Permanent magnet material

Abstract: A permanent magnet material having as main components thereof a rare earth element, a transition element (except for rare earth elements and Cu and Ag), and nitrogen and containing as an additive component thereof at least one element selected from the group consisting of Cu, Ag, Al, Ga, Zn, Sn, In, Bi, and Pb. It finds extensive utility in magnetic recording materials such as magnetic tapes, magnetic recording devices, and motors, for example.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention: This invention relates to a permanent magnet material or a hard magnetic material and more particularly to a rare earth alloy type permanent magnet material. 2. Description of the Prior Art: Rare earth alloy type permanent magnet materials fit a wide range of applications to magnetic recording materials such as magnetic tapes, magnetic recording devices, and motors and have been finding utility in various technical fields. There is known that nitrogen is incorporated into rare earth element-transition element type matric alloys, particularly Sm-Fe type matric alloys, to improve the magnetic properties thereof. These permanent magnet materials are produced by pulverizing a Sm-Fe type matric alloy into minute particles not exceeding several µm in diameter and subjecting the minute particles to a nitriding treatment in an atmosphere of N₂ gas at a temperature in the range of from 400 to 650 °C . The conventional rare earth alloy type permanent magnetic material, however, undergoes decomposition at temperatures exceeding 650 °C . While a compressed piece of pulverized particles obtained by compression molding the particles in a magnetic field is sintered to produce a permanent magnet for practical use, the retention of nitrogen and the magnetic properties of magnet are appreciably degraded. It is, therefore, impossible to form a permanent magnet for practical use by the sintering method without any sacrifice of the outstanding magnetic properties produced by the nitriding treatment. The Journal of Applied Physics 69 (9), 1.5.1991, pages 6735-6737, discloses metal-bonded Sm₂Fe₁₇N 3-δ magnets obtained by sintering micron-size Sm₂Fe₁₇N 3-δ powder containing 15 or 25 volume percent of a soft low-melting metal, at a temperature lower than 650°C. The large amounts of soft low-melting metals, chosen from Zn, Bi, Sn and Al are intended to bond SmFeN magnet particles so as to achieve anisotropic dense Sm₂Fe₁₇N 3-δ magnets while however sintering the magnet material at temperatures not exceeding 630°C (10°C above the melting point of the soft metals). EP 0 369 097 discloses magnetic materials containing a rare earth element, iron, nitrogen and hydrogen, and optionally an additive component selected from the group consisting of Sn, Ga, In, Bi, Pb, Zn, Al, Zr, Cu, Mo, Ti, Si, MgO, Al₂O₃, Sm₂O₃, AlF₃, ZnF₂, SiC, TiC, AIN and Si₃N₂. The process for obtaining these magnet materials consists in subjecting a pulverized basic alloy powder to nitrogen and hydrogen absorption. After these absorption steps, the additive component powder may be mixed to the finely pulverized nitrided magnetic material. There is no disclosure of the sintering of the resulting nitrided powder at a temperature above 650°C or of further processing of the resulting magnet material. SUMMARY OF THE INVENTION An object of this invention, therefore, is to provide a permanent magnet material possessing excellent magnetic properties such that a rare earth element-transition element type matric alloy is enabled to assimilate nitrogen positively during the process of manufacture of a magnet and, at the same time, is allowed to be shaped while the nitride consequently formed is restrained from thermal decomposition. Another object of this invention is to provide a permanent magnet material which, in the process of manufacture of a permanent magnet for practical use by the sintering method, experiences only a sparing degradation in the retention of nitrogen and the magnetic properties of magnet and permits safe retention of excellent magnetic properties. To accomplish the objects described above, the invention as claimed relates to a permanent magnet material having as main components thereof a rare earth element, a transition element (except for rare earth elements and Cu and Ag), and nitrogen and containing as an additive component at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb. According to the invention, the additive component is added in the magnet material as an inhibitor of thermal decomposition of nitrides. The content of the rare earth element is in the range of from 6 to 30 atomic %. The content of the transition element is in the range of from 60 to 91 atomic %. The content of nitrogen is in the range of from 3 to 15 atomic %. The content of the additive component is not more than 4.5 atomic %. Furthermore, the presence of hydrogen is excluded from the permanent magnet material. The content of the additive component ought to be set in a range in which the magnetic properties of a magnet material formed solely of the main components will not be degraded owing to the use of the additive component therein. As further claimed, the process of the invention for preparing a permanent magnet material having as main components thereof a rare earth element, a transition element (except for rare earth elements and Cu and Ag), and nitrogen and containing as an additive component at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb comprises : (i) vaporizing a material comprising the rare earth element, the transition element, and at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb, under reduced pressure ; (ii) nitriding the material in a vapor phase state in an atmosphere containing a nitrogen-containing gas to obtain a nitrided material ; and (iii) depositing the nitrided material on a substrate heated to a temperature up to about 800°C. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram illustrating a first example of the apparatus for the production of a permanent magnet material according to the present invention. Fig. 2 is a graph showing the relation of the Ga content in an alloy of Sm₁₁Fe 77-X N₁₂Ga X and the intrinsic magnetic coercive force of the alloy. Fig. 3 is a graph showing the relation of the Cu content in an alloy of Sm₁₁Fe 77-X N₁₂Cu X and the intrinsic magnetic coercive force of the alloy. Fig. 4 is a graph showing the relation of the Ag content in an alloy of Sm₁₁Fe 77-X N₁₂Ag X and the intrinsic magnetic coercive force of the alloy. Fig. 5 is a graph showing the relation of the Al content in an alloy of Sm₁₁Fe 77-X N₁₂Al X and the intrinsic magnetic coercive force of the alloy. Fig. 6 is a graph showing the relation of the Al content in an alloy of Sm₁₁Fe 76-X N₁₂Cu 1.0 Al X and the intrinsic magnetic coercive force of the alloy. Fig. 7 is a graph showing the relation of the Ga content in an alloy of Sm₁₁Fe 76-X N₁₂Cu 1.0 Ga X and the intrinsic magnetic coercive force of the alloy. Fig. 8 is a graph showing the relation of the Zn content in an alloy of Sm₁₁Fe 77-X N₁₂Zn X and the intrinsic magnetic coercive force of the alloy. Fig. 9 is a graph showing the relation of the Sn content in an alloy of Sm₁₁Fe 77-X N₁₂Sn X and the intrinsic magnetic coercive force of the alloy. Fig.10 is a graph showing the relation of the Pb content in an alloy of Sm₁₁Fe 77-X N₁₂Pb X and the intrinsic magnetic coercive force of the alloy. Fig.11 is a graph shpwing the relation of the In content in an alloy of Sm₁₁Fe 77-X N₁₂In X and the intrinsic magnetic coercive force of the alloy. Fig.12 is a schematic diagram illustrating a second example of the apparatus for the production of a permanent magnet material according to the present invention. DETAILED DESCRIPTION The permanent magnet material of this invention is composed of main components and an additive component. The main components include a rare earth element, a transition element (with the exception of rare earth elements and Cu and Ag), and nitrogen and the additive component is at least one element selected from the group consisting of Cu, Ag, Al, Ga, Zn, Sn, In, Bi, and Pb. In the main components, Sm, for example, is used as a rare earth element. The content of this element is set at a level of not less than 6 atomic % and not more than 30 atomic %. Any deviation of the content of this rare earth element from this range is undesirable because the intrinsic magnetic coercive force is unduly low if the content is less than 6 atomic %, whereas the saturated magnetization is notably low if the content exceeds 30 atomic %. Fe or Co, for example, is used as a transition element. The content of the transition element is set at a level of not less than 60 atomic % and not more than 91 atomic %. Any deviation of the content of this transition element from the range is undesirable because the saturated magnetization is degraded if the content is less than 60 atomic %, whereas the intrinsic magnetic coercive force is unduly low if the content exceeds 91 atomic %. The content of N is set at a level of not less than 3 atomic % and not more than 15 atomic %. Any deviation of the content of nitrogen from this range is undesirable because the rare earth element-transition element type alloy fails to manifest uniaxial magnetic anisotropy if the N content is less than 3 atomic %, whereas the alloy undergoes phase separation and loses magnetic coercive force if the content exceeds 15 atomic %. The additive component, in the process of manufacture of a permanent magnet, functions to curb possible thermal decomposition of the nitride of the main components described above. The content of the additive component is set in a range in which the magnetic properties of the nitride are not degraded owing to the use of this additive component. Among other elements usable for the additive component as mentioned above, Cu, Ag, Al, and Ga are capable of further improving the magnetic properties of the nitride, depending on the content thereof. On the other hand, Zn, Sn, In, and Bi are sparingly effective in enhancing the magnetic properties of the nitride. The content of the additive component will be described more specifically herein below. Now, this invention will be described more specifically below with reference to working examples. As a matter of course, this invention is not limited to the following examples. It ought to be easily understood by any person of ordinary skill in the art that this invention allows various modifications within the scope of the spirit of this invention. Fig. 1 illustrates an apparatus to be used for the production of a permanent magnet material contemplated by this invention. This apparatus is provided with a main chamber 1 and a sub-chamber 2 disposed below the main chamber 1. These two chambers 1 and 2 intercommunicate via a duct 3 of which upper opening part 4 is directed toward a hearth 8 made of copper disposed inside the main chamber 1. In the main chamber 1, a W electrode 6 is inserted and set in place so that the leading terminal part 7 thereof is positioned above the hearth 8 of Cu. The W electrode 6 and the Cu hearth 8 are connected to a power source 9. Inside the sub-chamber 2, a substrate 11 provided with a built-in heater 10 is disposed below the lower opening part 5 of the duct 3. The main chamber 1 is connected via a first valve 12 to a first vacuum pump 13, whereas the sub-chamber 2 is connected via a second valve 14 to a second vacuum pump 15. The main chamber 1 is further connected via a third valve 16 to a processing gas supply source 17 for handling N₂ gas, for example. For the production of the permanent magnet material, the following procedure may be adopted. (1) A matric alloy A is placed in the hearth 8 and the substrate 11 is heated to a prescribed temperature. (2) With the second and third valves 14 and 16 kept closed and the first valve 12 opened, the first vacuum pump 13 is set into operation to evacuate the interior of the main chamber 1 and the interior of the sub-chamber 2 each to the order of about 10⁻⁵ Torr. (3) With the first and second valves 12 and 14 kept closed and the third valve 16 opened, the processing gas supply source 17 is set into operation to supply such processing gas as N₂ gas into the main chamber 1 and the sub-chamber 2. The amounts of the processing gas so supplied are controlled so that the inner pressure of the main chamber 1 falls in the neighborhood of 50 cmHg. (4) A voltge of 20 V is applied between the W elestrode 6 and the hearth 8 to induce arc discharge and vaporize the matric alloy A . (5) The inner pressure of the sub-chamber 2 is decreased by opening the second valve 14 and setting the second vacuum pump 15 into operation and, at the same time, the amount of the processing gas being supplied is controlled so that the processing gas flows out of the main chamber 1 into the sub-chamber 2 via the duct 3. The vapor of the matric alloy reacts with the processing gas. The product of this reaction is carried on the current of the processing gas and then accumulated on the substrate 11 inside the sub-chamber 2, to give rise to a film of permanent magnet M . Besides the N₂ gas, HCN gas, NH₃ gas, and B₃N₃H₆ gas, etc. are available as the processing gas. Example 1: By using the apparatus described adove and following the procedure described above, a permanent magnet material, Sm₁₁Fe₇₅N₁₂ Ga₂ (wherein the numerals represent the relevant proportions in atomic %; similarly applicable hereinafter), of this invention about 3 µm in thickness was produced. The conditions for the production were as follows: Matric alloy : Sm₁₇Fe₈₁Ga₂, weight 150g Substrate: heat resistant glass sheet, temperature 460 °C Processing gas: N₂ gas (purity not lower than 99.99% ) Duration of accumulation: 20 minutes Comparative Experiment 1: A permanent magnet material for comparison, Sm₁₁Fe₇₈N₁₁, was produced by following the procedure described above, excepting Sm₁₇Fe₈₃ was used as a matric alloy. Table 1 shows the magnetic properties of the permanent magnet material of this invention and the comparative experiment. No. Intrinsic magnetic coercive force iHc (KOe) Saturated magnetization Ms (emu/g) Example 1 23 120 Comparative Experiment 1 20 123 It is clearly noted from Table 1 that the permanent magnet material of this invention, owing to the incorporation of Ga, possesses better intrinsic magnetic coercive force than the permanent magnet material of the comparative experiment. To study the permanent magnet materials of this invention and the comparative experiment as to susceptibility to thermal decomposition, the two permanent magnet materials were subjected to a heating test performed at 650 °C, the temperature at which the materials were shaped during their manufacture, for five hours and then tested for magnetic properties and residual ratio of N. The results are shown ih Table 2. The residual ratio of N was calculated by the following formula: Residual ratio of N (%) = Amount of N after the heating Amount of N before the heating X 100 No. Intrinsic magnetic coercive force iHc (kOe) Residual ratio of N (%) Example 1 21 90 Comparative Experiment 1 13 40 It is clearly noted from Table 2 that the permanent magnet material of this invention gave rise to the decomposition product only in a small amount in the heating test and retained its excellent magnetic properties even after the heating test, whereas the permanent magnet material of the comparative experiment succumbed to decomposition in the heating test and consequently suffered from notable degradation of the magnetic properties. Example 2: Various permanent magnet materials were produced by following the procedure of Example 1, excepting various additive components were used. Fig. 2 shows the relation between the Ga content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Ga X (inclusive of the aforementioned Sm₁₁Fe₇₅N₁₂Ga₂ ), and the intrinsic magnetic coercive force thereof. It is noted from Fig. 2 that the content of Ga was set at a level of not more than 4 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Ga X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 3 shows the relation between the Cu content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Cu X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 3 that the content of Cu should be set at a level of not more than 4.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Cu X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 4 shows the relation between the Ag content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Ag X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 4 that the content of Ag should be set at a level of not more than 4 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Ag X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 5 shows the relation between the Al content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Al X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 5 that the content of Al should be set at a level of not more than 4.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Al X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 6 shows the relation between the Al content in the permanent magnet material of this invention, Sm₁₁Fe 76-X N₁₂Cu 1.0 Al X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 6 that the content of Al should be set at a level of not more than 3.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 76-X N₁₂Cu 1.0 Al X would not fall below that of Sm₁₁Fe₇₈N₁₁ and the content of Cu is kept at 1 atomic % (constant). Fig. 7 shows the relation between the Ga content in the permanent magnet material of this invention, Sm₁₁Fe 76-X N₁₂Cu 1.0 Ga X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 7 that the content of Ga should be set at a level of not more than 3 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 76-X N₁₂Cu 1.0 Ga X would not fall below that of Sm₁₁Fe₇₈N₁₁ and the content of Cu is kept at 1 atomic % (constant). Fig. 8 shows the relation between the Zn content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Zn X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 8 that the content of Zn should be set at a level of not more than 2.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Zn X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 9 shows the relation between the Sn content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Sn X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 9 that the content of Sn should be set at a level of not more than 2.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Sn X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 10 shows the relation between the Pb content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂Pb X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 10 that the content of Pb should be set at a level of not more than 2 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂Pb X would not fall below that of Sm₁₁Fe₇₈N₁₁. Fig. 11 shows the relation between the In content in the permanent magnet material of this invention, Sm₁₁Fe 77-X N₁₂In X and the intrinsic magnetic coercive force thereof. It is noted from Fig. 11 that the content of In should be set at a level of not more than 2.5 atomic % under the conditions such that the intrinsic magnetic coercive force of Sm₁₁Fe 77-X N₁₂In X would not fall below that of Sm₁₁Fe₇₈N₁₁. Various permanent magnet materials shown in Fig. 3 to Fig. 11 were severally subjected to the same heating test at 650 °C for five hours as described above. The results were as shown in Table 3. The chemical formulas in the table represent the compositions of the permanent magnets of this invention prior to the heating test. Permanent magnet Intrinsic magnetic coercive force iHc (KOe) Residual ratio of N (%) Before heating After heating Sm₁₁Fe₇₅N₁₂Cu₂ 24.5 21.0 90 Sm₁₁Fe 75.2 N₁₂Ag 1.8 24.5 20.5 85 Sm₁₁Fe 75.8 N₁₂Al 1.2 24 19.5 85 Sm₁₁Fe₇₅N₁₂Cu 1.0 Al 1.0 24 20.0 83 Sm₁₁Fe 74.8 N₁₂Cu 1.0 Ga 1.2 24.8 21.5 88 Sm₁₁Fe₇₆N₁₂Zn 1.0 21 16.0 80 Sm₁₁Fe₇₆N₁₂Sn 1.0 20.5 16.0 78 Sm₁₁Fe₇₆N₁₂Pb 1.0 20.5 15.0 78 Sm₁₁Fe 75.5 N₁₂In 1.5 20.7 16.0 80 It is clearly noted from Table 3 that the permanent magnet materials of this invention retained excellent magnetic properties even after the heating test. The method of production depicted in Fig. 1 is advantageous in that the speed of accumulation of the product is high, the increase of surface area is easy to obtain, the pulverization of the product into minute particles is realized because the melting point of the matric alloy is lowered by the addition such as of Cu, and the permanent magnet of uniform high-density texture is obtained. Fig. 12 illustrates another apparatus to be used for the production of a permanent magnet conforming to this invention. In this apparatus, a water-cooled crucible 22 is disposed in a chamber 21 and a pair of discharge electrodes 24 and 25 connected to a power source 23 are disposed as opposed to each other above the crucible 22. A heating plate 26 is set in place above the two discharge electrodes 24 and 25. A substrate 27 formed of quartz glass or strontium titanate, for example, is attached to the lower surface of the heating plate 26. A laser oscillator 28 is installed in the ceiling part of the chamber 21 and adapted so that a pulse laser emanating from this oscillator 28 advances through a perforation 29 formed in the heating plate 26 and the substrate 27 and impinges on the water-cooled crucible 22. The chamber 21 is connected via first and second valves 30 and 32 respectively to a vacuum pump 31 and a processing gas supply source 33. For the production of a permanent magnet, the following procedure may be adopted. (1) A matric alloy A is placed in the water-cooled crucible 22 and the substrate 27 is heated to a temperature in the range of from 400 to 800 °C . (2) With the second valve 32 kept closed and the first valve 30 opened, the vacuum pump 31 is set into operation to decrease the inner pressure of the chamber 21 to a level of about 5 x 10⁻⁵ Torr. (3) With the first valve 30 kept closed and the second valve 32 opened, the processing gas supply source 33 is set into operation to supply the processing gas such as N₂ into the chamber 21. The amount of supply of the processing gas is regulated so that the inner pressure of the chamber 21 reaches a level in the range of from about 10 to about 70 cmHg. (4) A voltage of 2 kV is applied between the two discharge electrodes 24 and 25 to induce generation of plasma. The matric alloy A is vaporized by projecting the pulse laser from the laser oscillator 28 onto the matric alloy A . The resultant vapor of the matric alloy reacts with the plasma of the processing gas and the product of this reaction is deposited on the substrate 27, to give rise to a permanent magnet M . The method of production depicted in Fig. 12 is advantageous in respect that the vapor of the matric alloy is easily combined with N because the treatment proceeds under the reactive plasma, the defilement of the product with the dirt from the atmosphere occurs only sparingly, and the adjustment of the composition of the final product and that of the matric alloy due to the addition such as of Cu is easy to effect (since the matric alloy is fused with the pulse laser, local processing is easy to accomplish).

Claims: A permanent magnet material having as main components thereof a rare earth element, a transition element (except for rare earth elements and Cu and Ag), and nitrogen and containing as an additive component at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb, characterized in that the additive component is added in the magnet material as an inhibitor of thermal decomposition of nitrides and, in that the content of the rare earth element is in the range of from 6 to 30 atomic %, the content of the transition element is in the range of from 60 to 91 atomic %, the content of nitrogen is in the range of from 3 to 15 atomic %, the content of the additive component is not more than 4.5 atomic %, the presence of hydrogen being excluded from the permanent magnet material. A permanent magnet material according to claim 1, characterized in that the rare earth element is Sm. A permanent magnet material according to claim 1 or 2, characterized in that the transition element is Fe. A permanent magnet material according to claim 1 or 2, characterized in that the transition element is Co. A permanent magnet material according to claim 1, characterized in that it is a Sm-Fe-N magnet material containing as an additive component not more than 4.5 atomic % of Cu and/or Al. A permanent magnet material according to claim 1, characterized in that it is a Sm-Fe-N magnet material containing as an additive component not more than 4 atomic % of Ga and/or Ag. A permanent magnet material according to claim 1, characterized in that it is a Sm-Fe-N magnet material containing as an additive component not more than 4 atomic % of Ga and/or Cu. A permanent magnet material according to claim 1, characterized in that it is a Sm-Fe-N magnet material containing as an additive component not more than 2.5 atomic % of at least one element selected from among Zn, Sn and In. A permanent magnet material according to claim 1, characterized in that it is a Sm-Fe-N magnet material containing as an additive component not more than 2 atomic % of Pb. Process for preparing a permanent magnet material having as main components thereof a rare earth element, a transition element (except for rare earth elements and Cu and Ag), and nitrogen and containing as an additive component at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb, characterized in that it consists in (i) vaporizing a material comprising the rare earth element, the transition element, and at least one element selected from Cu, Ag, Al, Ga, Zn, Sn, In, Bi or Pb, under reduced pressure ; (ii) nitriding the material in a vapor phase state in an atmosphere containing a nitrogen-containing gas to obtain a nitrided material ; and (iii) depositing the nitrided material on a substrate heated to a temperature up to about 800°C. Process according to claim 10, characterized in that the nitrogen-containing gas is a gas selected from the group consisting of nitrogen gas, HCN gas, NH₃ gas and B₃N₃H₆ gas. Process according to claim 10 or 11, characterized in that the substrate is heated to a temperature between 400°C and 800°C.

Inventors: INOUE AKIHISA, KIMURA NAOMASA, YAMAGUCHI TADASHI, INOUE, AKIHISA, KIMURA, NAOMASA, YAMAGUCHI, TADASHI
Applicants: INOE AKIHISA, YKK CORP, INOUE, AKIHISA, YKK CORPORATION
Application year: 1992
Main classification: H01F1
IPC codes: H01F10, H01F41, H01F1, C22C38