WO2016194932A1 - 磁性コンパウンドおよびアンテナ - Google Patents
磁性コンパウンドおよびアンテナ Download PDFInfo
- Publication number
- WO2016194932A1 WO2016194932A1 PCT/JP2016/066136 JP2016066136W WO2016194932A1 WO 2016194932 A1 WO2016194932 A1 WO 2016194932A1 JP 2016066136 W JP2016066136 W JP 2016066136W WO 2016194932 A1 WO2016194932 A1 WO 2016194932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- magnetic powder
- magnetic
- resin
- compound
- metal
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 101
- 239000006247 magnetic powder Substances 0.000 claims abstract description 144
- 229920005989 resin Polymers 0.000 claims abstract description 112
- 239000011347 resin Substances 0.000 claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 claims abstract description 98
- 239000002184 metal Substances 0.000 claims abstract description 98
- 229920000412 polyarylene Polymers 0.000 claims abstract description 35
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 33
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 80
- 239000002131 composite material Substances 0.000 claims description 60
- 230000035699 permeability Effects 0.000 claims description 16
- 238000005259 measurement Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 238000004891 communication Methods 0.000 description 14
- 239000004734 Polyphenylene sulfide Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229920000069 polyphenylene sulfide Polymers 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000004898 kneading Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 239000000696 magnetic material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 alkali metal salt Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000009841 combustion method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000006249 magnetic particle Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920003233 aromatic nylon Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
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- 239000011810 insulating material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 239000004417 polycarbonate Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004739 DIC.PPS Substances 0.000 description 1
- 239000004740 DURAFIDE® Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004997 Liquid crystal elastomers (LCEs) Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WYZXIJYWXFEAFG-UHFFFAOYSA-N ethyl-(3-isocyanatopropyl)-dimethoxysilane Chemical compound CC[Si](OC)(OC)CCCN=C=O WYZXIJYWXFEAFG-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Polymers [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DDBUVUBWJVIGFH-UHFFFAOYSA-N trichloro(3-isocyanatopropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCN=C=O DDBUVUBWJVIGFH-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01F1/14—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 metals or alloys
- H01F1/20—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 metals or alloys in the form of particles, e.g. powder
-
- 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
- H01F1/14—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 metals or alloys
- H01F1/20—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 metals or alloys in the form of particles, e.g. powder
- H01F1/22—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 metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/24—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 metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
- H01F1/26—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 metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated by macromolecular organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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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
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/442—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a metal or alloy, e.g. Fe
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/12—Supports; Mounting means
- H01Q1/22—Supports; Mounting means by structural association with other equipment or articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0843—Cobalt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the present invention relates to a magnetic compound and an antenna.
- Patent Document 1 describes a magnetic composite material that also functions in a high-frequency region.
- This magnetic composite material preferably has needle-shaped magnetic metal particles having an aspect ratio (major axis length / minor axis length) of 1.5 to 20 in a dielectric material such as polyarylene ether resin or polyethylene resin.
- a dielectric material such as polyarylene ether resin or polyethylene resin.
- Patent Document 2 describes a composite magnetic material that can be used for a small antenna that can be used in a wide band.
- This composite magnetic material is obtained by dispersing a composite magnetic material in an insulating material.
- This composite magnetic material is a substantially spherical powder containing a soft magnetic metal, and has an average particle diameter D 50 of 0.1 to 3 ⁇ m and a crystallite having an average crystallite diameter of 2 to 100 nm in the particles.
- various resins are described as insulating materials (see Patent Document 2 [0018] to [0021]).
- an antenna is manufactured by mixing magnetic powder, a thermoplastic PC / ABS resin, and a solvent (see [0069]).
- This antenna has a configuration in which tan ⁇ at a frequency of 2 GHz is less than 0.01 and the volume ratio of the magnetic powder with respect to the total volume is 2 to 50 vol% (see the above [0031] and [0032]). Is described.
- Patent Document 3 describes that the loss factor in the GHz band of an inductor, an antenna, or the like can be kept low by using a metal magnetic powder.
- a magnetic component obtained by molding a metal powder having 9 kA / m (500 to 2500 Oe) and a saturation magnetization of 100 Am 2 / kg or more can have a low loss coefficient in the kHz to GHz band (Patent Document 3) [0011] to [0026]).
- Patent Document 4 discloses a heat-resistant bond magnet in which the content ratio of magnet powder in a magnetic compound containing magnet powder, polyphenylene sulfide (PPS) resin, and polyamide (PA) resin is 79 to 94.5 wt. %, A PPS resin content ratio of 5 to 20 wt%, and a PA resin content ratio of 0.1 to 2 wt% (see Patent Document 4 [Claim 1]).
- PPS polyphenylene sulfide
- PA polyamide
- JP 2014-116332 A JP2011-096923A JP 2013-236021 A JP2013-077802A
- Patent Documents 1 to 4 disclose a magnetic compound (composite magnetic body) of a magnetic material and a resin material that has a high content ratio of the magnetic material.
- a magnetic compound composite magnetic body of a magnetic material and a resin material that has a high content ratio of the magnetic material.
- Patent Document 1 exemplifies that various resins can be used, but the polyethylene resin shown as an example is a high-density one having relatively high mechanical strength. However, since the bending strength is as weak as about 6.9 MPa, it is difficult to use in an actual environment where an impact is easily applied.
- the present inventors have conceived that an improvement in mechanical strength can be expected by using a polyarylene sulfide resin typified by a polyphenylene sulfide resin as the resin.
- Patent Document 4 describes that other unexpected influences may occur during kneading and molding due to poor wettability between the polyphenylene sulfide resin and the magnet powder. And although polyarylene sulfide resin represented by polyphenylene sulfide resin is excellent in high frequency characteristics, it has been confirmed that kneading with metal magnetic powder is difficult.
- magnetic compounds magnetographic composites
- resin a polymer compound. That is, the magnetic compound and the resin are completely different from each other in chemical properties and physical properties. For this reason, it is difficult to predict what characteristics the magnetic compound will exhibit, and for example, various trials and errors are required as in the prior art.
- the present invention has been made under the above-described circumstances, and the problem to be solved is to use a metal magnetic powder and a polyarylene sulfide resin typified by a polyphenylene sulfide resin, which are excellent in high frequency characteristics and mechanical. It is to provide a magnetic compound having excellent strength, and to provide an antenna composed of the magnetic compound.
- an antenna when an antenna is configured from a magnetic compound in which a metal magnetic powder is mixed with a resin, the antenna itself can be miniaturized due to the wavelength shortening effect, and can further contribute to miniaturization of portable devices and smartphones.
- metal magnetic powder is mixed into a resin as a magnetic compound constituting an antenna, it has been conceived that the investigation has been limited to those related to metal magnetic materials (see, for example, Patent Document 1). .
- the present inventors have proceeded with studies with a new idea that a resin having a function of mixing metal magnetic powder will be studied.
- the present inventors have continued research and have come up with polyarylene sulfide resin as a resin which has a function of mixing metal magnetic powder, is excellent in mechanical properties (particularly bending strength), and has a small loss per se. Furthermore, if at least a part of the surface of the metal magnetic particles constituting the metal magnetic powder is coated with phthalic acid or a derivative thereof to form a magnetic powder composite and then kneaded with polyarylene sulfide resin, an ignition phenomenon can be avoided.
- the present invention was completed by obtaining technological knowledge.
- the term “derivative” refers to a compound that has been modified to such a degree that the structure and properties of the matrix are not significantly changed, such as introduction of a functional group, oxidation, reduction, or atom replacement. "Is a concept that includes those in which the terminal is substituted with an alkali metal to make it soluble.
- the first invention for solving the above-described problem is A magnetic compound comprising a magnetic powder composite in which at least a part of the surface of a metal magnetic powder is coated with at least one of phthalic acid or a derivative thereof, and a polyarylene sulfide resin.
- the second invention is When the magnetic compound is configured so that the content of the metal magnetic powder in the magnetic compound is 27.5 vol%,
- the magnetic compound according to the first invention wherein a real part ⁇ ′ of permeability at a measurement frequency of 2 GHz is 1.5 or more and tan ⁇ and tan ⁇ are 0.05 or less.
- the third invention is It is an antenna comprised by the magnetic compound as described in 1st or 2nd invention.
- the present invention was able to provide a magnetic compound that includes a metal magnetic powder and a polyarylene sulfide resin and has excellent high-frequency characteristics and excellent mechanical strength. And the antenna which was excellent in the high frequency characteristic comprised by the said magnetic compound and excellent in mechanical strength was able to be provided.
- the magnetic compound when the magnetic compound is configured such that the content of the metal magnetic powder in the magnetic compound is 27.5 vol%, the real part ⁇ ′ of the magnetic permeability at a measurement frequency of 2 GHz is
- the magnetic compound includes 1.5 or more and tan ⁇ and tan ⁇ of 0.05 or less.
- the present invention includes an antenna configured using the magnetic compound and an electronic device including the antenna configured using the magnetic compound.
- the magnetic compound is obtained by mixing metal magnetic powder and phthalic acid or a derivative thereof to form a magnetic powder composite, and then melt-kneading with a polyarylene sulfide resin.
- the amount of the resin is not too much and not too little.
- the compounding amount of the resin in the magnetic compound by having a configuration of “a metal magnetic powder, a predetermined resin, and in addition to them, any of phthalic acid or a derivative thereof that contributes to each other between the metal magnetic powder and the resin” It is possible for the first time to achieve a magnetic compound composed mainly of metal magnetic powder and a predetermined resin.
- Kneading process with resin evaluation of physical properties of magnetic compound) (Measurement method of bending strength of molded products) ⁇ 3.
- Modifications etc.> Metal magnetic powder, phthalic acid, etc. and resin) (application)
- “to” indicates a continuous range of a predetermined value or more and a predetermined value or less.
- the magnetic compound in the present embodiment includes a magnetic powder composite and a polyarylene sulfide resin as main components.
- the magnetic powder composite is a powder containing a composite of phthalic acid or a derivative thereof and a metal magnetic powder, and phthalic acid or a derivative thereof is formed as a coating layer on at least a part of the surface of the metal magnetic powder. It is a powder.
- the metal magnetic powder in the present embodiment has the following configuration as an example.
- a magnetic powder, a particle size, and the like that are appropriately designed may be used.
- the permeability and dielectric constant of the magnetic compound can be set by saturation magnetization ( ⁇ s).
- the coercive force (Hc), the squareness ratio (SQ), etc. may be adjusted as magnetic characteristics, and the particle size, shape, BET (specific surface area), TAP (tap) density, etc. may be adjusted as powder characteristics.
- the metal magnetic powder in the present embodiment when the rare earth element content is low, the axial ratio is increased, and a metal powder with further reduced loss can be obtained. Even in this case, if the rare earth element content is larger than the predetermined amount, the magnetic permeability can be secured. On the other hand, when the rare earth element content is large, the axial ratio is small and the loss is slightly large, but the magnetic permeability is large compared to the case where no rare earth element is contained.
- the metal magnetic powder in the present embodiment it is possible to achieve low loss and high magnetic permeability by setting an appropriate rare earth content.
- a metal magnetic powder that can be used in a wide range from the conventional kHz to GHz band can be obtained.
- the specific content range of elements suitable for maintaining the balance of characteristics is 0 at% (preferably more than 0 at%) in terms of the rare earth element content relative to the total of Fe and Co. It is preferably 10 at%, more preferably more than 0 at% and 5 at% or less.
- the rare earth element species to be used Y and La are preferable.
- the Co content is 0 to 60 at% in terms of atomic ratio of Co to Fe (hereinafter referred to as “Co / Fe atomic ratio”). .
- a Co / Fe atomic ratio of 5 to 55 at% is more preferable, and 10 to 50 at% is more preferable.
- the metal magnetic powder in the present embodiment has high saturation magnetization, and stable magnetic properties are easily obtained.
- Al or the like also has a sintering suppressing effect, and has an effect of suppressing particle coarsening due to sintering during heat treatment.
- Al or the like is treated as one of “sintering suppression elements”.
- the content of Al and the like with respect to the total of Fe and Co is preferably 1 at% to 20 at% from the viewpoint of sufficiently securing the magnetic properties of the metal magnetic powder. % To 18 at% is more preferable, and 5 to 15 at% is more preferable.
- the metal magnetic powder in the present embodiment has a core / shell structure including a core made of a metal component and a shell mainly made of an oxide component. Whether or not the metal magnetic powder has the core / shell structure can be confirmed by, for example, a TEM photograph.
- the composition analysis of the metal magnetic powder can be performed by a method such as ICP emission analysis, ESCA (also known as XPS), TEM-EDX, SIMS or the like.
- the average primary particle diameter of the metal magnetic powder in the present embodiment is preferably nanoparticles in the range of 10 nm or more and 500 nm or less, more preferably 100 nm or less. However, even a metal magnetic powder having a micro-level ( ⁇ m) size can be used, but a smaller particle size is preferable from the viewpoint of improving communication characteristics and miniaturization.
- the average primary particle diameter of the metal magnetic powder in this embodiment can be measured with a transmission electron microscope. Specifically, for example, a photograph of an enlarged particle group is obtained by directly taking a photograph with a transmission electron microscope (JEOL Ltd. JEM-100CXMark-II type) at a magnification of 10,000 times or more and enlarging the photograph. Can be obtained by randomly selecting 400 or more particles, measuring the particle diameter of each particle, and calculating the average value.
- the content of the metal magnetic powder in the magnetic compound in this embodiment is 50 vol% or less, preferably 40 vol% or less, and more preferably 35 vol% or less. This is because the elastic modulus can be improved without impairing the bending strength of the resin while obtaining desired excellent communication characteristics.
- Magnetic powder composite The magnetic powder composite in this embodiment is sometimes described as phthalic acid or a derivative thereof (hereinafter simply referred to as “phthalic acid or the like”) on the surface of the metal magnetic powder by a surface treatment process described later. ). As a result, it is considered that the phthalic acid or the like adheres to all or at least a part of the surface of the metal magnetic powder to form the magnetic powder composite in the present embodiment.
- the term “derivative” as used herein is a concept that refers to a compound that has been modified to such an extent that the structure and properties of the matrix are not significantly changed, such as the introduction of a functional group, oxidation, reduction, or atom replacement. "Atom replacement” is a concept that includes the case where the terminal is replaced with an alkali metal and is soluble.
- the coating amount of phthalic acid or the like in the magnetic powder composite is such that the mass of carbon calculated as a carbon measurement value in the high frequency combustion method is 0.1 wt% or more and 10 wt% or less with respect to the total weight of the magnetic powder composite. It is preferable that it is the range of these.
- phthalic acid and the like may be dispersed in the resin or combined with the resin in addition to the magnetic compound covering the surface of the metal magnetic powder particles. There is also sex. Therefore, it is preferable to set the metal magnetic powder amount and the resin amount in order to make the magnetic compound exhibit desired characteristics.
- the content of the magnetic powder composite in the magnetic compound in the present embodiment is not particularly limited as long as the effect of the present invention can be obtained.
- the content of the magnetic powder composite in the magnetic compound is 35 to 80 wt% from the viewpoint of improving the elastic modulus without deteriorating the bending strength of the resin while obtaining desired excellent electrical and magnetic characteristics. It is preferably 40 to 75 wt%, more preferably 45 to 70 wt%.
- the polyarylene sulfide resin in the present embodiment has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit.
- the following formula (1) (wherein R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, It represents a ethoxy group.) And has a structural unit represented by a repeating unit.
- R 1 and R 2 in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin.
- those bonded at the para position represented by the following formula (2) and those bonded at the meta position represented by the following formula (3) are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin.
- the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the formula (2), which indicates the heat resistance and crystallinity of the polyarylene sulfide resin. It is preferable in terms of
- the polyarylene sulfide resin not only the structural moiety represented by the formula (1) but also the structural moiety represented by the following formulas (4) to (7) is represented by the formula (1). It may be contained in a range of 30 mol% or less of the total with the structural site.
- the structural sites represented by the above formulas (4) to (7) are more preferably in the range of 10 mol% or less from the viewpoint of the heat resistance and mechanical strength of the polyarylene sulfide resin.
- the bonding mode thereof may be either a random copolymer or a block copolymer. .
- the polyarylene sulfide resin may have a trifunctional structural site represented by the following formula (8) or a naphthyl sulfide bond in the molecular structure,
- the range of 3 mol% or less is preferable with respect to the total number of moles, and the range of 1 mol% or less is more preferable.
- the melt viscosity of the polyarylene sulfide resin in the present embodiment is not particularly limited as long as the effects of the present invention can be obtained.
- the melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 to 1,000 [Pa ⁇ s]. The range is more preferably 150 [Pa ⁇ s], and most preferably 5 to 75 [Pa ⁇ s].
- the melt viscosity (V6) measured at 300 ° C. means that an orifice having a temperature / 300 ° C., a load of 1.96 MPa, and an orifice length / orifice diameter ratio of 10/1 using a flow tester. It is the melt viscosity after holding for 6 minutes.
- the method for producing the polyarylene sulfide resin is not particularly limited. 1) A method of polymerizing a dihalogenoaromatic compound and, if necessary, other copolymerization components in the presence of sulfur and sodium carbonate, 2) A method of self-condensing p-chlorothiophenol and, if necessary, other copolymer components, 3) A method of reacting a sulfidizing agent, a dihalogenoaromatic compound, and, if necessary, other copolymerization components in an organic polar solvent, 4) A method of melt polymerization in the presence of a diiodo aromatic compound and elemental sulfur and, if necessary, a polymerization inhibitor and a polymerization catalyst. Among these methods, the method 3) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or
- a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate that allows water to be removed from the reaction mixture, and the dihalogenoaromatic compound and the sulfiding agent are reacted in the organic polar solvent.
- a method for producing a polyarylene sulfide resin by controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent (Japanese Patent Application Laid-Open No. 07-228699).
- the magnetic compound in the present embodiment includes a filler and other additives in addition to the above components within the range where the present invention is effective. May be.
- the other additives include various additives such as a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant.
- a coupling agent can be used as an additive in the present embodiment, and a coupling agent such as silane or titanium can be used.
- a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with a carboxy group (for example, an epoxy group, an isocyanato group, an amino group, or a hydroxyl group) is preferable.
- examples of such silane coupling agents include epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- alkoxysilane compounds Containing alkoxysilane compounds, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylethyldimethoxysilane , ⁇ -isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as ⁇ -isocyanatopropyltrichlorosilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and ⁇ -aminopropyltrime
- filler in the present embodiment examples include fillers having various shapes such as granular and fibrous forms, such as glass fiber, silane glass fiber, ceramic fiber, aramid fiber, potassium titanate, silicon carbide, and calcium sulfate.
- Fibrous fillers such as fibers such as calcium silicate, natural fibers such as wollastonite, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulgite, Examples thereof include ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads.
- fillers and various additives vary depending on the purpose and cannot be defined generally, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. Therefore, the present invention may be appropriately adjusted according to the purpose and application so that the present invention is effective.
- These fillers and various additives can be used alone or in combination of two or more.
- the magnetic compound in the present embodiment includes a magnetic powder composite and a polyarylene sulfide resin, but as long as the main component is the polyarylene sulfide resin, a predetermined amount of other resin components are added according to the use, etc. It can be used as a kneaded product.
- resin components include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoride.
- Synthetic resins such as ethylene, polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, or elastomers such as fluorine rubber and silicone rubber, especially epoxy groups, amino groups, Carboxy group, isocyanato group or the following structural formula (1) and structural formula (2) (wherein R represents an alkyl group having 1 to 8 carbon atoms in the structural formula (1) and structural formula (2)). From the group consisting of partial structures represented by Resins such as polyolefin elastomer having at least one functional group barrel.
- the magnetic characteristic in the high frequency (2 GHz) region of the magnetic compound (the content of the metal magnetic powder in the magnetic compound is equivalent to 27.5 vol%) in the present embodiment is that the real part ⁇ ′ of the complex relative permeability is 1. It is 50 or more, preferably 1.70 or more.
- a magnetic compound having such characteristics has a high magnetic permeability, so that it can exhibit a sufficient miniaturization effect and is extremely useful for construction of an antenna with a small return loss.
- Step 2-1 various preparations related to the production of the magnetic compound are performed.
- various raw materials such as the above-mentioned metal magnetic powder, phthalic acid, etc., and a resin to be mixed are prepared.
- Phthalic acid or the like is added to the metal magnetic powder and mixed to obtain a magnetic powder composite.
- the ratio of adding phthalic acid or the like to the metal magnetic powder is not particularly limited as long as the effects of the present invention are exhibited.
- the amount of carbon calculated as the carbon measurement value in the high frequency combustion method in the magnetic powder composite is the magnetic powder composite.
- the amount is preferably 0.1 to 10 wt%, more preferably 2 to 5 wt%, based on the total amount of the body.
- phthalic acid or the like is preferably added at 2 to 15 parts by mass, and 2.5 to 10 parts by mass with respect to 100 parts by mass of the metal magnetic powder in the production process. It is more preferable to add 5 to 10 parts by mass.
- phthalic acid or the like When phthalic acid or the like is added in an amount of 2 parts by mass or more with respect to 100 parts by mass of the metal magnetic powder, the wettability between the magnetic powder composite and the resin is improved, and they become compatible with each other. As a result, the property stability of the product when produced is improved, which is preferable.
- phthalic acid or the like when phthalic acid or the like is added in an amount of 15 parts by mass or less with respect to 100 parts by mass of the metal magnetic powder, the amount of the nonmagnetic component in the magnetic powder composite is appropriate, and a decrease in magnetic properties of the magnetic powder composite itself can be avoided. As a result, the high frequency characteristics can be maintained relatively high when the magnetic powder composite is mixed with resin to form a magnetic compound. And the characteristic of the antenna finally formed is also preferable because it can be maintained high as well.
- the solvent added when adding phthalic acid or the like to the metal magnetic powder to obtain a magnetic powder composite is not necessarily phthalic acid. Etc. may not completely dissolve. Then, it is preferable to employ a method in which a metal magnetic powder is added to a mixed solution of phthalic acid or the like and the solvent, the metal magnetic powder is impregnated in the mixed solution, and then the solvent is removed from the mixed solution.
- a metal magnetic powder is added to the above solution of phthalic acid and the like, and a paste is formed by stirring with a rotation / revolution combined stirrer or applying a shearing force.
- a mixer or the like may be used for removing the solvent and drying while kneading. It is important to leave phthalic acid and the like on the surface of the metal magnetic powder after the solvent is removed and dried.
- a dispersion or kneader having a high shearing force may be used.
- the metal magnetic powder may be dispersed in the solvent while applying a strong shearing force to the solvent.
- T.M. K. As a disperser having a strong shearing force used when a method of drying and making it into a powder state after the production of the magnetic powder composite is used, T.M. K. Examples include Homomixer (registered trademark), Ultra-Turrax (registered trademark) of IKA, and the like. K. MyColloider (registered trademark), T.C. K. Homomic Line Mill (registered trademark), T. K. Preferred examples include High Line Mill (registered trademark), Static Mixer (registered trademark) of Noritake Company Limited, High Pressure Microreactor (registered trademark), and High Pressure Homogenizer (registered trademark).
- the strength of the shearing force can be evaluated by the peripheral speed of the stirring blade if the device has the stirring blade.
- the “strong shearing force” refers to a blade whose peripheral speed is preferably in the range of 3.0 (m / s) or more, more preferably in the range of 5.0 (m / s) or more.
- the blade peripheral speed is not less than the above value, the shearing force is moderately high, the production time of the magnetic powder composite can be shortened, and the production efficiency is moderately good.
- the blade peripheral speed can be calculated by the following equation: Circumference ratio x Turbine blade diameter (m) x Stirring rotation speed (rotation speed) per second. For example, if the turbine blade diameter is 3.0 cm (0.03 m) and the stirring rotation speed is 8000 rpm, the rotation speed per second is 133.3 (rps), and the blade peripheral speed is 12.57 (m / S).
- the obtained paste-like magnetic powder composite is preferably dried to remove the solvent.
- the paste can be spread on the vat and dried by setting the temperature to be equal to or higher than the drying temperature of the solvent and lower than the decomposition temperature of the coating substance.
- the solvent can be dried in an inert atmosphere or in nitrogen in terms of cost.
- a method for producing a magnetic powder composite when a metal magnetic powder is subjected to a coating treatment such as phthalic acid using a solvent, for example, filtration is performed to remove a certain amount of solvent and then drying is performed. May be adopted. By carrying out like this, since content of a solvent can be reduced previously, drying time can also be shortened. In order to confirm whether or not the coating is strong, for example, it is possible to evaluate how much residual components are present by evaporating the filtrate.
- the magnetic powder composite thus obtained is preferably classified using a classifier or a sieve. This is because it is preferable to remove excessively large coarse particles so that a force is applied to a portion where the coarse particles are present when the antenna is manufactured, and a situation in which the mechanical characteristics are deteriorated can be avoided. Therefore, it is preferable because the mechanical properties of the molded product are improved and cracking can be suppressed by classifying and aligning the particle size. In addition, when classifying using a sieve, it is preferable to use a mesh having a mesh size of 500 mesh or less.
- BET specific surface area A BET specific surface area is calculated
- the obtained magnetic powder composite and the above-mentioned resin are melt-kneaded to form a magnetic compound.
- the melt-kneading step the magnetic powder composite is mixed and dispersed in the resin.
- the state after kneading it is desirable that the magnetic powder composite is dispersed in a uniform concentration in the resin.
- the amount of the magnetic powder composite that can be mixed into the resin is large, the magnetic permeability when a high frequency is applied is particularly high, while the mechanical properties of the resin may be deteriorated. Therefore, it is preferable to examine the amount of magnetic powder composite added in consideration of the balance between the mechanical properties and high-frequency properties of the magnetic compound.
- the manufacturing method of the magnetic compound in the present embodiment is not particularly limited as long as the effect of the present invention is exhibited.
- the raw magnetic powder composite and polyarylene sulfide resin are uniformly mixed with a tumbler or Henschel mixer, and then melt-kneaded using a Banbury mixer, mixing roll, single- or twin-screw extruder and kneader.
- the method of doing is mentioned.
- a melt kneading method using a single or twin screw extruder having a sufficient kneading force is preferable.
- the magnetic powder composite and the polyarylene sulfide resin are further mixed with other fillers and additive components, if necessary, with a tumbler or a Henschel mixer, and then into a twin screw extruder.
- the mixture is melt kneaded under the condition that the ratio of the resin component discharge rate (kg / hr) to the screw speed (rpm) (discharge rate / screw speed) is 0.02 to 2 (kg / hr / rpm).
- the polyarylene sulfide resin can be used as a matrix (continuous phase) to form a morphology in which the magnetic powder composite is dispersed.
- the above production method will be described in more detail.
- a method in which the above-mentioned components are put into an extruder and melt-kneaded under a temperature condition of a preset temperature of 300 to 340 ° C. and a resin temperature of 320 to 360 ° C. is preferable. It is more preferable that the set temperature is 310 to 330 ° C. and the resin temperature is 330 to 350 ° C. from the viewpoint of thermal deterioration suppression and dispersibility of the powder composite.
- the discharge amount of the resin component is preferably in the range of 4 to 400 kg / hr at a rotation speed of 200 rpm, and more preferably 10 to 250 kg / hr from the viewpoint of dispersibility. Accordingly, the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is particularly 0.05 to 1.25 (kg / hr / rpm). Is preferred.
- the magnetic compound thus melt-kneaded is then directly molded into a molded body using various known molding methods, or once molded as pellets, and then subjected to various molding machines. By melt-molding, it can be molded into a desired molded body.
- Known molding methods include injection molding, press molding, calendar molding, roll molding, extrusion molding, cast molding, and blow molding.
- the high frequency characteristics of the obtained magnetic compound molded body are measured in the range of 0.5 to 5 GHz, the measurement width is in increments of 0.05 GHz, the real part of the magnetic permeability ( ⁇ ′), the magnetic permeability
- the high frequency characteristics can be confirmed by measuring the imaginary part ( ⁇ ′′), the real part ( ⁇ ′) of the dielectric constant, and the imaginary part ( ⁇ ′′) of the dielectric constant.
- tan ⁇ ⁇ ′′ / ⁇ ′
- test piece was prepared by injection molding.
- the test piece was formed as a dumbbell having a total length of 80 mm, a thickness of 1 mm, and a parallel part width of 5 mm. Measurement may be performed in accordance with JIS-K7171 “Plastics—Bending property test method” using the test piece.
- a polyarylene sulfide resin can be used to provide a magnetic compound excellent in high-frequency characteristics and excellent in mechanical strength and related products.
- Metal magnetic powder, phthalic acid, etc. and resin Metal magnetic powder, phthalic acid, etc. and resin
- the main elements and compounds have been described in detail with respect to the metal magnetic powder, phthalic acid and the like and the resin.
- the metal magnetic powder, phthalic acid and the like and the resin may contain substances other than the elements and compounds listed above as long as the effects of the present invention are not impaired.
- the magnetic compound in this embodiment can be used for an antenna, an inductor, and a radio wave shielding material.
- an antenna composed of the magnetic compound, and also an electronic communication device (electronic device) equipped with the antenna can enjoy relatively high communication characteristics as shown in the items of the examples described later. is there.
- Such an electronic communication device includes, for example, a portion that functions as an electronic communication device based on the radio wave received by the antenna in the present embodiment, and a control unit that controls the portion based on the received radio wave. Things.
- the electronic communication device in the present embodiment is preferably a communication device having a communication function because it includes an antenna.
- an electronic device that does not have a communication function such as a telephone call may be used as long as it is an electronic device that receives radio waves from an antenna and performs its function.
- Example 1 First, ethanol (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent was added to 25 g of phthalic acid (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) to dissolve the phthalic acid in ethanol. .
- metal magnetic powder DOWA Electronics Co., Ltd .: iron-cobalt metal particles, major axis length: 40 nm, coercive force Hc757 (Oe) or 60 (kA / m), saturation magnetization ⁇ s179.3 (Am 2 / kg), squareness ratio SQ0.337, coercive force distribution SFD 3.141, ⁇ s 7.6 (%), BET: 37.3 m 2 / g, carbon atom content (high frequency combustion method): 500 g in an inert atmosphere
- the metal magnetic powder was allowed to settle in the solution. This was mixed in the atmosphere by stirring at 8000 rpm for 2 minutes with a high-speed stirrer (TK homomixer Mark II manufactured by PRIMIX Corporation) to obtain a paste.
- TK homomixer Mark II manufactured by PRIMIX Corporation
- the obtained paste was spread on an aluminum vat, heated for 1 hour at around the volatilization temperature of ethanol (78 ° C), then heated to 120 ° C and heated for 1.5 hours, ethanol was removed from the paste, phthalic acid and metal Agglomerates mixed with magnetic powder were obtained.
- the obtained aggregate was passed through a 500 mesh sieve (manufactured by Tokyo Screen Manufacturing Co., Ltd.) to remove coarse particles to obtain a magnetic powder composite according to this example.
- the production of the magnetic powder composite shown above was repeated several times to produce the amount of magnetic powder composite required for the melt kneading shown below.
- Table 1 shows the obtained magnetic powder composite, polyphenylene sulfide resin (“DIC.PPS” V6 melt viscosity 15 Pa ⁇ s, manufactured by DIC Corporation), and fibrous reinforcing agent (glass fiber, fiber diameter 10 ⁇ m, fiber length 3 mm).
- the mixture was uniformly mixed with a tumbler to obtain the magnetic compound composition shown in FIG.
- the compounded material is put into a vented twin screw extruder “TEX-30” manufactured by Nippon Steel Co., Ltd., melted and kneaded at a discharge rate of 15 kg / hr, a screw rotation speed of 200 rpm, and a set temperature of 320 ° C., and then magnetic compound. Pellets were obtained.
- Example 2 In this example, in Example 1, the addition amount of the metal magnetic powder was changed to an amount corresponding to 24 vol%, and the addition amounts of the polyphenylene sulfide resin and the fibrous reinforcing material were combined and adjusted. The same operation was performed to produce a magnetic compound.
- ⁇ Comparative Example 1> a magnetic compound was produced in the same manner as in Example 1 except that metal magnetic powder not surface-treated with phthalic acid was used instead of the magnetic powder composite.
- ⁇ Comparative example 2> it was confirmed whether or not the same effect as in the example was observed after using a conventional resin mixture of thermoplastic resin and aromatic nylon. Specifically, in place of the magnetic powder composite, metal magnetic powder not surface-treated with phthalic acid is used, and DURAFIDE (registered trademark) (PPS / polyphenylene sulfide resin, manufactured by Polyplastics Co., Ltd. A0220A9 ”, V6 melt viscosity 80 Pa ⁇ s) and aromatic nylon 6T Vestamide (registered trademark) (HTplus M1000 manufactured by Daicel-Evonik Co., Ltd.) were used in the same manner as in Example 1 except that a mixture was used. A magnetic compound was produced.
- DURAFIDE registered trademark
- PPS / polyphenylene sulfide resin manufactured by Polyplastics Co., Ltd. A0220A9
- aromatic nylon 6T Vestamide registered trademark
- a magnetic compound was produced in the same manner as in Example 2 except that metal magnetic powder not surface-treated with phthalic acid was used instead of the magnetic powder composite.
- the polyphenylene sulfide resin can be used to provide a magnetic compound excellent in high-frequency characteristics and excellent in mechanical strength and related products. If an antenna is formed by mixing metal magnetic powder with polyphenylene sulfide resin, the antenna itself can be reduced by the wavelength shortening effect, which can contribute to miniaturization of portable devices and smartphones. In addition to antennas, it has been found that they can be used for radio wave shielding materials, inductors, and the like.
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Abstract
Description
そして、当該構成をとることにより、GHz帯の高周波領域で使用する電子機器、通信機器に装備する高周波電子部品に好適に用いられ、しかも、所定の針状金属粒子を用いることにより、誘電体材料中において磁性金属粒子を配向させるか否かに拘わらず、所定の磁気特性を備えることができる旨(特許文献1[0024][0029]参照。)が記載されている。
例えば、実施例において、磁性粉末と熱可塑性のPC/ABS系樹脂と溶剤等とを混合することで、アンテナを作製している(同[0069]参照。)。このアンテナは、周波数2GHzにおけるtanδεが0.01未満であり、全体積に対する前記磁性粉末の体積比率が2~50vol%の構成で、小型化を図れる旨(同[0031][0032]参照。)が記載されている。
鉄を主成分とする軟磁性金属粉末であり、平均粒子径が100nm以下、軸比(=長軸長/短軸長)が1.5以上、保磁力(Hc)が39.8~198.9kA/m(500~2500Oe)、飽和磁化100Am2/kg以上である金属粉末を成形して得られた磁性部品は、kHz~GHz帯での損失係数を低く抑える事ができる旨(特許文献3[0011]~[0026]参照。)が記載されている。
特許文献1から4には、磁性材料と樹脂材料との磁性コンパウンド(複合磁性体)であって、磁性材料の含有比率が高いものが開示されている。
一方、出願人らの検討によって達成できた金属磁性粉末の高周波特性の向上に伴い、磁性コンパウンド中の金属磁性粉末の含有量をある程度減じても、十分な高周波特性が得られるようになってきた。しかし、このような高特性な金属磁性粉末を樹脂に分散させた場合、混練段階で発火したり、金属磁性粉末を添加しない場合に比較して、樹脂の強度が著しく低下したりすることが知見された。すなわち、機械的強度と高周波特性とを共に満足するような磁性コンパウンド材料は未だ得られていない。
例えば、特許文献1には、様々な樹脂が使用可能であるとして例示されているが、実施例として示されているポリエチレン樹脂は、比較的に機械的強度が高いとされている高密度のものでも曲げ強度が6.9MPa程度と弱いため、衝撃が加わりやすい実環境では使用することが困難である。
ここで本発明者らは、樹脂として、ポリフェニレンスルフィド樹脂に代表されるポリアリーレンスルフィド樹脂を用いることにより、機械的強度の向上が期待できることに想到した。
尚、本発明において「誘導体」とは、官能基の導入、酸化、還元、原子の置き換えなど、母体の構造や性質を大幅に変えない程度の改変がなされた化合物をさし、「原子の置き換え」には、末端がアルカリ金属で置換がなされ、可溶性とされたものも含む概念である。
フタル酸またはその誘導体の少なくともいずれかにより金属磁性粉末の表面の少なくとも一部が被覆されている磁性粉末複合体と、ポリアリーレンスルフィド樹脂とを含む磁性コンパウンドである。
第2の発明は、
前記磁性コンパウンド中における前記金属磁性粉末の含有量が27.5vol%となるように前記磁性コンパウンドを構成したとき、
測定周波数2GHzにおける透磁率の実数部μ’が1.5以上、かつ、tanδμおよびtanδεが0.05以下を示す第1の発明に記載の磁性コンパウンドである。
第3の発明は、
第1または第2の発明に記載の磁性コンパウンドにより構成されるアンテナである。
さらに、本発明は、前記磁性コンパウンドを用いて構成されたアンテナ、上記の磁性コンパウンドにより構成されたアンテナを備えた電子機器を含むものである。
そして、前記磁性コンパウンドは、金属磁性粉末と、フタル酸若しくはその誘導体を混合して、磁性粉末複合体を形成した後に、ポリアリーレンスルフィド樹脂と溶融混練することにより得られる。
即ち、「金属磁性粉末、所定の樹脂、それらに加えて金属磁性粉末と前記樹脂の相互に寄与するフタル酸若しくはその誘導体のいずれか」という構成を備えることにより、磁性コンパウンド中の樹脂の配合量を所定の値以上としたり、金属磁性粉末および所定の樹脂を主成分としてなる磁性コンパウンドを生み出したりすることが初めて実現可能となったものである。
〈1.磁性コンパウンド〉
1-1.金属磁性粉末
1-2.磁性粉末複合体
1-3.樹脂
(ポリアリーレンスルフィド樹脂の製造方法)
(充填剤、その他添加剤)
〈2.磁性コンパウンドの製造方法〉
2-1.準備工程
2-2.被覆工程(表面処理)
(BET比表面積)
(磁性粉末複合体の磁気特性評価)
(TAP密度の測定)
2-3.樹脂との混練工程
(磁気コンパウンドの物性評価)
(成形品の曲げ強度測定方法)
〈3.変形例等〉
(金属磁性粉末、フタル酸等および樹脂)
(アプリケーション)
尚、本発明において「~」は、所定の値以上且つ所定の値以下の連続した範囲であることを指す。
本実施形態における磁性コンパウンドは、主成分として磁性粉末複合体とポリアリーレンスルフィド樹脂とを含む。
そして、前記磁性粉末複合体は、フタル酸またはその誘導体と金属磁性粉末との複合体を含む粉末であり、金属磁性粉末の表面の少なくとも一部に、フタル酸またはその誘導体が被覆層として形成されている粉末である。
1-1.金属磁性粉末
本実施形態における金属磁性粉末は、一例としては、以下の構成を有する。
金属磁性粉末は、磁性特性、粒径などを適宜設計したものを用いれば良い。
磁性特性として、飽和磁化(σs)により磁性コンパウンドの透磁率、誘電率を設定できる。他には磁性特性として、保磁力(Hc)、角形比(SQ)等、また粉体特性として、粒径、形状、BET(比表面積)、TAP(タップ)密度等を調整すればよい。
そして、本実施形態における金属磁性粉末は、その製造工程で用いる、原材料となる元素を含む水溶液中において、希土類元素含有量を制御することで、最終的に得られる金属粒子の軸比(=長軸長/短軸長)を制御することができる。
ここで、上述のように特性のバランスを維持するために適切な元素の具体的な含有範囲は、FeとCoとの総和に対する希土類元素含有量で0at%(好ましくは、0at%を超え)~10at%とすることが好ましく、0at%を超え5at%以下とすることがより好ましい。また、使用する希土類元素種としては、YやLaが好ましい。
金属磁性粉末が、当該コア/シェル構造を有しているか否かは、例えば、TEM写真により確認することができる。また、金属磁性粉末の組成分析は、例えばICP発光分析、ESCA(別名XPS)、TEM-EDX、SIMSなどの方法により実施できる。
尚、本実施形態における金属磁性粉末の平均一次粒子径は、透過型電子顕微鏡により測定することができる。具体的には、例えば、透過型電子顕微鏡(日本電子株式会社 JEM-100CXMark-II型)で直接倍率1万倍以上の写真を撮影し、その写真を引き伸ばすことによって、拡大された粒子群の写真を得た後に、ランダムに400個以上の粒子を選択して個々の粒子の粒子径を測定し、その平均値を算出することで求めることができる。
本実施形態における磁性粉末複合体は、後述する表面処理工程により、前記金属磁性粉末の表面へ、フタル酸もしくはその誘導体(以下、単に「フタル酸等」と記載する場合がある。)を被覆することにより得られる。この結果、当該フタル酸等は、金属磁性粉末の表面の全部、または、少なくとも一部に付着して、本実施形態における磁性粉末複合体が形成されていると思われる。
尚、ここでいう「誘導体」とは、官能基の導入、酸化、還元、原子の置き換えなど、母体の構造や性質を大幅に変えない程度の改変がなされた化合物を指す概念である。そして「原子の置き換え」には、末端がアルカリ金属で置換がなされ、可溶性される場合も含む概念である。
そこで、磁性コンパウンドに所望の各特性を奏させる為には、金属磁性粉末量と樹脂量とを設定することで実施することが好ましい。
本実施形態におけるポリアリーレンスルフィド樹脂(以下、単に「樹脂」と記載する場合がある。)は、芳香族環と硫黄原子とが結合した構造を繰り返し単位とする樹脂構造を有するものである。具体的には、下記式(1)(式中、R1及びR2は、それぞれ独立して水素原子、炭素原子数1~4のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。)で表される構造部位を繰り返し単位とする樹脂である。
尚、300℃で測定した溶融粘度(V6)とは、フローテスターを用いて、温度300℃、荷重1.96MPa、オリフィス長とオリフィス径との前者/後者の比が10/1であるオリフィスを使用して6分間保持した後の溶融粘度のことである。
ポリアリーレンスルフィド樹脂の製造方法例について説明する。
ポリアリーレンスルフィド樹脂の製造方法は、特に限定されないが、例えば、
1)ジハロゲノ芳香族化合物と、更に必要ならばその他の共重合成分とを、硫黄と炭酸ソーダの存在下で重合させる方法、
2)p-クロルチオフェノールと、更に必要ならばその他の共重合成分とを自己縮合させる方法、
3)有機極性溶媒中で、スルフィド化剤とジハロゲノ芳香族化合物と、更に必要ならばその他の共重合成分とを反応させる方法、
4)ジヨード芳香族化合物と単体硫黄と、必要に応じて重合禁止剤と重合触媒の存在下で溶融重合する方法、等が挙げられる。
これらの方法のなかでも、3)の方法が汎用的であり好ましい。反応の際に、重合度を調節するためにカルボン酸やスルホン酸のアルカリ金属塩を添加したり、水酸化アルカリを添加しても良い。
加熱した有機極性溶媒とジハロゲノ芳香族化合物を含む混合物へ、含水スルフィド化剤を水が反応混合物から除去され得る速度で導入し、有機極性溶媒中でジハロゲノ芳香族化合物とスルフィド化剤とを反応させること、および、反応系内の水分量を、当該有機極性溶媒1モルに対して0.02~0.5モルの範囲に制御することによりポリアリーレンスルフィド樹脂を製造する方法(特開平07-228699号公報参照。)や、
固形のアルカリ金属硫化物および非プロトン性極性有機溶媒の存在下で、ポリハロ芳香族化合物、アルカリ金属水硫化物及び有機酸アルカリ金属塩を、硫黄源1モルに対して0.01~0.9モルの有機酸アルカリ金属塩および反応系内の水分量を非プロトン性極性有機溶媒1モルに対して0.02モル以下の範囲に制御しながら反応させる方法(WO2010/058713号パンフレット参照。)、で得られるものが好ましい。
本実施形態における磁性コンパウンドには、本発明が効果を奏する範囲で、強度、耐熱性、寸法安定性等の性能を改善するため、上記成分に加え、さらに充填材やその他添加剤が含まれていてもよい。
当該その他添加剤としては、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤等の各種添加剤が挙げられる。
以下、本実施形態における磁性コンパウンドの製造方法例について説明する。
本工程においては、磁性コンパウンドの作製に係る諸々の準備を行う。例えば、上記の金属磁性粉末などの各種原材料や、フタル酸等や、混ぜ入れる対象となる樹脂を用意する。
金属磁性粉末へフタル酸等を添加して混合し、磁性粉末複合体を得る。
金属磁性粉末へフタル酸等を添加する割合は、本発明の効果を奏するのであれば、特に限定されるものではない。尤も、磁性粒子の樹脂への分散性を向上しつつ、かつ、優れた透磁率を有する観点から、磁性粉末複合体における高周波燃焼法での炭素計測値として算出される炭素量は、磁性粉末複合体の総量に対して0.1~10wt%であることが好ましく、さらに好ましくは2~5wt%である。
当該添加割合を実現するためには、製造工程において、フタル酸等を、金属磁性粉末100質量部に対して、2~15質量部で添加することが好ましく、2.5~10質量部で添加することがより好ましく、5~10質量部で添加することが一層好ましい。
一方、フタル酸等を金属磁性粉末100質量部に対して15質量部以下添加すると、磁性粉末複合体における非磁性成分量が適量であり、磁性粉末複合体自体の磁気特性の低下を回避できる。この結果、当該磁性粉末複合体を樹脂に混ぜ入れて磁性コンパウンドにしたときの高周波特性を比較的高く維持することができる。そして、最終的に形成されるアンテナの特性も、同様に高く維持することができるため好ましい。
そして、フタル酸等と当該溶媒との混合液中へ金属磁性粉末を加え、金属磁性粉末を当該混合液に含浸させた後、当該混合液から溶媒を除去する方法を採用することが好ましい。
(BET比表面積)
BET比表面積は、ユアサアイオニクス株式会社製の4ソーブUSを用いて、BET一点法により求められる。
得られた磁性粉末複合体(または金属磁性粉末)の磁気特性(バルク特性)として、東英工業株式会社製のVSM装置(VSM-7P)を使用して、外部磁場10kOe(795.8kA/m)で、保磁力Hc(OeまたはkA/m)、飽和磁化σs(Am2/kg)、角形比SQ、保磁力分布SFDを測定できる。Δσsは、磁性粉を60℃90%の高温多湿環境下に一週間放置した時の飽和磁化の低下割合を百分率(%)で示したものである。
JISK-5101:1991の手法に準じて測定できる。
得られた磁性粉末複合体と上述の樹脂とを溶融混練し、磁性コンパウンドを形成する。
当該溶融混練工程により、樹脂中に磁性粉末複合体が混ざり分散された状態となる。混練後の状態は、樹脂中に磁性粉末複合体が均一濃度に分散されているのが望ましい。樹脂に混ぜ込むことのできる磁性粉末複合体の量が多い場合、高周波を加えた際の透磁率がとりわけ高くなる一方、樹脂の有する機械的特性を劣化させる場合がある。そのため、磁性粉末複合体の添加量は、磁性コンパウンドの機械的特性と高周波特性との間のバランスを考慮して検討することが好ましい。
上述の方法により得られた磁性コンパウンド0.2gをドーナッツ状の容器内に入れて、ハンドプレス機、もしくはホットプレス機を用い、外径7mm、内径3mmのトロイダル形状を有する磁性コンパウンドの成形体を形成する。その後、アジレント・テクノロジー株式会社製のネットワーク・アナライザー(E8362C)と株式会社関東電子応用開発製の同軸型Sパラメーター法サンプルホルダーキット(製品型番:CSH2-APC7、試料寸法:φ7.0mm-φ3.04mm×5mm)を用い、得られた磁性コンパウンドの成形体の高周波特性の測定を0.5~5GHzの区間、測定幅は0.05GHz刻みで行い、透磁率の実数部(μ’)、透磁率の虚数部(μ”)、誘電率の実数部(ε’)、誘電率の虚数部(ε”)を測定し、高周波特性を確認出来る。ここで、tanδε=ε”/ε’であり、tanδμ=μ”/μ’で算出することができる。
成形品の曲げ強度を測定するため、射出成形によって試験片を作製した。試験片は全長80mm、厚み1mm、平行部分の幅5mmのダンベルを成形した。
当該試験片を用い、JIS-K7171「プラスチック-曲げ特性の試験方法」に準拠して測定すればよい。
なお、本発明の技術的範囲は上述した実施の形態に限定されるものではなく、発明の構成要件やその組み合わせによって得られる特定の効果を導き出せる範囲において、種々の変更や改良を加えた形態も含む。
本実施形態においては、金属磁性粉末、フタル酸等および樹脂に関し、主となる元素や化合物について詳述した。その一方、本発明の効果を損ねない範囲で、上記で列挙した元素や化合物以外のものを、金属磁性粉末、フタル酸等および樹脂が含有していても構わない。
本実施形態における磁性コンパウンドは、アンテナ、インダクタ、電波遮蔽材に用いることができる。特に、当該磁性コンパウンドにより構成されるアンテナ、更には当該アンテナを備えた電子通信機器(電子機器)においては、後述の実施例の項目で示すような比較的高い通信特性を享受することが可能である。
尚、各表の空欄は未測定または測定不能であった項目である。
<実施例1>
まず、フタル酸(和光純薬工業株式会社製特級試薬)25gへ、溶媒としてエタノール(和光純薬工業株式会社製特級試薬)を500gになるように添加し、フタル酸をエタノールへと溶解させた。この溶液に対し、金属磁性粉末(DOWAエレクトロニクス株式会社製:鉄-コバルト金属粒子、長軸長:40nm、保磁力Hc757(Oe)または60(kA/m)、飽和磁化σs179.3(Am2/kg)、角形比SQ0.337、保磁力分布SFD3.141、Δσs7.6(%)、BET:37.3m2/g、炭素原子量(高周波燃焼法):0.01wt%)500gを不活性雰囲気下で添加し、溶液中にて金属磁性粉末を沈降させた。これを大気中で高速攪拌機(プライミクス株式会社製TKホモミキサーMarkII)で8000rpmにおいて2分間にて撹拌により混合して、ペースト状態とした。
上記に示す磁性粉末複合体の製造を数回繰り返して実施し、以下に示す溶融混練に必要な量の磁性粉末複合体を作製した。
本例では、実施例1において、金属磁性粉末の添加量を24vol%に相当する量に変更し、ポリフェニレンスルフィド樹脂と繊維状強化材との添加量を合わせて、調整した以外は実施例1と同様に操作して、磁性コンパウンドを製造した。
本例においては、磁性粉末複合体に代えて、フタル酸で表面処理していない金属磁性粉末を用いた以外は、実施例1と同様に操作して、磁性コンパウンドを製造した。
本例においては、従来技術である熱可塑性樹脂と芳香族ナイロンとの混合樹脂を用いた上で、実施例と同様の効果が見られるかを確認した。
具体的には、磁性粉末複合体に代えて、フタル酸で表面処理していない金属磁性粉末を用い、かつ、樹脂としてジュラファイド(登録商標)(PPS/ポリフェニレンサルファイド樹脂 ポリプラスチックス株式会社製「A0220A9」、V6溶融粘度80Pa・s)と、芳香族ナイロン6T ベスタミド(登録商標)(ダイセル・エボニック株式会社製 HTplus M1000)との混合物を用いた以外は、実施例1と同様に操作して、磁性コンパウンドを製造した。
本例においては、磁性粉末複合体に代えて、フタル酸で表面処理していない金属磁性粉末を用いた以外は、実施例2と同様に操作して、磁性コンパウンドを製造した。
本例においては、比較例2におけるフタル酸で表面処理していない金属磁性粉末の添加量を24vol%に相当する量に変更し、繊維状強化材と樹脂の添加量を比較例3の添加量に合わせた以外は、比較例3と同様に操作して、磁性コンパウンドを製造した。
上記の各表を見ると、いずれの実施例も、各表に記載した全ての周波数において、透磁率の実数部(μ’)、透磁率の虚数部(μ”)、誘電率の実数部(ε’)、誘電率の虚数部(ε”)について、全てが良好な値となっていた。
一方、比較例においては、金属磁性粉末を樹脂へ混ぜ入れ磁性コンパウンドを製造する段階で、金属磁性粉末の発火に起因した焼失がおこり、磁性コンパウンドの作製ができなかった。
金属磁性粉末をポリフェニレンスルフィド樹脂に混ぜ込んだものでアンテナを形成すれば、波長短縮効果により、アンテナそのものを小さくすることができ、ひいては携帯機器やスマートフォンの小型化に貢献できる。アンテナの他、電波遮蔽材、インダクタなどへの利用も可能であることが判明した。
Claims (3)
- フタル酸またはその誘導体の少なくともいずれかにより金属磁性粉末の表面の少なくとも一部が被覆されている磁性粉末複合体と、ポリアリーレンスルフィド樹脂とを含む磁性コンパウンド。
- 前記磁性コンパウンド中における前記金属磁性粉末の含有量が27.5vol%となるように前記磁性コンパウンドを構成したとき、
測定周波数2GHzにおける透磁率の実数部μ’が1.5以上、かつ、tanδμおよびtanδεが0.05以下を示す請求項1に記載の磁性コンパウンド。 - 請求項1または2記載の磁性コンパウンドにより構成されるアンテナ。
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