JP4033112B2 - Self-organized hybrid rare earth bonded magnet, method for manufacturing the same, and motor - Google Patents

Description

  The present invention is widely used for control and drive of computer peripherals, printers, etc., so-called permanent magnet rotor type, or permanent magnet field type, which is actively undergoing technological innovation centering on miniaturization, weight reduction and high output. More specifically, the present invention relates to a self-organized rare earth bonded magnet to be mounted thereon, a method for manufacturing the same, and the small motor.

J. et al. J. et al. Croat, J. et al. F. Herbst, R.A. W. Lee and F.M. E. Pinkerton: J.M. Appl. Phys. , Vol. 55, 2078 (1984): According to Non-Patent Document 1, an R-Fe-B (R is Nd, Pr) type alloy melt-spun ribbon is Hci> 1.2 (MA / m), remanent magnetization (Mr) 800 ( mT), the maximum energy product (BH) _max 112 (kJ / m ³ ) magnetic characteristics were revealed. At the same time Sagawa, S .; Fujiwara, H .; Yamamoto and Y.J. Matsuura: J.M. Appl. Phys. , Vol. 55, 2083 (1984): According to Non-Patent Document 2, a sintered magnet of (BH) _max 304 (kJ / m ³ ) can be obtained by using a powder metallurgical technique using an Nd—Fe—B alloy as a starting material. It became clear. In 1986, J.M. F. Herbst, R.A. W. Lee and F.M. E. Pinkerton: Ann. Rev. Mater. Sci. , Vol. 16, 467 (1986). J. et al. Croat et al. It was revealed that the main phase of the Nd-Fe-B ternary alloy of Sagawa et al. Is an Nd ₂ Fe ₁₄ B intermetallic compound. As a method for producing the rare earth-iron magnet, a mechanical alloying method, a hot casting method, and the like have been proposed thereafter. However, representative rare earth-iron magnets that have created and expanded new markets from the late 1980s to the present are M.M. Sagawa's powder metallurgy-based atmospheric pressure sintered magnet; J. et al. It is divided into two types of quenching magnets starting from the melt spun ribbon of Croat et al.

First, although it is a normal pressure sintered magnet by a powder metallurgy technique, the production of this magnet is based on a method for producing a 1-5, 2-17 type Sm-Co sintered magnet that has already been produced on an industrial scale. It seems that production technology on an industrial scale was quickly established because of the advantages available. In addition, Dy addition increases the magnetocrystalline anisotropy to improve thermal stability, V and Mo addition improve both thermal stability and corrosion resistance, and surface treatment improves corrosion resistance. (BH) As a sintered magnet of max 216 to 296 (kJ / m ³ ), it has been widely spread to relatively large motors such as MRI, VCM, FA, EV, etc., which have a mechanical output of several hundred watts to several tens kW.

On the other hand, J.H. J. et al. The material form obtained with the Croat et al. Meltspan is limited to ribbons and other flakes or flaked powders. For this reason, in order to use a generally used bulk permanent magnet, it is necessary to change the material form, that is, a technique for fixing a ribbon or powder to a specific bulk by some method. Although the basic powder fixing means in powder metallurgy is atmospheric pressure sintering, it is difficult to apply atmospheric pressure sintering to the melt spun ribbon because it is necessary to maintain magnetic properties based on a metastable state. For this reason, it has been carried out that a ribbon or powder is fixed to a bulk of a specific shape exclusively with a binder such as an epoxy resin. R. W. Lee, E .; G. Brewere and N.M. A. Shaffel: IEEE Trans. Magn. , Vol. 21, 1958 (1985): In Non-Patent Document 4, when a melt spun ribbon of (BH) _max 111 (kJ / m ³ ) is fixed with a resin, an isotropic rare earth bond of (BH) _ma 72 (kJ / m ³ ) A magnet was made.

In 1986, the present inventors fixed the R-TM-B quenching powder obtained by pulverizing the above melt spun ribbon with a resin (BH)) small diameter annular isotropic rare earth of _max- 72 (kJ / m ³ ). It has been found that a bonded magnet is useful for a small motor, and has been made clear in Japanese Patent Application No. 61-38830: Patent Document 1. Thereafter, small motor characteristics of the small-diameter annular isotropic rare earth bonded magnet and the Sm—Co radial anisotropic rare earth bonded magnet were compared and verified, and the former was useful (T. Shimoda, SUPPLEMENTARY MATERIAL, “ PERMANENT MAGNETS 1988 UPDATE “Wheeler Associate, INC (1988): Non-Patent Document 5). Furthermore, a report that it is useful for a small motor is disclosed in W.W. Baran, The European Business and Technical Outlook for NdFeB Magnets "Nov. (1989): Non-Patent Document 6, GX Huang, WM Gao, SF Yu-," ApplicationNt. Fe-B Bonded Magnet to the Micro -motor ", Proc.of the 11 th International Rare-Earth Magnets and Their Applications, Pittsburgh, USA, pp.583-595, (1990): revealed by non-Patent Document 7 Since the 1990s, it has been used as a drive source for OA, AV, PC, peripheral equipment, information communication equipment, etc. It was widely used to seed a small high-performance motor.
JP-A-62-196057 JP-A-57-170501 J. et al. J. et al. Croat, J. et al. F. Herbst, R.A. W. Lee and F.M. E. Pinkerton: J.M. Appl. Phys. , Vol. 55, 2078 (1984) M.M. Sagawa, S .; Fujiwara, H .; Yamamoto and Y.J. Matsuura: J.M. Appl. Phys. , Vol. 55, 2083 (1984) J. et al. F. Herbst, R.A. W. Lee and F.M. E. Pinkerton: Ann. Rev. Mater. Sci. , Vol. 16, 467 (1986) R. W. Lee, E .; G. Brewere and N.M. A. Shaffel: IEEE Trans. Magn. , Vol. 21, 1958 (1985) T.A. Shimoda, SUPPLEMENTARY MATERIAL, “PERMANENT MAGNETS 1988 UPDATE” Wheeler Associate, INC (1988) W. Baran, The European Business and Technical Outlook for NdFeB Magnets "Nov. (1989) G. X. Huang, W.H. M.M. Gao, S .; F. Yu ,: "Application of Melt-Spun Nd-Fe-B Bonded Magnet to the Micro-motor", Proc. of the 11th International Rare-Earth Magnets and Their Applications, Pittsburgh, USA, pp. 583-595 (1990) M.M. Tokunaga, N .; Nozawa, K .; Iwasaki, M .; Endoh, S, Tanigawa and H .; Harada: IEEE Trans. Magn. , Vol. 25, 3561 (1989) H. Sakamoto, M .; Fujikura and T. Mukai: J.M. Appl. Phys. , Vol. 69, 5382 (1991) M.M. Doser, V.M. Panchanthan, and R.A. K. Misra: J.M. Appl. Phys. , Vol. 70, 6603 (1991) T.A. Takeshita, and R.A. Nakayama: Proc. of the 11th International worksshop on Rare-earth Magnets and Ther Applications, Pittsburgh, PA. , Vol. 1, 49 (1990) M.M. Doser, V.M. Panchanathan, “Pulverizing anisotropy rapidly solidified Nd—Fe—B materials for bonded magnet”, J. Am. Appl. Phys. 70 (10), 15, 1993 T.A. Takeshita and R.K. Nakayama: Proc. of the 10th RE Magnets and Ther Applications, Kyoto, Vol. 1,551 1989 K. Macida, K .; Noguchi, M .; Nushimura, Y .; Hamaguchi, G .; Adachi, Proc. 9th Int. Works on Rare-Earth Magnets and Ttheir Applications, Sendai, Japan, II, 845 2000 K. Macida, Y .; Hamaguchi, K .; Noguchi, G .; Adachi, Digests of the 25th Annual conference on Magnetcs in Japan, 28aC-6 2001

By the way, although research on improving the magnetic properties of melt spun ribbons has been conducted continuously and actively from the mid-1980s to the present, the (BH) _max of the ribbon itself is about 160 (kJ / m ³ ). The (BH) _max of the magnetically isotropic bond magnet in which the R-TM-B quenching powder obtained by pulverizing the ribbon is fixed with a resin is ˜80 kJ / m ³ industrially. Therefore, from 1985 until recently, the increase in the high (BH) _max of magnetically isotropic rare earth bonded magnets in which R-TM-B quenching powder obtained by crushing melt-spun ribbons was fixed with resin progressed much. Not done.

Regardless of the above, the present invention is widely used for control and driving of computer peripherals, printers, etc., and so-called permanent magnet rotor type or permanent magnet field type brushless motors and DC motors are used. With the background of high performance and high added value of electrical and electronic equipment, there is a constant demand for further reduction in size and weight and output of small magnet motors. Therefore, the small-diameter annular isotropic rare earth bonded magnet in which the R-TM-B quenching powder obtained by pulverizing the melt spun ribbon found by the present inventors in 1986 is fixed with a resin is no longer useful for the evolution of small motors. I can't say that there is.

On the other hand, since the late 1980s, research on magnetically anisotropic rare earth magnet powders using a melt spun ribbon having a high Nd composition as a starting material has been actively conducted from the Nd ₂ Fe ₁₄ B stoichiometric composition. In the conventional Sm-Co based bonded magnet, the ingot is finely pulverized to obtain a large coercive force Hci, whereas the Nd ₂ Fe ₁₄ B based alloy ingot and the Nd ₂ Fe ₁₄ B based atmospheric pressure sintered magnet are pulverized. Even then, only a small coercive force Hci can be obtained.

For this reason, a melt spun ribbon was first studied as a starting material for magnetically anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder.

In 1989, Tokunaga et al. Mechanically pulverized the bulk obtained by hot upsetting (Die-up-set) of Nd ₁₄ Fe _80-X B ₆ Ga _X (X = 0.4-0.5). An anisotropic Nd ₂ Fe ₁₄ B-based rare earth magnet powder having a coercive force Hci 1.52 (MA / m) was prepared, and this was solidified with a resin (BH) _max 127 (kJ / m ³ ) anisotropic rare earth bond Magnets [M. Tokunaga, N .; Nozawa, K .; Iwasaki, M .; Endoh, S, Tanigawa and H .; Harada: IEEE Trans. Magn. , Vol. 25, 3561 (1989): Non-Patent Document 8].

In 1991, T.W. Mukai et al. Hot rolled Nd ₁₄ Fe _79.8 B _5.2 Cu ₁ to produce anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder having a coercive force Hci 1.30 (MA / m). [H. Sakamoto, M .; Fujikura and T. Mukai: J.M. Appl. Phys. , Vol. 69, 5382 (1991): Non-Patent Document 9].

Thus, the addition of Ga or Cu can improve the hot workability and suppress the crystal grain size to approximately 500 (nm) or less. When the crystal grain growth is suppressed, a powder having a powder particle diameter of approximately 100 (μm) or more becomes a magnet powder in which the decrease in coercive force Hci is suppressed. 1991, M.M. Doser, V.M. Panchanathan et al. Described HD (Hydrogen Depreciation) anisotropic rare earth as a method of pulverizing the bulk after hot working, in which hydrogen was allowed to penetrate from the grain boundaries to be collapsed as Nd ₂ Fe ₁₄ BH _X and then dehydrogenated by vacuum heating. An anisotropic rare earth bonded magnet having (BH) _max 150 (kJ / m ³ ) is obtained by solidifying the magnet powder with a resin [M. Doser, V.M. Panchanthan, and R.A. K. Misra: J.M. Appl. Phys. , Vol. 70, 6603 (1991): Non-Patent Document 10].

However, the anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder obtained by hot-setting or hot-rolling the above melt spun ribbon has an Nd-rich phase at the grain boundary, and permanent demagnetization based on intergranular corrosion. There was a drawback that it is easy to cause. As a method for overcoming this drawback, hydrogenation of Nd ₂ (Fe, Co) ₁₄ B phase is performed by heat-treating an Nd—Fe (Co) —B alloy ingot added with elements such as Ga, Zr, Hf, etc. in hydrogen. (Hydrogenation, Nd ₂ [Fe, Co] ₁₄ BHx), phase decomposition (Decomposition, NdH ₂ + Fe + Fe ₂ B), dehydrogenation (Decomposition), recombination (Recombination) at 650 to 1000 (° C.), so-called HDDR process Have been proposed [e.g. Takeshita, and R.A. Nakayama: Proc. of the 11th International worksshop on Rare-earth Magnets and
Their Applications, Pittsburh, PA. , Vol. 1, 49 (1990): Non-Patent Document 11]. The anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder produced by this method is composed only of a texture of crystal grains of 0.5 μm or less, and no Nd-rich phase exists at the grain boundaries. Research on the mechanism of this HDDR phenomenon has also been vigorously conducted, and it is expected to have thermal stability equivalent to that of a rare-earth bonded magnet in which a powder close to the Nd ₂ Fe ₁₄ B stoichiometric composition is solidified with a resin by adding Dy or dehydrogenating conditions. An anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder having a coercive force Hci of 1.20 (MA / m) or more has also been developed.

However, the high (BH) _max rare earth bonded magnet using the anisotropic Nd ₂ Fe ₁₄ B type rare earth magnet powder described above is a prototype of a cylinder or a cube. Not used. The reason for this is that the shape of the magnet mounted on the small motor targeted by the present invention is not a simple cylinder or cube, such as a high (BH)) _max rare earth bonded magnet that was once prototyped, but a diameter of 25 (mm), for example. This is because the following annular shape or an arc shape having a thickness of 1 (mm) or less is required. For example, in the case of the annular magnet, a radially anisotropic rare earth bonded magnet magnetically anisotropic in the radial direction is required. As a means for generating such a radial orientation magnetic field, for example, as disclosed in JP-A-57-170501: Patent Document 2, a magnetic yoke and a non-magnetic yoke surrounding an annular mold cavity are used. Are used in combination, and a molding die in which an excitation coil is arranged on the outside is used. In this method, a radial orientation magnetic field having a predetermined strength is generated in the annular mold cavity, so that a high voltage, high current type power source is used to increase the magnetomotive force, for example, 170 (kAT).

However, in order to effectively focus the magnetic flux excited by the exciting coil by the magnetic yoke from the outer periphery of the annular mold cavity to the annular mold cavity, the magnetic path of the magnetic yoke must be lengthened. When the cavity has a small diameter (or long length), a considerable amount of magnetomotive force is consumed as leakage flux. As a result, there is a problem that the orientation magnetic field of the annular mold cavity is reduced. For example, the diameter is 25 (mm) or less, the wall thickness is 1 to 2 (mm), and the length to diameter ratio (L / D = 0.5 to 1). ) In the case of an annular magnet that is mounted on a small motor targeted by the present invention, the reduction in the degree of orientation of the rare earth magnet powder inevitably reduces the high (BH) _max of the rare earth bonded magnet. Only a ring-shaped motor magnet having a characteristic that is significantly lower than that of the prototype high (BH) _max rare earth bonded magnet could be produced.

A first invention for solving the above-described problem is a mononuclear cluster phase [A] mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa], A compound intermediate in which a polynuclear cluster phase [An] or a mixed phase thereof [A + An] , a stretched phase [B] in which a predetermined amount of a lubricant is dispersed, and a chemical contact [C] are kneaded magnetically anisotropic self-organization of sexual single domain particles type Sm ₂ Fe ₁₇ N ₃ -based rare-earth magnet powder [A'a] spherical granular spherical multinuclear cluster phase composed mainly of the [A'], the essential components This is a hybrid type rare earth bonded magnet.

The second invention also provides: (1) a mononuclear cluster phase [A] composed mainly of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa ], a multinuclear cluster; phase [an], or with their cluster phase [a + an], stretching phase dispersed a predetermined amount of lubricant and [B], compound intermediate by kneading the chemical contact [C] and [I-a], magnetic the single domain particles type Sm ₂ Fe ₁₇ N ₃ -based rare-earth magnet powder [A'a] spherical granular spherical multinuclear cluster phase mainly composed of anisotropic and [A'], if necessary and additives optionally added, the process of producing the compound [I] obtained by mixing, preparation of (2) wherein the compound [I] was oriented in a magnetic field, a plate-like green compact to compress the compound [I] [II] and step (3) before Kigu <br/> lean compact II] heat treatment of the mononuclear cluster phase [A], multinuclear cluster phase [A
n], or their clusters phase and [A + An], spherical multinuclear cluster phase and [A'], a manufacturing process of a stretching phase [B] and, magnet precursor self-assemble in the chemical contact [C] to [III] If, obtained by the production process comprising a step of shape conversion annularly [IVa] or arc-shaped magnet [IVb] by stretching (4) before Ki磁 stone precursor stretching phase contained in [III] [B] It is a self-organized hybrid rare earth bonded magnet.

The third invention is the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, wherein the mononuclear cluster phase [A], the multinuclear cluster phase [An], or a mixed phase thereof is used. [a + an] is constructed de magnetically polycrystalline aggregated Nd ₂ Fe ₁₄ B based rare earth magnet powder anisotropic [Aa] and oligomers [Ab], the oligomer [Ab] is stretching phase [B] and It is an oligomer having a chemical contact [C] and a reaction substrate that self-assembles.

The fourth aspect based on the first invention to third hybrid rare earth bonded magnet invention is one of self-organization of the spherical multinuclear cluster phase [A'] are magnetically anisotropic single of It constructed de domain particle-type Sm ₂ Fe ₁₇ N ₃ -based rare-earth magnet powder [A'a] and oligomers [A'B], the oligomer [A'B] is the stretching phase B and the chemical contact [C] And an oligomer having a reaction substrate that self-assembles.

A fifth aspect of the present invention is spherical granules of the above first aspect to fourth hybrid rare earth bonded magnet invention is one of self-organization of the spherical multinuclear cluster phase [A'] are ≦ 500 (μm) It is le.

Further, a sixth invention, in the hybrid-type rare-earth bonded magnet, which is self-organization of the fifth aspect, the spherical multinuclear cluster phase [A'] are previously magnetically single domain particles type anisotropic Sm ₂ Fe ₁₇ N ₃ -based rare-earth magnet powder [A'] and wet mixing an organic solvent solution of the oligomer [A'B], desolvation, compression, gel finish spherically by tumbling fluidized bed granulation method After classification .

Also, seventh aspect of the hybrid earth bonded magnet, which is self-organization of the sixth aspect, the tumbling fluidized bed granulation method, a pulse jet disperser mechanism (towards the center than the side wall of the granulation housing A fine granulation mechanism incorporating an intermittent air jet) is used .

Further, an eighth aspect based on the first aspect to seventh hybrid rare earth bonded magnet invention is one of self-organization of the mononuclear cluster phase [A], multinuclear cluster phase [An], or their mixed phase [a + an] oligomer contained in [Ab] and the spherical multinuclear cluster phase oligomer contained in [A'] [A'b] is solid at room temperature, and at least two oxirane rings in the molecular chain of the It is an organic compound having

Further, a ninth aspect based on the first invention to eighth hybrid rare earth bonded magnet invention is one of self-organization of the mononuclear cluster phase [A], multinuclear cluster phase [An], or their mixed phase and percentage of oligomers [Ab] contained in [a + an], and the proportion of the oligomer [A'B] contained in the spherical multinuclear cluster phase [A'], each of the mononuclear cluster phase [a], It is 0.5-3.0 (wt.%) With respect to multinuclear cluster phase [An], or those mixed phases [A + An], and the said spherical multinuclear cluster phase [A '] .

Further, a tenth aspect based on the first aspect to ninth hybrids rare earth bonded magnet invention is one of self-organization of mononuclear cluster phase [A], multinuclear cluster phase [An], or their The ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%).

Further, an eleventh aspect hybrid earth bonded magnet, which is self-organization of the upper Symbol second invention, a compound is the ratio of all the clusters ≦ occupied in [I] 97.5 (wt.% ).

According to a twelfth aspect , in the self-organized hybrid rare earth bonded magnet of the first aspect or the twelfth aspect , the ratio of the stretched phase [B] to the compound [I] is ≧ 2.5 (wt .%).

The invention of thirteenth on the first aspect to twelfth hybrid rare earth bonded magnet invention is one of self-organization of the molecular chain orientation ability stretching phase [B] is caused by uniaxial stretching, and at least Chemical Contacts A polymer containing a reaction substrate capable of reacting with C.

The fourteenth invention is the self-organized hybrid rare earth bonded magnet of the second invention , the eleventh invention or the twelfth invention , wherein the compound [I] has an apparent density according to JIS Z2501, And the powder fluidity is as follows.

Apparent density of compound [I] ≧ 2.4 (Mg / m ³ ) (Formula 1)

  Compound [I] powder flow rate ≧ 45 (sec / 50 g) (Formula 2)

The fifteenth invention is the self-organized hybrid rare earth bonded magnet of the second, eleventh , twelfth, or fourteenth invention , and a plate-like green compact [II] is produced. In this case, the oligomer [Ab] contained in the mononuclear cluster phase [A], the multinuclear cluster phase [An], or the mixed phase [A + An] of the compound [I] filled in the mold cavity, and the spherical multinuclear cluster phase [ It heats more than melting | fusing point of the oligomer [A'b] contained in A '], and after that, it compresses, applying an orientation magnetic field.

The sixteenth aspect of the invention is the self-organized hybrid rare earth bonded magnet of the second aspect , the eleventh aspect , the twelfth aspect, the fourteenth aspect, or the fifteenth aspect of the present invention . II] is made lower than the self-organization start temperature by chemical contact [C].

The seventeenth invention is the self-organized hybrid rare earth bond magnet of the second invention, the eleventh invention, the fourteenth invention , the fifteenth invention , or the sixteenth invention. When producing the compact [II], the longitudinal side surface corresponding to the plate thickness is compressed under an orthogonal orientation magnetic field of ≧ 1.5 (MA / m).

The eighteenth invention is the self-organized hybrid of the second invention, the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, or the seventeenth invention. When a plate-shaped green compact [II] is produced in a type rare earth bonded magnet, a molding die and a die set made of a nonmagnetic material having a plurality of cavities are used.

The nineteenth aspect of the invention is the second aspect of the invention, the eleventh aspect , the twelfth aspect, the fourteenth aspect, the fifteenth aspect, the sixteenth aspect, the seventeenth aspect, or the eighteenth aspect . When producing a plate-shaped green compact [II] in a self-organized hybrid rare earth bonded magnet, the maximum strain amount of the mold cavity in the center in the longitudinal direction corresponding to the plate thickness is ≦ 0.1 (mm) And

The twentieth invention is the above-mentioned second invention , eleventh invention, twelfth invention, fourteenth invention, fifteenth invention, sixteenth invention, seventeenth invention, eighteenth invention, or In the self-organized hybrid rare earth bonded magnet of the nineteenth invention, the density distribution of the plate-like green compact [II] is ≦ 0.1 (Mg / m ³ ).

The twenty-first invention is the second invention , the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, In the 19th or 20th invention of the self-organized hybrid rare earth bonded magnet, the plate-like green compact [II] has a plate thickness of 1.0 ± 0.5 (mm).

The twenty- second invention is the second invention , the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, In the self-organized hybrid rare earth bonded magnet of the 19th invention, the 20th invention, or the 21st invention, the self-organized magnet precursor [III] is a plate-like green compact [II] in the atmosphere at ≦ 160 ° C. ] Is heat-treated.

The twenty-third invention is the second invention, eleventh invention, twelfth invention, fourteenth invention, fifteenth invention, sixteenth invention, seventeenth invention, eighteenth invention, In the self-organized hybrid rare earth bonded magnet of the 19th invention, the 20th invention, the 21st invention, or the 22nd invention, the tensile strength of the self-organized magnet precursor [III] is a plate-like green compact [ II] exceeding 3 times.

The twenty-fourth invention is the second invention , the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, In the 19th invention, the 20th invention, the 21st invention, the 22nd invention, or the 23rd invention, in the self-organized hybrid rare earth bonded magnet, the maximum rolling reduction due to stretching of the magnet precursor [III] is 10 (%).

The twenty-fifth invention is the second invention , the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, The self-organized hybrid rare earth bonded magnet of the 19th invention, the 20th invention, the 21st invention, the 22nd invention, the 23rd invention, or the 24th invention is included in the magnet precursor [III]. The stretching of phase B is rolling, and after the rolling, the shape is converted to an annular magnet [IVa].

The twenty-sixth aspect of the invention is the above-mentioned second aspect , eleventh aspect , twelfth aspect, fourteenth aspect, fifteenth aspect, sixteenth aspect, seventeenth aspect, eighteenth aspect, In the self-organized hybrid rare earth bonded magnet of 19th invention, 20th invention, 21st invention, 22nd invention, 23rd invention, 24th invention, or 25th invention, an annular magnet [IVa ] Has an outer diameter ≦ 25 (mm).

The twenty-seventh invention includes the second invention , the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, The self-organized hybrid rare earth bonded magnet of the 19th invention, the 20th invention, the 21st invention, the 22nd invention, the 23rd invention, or the 24th invention is included in the magnet precursor [III]. The stretching of the stretched phase [B] is stamped and the shape is converted to an arc magnet [IVb].

The twenty-eighth invention includes the second invention, the eleventh invention, the twelfth invention, the fourteenth invention, the fifteenth invention, the sixteenth invention, the seventeenth invention, the eighteenth invention, Self-organized hybrid of 19th invention, 20th invention, 21st invention, 22nd invention, 23rd invention, 24th invention, 25th invention, 26th invention, or 27th invention In the type rare earth bonded magnet, the arc-shaped magnet [IVb] has an unequal thickness and different magnetic characteristics in the radial direction.

The invention of the 29 on the first aspect to the 28th hybrid rare earth bonded magnet invention is one of self-organization of, 1.2 (MA / m) 20 ℃ maximum energy of when the magnetization The product (BH) _max is ≧ 120 kJ / m ³ .

Further, thirtieth aspect, in the first aspect to the 28th hybrid rare earth bonded magnet invention is one of self-organization of the 2.0 maximum energy product of 20 ° C. when magnetized in (MA / m) (BH) _max is ≧ 160 kJ / m ³ .

The invention of 31, in the first aspect to the 30th hybrid rare earth bonded magnet invention is one of self-assembly of 100 square demagnetization curve at (℃) (Hk / Hci) is ≧ 0.4.

The invention of the 32 is a motor mounted with the first aspect to the 31st hybrid rare earth bonded magnet invention is one of self-assembly of [IVa].

A thirty-third invention is a motor equipped with an annular magnet [IVa] having an outer diameter ≦ 25 (mm) applied to the self-organized hybrid rare earth bonded magnet of the twenty-sixth invention.

The invention of the 34 is a brushless motor equipped with the first aspect to the arc-shaped magnet according to the 31 hybrid rare earth bonded magnet invention is one of self-assembly of [IVb].

Further, the 35th aspect of the present invention, in the first invention, second 31 equipped with a motor arcuate magnet [IVb] in maximum thickness ≦ 1 according to the self-assembled hybrid rare earth bonded magnet (mm) of the invention is there.

The thirty-sixth aspect of the present invention provides: (1) a mononuclear cluster phase [A] composed mainly of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa], polynuclear clusters; A compound intermediate [Ia] in which a phase [An] or a cluster phase [A + An] thereof, a stretched phase [B] in which a predetermined amount of lubricant is dispersed, and a chemical contact [C] are kneaded; And a spherical granule-shaped multinuclear cluster phase [A ′] mainly composed of anisotropic single-domain particle-type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a], and if necessary, Compound [I] production process in which additive is added, and (2) Production process of plate-like green compact [II] in which the compound [I] is oriented in a magnetic field and the compound [I] is compressed And (3) the green compact [ I] is heat-treated, and the mononuclear cluster phase [A], the multinuclear cluster phase [An], or their cluster phase [A + An], the spherical multinuclear cluster phase [A ′], and the stretched phase [B] are chemically treated. The process of producing the magnet precursor [III] self-assembled by the contact [C], and (4) the cyclic [IVa] or the arc-shaped magnet [by stretching the stretched phase [B] contained in the magnet precursor [III] IVb], and a hybrid rare earth bonded magnet manufacturing method for manufacturing a self-organized hybrid rare earth bonded magnet.

As described above, according to the present invention, the reduction in (BH) _max of a rare earth bonded magnet is improved even when the diameter is reduced (or lengthened) using anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder. Is done.

The self-organized high (BH) _max hybrid rare earth bonded magnet according to the present invention, which is compatible with various magnet shapes ranging from an annular shape to an arc shape for a small motor and magnetic characteristics, is magnetically anisotropic. A mononuclear cluster phase [A], a polynuclear cluster phase [An], or a mixed phase [A + An] composed mainly of polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] is magnetically different. Spherical multinuclear cluster phase [A ′] composed mainly of isotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a], stretched phase [B], and phases [A + An], [ A ′] and chemical contact [C] with phase [B] are used as components.

  And as a manufacturing method of the said magnet, (1) Compound phase [Ia] by cluster phase [A + An], extension phase [B], chemical contact [C], spherical polynuclear cluster phase [A '], and A compound [I] production process in which the two types and additives that are added as necessary are mixed, (2) a plate green compact [II] production process by compound compression, and (3) the green compact [ II] is heat-treated, and the step of producing the magnet precursor [III] in which the phase [A + An], the phase [A ′], and the phase [B] are self-assembled by the chemical contact [C], (4) And a step of transforming the shape into an annular [IVa] or an arcuate magnet [IVb] by stretching the phase [B] contained in the magnet precursor [III].

By applying the self-organized high (BH) _max rare earth bonded magnets obtained as described above to small motors, high performance of many electric and electronic devices such as power saving and miniaturization and weight reduction by high output. We can meet the demands for the development.

(Embodiment)
As described above, the present invention is widely used for control and driving of computer peripherals, printers, etc., and the so-called permanent magnet rotor type, or permanent magnet field type brushless motor and DC motor, In order to meet the demands for further miniaturization, lightening, and high output of the small magnet motors with higher performance of electric and electronic equipment, R (crushed melt spun ribbon that does not progress much (BH) _max ) -Even if the diameter is reduced by using anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder instead of a magnetically isotropic bond magnet in which TM-B quenching powder is fixed with resin, (BH ) Disclosed is a high-performance rare earth bonded magnet for a small motor in which _max does not decrease, a manufacturing method thereof, and a technique related to the small motor.

If any of the above-mentioned annular or arc shapes applicable to a small motor, for example, a high (BH) _max rare earth bonded magnet of 160 (kJ / m ³ ) or more can be easily produced, electrical and electronic equipment in recent years Encourage higher performance. That is, a novel high-output / power-saving small motor can be provided. This is because the (BH) _max of the isotropic rare earth bonded magnet in which R-TM-B quenching powder obtained by pulverizing a conventional melt spun ribbon is fixed with resin is 80 (kJ / m ³ ) as described above. . On the other hand, if a high (BH) _max rare earth bonded magnet with an annular shape or an arc shape of 160 (kJ / m ³ ) or more can be produced, the gap magnetic flux density between the motor magnet and the iron core is approximately the ratio of (BH) _max . Therefore, depending on the design philosophy of the small motor, about 1.4 times higher output and 30% reduction can be expected.

The above-described self-organized high (BH) _max hybrid rare earth bonded magnet according to the present invention, which is compatible with various magnet shapes ranging from an annular shape to an arc shape for a small motor and magnetic characteristics, is magnetically anisotropic. Mononuclear cluster phase [A], polynuclear cluster phase [An], or a mixed phase [A + An] thereof, mainly composed of highly crystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa], magnetic In addition, the spherical multinuclear cluster phase [A ′], the stretched phase [B], and the phase [A] mainly composed of an anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a]. , [A ′], and chemical contact [C] with phase [B] are essential components. The production method of the magnet includes (1) a compound of mononuclear cluster phase [A], multinuclear cluster phase [An], or their cluster phase [A + An], stretched phase [B], and chemical contact [C]. Production step of compound [I] in which intermediate [Ia], spherical polynuclear cluster phase [A ′], and the above-mentioned two kinds and additives added as necessary are mixed, (2) plate-like by compound compression Step of producing green compact [II], (3) A magnet in which the green compact [II] is heat-treated and the phases [A + An], [A ′] and the phase [B] are self-organized by chemical contacts [C]. Step of producing precursor [III], (4) Process for converting the shape into a circular [IVa] or arc-shaped magnet [IVb] by stretching the phase [B] contained in the magnet precursor [III] It consists of

  Hereinafter, the present invention will be described in more detail.

First, the mononuclear cluster phase [A], the multinuclear cluster phase [An], or the mixed phase [A + An] according to the present invention is magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder. The body [Aa], the stretched phase [B], and the chemical contact [C] and the oligomer [Ab] having a reaction substrate that self-assembles are constituted. Such a magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa], a stretched phase [B], and a chemical substrate [C] and a reaction substrate that self-assembles are included. The structure of the mononuclear cluster phase [A] and the multinuclear cluster phase [An] composed of the oligomer [Ab] is shown conceptually in FIG.

However, in the figure, [Aa] usually represents a magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder having a particle diameter of 50 to 200 μm, and each hexagon thereof is one by one. In the Nd ₂ Fe ₁₄ B crystal, the arrow in the hexagon represents the easy axis of magnetization (C axis). In this stage, the easy axis direction of the multinuclear cluster phase [An] is random and magnetically isotropic for each powder. In addition, as shown in the figure, the structure of the mononuclear cluster phase [A] containing [Aa] as a main component and the multinuclear cluster phase [An] are polycrystal aggregated Nd ₂ Fe ₁₄ B rare earths via the oligomer [Ab]. A mononuclear cluster phase [A] and a multinuclear cluster phase [An] are randomly produced according to the particle diameter and classification degree of the magnetic powder [Aa]. In the present invention, both mixed phases [A + An] are usually used.

The magnetically anisotropic polycrystalline aggregate anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] according to the present invention is prepared by hot upsetting (Die-Up-Setting). Polycrystalline Aggregated Anisotropic Nd ₂ Fe ₁₄ B Rare Earth Magnet Powder (for example, M. Doser, V. Panchanathan, “Pulverizing anisotropy rapidly solidified Nd—Fe—B materials for
bonded magnet ”, J. Appl. Phys. 70 (10), 15, 1993: Non-Patent Document 12), magnetically anisotropic polycrystalline aggregated Nd prepared by HDDR processing (hydrogen decomposition / recombination) ₂ Fe ₁₄ B based rare earth magnet powder, i.e., Nd-Fe (Co) -B alloy of the Nd ₂ (Fe, Co) hydrogenation of ₁₄ B phase _{(H ydrogenation, Nd 2 [Fe} , Co] 14 BHx) , 650 to 1000 (° C.) phase decomposition in _{(D ecomposition, NdH 2 + Fe} + Fe 2 B), the dehydrogenation (D esorpsion), recombination (R ecombination) to HDDR treatment (T.Takeshita and R.Nakayama: Proc.of the 10 ^th RE Magnets and Their Applicatio s, Kyoto, Vol.1,551 1989: a magnet powder prepared in Non-patent Document 13).

Note that the surface of the magnet powder is previously inactivated, such as Zn that has been photo-decomposed, such as K. Macida, K. Noguchi, M. Nashimura, Y. Hamaguchi, G. Adachi, Proc. 9th. Int.Workshop on Rare-Earth Magnets and Ttheir Applications, Sendai, Japan, II, 845 2000: non-Patent Document 14, or, K.Machida, Y.Hamaguchi, K.Noguchi, G.Adachi , Digests of the 25 th Annual conference
on Magnetcs in Japan, 28aC-6 2001: Non-Patent Document 15). The coercive force at 20 ° C. after 4 (MA / m) pulse magnetization of these magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] is 1 (MA / m The above is desirable.

On the other hand, the spherical multinuclear cluster phase [A ′] is usually a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] having a particle diameter of 2 to 5 μm and an expanded phase [B]. And the chemical contact [C] and the self-organized oligomer [A′b] as shown in FIG. At this stage, it is shown that the easy axis direction of the spherical multinuclear cluster phase [A′n] is random and magnetically isotropic for each powder. However, the spherical polynuclear cluster phase [A ′] is a spherical granule of ≦ 500 (μm), and it is necessary to impart powder flowability to itself. The spherical polynuclear cluster phase [A ′] is, for example, a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] and an oligomer [A′b] organic. The solvent solution is wet-mixed, desolvated, compressed, classified, and then finished into a spherical shape by a rolling fluidized bed granulation method. Here, the compression refers to the mixed phase [A′a + A′b] of the solid magnetic powder [A′a] and the oligomer [A′b] that have been desolvated, for example, the melting point of the oligomer [A′b]. It is preferable for industrial production that the above-described heated constant-speed rolling mill is charged and continuously compressed. The mixture [A′a + A′b] compressed by a rolling mill or the like is formed into spherical granules by rolling fluidized bed granulation. In particular, when rolling fluidized bed granulation, if a fine granulation mechanism that incorporates a pulse jet dispersion mechanism (air jet is intermittently injected from the side wall of the granulation casing toward the center), the multinuclear is more spherical A cluster phase [A ′] is obtained, and as a result, a powder fluidity is developed.

On the other hand, a mononuclear cluster phase [A], a polynuclear cluster phase [An], or a mixture thereof, mainly composed of magnetically anisotropic polycrystalline aggregated anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder Included in the oligomer [Ab] contained in the phase [A + An] or in the multinuclear cluster phase [A ′] mainly composed of magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder The oligomer [Ab] or [A′b] is preferably an organic compound that is solid at room temperature and has at least two oxirane rings in the molecular chain. The organic compound having at least two oxirane rings in the molecular chain may be obtained from bisphenols and epichlorohydrin or substituted epichlorohydrin, or obtained by various other methods, for example, an epoxy represented by (Chemical Formula 1) There are oligomers.

However, in R1 and R2 of (Chemical Formula 19), R1 is —O—, —S—, —SO—, —SO ₂ —, or —CH ₂ —, —CH ₂ CH ₂ —, —C (CH ₃ ) ₂ -equal-CpH ₂ p (p is an integer), R2 is -H, or -CH ₃ , -C ₂ H ₅ etc. C _q H _{2q + 1} (q is an integer) Is. Particularly preferred among these are those in which R1 is —C (CH ₃ ) ₂ — and R2 is H. These may be a copolymer. The oligomer according to the present invention is preferably one that is solid at room temperature and has high crystallinity. The reason is that mononuclear cluster phase [A], multinuclear cluster phase [An], or a mixed phase thereof [A + An], or magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder. When a granular material such as a spherical polynuclear cluster phase [A ′] containing [A′a] as a main component has good powder flowability as an aggregate and is heated to a temperature higher than the melting point of the oligomer, FIG. As shown in FIG. 3B, all the cluster phases are immediately thermally dissociated, and the easy magnetization axis (C axis) of all rare earth magnet powders is oriented in a specific direction by the orientation magnetic field H as shown in FIG. This is to facilitate (rearrangement). Accordingly, various lubricants and the like can be used in combination as necessary in order to further facilitate the thermal dissociation and rearrangement.

The ratio of the oligomer [Ab] or [A′b] is 0.5 to 3.0 (wt.%). The reason for this is that formation of various cluster phases according to the present invention shown in FIGS. This is because the residual magnetization Jr and (BH) _max are reduced accordingly.

On the other hand, the ratio of the multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%). The reason for this is that, after rearrangement by the orientation magnetic field H shown in FIG. 4 (a), when the pressure P is applied and densified as shown in FIG. The direct contact of the anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] is avoided, and the single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] is densely packed. It is for making it. Thus, the proportion of the spherical multinuclear cluster phase [A ′] for densification via the single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] needs to be approximately 30% or more. To do. Thus, when densification is performed through the single domain particle type Sm ₂ Fe ₁₇ N ₃ system rare earth magnet powder [A′a], the surface density of the polycrystalline aggregated Nd ₂ Fe ₁₄ B system rare earth magnet powder [Aa] is increased. This is because damage and crushing due to friction at the time of conversion are suppressed, and a high-density green compact [II] can be obtained. Here, the significance of suppressing damage and fracture due to friction at the time of densification of the polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa] is the squareness of the demagnetization curve (Hk / Hci). This is also to suppress deterioration and increase in irreversible demagnetization rate. However, when the ratio of the single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] exceeds 60%, the density of the green compact [II] starts to decrease. An increase in magnetization Jr and (BH) _max cannot be expected.

  The proportion of all the cluster phases in the compound [I] is ≦ 98 (wt.%), And the proportion of the stretched phase [B] is ≧ 2 (wt.%). This is because if the ratio of the phase [B] is less than 2 (wt.%), It is difficult to change the shape to the optimum magnet shape for various motors based on the stretching of the phase. The stretched phase [B] needs to be a polymer containing a reaction substrate capable of reacting with at least the chemical contact [C] in addition to the molecular chain orientation ability by stretching. Examples of the polymer include homopolyamides synthesized from lactam or aminocarboxylic acid, and one or more polyamides synthesized from diamine and dicarboxylic acid, or esters or halides thereof, 2.5 wt. It is preferable that the chemical contact for forming a continuous phase of the above components is an essential component. Such homopolyamides include those synthesized from lactams or aminocarboxylic acids, and those synthesized from diamines and dicarboxylic acids, or esters or halides thereof, and are represented by (Chemical Formula 2).

In the above (Chemical Formula 2), R ₁ , R ₂ , R ₃ are generally polymethylene groups, R ₁ is — (CH ₂ ) _m —, nylon (m + 1), and R ₂ is — (CH ₂ ). _p -, R ₃ is - (CH _{2) q-2} some are nylon p · q. Further, it may be a copolymer further added with a third monomer.

As described above, the mononuclear cluster phase [A], the polynuclear cluster phase [An], which mainly contains the magnetically anisotropic polycrystalline aggregate anisotropic Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa], or A mixed phase [A + An], a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] as a main component, and a spherical multinuclear cluster phase [A ′], and Along with the phase [B], in the present invention, the chemical contact [C] that self-assembles them by chemical bonding is an essential component. Chemical contact [C] is a reaction substrate possessed by oligomers [Ab] and [A′b] selected from cluster phases [A], [An], [A + An], and [A ′], and stretched phase [B]. It is appropriately selected depending on the type. The oligomer [Ab], [A′b] is an epoxy oligomer such as (Chemical Formula 1) having an oxirane ring, and the phase [B] is (—NHCO—) in the molecular chain as (Chemical Formula 2). If the polymer has a substrate, direct reaction with the oligomer [Ab], [A′b] and the phase [B] is also expected. In such a case, it is possible to use only an epoxy resin curing agent that firmly crosslinks only the oligomers [Ab] and [A′b]. Examples of such substances include one or more selected from the group of dicyandiamide and derivatives thereof, carboxylic acid dihydrazide, diaminomaleonitrile and hydrazides of derivatives thereof. These are generally high melting point compounds that are hardly soluble in organic solvents, but those having a particle size adjusted to several to several tens of μm are preferred. Examples of the dicyandiamide derivative include o-tolylbiguanide, α-2 · 5-dimethylbiguanide, α-ω-diphenylbiguanide, 5-hydroxybutyl-1-biguanide, phenylbiguanide, α-, ω-dimethylbivic. There are anides. Further, examples of the carboxylic acid dihydrazide include succinic acid hydrazide, adipic acid hydrazide, isophthalic acid hydrazide, and p-axylbenzoic acid hydrazide. On the other hand, as the chemical contact [C] capable of reacting with both the oligomer [Ab], [A′b] and the stretched phase [B], for example, an isocyanate regenerated material can be mentioned. An isocyanate regenerator is a generic term for compounds obtained by addition reaction of an isocyanate group and an active hydrogen compound and capable of regenerating a free isocyanate group by thermal dissociation. The reaction substrate capable of reacting with the free isocyanate groups regenerated, for example -OH, -COOH, -NHCO -, - NHCOO -, - NHCONH -, - NH 2, -NHNH 2, -SH, -CHS, -CSOH , Active methylene, etc., and if the isocyanate regenerated product is cited as the chemical contact C, conversely, these —OH, —COOH, —NHCO—, —NHCOO—, —NHCONH—, —NH ₂ , — Any oligomer or polymer having a reaction substrate such as NHNH ₂ , —SH, —CHS, —CSOH, or active methylene can be used as the oligomer [Ab], [A′b], and the phase [B]. Among them, preferred reaction substrates are —OH, —NHCO—, —NHCOO—.
, NHCONH-, and the like. In addition, when it is completely dissolved with the epoxy oligomer as in the above-mentioned isocyanate regenerated material and is inactive at room temperature, it may be appropriately dissolved in the oligomers [Ab] and [A′b].

As described above, the mononuclear cluster phase [A], the polynuclear cluster phase [An], which mainly contains the magnetically anisotropic polycrystalline aggregated anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa], or A mixed phase [A + An], a magnetically anisotropic single-domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] as a main component, and a spherical multinuclear cluster phase [A ′], and A manufacturing method for producing a green compact [II] from a compound [I] according to the present invention having a chemical contact [C] which is self-assembled by chemical bonding together with the phase [B] as an essential component, with reference to the drawings. This will be described below.

Fig.5 (a) is a photograph which shows the shaping | molding die which produces the plate-shaped green compact concerning this invention. FIG. 5B is a photograph showing an external view of the orthogonal magnetic field oriented powder molding machine. First, the compound [I] according to the present invention is accommodated in the feeder box 1 as shown in FIG. Feeder box 1 moves forward to die set 2 side heated above the melting point of oligomer [Ab], [A'b], and cavity CV1, 2, 3, 4 (width 1.03 mm, length 90 mm x 4) Is filled with compound [I]. At that time, in order to uniformly fill the compound [I] into the cavities CV1, 2, ³ , and 4, the apparent density according to JIS Z2501 ≧ 2.6 (Mg / m ³ ) and the powder fluidity ≧ 45 (sec / 50 g). There was a need to do.

  The compound [I] filled in the mold cavity is formed by the mononuclear cluster phase [A] and the multinuclear cluster phase [A] by the heat conduction from the mold while the upper punch (UP1, 2, 3, 4) is lowered. An], or the oligomer [Ab] contained in the mixed phase [A + An], and the oligomer [A′b] contained in the spherical multinuclear cluster phase [A ′] are heated above the melting point, and all the cluster phases are heated. Dissociate. In this example, as shown in FIG. 5B, the die set 2 is thermally dissociated while being transported from the filling position between the magnetic poles 3a and 3b of the electromagnet. After that, the pressure P is applied while applying the orientation magnetic field H to make it dense. At that time, the longitudinal side surface corresponding to the plate thickness is compressed under the orthogonal orientation magnetic field H of ≧ 1.5 (MA / m) below the self-assembly start temperature by the chemical contact C.

When producing the plate-like green compact [II] as described above, a plate-like plate thickness is obtained by using a mold and a die set 2 made of a nonmagnetic material having a plurality of cavities as shown in FIG. The maximum strain amount of the mold cavity at the center in the longitudinal direction corresponding to ≦ 0.1 (mm), and the density distribution of the plate-like green compact [II] is ≦ 0.1 (Mg / m ³ ) The thickness is 1.0 ± 0.5 (mm).

  Next, when producing the self-organized magnet precursor [III], the plate-like green compact [II] is heat-treated in the atmosphere at ≦ 160 ° C., and the tensile strength of the self-organized magnet precursor [III] is plate-like. Prepare to be at least 3 times the Green Compact [II].

The stretching is rolled under the condition that the maximum reduction ratio by stretching of the magnet precursor [III] is 10 (%), and after the rolling, the annular magnet [IVa] whose shape is converted to the annular magnet [IVa] is obtained. In particular, an annular magnet [IVa] having an outer diameter ≦ 25 (mm) is effective in improving the performance of the motor. Further, the stretching of the stretched phase [B] is used as stamping, and the shape is converted into the arc-shaped magnet [IVb]. In particular, when the arcuate magnet [IVb] having an unequal wall thickness with a maximum wall thickness ≦ 1 (mm) is effective in improving the motor performance while suppressing the cogging torque. Such a magnet is finally magnetized and used, but the maximum energy product (BH) _max at 20 ° C. when magnetized at 1.2 (MA / m) is ≧ 120 (kJ / m ³ ), or It is desirable that the maximum energy product (BH) _max at 20 (° C.) when magnetized at 2.0 (MA / m) is ≧ 160 (kJ / m ³ ). Furthermore, in order to suppress the initial irreversible demagnetization of the magnet, it is desirable that the square shape (Hk / Hci) of the demagnetization curve at 100 (° C.) is ≧ 0.4.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

  1. The raw material will be described.

In this example, the polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] (Nd _12.3 Dy) having an anisotropic average particle size of 80 (μm) prepared by HDDR treatment (hydrogen decomposition / recombination). _0.3 Fe _64.7 Co _12.3 B _6.0 Ga _0.6 Zr _0.1 ), RD (oxidation reduction) single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] having an average particle diameter of 3 (μm) was used. .

  The oligomers [Ab] and [A′b] according to the present invention are polyglycidyl ether-o-cresol having an epoxy equivalent of 205 to 220 (g / eq) represented by (Chemical Formula 3) and a melting point of 70 to 76 (° C.). The novolak-type epoxy oligomer, cluster [C] is a latent epoxy resin curing agent (acid dihydrazide) having a particle diameter of 10 (μm) or less and a melting point of 90 to 110 (° C.) represented by (Chemical Formula 4), and a stretched phase [B]. Uses a polyamide-12 powder with a melting point of 180 (° C) containing a plasticizer, and a lubricant (calcium stearate) with a particle size of 10 (μm) or less and a melting point of about 150 (° C) as an additive to be added as necessary. It was.

(NH ₂ NHCOCH ₂ CH ₂ ) ₂ N (CH ₂ ) ₁₁ CONHNH ₂ (Chemical Formula 4)

  2. The production of the rare earth bonded magnet will be described.

The self-organized high (BH) _max hybrid rare earth bonded magnet according to the present invention is mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa]. Mononuclear cluster phase [A], multinuclear cluster phase [An], or a mixed phase thereof [A + An], magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a ] The main component is a spherical polynuclear cluster phase [A '], a stretched phase [B], and chemical contacts [C] with the phases [A + An], [A'] and the phase [B]. And as a manufacturing method of the said magnet, (1) Compound phase [Ia] by cluster phase [A + An], extension phase [B], chemical contact [C], spherical multinuclear cluster phase [A '], and A compound [I] production process in which the two types and additives that are added as necessary are mixed, (2) a plate green compact [II] production process by compound compression, and (3) the green compact [ II] is heat-treated, and a process of producing a magnet precursor [III] in which phases [A + An], [A ′] and phase [B] are self-assembled by chemical contact [C], and (4) the magnet precursor And transforming the shape into an annular [IVa] or arcuate magnet [IVb] by stretching the phase [B] contained in [III].

First, a mononuclear cluster phase [A], a polynuclear cluster phase [An], which is mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa], or those A preparation example of the mixed phase [A + An] will be described. A predetermined amount of anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] was heated to 60 (° C.) and charged into a Σ blade mixer, and 50 (wt.%) Acetone of oligomer [Ab] was charged. Solution 1 (wt.%) Was added dropwise and wet mixed.

After that, it is heated to 80 (° C.) to remove the solvent, pulverized, and mononuclear mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa]. A mixed phase [A + An] with a cluster phase [A] and a multinuclear cluster phase [An] was prepared.

Next, a mixed phase [A + An] containing the magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] as a main component, a stretched phase [B in which a predetermined amount of lubricant is dispersed in advance [B] The chemical contact [C] was charged into a Σ blade mixer and dry kneaded to obtain a compound intermediate [Ia].

On the other hand, a spherical multinuclear cluster phase [A ′] composed mainly of magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] was prepared. It is important that the spherical multinuclear cluster phase [A ′] according to the present invention is a spherical granule of ≦ 500 (μm) and imparts powder flowability to itself. The spherical granule is composed of a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] and an oligomer [A′b] in 50 (wt.%) Acetone solution. The mixture was wet-mixed at room temperature, desolvated, compressed and classified at 80 (° C.), and then finished by a rolling fluidized bed granulation method. In this example, a solvent-removed mixture [A′a + A′b] of solid single-domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] and oligomer [A′b] It charged in the constant-speed roll mill heated to the melting | fusing point or more (100 degreeC) of oligomer [A'b], and compressed. Subsequently, the mixture [A′a + A′b] compressed by rolling was classified into ≦ 500 (μm). However, since the mixture [A′a + A′b] in this state is a flake-like granulated body, it does not exhibit powder flowability. Accordingly, the mixture [A′a + A′b] is formed into a spherical shape in order to impart powder fluidity. In order to obtain a spherical shape, rolling fluidized bed granulation was employed in this example. In particular, in this embodiment, a fine granulation mechanism incorporating a pulse jet dispersion mechanism (air jets are intermittently ejected from the side wall of the granulation casing toward the center) during rolling fluidized bed granulation. Then, as shown in the external view of the scanning electron micrograph of FIG. 6, a spherical polynuclear cluster phase [A ′] was obtained, and as a result, powder flowability was expressed without adding an additive such as a lubricant.

FIG. 7 is a characteristic diagram showing changes in the proportion of fine particles of the spherical multinuclear cluster phase [A ′] and the apparent density with respect to the proportion of the oligomer [A′b] in the mixture [A′a + A′b]. The two types of curves in the figure show the ratio of 10 μm or less to the spherical multinuclear cluster phase [A ′] of ≦ 500 (μm) and the spherical multinuclear cluster phase [A ′] observed by a laser diffraction particle size distribution analyzer. It shows the change in the hook density. As is apparent from the figure, the ratio of the spherical multinuclear cluster phase [A ′] is 10 (μm) or less with the increase of the oligomer [A′b]. This suggests that an appropriate ratio of the oligomer [A′b] is about 3 (wt.%) From the viewpoint of the yield of the spherical polynuclear cluster phase [A ′] and mechanical strength. Correspondingly, the apparent density increases. In the vicinity of the oligomer [A′b] 3 (wt.%), The powder fluidity according to JIS Z2501 is ≦ 45 (sec / 50 g), and the apparent density ≧ 2. 25 (Mg / m ³ ).

The spherical polynuclear cluster phase [A ′] as described above was finally mixed with a previously prepared compound intermediate [Ia] using a V blender or the like, and finished as the compound [I] according to the present invention. . The compound [I] has a powder flow rate of ≦ 45 (sec / 50 g) and an apparent density even when the ratio of the spherical multinuclear cluster phase [A ′] is 50 (wt.%). ≧ 2.4 (Mg / m ³ ). Therefore, the ratio of the spherical multinuclear cluster phase [A ′] can be arbitrarily set over a wide range without impairing the moldability in powder molding.

  Next, the compound was filled in a mold cavity of an orthogonal magnetic field oriented powder molding machine. However, the upper and lower punches and the cavity of the mold are heated to 100 (° C.).

  Subsequently, anisotropic rare earth magnet powders [A1a] and [A′a] contained in the cluster mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] filled in the mold cavity are 1.5 (MA / m ), Followed by compression, demagnetization, and release at 0.55 (GPa) to obtain a plate-like green compact [II] according to the present invention having a thickness of about 1 to 2 (mm).

This plate-like green compact [II] was heat-treated to obtain a rigid magnet precursor [III] capable of shape conversion based on the orientation of the self-assembled molecular chain according to the present invention. In this example, the tensile strength of the self-organized magnet precursor [III] starts to increase when the heat treatment temperature exceeds 120 (° C.), and at 160 (° C.), 100 to 120 (kg / cm ² ) at room temperature. Reached. The value was about four times the standard of the tensile strength of the green compact, and sufficient mechanical strength was exhibited as a rare earth bonded magnet. This increase in tensile strength supports the self-organization phenomenon between the oligomer [Ab], [A′b] and the stretched phase [B] accompanied by heat treatment conditions and chemical bonding by the chemical contact C. Furthermore, small shapes having various shapes ranging from the annular magnet [IVa] to the arc-shaped magnet [IVb] according to the present invention by the stamping shaping mold heated to 80 to 100 (° C.), the stretching roll, or the secondary processing by using them together. A self-organized hybrid rare earth bonded magnet for motor was obtained.

  3. The characteristics of the self-organized magnet precursor [III] will be described.

FIG. 8 shows the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] constituting the self-organized magnet precursor [III] according to the present invention. On the other hand, it is a characteristic diagram in which (BH) _max and density of magnet precursor [III] are plotted. However, the stretched phase [B] is 2.5 (wt.%), The mold cavity temperature is constant at 120 (° C.), (BH) _max is 4 (MA / m), and VSM (sample vibration) Type magnetometer) and density were measured by Archimedes method.

As apparent from the figure, when the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%), (BH ) _Max and density once increase and then decrease. The maximum values in this example were (BH) _{max of} about 182 (kJ / m ³ ) and density of about 6.25 (Mg / m ³ ). That is, by optimizing the proportion of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′], a high orientation rather than a high density is achieved, and thus a high ( BH) _max is obtained. Separately, when the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%), The rearrangement by the orientation magnetic field H Later, when densifying with the pressure P while applying the orientation magnetic field H, direct contact of the magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] is avoided, and the single magnetic domain It can be densified via the particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a]. The spherical multinuclear cluster phase [A ′] needs to be approximately ≧ 30 (wt.%) In order to make it dense via the single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a]. . Thus, when densification is performed through the single domain particle type Sm ₂ Fe ₁₇ N ₃ system rare earth magnet powder [A′a], the density of the surface of the polycrystalline aggregated Nd ₂ Fe ₁₄ B system rare earth magnet powder [Aa] is increased. Damage and crushing due to friction at the time of conversion are suppressed.

FIG. 9 shows the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] constituting the self-organized magnet precursor [III] according to the present invention. On the other hand, it is a characteristic diagram in which the squareness (Hk / Hci) of a demagnetization curve at 100 (° C.) of the magnet precursor [III] is plotted. As is apparent from the figure, it can be seen that the squareness (Hk / Hci) of the demagnetization curve at the time of high temperature exposure improves according to the proportion of the spherical multinuclear cluster phase [A ′]. This is because the green compact [II] of polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] in the mixed phase [A + An] is produced according to the ratio of the spherical multinuclear cluster phase [A ′]. It can be explained that this deterioration is suppressed by the interposition of the spherical multinuclear cluster phase [A ′].

The fact that the deterioration of the squareness (Hk / Hci) upon high-temperature exposure as described above is suppressed according to the ratio of the spherical multinuclear cluster phase [A ′] is substantially the green compact [II shown in FIG. ] Is also related to the change in (BH) _max when producing a self-assembled magnet precursor [III] by heat treatment. Note that the comparative example shown in FIG. 10 does not include the spherical polynuclear cluster phase [A ′], but only the mixed phase [A + An] mainly composed of polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa]. The characteristic curve of magnet precursor [III] produced from Fig. 3 is shown. As is apparent from the figure, in this example, surface damage and crushing due to friction during densification of the surface of the polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] are suppressed even if heat treatment is performed in the atmosphere. _Therefore , the deterioration of (BH) _max is substantially suppressed. In order to suppress the initial irreversible demagnetization of the magnet, it is desirable that the square shape (Hk / Hci) of the demagnetization curve at 100 (° C.) is ≧ 0.4, and for this purpose, a self-organized magnet precursor The ratio of the spherical multinuclear cluster phase [A ′] to the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] constituting the body [III] was required to be approximately 30 (wt.%).

On the other hand, in the small motor targeted by the present invention, irreversible demagnetization caused when the magnet is heated is regarded as important. Therefore, FIG. 11 shows the relationship of the irreversible demagnetization factor with respect to the exposure temperature of the magnet precursor [III] according to the present invention in which the ratio of the spherical multinuclear cluster phase [A ′] is 40 (wt.%). However, the irreversible demagnetizing factor FL was obtained from (φo−φ) / φo (where φo is a magnetic flux before exposure and φ is a magnetic flux after high temperature exposure). The comparative example in the figure does not include the spherical polynuclear cluster phase [A ′], but is produced only from the mixed phase [A + An] mainly composed of polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa]. 2 shows a characteristic curve of the magnet precursor [III]. As is clear from the figure, a significant difference in characteristics is observed between the two exposed to high temperatures of 100 ° C. or higher, and the irreversible demagnetization of the magnet precursor [III] according to the present invention is small. Also, the difference between the two irreversible demagnetization rates becomes significant when exposed at higher temperatures.

Therefore, the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is left for 1 (hr) at exposure temperatures of 100 and 120 (° C.). FIG. 12 shows the irreversible demagnetization factor at the time. However, the irreversible demagnetization factor FL is (φo−φ) / φ
o (where φo is magnetic flux before exposure and φ is magnetic flux after high temperature exposure). As is clear from the figure, the irreversible demagnetization of the magnet can be suppressed when the multinuclear cluster phase [A ′] according to the present invention is present. For example, assuming that the ratio of the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%), The irreversible demagnetization rate after exposure to 100 (° C.) does not include the spherical multinuclear cluster phase [A ′] according to the present invention. Compared to 1/2 or less.

As described above, it has been clarified that the magnet precursor [III] according to the present invention has a high (BH) _max and improved magnetic stability represented by irreversible demagnetization. However, on the other hand, in the motor targeted by the present invention, it is usually required to sufficiently magnetize and use the magnet.

  In general, a high coercivity type magnet is disadvantageous for magnetizing a magnet with a small amount of energy. However, a high coercivity magnet is advantageous for irreversible demagnetization. Therefore, the relationship of the coercive force Hci to the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] was examined.

  FIG. 13 shows the relationship between the coercive force Hci at room temperature, which is important when magnetizing, with respect to the ratio of the spherical multinuclear cluster phase [A ′] in the sum of the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′]. FIG.

As is apparent from the figure, the present embodiment includes, for example, 40 (wt.%) Of a spherical multinuclear cluster phase [A ′] with respect to the coercive force 905 (kA / m) of the comparative example not including the multinuclear cluster phase [A ′]. The example showed a value as small as about 860 (kA / m) and about 5 (%). As described above, the present embodiment has a small coercive force Hci at room temperature, which has less irreversible demagnetization in high temperature exposure. In other words, the magnet according to the present invention is high (BH) _max , low irreversible demagnetization, and can be magnetized with low energy. Therefore, it can be concluded that the present invention is extremely suitable as a magnet for a small motor.

  4). The production of the annular magnet [IVa] and the arc-shaped magnet [IVb] will be described.

FIG. 14 shows that when a self-organized magnet precursor [III] having a thickness of 0.4 to 2.5 (mm) is magnetized in advance with a pulse magnetic field of 4 (MA / m) and rolled at a constant speed, rolling is performed. It is the characteristic view which plotted the change of surface magnetic flux with respect to the thickness after rolling. In the figure, a circle (white circle) is a plot before rolling, and a circle (black circle) is a plot after rolling. For example, the result in the range shown as the comparative example shows a characteristic curve when the thickness of the magnet precursor [III] is ≧ 2 (mm). CURVE-1 is a characteristic curve showing the relationship between the thickness of the magnet precursor [III] before rolling and the surface magnetic flux. As is apparent from the figure, the surface magnetic flux of the magnet precursor [III] finished relatively thick at 2.1 to 2.5 (mm) is greatly reduced by a slight thickness reduction due to rolling. When the surface magnetic flux curve [CURVE-1] with respect to the thickness of the unrolled magnet precursor [III] is used as a reference, the orientation of the magnetic powder [Aa] or [A'a] is clearly disturbed due to rolling. It can be said that the surface magnetic flux is reduced due to the above. On the other hand, the plot of the surface magnetic flux by rolling of the magnet precursor [III] having a thickness of about 1.3 (mm) shown as an example almost coincides with [CURVE-1]. Therefore, in this case, the surface magnetic flux drop due to the disorder of orientation due to rolling of the magnetic powder [Aa] or [A′a] is clearly not observed. In other words, if the magnet precursor [III] has a thickness of about 1 to 2 (mm), it is possible to suppress a decrease in surface magnetic flux due to disorder of orientation due to rolling. For example, in the case of an annular magnet having a diameter of 25 (mm) or less, a thickness of 1 to 2 (mm), and a ratio of length to diameter (L / D = 0.5 to 1), the present invention targets compression and injection. Regardless of the manufacturing method such as extrusion, a decrease in the degree of orientation of the rare earth magnet powder due to a decrease in the radial orientation magnetic field inevitably caused a decrease in the high (BH) _max of the rare earth bonded magnet, and it was prototyped as a cylinder or a cube. Although only a radially anisotropic annular magnet having characteristics that are significantly lower than those of a high (BH) _max rare earth bonded magnet can be produced, it is clear that the present invention can eliminate the problem.

  FIG. 15A shows a magnet precursor [III] having a thickness of 1.05 (mm), a length of 90 (mm), and a width of 4.5 (mm) when rolled to a thickness of 1.02 (mm). It is a photograph which shows the external view of a magnet.

In the figure, [III] indicates a magnet precursor, and [IV] indicates a hybrid rare earth bonded magnet according to the present invention after rolling. As is apparent from the figure, the magnet precursor [III] is hard, but the hybrid rare earth bonded magnet [IV] according to the present invention finished by rolling the stretched phase [B] has a rolling direction (in this case, the longitudinal direction). It is understood that it is extremely supple. This is a result of the stretching phase [B] being mechanically uniaxially stretched in the rolling direction by rolling, and this is wound around a laminated electrical steel sheet (Laminated steel core) as shown in the photograph of FIG. 15 (b), for example. And the annular magnet [IVa] concerning this invention is obtained. The annular magnet [IVa] is a radially anisotropic annular hybrid rare earth bonded magnet [IVa] having a constant (BH) _max value regardless of the diameter of the magnet.

By the way, when the stretch phase [B] of the self-organized magnet precursor [III] is stretched by rolling, if a large density difference occurs in the magnet precursor [III], it causes meandering during rolling. The cause of the difference in density includes homogeneous filling into the mold cavity when producing the plate-like green compact [I], compression non-uniformity for densification from above and below, and the like. In this example, if the density distribution of the plate-like green compact [II] is approximately ≦ 0.1 (Mg / m ³ ), the thickness is 1.05 (mm), the length is 90 (mm), and the width is 4.5. When the (mm) magnet precursor [III] was rolled to a thickness of 1.02 (mm), the meandering (maximum deflection) caused by the rolling was almost ≦ 0.1 (mm), which was almost negligible.

Further, the extension of the extension phase [B] can be used as stamping, and the shape can be changed to the arc magnet [IVb]. In particular, when the arc-shaped magnet [IVb] having an unequal wall thickness with a maximum wall thickness ≦ 1 (mm) is used, it is effective for improving the motor performance while suppressing the cogging torque. Such a magnet is finally magnetized and used, but the maximum energy product (BH) _max at 20 ° C. when magnetized at 1.2 (MA / m) is ≧ 120 (kJ / m ³ ), or It is desirable that the maximum energy product (BH) _max at 20 (° C.) when magnetized at 2.0 (MA / m) is ≧ 160 (kJ / m ³ ).

  The self-organized hybrid rare earth bonded magnet, the manufacturing method thereof, and the motor according to the present invention have the effect of increasing the motor efficiency by increasing the output, so-called permanent magnet rotor type, permanent magnet type motor, or Is useful as a permanent magnet field type brushless motor, DC motor, or the like.

Conceptual diagram showing the structure of mononuclear cluster phase [A] and multinuclear cluster phase [An] Conceptual diagram showing the structure of the multinuclear cluster phase [A '] Conceptual diagram of thermal dissociation and rearrangement of mixed phase [A + An] and multinuclear cluster phase [A ′], (a) conceptual diagram of thermal dissociation, (b) conceptual diagram of rearrangement Conceptual diagram of rearrangement and densification of mixed phase [A + An] and multinuclear cluster phase [A ′], (a) conceptual diagram of rearrangement, (b) conceptual diagram of densification Fig. 2 is an external view of a molding die and a molding machine, (a) is a molding die for producing a plate-like green compact according to the present invention, and (b) is an external view of an orthogonal magnetic field oriented powder molding machine. External view of Spherical Multinuclear Cluster Phase [A '] by scanning electron micrograph Characteristic diagram showing changes in the proportion of fine particles and the apparent density of the spherical multinuclear cluster phase [A '] Characteristic diagram showing the relationship between the ratio of spherical polynuclear cluster phase [A '], (BH) _max and density Characteristic diagram showing the relationship between the ratio of the spherical multinuclear cluster phase [A '] and the squareness of the demagnetization curve Characteristic diagram showing changes in heat treatment temperature and (BH) _max Characteristic diagram showing the relationship between exposure temperature and irreversible demagnetization Characteristic diagram showing the relationship between the ratio of multinuclear cluster phase [A '] and irreversible demagnetization Characteristic diagram showing the relationship between the ratio of spherical polynuclear cluster phase [A '] and coercivity at room temperature Characteristic diagram showing changes in surface magnetic flux due to rolling Appearance of the magnet precursor [III] and the annular magnet of the present invention as photographed, (a) is an appearance of the precursor [III] when rolled to a thickness of 1.02 (mm), and (b) is laminated electromagnetic. External view of annular magnet [IVa] according to the present invention wound around a steel plate

Explanation of symbols

A Mononuclear cluster phase A 'Multinuclear cluster phase H Oriented magnetic field

Claims (36)

A mononuclear cluster phase [A], a polynuclear cluster phase [An], or a mixed phase thereof mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] A + An] , a stretched phase [B ] in which a predetermined amount of lubricant is dispersed, and a chemical intermediate [C] kneaded ,
Essential components magnetically single domain particles type anisotropic Sm ₂ Fe ₁₇ N ₃ -based rare-earth magnet powder [A'a] spherical granular spherical multinuclear cluster phase composed mainly of the [A'], the A self-organized hybrid rare earth bonded magnet. (1) A mononuclear cluster phase [A], a polynuclear cluster phase [An] mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa ], or their cluster phase and [a + an], stretching phase dispersed a predetermined amount of lubricant and [B], compound intermediate by kneading the chemical contact [C] and [I-a],
A spherical granule-like spherical multinuclear cluster phase [A ′] mainly composed of magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] ;
The process of producing the compound [I] was mixed with the additives optionally added, the as needed,
(2) oriented by the compound [I] in a magnetic field, the process of producing the compound [I] the pressure <br/> reduced plate-shaped green compact [II],
(3) before Kigu heat treating the lean compact [II], mononuclear cluster phase [A], multinuclear cluster phase [An], or their clusters phase and [A + An], spherical multinuclear cluster phase [A'], stretching phase and [B], the manufacturing process of the self-assembled magnet precursor [III] in the chemical contact [C] a,
A step of shape conversion annularly [IVa] or arc-shaped magnet [IVb] by stretching (4) stretching phase contained before Ki磁 stone precursor [III] [B],
A self-organized hybrid rare earth bonded magnet obtained by a manufacturing method comprising: Monocrystalline cluster phase [A], polynuclear cluster phase [An], or a mixed phase [A + An] of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] and oligomer The oligomer according to claim 1 or 2 , wherein the oligomer [Ab] is an oligomer having a reaction substrate that self-assembles with the stretched phase [B] and the chemical contact [C]. Self-organized hybrid rare earth bonded magnet. The spherical multinuclear cluster phase [A ′] is composed of magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] and oligomer [A′b], hybrid rare earth oligomer [A'B] has self-assembly according to any one of claims 1 to 3 is an oligomer having a reaction substrate for the stretching phase B and self-organization and the chemical contact [C] Bond magnet. 5. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the spherical multinuclear cluster phase [A ′] is a spherical granule of ≦ 500 (μm). The spherical polynuclear cluster phase [A ′] is a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A ′] and an organic solvent solution of an oligomer [A′b]. 6. The self-organized hybrid rare earth bonded magnet according to claim 5, which is wet-mixed, desolvated, compressed, classified and then finished into a spherical shape by a rolling fluidized bed granulation method. The tumbling fluidized bed granulation method, self as claimed in claim 6 wherein utilizing a pulsed jet disperser mechanism (intermittently injecting air jets toward the center than the side wall of the granulation casing) fine granulation mechanism incorporating An organized hybrid rare earth bonded magnet. The mononuclear cluster phase [A], multinuclear cluster phase [An], or mixed phases thereof oligomer contained in [A + An] [Ab] and the spherical multinuclear cluster phase [A'] oligomer contained in [A'B] hybrid rare earth bonded magnet, which is self-organized according to any one of claims 1 to 7 is an organic compound having at least two oxirane rings but solid at room temperature, and in the molecular chain. The mononuclear cluster phase [A], multinuclear cluster phase [An], or the proportion of the oligomer [Ab] contained in the mixed phase thereof [A + An], oligomers contained in the spherical multinuclear cluster phase [A'] [A The ratio of 'b ' is 0.5 to 0.5 for the mononuclear cluster phase [A], the multinuclear cluster phase [An], or the mixed phase [A + An] and the spherical multinuclear cluster phase [A '], respectively. 3.0 (wt.%) a hybrid rare earth bonded magnet, which is self-organized according to any one of claims 1 to 8. The proportion of the mononuclear cluster phase [A], multinuclear cluster phase [An], or mixed phases thereof [A + An] and the spherical multinuclear cluster phase [A'] and the spherical multinuclear cluster phase occupying the sum of [A'] There 30 to 50 (wt.%) a hybrid rare earth bonded magnet, which is self-organized according to any one of claims 1 to 9. 3. The self-organized hybrid rare earth bonded magnet according to claim 2, wherein a ratio of all the clusters in the compound [I] is ≦ 97.5 (wt.%). 12. The self-organized hybrid rare earth bonded magnet according to claim 2, wherein a ratio of the stretched phase [B] to the compound [I] is ≧ 2.5 (wt.%). Hybrid self-assembled according to any one of the stretching phase [B] is the molecular chain orientation ability of uniaxial stretching, and claims 1 to 12, which is a polymer containing a reaction substrate capable of reacting with at least Chemical Contacts C Type rare earth bonded magnet. The compound [I] is the apparent density ≧ 2.4 by ^{JIS Z 2501 (Mg / m 3} ), powder flowability ≧ 45 (sec / 50g) to claim 2, claim 11, or claim 1
2. A self-organized hybrid rare earth bonded magnet according to 2. When the plate-like green compact [II] is produced, it is contained in the mononuclear cluster phase [A], the multinuclear cluster phase [An], or the mixed phase [A + An] of the compound [I] filled in the mold cavity. oligomer [Ab], and spherical multinuclear cluster phase [A'] heated above the melting point of the oligomer [A'B] contained in, claim 2 which compresses while applying the later orientation magnetic field accordingly, claim 11, claim The self-organized hybrid rare earth bonded magnet according to claim 12 or 14 . The said compact green [II] WHEREIN: It is below the self-organization start temperature by the said chemical contact [C] , Claim 11, Claim 12, Claim 14, or Claim 15 . Self-organized hybrid rare earth bonded magnet. The plate-like green making the compact [II], ≧ 1.5 under the orthogonal orientation magnetic field (MA / m), claim 2 for compressing the longitudinal sides corresponding to the plate thickness of the plate, according to claim 11 , claim 12, claim 14,請 Motomeko 15, or a hybrid rare earth bonded magnet, which is self-organized according to claim 16. When manufacturing the plate-like green compact [II], claim 2 using a mold and die set is constituted by a nonmagnetic material having a plurality of mold cavities, claim 11, claim 12, claim 14, wherein 15. claim 16 or a hybrid rare earth bonded magnet, which is self-organized according to claim 1 7. The plate-like green making the compact [II], claim 2 the maximum strain in the longitudinal center mold cavity which corresponds to the plate thickness of the plate-like ≦ 0.1 and (mm), according to claim 11, 12., 14, 15, 16, 17, or hybrid rare earth bonded magnet, which is self-organized according to claim 1 8. The plate-like green compact [II] according to claim 2 density distribution is ≦ 0.1 (Mg / m ³⁾ of claim 11, claim 12, claim 14, claim 15, claim 16, claim The self-organized hybrid rare earth bonded magnet according to claim 17, claim 18, or claim 19 . The plate-like green compact according to claim 2 thickness of [II] is 1.0 ± 0.5 (mm), according to claim 11, claim 12, claim 14, claim 15, claim 16, claim The self-assembled hybrid rare earth bonded magnet according to claim 17, claim 18, claim 19, or claim 20 . The self-organized magnet precursor [III] is for heat-treating the plate-like green compact [II] in the atmosphere at ≦ 160 ° C. The claim 2, claim 11, claim 14, claim 15, claim 15 A self-assembled hybrid rare earth bonded magnet according to claim 16, claim 17, claim 18, claim 19, claim 20, or claim 21 . The tensile strength of the self-organized magnet precursor [III] is more than three times that of the plate-like green compact [II], claim 2 , claim 11, claim 14, claim 15, claim 16, The self-assembled hybrid rare earth bonded magnet according to claim 17, claim 18, claim 19, claim 20, claim 21, or claim 22 . The maximum reduction ratio due to stretching of the magnet precursor [III] is 10 (%), claim 2, claim 11, claim 14, claim 15, claim 16, claim 17, claim 18 The self-organized hybrid rare earth bonded magnet according to claim 19, claim 20, claim 21, claim 22, or claim 23 . Claim 2, Claim 11, Claim 14, Claim 15 , wherein the extension of the extension phase B contained in the magnet precursor [III] is rolling, and after the rolling, the shape is converted to an annular magnet [IVa]. A self-assembled hybrid rare earth bonded magnet according to claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, or claim 24. . The annular magnet [IVa] has an outer diameter ≦ 25 (mm) , claim 11, claim 12, claim 14, claim 15, claim 16, claim 17, claim 18, and claim 19. A self-organized hybrid rare earth bonded magnet according to claim 20, claim 21, claim 22, claim 23, claim 24, or claim 25 . Claim 2, Claim 11, Claim 14, Claim 15, wherein the extension of the extension phase [B] contained in the magnet precursor [III] is stamped and converted into an arc magnet [IVb] . The self-assembled hybrid rare earth bonded magnet according to claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, or claim 24 . The arc-shaped magnet [IVb] has an unequal thickness and a different radial magnetic property, wherein the magnetic properties in the radial direction are different from those of claim 2, claim 11, claim 12, claim 15, claim 16, claim 17, claim 18. A self-assembled hybrid rare earth bonded magnet according to claim 19, claim 20, claim 21, claim 22, claim 23, claim 24, claim 25, claim 26, or claim 27. . 1.2 hybrid type self-assembled according to any one of (MA / m) maximum energy product (BH) _max of 20 ° C. when the magnetization is ≧ 120 kJ / m ³ in claims 1 to 28 Rare earth bonded magnet. 2.0 hybrid type self-assembled according to any one of (MA / m) maximum energy product (BH) _max of 20 ° C. when the magnetization is ≧ 160 kJ / m ³ in claims 1 to 28 Rare earth bonded magnet. 100 square demagnetization curve at (℃) (Hk / Hci) is a hybrid rare earth bonded magnet, which is self-organized according to any one of claims 1 to 30 is ≧ 0.4. Motor equipped with a ring magnet [IVa] according to the hybrid-type rare-earth bonded magnet, which is self-organized according to any one of claims 1 to 31. A motor equipped with an annular magnet [IVa] having an outer diameter ≦ 25 (mm) applied to the self-organized hybrid rare earth bonded magnet according to claim 26 . Brushless motor equipped with arc-shaped magnet [IVb] according to the hybrid-type rare-earth bonded magnet, which is self-organized according to any one of claims 1 to 31. Motor equipped with arc-shaped magnet [IVb] according to claim 1 to the maximum thickness ≦ 1 according to the hybrid-type rare-earth bonded magnet, which is self-organized according to any of claims 31 (mm). (1) A mononuclear cluster phase [A], a polynuclear cluster phase [An] mainly composed of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa], or their A cluster phase [A + An], a stretched phase [B] in which a predetermined amount of lubricant is dispersed, and a chemical contact [C]
Compound intermediate [Ia] kneaded with
A spherical granule-shaped spherical multinuclear cluster phase [A ′] mainly composed of a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a];
A process for producing a compound [I] in which additives that are appropriately added as necessary are mixed,
(2) Orienting the compound [I] in a magnetic field and pressing the compound [I]
A process for producing a shrinking plate green compact [II];
(3) The green compact [II] is heat-treated, and the mononuclear cluster phase [A], the multinuclear cluster phase [An], or their cluster phase [A + An], the spherical multinuclear cluster phase [A ′], and the stretched phase [B] and a process for producing a magnet precursor [III] that is self-assembled with chemical contact [C],
(4) a step of transforming the shape into an annular [IVa] or an arcuate magnet [IVb] by stretching the stretched phase [B] contained in the magnet precursor [III];
Method for producing a hybrid type rare-earth bonded magnet to produce a hybrid-type rare-earth bonded magnet, which is self-organizing with a.