen system magnetic material which is a particle having a high magnetic characteristic. CONSTITUTION:This thermosetting magnetic material composite material is composed of a rare-earth-iron-nitrogen system magnetic pulverized body of 79 to 99.5wt.%, a lubricant of 0.001 to 5wt.%, a coupling agent of 0.001 to 5wt.%, and epoxy resin of 0.2 to 20wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting type magnetic material resin composite material using a rare earth-iron-nitrogen based material which is excellent in corrosion resistance, oxidation resistance and magnetic properties.

[0002]

2. Description of the Related Art Bonded magnets have attracted special attention in recent years because they have excellent molding processability as compared with sintered magnets, can be formed into complex shapes and can be integrally molded, are resistant to cracking, and have good dimensional accuracy. The range of usage is expanding.

In particular, the market for high-characteristic bonded magnets using rare earth magnetic materials such as Sm-Co and Nd-Fe-B is rapidly growing.

In addition to these, as a rare earth magnetic material, a rare earth-iron-nitrogen magnetic material has been invented (for example, JP-A-2-57663). This material is Sm-Co based or N
Unlike d-Fe-B based materials, even fine powders of 10 μm or less have high magnetic properties. If this material having small grains is used, a magnetic material resin composite material having excellent magnetic characteristics and excellent surface smoothness and mechanical strength and its magnet can be expected.

However, since this material has a high magnetic property, and has a small particle size and a large specific surface area, the magnetic powder particles are agglomerated with each other and it is difficult to uniformly mix and knead the resin. Therefore, it is difficult to obtain a magnetic material resin composite material for use in a bonded magnet, which has insufficient magnetic powder surface coating, has many voids, has a high density, and has sufficient corrosion resistance, oxidation resistance and high magnetic properties.

In particular, in order to obtain a bonded magnet with high magnetic characteristics, a magnetic field is applied from the outside to magnetically orient the magnetic particles. However, when the magnetic particles are agglomerated intensely, the magnetic field orientation is deteriorated and the material is originally It cannot exhibit its high magnetic force. Furthermore, since the particle size is small, it is easily oxidized during the process treatment, and the magnetic properties are greatly deteriorated. Therefore, in order to obtain a bonded magnet having high magnetic properties, corrosion resistance, and oxidation resistance, and having excellent surface smoothness, mechanical strength, and dimensional stability, it contains a rare earth-iron-nitrogen system, has a high density, and The advent of magnetic material-resin composite materials having excellent magnetic field orientation is strongly desired.

[0007]

DISCLOSURE OF THE INVENTION The present invention uses a rare earth-iron-nitrogen based magnetic material which is a fine particle and has high magnetic properties, and has a high density, a magnetic material resin composite material excellent in magnetic field orientation and oxidation resistance. Is to provide.

[0008]

[MEANS FOR SOLVING THE PROBLEMS] A magnetic material resin having a high density, excellent magnetic field orientation, corrosion resistance, and oxidation resistance, using a rare earth-iron-nitrogen-based magnetic material whose primary particles are fine particles and which has high magnetic characteristics. In order to obtain a composite material, as a result of diligent studies on the magnetic powder surface treatment method, the affinity between the surface treatment agent and the resin, the kneading method, the molding method and the combination thereof, the magnetic field orientation and the oxidation resistance are excellent. The present invention has led to the discovery of such a composition.

The present invention is a rare earth-iron-nitrogen based magnetic powder 79.
.About.99.5% by weight, lubricant 0.001 to 5% by weight, coupling agent 0.001 to 5% by weight, and epoxy resin 0.
The magnetic material-resin composite material is characterized by comprising 2 to 20% by weight.

Further, it has the following features. That is, (1) the lubricant described above is a magnetic material resin composite material containing one kind or two or more kinds of fatty acids, amines, fatty acid salts, and fatty acid amides.

(2) The coupling agent described above is titanium,
The magnetic material resin composite material is a coupling agent containing at least one kind of silicon.

Using this magnetic material-resin composite material, a bonded magnet can be produced by compression molding, extrusion molding, injection molding or the like.

The present invention will be described in detail below.

The rare earth-iron-nitrogen (R-F) used in the present invention
The e-N) -based magnetic material will be described.

As the rare earth (R), Y, La, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H
It suffices to include at least one of o, Er, Tm, Yb and Lu. Therefore, a mixture of two or more kinds of rare earth elements such as misch metal and didymium may be used, but preferable rare earths are Y, Nd and Ce. , Pr, Sm, Gd,
Dy and Er. More preferably, Y, Nd, Ce,
Pr and Sm.

Iron (Fe) is the basic composition of the present magnetic material which is responsible for ferromagnetism, but 0.01 to 49 atomic% of Fe is Co, N
i, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Mn, Pd, Zn, B, Al, Ga, C, Si, G
The element (M) of e and Sn can be replaced with one kind or two or more kinds. Of these, Ti, Zr, Hf,
One or more of V, Mo, Mn, B, Al, C, Si and Ge are preferable. More preferably, Zr,
One or more of V, Cr, Mo, B, and C. Hereinafter, when it is described as iron or an iron component, the case where a part of Fe is replaced by M is also included.

The amount of iron replaced by M, excluding the case where only one kind of Co is replaced, is preferably 0.01 to 34 atomic%.
More preferably, it is 0.01 to 20% atom.

It is important that the composition of the rare earth-iron-nitrogen based magnetic material is within a composition range containing at least rare earth, iron and nitrogen and exhibiting ferromagnetism. Among the present invention, in order to obtain high magnetic properties, R is preferably in the composition range of 5 to 20 atom%, iron component is 40 to 90 atom%, and nitrogen (N) is 1 to 25 atom%. Regarding the composition range of nitrogen,
More preferably 2 to 25 atom%, most preferably 3 to
It is 20 atomic%.

In addition to nitrogen, the rare earth-iron-nitrogen based magnetic material used in the present invention contains 0.01 to 5 atom% of hydrogen (H) and 0.01 to 10 atom% of oxygen (O). In some cases

The crystal structure of the rare earth-iron-nitrogen magnetic material includes hexagonal and rhombohedral systems such as R ₂ Fe ₁₇ N _X type and R ₂ Fe ₁₇ C _Y N _X type, and R ₂ Fe ₁₄ BN _X. Mold, R ₂ Fe ₁₄
One or more of the tetragonal systems such as CN _X type and R (Fe _{1 -Z} M _Z ) ₁₂ type are taken. The preferable Y value is 0.00022 to 3, the atomic ratio of M to iron at this time is 0.001 to 13.6 atomic%, and Z is preferable.
Is 0.000012 to 0.33, and the atomic ratio of M to iron at this time is 0.001 atom% to 33.3 atom%.

In addition to the M component, Li, Na,
K, Mg, Ca, Sr, Ba, Ti, Zr, Hf, V,
Nb, Ta, Cr, Mo, W, Mn, Pd, Cu, A
g, Zn, B, Al, Ga, In, C, Si, Ge, S
n, Pb, Bi elements, and oxides, fluorides, carbides, nitrides, nitrides, hydrides, carbonates, sulfates, silicates, chlorides, and nitrates of these elements and Re, at least one of rare earth- 0.01-49 for iron-nitrogen based magnetic materials
It is also possible to include wt%.

The content of the rare earth-iron-nitrogen based magnetic material in the magnetic material resin composite material of the present invention is 79-9.
It should be 9.5% by weight. When the content is less than 79% by weight, the residual magnetic flux density is low, the utility as a permanent magnet is low, and the effect of the resin on the magnetic field orientation of the present invention is small. On the other hand, if it exceeds 99.5% by weight, the amount of magnetic powder per unit volume increases, but the magnetic field orientation is inferior, the residual magnetic flux density is not improved due to the decrease of the resin component, and the amount of resin is small. Since the surface of the magnetic powder cannot be covered, it has poor oxidation resistance. The average particle size of the rare earth-iron-nitrogen based magnetic powder is preferably in the range of 0.1 to 80 μm.

When a material having particularly excellent dimensional stability and surface smoothness, which are features of the composite magnetic material of the present invention, is produced, the average particle size is preferably 1 to 10 μm. In order to further improve the density, it is effective to give the particle size an appropriate distribution.

Examples of the lubricant in the present invention include fatty acids such as stearic acid, oleic acid, palmitic acid, linoleic acid, lauric acid, 1,2-oxstearic acid and ricinoleic acid, and amines such as oleylamine, stearylamine and laurylamine. , Amino acids such as glycine, alanine, aspartic acid, arginine and histidine, zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, zinc laurate, calcium laurate, zinc ricinoleate, calcium ricinoleate , Fatty acid salts such as zinc 2-ethylhexoate, fatty acid amides such as stearic acid amide, hydroxystearic acid amide and palmitic acid amide, Si ₃ N ₄ , SiC, MgO, Al
Inorganic compound powder such as ₂ O ₃ , TiC, Sb ₂ O ₃ , silicone oil, silicone grease, silicone resin, polysiloxane such as polysilane coupling agent, fatty acid ester such as butyl stearate, ethylene glycol, stearyl alcohol Such as alcohols, paraffin wax, liquid paraffin, polyethylene wax, polypropylene wax, ester wax, carnauba, micro wax, and other waxes, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro Alkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene-perofluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer Coalesce, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer,
Examples thereof include one type or two or more types of fluorine-based resins such as polyvinylidene fluoride, polyvinyl fluoride, and polyfluorinated urethane resins.

The magnetic powder of the present invention includes, in particular, amines such as oleylamine, stearylamine and laurylamine,
Amino acids such as glycine, alanine, aspartic acid, arginine, and histidine and other compounds having an amino group improve the density and magnetic field orientation, and show good results. The fatty acids include both-terminal carvone,
Both amines are included in the amines.

The content of the lubricant is preferably 0.001 to 5% by weight, and if it exceeds 5% by weight, the magnetic field orientation is not improved as the content is increased, and the mechanical strength is lowered, which is not preferable. .. When the amount is less than 0.001% by weight, the effect of addition is hardly seen. Regarding the amount of the lubricant added, 0.001 to 50% by weight in consideration of the loss due to filtration during the mixing process and the leakage from the mold during the molding process.
It is good to In addition, the amount of the inorganic compound powder such as Si ₃ N ₄ used in the rare earth-iron-nitrogen based magnetic powder as the above-mentioned M component, the inorganic compound powder is the magnetic material resin composite material of the present invention. It can be contained in the range of 0.1 to 54% by weight.

The effects of the lubricant are mainly the following two points.

The first effect is that it is adsorbed, reacted or coordinated on the surface of the rare earth-iron-nitrogen based magnetic powder to prevent aggregation of the magnetic powder, thereby contributing to the improvement of magnetic field orientation. For example, when the magnetic powder whose surface is treated with amines, amino acids, fatty acids and fatty acid salts is contained, the effect of improving the magnetic field orientation becomes remarkable.

The second effect is that it penetrates into the gap of the composition composed of the rare earth-iron-nitrogen based magnetic powder, the coupling agent and the thermosetting resin to reduce voids and the magnetic field orientation of the composition. It is the effect of enhancing the sex.

Although the above-mentioned effects can be seen in any lubricant, there are cases in which density and magnetic characteristics are improved due to other effects. For example, in the case of using Re-Fe-N-H-O based magnetic powder, the composition and distribution of the oxide surface layer is changed by amines or acids, so that rare earth-
The effect is to improve the magnetic properties of the iron-nitrogen based magnetic powder itself.

As the coupling agent in the present invention,
Isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, isopropyl trioctanoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl dimethacryl isostearoyl titanate, tetra (2,2-) Diallyloxymethyl-1-butyl) bis (ditridecylpho (Phito) titanate, isopropyl tricumyl phenyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, titanium-based coupling agents such as isopropyl isostearoyl diacrylic titanate, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -Γ-aminopropyltrimethoxysilane, γ-glycidoxy-propyltrimethoxysilane, β- (3,4-epoxy-cycloxyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris (2-methoxyethoxy) silane, γ-mercaptopropyltrimethoxysilane, N
-Β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (3-triethoxysilylpropyl)
Urea, methyltrimethoxysilane, octadecyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] In addition to coupling agents containing silicon such as ammonium chloride, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, polyalkylene oxide silanes, perfluoroalkyltrimethoxysilanes, acetoalkoxyaluminum diisopropylate, etc. One or more coupling agents such as aluminum-based, zirconium-based, chromium-based, iron-based, and tin-based coupling agents may be mentioned, and particularly isopropyltriisostearoyl titanate. , Isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl titanate, γ-aminopropyltriethoxysilane, N-β- ( Aminoethyl)-
γ-aminopropyltrimethoxysilane, γ-glycidoxy-propyltrimethoxysilane, β- (3,4-epoxy-cycloxyl) ethyltrimethoxysilane titanium-based or silicon-based, containing alkyl group, amino group, glycidyl group Coupling agents are preferred.

Generally, when a large amount of titanium-based coupling agent is added, the dispersibility is improved, and as a result, the orientation of the magnetic powder is remarkably improved and the material has excellent magnetic properties. On the other hand, when a silicon-based coupling agent is used, the effect of improving the orientation of the magnetic powder and at the same time increasing the mechanical strength can be obtained. In order to utilize the advantages of both of them, a coupling agent containing titanium and silicon is mixed and added to obtain a material having excellent magnetic characteristics and mechanical characteristics.

The content of the coupling agent is the particle size of the magnetic powder,
Although it is determined by the particle shape and the specific surface area, the rare earth-iron-nitrogen-based material mainly contains powder of about several μm, so if the content exceeds 5% by weight, the dispersibility of the magnetic powder will increase as the content increases. It is not preferable because the magnetic properties and the mechanical strength are deteriorated in addition to no improvement.

The content of the coupling agent is 0.0
01 to 5% by weight is preferable, and if it exceeds 5% by weight, the magnetic field orientation and mechanical strength are not improved as the content increases, and the magnetization is lowered, which is not preferable. 0.00
If it is less than 1% by weight, the effect of addition is scarcely seen.
The amount of the coupling agent added is preferably 0.001 to 50% by weight, in consideration of loss of alkoxy groups and loss during the process.

The addition amount is preferably 20% by weight or less in consideration of the loss of the coupling agent and the reduction due to the elimination of the organic chain portion in the steps of mixing and kneading.

Further, as a coupling reaction catalyst,
Water, amines and the like may be added together with the coupling agent.

When the lubricant and the coupling agent are used in combination, the effect is high, and the combination effect varies depending on their types. Generally, if the total amount of the lubricant and the titanium-based coupling agent is increased, the magnetic field orientation is increased and the magnetic properties are improved. Noticeably improved.
On the other hand, when a large amount of a coupling agent containing silicon is used, the magnetic properties as well as the mechanical strength increase. However, it cannot be said unconditionally depending on the type of combination and the processing method, and it is important to select a manufacturing method whose characteristics can be controlled.

As the main component of the epoxy resin in the present invention, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, resorcinol diglycidyl ether, hexahydrobisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether,
Bifunctional resin such as neopentyl glycol diglycidyl ether, phthalic acid diglycidyl ester, dimer acid diglycidyl ester, N, N-diglycidyl-5,5-dimethylhydantoin, 1,3-bis (diglycidylaminomethyl) cyclohexane , Triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylenediamine, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, diglycidyl aniline, diglycidyl orthotoluidine, hexaglycidyl mesitylene triamine, hexaglycidyl hydrogenated mesitylene triamine, Tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl isocyanate Polyfunctional resins such as nurate, m- (diglycidylamino) glycidylphenyl ether, p- (diglycidylamino) glycidylphenyl ether, p- (diglycidylamino) glycidylcrezoyl ether, tetrabromobisphenol A diglycidyl ether, Bisphenol hexafluoroacetone diglycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2
-Trifluoroethyl] benzene, 1,4-bis [1-
(2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene,
Halogenated resin such as 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, bisphenol A-β-methyl glycidyl ether, bisphenol F-β-methyl glycidyl ether, bisphenol S
One or more of methyl-substituted epoxy resins in which the glycidyl group of the above resin such as -β-methyl glycidyl ether is replaced with β-methyl glycidyl may be used.

As the curing agent for the epoxy resin, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and diethylaminopropylamine, polyamidediamines such as aminopolycaproamide at both ends and polyamides such as polyamidepolyamine, Mensendiamine, isophoronediamine,
N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3)
Alicyclic polyamines such as -methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, 1-
Pentachlorophenyldiethylenetriamine, N, N '
-Aromatic polyamines such as (hexachlorobiphenylene) bisethylenediamine, amides such as dicyandiamide, diacetoneacrylamide / amine complex, hydrazides such as adipic acid dihydrazide, 2-
(2-Dimethylaminoethoxy) 4-methyl-1,3
Amines such as 2-dioxabornane, modified amines such as epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride Acids, monofunctional acid anhydrides such as methyl nadic acid anhydride, dodecyl succinic anhydride, chlorendic acid anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexene Bifunctional acid anhydrides such as tetracarboxylic acid anhydrides, free acid anhydrides such as trimellitic anhydride, polyazelainic acid anhydride, polyphenols such as phenol novolac and polymercaptan, benzyldimethylamido , 2- (dimethylaminomethyl)
Aromatic tertiary amines such as phenol, 2,4,6-tris (diaminomethyl) phenol, DMP-30 tri-2-ethylhexylate, 2-methylimidazole,
2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,
2,4-diamino-6- [2-methylimidazolyl-
(1)]-ethyl S-triazine and other imidazoles, dicyandiamide, adipic acid hydrazide, diaminomaleonitrile, diallyl melamine, poly (piperidine sebacic acid) amide and other dispersion type curing agents, aromatic diazonium salts, diallyl iodonium salts, Photolytic curing agents such as triallyl sulfonium salts and triallyl selenium salts, polysulfide resins, boron trifluoride amine complexes such as boron trifluoride monoethylamine complex, moisture curing type curing agents such as ketoimine compounds, aniline-formaldehyde Resin, phenyltris (methylamino) silane, phenyltris (ethylamino) silane, vinyltris (hexylamino) silane,
Examples include silanes such as aminosiloxanes, polymercaptans, silicic acids such as supercoordinated silicates, and the like, or two or more kinds thereof.

As the epoxy resin used in the present invention, one set or two or more sets are used among the arbitrary combinations of the above-mentioned main component and curing agent.

The types of epoxy resin include pot life, heat resistance, corrosion resistance, flame retardancy, low temperature characteristics, coefficient of thermal expansion, thermal deformation temperature, mechanical strength, abrasion resistance, adhesiveness, elasticity, Impact resistance, flexibility, dimensional stability, chemical resistance, weather resistance, oil resistance, water resistance, hot water resistance, moisture resistance, radiation resistance,
It is appropriately selected according to the required performance of the product such as electrical characteristics, dielectric characteristics, dielectric breakdown, arc resistance, etc., and is also limited by moldability and productivity.

The content of the epoxy resin of the present invention is 0.2-
It must be in the range of 20% by weight. 0.2% by weight
If it is less, the mechanical strength will be insufficient, and if it is more than 20% by weight, the magnetization will be low and the practicality as a permanent magnet application will be low.

The feature of the present invention is remarkable when epoxy is used as the binder for the rare earth-iron-nitrogen based material, and the combined effect of the lubricant and the coupling agent is comparable when other thermosetting resins are used. That is. Therefore, other resins may be used in combination with the epoxy resin, but the content is 50% by weight or less of 50 resins of the epoxy resin, and the total amount of the resins is 0.
It should be in the range of 2 to 20% by weight.

Further, in the present invention, a reactive diluent, a reactive plasticizer and a non-reactive plasticizer can be added if necessary.

For example, n-butyl glycidyl ether,
2-ethylhexyl glycidyl ether, octylene oxide, cyclohexene vinyl monooxide, dipentene monooxide, α-pinene oxide, olefin oxides, glycidyl methacrylate, p-butylphenol glycidyl ether, cresyl glycidyl ether, 3 (pentadecyl) phenyl glycidyl ether, Allyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate, tertiary carboxylic acid glycidyl ester, diglycidyl ester, (poly) ethylene glycol diglycidyl ether, (poly ) Propylene glycol diglycidyl ether, butanediol diglycidyl ether Le, monoglycidyl ethers such as diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, reactive diluents, such as dimers, Kada Nord epoxidized,
Butadiene oxide, dimethylpentane dioxide, diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, limonene dioxide, vinyl cyclohexene dioxide, bis (2,3-epoxycyclopentyl) ether, divinylbenzene dioxide, 3, 4-epoxy-6-methylcyclohexylmethyl-3,4-epoxymethylcyclohexanecarboxylate, resorcin diglycidyl ether, 2-glycidyl phenyl glycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, diphenol of bisphenol A alkylene oxide adduct Glycidyl ether, polymeric fatty acid adduct of bisphenol A diglycidyl ether, dimer acid polyglycidyl ester Which diglycidyls, polypropylene glycol, polytetramethylene glycol, polyethylene glycol, polyols such as polyester with hydroxyl groups at both ends, polythiols such as polysulfide thiol, polycarboxys, urethanes, diphenyl chlorides, phthalates such as dibutyl phthalate And one or more reactive plasticizers or non-reactive plasticizers.

The reactive diluent and the reactive plasticizer are used for the purpose of lowering the viscosity of the epoxy resin to improve the magnetic field orientation and improving the moldability to improve the density. However, if it is added too much, the mechanical strength is lowered, which is not preferable, and it is usually desirable to use it in the range of 0.05 to 30% by weight with respect to the epoxy resin. The non-reactive plasticizer is highly effective when added at the time of molding, but it is better not to use it too much, and it should be kept within 5% by weight at most.

The magnetic resin composite material of the present invention is mainly mixed with a stabilizer such as a heat-resistant antioxidant and an antioxidant in order to improve the heat resistance of the thermosetting resin. Alternatively, it can be added in advance to the thermosetting resin component.

Examples of the heat and antioxidants and heat stabilizers include N, N'-hexamethylene-bis (3,5)
-Di-tert-butyl-hydroxycinnamic acid amide), 4,
4'-bis (2,6-di-tert-butylphenol), 2,
Various hindered phenols such as 2′-methylenebis (4-ethyl-6-tert-butylphenol), N, N-bis (β-naphthyl) -p-phenylenediamine, N,
N'-diphenyl-p-phenylenediamine, aromatic amines such as poly (2,2,4-trimethyl-1,2-dihydroquinoline), copper salts such as copper chloride and copper iodide,
Examples thereof include sulfur compounds such as dilauryl thiodipropionate and phosphorus compounds.

Further, a non-reactive diluent, a thixotropic agent, a sealant, an ultraviolet absorber, an antistatic agent, a colorant, a filler, etc. are added to the magnetic material resin composite material in the present invention, if necessary. Agent, silica, whiskers, talc,
Fillers such as asbestos, ferrite, SmCo and Nd-Fe-
Magnet powder such as B and a thermoplastic resin can be added.

Next, a method for manufacturing the magnetic material-resin composite material according to the present invention will be described, but the invention is not limited to the manufacturing method described below.

(1) Mixing Step This step is a step of mixing a rare earth-iron-nitrogen based magnetic powder having an average particle diameter of several μm with a lubricant or a coupling agent. At this time, in order to homogeneously mix the magnetic powder and the lubricant or the coupling agent, it is desirable to dissolve or disperse the lubricant or the coupling agent in a solvent such as an organic solvent or an aqueous solvent in advance before use.

The mixer is not particularly limited, and examples thereof include a ribbon mixer, a V-type mixer, a rotary mixer, a Henschel mixer, a flash mixer, a Nauta mixer, a super mixer and a tumbler.
If a mixer such as a Henschel mixer, which has a large share, is used, it is possible to sufficiently mix the lubricant and / or the coupling agent without being dissolved in the solvent.

A rotary ball mill, a vibrating ball mill,
A method of adding and mixing by using a pulverizer such as a planetary ball mill, a wet mill, a jet mill, a hammer mill, and a cutter mill is also effective.

In the case of mixing using a solvent, it is effective to carry out a heat treatment while recovering the solvent after stirring and mixing so that the surface of the magnetic powder and the lubricant or coupling agent are sufficiently reacted. The temperature is preferably 250 ° C. or lower, and may be under normal pressure, reduced pressure, or increased pressure. However, when the solvent is recovered at the same time as the heat treatment, it is preferably lower than normal pressure. The atmosphere may be air, but when the temperature exceeds 100 ° C., it is desirable to use an inert gas such as nitrogen gas, argon gas, or helium gas, or a vacuum.
Even during the stirring and mixing, the surface of the magnetic powder may react with the lubricant or the coupling agent in some cases.

A method of mixing the lubricant and the solvent and then filtering to remove the solvent is also effective. However, if the lubricant has solubility in the solvent, the amount of lubricant added must be determined in consideration of the loss contained in the filtrate.

When a lubricant and a coupling agent are used in combination, either a method of mixing at the same time, a method of adding and mixing one and then a method of adding and mixing the other may be used, but the optimum mixing conditions are the same combination of the lubricant and the coupling agent. It is also different in, so be careful.

Of course, the lubricant and the coupling agent can be added in the kneading step and the molding step after the mixing step, but at least one of them is preferably added in the mixing step.

The thermosetting resin is preferably added after the surface of the magnetic powder is treated with a lubricant or a coupling agent, but a resin containing a lubricant or a coupling agent in advance may be added. is there.

In order to facilitate the kneading in the next step,
It is also possible to add the thermosetting resin by dissolving it in a solvent, or to add a reactive diluent together.

Furthermore, when a two-pack type epoxy resin is used,
In order not to accelerate the curing during the process, the main agent alone or the curing agent alone is mixed with the magnetic powder, and the other is added in the subsequent step, or the main agent and the curing agent are separately mixed with the magnetic powder and kneaded. A method of dry or wet mixing at the time of molding or at the time of molding is also effective.

(2) Kneading Step A mixture of the mixed magnetic powder, lubricant, and / or coupling agent, thermosetting resin and other additives is added to a batch kneader, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single shaft. Extruder, twin-screw extruder,
Using an automatic mortar, etc., in the temperature range of -50 to 300 ° C,
This is the step of kneading.

The kneading temperature is selected in a region where curing of the thermosetting resin does not proceed. When a solvent is added to the mixture, a method of collecting the solvent simultaneously with kneading is effective.

The kneading step is not essential, and the solvent is instantly recovered by using, for example, spray drying, and the surface of the magnetic powder is coated with a resin, a lubricant, a coupling agent and a resin, or a granulated body is formed. It is also effective to use a material having good flowability during molding.

(3) Molding Step When a bonded magnet is manufactured from the magnetic material-resin composite material obtained in the present invention, a molding treatment is further performed.

Among them, as a method for producing a bonded magnet having high magnetic properties, there is a method of performing compression molding, extrusion molding or injection molding while applying a magnetic field. In particular, the compression molding method can obtain a bonded magnet having excellent surface smoothness and magnetic properties.

When molding without applying a magnetic field, an isotropic bonded magnet is obtained.

In this molding step, it is effective to add a lubricant and a solvent after charging the magnetic material-resin composite material into the mold.

In this case, it is effective in improving the density and magnetic field orientation. The thermosetting resin is usually cured by applying heat, but a hot pressing method in which heat is applied during molding, or a method in which a molded product is removed from a mold and cured.

Of course, when a resin which cures at room temperature is used, it is not necessary to carry out the curing treatment.

Further, a method of crushing a molded body once subjected to compression molding, extrusion molding, and injection molding and using it again as a material for compression molding and injection molding is effective in improving flowability and magnetic field orientation during molding.

The molded body is usually further magnetized to enhance its performance as a permanent magnet. The magnetization is performed by a commonly used method such as an electromagnet that generates a static magnetic field and a condenser magnetizer that generates a pulsed magnetic field. The magnetic field strength for sufficiently magnetizing is preferably 15 kO.
e or more, more preferably 30 kOe or more.

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EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

The evaluation method is as follows.

(1) Magnetic Properties The magnetic material resin composite material is molded into a plate shape of about 5 × 10 × 2 mm in a magnetic field, or cut out from a large-sized molded product,
This was press-magnetized at 60 kOe at room temperature and then measured using a vibrating sample magnetometer (VSM). The measured magnetic characteristics are the saturation magnetization 4 when an external magnetic field of 15 kOe is applied.
πIs (kG), residual magnetic flux density Br (kG), squareness ratio B
r / πIs (%), holding power (specific holding power) iHc (kO
e), the maximum energy product (BH) _max (MGOe).

(2) Bending rupture strength A plate-shaped sample having a length of 10 mm, a width of 5 mm and a thickness of 1 mm was measured according to JIS K 7203 except for the dimensions of the test piece.

(3) Corrosion resistance test The plate-shaped or ring-shaped bonded magnet used in (1) was
The appearance was left for 96 hours in a constant temperature and humidity chamber at 60 ° C. and 90% relative humidity, and the appearance was evaluated according to the following three grades.

◯: No rust was generated, Δ: Slight rust was generated, X: Rust was generated (4) Oxidation resistance test The plate-shaped bonded magnet used in (1) was placed in an oven at 150 ° C. After 20 hours, the magnetic characteristics were measured in the same manner as in (1) and compared with the result in (1).

Example 1 Sm _8.4 Fe _71.0 N _14.2 H _1.4 O having an average particle size of 2.5 μm
_5.0 g of the magnetic powder and 0.015 g of γ-aminopropyltriethoxysilane in an isopropanol solution were mixed in a ball mill for 30 minutes and heated in vacuum at 100 ° C. for 1 hour. This magnetic powder was mixed with a solution of 0.05 g of oleylamine dissolved in methyl ethyl ketone diluent in a mortar.
Mix for 0 minutes.

After drying the surface-treated magnetic powder,
Bisphenol A dissolved in methyl ethyl ketone diluent
0.1 g of diglycidyl ether and 0.028 g of diaminodiphenylmethane were placed in a mortar and kneaded at room temperature for 1 hour,
The diluent was vaporized. Next, this magnetic powder was added to 15 kOe
Was compression-molded in a magnetic field of 14 ton / cm ² .
Thereafter, the compact was heated at 80 ° C. for 1 hour under reduced pressure to produce a compression-molded bonded magnet. Tables 1 and 2 show the test results of the magnetic properties, corrosion resistance, and oxidation resistance of this product.

Comparative Example 1 A compression-molded bonded magnet was produced in the same manner as in Example 1 except that no surface treatment was applied. The results of magnetic properties, corrosion resistance and oxidation resistance of this product are shown in Tables 1 and 2. Examples 2 to 4 Bond magnets were produced in the same manner as in Example 1 except that the types of lubricants, coupling agents, resins, and addition amounts were changed to those in Table 1. Tables 1 and 2 show the magnetic properties, corrosion resistance, and oxidation resistance of these materials.

Examples 5 to 6 Bond magnets were produced in the same manner as in Example 1 except that the rare earth-iron-nitrogen based powder was changed to the substances shown in Table 2. Table 3 shows the magnetic properties, corrosion resistance, and oxidation resistance of these materials.

Comparative Examples 2 to 3 Bond magnets were produced in the same manner as in Comparative Example 1 except that the rare earth-iron-nitrogen based powder was changed to the substances shown in Table 1. Table 3 shows the magnetic properties, corrosion resistance, and oxidation resistance of these materials.

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[Table 1]

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[Table 2]

[0085]

[Table 3]

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As described above, according to the present invention,
It is possible to obtain a magnetic material resin composite material containing a rare earth-iron-nitrogen material having a small particle size and high magnetic properties, and also having high magnetic field orientation, corrosion resistance, and oxidation resistance, and further using these materials. It is possible to produce a bond magnet having high magnetic characteristics, which is excellent in surface smoothness, mechanical characteristics, and dimensional stability.

Claims (1)

[Claims] 1. A rare earth-iron-nitrogen based magnetic powder 79-9.
9.5% by weight, lubricant 0.001-5% by weight, coupling agent 0.001-5% by weight and epoxy resin 0.2
A thermosetting magnetic material resin composite material, characterized in that the thermosetting magnetic material resin composite material is contained.