JP3447183B2 - High frequency composite material with soft magnetism and dielectric properties - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal television antenna, a magnetic head core, a pulse motor magnetic core, and the like.
The present invention relates to a high-frequency composite material having soft magnetism and dielectric property, which can be suitably used in a magnetic application field such as a magnetic core of a choke coil and a transformer, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, demands for smaller and lighter electronic devices and higher performance have been further increased. In order to meet such demands, the drive frequency of inductors such as power transformers is becoming higher. . In order to deal with these, a magnetic material having a higher specific resistance in addition to the conventional soft magnetic characteristics has been required.

Therefore, the present inventors have found that Fe-based crystals and H
Fe-Hf-O-based alloy or Fe-Ta-O-based alloy in which f or Ta amorphous is mixed, Japanese Patent Application No. 5-338333
The composition formula of No. is Fe _a M _b O _c (M represents at least one element of rare earth elements or a mixture thereof.)
It has been found that the alloy represented by (1) has a high specific resistance and excellent magnetic properties. However, these soft magnetic alloys are obtained by the sputtering method, and since they are thin films when manufactured, they are rod-shaped such as antennas of liquid crystal televisions, cores and pulse of magnetic heads. There is a problem that it is difficult to use it as a magnetic core of a motor.

The frequency of Ni ferrite used in conventional magnetic materials up to the highest frequency is 1
When it exceeds 50 MHz, Q (which shows the loss characteristic of the core material) is rapidly lowered, and the core loss is increased. In addition, even in the magnet-plumbite type ferrite developed as a magnetic material for high frequencies, Q = 1 at 1 GHz, which is unsatisfactory in the loss in the high frequency region of several hundred MHz. The Q is a loss coefficient (ta
It is the reciprocal of nδ), and the larger this value is, the better the high frequency material is. Further, when used in a frequency band of several hundred MHz or more, a magnetic material having a dielectric property was required.

Therefore, the inventors of the present invention have considered the soft magnetic alloy having excellent magnetic characteristics to be applied to an antenna of a liquid crystal television, a core of a magnetic head, a magnetic core of a pulse motor, or the like, and have excellent soft magnetic characteristics. The inventors arrived at the present invention by attempting to shape the alloy powder into a desired shape by dispersing and kneading the alloy powder in a synthetic resin having a small dielectric loss, and then shaping the alloy powder.

[0006]

The present invention has been made in view of the above circumstances, and can be easily formed into a desired shape.
It is an object of the present invention to provide a high frequency composite material having a high soft magnetic property and a low dielectric loss, which has excellent soft magnetic characteristics and low dielectric loss, and a method for producing the same.

[0007]

A high frequency composite material having soft magnetic properties and dielectric properties according to the present invention has a composition formula of A _a M _b
O _c (in the above composition formula, A represents at least one element selected from the group of Fe, Co and Ni or a mixture thereof, and M represents at least one element selected from Zr and W or a mixture thereof. The composition of A above
The range a in atomic% is 45 ≦ a ≦ 65, and the composition range of O is c
It is characterized by comprising a soft magnetic alloy powder made of a soft magnetic alloy powder having an atomic percentage of 30 ≦ c ≦ 45 and a synthetic resin.

In the composition formula of the present invention, A is Fe and Co.
Consists, composition _{formula, (Fe 100-x Co x} ) a M b
It may be represented by O _c , and x may be in the range of 0 <x ≦ 90.
In the above structure of the present invention, an insulating layer may be formed on the surface of the soft magnetic alloy powder .

[0009]

[0010]

[0011]

The method for producing a high frequency composite material according to the present invention is the same as the method for producing a high frequency composite material as described above, except that A-obtained by a liquid quenching method in place of the A powder and the M powder.
This is a method characterized by using pulverized powder of M alloy ribbon.

[0013]

[0014]

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A first example of a method for producing a high frequency composite material having soft magnetism and dielectric properties according to the present invention will be described below. First, each raw material is weighed so that the composition formula in the present invention is the composition of the soft magnetic alloy powder represented by A _a M _b D _c . As the raw material here, A powder and M powder are used. As the powder of A, a powder selected from a simple substance of at least one element selected from the group of Fe, Co and Ni, oxides, carbides, carbonates, nitrides and borides is used. As the powder of M, Hf, Zr, W, Ti, V, N
b, Mo, Cr, Mg, Mn, Al, Si, Ca, S
r, Ba, Cu, Ga, Ge, As, Se, Zn, C
d, In, Sn, Sb, Te, Pb, Bi, powder of at least one element selected from the group of rare earth elements, oxides, carbides, carbonates, nitrides, borides Used. Examples of the rare earth element include Sc, Y, or La, C belonging to Group 3A of the periodic table.
e, Pr, Nd, Pm, Sm, Eu, Gd, Td, D
At least one element selected from the group of lanthanoids such as y, Ho, Er, Tm, Yb and Lu, or a mixture thereof can be mentioned. At this time, the powder of A has a particle size of 100.
It is desirable that the powder of M or less and M has a particle diameter of 2 μm or less.

Next, in the case of adding O, C and N among D, the powder of A and the powder of M described above are enclosed in a stainless steel pot together with a stainless ball made of the same material as the pot, and O is added. , A gas of at least one element selected from the group of C, N, a gas of D selected from oxide gas, and a carbide gas. Then, by mechanical alloying in which a high energy type planetary ball mill is used for grinding and stirring for a predetermined time, the composition formula is A _a M _b D _c (the above composition formula R
>, A represents at least one element selected from the group of Fe, Co and Ni or a mixture thereof, and M represents Hf,
Zr, W, Ti, V, Nb, Mo, Cr, Mg, Mn,
Al, Si, Ca, Sr, Ba, Cu, Ga, Ge, A
s, Se, Zn, Cd, In, Sn, Sb, Te, P
b, Bi, at least one element selected from the group of rare earth elements or a mixture thereof, and D is O, C, N,
It represents at least one element selected from the group B or a mixture thereof. Further, in the composition formula, a, b, and c satisfy the relations of 40 ≦ a <87, 0 <b ≦ 20, and 0 <c ≦ 50 in atomic%. The soft magnetic alloy powder shown by the above) is obtained. In the above composition formula, Fe and Co are used as A, and the composition formula at that time is (Fe _100-x C
O _x ) _a M _b D _c , and the respective components can be mixed so that x representing the composition ratio is in the range of 0 <x ≦ 90. With such a composition, in particular, the value of Qε can be increased and the frequency characteristic of Qμ can be made excellent as described later. The time for mechanical alloying is
It is preferably 2 hours or more, more preferably 8 to 6
It will be about 0 hours. When it is less than 2 hours, the bcc structure or the fcc structure, or the crystal of A in which these are mixed is not sufficiently refined, which is not preferable.

In this example, crushing and stirring are carried out in a D gas atmosphere, but by carrying out in a mixed gas atmosphere of the D gas and an inert gas such as Ar gas, oxygen in the material, The amount of carbon and nitrogen can be adjusted. still,
In addition to the planetary ball mill, a crushing machine such as a rotor speed mill may be used for crushing.

The soft magnetic alloy powder obtained here has an A having a bcc structure with an average crystal grain size on the order of several nm to several tens of nm.
The microcrystalline phase (1) has a structure such that it is surrounded by an amorphous phase containing a large amount of M and D, and becomes an agglomerated particle having an average particle size of about 1 to 2 μm. This soft magnetic alloy powder exhibits excellent soft magnetic characteristics because the bcc structure or fcc structure forming agglomerated particles, or the average grain size of the fine crystals of A in which they are mixed is fine, and the soft magnetic alloy powder has a bcc structure. Or fcc
Since the structure or the microcrystal of A in which these are mixed is surrounded by the amorphous phase of high resistance, there is a feature that the eddy current loss can be suppressed small.

Next, the obtained soft magnetic alloy powder is dispersed in a synthetic resin liquid using an organic solvent as a solvent to obtain a slurry,
This slurry is repeatedly passed through three rolls and kneaded until the slurry becomes powdery to obtain a kneaded product. The synthetic resin used here is a material with a small dielectric loss (that is, Q
With a large Q value of 400 or more), such as polypropylene, polyethylene, polystyrene,
Paraffin, polytetrafluoroethylene, polycarbonate, silicone resin, etc. may be mentioned. As an organic solvent for dissolving this synthetic resin, xylene, toluene,
Examples thereof include benzene.

The addition ratio of the soft magnetic alloy powder to the synthetic resin can be appropriately changed depending on the magnetic properties and dielectric properties of the target composite material, but is 50 to 8 by volume in the slurry.
It is preferable to add it so as to be about 0 vol%. If the volume ratio of the soft magnetic alloy powder is less than 50 vol%, the magnetic permeability may be lowered, whereas if it exceeds 80 vol%, it may be difficult to perform molding by injection molding or the like. There is a fear.

The soft magnetic alloy powder is dispersed in a synthetic resin liquid,
Before kneading, it is desirable to perform heat treatment in an atmosphere selected from air, oxygen, nitrogen, steam or a mixed atmosphere thereof. The heating temperature here is 25 ° C to
The heating time is preferably about 300 ° C. and the heating time is about 0.5 to 48 hours. In this case, the insulating layer made of oxide is formed on the surface of the soft magnetic alloy powder, so that the specific resistance of the soft magnetic alloy powder is increased and the dielectric constant at high frequency can be further lowered. Note that the insulating layer here is not limited to the oxide film and may be formed using another insulating film.

Then, the kneaded product is placed in a drier or the like to heat it to evaporate the organic solvent, and then the product is molded into a desired shape by using a press molding machine, an injection molding machine, an extrusion device or the like. To make. After this, the molded body is
By heating at about 400 ° C. for about 1 hour, a molded product of the intended high frequency composite material having soft magnetism and dielectric properties can be obtained. In addition to the compression molding method, an injection molding method or an extrusion molding method can be used as the molding method.

Next, a second example of the method for producing a high frequency composite material having soft magnetism and dielectric properties according to the present invention will be described. The manufacturing method of the high frequency composite material of the second example is different from the manufacturing method of the high frequency composite material of the first example in A
After mixing the powder of M and the powder of M, instead of pulverizing and stirring in a gas atmosphere of D, the powder of A, the powder of M, and the powder of D
After mixing with the powder of
This is the point of pulverizing and stirring in a gas atmosphere of D selected from a simple substance gas of at least one element selected from the group of C and N, an oxide gas, and a carbide gas. As the powder of D, at least one selected from carbon and B or a mixture thereof is used. In addition, in this example, the powder of A, the powder of M and the powder of D are crushed and stirred in a gas atmosphere of D or in an inert gas atmosphere such as Ar gas, or when the gas of D and Ar gas are mixed. It is performed in a mixed gas atmosphere with an inert gas. When the mixed gas atmosphere is used, the amounts of oxygen, carbon and nitrogen in the material can be adjusted. Also by the manufacturing method of the second example, a high frequency composite material having soft magnetism and dielectric properties can be obtained.

Next, a third example of the method of manufacturing the high frequency composite material having soft magnetism and dielectric properties of the present invention will be described. The manufacturing method of the high frequency composite material of the third example is different from the manufacturing method of the high frequency composite material of the first example or the second example, except that the liquid quenching method is used instead of the powder of A and the powder of M. The point is to use the pulverized powder of the A-M alloy ribbon obtained by.

To prepare an AM alloy ribbon by the liquid quenching method, for example, a single roll method in which the molten AM alloy is sprayed on the surface of one cooled roll rotating at high speed through a nozzle, It can be manufactured by a twin roll method or the like in which the molten A-M alloy is jetted between two cooling rolls which rotate while contacting each other. In the single roll method, the molten AM alloy comes into contact with the surface of the cooling roll and is cooled, and the surface roughness is different between the roll contact surface (roll surface) and the non-contact surface (free surface), and the thickness is 8 to 35 μm. A wide and long product can be obtained. In the twin roll method, both sides of the ribbon contact the rolls and are cooled under pressure, so thicker ones are easier to obtain than the single roll method, and the surface roughness and plate thickness accuracy are also good, but wide, It is difficult to obtain long ones. The A-M alloy ribbon thus produced is crushed and pulverized, and then put into a high energy planetary ball mill. Also by the manufacturing method of the third example, a high frequency composite material having soft magnetic properties and dielectric properties can be obtained.

Next, a fourth example of the method for producing a high frequency composite material having soft magnetism and dielectric properties according to the present invention will be described. The manufacturing method of the high frequency composite material of the fourth example is different from the manufacturing method of the high frequency composite material of the first example or the second example, except that A powder, M powder, D powder and /
Alternatively, in addition to the gas of D, A- obtained by the liquid quenching method
It is also a point that pulverized powder of M alloy ribbon is used. Also by the manufacturing method of the fourth example, a high frequency composite material having soft magnetism and dielectric properties can be obtained.

In the high frequency composite material produced as described above, the synthetic resin having a small dielectric loss and the soft magnetic alloy powder represented by the composition formula A _a M _b D _c are compounded. , The resulting composite material has a resistivity of 10 ⁸ Ω · c
Insulation (dielectric) that synthetic resin has in addition to m or more
And the soft magnetic characteristics of the soft magnetic alloy powder can be combined, and in particular, in a high frequency band of several hundred MHz or more, not only the magnetic characteristics but also the Q is high. For example, at 1 GHz, Q = Since it is 30 or more, it can be used in the several hundred MHz to GHz band, which cannot be achieved by the conventional magnetic material. Further, since the soft magnetic alloy powder is dispersed in the synthetic resin, the composite material for high frequencies is easier to mold than the case where it is composed only of the soft magnetic alloy powder.

Therefore, the high-frequency composite material of the present invention can be easily formed into a desired shape such as a rod shape, as compared with the conventional thin-film material, so that it can be used as an antenna of a liquid crystal television or a magnetic head. It can be widely applied as a core, a core of a transformer, and a magnetic component such as a magnetic needle of a pulse motor. Further, compared to the conventional material, it is possible to obtain magnetic parts having excellent magnetic characteristics at high frequencies and low dielectric loss, and further miniaturization of these magnetic parts can be achieved. For example, the high frequency composite material of the present invention By manufacturing an antenna for a liquid crystal television using the, the transmission / reception level can be improved, and the antenna can be downsized.

[0029]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. (Example 1) 11.49 g of electrolytic iron (manufactured by Toho Zinc Co., Ltd., 200 mesh pass) and 4.61 g of zirconium oxide (manufactured by No. 1 rare element, 45 μm pass) were weighed and made of stainless steel (SUS304). Pot (content capacity 17
(0 ml), 0.92 g of O ₂ gas was enclosed, and mechanical alloying was performed. For the mechanical alloying, a high energy type planetary ball mill (Kurimoto Iron Works Co., Ltd.) is used, and a stainless steel ball (diameter 4 m) made of the same material as the pot is used in the pot.
m) is put in 238g, centrifugal acceleration 100G, rotation speed /
In the revolution speed = 448rpm / 588rpm, 8 hours, mixing, grinding, the resulting mixture was being stirred, Fe _a Zr _b O _c alloy powder was obtained (a = 55 here, b = 10, c = 35 ). FIG. 1 shows an electron micrograph showing the particle structure of this Fe _a Zr _b O _c alloy powder.

The Fe _a Zr _b O _c alloy powder obtained by the mechanical alloying is heated in air at 100 ° C. for 2 hours to oxidize the surface to form an insulating layer made of an oxide. Polystyrene resin (using xylene as solvent)
Was added to the Fe _a Zr _b O _c alloy powder in an amount of 50 vol% by volume to obtain a slurry. Then, this slurry was repeatedly passed through a three-roll mill, and when the slurry became powdery, kneading was terminated to obtain a composite powder composed of Fe _a Zr _b O _c alloy powder and polystyrene resin. Then, the obtained composite powder was placed in a dryer having an ambient temperature of 80 ° C. for 12 hours to be dried, and xylene was evaporated. Next, a disk-shaped molded body is produced from the dried composite powder by using a press molding machine, and the molded body is heated at 150 ° C. for 1 hour to obtain an F having an outer diameter of 15 mm and a thickness of 3 mm.
An e-Zr-O polystyrene resin composite material was obtained. FIG. 2 shows an electron micrograph showing the particle structure on the surface of this Fe-Zr-O polystyrene resin composite material.

Example 2 The Fe _a Zr _b O _c alloy powder obtained by the mechanical alloying is heated in air at 120 ° C. for 4 hours to oxidize the surface to form an insulating layer made of an oxide. Fe-Zr- in the same manner as in Example 1 except that
O polystyrene resin composite material was obtained.

Comparative Example Conventionally, as a magnetic material used in the highest frequency band, there is Ni ferrite used as an antenna material for pagers. Therefore, Ni ferrite (composition: Fe ₂ O ₃ = 48mo) used in a Motorola pager (resonance frequency 172 MHz).
1%, NiO = 47 mol%, SiO ₂ = 2 mol%,
PbO ₂ = 3 mol%) from φ8.0-φ4.0-t1.5
A ring-shaped sample of mm and a disk sample of φ15.0-t2.0 mm were cut out to obtain a magnetic material for comparison.

(Test 1) The composite materials obtained in Examples 1 and 2 and the magnetic materials obtained in Comparative Examples were examined for specific resistance, magnetic permeability, and Q as a magnetic material. The specific resistance here is
Carbon double-sided tape (manufactured by Nisshin EM Co., Ltd.) was attached to both sides of the disk sample, and measurement was performed using a super mega ohm meter (Model SM-9E manufactured by Toa Denpa Kogyo Co., Ltd.). For permeability and Q as a magnetic material, a ring-shaped sample of φ8.0-φ4.0-t1.5 mm and a disc sample of φ15.0-t2.0 mm were cut out from a disk sample, and a material analyzer was used. (Hewlett-Packard, 4291A) frequency 1MHz ~
It was measured up to 1.8 GHz. The results are shown in FIGS.
Shown in.

FIG. 3 is a graph showing the relationship between the dielectric constant (ε) and the frequency. FIG. 4 shows Q (Q
It is a graph which showed the relationship between (epsilon) and frequency. Figure 5
6 is a graph showing the relationship between magnetic permeability (μ) and frequency.
FIG. 6 is a graph showing the relationship between Q (Qμ) as a magnetic material and frequency.

As is clear from the results shown in FIG. 3, the composite material obtained in Example 1 has the same dielectric property as the magnetic material of the comparative example, the heating temperature of the alloy powder is high, and It was found that the composite material of Example 2 in which the heating time was lengthened had a smaller dielectric constant than those of Example 1 and Comparative Example. Further, as is clear from the results shown in FIG. 4, the composite materials of Examples 1 and 2 have a larger Q ε and exhibit excellent loss characteristics at a high frequency of about 800 MHz or higher than the magnetic material of the comparative example. I understood.

Further, as is clear from the results shown in FIG. 5, the composite materials of Examples 1 and 2 exhibit stable magnetic permeability at high frequencies of about 800 MHz or higher, while the magnetic properties of the comparative example are high. As the material increases in frequency,
The magnetic permeability is low. Further, it was found that the composite material of Example 1 had a larger magnetic permeability than the magnetic material of Comparative Example at a high frequency of about 1500 MHz or more. In addition, as is clear from the results shown in FIG.
It was found that the composite material (1) had a larger Qμ than the magnetic material of the comparative example at a high frequency of about 400 MHz or higher.

(Test 2) In an Fe-Zr-O silicone resin composite material obtained by dispersing, kneading and molding an alloy powder represented by Fe _a Zr _b O _c in a silicone resin in the same manner as in Example 1 above. , Fe atomic% 45 or more 100
Below, the atomic% of Zr is 5 or more and 20 or less, and the atomic% of O is 1
Test pieces were prepared by changing the range of 5 or more and 45 or less (Sample Nos. 1 to 15). Then, in each test piece, the composition ratio of the alloy powder represented by Fe _a Zr _b O _c contained,
The μ ′ at 100 MHz and 500 Hz at room temperature and the Qμ at 100 MHz, 500 Hz and 1 GHz at room temperature were examined. The measurement results are shown in Table 1 and FIGS.

[0038]

[Table 1]

FIG. 7 shows the composition of each Fe-Zr-O silicone resin composite material and Fe silicone resin composite material.
FIG. 8 is a triangular composition diagram showing the composition ratio of the contained alloy powder represented by Fe _a Zr _b O _c and μ ′ at 100 MHz at room temperature, and is added to the upper part of each point (•) showing the composition ratio in FIG. 7. The given value is μ '. Fig. 8 shows each Fe-Z
In the r—O silicone resin composite material and the Fe silicone resin composite material, the composition ratio of the alloy powder represented by Fe _a Zr _b O _c and the Q at 100 MHz at room temperature
FIG. 9 is a triangular composition diagram showing μ, and the value attached to the upper part of each point (·) showing the composition ratio in FIG. 8 is Qμ.

FIG. 9 shows the composition of each Fe-Zr-O silicone resin composite material and Fe silicone resin composite material.
FIG. 10 is a triangular composition diagram showing the composition ratio of the contained alloy powder represented by Fe _a Zr _b O _c and μ ′ at 500 MHz at room temperature, which is added to the upper part of each point (•) showing the composition ratio in FIG. 9. The given value is μ '. Fig. 10 shows each Fe-
FIG. 11 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a Zr _b O _c and the Qμ at 500 MHz at room temperature in the Zr—O silicone resin composite material and the Fe silicone resin composite material. The value attached to the upper part of each point (•) indicating the composition ratio is Qμ. FIG. 11 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a Zr _b O _c contained in each Fe-Zr-O silicone resin composite material and the Fe silicone resin composite material and the Qμ at 1 GHz at room temperature. And Figure 1
1, the value attached to the upper part of each point (•) indicating the composition ratio is Qμ.

As is clear from Table 1 and FIGS. 7 to 11, the Fe-Zr-O silicone resin composite materials of the sample Nos. 1 to 13 of the example of the present invention are the sample No. of the comparative example. It was found that the Qμ was larger at 100 MHz, 500 MHz, and 1 GHz than the Fe silicone resin composite material of 14 to 15. Next, FIG. 8 and FIG.
Considering the results shown in, Q μ at a frequency of 100 MHz
In order to make ≧ 100, the composition range a of A is 4 in atomic%.
The range of 9 ≦ a ≦ 87 is preferable, and 500 MH
To make Q μ ≧ 40 at the frequency of z, 45
It is more preferable to set the range of ≦ a ≦ 65. Also,
To make Q μ ≧ 120 at the frequency of 100 MHz,
The composition range b of M is preferably in the range of 3 ≦ b ≦ 12 in atomic%. Furthermore, at a frequency of 100 MHz, Q μ ≧ 10
In order to obtain 0, the composition range c of O in atomic% is 10 ≦ c
It is preferable that the range is ≦ 50, and in order to satisfy Q μ ≧ 40 at a frequency of 500 MHz, 30% in atomic%
The range of c ≦ 45 is preferable.

(Test 3) An alloy powder represented by Fe _a W _b O _c was dispersed in a silicone resin in the same manner as in Example 1 above.
In the Fe-W-O silicone resin composite material obtained by kneading and molding, the atomic% of Fe is 55 or more and 75 or less, W
Atomic% of 5 to 20 and O atomic% of 15 to 35
The test pieces were made by changing them in the following ranges (Sample Nos. 16 to 25). Then, in each test piece, the composition ratio of the contained alloy powder represented by Fe _a W _b O _c and the Qμ at 1 GHz at room temperature were examined. The measurement results are shown in Table 2 and FIG.

[0043]

[Table 2]

FIG. 12 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a W _b O _c and the Qμ at 1 GHz at room temperature in each Fe-W-O silicone resin composite material, In FIG. 12, the value attached to the upper part of each point (•) indicating the composition ratio is Qμ.

As is apparent from Tables 1 and 2 and FIG. 12, sample Nos. 16 to 25, which are examples of the present invention.
It was found that the Fe-W-O silicone resin composite material of No. 2 has a larger Qμ at 1 GHz, as compared with the Fe silicone resin composite materials of Comparative Example samples Nos. 14 to 15.

( Example 3) Electrolytic iron (manufactured by Toho Zinc Co., Ltd., 200 mesh pass)
9.860 g and zirconium oxide (made by No. 1 rare element, 4
5μm pass) 4.944g and zirconium 2.196g
Were weighed and put in a stainless steel (SUS304) pot (internal volume: 170 ml), and then an inert gas was sealed therein, and a mechanical alloying was performed. Mental alloying is a high-energy planetary ball mill (Kurimoto Iron Works)
238 g of stainless steel balls (diameter 4 mm) made of the same material as the pot were put in the pot, and the centrifugal acceleration was 100 G,
Rotation speed / revolution speed = 448 rpm / 588 rpm, mixing, crushing, and stirring were performed for 8 hours, and Fe ₅₅ Zr
₂₀ O ₂₅ alloy powder was obtained. FIG. 13 shows the result of the X-ray diffraction test of the Fe ₅₅ Zr ₂₀ O ₂₅ alloy powder obtained in Example 3.

( Example 4) Electrolytic iron (manufactured by Toho Zinc Co., Ltd., 200 mesh pass) 1
3.044 g and zirconium oxide (made by No. 1 rare element, 4
5μm pass) 2.398g and weigh these, stainless steel (SUS304) pot (internal volume 170ml)
Then, 1.577 g of O ₂ gas was enclosed, and mechanical alloying was performed. For the mechanical alloying, a high energy type planetary ball mill (Kurimoto Iron Works Co., Ltd.) is used, and a stainless steel ball (diameter 4 m) made of the same material as the pot is used in the pot.
m) is put in 238g, centrifugal acceleration 100G, rotation speed /
Fe ₆₀ Zr ₅ O ₃₅ alloy powder was obtained by mixing, pulverizing, and stirring at orbital speed = 448 rpm / 588 rpm for 8 hours. The result of the X-ray diffraction test of the Fe ₆₀ Zr ₅ O ₃₅ alloy powder obtained in Example 4 is also shown in FIG. 13.

[0048] As is clear from the results of X-ray diffraction test shown in FIG. 13, and _Fe 55 _Zr 20 _{O 25} alloy powder instances 3, the _Fe 60 _Zr 5 _{O 35} alloy powder illustrative 4, IL raw material It can be seen that it shows a similar X-ray diffraction pattern, although it was obtained by mechanical alloying with.

( Examples 5 to 9) Electrolytic iron (manufactured by Toho Zinc Co., Ltd., 200 mesh pass)
7.935 g and hafnium oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd., 2 μm) 9.065 g were weighed, and these were made in a stainless steel (SUS304) pot (capacity 170 m).
l) and then filled with an inert gas, and the mechanyl alloying time is 0.5 hours, 2 hours, 8 hours, 16 hours,
Change the 60 hours, it carried out mixing, grinding, stirring, Fe _a
Hf _b O _c alloy powder (here, a = 54.9, b = 1
1, c = 34.1. ) Got.

For the mechanical alloying here, a high energy type planetary ball mill (Kurimoto Iron Works Co., Ltd.) was used, and a stainless steel ball (diameter 4 mm) made of the same material as the pot was used in the pot.
238 g was put into the solution, and the centrifugal acceleration was 100 G and the rotation speed / revolution speed was 448 rpm / 588 rpm. The Fe _a Hf _b O _c alloy powder of Example 5 was obtained when the mechanical alloying time was 0.5 hours, and the example 6 was obtained when the mechanical alloying time was 2 hours.
Of _Fe a _Hf b _{O c} alloy powder, Fe _a instances 7 those obtained when 8 hours time mechanical alongs
Hf _b O _c alloy powder, mechanical along time 16
The result obtained when the time is set is Fe _a Hf _b of Example 8.
The Fe _a Hf _b O _c alloy powder of Example 9 was obtained by setting the O _c alloy powder and the mechanical alloying time to 60 hours. The results of the X-ray diffraction test of the Fe-Hf-O alloy powders obtained in Examples 5 to 9 are shown in Fig. 14.

As is clear from the results shown in FIG. 14, Fe under the same conditions except that the mechanical alloying time is different.
_{When an a} Hf _b O _c alloy powder is produced, Hf and O are taken into Fe as the mechanical alloying time increases, and the peaks at 2θ = 55 ° and 2θ = 100 ° become smaller, It can be seen that alloying is progressing.

(Embodiment 10) A liquid quenching apparatus having a structure in which Co powder and Fe powder are arc-melted as raw materials, and a crucible equipped with a quartz nozzle and a Cu roll installed below the crucible are installed in a vacuum atmosphere. By a liquid quenching method using a vacuum of 3 × 10 ⁻⁵ Torr, an Ar partial pressure of 50 cmHg, a quartz nozzle injection pressure of 0.4 kgf / cm ² , and a Cu roll rotation speed of 3000 rpm. The alloy ribbon of the composition is manufactured, and these are crushed to make Fe-Co.
An alloy powder was obtained, and Hf powder and H were added to this Fe-Co alloy powder.
Mechanical alloying was performed by mixing fO ₂ powder, CoO powder and the like. The apparatus used for mechanical alloying and the kneading conditions were the same as in Example 1.

FIG. 15 shows the Co obtained by the above-mentioned manufacturing method.
FIG. 16 shows an X-ray diffraction pattern of a mechanical alloy treated powder sample of each composition of —Fe—Hf—O system (hereinafter, abbreviated as Co—Fe—Hf—O system MA powder sample). X of Co-Fe powder sample obtained by crushing a ribbon obtained by arc-melting a mixture of Fe powder and quenching the liquid.
FIG. 17 shows a line diffraction pattern, and FIG. 17 shows a mechanical alloy-treated powder sample (hereinafter, Co-Fe-Hf) obtained by using the Co-Fe powder sample having the X-ray diffraction pattern shown in FIG.
It is abbreviated as -O (Co-FeRQ) MA powder sample. ) X
A line diffraction pattern is shown. The structure of the mechanical alloy powder sample (Co-Fe-Hf-O-based MA powder sample) shown in FIG. 15 is Fe (bcc) in the case of Co-Fe-Hf-O-based,
Fe (bcc) + HfO ₂ , Co (fcc) + HfO ₂ ,
It can be classified into four diffraction patterns of Co (fcc) + HfO ₂ + CoHf. The bcc structure, the fcc structure, or a mixture thereof may be considered, and the tendency is seen from these figures, a diffraction pattern of Fe (bcc) is shown when HfO ₂ is not used as a raw material. If Fe powder is not used for Co (fcc) + HfO
₂ shows the diffraction patterns of Co (fcc) + HfO ₂ + CoHf. In the case of the mechanical alloy treated powder sample (Co-Fe-Hf-O (Co-FeRQ) MA powder sample) shown in FIG. 17, there is a similar tendency, and Fe (bc
c), Fe (bcc) + HfO ₂ diffraction patterns were obtained.

The liquid rapidly crushed Co-F shown in FIG.
Looking at the crystal structure of the e powder sample, when the ratio of Co to Fe is 75% to 85%, both the diffraction lines of Fe and Co are obtained, and when it is 85% or more, the diffraction pattern of only Co is shown. There is. In the other compositions, a diffraction pattern of only Fe was shown. However, Co-Fe-Hf- shown in FIG.
In the O (Co-FeRQ) MA powder sample, Fe (bc
c) and Fe (bcc) + HfO ₂ diffraction patterns. This result shows that Co-F with a high Co ratio is used.
e shows that the structure of the powder changed during the mechanical alloy treatment, and during the mechanical alloy treatment, the pot,
It is considered that Fe was invaded from the ball, Co was attached to the pot, and adhered to the ball.

18 to 25 show Co-Fe-Hf-O type MA powder samples and Co-Fe-Hf-O (Co-FeRQ) M.
The resin composite sample was formed using the A powder sample, and the results of measuring the magnetic properties of these samples are shown. Here, in order to prepare a resin composite sample, the above-mentioned Co-Fe-Hf-O-based M
A powder sample and Co-Fe-Hf-O (Co-FeRQ) MA
The powder samples were added to the silicon resin so as to be 50 vol% to prepare respective resin composite samples.

FIG. 18 shows the value of the real part (μ ′) of the magnetic permeability of the Co—Fe—Hf—O type MA powder resin composite sample of each composition at a frequency of 50 MHz, and FIG. 20 shows the value at a frequency of 50 MHz. , Co-Fe-Hf-O (C
The value of the real part (μ ′) of the magnetic permeability of the o-FeRQ) MA powder resin composite sample is shown. Μ'of the Co-Fe-Hf-O-based MA powder resin composite sample increases with a decrease in oxygen content,
When the composition of e was 10 atomic%, it tended to increase. On the other hand, the Co composition of the Co-Fe-Hf-O (Co-FeRQ) MA powder resin composite sample showed a peak of 3.8 at around 50 to 60 atomic%.

FIG. 19 shows the results of f (Q μ = 100) of the Co-Fe-Hf-O type MA powder resin composite sample, and FIG. 21 shows Co-Fe-Hf-O (Co-FeRQ). The result of f (Q μ = 100) of the MA powder resin composite sample is shown. f
The value of (Q μ = 100) is 496 MHz for the composition of Co ₆₀ Hf ₁₀ O _{30 in} the Co—Fe—Hf—O type MA powder resin composite sample, whereas the value of Co—Fe—Hf-
O (Co-FeRQ) In MA powder resin complex _samples, 650M with the composition of Co ₅₀ Fe _{10 Hf 10 O 30}
Hz, which is a dramatic improvement over the value of about 260 MHz, which is the value of the Fe-Hf-O-based MA powder resin composite sample. What can be said in common to these two systems is that good results are shown in a region where the oxygen composition is high and the Fe composition is low.

FIG. 22 shows the value of ε'of the magnetic permeability of the Co-Fe-Hf-O type MA powder resin composite sample of each composition at the frequency f of 50 MHz, and FIG. 24 shows the value at the frequency f of 50 MHz. , Co-Fe-Hf-O (C
The value of ε'of the o-FeRQ) MA powder resin composite sample is shown. In addition, in FIG. 23, when the frequency f is 50 MHz,
The values of Qε of the magnetic permeability of the Co-Fe-Hf-O-based MA powder resin composite samples of the respective compositions are shown.
Co-Fe-Hf-O (Co-F of each composition in MHz
The value of Qε of the eRQ) MA powder resin composite sample is shown. C
The value of ε'of the o-Fe-Hf-O-based MA powder resin composite sample tended to decrease as the proportion of oxygen decreased. Qε
Shows the maximum value of 56.2 in the composition of Co ₆₀ Fe ₁₀ Hf ₁₀ O ₂₀ .

[0059]

Composite material for a high frequency having a soft magnetic and dielectric properties of the present invention described above, according to the present invention includes a small synthetic resin dielectric loss, the composition formula is represented by A _a M _b O _c, a M Zr
Alternatively, W is set, and the composition range a of A is 45% by atomic%.
≦ 65, the composition range c of O is 30% in atomic% and 30 ≦ c ≦ 45.
The composite resistance of the obtained composite material is about 10 ⁸ Ω · cm or more, and the dielectric properties of the synthetic resin as an insulator (dielectric) are It can have the soft magnetic characteristics of the soft magnetic alloy powder, and in particular, in the high frequency band of several hundred MHz or more, not only the magnetic characteristics but also the high Q, for example, 1 GH
In z, Q = 30 or more, and it is possible to use in the several hundred MHz to GHz band, which cannot be achieved by the conventional magnetic material. Further, since the soft magnetic alloy powder is dispersed in the synthetic resin, the composite material for high frequencies is easier to mold than the case where it is composed only of the soft magnetic alloy powder.

Therefore, the high-frequency composite material of the present invention can be easily formed into a desired shape such as a rod shape as compared with the thin film shape of the conventional material.
Or as the core of a magnetic head or the core of a transformer,
Further, it can be widely applied as a magnetic component such as a magnetic needle of a pulse motor. Further, it is possible to obtain magnetic parts having excellent magnetic properties at high frequencies and low dielectric loss as compared with conventional materials, and further miniaturization of these magnetic parts can be achieved. By manufacturing an antenna for a liquid crystal television by using the material, the transmission / reception level can be improved and the antenna can be downsized. Further, in the production method of the present invention, the synthetic resin having a small dielectric loss as described above and the soft magnetic alloy powder having the composition formula represented by A _a M _b O _c are compounded.
It can be suitably used for producing a high frequency composite material having soft magnetism and dielectric properties.

Next, in the above composition formula, A is F
Using e and Co, the composition formula in that case is (Fe _100-x C
_{o x) a M b O c} (M is represented by Zr or W), can also be x indicating the composition ratio mixing the components to be in the range of 0 <x ≦ 90. With such a composition, in particular, the value of Qε can be improved and the frequency characteristic of Qμ can be improved.

[Brief description of drawings]

FIG. 1 is an electron micrograph showing a particle structure of a Fe _a Zr _b O _c alloy powder obtained in Example 1.

FIG. 2 is an electron micrograph showing a particle structure on the surface of the Fe—Zr—O polystyrene resin composite material obtained in Example 1.

FIG. 3 is a graph showing the relationship between dielectric constant (ε) and frequency.

FIG. 4 is a graph showing the relationship between Q (Qε) as a dielectric and frequency.

FIG. 5 is a graph showing the relationship between magnetic permeability (μ) and frequency.

FIG. 6 is a graph showing the relationship between Q (Qμ) as a magnetic material and frequency.

FIG. 7: F contained in each Fe-Zr-O silicone resin composite material and Fe silicone resin composite material
FIG. 3 is a triangular composition diagram showing a composition ratio of an alloy powder represented by e _a Zr _b O _c and μ ′ at 100 MHz at room temperature.

FIG. 8: F contained in each Fe—Zr—O silicone resin composite material and Fe silicone resin composite material
FIG. 3 is a triangular composition diagram showing a composition ratio of an alloy powder represented by e _a Zr _b O _c and Qμ at 100 MHz at room temperature.

FIG. 9: F contained in each Fe-Zr-O silicone resin composite material and Fe silicone resin composite material
FIG. 3 is a triangular composition diagram showing a composition ratio of an alloy powder represented by e _a Zr _b O _c and μ ′ at 500 MHz at room temperature.

FIG. 10: Fe-Zr-O silicone resin composite material,
FIG. 3 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a Zr _b O _c contained in the Fe silicone resin composite material and the Qμ at 500 MHz at room temperature.

FIG. 11: Fe-Zr-O silicone resin composite material,
FIG. 3 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a Zr _b O _c contained in the Fe silicone resin composite material and the Qμ at 1 GHz at room temperature.

FIG. 12 is a triangular composition diagram showing the composition ratio of the alloy powder represented by Fe _a W _b O _c contained in each Fe—W—O silicone resin composite material and the Qμ at 1 GHz at room temperature.

13 is a diagram showing the results of an X-ray diffraction test of the Fe ₅₅ Zr ₂₀ O ₂₅ alloy powder of Example 3 and the Fe ₆₀ Zr ₅ O ₃₅ alloy powder of Example 4. FIG.

FIG. 14 is a diagram showing the results of an X-ray diffraction test of Fe—Hf—O alloy powders obtained in Examples 5-9.

FIG. 15 is a diagram showing an X-ray diffraction pattern of a Co—Fe—Hf—O-based MA powder sample.

FIG. 16 is a view showing an X-ray diffraction pattern of a Co—Fe powder sample obtained by pulverizing a ribbon obtained by rapidly cooling Co powder and Fe powder by liquid.

FIG. 17 is a Co showing the X-ray diffraction pattern shown in FIG.
-Fe-Hf-O (C
It is a figure which shows the X-ray-diffraction pattern of the o-FeRQ) MA powder sample.

FIG. 18: Co of each composition at a frequency of 50 MHz
It is a figure which shows the value of the real part of the magnetic permeability of a -Fe-Hf-O type MA powder resin composite sample.

FIG. 19 is a diagram showing the results of f (Q μ = 100) of a Co—Fe—Hf—O-based MA powder resin composite sample.

FIG. 20: Co of each composition at a frequency of 50 MHz
It is a figure which shows the value of the real part of the magnetic permeability of a -Fe-Hf-O (Co-FeRQ) MA powder resin composite sample.

FIG. 21: Co-Fe-Hf-O (Co-FeRQ) MA
It is a figure which shows the result of f ( Qmicro = 100) of a powder resin complex sample.

FIG. 22 is a diagram showing a value of ε ′ of magnetic permeability of a Co—Fe—Hf—O-based MA powder resin composite sample of each composition at a frequency f of 50 MHz.

FIG. 23 is a diagram showing a value of Qε of magnetic permeability of a Co—Fe—Hf—O-based MA powder resin composite sample of each composition at a frequency f of 50 MHz.

FIG. 24 is a diagram showing a value of ε ′ of a Co—Fe—Hf—O (Co—FeRQ) MA powder resin composite sample of each composition at a frequency f of 50 MHz.

FIG. 25 is a diagram showing the values of Qε of Co-Fe-Hf-O (Co-FeRQ) MA powder resin composite sample of each composition at a frequency f of 50 MHz.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Makino 1-7 Yukiya Otsuka-cho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Teruyoshi Kubogawa 1-7 Otsuka-cho, Yukiya, Ota-ku, Tokyo Al (56) References JP 64-28301 (JP, A) JP 6-316748 (JP, A) JP 3-10001 (JP, A) (58) Fields investigated (58) Int.Cl. ⁷ , DB name) H01F 1/12-1/38

Claims (3)

(57) [Claims] 1. A composition formula is A _a M _b O _c (wherein A represents at least one element selected from the group consisting of Fe, Co and Ni, or a mixture thereof,
M represents at least one element selected from Zr and W or a mixture thereof. ), The composition range of A above
a in atomic% is 45 ≦ a ≦ 65, and the O composition range c
A high-frequency composite material having a soft magnetic property and a dielectric property, which is composed of a soft magnetic alloy powder having a child content of 30 ≦ c ≦ 45 and a synthetic resin. 2. A is composed of Fe and Co, a composition formula is represented by (Fe _100-x Co _x ) _a M _b O _c , and x is 0 <x ≦ 90. A high frequency composite material having soft magnetic properties and dielectric properties according to claim 1 . 3. A composite material for a high frequency having a soft magnetic and dielectric properties according to claim 1 or 2, wherein an insulating layer on the surface of the soft magnetic alloy powder is formed.