JP2005158863A - Self-organized hybrid rare earth bond magnet and its manufacturing method, and motor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent a decline in the (BH)max of a rare earth bond magnet which is an annular magnet carried in a small motor even if a diameter is reduced (or a length is increased) by using anisotropic Nd<SB>2</SB>Fe<SB>14</SB>B-based rare earth magnet powder. <P>SOLUTION: The self-organized hybrid rare earth bond magnet contains, as essential components, a single nucleus cluster phase [A], the chief of which is the magnetically anisotropic polycrystal-assembled Nd<SB>2</SB>Fe<SB>14</SB>B-based rare earth magnet powder [Aa], a multi-nucleus cluster phase [An], or a mixed phase of these [A+An]; a spherical multi-nucleus cluster phase [A'], the chief of which is magnetically anisotropic single-domain particle type Sm<SB>2</SB>Fe<SB>17</SB>N<SB>3</SB>-based rare earth magnet powder [A'a], and an extension phase [B]; the mixed phase [A+An] and the phase [A']; and chemical contact [C] with the phase [B]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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 an atmospheric 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 that can be used. In addition, Dy addition enhances 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 having a maximum of 216 to 296 (kJ / m ³ ), it has been widely spread to relatively large motors such as MRI, VCM, FA, and EV, 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 and flake 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 a 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, the small motor characteristics of the small-diameter annular isotropic rare earth bonded magnet and the Sm—Co radial anisotropic 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 the melt spun ribbon has been continuously and actively conducted from the mid-1980s to the present, the (BH) _max of the ribbon itself is about 160 (kJ / m ³ ). The (BH) _max of a magnetically isotropic bond magnet in which an R-TM-B quenching powder obtained by pulverizing the ribbon is fixed with a resin is industrially ~ 80 kJ / m ³ . Therefore, from 1985 until recently, the increase in the (BH) _max of magnetically isotropic rare earth bonded magnets in which R-TM-B quenching powder obtained by pulverizing melt-spun ribbons was fixed with resin has made great progress. Not done.

  Regardless of the above, 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 brushless motors and DC motors. Under the background of high performance and high added value of electrical and electronic equipment, there is a constant demand for further reduction in size, weight and output of small magnet motors. Therefore, the small-diameter annular isotropic rare earth bonded magnet in which R-TM-B quenching powder obtained by pulverizing the melt spun ribbon found by the present inventors in 1986 is fixed to 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 conventional Sm-Co based bonded magnets, the ingot is finely pulverized to obtain a large coercive force Hci, whereas Nd ₂ Fe ₁₄ B based alloy ingots and Nd ₂ Fe ₁₄ B based atmospheric pressure sintered magnets 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 a bulk obtained by hot upsetting (Die-up-set) of Nd ₁₄ Fe _80-X B ₆ Ga _X (X = 0.4 to 0.5). An anisotropic Nd ₂ Fe ₁₄ B-based rare earth magnet powder having a coercive force Hci 1.52 (MA / m) is prepared, and this is 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 with 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, Cu or the like 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 in which the above melt spun ribbon is hot-set or hot-rolled has a Nd-rich phase at the crystal grain boundary and is permanently demagnetized based on the grain boundary corrosion. There was a drawback that it is easy to cause. As a method of overcoming this drawback, Nd—Fe (Co) —B alloy ingots added with elements such as Ga, Zr, Hf, etc. are heat-treated in hydrogen to hydrogenate Nd ₂ (Fe, Co) ₁₄ B phase. (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 Ther Applications, Pittsburgh, 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 the same thermal stability as a rare earth bonded magnet in which a powder close to the Nd ₂ Fe ₁₄ B stoichiometric composition is solidified with resin by Dy addition or dehydrogenation 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 above-mentioned high (BH) _max rare earth bonded magnets using anisotropic Nd ₂ Fe ₁₄ B rare earth magnet powders are prototyped in cylinders or cubes. 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 exciting coil is arranged outside is used. In this method, a radial orientation magnetic field having a predetermined strength is generated in the annular mold cavity, and therefore, a high-voltage, high-current 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 magnetic coil 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 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 a 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 spherical shape mainly composed of a multinuclear cluster phase [An] or a mixed phase thereof [A + An] and a magnetically anisotropic single domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a]. Self-organized hybrid rare earth containing, as an essential component, a multinuclear cluster phase [A ′], an extended phase [B], and phases [A], [A ′], and a chemical contact [C] with the phase [B] Bond magnet.

In addition, the second invention,
(1) A mononuclear cluster phase [A], a polynuclear cluster phase [An], or a compound intermediate [Ia], a spherical polynuclear by the cluster phase [A + An], an extended phase [B], and a chemical contact [C]. A process for producing a compound [I] in which the cluster phase [A ′] and the above-mentioned two types and additives that are appropriately added as necessary are mixed,
(2) Production process of plate green compact [II] by compound compression;
(3) The green compact [II] is heat-treated, and a step of producing a magnet precursor [III] in which the phases [A + An], [A ′] and the phase [B] are self-organized by chemical contacts [C];
(4) A self-organized hybrid type obtained by a manufacturing method comprising a step of transforming the shape into an annular [IVa] or arcuate magnet [IVb] by stretching the phase [B] contained in the magnet precursor [III] It is a 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 composed of a magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa] and an oligomer [Ab], and the oligomer [Ab] includes the stretched phase [B] and It has a chemical contact [C] and a reaction substrate that self-assembles.

The fourth invention is a single-domain particle type in which the spherical multinuclear cluster phase [A ′] is magnetically anisotropic in the self-organized hybrid rare earth bonded magnet of the first invention or the second invention. Reaction composed of Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] and oligomer [A′b], and the oligomer [A′b] self-assembles with phase B and chemical contact [C]. Has a substrate.

  The fifth invention is a spherical granule having a spherical multinuclear cluster phase [A ′] of ≦ 500 (μm) in the self-organized hybrid rare earth bonded magnet of the fourth invention.

The sixth invention is the self-organized hybrid rare earth bonded magnet of the fifth invention, wherein the spherical multinuclear cluster phase [A ′] is previously magnetically anisotropic single domain particle type Sm ₂ Fe. ₁₇ N ₃ rare earth magnet powder [A ′] and an organic solvent solution of oligomer [A′b] are wet mixed, desolvated, compressed and classified, and then finished into a spherical shape by a rolling fluidized bed granulation method.

  According to a seventh invention, in the self-organized hybrid rare earth bonded magnet of the sixth invention, the rolling fluidized bed granulation is performed by a pulse jet dispersion mechanism (air jet is directed toward the center from the side wall of the granulation casing). A fine granulation mechanism that incorporates intermittent injection) is used.

  The eighth 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. An organic compound in which the oligomer [Ab] contained in [A + An] and the oligomer [A′b] contained in the spherical polynuclear cluster phase [A ′] are solid at room temperature and have at least two oxirane rings in the molecular chain It is.

  The ninth 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. The ratio of the oligomer [Ab] contained in [A + An] and the oligomer [A′b] contained in the spherical polynuclear cluster phase [A ′] is 0.5 to 3.0 (wt.%).

  The tenth 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. The ratio of the spherical multinuclear cluster phase [A ′] to the sum of [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 50 (wt.%).

  According to an eleventh aspect of the invention, in the self-organized hybrid rare earth bonded magnet according to the first or second aspect of the invention, the proportion of all clusters in the compound [I] is ≦ 97.5 (wt.%) ).

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

  A thirteenth aspect of the present invention is the self-organized hybrid rare earth bonded magnet of the first aspect or the second aspect of the present invention, wherein the stretched phase [B] has molecular chain orientation ability by uniaxial stretching, and at least the chemical contact C. A polymer containing a reaction substrate capable of reacting.

  According to a fourteenth aspect of the present invention, in the self-organized hybrid rare earth bonded magnet of the first aspect or the second aspect, the compound [I] has an apparent density according to JIS Z2501 and a powder fluidity of the following: It 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)

  Further, the fifteenth aspect of the invention is the self-organized hybrid rare earth bonded magnet of the first aspect of the invention or the second aspect of the invention, wherein when the plate-shaped green compact [II] is produced, the compound [ I], a mononuclear cluster phase [A], a multinuclear cluster phase [An], or an oligomer [Ab] contained in a mixed phase [A + An] thereof, and an oligomer [A ′] contained in a spherical multinuclear cluster phase [A ′]. b] above the melting point, and then compressing while applying an orientation magnetic field.

  The sixteenth invention is the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, wherein self-organization by chemical contact [C] is started when green compact [II] is manufactured. Below the temperature.

  The seventeenth invention is a self-organized hybrid rare earth bonded magnet according to the first invention, the second invention, the fourteenth invention, or the fifteenth invention. In this case, the longitudinal side surface corresponding to the plate thickness is compressed under an orthogonal orientation magnetic field of ≧ 1.5 (MA / m).

  The eighteenth aspect of the invention is the self-organized hybrid rare earth bonded magnet of the first aspect, the second aspect, or the sixteenth aspect of the present invention. A mold and a die set made of a nonmagnetic material having a cavity are used.

  The nineteenth invention is a plate-like green compact [II] in the self-organized hybrid rare earth bonded magnet of the first invention, the second invention, or the seventeenth invention. The maximum strain amount of the mold cavity at the center in the longitudinal direction corresponding to the plate thickness is set to ≦ 0.1 (mm).

According to a twentieth aspect, in the self-organized hybrid rare earth bonded magnet according to the first aspect or the second aspect, the density distribution of the plate-like green compact [II] is ≦ 0.1 (Mg / m ³ ).

  The twenty-first invention is the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, wherein the plate-like green compact [II] has a thickness of 1.0 ± 0.5 (mm ).

  According to a twenty-second invention, in the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, the self-organized magnet precursor [III] is plate-shaped in the atmosphere at ≦ 160 ° C. Green compact [II] is heat-treated.

  The twenty-third invention is the self-organized hybrid rare earth bond magnet of the first invention, the second invention, or the twenty-first invention, wherein the tensile strength of the self-organized magnet precursor [III] is It is more than 3 times the plate-shaped green compact [II].

  According to a twenty-fourth invention, in the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, the maximum rolling reduction due to stretching of the magnet precursor [III] is 10 (%).

  According to a twenty-fifth aspect of the present invention, in the self-organized hybrid rare earth bonded magnet according to the first or second aspect of the present invention, the extension of phase B contained in the magnet precursor [III] is rolled, and after the rolling The shape is converted into an annular magnet [IVa].

  The twenty-sixth invention is the self-organized hybrid rare earth bonded magnet of the first invention, the second invention, or the twenty-third invention, wherein the annular magnet [IVa] has an outer diameter ≦ 25 (mm). is there.

  According to a twenty-seventh aspect of the present invention, in the self-organized hybrid rare earth bonded magnet according to the first or second aspect of the present invention, the stretching of the stretched phase [B] contained in the magnet precursor [III] is stamping, The shape is converted into an arc-shaped magnet [IVb].

  According to a twenty-eighth aspect of the invention, in the self-organized hybrid rare earth bonded magnet of the first aspect, the second aspect, or the twenty-sixth aspect, the arc-shaped magnet [IVb] has an unequal thickness and a radial direction. Have different magnetic properties.

According to a twenty-ninth invention, in the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, a maximum energy product of 20 ° C. when magnetized at 1.2 (MA / m) ( BH) _max is ≧ 120 kJ / m ³ .

The thirtieth invention is the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, wherein the maximum energy product (BH) at 20 ° C. when magnetized at 2.0 (MA / m). ) _Max is ≧ 160 kJ / m ³ .

  According to a thirty-first invention, in the self-organized hybrid rare earth bonded magnet of the first invention or the second invention, the square shape (Hk / Hci) of the demagnetization curve at 100 (° C.) is ≧ 0. 4.

  A thirty-second invention is a motor on which the self-organized hybrid rare earth bonded magnet [IVa] of the first invention or the second invention is mounted.

  A thirty-third invention provides an annular magnet [IVa] having an outer diameter ≦ 25 (mm) according to the self-organized hybrid rare earth bonded magnet of the first invention, the second invention, or the twenty-fifth invention. It is a mounted motor.

  A thirty-fourth invention is a brushless motor on which an arc-shaped magnet [IVb] according to the self-organized hybrid rare earth bonded magnet of the first invention or the second invention is mounted.

  A thirty-fifth aspect of the present invention is an arc magnet having a maximum thickness ≦ 1 (mm) according to the self-organized hybrid rare earth bonded magnet of the first aspect, the second aspect, or the twenty-seventh aspect [IVb ].

  The thirty-sixth invention is a method for producing a hybrid rare earth bonded magnet for producing the self-organized hybrid rare earth bonded magnet of the first to thirty first inventions.

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 magnet,
(1) Cluster phase [A + An], stretched phase [B], compound intermediate [Ia] by chemical contact [C], spherical multinuclear cluster phase [A ′], and the above-mentioned two types are added as necessary. A process for producing a compound [I] mixed with an additive;
(2) Production process of plate green compact [II] by compound compression;
(3) Heat treatment of the green compact [II] to produce a magnet precursor [III] in which the phase [A + An], the phase [A ′], and the phase [B] are self-organized by the chemical contact [C]. Process,
(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 bonded 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, which is mainly composed of crystalline polycrystalline Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa], magnetic In addition, the spherical multinuclear cluster phase [A ′], the extended phase [B], and the phase [A] mainly composed of 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. And as a manufacturing method of the magnet,
(1) A mononuclear cluster phase [A], a polynuclear cluster phase [An], or a compound intermediate [Ia], a spherical polynuclear by the cluster phase [A + An], an extended phase [B], and a chemical contact [C]. A production step of a compound [I] in which the cluster phase [A ′] and the above-mentioned two types and additives that are appropriately added as necessary are mixed,
(2) Production process of plate-like green compact [II] by compound compression,
(3) The green compact [II] is heat-treated, and a step of producing a magnet precursor [III] in which the phases [A + An], [A ′] and the phase [B] are self-assembled with chemical contacts [C].
(4) The step of converting the shape into an annular [IVa] or an arcuate magnet [IVb] by stretching the phase [B] contained in the magnet precursor [III].

  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 a 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 reaction substrate that self-assembles with a chemical contact [C] 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 magnetization axis (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 polynuclear 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 aggregated 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 powders (for example, M. Doser, V. Panchanathan, “Pulverizing anisotropic”).
rapidly solidified Nd-Fe-B materials for bonded magnet ", J. Appl. Phys. 70 (10), 15, 1993: Non-patent document 12), magnetically prepared by HDDR processing (hydrogen decomposition / recombination). polycrystalline aggregate type Nd ₂ Fe ₁₄ B based rare earth magnet powder anisotropy, i.e., Nd-Fe (Co) of -B alloy _{Nd 2 (Fe, Co) 14} B phase hydrogenation of (H ydrogenation, Nd _{2 [Fe, Co] 14 BHx} ), 650~1000 (℃) 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} Applications, Kyoto, Vol.1,551 1989: a magnet powder prepared in Non-patent Document 13).

In addition, the surface of the magnet powder is previously deactivated such as Zn that has been photodecomposed (for example, 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 the 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 polynuclear 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 extended phase [B]. , And chemical contact [C] and self-organized oligomer [A′b] as shown in FIG. At this stage, 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 multinuclear cluster phase [A ′] is, for example, an organic material 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]. The solvent solution can be 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 it is a fine granulation mechanism incorporating 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 aggregate 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. As an organic compound having at least two oxirane rings in the molecular chain, those obtained by bisphenols and epichlorohydrin or substituted epichlorohydrin, or other various methods, for example, 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 if it is less than 0.5 (wt.%), It becomes difficult to form 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 , and R ₃ are generally polymethylene groups, R ₁ is — (CH ₂ ) _m —, which is 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 exemplified. An isocyanate regenerator is a generic name for compounds that can be obtained by addition reaction of an isocyanate group and an active hydrogen compound and that can regenerate 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 include —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 aggregate anisotropic Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa], or Their mixed phase [A + An], 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], 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.5 (b) is a photograph which shows the external view of an orthogonal magnetic field orientation 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 advances to die set 2 side heated to the melting point of oligomer [Ab], [A'b] or higher, and cavity CV1, 2, 3, 4 (width 1.03 mm, length 90 mm × 4 pieces) 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 the plate-like green compact [II] as described above is produced, a plate-like plate thickness is obtained by using a forming die 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 rolling reduction by stretching of the magnet precursor [III] is 10 (%), and after the rolling, the shape is converted to the annular magnet [IVa]. 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 stamped, and the shape is converted to the arc-shaped magnet [IVb]. In particular, when the arc-shaped magnet [IVb] having an unequal wall thickness with a maximum wall thickness ≦ 1 (mm) is effective in improving the performance of the motor 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 ). Further, 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.

  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 ], And the chemical contact [C] with the spherical polynuclear cluster phase [A ′], the stretched phase [B], the phases [A + An], [A ′], and the phase [B]. And as a manufacturing method of the magnet,
(1) Cluster phase [A + An], stretched phase [B], compound intermediate [Ia] by chemical contact [C], spherical multinuclear cluster phase [A ′], and the above-mentioned two types are added as necessary. A process for producing a compound [I] mixed with an additive;
(2) Production process of plate green compact [II] by compound compression;
(3) The green compact [II] is heat-treated, and a step of producing a magnet precursor [III] in which the phases [A + An], [A ′] and the phase [B] are self-organized by chemical contacts [C];
(4) 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].

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, and a stretched phase [B in which a predetermined amount of a lubricant is dispersed in advance. 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] The mixture was charged in a constant-speed roll mill heated to a temperature equal to or higher than the melting point of the oligomer [A′b] (100 ° C.) 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 a ratio of 10 (μm) or less in 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 as the oligomer [A′b] increases. 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, and 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 higher than the green compact tensile strength, and sufficient mechanical strength was exhibited as a rare earth bonded magnet. This increase in tensile strength confirms 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 the 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 is 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 ratio 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 pressure P while applying an orientation magnetic field H, direct contact of magnetically anisotropic polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa] is avoided, 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 surface density 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 the demagnetization curve of the magnet precursor [III] at 100 (° C.) is plotted. As can be seen from the figure, the squareness (Hk / Hci) of the demagnetization curve at the time of high temperature exposure is improved 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 proportion 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) during 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 rare earth magnet powder [Aa]. The characteristic curve of the magnet precursor [III] produced from Fig. 3 is shown. As is apparent from the figure, in this example, even if heat treatment is performed in the air, surface damage and crushing due to friction during densification of the polycrystalline aggregated Nd ₂ Fe ₁₄ B-based rare earth magnet powder [Aa] surface are suppressed. _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] constituting the body [III] and the spherical multinuclear cluster phase [A ′] 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 ′], and is produced only from the mixed phase [A + An] mainly composed of polycrystalline aggregated Nd ₂ Fe ₁₄ B rare earth magnet powder [Aa]. The characteristic curve of the magnet precursor [III] obtained is shown. 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. In addition, the difference between the irreversible demagnetization rates becomes significant when exposed at a higher temperature.

  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 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). As is apparent from the figure, the irreversible demagnetization of the magnet can be suppressed when the multinuclear cluster phase [A ′] according to the present invention exists. For example, when 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. In comparison, it can be suppressed to ½ 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 also has 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 clear from the figure, the present embodiment includes, for example, 40 (wt.%) Of spherical multinuclear cluster phase [A ′] with respect to the coercive force 905 (kA / m) of the comparative example not including 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 with little 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 previously magnetized with a pulse magnetic field of 4 (MA / m) and is subjected to constant speed roll rolling, 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 magnet powder [Aa] or [A′a] is clearly disturbed by 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 reduction 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 wall 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 in 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 could be produced, it is clear that the present invention can eliminate the problem.

  FIG. 15A shows a case where a magnet precursor [III] having a thickness of 1.05 (mm), a length of 90 (mm), and a width of 4.5 (mm) is 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. 15B, 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 drawn phase [B] of the self-organized magnet precursor [III] is drawn 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 the plate-like green compact [I] is produced, and compression non-uniformity for densification from above and below. 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 converted into the arc-shaped magnet [IVb]. In particular, when the arcuate magnet [IVb] having an unequal thickness with a maximum thickness ≦ 1 (mm) is used, it is effective to improve the performance of the motor 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 multinuclear 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 Orientation 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], magnetically anisotropic single-domain particle type Sm ₂ Fe ₁₇ N ₃ rare earth magnet powder [A′a] as a main component, spherical multinuclear cluster phase [A ′], stretched phase [B], In addition, a self-organized hybrid rare earth bonded magnet having the chemical contact [C] with the phases [A] and [A ′] and the phase [B] as essential components. (1) A mononuclear cluster phase [A], a polynuclear cluster phase [An], or a compound intermediate [Ia], a spherical polynuclear by the cluster phase [A + An], an extended phase [B], and a chemical contact [C]. A production step of a compound [I] in which the cluster phase [A ′] and the above-mentioned two types and additives that are appropriately added as necessary are mixed,
(2) Production process of plate-like green compact [II] by compound compression,
(3) The green compact [II] is heat-treated, and a step of producing a magnet precursor [III] in which the phases [A + An], [A ′] and the phase [B] are self-assembled with chemical contacts [C].
(4) Self-organized by a manufacturing method comprising the step of transforming the shape into an annular [IVa] or arc-shaped magnet [IVb] by stretching the phase [B] contained in the magnet precursor [III]. Hybrid type rare earth bonded magnet. 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 3. The oligomer according to claim 1, 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. Spherical polynuclear 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], and the oligomer 3. The self-assembled hybrid rare earth bonded magnet according to claim 1, wherein [A'b] is an oligomer having a reaction substrate that self-assembles with phase B and chemical contact [C]. 5. The self-organized hybrid rare earth bonded magnet according to claim 4, wherein the spherical multinuclear cluster phase [A ′] is a spherical granule of ≦ 500 (μm). The spherical polynuclear cluster phase [A ′] is obtained by previously preparing 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-assembled 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. 7. The self-organized hybrid according to claim 6, wherein the rolling fluidized bed granulation is a fine granulation mechanism incorporating a pulse jet dispersion mechanism (air jet is intermittently injected toward the center from the side wall of the granulation casing). Type rare earth bonded magnet. The oligomer [Ab] contained in the mononuclear cluster phase [A], the polynuclear cluster phase [An], or the mixed phase [A + An] thereof and the oligomer [A′b] contained in the spherical polynuclear cluster phase [A ′] The self-assembled hybrid rare earth bonded magnet according to claim 1, which is an organic compound which is solid and solid and has at least two oxirane rings in the molecular chain. Of oligomer [Ab] contained in mononuclear cluster phase [A], multinuclear cluster phase [An], or mixed phase [A + An] thereof, and oligomer [A′b] contained in spherical multinuclear cluster phase [A ′] 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the ratio is 0.5 to 3.0 (wt.%). The proportion of the spherical multinuclear cluster phase [A ′] in the sum of the mononuclear cluster phase [A], the multinuclear cluster phase [An], or the mixed phase [A + An] and the spherical multinuclear cluster phase [A ′] is 30 to 30 3. The self-organized hybrid rare earth bonded magnet according to claim 1, which is 50 (wt.%). 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the ratio of all clusters in the compound [I] is ≦ 97.5 (wt.%). 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the proportion of the stretched phase [B] in the compound [I] is ≧ 2.5 (wt.%). The self-organized hybrid type according to claim 1 or 2, wherein the stretched phase [B] is a polymer containing a molecular substrate orientation ability by uniaxial stretching and a reaction substrate capable of reacting at least with the chemical contact C. Rare earth bonded magnet. The self-organization according to claim 1 or 2, wherein the compound [I] has an apparent density of JIS Z 2501 ≧ 2.4 (Mg / m ³ ) and a powder fluidity ≧ 45 (sec / 50 g). Hybrid rare earth bonded magnet. Oligomer contained in mononuclear cluster phase [A], multinuclear cluster phase [An], or mixed phase [A + An] of compound [I] filled in the mold cavity when producing plate-like green compact [II] Either [Ab] or the oligomer [A′b] contained in the spherical multinuclear cluster phase [A ′] is heated to a melting point or higher, and then compressed while applying an orientation magnetic field. The self-organized hybrid rare earth bonded magnet as described. 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the green compact [II] is not higher than a self-organization start temperature by chemical contact [C] when the green compact [II] is manufactured. When producing the plate-like green compact [II], the longitudinal side surface corresponding to the plate-like plate thickness is compressed under an orthogonal orientation magnetic field of ≧ 1.5 (MA / m). The self-organized hybrid rare earth bonded magnet according to claim 14 or 15. The self-organization according to any one of claims 1, 2, and 16, wherein a mold and a die set made of a nonmagnetic material having a plurality of cavities are used when producing the plate-like green compact [II]. Hybrid rare earth bonded magnet. When producing the plate-like green compact [II], the maximum strain amount of the mold cavity at the center in the longitudinal direction corresponding to the plate-like plate thickness is set to ≦ 0.1 (mm). The self-organized hybrid rare earth bonded magnet according to claim 17. ^3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the density distribution of the plate-like green compact [II] is ≦ 0.1 (Mg / m ³ ). 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the plate-like green compact [II] has a plate thickness of 1.0 ± 0.5 (mm). The self-organized hybrid type according to any one of claims 1 and 2, wherein the self-organized magnet precursor [III] heat-treats the plate-like green compact [II] in the atmosphere at ≤160 ° C. Rare earth bonded magnet. The self-organized hybrid type according to any one of claims 1, 2, and 21, wherein the tensile strength of the self-organized magnet precursor [III] exceeds three times that of the plate-like green compact [II]. Rare earth bonded magnet. The self-organized hybrid rare earth bonded magnet according to claim 1 or 2, wherein the maximum rolling reduction due to stretching of the magnet precursor [III] is 10 (%). 3. The self-organized hybrid rare earth according to claim 1, wherein the stretching of the phase B contained in the magnet precursor [III] is rolled, and after the rolling, the shape is converted to an annular magnet [IVa]. Bond magnet. 24. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the annular magnet [IVa] has an outer diameter ≦ 25 (mm). 3. The self-organized hybrid rare earth according to claim 1 or 2, wherein the extension of the extension phase [B] contained in the magnet precursor [III] is stamped and the shape is converted into an arc magnet [IVb]. Bond magnet. 27. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein the arc-shaped magnet [IVb] has an unequal thickness and a different radial magnetic property. ^3. The self-organized hybrid type according to claim 1, wherein a maximum energy product (BH) _max at 20 ° C. when magnetized at 1.2 (MA / m) is ≧ 120 kJ / m ^3. Rare earth bonded magnet. ^3. The self-organized hybrid type according to claim 1, wherein a maximum energy product (BH) _max at 20 ° C. when magnetized at 2.0 (MA / m) is ≧ 160 kJ / m ^3. Rare earth bonded magnet. 3. The self-organized hybrid rare earth bonded magnet according to claim 1, wherein a square shape (Hk / Hci) of a demagnetization curve at 100 (° C.) is ≧ 0.4. A motor on which an annular magnet [IVa] according to the self-organized hybrid rare earth bonded magnet according to claim 1 is mounted. 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 1, claim 2, or claim 25. A brushless motor on which the arc-shaped magnet [IVb] according to the self-organized hybrid rare earth bonded magnet according to claim 1 is mounted. A motor equipped with an arc-shaped magnet [IVb] having a maximum wall thickness ≦ 1 (mm) applied to the self-organized hybrid rare earth bonded magnet according to claim 1, claim 2, or claim 27. 32. A method of manufacturing a hybrid rare earth bonded magnet for manufacturing the self-organized hybrid rare earth bonded magnet according to any one of claims 1 to 31.