JP6770704B2 - Nano heterostructure permanent magnet and its manufacturing method - Google Patents

Description

The present invention relates to a permanent magnet having a nanoheterostructure and a method for producing the same.

With the miniaturization, high output, and high density of generators and motors, magnets having high magnetic characteristics, particularly saturation magnetization and coercive force, are required at a high level. Examples of magnets having such high magnetic properties include Apple. Phys. Lett. , 2005, Vol. 86, pp. 122509-1 to 3 (Non-Patent Document 1), proposed a multilayer film in which ₅ layers of Sm (Co, Cu) and Fe layers were alternately laminated at the nano level by sputtering. ing. However, the maximum magnetic energy product of the multilayer film of Non-Patent Document 1 is about 10% higher than that of the SmCo ₅ single-phase magnet, and a permanent magnet having a higher maximum magnetic energy product has been required.

Therefore, as a permanent magnet having a higher maximum magnetic energy product, International Publication No. 2013/0392116 (Patent Document 1) states that hard magnets are contained in a matrix composed of an inorganic component of one of a hard magnetic material and a soft magnetic material. The other inorganic component of the magnetic material and the soft magnetic material is arranged three-dimensionally and periodically, and one unit of the repeating structure has a three-dimensional periodic structure of a predetermined length. Magnets have been proposed. However, the maximum magnetic energy product of the nanoheterostructure permanent magnet described in Patent Document 1 is not always sufficiently high, and a permanent magnet having a higher maximum magnetic energy product is required.

International Publication No. 2013/0392216

J. Zhang et al., Apple. Phys. Lett. , 2005, Vol. 86, pp. 122509-1-3

The present invention has been made in view of the above-mentioned problems of the prior art, and is a permanent magnet having a nanoheterostructure and a high maximum magnetic energy product, that is, a permanent magnet having saturation magnetization and coercive force at a high level. It is an object of the present invention to provide a magnet and a method for manufacturing the magnet.

As a result of diligent research to achieve the above object, the present inventors have made the first polymer block component constituting the block copolymer and one of the hard magnetic precursor and the soft magnetic precursor inorganic precursor. , The second polymer block component and the other inorganic precursor of the hard magnetic material precursor and the soft magnetic material precursor so that the hard magnetic material precursor and the soft magnetic material precursor have a specific ratio. By using them in combination with each other, a nanophase-separated structure was formed by utilizing the self-assembly of the block copolymer, and the inorganic precursor was converted into a hard magnetic material and a soft magnetic material, respectively, and the block copolymer was removed. In some cases, a hard magnetic material and a soft magnetic material are contained in a specific ratio, and the other inorganic component is three-dimensionally nano-sized in a matrix composed of the hard magnetic material and one of the soft magnetic materials. We have found that a nanoheterostructure permanent magnet having a nanoheterostructure arranged with scale periodicity and having both saturation magnetization and coercive force at a high level can be obtained, and have completed the present invention.

That is, in the first nanoheterostructure permanent magnet of the present invention, the combination of the hard magnetic material and the soft magnetic material is a combination of Nd ₂ Fe ₁₄ B which is a hard magnetic material and Fe which is a soft magnetic material; A combination of SmCo ₅ and Fe, which is a soft magnetic material; one of a combination of Nd ₂ Fe ₁₄ B, which is a hard magnetic material, and FeCo, which is a soft magnetic material, from the hard magnetic material. to become in the matrix, the soft magnetic material, three-dimensionally and periodically arranged, has a three-dimensional periodic structure average length of one unit of the repeating structure is 1 nm~100 nm, wherein It is characterized in that the molar ratio of the hard magnetic material to the soft magnetic material is 1: 0.02 to 1: 0.6. Further, in the second nanoheterostructure permanent magnet of the present invention, FePt , which is a hard magnetic material , is three-dimensionally and periodically arranged in a matrix made of iron, which is a soft magnetic material, and is a unit of a repeating structure. It has a three-dimensional periodic structure with an average length of 1 nm to 100 nm, and the molar ratio of the hard magnetic material to the soft magnetic material is 1: 0.02 to 1: 0.6. It is characterized by that.

The shape of the soft magnetic material three-dimensionally and periodically arranged in the matrix in the first nanoheterostructure permanent magnet and the three-dimensional and periodicity in the matrix in the second nanoheterostructure permanent magnet. As the shape of the hard magnetic material arranged in, a shape selected from the group consisting of a spherical shape, a columnar shape, and a gyroid shape is preferable.

Further, the method for producing a nanoheterostructure permanent magnet of the present invention includes a block copolymer formed by bonding at least a first polymer block component and a second polymer block component that are immiscible with each other, and a method for producing the first nanoheterostructure permanent magnet. In the method for producing the second nanoheterostructure permanent magnet, the first inorganic precursor, which is a hard magnetic material precursor, and the second inorganic precursor, which is a soft magnetic material precursor, are dissolved in a solvent. , The first inorganic precursor which is a soft magnetic material precursor and the second inorganic precursor which is a hard magnetic material precursor are dissolved in a solvent to obtain the hard magnetic material precursor and the soft magnetic material precursor. Is contained in a molar ratio of 1: 0.02 to 1: 0.6, and in the method for producing the first nanoheterostructure permanent magnet, the combination of the hard magnetic material precursor and the soft magnetic material precursor is used. , A combination of Nd ₂ Fe ₁₄ B precursor, which is a hard magnetic material precursor, and Fe precursor, which is a soft magnetic material precursor; SmCo ₅ precursor, which is a hard magnetic material precursor, and Fe, which is a soft magnetic material precursor. Combination with a precursor; any one of a combination of an Nd ₂ Fe ₁₄ B precursor which is a hard magnetic precursor precursor and a FeCo precursor which is a soft magnetic material precursor, and is the second nanoheterostructure. In the method for producing a permanent magnet, the first step of preparing a raw material solution , wherein the hard magnetic material precursor is an iron precursor and the soft magnetic material precursor is a FePt precursor ,
At least, a first polymer phase composed of the first polymer block component into which the first inorganic precursor has been introduced, and a second polymer phase composed of the second polymer block component into which the second inorganic precursor has been introduced. Is self-assembled to form a nanophase-separated structure in which the second polymer phase is regularly arranged in the first polymer phase, and the hard magnetic precursor and the soft magnetic precursor. a conversion process of converting each of the hard magnetic and soft magnetic material, and a removal process of removing the block copolymer from the nano phase separation structure, in the manufacturing method of the first nano-hetero structure permanent magnets, wherein The combination of the hard magnetic material and the soft magnetic material is a combination of Nd ₂ Fe ₁₄ B, which is a hard magnetic material, and Fe, which is a soft magnetic material; SmCo ₅ which is a hard magnetic material and Fe which is a soft magnetic material. Combination: Any one of a combination of Nd ₂ Fe ₁₄ B, which is a hard magnetic material, and FeCo, which is a soft magnetic material, and the soft magnetic material is three-dimensionally formed in a matrix composed of the hard magnetic material. In the method for producing the second nanoheterostructure permanent magnet obtained by obtaining the periodically arranged nanoheterostructure permanent magnets, the hard magnetic material FePt is three-dimensionally formed in the matrix made of iron which is the soft magnetic material. The second step of obtaining the nano-heterostructure permanent magnets arranged in a targeted and periodic manner,
It is a method characterized by including.

The "mean value of the length of one unit of the repeating structure" in the present invention is the average of the distances between the centers of adjacent ones of the other inorganic components arranged in the matrix composed of one inorganic component. It is a value and corresponds to the so-called periodic structure interval (d). The interval (d) of the periodic structure is obtained by small-angle X-ray diffraction as follows. Further, the spherical, columnar, gyroid-like, or layered structure according to the present invention can also be defined by a characteristic diffraction pattern measured by small-angle X-ray diffraction as follows.

That is, by small-angle X-ray diffraction, Bragg reflection from the characteristic lattice plane of the pseudo-crystal lattice in which structures having a spherical, columnar, gyroid-like, or layered shape are periodically arranged in the matrix is observed. .. At that time, when a periodic structure is formed, diffraction peaks are observed, and a spherical, columnar, gyroid, or layered structure is specified from the ratio of the magnitudes (q = 2π / d) of the diffraction spectra. be able to. Further, from the peak position of the diffraction peak, the interval (d) of the periodic structure can be obtained by Bragg's equation (nλ = 2dsinθ; λ indicates the X-ray wavelength and θ indicates the diffraction angle). Table 1 below shows the relationship between each structure and the ratio of the magnitude (q) of the diffraction spectrum at the peak position. It is not necessary to confirm all the peaks shown in Table 1, and it is sufficient if the structure can be specified from the observed peaks.

Furthermore, it is also possible to specify a spherical, columnar, gyroid-like, or layered structure according to the present invention using a transmission electron microscope (TEM), thereby discriminating and evaluating its shape and periodicity. Can be done. Furthermore, it is possible to discriminate the three-dimensionality in more detail by observing from various directions and using three-dimensional tomography.

Further, although the reason why the nanoheterostructure permanent magnet of the present invention can be obtained by the method of the present invention is not necessarily clear, the present inventors presume as follows. That is, first, the block copolymer formed by bonding two types of polymer block components, A and B, which are immiscible with each other, is nano-sized in which the A phase and the B phase are spatially separated by heat treatment at a temperature higher than the glass transition point. Consists of a phase-separated structure (self-organization). At that time, the phase separation structure generally changes depending on the molecular weight ratio of the polymer block component. Specifically, when the molecular weight ratio of A: B is 1: 1, it generally has a layered layered structure, and as the molecular weight ratio deviates from 1: 1, it looks like two continuous phases are entwined. It changes from a gyroid-like structure to a columnar structure and then to a spherical structure. Note that FIG. 1 is a schematic view showing a nanophase-separated structure produced from a block copolymer, and from the left, a layered structure (a), a gyroid-like structure (b), a columnar structure (c), and a spherical structure (d). ), And the structure on the right side generally has a higher proportion of A.

In the method for producing a nanoheterostructure permanent magnet of the present invention, first, a plurality of inorganic precursors are three-dimensionally arranged with nanoscale periodicity by utilizing the self-assembly of the block copolymer described above. That is, the block copolymer composed of a plurality of polymer block components that are immiscible with each other undergoes phase separation on a nanoscale by self-assembly as described above. At that time, in the present invention, the first polymer block component, the hard magnetic precursor, and the first inorganic precursor, which is one of the hard magnetic precursor and the soft magnetic precursor, which constitute the block copolymer, the second polymer block component, and the hard The second inorganic precursor, which is the other of the magnetic precursor and the soft magnetic precursor, is used in combination with the hard magnetic precursor and the soft magnetic precursor in a specific ratio. As a result, the first inorganic precursor and the second inorganic precursor form a nanophase separated structure together with the self-assembly of the block copolymer in a state of being introduced into the first polymer block component and the second polymer block component, respectively. By making the nanophase separated structure a predetermined structure, the inorganic precursor is three-dimensionally arranged with nanoscale periodicity.

Further, in the present invention, the hard magnetic material precursor and the soft magnetic material precursor are converted into the hard magnetic material and the soft magnetic material, respectively, and the block copolymer is removed, so that the nanophase-separated structure can be formed according to the shape of the nanophase-separated structure. The other inorganic component has a nanoheterostructure in which the other inorganic component is three-dimensionally arranged in a matrix composed of one of the hard magnetic material and the soft magnetic material with a specific nanoscale periodicity in a predetermined shape. A permanent magnet containing a hard magnetic material and the soft magnetic material in a specific ratio can be obtained. In the present invention, since the first inorganic precursor and the second inorganic precursor are used in combination with the first polymer block component and the second polymer block component, respectively, each inorganic precursor for each polymer block component is used. The amount of the introduced body is sufficiently large, so that the hard magnetic precursor and the soft magnetic precursor are converted into the hard magnetic material and the soft magnetic material, respectively, and even if the block copolymer is removed, the nanoscale three-dimensional The present inventors speculate that the periodic structure is maintained.

According to the present invention, saturation magnetization has a nanoheterostructure in which the other inorganic component is three-dimensionally arranged with nanoscale periodicity in a matrix composed of one of the hard magnetic material and the soft magnetic material. It is possible to obtain a permanent magnet that has a high level of coercive force.

It is a schematic diagram which shows the nano-phase separation structure produced from the AB type block copolymer.

Hereinafter, the present invention will be described in detail according to its preferred embodiment.

First, the nanoheterostructure permanent magnet of the present invention will be described. In the nanoheterostructure permanent magnet of the present invention, the other inorganic component of the hard magnetic material and the soft magnetic material is three-dimensional and periodic in the matrix composed of the inorganic component of one of the hard magnetic material and the soft magnetic material. It has a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm (more preferably 1 nm to 50 nm, particularly preferably 1 to 30 nm). The molar ratio of the magnetic material to the soft magnetic material is in the range of 1: 0.02 to 1: 0.6.

Such a nanoheterostructure permanent magnet of the present invention has a nanostructure such as a spherical structure, a columnar structure, a gyroid-like structure, and a layered structure (preferably a spherical structure or a columnar structure), and is a hard magnetic material and a soft magnetic material. It is possible to obtain a combination with a body as having a nanoheterostructure in which their arrangement, composition, structural scale, etc. are variously controlled. Therefore, according to the nano-heterostructure permanent magnet of the present invention, the pinning effect is exhibited by the magnetic exchange interaction between the hard magnetic material and the soft magnetic material, and the interface increasing effect and the nano-size are higher than those of the conventional nano-structured permanent magnet. The effect, durability, etc. are dramatically improved, and as a result, the hard magnetic material has a high coercive force and the soft magnetic material has a high saturation magnetization.

Further, the nanoheterostructure permanent magnet of the present invention contains the hard magnetic material and the soft magnetic material in a molar ratio of hard magnetic material: soft magnetic material = 1: 0.02 to 1: 0.6. .. By containing a hard magnetic material and a soft magnetic material in such a molar ratio, the obtained nanoheterostructure permanent magnet has both saturation magnetization and coercive force at a high level, and the hard magnetic material single-phase permanent magnet. The rate of increase of the maximum magnetic energy product with respect to the magnet increases. On the other hand, if the molar ratio of the hard magnetic material to the soft magnetic material is less than the lower limit or exceeds the upper limit, the saturation magnetization and coercive force are difficult to improve, and the maximum magnetic energy for the permanent magnet of the hard magnetic material single phase The rate of increase in the product becomes smaller.

Further, in the nanoheterostructure permanent magnet of the present invention, the volume of the portion of the region made of the soft magnetic material that satisfies the condition that the distance from the interface with the hard magnetic material is 10 nm or less is the volume of the soft magnetic material. It is preferably 50 vol% or more of the total volume of. When the volume of the soft magnetic material in the portion satisfying the above conditions is less than the lower limit, there are many portions of the soft magnetic material in which the magnetic exchange interaction does not work, and the coercive force tends to decrease.

As the hard magnetic material constituting the nanoheterostructure permanent magnet of the present invention, a known hard magnetic material can be used as long as it has a high coercive force. For example, BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ , BaFe. Ferrite magnets such as ₁₈ O ₂₇ and SrFe ₁₈ O ₂₇ , SmCo ₅ , Pr ₂ Fe ₁₄ B, Nd ₂ Fe ₁₄ B, Dy ₂ Fe ₁₄ B, Sm (Fe ₁₁ Ti), Y (Fe ₁₁ Ti), Sm Rare earth magnets such as ₂ Co ₁₇ , Er ₂ Co ₁₇ , Y ₂ Co ₁₇ , Sm ₂ Fe ₁₇ N ₃ and precious metal magnets such as FePt and FePd are preferable. These hard magnetic materials may be used alone or in combination of two or more.

Further, as the soft magnetic material constituting the nanoheterostructure permanent magnet of the present invention, a known soft magnetic material can be used as long as it has a small coercive force and a large magnetic permeability, but iron, cobalt, and iron-cobalt can be used. Alloys (permendur, etc.), iron-nickel alloys (permalloy, etc.), iron-noble metal alloys (Fe ₃ Pt, etc.), silicon steel, sentust, and soft ferrite are preferable. These soft magnetic materials may be used alone or in combination of two or more.

Next, a method for manufacturing such a nanoheterostructure permanent magnet of the present invention will be described. The method for producing a nanoheterostructure permanent magnet of the present invention is
A block copolymer formed by bonding at least a first polymer block component and a second polymer block component that are immiscible with each other, a first inorganic precursor that is one of a hard magnetic precursor and a soft magnetic precursor, and a hard The second inorganic precursor, which is the other of the magnetic precursor and the soft magnetic precursor, is dissolved in a solvent, and the hard magnetic precursor and the soft magnetic precursor are 1: 0.02. The first step of preparing a raw material solution containing a molar ratio of ~ 1: 0.6, and
At least, a first polymer phase composed of the first polymer block component into which the first inorganic precursor has been introduced, and a second polymer phase composed of the second polymer block component into which the second inorganic precursor has been introduced. A phase separation process for forming a nanophase-separated structure regularly arranged by self-assembly and a conversion process for converting the hard magnetic polymer precursor and the soft magnetic material precursor into a hard magnetic material and a soft magnetic material, respectively. A second step of obtaining a nanoheterostructure permanent magnet composed of the hard magnetic material and the soft magnetic material, which comprises a removal treatment for removing the block polymer from the nanophase separated structure.
It is a method including. Each process will be described below.

[First step: Raw material solution preparation step]
Such a step is a step of dissolving the block copolymer described below and the inorganic precursor described below in a solvent to prepare a raw material solution.

The block copolymer used in the present invention is formed by combining at least the first polymer block component and the second polymer block component. As a specific example of such a block copolymer, a polymer block component A having a repeating unit a (first polymer block component) and a polymer block component B having a repeating unit b (second polymer block component) are end-to-end. There are AB type and ABA type block copolymers having a bonded structure of-(aa ... aa)-(bb ... bb)-. Further, it may be a star type in which one or more kinds of polymer block components are radially extended from the center, or a form in which another polymer component is hung from the main chain of the block copolymer.

The types of polymer block components constituting the block copolymer used in the present invention are not particularly limited as long as they are immiscible with each other. Therefore, the block copolymer used in the present invention is preferably composed of polymer block components having different polarities. Specific examples of such block copolymers include polystyrene-polymethylmethacrylate (PS-b-PMMA), polystyrene-polyethylene oxide (PS-b-PEO), polystyrene-polypolypyridine (PS-b-PVP), and polystyrene-polyferrose. Nyldimethylsilane (PS-b-PFS), polyisoprene-polystyrene oxide (PI-b-PEO), polybutadiene-polystyrene oxide (PB-b-PEO), polyethylethylene-polystyrene oxide (PEE-b-PEO), Polybutadiene-polyvinylpyridine (PB-b-PVP), polyisoprene-polymethylmethacrylate (PI-b-PMMA), polystyrene-polyacrylic acid (PS-b-PAA), polybutadiene-polymethylmethacrylate (PB-b-PMMA) ) Etc. can be mentioned. Above all, since the precursor to be introduced can be used as the precursor having a large difference in polarity as the difference in polarity of the polymer block components is large, PS-b can be easily introduced from the viewpoint of facilitating the introduction of the precursor into each polymer block component. -PVP, PS-b-PEO, PS-b-PAA and the like are preferable.

The molecular weight of the block copolymer and each polymer block component constituting the block copolymer may be appropriately selected according to the structural scale (size and spacing of spheres, columns, layers, etc.) and arrangement of the nanoheterostructure permanent magnets to be produced. For example, among the polymer block components constituting the block copolymer, the molecular weight of the polymer block component constituting the polymer phase into which the soft magnetic precursor of the nanophase separated structure has been introduced is adjusted to determine a predetermined value of the soft magnetic material. The volume of the portion can be controlled to a desired ratio, and when the molecular weight of the polymer block component constituting the polymer phase into which the soft magnetic material precursor is introduced is increased, the ratio of the volume of a predetermined portion of the soft magnetic material is increased. can do. Further, the soft magnetic material is prepared by adjusting the ratio of the molecular weights of the polymer block component constituting the polymer phase into which the soft magnetic material precursor is introduced and the polymer block component constituting the polymer phase into which the hard magnetic material precursor is introduced. The volume of the predetermined portion of the soft magnetic material can be controlled to a desired ratio, and when the molecular weight of the polymer block component constituting the polymer phase into which the soft magnetic material precursor is introduced is relatively increased, the predetermined portion of the soft magnetic material is formed. The proportion of the volume of can be increased. The number average molecular weight of each polymer block component is preferably 1 to 10 million (more preferably 10 to 1 million). Further, it is preferable to use a block copolymer which is easily decomposed by heat treatment (calcination) or light irradiation described later, or a block copolymer which is easily removed by a solvent.

The hard magnetic material precursor and the soft magnetic material precursor used in the present invention are not particularly limited as long as they are inorganic precursors that can be formed by the conversion treatment described above for the hard magnetic material and the soft magnetic material, respectively. Specifically, salts of the hard magnetic material and the metal or semi-metal constituting the soft magnetic material (for example, carbonate, nitrate, phosphate, sulfate, acetate, chloride, organic acid salt (acrylic acid). Salts, etc.)), alkoxides having 1 to 4 carbon atoms containing the metal or the semimetal (eg, methoxydo, ethoxydo, propoxide, butoxide), complexes of the metal or the semimetal (eg, acetylacetonate complex), It is composed of the metal or an organic metal compound containing the semimetal or an organic semimetal compound (for example, a phenyl group, a long chain hydrocarbon chain having 5 or more carbon atoms, a cyclooctatetraene ring, a cyclopentadienyl ring, and an amino group. Those having at least one structure selected from the group) are preferred. Such hard magnetic precursors and soft magnetic precursors satisfy the above-mentioned conditions according to the combination of the hard magnetic material and the soft magnetic material constituting the target nanoheterostructure permanent magnet. As described above, one type or two or more types are appropriately selected and used.

The solvent used in the present invention may be any solvent that can dissolve the block copolymer used and the first and second inorganic precursors, and is not particularly limited, but for example, acetone, tetrahydrofuran (THF), toluene, propylene glycol monomethyl. Examples thereof include ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), chloroform, benzene and the like. As such a solvent, one kind may be used alone, or two or more kinds may be mixed and used.

In the present specification, "dissolution" is a phenomenon in which a substance (solute) dissolves in a solvent to form a homogeneous mixture (solution), and when at least a part of the solute becomes an ion after dissolution, the solute becomes This includes cases where the substances are present in a molecular form without being dissociated into ions, cases where molecules and ions are associated with each other, and the like.

In the present invention, one of the first polymer block component, the hard magnetic precursor, and the soft magnetic precursor, the first inorganic precursor, the second polymer block component, and the precursor. The second inorganic precursor, which is the other of the above, is used in combination so that the molar ratio of the hard magnetic precursor and the soft magnetic precursor is 1: 0.02 to 1: 0.6. .. By using the hard magnetic material precursor and the soft magnetic material precursor in such a molar ratio, the hard magnetic material and the soft magnetic material can be made into a hard magnetic material: soft magnetic material = 1: 0.02 to 1: 0. It is possible to obtain a nanoheterostructure permanent magnet containing a molar ratio of 6 and having a high level of saturation magnetization and coercive force, and a large increase rate of the maximum magnetic energy product with respect to a hard magnetic single-phase permanent magnet. On the other hand, when the molar ratio of the hard magnetic material precursor to the soft magnetic material precursor is less than the lower limit or exceeds the upper limit, the obtained nanoheterostructure permanent magnet is obtained by the molar ratio of the hard magnetic material and the soft magnetic material. Since the ratio is less than the lower limit or exceeds the upper limit, the saturation magnetization and coercive force are difficult to improve, and the rate of increase of the maximum magnetic energy product with respect to the permanent magnet of the hard magnetic material single phase becomes small.

Further, in the present invention, the solubility parameter of the first inorganic precursor having a solubility parameter difference of 2 (cal / cm ³ ) ^1/2 or less from the first polymer block component and the second polymer block component. It is preferable to use it in combination with a second inorganic precursor having a difference of 2 (cal / cm ³ ) ^1/2 or less. By using the first inorganic precursor and the second inorganic precursor in combination to satisfy such conditions, the first polymer block component is more reliably contained in the step of forming the nanophase separated structure described later. A nanophase-separated structure is formed by self-assembling the block copolymer in a state where the one inorganic precursor is sufficiently introduced into the second polymer block component, and the inorganic precursor is three-dimensional. It is arranged with nanoscale periodicity.

The difference in solubility parameter between the first polymer block component and the first inorganic precursor used in the present invention is preferably smaller than the difference in solubility parameter between the first polymer block component and the second inorganic precursor. .. Further, it is preferable that the difference in the solubility parameter between the second polymer block component and the second inorganic precursor is smaller than the difference in the solubility parameter between the second polymer block component and the first inorganic precursor. Further, it is more preferable to satisfy both of these conditions.

Further, the first inorganic precursor used in the present invention preferably has a solubility parameter difference of more than 2 (cal / cm ³ ) ^{1/2 from} the second polymer block component. Further, it is preferable that the difference in solubility parameter between the second inorganic precursor and the first polymer block component is more than 2 (cal / cm ³ ) ^1/2 . Further, it is more preferable to satisfy both of these conditions.

By using the first inorganic precursor and the second inorganic precursor in combination to satisfy such conditions, in the step of forming the nanophase-separated structure described later, the second inorganic as an impurity in the first polymer block component. In the obtained nanoheterostructure permanent magnet, a part of the precursor and a part of the first inorganic precursor as an impurity tend to be more surely prevented from being introduced into the second polymer block component. The purity of the inorganic components constituting the matrix and / or the purity of the inorganic components arranged in the matrix tends to be further improved.

As a combination of the first and second polymer block components and the first and second inorganic precursors satisfying such conditions, the first polymer block component is selected from the group consisting of the polystyrene component, the polyisoprene component and the polybutadiene component. At least one polymer block component having a low polarity, and the second polymer block component is selected from the group consisting of a polymethyl methacrylate component, a polyethylene oxide component, a polyvinyl pyridine component, and a polyacrylic acid component. It is a large polymer block component, the first inorganic precursor is at least one less polar inorganic precursor selected from the group consisting of the organometallic compound and the organic semi-metal compound, and the second inorganic precursor is said. At least one highly polar selected from the group consisting of a metal or a salt of the half metal, an alkoxide having 1 to 4 carbon atoms containing the metal or the half metal, and an acetylacetonate complex of the metal or the half metal. Combinations that are inorganic precursors are preferred.

Further, at least one (more preferably both) of the first inorganic precursor and the second inorganic precursor has a solubility parameter difference of 2 (cal / cm ³ ) ^1/2 or less from the solvent used. Is preferable. By using the first inorganic precursor and / or the second inorganic precursor satisfying such conditions, the inorganic precursor is more reliably dissolved in the solvent, and the polymer block is formed in the step of forming the nanophase separated structure described later. Inorganic precursors tend to be more reliably introduced into the components.

The "solubility parameter" in the present invention is a so-called "SP value" defined by the regular solution theory introduced by Hildebrand, and the following equation:
Solubility parameter δ [(cal / cm ³ ) ^1/2 ] = (ΔE / V) ^1/2
(In the formula, ΔE indicates the molar evaporation energy [cal], and V indicates the molar volume [cm ³ ].)
It is a value obtained based on.

Further, the ratio of solutes (block copolymer, first inorganic precursor and second inorganic precursor) in the obtained raw material solution is not particularly limited, but when the total amount of the raw material solution is 100% by mass, the total amount of solutes is taken. It is preferably about 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. Further, by adjusting the amount of the first and second inorganic precursors used for the block copolymer, the amount of each inorganic precursor introduced into each polymer block component is adjusted, so that the softness in the obtained nanoheterostructure permanent magnet is adjusted. The volume of a predetermined portion of the magnetic material can be controlled to a desired ratio. For example, by increasing the amount of the inorganic precursor introduced into the polymer block component constituting the polymer phase into which the soft magnetic precursor is introduced, the ratio of the volume of a predetermined portion of the soft magnetic material can be increased.

[Second step: Nano heterostructure permanent magnet forming step]
This step includes a phase separation treatment, a conversion treatment, and a removal treatment described in detail below, and is a step of preparing a nanoheterostructure permanent magnet composed of a hard magnetic material and a soft magnetic material.

First, the raw material solution prepared in the first step contains a block copolymer, a hard magnetic precursor and a soft magnetic precursor, but in the present invention, the first polymer block component and the hard magnetic precursor are contained. The first inorganic precursor, which is one of the body and soft magnetic precursors, and the second inorganic precursor, which is the other of the second polymer block component and the precursor, are the hard magnetic precursors. And the soft magnetic precursor are used in combination so that the molar ratio is 1: 0.02 to 1: 0.6. At this time, the difference in solubility parameter between the first polymer block component and the first inorganic precursor is 2 (cal / cm ³ ) ^1/2 or less, and the difference in solubility parameter between the second polymer block component is 2 (Cal / cm ³ ) It is preferable to use it in combination with a second inorganic precursor having a concentration of ^1/2 or less. As a result, the first inorganic precursor and the second inorganic precursor are present in a state of being sufficiently introduced into the first polymer block component and the second polymer block component, respectively. Therefore, the first polymer phase and the second inorganic precursor consisting of the first polymer block component into which the first inorganic precursor was introduced are introduced by the phase separation treatment that forms the nanophase separated structure by the self-assembly of the block copolymer. The second polymer phase composed of the second polymer block component is regularly arranged, and the inorganic precursor is three-dimensionally arranged with nanoscale periodicity.

Such a phase separation treatment is not particularly limited, but by heat treatment at a temperature equal to or higher than the glass transition point of the block copolymer to be used, the block copolymer is self-assembled and a phase separation structure is obtained.

Next, in the present invention, the nanophase-separated structure formed by the phase separation treatment is converted into a hard magnetic material and a soft magnetic material, respectively, of the hard magnetic material precursor and the soft magnetic material precursor. A treatment and a removal treatment for removing the block copolymer from the nanophase separated structure are performed. By the conversion treatment, the hard magnetic material precursor and the soft magnetic material precursor are converted into the hard magnetic material and the soft magnetic material, respectively, and by removing the block copolymer by the removal treatment, a type of nanophase-separated structure ( Depending on the shape), the other inorganic component is in a matrix composed of one of the hard magnetic material and the soft magnetic material in a spherical, columnar, gyroid-like, or layered shape, which is a three-dimensionally specific nanoscale. The nanoheterostructure permanent magnet of the present invention is obtained, which is arranged with a periodicity of 1 and contains the hard magnetic material and the soft magnetic material in a molar ratio of 1: 0.02 to 1: 0.6.

Such a conversion treatment may be a step of heating the inorganic precursor at a temperature higher than the temperature at which it is converted into the inorganic component to convert it into an inorganic component, or hydrolyzing the inorganic precursor and dehydrating condensation. It may be a step of converting the mixture into an inorganic component.

Further, the removal treatment may be a step of decomposing the block copolymer by heat treatment (calcination) at a temperature higher than the temperature at which the block copolymer is decomposed, but a step of dissolving and removing the block copolymer with a solvent, ultraviolet rays, etc. The step may be a step of decomposing the block copolymer by irradiation with light.

Further, in the second step of the present invention, the phase separation treatment is carried out by subjecting the raw material solution prepared in the first step to a heat treatment (calcination) at a temperature higher than the temperature at which the block copolymer decomposes. The conversion treatment and the removal treatment can be performed by a single heat treatment. In order to complete the phase separation treatment, the conversion treatment, and the removal treatment by one heat treatment in this way, the temperature varies depending on the type of block copolymer or inorganic precursor used, but is 300 to 1200 ° C. (more preferably 400 to 400 to 200 ° C.). It is preferable to perform heat treatment at 900 ° C. for about 0.1 to 50 hours.

Such heat treatment may be performed in an inert gas atmosphere (for example, nitrogen gas), an oxidizing gas atmosphere (for example, air), or a reducing gas atmosphere (for example, hydrogen). By converting the inorganic precursors to inorganic components and removing the block copolymer in an inert gas atmosphere, the nanoscale three-dimensional periodic structure tends to be more reliably maintained. Further, by converting the inorganic precursor into an inorganic component in an oxidizing gas atmosphere, a permanent magnet having a hard magnetic material and a soft magnetic material made of a metal or metalloid oxide can be obtained. Further, by converting the inorganic precursor into an inorganic component in a reducing gas atmosphere, a permanent magnet having a hard magnetic material and a soft magnetic material made of a metal or a semimetal can be obtained. The conditions of the heat treatment in such an inert gas atmosphere, an oxidizing gas atmosphere, or a reducing gas atmosphere are not particularly limited, but are 0.1 to 50 hours at 300 to 1200 ° C. (more preferably 400 to 900 ° C.). Degree of treatment is preferred.

In the method for producing a nanoheterostructure permanent magnet of the present invention, after the first step, the raw material solution may be charged into a heat treatment container and the second step may be performed, or the raw material solution may be used. After applying to the surface of the base material, the second step may be performed. According to the latter method, a film-like nanoheterostructure permanent magnet can be directly formed on the surface of the base material. The type of base material used is not particularly limited, and may be appropriately selected depending on the intended use of the obtained nanoheterostructure permanent magnet. Further, as a method for applying the raw material solution, a brush coating method, a spray method, a dipping method, a spin method, a curtain flow method and the like are used.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1-1)
As a block copolymer, polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP, number average molecular weight of PS component: 13 × 10 ³ , solubility parameter of PS component: 9.1 (cal / cm ³ ) ^{1 / 2.} Number average molecular weight of P4VP component: 50 × 10 ³ , solubility parameter of P4VP component: 12.0 (cal / cm ³ ) ^1/2 ) 0.1 g, and Nd ₂ Fe ₁₄ B, which is a hard magnetic precursor Neodim acetylacetonate (Nd (acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.042 g and iron acetylacetonate (Fe (Fe)) as precursors (Nd precursor and Fe precursor) acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.214 g, and iron pyrrolidine dithiocarbamate (FePDC, solubility parameter: 11.4 (FePDC, solubility parameter: 11.4) as Fe precursor, which is a soft magnetic precursor. cal ^/ cm ³⁾ 1/2) 0.006g and the 10mL of tetrahydrofuran (THF, solubility parameter: dissolved in ^{9.1 (cal / cm 3) 1/2} ), to obtain a raw material solution. The amount of Fe precursor to 1 mol of Nd ₂ Fe ₁₄ B precursor in this raw material solution is 0.1 mol.

Next, the obtained raw material solution was placed in a heat treatment container together with 0.024 g of boric acid and 1.54 g of calcium hydride, heat-treated at 700 ° C. for 6 hours in argon containing 5% hydrogen, and washed with acetic acid. , Nd ₂ Fe ₁₄ B Spherical Fe is arranged three-dimensionally and periodically in the B matrix, and has a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. A nanoheterostructure (0.8 cm × 0.8 cm × 2 μm, Nd ₂ Fe ₁₄ B: Fe = 1: 0.1) was obtained.

(Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3)
The amount of Fe precursor per 1 mol of Nd ₂ Fe ₁₄ B precursor was 0.02 mol (Example 1-2), 0.05 mol (Example 1-3), 0.3 mol (Example 1-), respectively. 4), 0.5 mol (Example 1-5), 0.6 mol (Example 1-6), 0.01 mol (Comparative Example 1-1), 0.7 mol (Comparative Example 1-2) Spherical Fe is three-dimensionally and periodically in the Nd ₂ Fe ₁₄ B matrix in the same manner as in Example 1-1 except that the raw material solution is prepared so as to be 1 mol (Comparative Example 1-3). A nanoheterostructure (0.8 cm x 0.8 cm x 2 μm, Nd ₂ Fe ₁₄ ) that is arranged and has a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. B: Fe = 1: 0.02 (Example 1-2), 1: 0.05 (Example 1-3), 1: 0.3 (Example 1-4), 1: 0.5 (Example) Example 1-5), 1: 0.6 (Example 1-6), 1: 0.01 (Comparative Example 1-1), 1: 0.7 (Comparative Example 1-2), 1: 1 (Comparison) Examples 1-3)) were obtained.

<Maximum magnetic energy>
The magnetization curves of the nanoheterostructures obtained in Examples and Comparative Examples were measured at room temperature in the range up to 20 kOe using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd., trade name: VSM-3S-15). The maximum magnetic energy product was obtained, and the rate of increase with respect to the permanent magnet consisting only of the hard magnetic material Nd ₂ Fe ₁₄ B was calculated. The results are shown in Table 2.

(Example 2-1)
As a block copolymer, polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP, number average molecular weight of PS component: 50 × 10 ³ , solubility parameter of PS component: 9.1 (cal / cm ³ ) ^{1 / 2.} Number average molecular weight of P4VP component: 13 × 10 ³ , solubility parameter of P4VP component: 12.0 (cal / cm ³ ) ^1/2 ) 0.1 g, FePt precursor (Fe) which is a hard magnetic precursor precursor Iron acetylacetonate (Fe (acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.066 g and platinum acetylacetonate (Pt (acac) ₂ , as precursors and Pt precursors) Solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.064 g, and iron pyrrolidine dithiocarbamate (FePDC, solubility parameter: 11.4 (cal / cm ³ ) as Fe precursor, which is a soft magnetic precursor. ) ^1/2 ) 0.019 g was dissolved in 10 mL of tetrahydrofuran (THF, solubility parameter: 9.1 (cal / cm ³ ) ^1/2 ) to obtain a raw material solution. The amount of Fe precursor per 1 mol of FePt precursor in this raw material solution is 0.1 mol.

Next, the obtained raw material solution was placed in a heat treatment container and heat-treated in argon at 700 ° C. for 6 hours, whereby spherical FePt (platinum-iron alloy) was three-dimensionally and periodically arranged in the Fe matrix. A nanoheterostructure (0.8 cm × 0.8 cm × 2 μm, FePt: Fe = 1:) having a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. 0.1) was obtained.

(Examples 2-2 to 2-6 and Comparative Examples 2-1 to 2-3)
The amount of Fe precursor per 1 mol of FePt precursor is 0.02 mol (Example 2-2), 0.05 mol (Example 2-3), 0.3 mol (Example 2-4), 0, respectively. .5 mol (Example 2-5), 0.6 mol (Example 2-6), 0.01 mol (Comparative Example 2-1), 0.7 mol (Comparative Example 2-2), 1 mol ( Spherical FePt (platinum-iron alloy) is three-dimensionally and periodically arranged in the Fe matrix in the same manner as in Example 2-1 except that the raw material solution is prepared so as to be in Comparative Example 2-3). A nanoheterostructure (0.8 cm × 0.8 cm × 2 μm, FePt: Fe = 1:) having a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. 0.02 (Example 2-2), 1: 0.05 (Example 2-3), 1: 0.3 (Example 2-4), 1: 0.5 (Example 2-5), 1: 0.6 (Example 2-6), 1: 0.01 (Comparative Example 2-1), 1: 0.7 (Comparative Example 2-2), 1: 1 (Comparative Example 2-3)) Got

<Maximum magnetic energy>
The magnetization curves of the nanoheterostructures obtained in Examples and Comparative Examples were measured at room temperature in the range up to 20 kOe using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd., trade name: VSM-3S-15). The maximum magnetic energy product was obtained, and the rate of increase for a permanent magnet consisting only of FePt, which is a hard magnetic material, was calculated. The results are shown in Table 3.

(Example 3-1)
As a block copolymer, polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP, number average molecular weight of PS component: 18 × 10 ³ , solubility parameter of PS component: 9.1 (cal / cm ³ ) ^{1 / 2.} Number average molecular weight of P4VP component: 40 × 10 ³ , solubility parameter of P4VP component: 12.0 (cal / cm ³ ) ^1/2 ) 0.1 g, and SmCo ₅ precursor which is a hard magnetic precursor (SmCo ₅ precursor) Samalium acetylacetonate (Sm (acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.042 g and cobalt acetylacetonate (Co (acac) ₃ ) as Sm precursor and Co precursor) , Solubility parameter: 8.8 (cal / cm ³ ) ^1/2 ) 0.084 g, and iron pyrrolidine dithiocarbamate (FePDC, solubility parameter: 11.4 (cal / cm) as Fe precursor, which is a soft magnetic precursor precursor. ³ ) ^1/2 ) 0.022 g was dissolved in 10 mL of tetrahydrofuran (THF, solubility parameter: 9.1 (cal / cm ³ ) ^1/2 ) to obtain a raw material solution. The amount of Fe precursor to 1 mol of SmCo ₅ precursor in this raw material solution is 0.4 mol.

Next, the obtained raw material solution was placed in a heat treatment vessel together with 1.6 g of calcium hydride, heat-treated at 700 ° C. for 6 hours in argon containing 5% hydrogen, and washed with acetic acid to bring it into the SmCo ₅ matrix. A nanoheterostructure (0.8 cm) having columnar Fes arranged three-dimensionally and periodically and having a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. × 0.8 cm × 2 μm, SmCo ₅ : Fe = 1: 0.4) was prepared.

(Comparative Example 3-1)
In the same manner as in Example 3-1 except that the raw material solution was prepared so that the amount of Fe precursor was 1 mol with respect to 1 mol of SmCo ₅ precursor, columnar Fe was three-dimensionally and periodically in the SmCo ₅ matrix. Nanoheterostructure (0.8 cm × 0.8 cm × 2 μm, SmCo ₅ ) having a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. : Fe = 1: 1) was obtained.

<Maximum magnetic energy>
The magnetization curves of the nanoheterostructures obtained in Examples and Comparative Examples were measured at room temperature in the range up to 20 kOe using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd., trade name: VSM-3S-15). The maximum magnetic energy product was obtained, and the rate of increase for a permanent magnet consisting only of SmCo ₅ , which is a hard magnetic material, was calculated. The results are shown in Table 4.

(Example 4-1)
As a block copolymer, polystyrene-b-poly (4-vinylpyridine) (PS-b-P4VP, number average molecular weight of PS component: 13 × 10 ³ , solubility parameter of PS component: 9.1 (cal / cm ³ ) ^{1 / 2.} Number average molecular weight of P4VP component: 50 × 10 ³ , solubility parameter of P4VP component: 12.0 (cal / cm ³ ) ^1/2 ) 0.1 g, and Nd ₂ Fe ₁₄ B, which is a hard magnetic precursor Neodim acetylacetonate (Nd (acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.042 g and iron acetylacetonate (Fe (Fe)) as precursors (Nd precursor and Fe precursor) acac) ₃ , solubility parameter: 9.0 (cal / cm ³ ) ^1/2 ) 0.214 g, and iron pyrrolidine dithiocarbamate (FePDC, solubility parameter: 11.4 (FePDC, solubility parameter: 11.4) as FeCo precursor, which is a soft magnetic precursor precursor Cal / cm ³ ) ^1/2 ) 0.012 g and cobalt pyrrolidine dithiocarbamate (CoPDC, solubility parameter: 11.4 (cal / cm ³ ) ^1/2 ) 0.012 g and 10 mL tetrahydrofuran (THF, solubility parameter:: It was dissolved in 9.1 (cal / cm ³ ) ^1/2 ) to obtain a raw material solution. The amount of FeCo precursor to 1 mol of Nd ₂ Fe ₁₄ B precursor in this raw material solution is 0.2 mol.

Next, the obtained raw material solution was placed in a heat treatment vessel together with 0.024 g of boric acid and 1.54 g of calcium hydride, heat-treated at 700 ° C. for 6 hours in argon containing 5% hydrogen, and washed with acetic acid. , Nd ₂ Fe ₁₄ B Spherical FeCo is three-dimensionally and periodically arranged in the B matrix, and has a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. A nanoheterostructure (0.8 cm × 0.8 cm × 2 μm, Nd ₂ Fe ₁₄ B: FeCo = 1: 0.2) was obtained.

(Comparative Example 4-1)
Spherical in the Nd ₂ Fe ₁₄ B matrix in the same manner as in Example 4-1 except that the raw material solution was prepared so that the amount of FeCo precursor was 0.8 mol with respect to 1 mol of Nd ₂ Fe ₁₄ B precursor. FeCo is three-dimensionally and periodically arranged, and a nanoheterostructure (0.8 cm ×) having a three-dimensional periodic structure in which the average value of the length of one unit of the repeating structure is 1 nm to 100 nm. 0.8 cm × 2 μm, Nd ₂ Fe ₁₄ B: FeCo = 1: 0.8) was obtained.

<Maximum magnetic energy>
The magnetization curves of the nanoheterostructures obtained in Examples and Comparative Examples were measured at room temperature in the range up to 20 kOe using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd., trade name: VSM-3S-15). The maximum magnetic energy product was obtained, and the rate of increase with respect to the permanent magnet consisting only of the hard magnetic material Nd ₂ Fe ₁₄ B was calculated. The results are shown in Table 5.

As is clear from the results shown in Tables 2 to 5, in the nanoheterostructure permanent magnet containing a hard magnetic material and a soft magnetic material, the molar ratio of the hard magnetic material to the soft magnetic material is 1: 0.02-1. It was confirmed that the rate of increase of the maximum magnetic energy product with respect to the permanent magnet consisting only of the hard magnetic material was remarkably increased by setting: 0.6.

Specifically, in a nanoheterostructure permanent magnet containing Nd ₂ Fe ₁₄ B which is a hard magnetic material and Fe which is a soft magnetic material, the molar ratio of Nd ₂ Fe ₁₄ B and Fe is 1: 0.02. Permanent Nd ₂ Fe ₁₄ B single phase by ~ 1: 0.6 (preferably 1: 0.02 to 1: 0.3, more preferably 1: 0.02 to 1: 0.1). It was confirmed that the maximum magnetic energy product was 35% or more (preferably 38% or more, more preferably 40% or more) higher than that of the magnet.

Further, in the nanoheterostructure permanent magnet containing FePt which is a hard magnetic material and Fe which is a soft magnetic material, the molar ratio of FePt and Fe is 1: 0.02 to 1: 0.6 (preferably 0. It was confirmed that the maximum magnetic energy product was 34% or more (preferably 38% or more) higher than that of the FePt single-phase permanent magnet by setting the value to 1 to 0.5).

Further, in a nanoheterostructure permanent magnet containing SmCo ₅ which is a hard magnetic material and Fe which is a soft magnetic material, the molar ratio of SmCo ₅ and Fe is 1: 0.02 to 1: 0.6 (preferably). It was confirmed that the maximum magnetic energy product was 36% or more higher than that of the SmCo ₅ single-phase permanent magnet by setting the value to 0.3 to 0.5).

Further, in the nanoheterostructure permanent magnet containing Nd ₂ Fe ₁₄ B which is a hard magnetic material and Fe Co which is a soft magnetic material, the molar ratio of Nd ₂ Fe ₁₄ B and FeCo is 1: 0.02 to 1: 1. It was confirmed that the maximum magnetic energy product was 46% or more higher than that of the Nd ₂ Fe ₁₄ B single-phase permanent magnet by setting it to 0.6 (preferably 1: 0.1 to 1: 0.3). Was done.

As described above, according to the present invention, in a matrix composed of one inorganic component of a hard magnetic material and a soft magnetic material, the other inorganic component has a predetermined shape and is three-dimensionally periodiced at a predetermined nanoscale. It is possible to obtain a permanent magnet having a nanoheterostructure in which the hard magnetic material and the soft magnetic material are contained in a specific ratio.

A permanent magnet having such a nanoheterostructure and containing the hard magnetic material and the soft magnetic material in a specific ratio exhibits a pinning effect by magnetic exchange interaction between the hard magnetic material and the soft magnetic material. At the same time, the interface enhancement effect, nano size effect, durability, etc. are dramatically improved over the conventional nano-structure permanent magnets, and as a result, the high coercive force of the hard magnetic material and the high saturation magnetization of the soft magnetic material are further improved. It will be highly combined. Therefore, the nanoheterostructure permanent magnet of the present invention is useful as a permanent magnet used in motors, generators, coils for various sensors, cap magnets, and the like.

Claims (6)

The combination of the hard magnetic material and the soft magnetic material is a combination of Nd ₂ Fe ₁₄ B which is a hard magnetic material and Fe which is a soft magnetic material; a combination of SmCo ₅ which is a hard magnetic material and Fe which is a soft magnetic material. It is one of a combination of Nd ₂ Fe ₁₄ B, which is a hard magnetic material, and FeCo, which is a soft magnetic material.
Wherein the matrix of the hard magnetic material, the soft magnetic material, three-dimensionally and periodically arranged, have a three-dimensional periodic structure average length of one unit of the repeating structure is 1nm~100nm And
The molar ratio of the hard magnetic material to the soft magnetic material is 1: 0.02 to 1: 0.6.
A nano-heterostructure permanent magnet characterized by this. According to claim 1, the shape of the soft magnetic body that is three-dimensionally and periodically arranged in the matrix is, globular, columnar, characterized in that it is a shape selected from the group consisting of gyroid shape Nano heterostructure permanent magnet. A block copolymer formed by bonding at least a first polymer block component and a second polymer block component that are immiscible with each other, a first inorganic precursor that is a hard magnetic precursor, and a second inorganic precursor that is a soft magnetic precursor. The body and the body were dissolved in a solvent, and the hard magnetic precursor and the soft magnetic precursor were contained in a molar ratio of 1: 0.02 to 1: 0.6 to obtain the hard magnetic precursor. The combination with the soft magnetic precursor is a combination of Nd ₂ Fe ₁₄ B precursor which is a hard magnetic precursor and Fe precursor which is a soft magnetic precursor; SmCo ₅ precursor which is a hard magnetic precursor. Combination of body and Fe precursor which is a soft magnetic precursor; any one of a combination of Nd ₂ Fe ₁₄ B precursor which is a hard magnetic precursor precursor and FeCo precursor which is a soft magnetic precursor precursor. The first step of preparing the raw material solution that is the seed ,
At least, a first polymer phase composed of the first polymer block component into which the first inorganic precursor has been introduced, and a second polymer phase composed of the second polymer block component into which the second inorganic precursor has been introduced. Is self-assembled to form a nanophase-separated structure in which the second polymer phase is regularly arranged in the first polymer phase, and the hard magnetic material precursor and the soft magnetic material precursor. and respective hard magnetic material and the conversion process of converting the soft magnetic material, and a removal process of removing the block copolymer from the nano phase separation structure, a combination of the hard magnetic and the soft magnetic material, hard Combination of magnetic material Nd ₂ Fe ₁₄ B and soft magnetic material Fe; Combination of hard magnetic material SmCo ₅ and soft magnetic material Fe; Hard magnetic material Nd ₂ Fe ₁₄ B and soft material A nanoheterostructure permanent magnet in which the soft magnetic material is three-dimensionally and periodically arranged in a matrix made of the hard magnetic material, which is any one of combinations with FeCo which is a magnetic material, is obtained. The second step and
A method for producing a nanoheterostructure permanent magnet, which comprises. FePt , which is a hard magnetic material , is arranged three-dimensionally and periodically in a matrix made of iron, which is a soft magnetic material, and the average value of the length of one unit of the repeating structure is three-dimensionally 1 nm to 100 nm. It has a periodic structure and
The molar ratio of the hard magnetic material to the soft magnetic material is 1: 0.02 to 1: 0.6.
A nano-heterostructure permanent magnet characterized by this. The fourth aspect of claim 4 , wherein the shape of the hard magnetic material three-dimensionally and periodically arranged in the matrix is a shape selected from a group consisting of a spherical shape, a columnar shape, and a gyroid shape. Nano heterostructure permanent magnet. A block copolymer formed by bonding at least a first polymer block component and a second polymer block component that are immiscible with each other, a first inorganic precursor composed of an iron precursor which is a soft magnetic precursor, and a hard magnetic precursor. A second inorganic precursor composed of a certain FePt precursor is dissolved in a solvent, and the hard magnetic precursor and the soft magnetic precursor have a molar ratio of 1: 0.02 to 1: 0.6. The first step of preparing the raw material solution to be contained,
At least, a first polymer phase composed of the first polymer block component into which the first inorganic precursor has been introduced, and a second polymer phase composed of the second polymer block component into which the second inorganic precursor has been introduced. Is self-assembled to form a nanophase-separated structure in which the second polymer phase is regularly arranged in the first polymer phase, and the hard magnetic material precursor and the soft magnetic material precursor. The hard magnetism is contained in a matrix made of iron, which is the soft magnetic material, including a conversion treatment for converting the above into a hard magnetic material and a soft magnetic material, and a removal treatment for removing the block polymer from the nanophase separated structure. The second step of obtaining a nanoheterostructure permanent magnet in which the body FePt is arranged three-dimensionally and periodically, and
A method for producing a nanoheterostructure permanent magnet, which comprises.