CN102132456A - Magnetic composite body for antenna and antenna element using same - Google Patents
Magnetic composite body for antenna and antenna element using same Download PDFInfo
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- CN102132456A CN102132456A CN2009801326320A CN200980132632A CN102132456A CN 102132456 A CN102132456 A CN 102132456A CN 2009801326320 A CN2009801326320 A CN 2009801326320A CN 200980132632 A CN200980132632 A CN 200980132632A CN 102132456 A CN102132456 A CN 102132456A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q7/00—Loop antennas with a substantially uniform current distribution around the loop and having a directional radiation pattern in a plane perpendicular to the plane of the loop
- H01Q7/06—Loop antennas with a substantially uniform current distribution around the loop and having a directional radiation pattern in a plane perpendicular to the plane of the loop with core of ferromagnetic material
- H01Q7/08—Ferrite rod or like elongated core
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
- H01F1/37—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q7/00—Loop antennas with a substantially uniform current distribution around the loop and having a directional radiation pattern in a plane perpendicular to the plane of the loop
- H01Q7/06—Loop antennas with a substantially uniform current distribution around the loop and having a directional radiation pattern in a plane perpendicular to the plane of the loop with core of ferromagnetic material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
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Abstract
A graft copolymer (P) is obtained by graft-polymerizing 18-67 parts by mass of a monomer (B) to 100 parts by mass of a polymer (A). The polymer (A) is obtained by polymerizing an alpha-olefin, a conjugated diene, an unsaturated cyclic hydrocarbon or an ethylenically unsaturated bond-containing aromatic monomer. The monomer (B) is composed of an aromatic monofunctional ethylenically unsaturated monomer (b1) and a bifunctional ethylenically unsaturated monomer (b2), and the mass ratio (b1)/(b2) is within the range from 70/30 to 95/5. A magnetic composite body for an antenna is obtained by kneading a composition which contains the graft copolymer (P) and a spinel ferrite powder (F) having an average particle diameter of 0.05-20 micrometers at a mass ratio (P)/(F) of from 10/90 to 60/40.
Description
Technical field
The present invention relates to a kind of antenna with magnetic compound and use its antenna element, described antenna can make big I with magnetic compound and be built in mobile phone etc. and the high antenna that gains.
Background technology
In recent years, in mobile phone, except that common airtime communication function, also require it to carry for example FM radio broadcasting, receive from the functions such as mobile radio telecommunications of VHF wave band across the TV broadcast signal or the UHF high frequency of UHF wave band.Especially in Multi-featured Mobile Terminal, owing to will carry a plurality of above-mentioned functions, therefore built-in antenna number quantitative change is many, in the miniaturization of terminal self, give and having problems aspect the outward appearance of aesthetic feeling.For fear of this problem, but require with the Multi-Function Antenna of monomer with regard to the wide electric wave of receive frequency range.What particularly require overlappingization of function is, distribute to the FM radio broadcasting the VHF wave band, distribute to two frequency bands of the UHF wave band of ground wave digital broadcasting.The electric wave that receive frequency range is wide, needing certainly can be corresponding to antenna each signal frequency, band frequency amplitude broad.But, for example the electric wave wavelength of UHF is tens of centimetres, and is relative therewith, and the electric wave wavelength of VHF reaches several meters, therefore making just can corresponding UHF and two frequency bands of VHF and when it is built in the limited portable terminal of volume with monomer, the miniaturization of antenna and the problem of widebandization can occur.
In general, antenna volume basically with long-pending 1/2 power (i.e. (ε μ) of the dielectric constant (ε) of the material that is used for the antenna magnetic core and magnetic permeability (μ)
1/2) be inversely proportional to.From this relation as can be seen, the material of high-k, high magnetic permeability is used for the antenna magnetic core, can makes antenna miniaturization.In addition, in employed frequency band, the dielectric absorption of antenna magnetic core and magnetic loss need enough little.These lose when big, can cause the smoothing of signal, Signal Degrade.
If make the compact outline of antenna merely, gain (perhaps also can be described as receiving and transmitting signal power, sensitivity) will reduce.Therefore, the magnetic core of a lot of the dielectric systems that have certain degree dielectric constant by use or the magnetic core of soft magnetism system have been proposed, reel thereon conductor or be formed on and be wound in spiral helicine conductor fig around the magnetic core, thus when keeping gain, can make the technology of antenna miniaturization.But, since high and enbrittle in the above-mentioned technology as the sintered body hardness of the soft magnetic bodies of small size antenna magnetic core, the shortcoming that processing characteristics is short of to some extent therefore had.As the technology of avoiding this shortcoming, disclose among the patent documentation 1-3 with the soft magnetic bodies powder in resin as magnetic compound, thereby obtain having high-k, the technology of the antenna magnetic core of high magnetic permeability, good forming ability.
In order to make the corresponding broadband of antenna, in the object frequency band, dielectric property (dielectric constant, dielectric absorption), magnetic characteristic (magnetic permeability, magnetic loss) must be stable.Therefore, antenna core material dielectric constant height, magnetic permeability height, dielectric absorption is low, magnetic loss is low, resin material magnetic permeability height, dielectric absorption as the core material basis are low, when these values are stablized in broadband, can obtain more small-sized corresponding wide band antenna.
Disclose the ferrite slurry that constitutes by soft magnetic ferrite and thermoplastic resin in the patent documentation 1, but this thermoplastic resin is for wanting polyamide, the polyphenylene sulfide of point selection with thermal endurance, intensity and rigidity.These resin dielectric absorptions are big, and its change along with frequency band simultaneously is also big.Therefore, owing to can in broadband, keep certain dielectric constant, so the antenna that the slurry of the ferrite in the patent documentation 1 can not obtain tackling widebandization.
Patent documentation 2 discloses a kind of magnetic composition that magnetic and thermoplastic norbornene resinoid, poly arylidene thio-ester etc. have the thermoplastic resin of circulus that contains.In addition, patent documentation 3 discloses a kind of resin combination that contains thermoplastic resins such as soft magnetic ferrite powder and poly arylidene thio-ester, polyamide, polyolefin.When thermoplastic resin was polyamide, the composition of patent documentation 2,3 was identical with the situation of patent documentation 1, can not obtain to tackle the antenna of widebandization.When thermoplastic resin was norbornene resin or polyolefin resin, the dielectric constant of these resins was low, dielectric absorption is low, dielectric absorption is also stable, inferred that therefore the composition of patent documentation 2,3 can tackle broadband.
As the norbornene resin material, the thermoplastic resin low as dielectric constant, that dielectric absorption is low, in addition also known have polytetrafluoroethylene, various liquid crystal polymer, a Noryl etc.These resin materials can obtain excellent dielectric property in broadband, but then because it has very upright and outspoken structure, therefore have fusing point or the very high characteristics of vitrification point.Therefore, when above-mentioned resin material is mixed with the magnetic powder, fusion under the temperature of melting point resin or vitrification point+50 ℃～+ 150 ℃ need be higher than, thereby in order fully to mix, need mix under quite high temperature, the result can cause the oxidative degradation of resin or soft magnetic bodies.Therefore, may damage the low magnetic loss of the antenna made from the soft magnet material that obtains.
On the other hand, because vistanex is different with norbornene resin material or resin material similarly, its fusing point is low, therefore can mix with the magnetic powder at a lower temperature.But in the reality, when the soft magnetic bodies powder was made the antenna magnetic core as antenna element in polypropylene, magnetic permeability was also littler than anticipation, can not realize enough miniaturizations.This phenomenon can be thought to make the result of resin deterioration, low-molecular-weightization owing to the mixing needed shearing force in resin time of soft magnetic bodies powder, allow resin undertake excessive heat load.If remedy the problems referred to above and increase the combined amount of soft magnetic bodies powder, then because magnetic hysteresis loss causes that gain reduces feasible gain such as phenomenon and significantly reduces.In sum, need a kind of high and can make the antenna magnetic compound of the little antenna of profile for the broadband electric wave from VHF to UHF gain.
Existing document
Patent documentation 1: Japanese patent laid-open 7-142228 communique
Patent documentation 2: Japanese patent laid-open 10-77381 communique
Patent documentation 3: the Japan Patent spy opens the 2000-91115 communique
Summary of the invention
The technical problem that invention will solve
The object of the present invention is to provide a kind of antenna with magnetic compound and use its antenna element, described antenna is high and can realize the antenna element miniaturization for the gain of the broadband electric wave from VHF to UHF with magnetic compound.
The technological means of technical solution problem
The inventor furthers investigate in order to address the above problem, found that in magnetic compound, the graft polymers (P) of ad hoc structure and specific spinel type ferrite powder (F) are mixed with special ratios, can address the above problem, thereby finish the present invention.
Promptly, the antenna magnetic compound of one embodiment of this invention, it is to contain mixing the forming of composition that graft copolymer (P) and average grain diameter are the spinel type ferrite powder (F) of 0.05～20 μ m, and the mass ratio of two kinds of compositions (P)/(F) is 10/90～60/40; Described graft copolymer (P) is that the monomer (B) of glycerol polymerization 18～67 mass parts on 100 mass parts polymer (A) obtains, described polymer (A) is that alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or the aromatic monomer that contains the vinyl unsaturated bond are polymerized, described monomer (B) is made of with difunctionality vinyl unsaturated monomer (b2) the simple function vinyl unsaturated monomer (b1) of the fragrant same clan, and the mass ratio of two monomers (b1)/(b2) is 70/30～95/5.
In an example, described spinel type ferrite powder (F) is used chemical formula MOFe
2O
3(M represents metallic element) expression, the electronegativity of described metallic element M is 1.55～2.33.
In an example, described spinel type ferrite powder (F) is used chemical formula MOFe
2O
3(M represents metallic element) expression, described metallic element M is at least a metallic element that is selected from manganese, nickel, copper or the zinc.
In an example, coat the surface of described spinel type ferrite powder (F) with silane coupler.
An other execution mode of the present invention provides a kind of antenna element, and it is on the surface of the formed body that above-mentioned antenna is obtained with the magnetic compound moulding or internal configurations conductor and the antenna element that obtains.
Another embodiment of the present invention provides the manufacture method of above-mentioned antenna with magnetic compound.This manufacture method is: preparation is with alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or contain the polymer (A) that the aromatic monomer polymerization of vinyl unsaturated bond obtains; Preparation is 70/30～95/5 monomer (B) by the simple function vinyl unsaturated monomer (b1) of the fragrant same clan and difunctionality vinyl unsaturated monomer (b2) mass ratio that constitute, (b1)/(b2); The described monomer (B) of glycerol polymerization 18～67 mass parts on the described polymer (A) of 100 mass parts, preparation graft copolymer (P); The spinel type ferrite powder (F) that with described graft copolymer (P) and average grain diameter is 0.05～20 μ m is 10/90～60/40 mixing with the mass ratio of (P)/(F), makes described antenna magnetic compound.
The invention effect
According to the present invention, can give play to following effect.
By the present invention, can access antenna with magnetic compound and use this antenna antenna element with magnetic compound, described antenna with magnetic compound when having high working property, (ε ' μ ') of antenna element capable of miniaturization index
1/2More than 3.0, can realize sufficient miniaturization; Simultaneously, in broadband, the rate of change μ of μ '
vIn ± 13%, can make and to tackle wide band antenna element.
Description of drawings
Fig. 1 (a) (b) is respectively vertical view, upward view according to the antenna element of execution mode.
Embodiment
Antenna to one of foundation embodiment of the present invention is elaborated with magnetic compound and antenna element below.
The antenna of present embodiment is to contain mixing the forming of composition of specific graft copolymer (P) and specific spinel type ferrite powder (F) as follows with magnetic compound (the following magnetic compound that also only is called), and the mass ratio of two kinds of compositions is set at (P)/(F)=10/90～60/40.Graft copolymer (P) is that the monomer (B) of glycerol polymerization 18～67 mass parts on 100 mass parts polymer as follows (A) obtains.
Polymer (A): alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or the aromatic monomer polymerization that contains the vinyl unsaturated bond are obtained.
Monomer (B): simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2) by the fragrant same clan constitute, and the mass ratio of two monomers (b1)/(b2) is 70/30～95/5.
Spinel type ferrite powder (F): average grain diameter is the spinel type ferrite powder of 0.05～20 μ m.
[graft copolymer (P)]
Described graft copolymer (P) is to obtain by being gone up by the polymer of grafting composition (A) to conduct as monomer (B) glycerol polymerization of grafting composition.
＜polymer (A) 〉
Constituting the polymer (A) of graft copolymer (P), can improve the dielectric property and the magnetic characteristic of graft copolymer (P), is to have thermoplastic main component, also is the main chain composition of graft copolymer (P).Specifically, polymer (A) is with alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or contains the aromatic monomer polymerization of vinyl unsaturated bond and the polymer that obtains.This polymer demonstrates low dielectric loss value, and has the little characteristic of dielectric loss variation in broadband, is absolutely necessary as the segment that constitutes graft copolymer (P).
As this polymer, polyolefin such as polyethylene, polypropylene, poly-1-butylene, polymethylpentene are for example arranged; Ethene-alpha-olefin copolymer such as ethylene-propylene copolymer, ethene-butene-1 copolymer; Ethene-cyclic olefine copolymers such as ethylene-norbornene copolymer; It with the dicyclopentadiene hydrogenation products of ring-opened metathesis polymers of the cycloolefin of representative; Polystyrene, poly-p-methylstyrene, poly-to ethyl styrene, poly-to polystyrenic copolymer such as t-butyl styrene; The SBC of the hydrogenation products of the hydrogenation products of styrene-isoprene-phenylethene two (three) block copolymers, s-B-S two (three) block copolymers etc. etc.In these polymer, consider, be preferably polypropylene, polymethylpentene etc. from the thermal endurance angle of the magnetic compound that finally obtains.These polymer can use with monomer, also can be use mixing two or more.In addition, can also use two or more polymer in advance by mixing, the mixed product of known method.
＜monomer (B) 〉
Monomer (B) is the composition of favorable dispersibility that makes the dissimilar materials of the flow behavior of graft copolymer (P) and mixing one-tenth, becomes the grafting composition of graft copolymer (P) after graft copolymerization.Usually, make dissimilar materials mixing, when being distributed in the polymer (A), its dispersiveness is the shearing force realization when mixing only.On the other hand, monomer (B) grafting is connected to the graft copolymer (P) that graft copolymer (A) upward obtains, in its structure, has firm cross-linked structure, therefore the construction unit that forms by monomer (B) can play the effect of aid dispersion when mixing dissimilar materials, can access the magnetic compound with polymolecularity.Monomer (B) specifically can be following monomer, and described monomer makes the dielectric absorption of graft copolymer (P) reach below 0.002 in the frequency band from VHF to UHF, has any cross-linked structure of the dispersed effect of raising spinel type ferrite powder (F) in the time of can being formed on graft copolymer (P) fusion.So long as can constitute the composition of three-dimensional crosslinking structure and get final product, particularly can use the simple function vinyl unsaturated monomer (b1) and the difunctionality vinyl unsaturated monomer (b2) of the fragrant same clan as above-mentioned monomer (B).
Simple function vinyl unsaturated monomer (b1) as the fragrant same clan has exemplified styrene; P-methylstyrene, styrene to being replaced by alkyl on the phenyl ring such as ethyl styrene; Alpha-alkyl such as AMS, α-ethyl styrene substituted phenylethylene; Ring such as vinyl naphthalene, vinyl anthracene is gone up by the Ppolynuclear aromatic monomer of vinyl substituted etc.Wherein, from the aspect that is easy to obtain, most preferably styrene.
In addition, as difunctionality vinyl unsaturated monomer (b2), it is preferably divinylbenzene, divinyl biphenyl, divinyl naphthalene, divinyl anthracene etc.Wherein, from the aspect that is easy to obtain, preferred especially divinylbenzene.
Graft copolymer (P) has monomer (B) grafting and is connected to structure on the polymer (A).Usually, in polymer (A), be dispersed with the compound of the cross-linked structure that forms by simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2), in heating process based on processing and forming operation, scolding tin etc., can show the thermoplasticity of polymer (A) strongly, cause resin flows, change of shape, resin attenuation etc. occur.Above-mentioned moulding product during as antenna element etc., can be deformed when being connected with substrate, wiring etc., possibly can't show the function of being expected.
Flowing and distortion during above-mentioned heating can be solved by monomer (B) grafting that is made of simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2) is connected in the polymer (A).The grafting connection that monomer (B) grafting is connected to polymer (A) is the free-radical polymerized property organic peroxide that adds in simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2) as the 3rd monomer, realizes by giving the peroxidating ability to the cross-linked structure that is formed by simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2).Be endowed the monomer (B) of peroxidating ability, addition reaction has taken place in mixing with polymer (A), can access monomer (B) grafting and be connected to graft copolymer (P) on the polymer (A).The addition of free-radical polymerized property organic peroxide is for can make graft copolymer (P) keep its shape to get final product when fusing point is above, as a rule, serve as an amount of about 0.5～3.0 quality % with simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2) total amount.
The simple function vinyl unsaturated monomer (b1) of the fragrant same clan in the monomer (B) is 70/30～95/5 with the mass ratio (b1)/(b2) of difunctionality vinyl unsaturated monomer (b2).Difunctionality vinyl unsaturated monomer (b2) than 5 quality % more after a little while because the dispersion effect of the spinel type ferrite powder (F) that causes based on the cross-linked structure of monomer (B) reduces, the result makes the magnetic permeability instability of the magnetic compound that makes.On the other hand, difunctionality vinyl unsaturated monomer (b2) than 30 quality % more for a long time, the mobile variation when graft copolymer (P) and spinel type ferrite powder (F) are mixing hinders the mixing and the dispersion of spinel type ferrite powder (F).
Polymer (A) is corresponding 18～67 mass parts monomers (B) of per 100 mass parts polymer (A) with the mass ratio of monomer (B).Monomer (B) than 18 mass parts more after a little while because the dispersion effect of the spinel type ferrite powder (F) that causes based on the cross-linked structure of monomer (B) reduces, the result makes the magnetic permeability instability of the magnetic compound that makes.On the other hand, monomer (B) than 67 mass parts more for a long time, the mobile variation when graft copolymer (P) and spinel type ferrite powder (F) are mixing hinders the mixing and the dispersion of spinel type ferrite powder (F).
Manufacturing---the graft copolymerization of＜graft copolymer (P) 〉
Grafting method when making graft copolymer (P) can be used any means such as known chain transfer method, ionization radiation method usually.In these methods, thereby from the grafting efficiency height, the secondary aggregation that do not take place to be caused by heat more effectively represents performance, the simple angle of manufacture method is considered the dipping glycerol polymerization method shown in being preferably as follows simultaneously.
When adopting dipping glycerol polymerization method, graft copolymer (P) can make usually with the following method.At first, with 100 mass parts by alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or contain the polymer (A) that the aromatic monomer of vinyl unsaturated bond constitutes and suspend in water the preparation aqueous suspension.Prepare the monomer that adds up to 5～400 mass parts (B) of simple function vinyl unsaturated monomer (b1) and difunctionality vinyl unsaturated monomer (b2) in addition.Preparation be dissolved with at least a free-radical polymerized property organic peroxide and for the decomposition temperature that obtains 10 hour half-life be the solution of 40～90 ℃ radical polymerization initiator.In this solution, described at least a free-radical polymerized property organic peroxide is 0.1～10 mass parts with respect to 100 mass parts monomers (B); Described radical polymerization initiator is 0.01～5 mass parts with respect to monomer (B) with 100 mass parts that free-radical polymerized property organic peroxide adds up to.This solution is joined in 5～400 mass parts monomers (B).
Then, the described solution that has added monomer (B) is joined in the aqueous suspension of described polymer (A), described at least a free-radical polymerized property organic peroxide is dipped in the polymer (A), then, do not causing that the temperature that makes this aqueous suspension under the condition that substantial radical polymerization initiator decomposes raises, make monomer (B) and free-radical polymerized property organic peroxide that copolymerization take place in polymer (A), obtain the grafting presoma.At last, this grafting presoma is mixing under 100～300 ℃ of fusions, thus can make graft copolymer (P) as target.
As monomer (B) and free-radical polymerized property organic peroxide are dipped in the polymer (A), in polymer (A), make monomer (B) copolymerization obtain the grafting presoma, obtain the method for graft copolymer (P) by above-mentioned grafting presoma, can use known heating mixed method.Specifically can exemplify the method for using the mixing such as closed mixing machine, pressure kneader, roller, single shaft or twin shaft screw extruder that possess heating function and mixing function.In these methods, owing to use the twin shaft screw extruder, supply with graft copolymer from main hopper, behind the melting mixing, the bar-shaped article shaped that spues from mould is easy and cheap by the method that the comminutor granulation obtains granulation thing (particle), is preferred therefore.As long as the temperature of this moment makes graft copolymer (P) fully softening, common scope at 150～300 ℃.
At this moment, the grafting presoma that will obtain by above-mentioned steps, and use alpha-olefin, conjugated diene, the unsaturated cyclic hydrocarbon different or contain the grafting presoma mixing that polymer that the aromatic monomer of vinyl unsaturated bond obtains is made with the polymer (A) in this grafting presoma, mixing under 150～300 ℃ of fusions, implement grafting and also can access graft copolymer (P).
Free-radical polymerized property organic peroxide is the compound that has the monomer characteristic and the organic peroxide characteristic of free redical copolymerization in the molecule concurrently, is preferably tert-butyl hydroperoxide acryloxy ethyl carbonate ester, tert-butyl hydroperoxide methacryloxyethyl carbonic ester, tert-butyl hydroperoxide allyl carbonate, tert-butyl hydroperoxide methacrylic carbonic ester etc.Wherein, be preferably tert-butyl hydroperoxide methacryloxyethyl carbonic ester especially.
The graft copolymer that so makes (P) shows the zone of monomer (B) based on size about 0.1～1.0 μ m and is distributed to form in the matrix that is formed by polymer (A).Because it is crosslinked that this zone is undertaken by difunctionality vinyl unsaturated monomer (b2), so not fusion and keep solid state when mixing.Therefore play the effect that grinds the secondary that spinel type ferrite powder (F) is condensed into down mixing, and help spinel type ferrite powder (F) to be distributed in the graft copolymer (P).The high dispersion state of this spinel type ferrite powder (F), even not using described graft copolymer (P) also can realize by using high moment of torsion, high rotary-type special mixing roll, but because will apply high shearing force this moment to molten resin, so strand is cut off, the resin flow raising.Therefore, though can access the magnetic compound of spinel type ferrite powder (F) favorable dispersibility, but the problem that mouldability that dielectric property that mechanical strength reduces, caused by the low-molecular-weightization of resin reduces, causes by flowing reduces can occur, thereby can not obtain small-sized antenna element.
Therefore, by using described graft copolymer (P) with specific cross-linked structure, can avoid the problems referred to above, can use cheap kneading device to realize high dispersion state, the resin deterioration that can suppress strand by resin to be cut off and cause, the magnetic compound that therefore can access performance height not only and have excellent reliability.
[spinel type ferrite powder (F)]
At the general soft magnetic ferrite that uses of the magnetic compound that is used for antenna.Soft magnetic ferrite be in the sintered body of metal oxide that with the iron oxide is main component crystal formation be cubic, ferrite with soft magnetism.The employed spinel type ferrite powder of the magnetic compound of present embodiment (F) is the ferrospinel with spinel type crystal structure, uses chemical formula MOFe
2O
3(M represents metallic element) expression.Here, M is preferably electronegativity at 1.55～2.33 metallic element.
In ferrospinel, exemplify the oxide of the multiple divalent metal in the periodic table of elements the 2nd～15 family as the metal oxide that can replace MO, but the metal M that constitutes in the present embodiment, described metal oxide MO is at least a metal that is selected among Cr, Mn, Fe, Mo, Cd, Pb, Ni, Cu, Sn, Zn and the Co.This metal M is the Pauling electronegativity at 1.55～2.33 metal, specifically, Cr 1.66, Mn 1.55, Fe 1.83, Mo 2.16, Cd 1.69, Pb 2.33, Ni 1.91, Cu 1.90, Sn 1.96, Zn 1.65 and Co 1.88 are (about the Pauling electronegativity, referring to Linus Pauling work, " theory of chemical bonds is crossed the threshold " that the positive husband of Junichiro Koizumi translates (upright altogether publish, 1971)).
Since the electronegativity of metal M get this scope than low value, therefore in the metal oxide (MO) in spinel type ferrite powder (F), key between metal-oxygen atom ionic got lower value, makes the surface free energy of spinel type ferrite powder (F) remain suitable value.Therefore, spinel type ferrite powder (F) is lower with the boundary strength of graft copolymer (P), and this can improve the compatibility with graft copolymer (P), and can obtain polymolecularity when mixing.And, in above-mentioned M, consider from angle as ferritic resistance sizes and the magnetic permeability stability broadband, be preferably manganese (Mn), nickel (Ni), copper (Cu) and zinc (Zn).Above-mentioned metal M can have only a kind ofly in spinel type ferrite powder (F), also can contain multiple.In addition, the trace meter oxide that unavoidably contains in the above-mentioned metal M, only however physics, the chemical feature of infringement spinel type ferrite powder (F) just can.
The ratio of metal oxide MO is preferably 17～55 quality %, more preferably 20～50 quality % in the spinel type ferrite powder (F).When the ratio of MO departs from this scope, can occur reducing, reducing for the variable quantity increase of frequency, the magnetic characteristic the magnetic loss increase such as the magnetic permeability of spinel type ferrite powder (F), in addition, the Curie temperature that spinel type ferrite powder (F) also may occur reduces, has problems aspect the magnetic characteristic stability when using the normal temperature left and right sides of magnetic compound.
As the manufacture method of spinel type ferrite powder (F), can adopt known manufacture methods such as dry method, coprecipitation, spray heating decomposition.For example, when adopting dry method, can fully mix with blenders such as ball mills by compounds such as the oxide of each element of deciding proportioning weighing, hydroxide, carbonate, oxalates, nitrate, then with pre-burning obtain behind the setting-up time that block is pulverized, classification, obtain powder.When adopting coprecipitation, can with press as the solution of water soluble salts such as the oxalates of each element of raw material, nitrate fixed proportioning mix, regulate pH etc. as required and make its precipitation; Filtering-depositing will obtain powder imposing a condition block pulverizing, the classification that obtain after the pre-burning then.When adopting spray heating decomposition, can this solution be imported, be sprayed in the heating furnace of design temperature, remove and desolvate, make the solute thermal decomposition, reclaim product, thereby obtain powder with containing the solution of each element with the same method preparation of coprecipitation.
The particle diameter of spinel type ferrite powder (F) for the average grain diameter that records by dynamic light scattering method at 0.05～20 μ m, be preferably 0.1～10 μ m.When the average grain diameter of this spinel type ferrite powder (F) was lower than 0.05 μ m, the surface area of the graft copolymer (P) that need soak into was excessive, can't obtain sufficient dispersiveness.On the other hand, when average grain diameter is higher than 20 μ m, promptly enable to obtain dispersion effect, also can not achieve the goal because magnetic permeability reduces.
The shape of spinel type ferrite powder (F) is considered from the easiness angle of mixing, being distributed to the graft copolymer (P), and it is spherical to spherical to be preferably class.
In addition, spinel type ferrite powder (F) is used the silane coupler clad surface, thereby can realize better dispersion.This is the coating scope that forms because of by the silane coupler between particle surface and graft copolymer (P), the median of getting the surface both free energy.As the silane coupler that is used for clad surface, in order to improve the compatibility with graft copolymer (P), the preferred organic silane compound that uses the aryl of alkyl with carbon number 6～22 or carbon number 8～14.Specifically, can exemplify out to the styryl triethoxysilane, to styryl trimethoxy silane, decyl trimethoxy silane etc.As the method that covers spinel type ferrite powder (F) with these silane couplers, can preferably use wet method, dry method, global approach known method such as (integral).
As mentioned above, with spinel type ferrite powder (F) during, make that coating 0.5～3.0 times of area with respect to spinel type ferrite powder (F) specific area adds silane coupler for well with the silane coupler clad surface.When coating area less than 0.5 times of spinel type ferrite powder (F) specific area, contribution for the surface free energy difference between graft copolymer (P) and spinel type ferrite powder (F) is little, can not get the magnetic compound of the favorable dispersibility of spinel type ferrite powder (F).On the other hand, when coating area greater than 3.0 times of spinel type ferrite powder (F) specific area, compare with the specific area of spinel type ferrite powder (F), dosage of silane coupling agent is excessive, therefore spinel type ferrite powder (F) is mixing in the graft copolymer (P) time, silane coupler comes off from the surface of spinel type ferrite powder (F), can not bring into play the effect that reduces the surface free energy difference between graft copolymer (P) and spinel type ferrite powder (F).In addition, the silane coupler that has come off is diffused in the graft polymers (P), shows the effect of plasticizer, causes that the thermal endurance of the article shaped that is obtained by magnetic compound reduces, magnetic characteristic (magnetic loss) reduces.
The spinel type ferrite powder (F) of the compatibility excellence of aforesaid and graft copolymer (P), because of with the high-affinity of graft copolymer (P), make mixing graft copolymer (P) and the needed mixing moment of torsion of spinel type ferrite powder (F) littler.Promptly can say so based on above-mentioned specific graft copolymer (P) and spinel type ferrite powder (F), can access the magnetic compound that shows the purpose antenna performance under the condition more slowly in heat, mechanicalness.The result can obtain the better magnetic compound of state, can access the small size antenna unit with excellent specific property, and then obtain small size antenna.
Described graft copolymer (P) with the proportioning of spinel type ferrite powder (F) is: the mass ratio of two compositions (P)/(F) is 10/90～60/40.When spinel type ferrite powder (F) was less than 40 quality %, the dielectric constant of the magnetic compound that makes and magnetic permeability reduced, and antenna element is difficult to abundant miniaturization.On the other hand, when spinel type ferrite powder (F) during more than 90 quality %, the illiquidity of magnetic compound may make mouldability, manufacturing worsen, and dielectric absorption and magnetic loss are increased, and the result can not fully gain to the broadband electric wave.
[antenna magnetic compound]
The antenna magnetic compound is by making graft copolymer (P) and spinel type ferrite powder (F) decide the recently mixing composition that contains described graft copolymer (P) and spinel type ferrite powder (F) of quality and obtain for aforesaid.At this moment, exemplify the mixing methods such as closed mixing machine, pressure kneader, roller, single shaft or twin shaft screw extruder of using as compounding process with heating function and mixing function.Particularly preferred compounding process is the method based on the twin shaft screw extruder, can with the same terms that obtains graft copolymer (P) under implement.
In addition, for the antenna magnetic compound, in the scope of not damaging its purpose, can add the additives such as deactivator of nucleator, lubricant, plasticizer, antioxidant, matal deactivator, ultra-violet absorber, fire retardant, colouring agent, catalyst.These additives can be mixing in advance, be formulated in the graft copolymer (P); Can also when graft copolymer (P) and spinel type ferrite powder (F) are mixing, add simultaneously.
Antenna magnetic compound of the present invention under the identical situation of magnetic content, is compared with the compound that uses other low dielectric absorption resins, because the dispersity of magnetic powder is good, therefore can show high magnetic permeability.At this moment, magnetic loss does not almost change.Thereby can seek the further miniaturization of antenna element.
In addition, as a rule, the electrical characteristics of material and magnetic characteristic for its material, are represented with complex dielectric permittivity and complex permeability that the general formula shown in following is represented.
Complex dielectric permittivity: ε=ε '+i ε "
Complex permeability: μ=μ '+i μ "
Here, real part ε ' among ε expression dielectric constant is according to imaginary part ε ", ε "/the dielectric absorption degree of ε ' expression material.This ε "/ε ' is usually as dielectric loss tan δ and well-known.As for μ, also identical with ε, μ ' represents magnetic permeability, μ "/degree of μ ' expression magnetic loss.
Therefore, antenna magnetic compound, ε ' are about 5～7, μ ' is about 1.5～2.5.Based on the effect of this dielectric constant and magnetic permeability, antenna element can miniaturization to 10 * 30～10 * 42 (unit: mm) size.In addition, because ε "/ε ' is about 0.03～0.05, μ "/μ ' is about 0.10～0.30, so dielectric absorption and magnetic loss are little, this variable quantity is also stable in broadband, therefore can keep high-gain.And then ε ' basic fixed in from VHF to UHF, the variation of μ ' about ± 10%, does not have big variation yet.Therefore, can realize the broadband electric wave is kept the small size antenna of high-gain with magnetic compound based on antenna.And then because antenna has thermoplasticity with magnetic compound, the manufacture method that therefore has high rate/low cost productions such as the enough injection molding methods of energy, extrusion moulding, pressurization pressing is made the advantage of antenna magnetic core.
[antenna element]
Antenna element of the present invention obtains at the surface or the internal configurations conductor of the formed body that described magnetic compound moulding is obtained.As the forming method of magnetic compound, can adopt known methods such as T type mouth method, expansion molding method, the roller method of forming, punch forming method, injection molding method, preferably use formed body to be difficult to the roller method of forming or the injection molding method of residual internal stress.As being disposed at formed body surface or conductor inside, can use the conductor of wire or punch metal shape.And then can also use picture (multilayer) printed circuit board (PCB) this, will be on formed body surface or innerly directly deposit or bury underground the conductor that diagram shape conductor that obtains and the through hole that is connected between each conductor combine.During as helical antenna, can use coated wires such as hot weld line around configuration with helical coil from the teeth outwards.Perhaps can also be shapes such as paster antenna.In addition, can also between formed body and conductor, form the film of nonmagnetic substance.The antenna that is applicable to present embodiment with one of example of the antenna element of magnetic compound as shown in Figure 1.
Antenna element shown in Figure 1 is that (Fig. 1 (a)) and the back side (Fig. 1 (b)) forms conductor fig 3a～3d and 4a～4c, just holds figure 6 and terminal figure 7 on the surface of magnetic core 1, be electrically connected with metallic conductor 5 between figure, form spirally-wound coil-conductor 2.In the example of indefiniteness, magnetic core 1 is a tabular.Form first control terminal 8, second control terminal 9, earth terminal 11 and input and output terminal 12 at the back side of magnetic core 1.First control terminal 8 directly is electrically connected with just holding figure 6, and second control terminal 9 is connected with first end figure 6 by the variable capacitance diode 10 of shaped like chips independent electronic element.And, be the structure that earth terminal 11 is connected with terminal figure 7, input and output terminal 12 is connected with conductor fig 4c.
Embodiment
Exemplify reference example, embodiment and comparative example below above-mentioned execution mode is carried out more specific description.
The assessment item and the test method of employed magnetic compound in embodiment and comparative example at first are described.
The evaluation of＜electrical characteristics and magnetic characteristic 〉
Have the excellent electrical characteristics and the antenna core material of magnetic characteristic in order when keeping antenna gain, to make antenna miniaturization, must to have.As the evaluation of electrical characteristics and magnetic characteristic, carried out based on the complex dielectric permittivity of bounce technique and the mensuration of complex permeability.Obtain ε ', ε by complex dielectric permittivity and complex permeability ", μ ' and μ ".In view of the above, be ε ' with the relative dielectric constant, be ε with the dielectric absorption "/ε ', be μ ' with the relative permeability, be μ with the magnetic loss "/μ ', these values are the mean value in measuring frequency band 77～990MHz.And, calculate (ε ' μ ')
1/2As the index that can make the antenna element miniaturization.In addition, common core material magnetic permeability in VHF reduces, antenna performance reduces.As the ability of this phenomenon of reply, with respect to the rate of change of the mean value of the μ ' in the described frequency band range as μ
v
The judgment standard of＜＜ε ', μ '〉〉
Zero: (ε ' μ ')
1/2More than 3.0.
*: (ε ' μ ')
1/2Less than 3.0.
＜＜ε ", μ " judgment standard
Zero: ε "/ε ' below 0.05 and μ "/μ ' is below 0.20.
*: ε "/ε ' greater than 0.05 or μ "/μ ' is greater than 0.20.
＜＜μ
vJudgment standard
More than zero :-13% ,+below 13%.
*: less than-13%, greater than+13%.
Can be described as because (ε ' μ ')
1/2More than 3.0, thereby can make the antenna element miniaturization.
And, can be described as because ε "/ε ' below 0.05, μ "/μ ' is below 0.20, thereby can access antenna element with high-gain.And, can also say so because μ
vScope-13%～+ 13%, thus can access stable antenna element in the service band scope with antenna gain.Can obtain following magnetic compound by all satisfying above-mentioned condition, described magnetic compound can access small size antenna unit stable in the service band scope, high-gain.
＜as the dispersed evaluation method of the spinel type ferrite powder (F) of magnetic powder 〉
In order to make magnetic compound demonstrate excellent dielectric property and magnetic characteristic, the dispersiveness that the spinel type ferrite powder in the magnetic compound (F) is distributed in the graft copolymer (P) is a key factor.The dispersiveness that spinel type ferrite powder in the magnetic compound (F) is distributed in the graft copolymer (P) is by the wettability decision of graft copolymer (P) with spinel type ferrite powder (F).
Graft copolymer (P) is undertaken by heat-resisting cyclic test with the infiltrating evaluation of spinel type ferrite powder (F), and described heat-resisting cyclic test is the crackle that observation is produced under 30 minutes state alternate repetition of 30 minutes state of-55 ℃ of maintenances and+105 ℃ of maintenances.The wettability of graft copolymer (P) and spinel type ferrite powder (F) can be used as their boundary strength and estimates.Boundary strength can be estimated indirectly by heat-resisting cyclicity.Period when observing crackle is during less than 500 times, and graft copolymer (P) is low with the boundary strength of spinel type ferrite powder (F), thereby we can say wettability and dispersed low.On the contrary, when also not observing crackle more than 500 times, boundary strength, wettability and the favorable dispersibility of graft copolymer (P) and spinel type ferrite powder (F) can obtain to demonstrate the magnetic compound of high dielectric property and magnetic characteristic.
＜＜dispersed judgment standard〉〉
Zero: heat-resisting cyclicity is more than 500 times.
*: heat-resisting cyclicity is less than 500 times.
Below as a reference example, the manufacture method of representing employed graft copolymer (P) in each example.
(reference example 1)
In internal volume is 5 liters stainless steel autoclave, add the 2500g pure water, and then dissolving 2.5g is as the polyvinyl alcohol of suspension.To wherein adding 700g polypropylene (" SunAllomer (サ Application ア ロ マ one) PM671A " SunAllomer (strain) system, MFR:7g/ (10min)), stir, disperse.In addition, with the benzoyl peroxide (trade name " NYPER BW " of 2.0g as radical polymerization initiator, day oil (strain) system, the water-containing products of purity 75%), 7.5g is as tert-butyl hydroperoxide methacryloxyethyl carbonic ester (day oil (strain) system of free-radical polymerized property organic peroxide, 40% toluene solution) is dissolved in the 60g divinylbenzene and 240g styrene as fragrant same clan vinyl monomer, this solution is put in the above-mentioned autoclave, stirred.
Then, the temperature of autoclave is warming up to 85～95 ℃, stirred 2 hours, thereby the fragrant same clan vinyl monomer that contains radical copolymerization initator and free-radical polymerised organic peroxide is impregnated in the polypropylene.Temperature is reduced to 75～85 ℃ then, under this temperature, keeps polymerization being finished in 5 hours, filter after washing, drying, obtain the grafting presoma.Then, this grafting presoma is extruded under 210 ℃ with LABO PLASTOMILL (ラ ボ プ ラ ス ト ミ Le) single shaft extruder (the smart mechanism of (strain) Japan is done made), carried out the grafting reaction, thereby obtain graft copolymer (P).
(reference example 2～10)
With the method identical, obtain belonging to the graft copolymer of the graft copolymer (P) that constitutes by various polymer (A) and monomer (B) with reference example 1.The structure of table 1 each polymer of expression (A).At this moment, in the polymer (A), during commercially available product, the monomer of segment is expressed as composition (1) and composition (2) with constituting separately when using the synthetic in advance copolymer that is made of a plurality of segments.In addition, table 2 expression is by the various combinations of polymer (A) and monomer (B) and the graft copolymer (P) that ratio constituted.
Table 1
The meaning of employed abbreviation is as described below in the table.
PP: acrylic resin " SunAllomer PM671A " (trade name, SunAllomer (strain) system)
TPX: poly 4-methylpene-1 resin " TPX RT18 " (trade name, Mitsui Chemicals (strain) system)
ZEONEX: norborneol alkene thermoplastic resin " ZEONEX RS420 " (trade name, Japanese ZEON (strain) system)
SEPS2007: styrene-ethylene-propylene-styrene copolymer resin " seputon (セ プ ト Application) " (trade name, (strain) Kuraray system)
SEPS2063: styrene-ethylene-propylene-styrene copolymer resin " seputon " (trade name, (strain) Kuraray system)
TTM1943: hydrogenation butadiene-styrene block copolymer resin: " Tuftec (タ Off テ Star Network) " (trade name, Asahi Chemical Industry's (strain) system)
EPR: ethylene-propylene rubber
BR: butadiene rubber
St: styrene
Table 2
The meaning of employed abbreviation is as described below in the table.
MeSt: p-methylstyrene
DVB: divinylbenzene
(reference example 11 and 12)
And the graft copolymer among the present invention (P) can be to mix two or more grafting precursors, and this mixing can also can be preferably mixing of easier mixing before grafting after grafting before grafting.At this moment, will obtain graft copolymer (P) before two kinds of thermoplastic resins in stage record and narrate respectively to (A1), (A2), shown its structure in the table 3.
Below as a reference example, represent employed spinel type ferrite powder in each example
(F) manufacture method.
(reference example 13～19)
To mix as the metal oxide powder of magnetic powder stock with the ratio shown in the table 3, after dehydration, the drying, under 800 ℃, 4 hours condition, in air, carry out precalcining.Then it is pulverized, calcine with the calcining heat shown in the table 3 then, thereby obtain the spinel type ferrite powder (F) of reference example 13～17.Be displayed in Table 3 and be soft magnetic powder (M).
(reference example 20)
In addition, spinel type ferrite powder (F) can use in advance with fixed mixed, the commercially available spinel type ferrite powder that is sintered into.To meet commercially available spinel type ferrite powder 20 expressions as a reference example of spinel type ferrite powder (F) in the table 3.
Table 3
The meaning of employed abbreviation is as described below in the table.
FLR-2C:Ni-Zn-Cu based ferrite powder (Dongguang (strain) system)
＜embodiment 1 〉
At first, with 36g to styrene trimethoxy silane (trade name " KBM1403 ", SHIN-ETSU HANTOTAI's chemical industry (strain) system) is dissolved in the 45mL methyl alcohol, the solution that obtains is mixed as the F5050b of the reference example 15 of spinel type ferrite powder (F) with 6kg, under 150 ℃, 1h condition, heat-treat, thereby obtain F5050b with the silane coupler clad surface.Then in the graft copolymer (P) that 4kg reference example 1 obtains, do respectively and mix 10g as 1 of antioxidant, 3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (trade name " Irganox1330 ", Ciba (strain) system), two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate (trade name " ADK STAB (ア デ カ ス タ Block) PEP-36 ", (strain) ADEKA system) is done the F5050b that mixes described clad surface again.The mixed thing of doing that obtains is expected that the feeding cylinder temperature is set at the coaxial twin shaft screw extruder of 210 ℃ screw diameter 30mm (TEX-30 α, (strain) JSW system), obtains magnetic compound.
＜embodiment 2～15 〉
By the spinel type ferrite powder shown in the table 3 (F) is mixed in the graft copolymer shown in the table 2 (P) with institute's certainty ratio, thereby obtain magnetic compound.In addition, spinel type ferrite powder (F) can use the silane coupler clad surface, can also mix multiple graft copolymer (P) simultaneously when mixing spinel type ferrite powder (F).The evaluation result of these magnetic compounds of table 4 expression.
Material described in the table is specific as follows described.
Decyl trimethoxy silane: (trade name " KBM3103 ", SHIN-ETSU HANTOTAI's chemical industry (strain) system)
3-glycidyl ether oxygen propyl trimethoxy silicane: (trade name " KBM403 ", SHIN-ETSU HANTOTAI's chemical industry (strain) system)
In table 4, the performance evaluation result of the antenna element that obtains with magnetic compound based on the antenna of the present invention among the embodiment 1～15 (ε ' μ ')
1/2All more than 3.0, ε simultaneously "/ε ' all below 0.05, μ "/μ ' is all below 0.20.This result shows, based on antenna compound of the present invention, can make the remarkable miniaturization of antenna element, can access the antenna element with high-gain simultaneously.And then, μ
vScope-13%～+ 13% shows, antenna compound of the present invention is the material that is suitable for showing the small size antenna unit of constant gain in broadband.
＜comparative example 1～8 〉
In comparative example 1～8, by with the spinel type ferrite powder shown in the table 3 (F) with in the graft copolymer (P) of various mixed shown in the above-mentioned table 2, thereby obtain magnetic compound.The structure and the evaluation result of this magnetic compound are as shown in table 5.
As shown in table 5, comparative example 1: in the graft copolymer (P) that constitutes magnetic compound, the ratio of monomer (B) is few, and the effect that spinel type ferrite powder (F) is disperseed diminishes, therefore the magnetic permeability of magnetic compound reduces, and the result is unsuitable for the miniaturization of antenna element.In addition, comparative example 2: the ratio of the monomer (B) in graft copolymer (P) is excessive, significantly damages the flowability of graft copolymer (P), therefore is difficult to obtain magnetic compound.
Comparative example 3: the ratio of the difunctionality vinyl unsaturated monomer (b2) of formation monomer (B) is little, the degree of cross linking of monomer (B) reduces, therefore the effect that spinel type ferrite powder (F) is disperseed diminishes, and the magnetic permeability of magnetic compound reduces, and the result is unsuitable for the miniaturization of antenna element.In addition, comparative example 4: the ratio of (b2) is excessive in monomer (B), significantly damages the flowability of graft copolymer (P), therefore is difficult to obtain magnetic compound.
Comparative example 5: the ratio of the spinel type ferrite powder in magnetic compound (F) diminishes, and the magnetic permeability of magnetic compound reduces, and is unsuitable for the miniaturization of antenna element.In addition, comparative example 6: the ratio of spinel type ferrite powder in magnetic compound (F) is excessive, is difficult to by the mixing magnetic compound that obtains.
In comparative example 7, the average grain diameter of spinel type ferrite powder (F) is compared too small with scope given to this invention, therefore graft copolymer (P) becomes excessive with the total surface area that spinel type ferrite powder (F) should soak into, spinel type ferrite powder (F) forms secondary as a result, and the dispersed of spinel type ferrite powder (F) significantly reduces.On the other hand, in the comparative example 8, particle diameter is excessive, and therefore the responsiveness for magnetic field reduces, and the result significantly reduces magnetic permeability.
＜comparative example 9 and 10 〉
Norborneol alkene thermoplastic resin ZEONEX or polyolefins thermoplastic resin PP (SunAllomer PM671A) mixed obtaining magnetic compound with the spinel type ferrite powder shown in the table 3 (F), its structure and evaluation result are shown in above-mentioned table 5.
As a result, in comparative example 9 and 10, owing to be that thermoplastic resin with non-graft copolymer mixes with spinel type ferrite powder (F), so can not get the dispersion effect of spinel type ferrite powder (F) based on monomer.Therefore, although to mix with embodiment 1 same ratio, magnetic permeability still reduces; And, need to disperse high shear force in order to make spinel type ferrite powder (F), therefore dielectric absorption and the magnetic loss based on the resin deterioration increases, and fails to obtain being designed to the magnetic compound of small size antenna unit.
Claims (6)
1. antenna magnetic compound, it is to contain mixing the forming of composition that graft copolymer (P) and average grain diameter are the spinel type ferrite powder (F) of 0.05～20 μ m, the mass ratio of two kinds of compositions (P)/(F) is 10/90～60/40; Described graft copolymer (P) is that the monomer (B) of glycerol polymerization 18～67 mass parts on 100 mass parts polymer (A) obtains, described polymer (A) is that alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or the aromatic monomer that contains the vinyl unsaturated bond are polymerized, described monomer (B) is made of with difunctionality vinyl unsaturated monomer (b2) the simple function vinyl unsaturated monomer (b1) of the fragrant same clan, and the mass ratio of two monomers (b1)/(b2) is 70/30～95/5.
2. antenna magnetic compound as claimed in claim 1, described spinel type ferrite powder (F) is used chemical formula MOFe
2O
3(M represents metallic element) expression, the electronegativity of described metallic element M is 1.55～2.33.
3. antenna magnetic compound according to claim 1, described spinel type ferrite powder (F) is used chemical formula MOFe
2O
3(M represents metallic element) expression, described metallic element M is at least a metallic element that is selected from manganese, nickel, copper or the zinc.
4. as any described antenna magnetic compound of claim 1-3, coat the surface of described spinel type ferrite powder (F) with silane coupler.
5. antenna element, it is on the surface of the formed body that any described antenna of claim 1-4 is obtained with the magnetic compound moulding or internal configurations conductor and obtaining.
6. the described antenna of claim 1 is with the manufacture method of magnetic compound, and this manufacture method is:
Preparation is with alpha-olefin, conjugated diene, unsaturated cyclic hydrocarbon or contain the polymer (A) that the aromatic monomer polymerization of vinyl unsaturated bond obtains;
Preparation is 70/30～95/5 monomer (B) by the simple function vinyl unsaturated monomer (b1) of the fragrant same clan and difunctionality vinyl unsaturated monomer (b2) mass ratio that constitute, (b1)/(b2);
The described monomer (B) of glycerol polymerization 18～67 mass parts on the described polymer (A) of 100 mass parts, preparation graft copolymer (P);
The spinel type ferrite powder (F) that with described graft copolymer (P) and average grain diameter is 0.05～20 μ m is 10/90～60/40 mixing with the mass ratio of (P)/(F), makes described antenna magnetic compound.
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| JP2008-250954 | 2008-09-29 | ||
| JP2008250954 | 2008-09-29 | ||
| PCT/JP2009/066974 WO2010035874A1 (en) | 2008-09-29 | 2009-09-29 | Magnetic composite body for antenna and antenna element using same |
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| JP (1) | JPWO2010035874A1 (en) |
| KR (1) | KR20110081145A (en) |
| CN (1) | CN102132456A (en) |
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| CN108028466A (en) * | 2015-03-31 | 2018-05-11 | 株式会社Emw | Anneta module and the portable terminal computer with the Anneta module |
| CN112538253A (en) * | 2020-12-07 | 2021-03-23 | 陕西生益科技有限公司 | Magnetic dielectric resin composition, laminated board containing same and printed circuit board containing laminated board |
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| US8455657B2 (en) | 2010-12-28 | 2013-06-04 | Bayer Cropscience Ag | Process for the preparation of 3-alkylsulfinylbenzoyl derivatives |
| KR102406259B1 (en) * | 2015-12-28 | 2022-06-10 | 주식회사 아모그린텍 | Antenna module and manufacturing method thereof |
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| JPH0923087A (en) * | 1995-07-06 | 1997-01-21 | Nippon Paint Co Ltd | Low reflection sheet for office use and its manufacture |
| JPH1032396A (en) * | 1996-07-15 | 1998-02-03 | Nippon Paint Co Ltd | Housing for electronic apparatus and method for reducing unwanted radiation |
| JP4689326B2 (en) * | 2005-04-05 | 2011-05-25 | 三井化学株式会社 | Rubber composition and use thereof |
| JP4626413B2 (en) * | 2005-06-14 | 2011-02-09 | 株式会社村田製作所 | Composite magnetic material, coil antenna structure, and portable communication terminal |
| JP2008195795A (en) * | 2007-02-09 | 2008-08-28 | Nippon Zeon Co Ltd | Polymerizable composition and molded article |
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2009
- 2009-09-29 JP JP2010530901A patent/JPWO2010035874A1/en active Pending
- 2009-09-29 KR KR1020117004215A patent/KR20110081145A/en not_active Application Discontinuation
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108028466A (en) * | 2015-03-31 | 2018-05-11 | 株式会社Emw | Anneta module and the portable terminal computer with the Anneta module |
| CN112538253A (en) * | 2020-12-07 | 2021-03-23 | 陕西生益科技有限公司 | Magnetic dielectric resin composition, laminated board containing same and printed circuit board containing laminated board |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110081145A (en) | 2011-07-13 |
| JPWO2010035874A1 (en) | 2012-02-23 |
| BRPI0923979A2 (en) | 2019-09-24 |
| WO2010035874A1 (en) | 2010-04-01 |
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Application publication date: 20110720 |