JP2022114252A - Polyarylene sulfide resin composition and method for producing the same - Google Patents
Polyarylene sulfide resin composition and method for producing the same Download PDFInfo
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- JP2022114252A JP2022114252A JP2021010469A JP2021010469A JP2022114252A JP 2022114252 A JP2022114252 A JP 2022114252A JP 2021010469 A JP2021010469 A JP 2021010469A JP 2021010469 A JP2021010469 A JP 2021010469A JP 2022114252 A JP2022114252 A JP 2022114252A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 32
- -1 aryl compound Chemical class 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
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- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012765 fibrous filler Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
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- 238000004898 kneading Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
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- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 230000026045 iodination Effects 0.000 description 3
- 238000006192 iodination reaction Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920001230 polyarylate Polymers 0.000 description 3
- 239000000843 powder 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
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QQFIQWBUKYSUHM-UHFFFAOYSA-N (2,3-diiodophenyl)-phenylmethanone Chemical compound IC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1I QQFIQWBUKYSUHM-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- UYHYZAYIQAVJCN-UHFFFAOYSA-N 1,2-diiodonaphthalene Chemical compound C1=CC=CC2=C(I)C(I)=CC=C21 UYHYZAYIQAVJCN-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- VALABLHQPAMOBO-UHFFFAOYSA-N 2,4-diiodo-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1I VALABLHQPAMOBO-UHFFFAOYSA-N 0.000 description 1
- JEVDBSPYZIVTGM-UHFFFAOYSA-N 2,6-diiodonaphthalene Chemical compound C1=C(I)C=CC2=CC(I)=CC=C21 JEVDBSPYZIVTGM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical group C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UVGTXNPVQOQFQW-UHFFFAOYSA-N Disophenol Chemical compound OC1=C(I)C=C([N+]([O-])=O)C=C1I UVGTXNPVQOQFQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical class N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
本発明は、ポリアリーレンスルフィド樹脂、金属被覆炭素繊維および変性超高分子量ポリエチレンよりなる樹脂組成物であって、優れた機械強度を維持しつつ、電磁波遮蔽性に優れる樹脂組成物に関するものである。 TECHNICAL FIELD The present invention relates to a resin composition comprising a polyarylene sulfide resin, a metal-coated carbon fiber, and a modified ultra-high molecular weight polyethylene, and having excellent electromagnetic wave shielding properties while maintaining excellent mechanical strength.
ポリアリーレンスルフィド樹脂は、耐薬品性、耐熱性、機械的特性などに優れるエンジニアリングプラスチックである。このため、ポリアリーレンスルフィド樹脂は、優れた特性を活かし金属代替材料として、電気電子、車両関連、航空機、住設などの用途に広く利用されている。 Polyarylene sulfide resins are engineering plastics that are excellent in chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used in applications such as electrics and electronics, vehicles, aircraft, and housing equipment as metal substitute materials by taking advantage of their excellent properties.
近年、電子機器の小型軽量化に伴う回路の高集積化および高密度化に伴い、電子機器が電磁波によって誤作動を引き起こすことが問題となっている。その為、電子機器の筐体には、外部からの電磁波を遮蔽するための電磁波遮蔽効果および外部への電磁波の漏洩を防止するための電磁波遮蔽効果を付与することが求められている。電磁波遮蔽効果を得る為には、電子機器筐体に導電性が必要であり、一般的に導電性が高いほど良好な電磁波遮蔽性を有する。従来、このような筐体には金属が使用されていたが、加工性、軽量化の観点からポリアリーレンスルフィド樹脂などのプラスチックを使用する試みがなされている。しかし、一般的にプラスチックは金属のような導電性を有していないので、電磁妨害波および電磁波ノイズ対策のために導電性の付与が必要となる。プラスチックに電磁波遮蔽性を付与する方法として、メッキなどの導電性表面処理や金属粉、金属繊維、炭素繊維、金属被覆炭素繊維等を含有させる方法が代表的な方法として例示される。プラスチックの電磁波遮蔽性をさらに向上させる試みとしては、例えば特許文献1には、導電性繊維を含有する熱可塑性樹脂およびカルボン酸無水物グループおよび/またはカルボキシ基を有するオレフィン系ワックスまたはオレフィン系重合体からなる電磁波遮蔽用樹脂組成物が提案されており、特許文献2にはニッケル金属被覆炭素繊維のニッケル金属被覆処理前の炭素繊維表面におけるESCA法で測定されるO1S/C1Sを特定範囲に調整して得られたニッケル金属被覆炭素繊維を含有する熱可塑性樹脂組成物が提案されている。しかしながら、ポリアリーレンスルフィド樹脂に対して有用な方法ではなく、電磁波遮蔽性も十分ではなかった。また、特許文献3にはポリアリーレンスルフィド樹脂、変性ポリオレフィン組成物および繊維状充填剤からなる樹脂組成物が提案されているが、電磁波遮蔽性について何ら記載されていなかった。 2. Description of the Related Art In recent years, as electronic devices have become smaller and lighter, and circuits have become more highly integrated and denser, it has become a problem that electronic devices may malfunction due to electromagnetic waves. Therefore, it is demanded that the housing of the electronic device has an electromagnetic wave shielding effect for shielding electromagnetic waves from the outside and an electromagnetic wave shielding effect for preventing the electromagnetic waves from leaking to the outside. In order to obtain an electromagnetic wave shielding effect, an electronic device housing must have electrical conductivity, and generally, the higher the electrical conductivity, the better the electromagnetic wave shielding properties. Conventionally, metal has been used for such housings, but attempts have been made to use plastics such as polyarylene sulfide resins from the viewpoint of workability and weight reduction. However, since plastic generally does not have conductivity like metal, it is necessary to impart conductivity to counter electromagnetic interference waves and electromagnetic noise. Typical examples of methods for imparting electromagnetic wave shielding properties to plastics include conductive surface treatments such as plating, and methods for incorporating metal powder, metal fibers, carbon fibers, metal-coated carbon fibers, and the like. As an attempt to further improve the electromagnetic wave shielding properties of plastics, for example, Patent Document 1 discloses a thermoplastic resin containing conductive fibers and an olefinic wax or olefinic polymer having a carboxylic anhydride group and/or a carboxyl group. In Patent Document 2, the O1S/C1S measured by the ESCA method on the carbon fiber surface before the nickel metal coating treatment of the nickel metal-coated carbon fiber is adjusted to a specific range. A thermoplastic resin composition containing nickel metal-coated carbon fibers obtained by the above method has been proposed. However, the method was not useful for polyarylene sulfide resins, and the electromagnetic wave shielding properties were not sufficient. Moreover, Patent Document 3 proposes a resin composition comprising a polyarylene sulfide resin, a modified polyolefin composition, and a fibrous filler, but does not describe electromagnetic wave shielding properties.
本発明の目的は、優れた機械強度を維持しつつ、電磁波遮蔽性に優れる樹脂組成物を提供することである。 An object of the present invention is to provide a resin composition having excellent electromagnetic shielding properties while maintaining excellent mechanical strength.
本発明者は鋭意検討を重ねた結果、ジヨードアリール化合物、固体硫黄並びに重合停止剤および/または重合反応触媒を、極性溶媒を使用せずに直接加熱して重合させる方法に
よって得られるポリアリーレンスルフィド樹脂、金属被覆炭素繊維および変性超高分子量ポリエチレンを含有する樹脂組成物が、優れた機械強度を維持しつつ、電磁波遮蔽性に優れる樹脂組成物であることを見出し本発明に至った。
As a result of extensive studies, the present inventors have found that a polyarylene sulfide obtained by a method of directly heating a diiodoaryl compound, solid sulfur, a polymerization terminator and/or a polymerization reaction catalyst without using a polar solvent for polymerization. The inventors have found that a resin composition containing a resin, metal-coated carbon fiber and modified ultra-high molecular weight polyethylene is a resin composition that maintains excellent mechanical strength and is excellent in electromagnetic wave shielding properties, leading to the present invention.
具体的には、上記課題は、(A)ジヨードアリール化合物、固体硫黄並びに重合停止剤および/または重合反応触媒を、極性溶媒を使用せずに直接加熱して重合させる方法によって得られるポリアリーレンスルフィド樹脂(A成分)100重量部に対し、(B)金属被覆炭素繊維(B成分)5~100重量部および(C)変性超高分子量ポリエチレン(C成分)1~50重量部を含有する樹脂組成物により達成される。 Specifically, the above problem is (A) a polyarylene obtained by a method of directly heating and polymerizing a diiodoaryl compound, solid sulfur, a polymerization terminator and/or a polymerization reaction catalyst without using a polar solvent. Resin containing (B) 5 to 100 parts by weight of metal-coated carbon fiber (B component) and (C) 1 to 50 parts by weight of modified ultra-high molecular weight polyethylene (C component) with respect to 100 parts by weight of sulfide resin (A component) achieved by the composition.
以下、本発明の詳細について説明する。 The details of the present invention will be described below.
(A成分:ポリアリーレンスルフィド樹脂)
本発明のA成分として使用されるポリアリーレンスルフィド樹脂は、ジヨードアリール化合物、固体硫黄並びに重合停止剤および/または重合反応触媒を、極性溶媒を使用せずに直接加熱して重合させる方法によって得られるポリアリーレンスルフィド樹脂である。
(A component: polyarylene sulfide resin)
The polyarylene sulfide resin used as the A component of the present invention is obtained by a method of directly heating and polymerizing a diiodoaryl compound, solid sulfur, a polymerization terminator and/or a polymerization reaction catalyst without using a polar solvent. It is a polyarylene sulfide resin that is used.
ポリアリーレンスルフィド樹脂としては、その構成単位として、例えばp-フェニレンスルフィド単位、m-フェニレンスルフィド単位、o-フェニレンスルフィド単位、フェニレンスルフィドスルホン単位、フェニレンスルフィドケトン単位、フェニレンスルフィドエーテル単位、ジフェニレンスルフィド単位、置換基含有フェニレンスルフィド単位、分岐構造含有フェニレンスルフィド単位、等よりなるものを挙げることができ、その中でも、p-フェニレンスルフィド単位を70モル%以上、特に90モル%以上含有しているものが好ましく、さらに、ポリ(p-フェニレンスルフィド)がより好ましい。 Examples of polyarylene sulfide resins include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and diphenylene sulfide units. , substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units Preferred, and more preferred is poly(p-phenylene sulfide).
本発明のA成分として使用されるポリアリーレンスルフィド樹脂の重量平均分子量(Mw)と数平均分子量(Mn)で表される分散度(Mw/Mn)は好ましくは2.7以上、より好ましくは2.8以上、さらに好ましくは2.9以上である。分散度が2.7未満の場合は、成形時のバリ発生が多くなる場合がある。なお、分散度(Mw/Mn)の上限は特に規定されないが、10以下であることが好ましい。ここで、重量平均分子量(Mw)および数平均分子量(Mn)はゲルパーミネーションクロマトグラフィー(GPC)により、ポリスチレン換算で算出された値である。なお、溶媒には1-クロロナフタレンを使用し、カラム温度は210℃とした。 The polyarylene sulfide resin used as the A component of the present invention preferably has a dispersity (Mw/Mn) represented by a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 2.7 or more, more preferably 2. 0.8 or more, more preferably 2.9 or more. If the degree of dispersion is less than 2.7, burrs may occur more frequently during molding. Although the upper limit of the degree of dispersion (Mw/Mn) is not particularly defined, it is preferably 10 or less. Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC). 1-Chloronaphthalene was used as a solvent, and the column temperature was 210°C.
ポリアリーレンスルフィド樹脂の製造方法としては、例えば米国登録特許第4,746,758号、第4,786,713号、特表2013-522385、特開2012-233210および特許5167276等に記載された製造方法が挙げられる。 As a method for producing a polyarylene sulfide resin, for example, the production described in US Patent Nos. 4,746,758, 4,786,713, JP 2013-522385, JP 2012-233210 and JP 5167276, etc. method.
前記製造方法はヨウ化工程および重合工程を含む。該ヨウ化工程ではアリール化合物をヨードと反応させて、ジヨードアリール化合物を得る。続く重合工程で、重合停止剤を用いてジヨードアリール化合物を固体硫黄と重合反応させてポリアリーレンスルフィド樹脂を製造する。ヨードはこの工程で気体状で発生し、これを回収して再びヨウ化工程に用いられる。実質的にヨードは触媒である。 The manufacturing method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to give a diiodoaryl compound. In the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a polymerization terminator to prepare a polyarylene sulfide resin. Iodine is generated in gaseous form in this process, and this is recovered and used again in the iodination process. Iodine is essentially a catalyst.
前記製造方法で用いられる代表的な固体硫黄としては、室温で8個の原子が連結されたシクロオクタ硫黄形態(S8)が挙げられる。しかしながら重合反応に用いられる硫黄化合物は限定されるものではなく、常温で固体または液体であればいずれの形態でも使用し得る。 A representative solid sulfur used in the method of preparation includes the cyclooctasulphur form (S 8 ) with 8 atoms linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited and may be used in any form as long as it is solid or liquid at room temperature.
前記製造方法で用いられる代表的なジヨードアリール化合物としては、ジヨードベンゼ
ン、ジヨードナフタレン、ジヨードビフェニル、ジヨードビスフェノールおよびジヨードベンゾフェノンからなる群より選ばれる少なくとも1種が挙げられ、またアルキル基やスルホン基が結合していたり、酸素や窒素が導入されたりしているヨードアリール化合物の誘導体も使用される。ヨードアリール化合物はそのヨード原子の結合位置によって異なる異性体に分類され、これらの異性体のうち好ましい例は、p-ジヨードベンゼン、2,6-ジヨードナフタレン、及びp,p’-ジヨードビフェニルのようにヨードがアリール化合物の分子両端に対称的に位置する化合物である。該ヨードアリール化合物の含有量は前記固体硫黄100重量部に対し500~10,000重量部であることが好ましい。この量はジスルフィド結合の生成を考慮して決定される。
Typical diiodoaryl compounds used in the production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl Derivatives of iodoaryl compounds to which a group or sulfone group is attached, or to which oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodine. It is a compound in which iodine is symmetrically positioned at both ends of an aryl compound, such as biphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.
前記製造方法で用いられる代表的な重合停止剤としては、ジフェニルスルフィド、ジフェニルジスルフィドなどが挙げられる。重合停止剤の含有量は前記固体硫黄100重量部に対し1~30重量部であることが好ましい。この量はジスルフィド結合の生成を考慮して決定される。 Typical polymerization terminator used in the production method includes diphenyl sulfide and diphenyl disulfide. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.
前記製造方法では重合反応触媒を使用しても良く、代表的な重合反応触媒としては、ニトロベンゼン系触媒が挙げられる。ニトロベンゼン系触媒のうち好ましい例としては、1,3-ジヨード-4-ニトロベンゼン、1-ヨード-4-ニトロベンゼン、2,6-ジヨード-4-ニトロフェノール、ヨードニトロベンゼン、2,6-ジヨード-4-ニトロアミンからなる群より選ばれる少なくとも1種が挙げられる。重合反応触媒の含有量は前記固体硫黄100重量部に対し0.01~20重量部であることが好ましい。この量はジスルフィド結合の生成を考慮して決定される。 A polymerization reaction catalyst may be used in the production method, and a typical polymerization reaction catalyst is a nitrobenzene-based catalyst. Preferred examples of nitrobenzene-based catalysts include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, 2,6-diiodo-4- At least one selected from the group consisting of nitroamines can be mentioned. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.
この重合方法で調製されたポリアリーレンスルフィド樹脂を使うことにより、変性超高分子量ポリエチレンを添加することでポリアリーレンスルフィド樹脂と金属被覆炭素繊維との密着性が低下し、溶融混錬時の金属被覆炭素繊維の折れを抑制することができ、電磁波遮蔽性が向上すると考えられる。 By using the polyarylene sulfide resin prepared by this polymerization method, the addition of modified ultra-high molecular weight polyethylene reduces the adhesion between the polyarylene sulfide resin and the metal-coated carbon fiber, and the metal coating during melt kneading. It is thought that the breakage of the carbon fibers can be suppressed and the electromagnetic wave shielding properties are improved.
(B成分:金属被覆炭素繊維)
本発明で使用される金属被覆炭素繊維は、炭素繊維にメッキ法および蒸着法などの公知の方法で金属を被覆したものであり、導電性、耐食性、生産性および経済性の観点から、ニッケルを被覆したものが好ましい。金属が被覆されていない炭素繊維を使用した場合、電磁波遮蔽性に劣る。さらに本発明の金属被覆炭素繊維は、炭素繊維表面に電気メッキにより金属被覆を設けることが好ましい。電気メッキによってより強固な金属被覆が形成され、良好な電磁波遮蔽性を有する樹脂組成物が提供される。
(B component: metal-coated carbon fiber)
The metal-coated carbon fiber used in the present invention is obtained by coating a carbon fiber with a metal by a known method such as a plating method and a vapor deposition method. A coated one is preferred. When carbon fibers that are not coated with metal are used, the electromagnetic wave shielding properties are poor. Furthermore, in the metal-coated carbon fiber of the present invention, it is preferable to provide a metal coating on the surface of the carbon fiber by electroplating. Electroplating forms a stronger metal coating and provides a resin composition having good electromagnetic wave shielding properties.
金属被覆される炭素繊維としては、例えば、フェノール樹脂、レーヨン、およびポリアクリロニトリルなどの高分子繊維を出発原料とする炭素繊維、並びに石炭系ピッチ、石油系ピッチまたは液晶ピッチなどのピッチ系繊維を出発原料とする炭素繊維が代表的に例示される。また、芳香族スルホン酸類またはそれらの塩のメチレン型結合による重合体との溶媒よりなる原料組成物を紡糸または成形し、次いで炭化する方法に代表される不融化工程を経ることなく紡糸を行う方法により得られた炭素繊維も使用可能である。更に汎用タイプ、中弾性率タイプ、および高弾性率タイプのいずれも使用可能である。 Examples of carbon fibers to be metal-coated include carbon fibers starting from polymer fibers such as phenolic resin, rayon, and polyacrylonitrile, and pitch-based fibers such as coal-based pitch, petroleum-based pitch, and liquid crystal pitch. Carbon fiber as a raw material is typically exemplified. Alternatively, a method of spinning or molding a raw material composition comprising a polymer with a methylene bond of an aromatic sulfonic acid or a salt thereof and a solvent, followed by carbonization, in which spinning is performed without undergoing an infusibilization step. It is also possible to use carbon fibers obtained by Furthermore, general-purpose type, medium modulus type, and high modulus type can all be used.
尚、炭素繊維の炭化または黒鉛化処理は、炭化処理においては炭素繊維化可能な繊維を、例えば450~1,500℃程度の温度で焼成処理することが好ましく、黒鉛化処理においては例えば1,500~3,300℃程度の温度で焼成処理することが好ましい。尚、かかる熱処理によって必ずしも黒鉛の結晶構造を生ずることは必要とされない。 In the carbonization or graphitization of carbon fibers, it is preferable to calcine fibers that can be converted into carbon fibers at a temperature of, for example, about 450 to 1,500°C. It is preferable to carry out the firing treatment at a temperature of about 500 to 3,300°C. It should be noted that such heat treatment does not necessarily require the formation of a graphite crystal structure.
B成分の含有量は、A成分100重量部に対し、5~100重量部であり、好ましくは
10~80重量部、より好ましくは20~60重量部である。B成分の含有量が5重量部未満では、十分な機械強度が得られず、電磁波遮蔽性も劣る。他方、100重量部を超えると生産性または成形加工性が低下する。
The content of component B is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 5 parts by weight, sufficient mechanical strength cannot be obtained and the electromagnetic wave shielding properties are also inferior. On the other hand, if it exceeds 100 parts by weight, the productivity or moldability will be lowered.
(C成分:変性超高分子量ポリエチレン)
本発明で使用される変性超高分子量ポリエチレンは超高分子量ポリエチレンを変性した重合体である。変性超高分子量ポリエチレンは、例えば、超高分子量ポリエチレンおよび変性基を含有する化合物を溶融混練し、超高分子量ポリエチレンをグラフト変性して変性基を導入することにより得られる。変性されるポリエチレンはポリエチレンと超高分子量ポリエチレンの混合物であっても良い。変性に用いられる変性成分としては、無水マレイン酸、無水イタコン酸などが挙げられるが、特に無水マレイン酸が好ましい。C成分の変性基の含有率は0.05~3重量%であることが好ましい。0.05重量%未満では電磁波遮蔽性に劣る場合があり、他方、3重量%を超えると機械物性に劣る場合がある。このような変性ポリエチレンとしては三井化学(株)よりリュブマー LY1040として容易に入手可能である。なお、変性されていない超高分子量ポリエチレンを使用した場合、電磁波遮蔽性に劣る。また、変性超高分子量ポリエチレンの重量平均分子量は6,000,000未満であることが好ましく、3,000,000未満であることがより好ましく、1,000,000未満であることがさらに好ましい。なお、重量平均分子量の下限は100,000以上が好ましく、150,000以上がより好ましい。重量平均分子量が6,000,000以上の場合、生産性または加工性に劣る場合があり、100,000未満の場合、電磁波遮蔽性に劣る場合がある。
(C component: modified ultra-high molecular weight polyethylene)
The modified ultra-high molecular weight polyethylene used in the present invention is a polymer obtained by modifying ultra-high molecular weight polyethylene. Modified ultra-high molecular weight polyethylene can be obtained, for example, by melt-kneading ultra-high molecular weight polyethylene and a compound containing a modifying group, and graft-modifying the ultra-high molecular weight polyethylene to introduce modifying groups. The modified polyethylene may be a mixture of polyethylene and ultra high molecular weight polyethylene. Examples of modifying components used for modification include maleic anhydride and itaconic anhydride, with maleic anhydride being particularly preferred. The content of the modifying group in component C is preferably 0.05 to 3% by weight. If it is less than 0.05% by weight, the electromagnetic wave shielding properties may be inferior, and if it exceeds 3% by weight, the mechanical properties may be inferior. Such modified polyethylene is readily available from Mitsui Chemicals, Inc. as Lubmer LY1040. When non-modified ultra-high molecular weight polyethylene is used, the electromagnetic wave shielding property is inferior. Also, the weight average molecular weight of the modified ultra-high molecular weight polyethylene is preferably less than 6,000,000, more preferably less than 3,000,000, even more preferably less than 1,000,000. In addition, the lower limit of the weight average molecular weight is preferably 100,000 or more, more preferably 150,000 or more. If the weight-average molecular weight is 6,000,000 or more, the productivity or workability may be poor, and if it is less than 100,000, the electromagnetic shielding property may be poor.
C成分の含有量は、A成分100重量部に対し、1~50重量部であり、好ましくは2~40重量部、より好ましくは3~30重量部である。含有量が1重量部未満の場合、電磁波遮蔽性が不十分であり、50重量部を超えると機械物性が著しく低下する。 The content of component C is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight, per 100 parts by weight of component A. If the content is less than 1 part by weight, the electromagnetic wave shielding properties are insufficient, and if it exceeds 50 parts by weight, the mechanical properties are remarkably lowered.
(その他の成分)
本発明における樹脂組成物は本発明の効果を損なわない範囲で金属被覆炭素繊維以外の無機充填剤を併用することができる。無機充填剤としては、金属被覆炭素繊維以外の繊維状充填剤、粉末状充填剤、板状充填剤などが挙げられる。繊維状充填剤としてはガラス繊維、アラミド繊維、チタン酸カリウムウィスカー、酸化亜鉛ウィスカー、アルミナ繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石コウ繊維、金属繊維、金属以外の導電性物質で被覆された無機繊維などが挙げられる。金属以外の導電性物質で被覆された無機繊維における導電性物質の具体例としてはSnO2(アンチモンドープ)、In2O3(アンチモンドープ)などが例示できる。また被覆される無機繊維としては、ガラス繊維、チタン酸カリウムウィスカー、酸化亜鉛ウィスカー、チタン酸系ウィスカー、炭化珪素ウィスカーなどが例示できる。被覆方法としては真空蒸着法、スパッタリング法、無電解メッキ法、焼き付け法などが挙げられる。またこれらはチタネート系、アルミ系、シラン系カップリング剤などの表面処理剤で表面処理を施されていてもよい。また、これら繊維状充填剤をイソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物およびエポキシ化合物などのカップリング剤で予備処理して使用することは、より優れた機械的強度を得る意味において好ましい。粉末状充填剤としてはカーボンブラック、炭酸カルシウム、シリカ、酸化チタン、黒鉛、カーボンナノチューブ、金属粉などが挙げられ、板状充填剤としてはタルクやマイカなどが挙げられる。
(other ingredients)
Inorganic fillers other than metal-coated carbon fibers can be used in combination with the resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of inorganic fillers include fibrous fillers other than metal-coated carbon fibers, powder fillers, and plate-like fillers. Examples of fibrous fillers include glass fibers, aramid fibers, potassium titanate whiskers, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, and non-metallic conductive substances. and inorganic fibers. SnO 2 (antimony-doped), In 2 O 3 (antimony-doped), etc. can be given as specific examples of the conductive substance in the inorganic fiber coated with a conductive substance other than metal. Inorganic fibers to be coated include glass fibers, potassium titanate whiskers, zinc oxide whiskers, titanate whiskers, silicon carbide whiskers, and the like. Examples of coating methods include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. Moreover, these may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent. In addition, pretreatment of these fibrous fillers with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound leads to better mechanical strength. is preferable in the sense of obtaining Examples of powdery fillers include carbon black, calcium carbonate, silica, titanium oxide, graphite, carbon nanotubes, and metal powders. Examples of plate-like fillers include talc and mica.
本発明における樹脂組成物は本発明の効果を損なわない範囲で、エラストマー成分を含むことができる。好適なエラストマー成分としては、アクリロニトリル・ブタジエン・スチレン系共重合体(ABS樹脂)、メチルメタクリレート・ブタジエン・スチレン共重合体(MBS樹脂)およびシリコーン・アクリル複合ゴム系グラフト共重合体などのコア-シェルグラフト共重合体樹脂、あるいはシリコーン系熱可塑性エラストマー、オレフィン
系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマーなどの熱可塑性エラストマーが挙げられる。
The resin composition in the present invention can contain an elastomer component within a range that does not impair the effects of the present invention. Suitable elastomer components include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and core-shell such as silicone-acrylic composite rubber graft copolymer. Examples include graft copolymer resins, thermoplastic elastomers such as silicone thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers.
本発明における樹脂組成物は本発明の効果を損なわない範囲で、他の熱可塑性樹脂を含むことができる。他の熱可塑性樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアルキルメタクリレート樹脂などに代表される汎用プラスチックス、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、芳香族ポリエステル樹脂、液晶性ポリエステル樹脂、ポリアミド樹脂、環状ポリオレフィン樹脂、ポリアリレート樹脂(非晶性ポリアリレート、液晶性ポリアリレート)等に代表されるエンジニアリングプラスチックス、ポリテトラフルオロエチレン、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリサルフォン、ポリエーテルサルフォン、などのいわゆるスーパーエンジニアリングプラスチックスと呼ばれるものを挙げることができる。 The resin composition in the present invention can contain other thermoplastic resins as long as the effects of the present invention are not impaired. Other thermoplastic resins include, for example, polyethylene resins, polypropylene resins, general-purpose plastics represented by polyalkyl methacrylate resins, polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystalline polyester resins, polyamide resins, cyclic Engineering plastics represented by polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), polytetrafluoroethylene, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, etc. So-called super engineering plastics can be mentioned.
本発明における樹脂組成物は本発明の効果を損なわない範囲で、酸化防止剤や耐熱安定剤(ヒンダードフェノール系、ヒドロキノン系、ホスファイト系およびこれらの置換体等)、耐候剤(レゾルシノール系、サリシレート系、ベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系等)、離型剤および滑剤(モンタン酸およびその金属塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミド、各種ビスアミド、ビス尿素およびポリエチレンワックス等)、顔料(硫化カドミウム、フタロシアニン、カーボンブラック等)、染料(ニグロシン等)、結晶核剤(タルク、シリカ、カオリン、クレー等)、可塑剤(p-オキシ安息香酸オクチル、N-ブチルベンゼンスルホンアミド等)、帯電防止剤(アルキルサルフェート型アニオン系帯電防止剤、4級アンモニウム塩型カチオン系帯電防止剤、ポリオキシエチレンソルビタンモノステアレートのような非イオン系帯電防止剤、ベタイン系両性帯電防止剤等)、難燃剤(赤燐、リン酸エステル、メラミンシアヌレート、水酸化マグネシウム、水酸化アルミニウム等の水酸化物、ポリリン酸アンモニウム、臭素化ポリスチレン、臭素化ポリフェニレンエーテル、臭素化ポリカーボネート、臭素化エポキシ樹脂あるいはこれらの臭素系難燃剤と三酸化アンチモンとの組み合わせ等)および他の重合体を添加することができる。 The resin composition of the present invention contains antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites, and substituted compounds thereof), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), release agents and lubricants (montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene waxes, etc.) , pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.) ), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc. ), flame retardants (red phosphorus, phosphates, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin Alternatively, combinations of these brominated flame retardants with antimony trioxide, etc.) and other polymers can be added.
(樹脂組成物の製造)
本発明の樹脂組成物は上記各成分を同時に、または任意の順序でタンブラー、V型ブレンダー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機等の混合機により混合して製造することができる。好ましくは2軸押出機による溶融混練が好ましく、必要に応じて、任意の成分をサイドフィーダー等を用いて第2供給口より、溶融混合された他の成分中に供給することが好ましい。
(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above components at the same time or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading rolls, and extruder. Melt-kneading by a twin-screw extruder is preferable, and if necessary, it is preferable to feed optional components into other melt-mixed components from the second supply port using a side feeder or the like.
上記の如く押出された樹脂は、直接切断してペレット化するか、またはストランドを形成した後かかるストランドをペレタイザーで切断してペレット化される。ペレット化に際して外部の埃などの影響を低減する必要がある場合には、押出機周囲の雰囲気を清浄化することが好ましい。得られたペレットの形状は、円柱、角柱、および球状など一般的な形状を取り得るが、より好適には円柱である。かかる円柱の直径は好ましくは1~5mm、より好ましくは1.5~4mm、さらに好ましくは2~3.5mmである。一方、円柱の長さは好ましくは1~30mm、より好ましくは2~5mm、さらに好ましくは2.5~4mmである。 The resin extruded as described above is either directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization. The shape of the obtained pellets can take general shapes such as cylinders, prisms, and spheres, but cylinders are more preferable. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.5 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-4 mm.
(成形品について)
本発明の樹脂組成物を用いてなる成形品は、上記の如く製造されたペレットを成形して得ることができる。好適には、射出成形、押出成形により得られる。射出成形においては、通常の成形方法だけでなく、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体を注入する方法を含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、多色成形、サンドイッチ成形、および超高速射出成形等を挙げることができる。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。また押出成形では、各種異形押出成形品、シート、フィルム等が得られる。シート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法等も使用可能である。更に特定の延伸操作をかけることにより熱収縮チューブとして成形することも可能である。また本発明の樹脂組成物を回転成形やブロー成形等により成形品とすることも可能である。
(About molded products)
A molded article using the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, heat insulation Mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, ultra-high speed injection molding and the like can be mentioned. For molding, either cold runner method or hot runner method can be selected. Extrusion molding can also provide various shaped extruded products, sheets, films, and the like. Inflation method, calendering method, casting method and the like can be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.
更に上記各種の方法で製造された成形品には、各種の表面処理を行うことが可能である。ここでいう表面処理とは、蒸着(物理蒸着、化学蒸着など)、メッキ(電気メッキ、無電解メッキ、溶融メッキなど)、塗装、コーティング、印刷などの樹脂成形品の表層上に新たな層を形成させるものであり、樹脂成形品に用いられる各種方法が適用できる。更にシート成形品(リボン状成形品を含む)を更に各種真空成形、熱プレス成形、および曲げ加工などすることにより、各種の搬送容器や電磁波遮蔽カバーなどを製造することもできる。 Further, various surface treatments can be applied to the molded articles produced by the various methods described above. Surface treatment here refers to deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. Various methods used for resin molded products can be applied. Furthermore, by subjecting the sheet molded product (including the ribbon-shaped molded product) to various vacuum forming, hot press forming, bending, etc., various transport containers, electromagnetic wave shielding covers, and the like can be produced.
本発明の樹脂組成物は、優れた機械強度を維持しつつ、電磁波遮蔽性に優れるため、本発明の樹脂組成物より得られる成形体は電子機器やアンテナなどのカバーとして好適に用いられる。 The resin composition of the present invention is excellent in electromagnetic wave shielding properties while maintaining excellent mechanical strength. Therefore, molded articles obtained from the resin composition of the present invention are suitably used as covers for electronic devices, antennas, and the like.
本発明者が現在最良と考える本発明の形態は、前記の各要件の好ましい範囲を集約したものとなるが、例えば、その代表例を下記の実施例中に記載する。もちろん本発明はこれらの形態に限定されるものではない。 The best mode of the present invention, which the present inventors consider to be the best, summarizes the preferable range of each of the requirements described above, and representative examples thereof are described in the following examples, for example. Of course, the present invention is not limited to these forms.
[樹脂組成物の評価]
(1)引張破断強度
ISO527(測定条件23℃)に準拠して測定した。なお、試験片は、下記の方法で成形した。この数値が大きいほど樹脂組成物の機械的強度が優れていることを意味する。
[Evaluation of Resin Composition]
(1) Tensile strength at break Measured according to ISO527 (measurement conditions: 23°C). In addition, the test piece was molded by the following method. It means that the larger the numerical value, the better the mechanical strength of the resin composition.
(2)電磁波遮蔽性
150×150×2mmtの試験片を用いてネットワークアナライザー(キーサイトテクノロジー社製)およびKEC法測定装置(JSE社製)で電界波(周波数500MHz)について電磁波遮蔽性を測定した。この数値が大きいほど電磁波遮蔽性に優れていることを意味する。
(2) Electromagnetic wave shielding property Using a test piece of 150 x 150 x 2 mmt, electromagnetic wave shielding property was measured with respect to an electric field wave (frequency of 500 MHz) with a network analyzer (manufactured by Keysight Technologies) and a KEC method measuring device (manufactured by JSE). . It means that the larger the numerical value, the better the electromagnetic wave shielding property.
[実施例1~6、比較例1~8]
ポリアリーレンスルフィド樹脂、金属被覆炭素繊維および変性超高分子量ポリエチレンを表1に記載の各配合量で、ベント式二軸押出機を用いて溶融混練してペレットを得た。ベント式二軸押出機は日本製鋼所(株)製:TEX30α‐38(完全かみ合い、同方向回転)を使用した。押出条件は吐出量20kg/h、スクリュー回転数200rpm、ベントの真空度3kPaであり、また押出温度は第一供給口からダイス部分まで320℃とした。なお、金属被覆炭素繊維は上記押出機のサイドフィーダーを使用し第二供給口から供給し、ポリアリーレンスルフィド樹脂および変性超高分子量ポリエチレンは第一供給口から押出機に供給した。ここでいう第一供給口とはダイスから最も離れた供給口であり、第二供給口とは押出機のダイスと第一供給口の間に位置する供給口である。得られたペレットを130℃で6時間、熱風循環式乾燥機にて乾燥した後、射出成形機(東芝機械(株)製 EC160NII-4Y)によりシリンダー温度320℃、金型温度140℃で評価用の試験片を成形した。
[Examples 1 to 6, Comparative Examples 1 to 8]
Polyarylene sulfide resin, metal-coated carbon fiber, and modified ultra-high molecular weight polyethylene were melt-kneaded in the amounts shown in Table 1 using a vented twin-screw extruder to obtain pellets. The vented twin-screw extruder used was TEX30α-38 (completely meshed, co-rotating) manufactured by Japan Steel Works, Ltd. The extrusion conditions were a discharge rate of 20 kg/h, a screw rotation speed of 200 rpm, and a vent vacuum degree of 3 kPa. The metal-coated carbon fiber was supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin and the modified ultrahigh molecular weight polyethylene were supplied to the extruder from the first supply port. The first feed port here is the feed port farthest from the die, and the second feed port is the feed port located between the die and the first feed port of the extruder. After drying the obtained pellets at 130 ° C. for 6 hours with a hot air circulating dryer, an injection molding machine (EC160NII-4Y manufactured by Toshiba Machine Co., Ltd.) was used for evaluation at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. A test piece was molded.
表1中の記号表記の各成分は下記の通りである。
<A成分>
A-1:以下の製造方法で得られたポリフェニレンスルフィド樹脂
[製造方法]
パラジヨードベンゼン300.00g及び硫黄27.00gに、重合停止剤としてジフェニルジスルフィド0.60g(最終的に重合されたPPSの重量に基づいて0.65重量%の含量)を投入して180℃に加熱して完全にそれらを溶融及び混合した後、温度を220℃に昇温し、且つ、圧力を200Torrに降圧した。得られた混合物を、最終温度及び圧力が夫々320℃及び1Torrとなるように温度及び圧力を段階的に変化させつつ、8時間重合反応させて末端基がフェニル基であるポリフェニレンスルフィド樹脂(A-1)を得た。
Each component of symbol notation in Table 1 is as follows.
<A component>
A-1: Polyphenylene sulfide resin obtained by the following production method [manufacturing method]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide as a polymerization terminator (content of 0.65% by weight based on the weight of the final polymerized PPS) was added and heated to 180°C. After heating to completely melt and mix them, the temperature was raised to 220°C and the pressure was lowered to 200 Torr. The obtained mixture is polymerized for 8 hours while changing the temperature and pressure stepwise so that the final temperature and pressure are 320° C. and 1 Torr, respectively, to obtain a polyphenylene sulfide resin (A- 1) was obtained.
A-2:以下の製造方法で得られたポリフェニレンスルフィド樹脂
[製造方法]
攪拌機を装備する15リットルオートクレーブに、フレーク状硫化ソーダ(Na2S・2.9H2O)1814g、粒状の苛性ソーダ(100%NaOH:和光純薬特級)8.7g及びN-メチル-2-ピロリドン3232gを仕込み、窒素気流下攪拌しながら徐々に200℃まで昇温して、339gの水を留去した。190℃まで冷却した後、p-ジクロロベンゼン2129g、N-メチル-2-ピロリドン1783gを添加し、窒素気流下に系を封入した。この系を2時間かけて225℃に昇温し、225℃にて1時間重合させた後、25分かけて250℃に昇温し、250℃にて2時間重合を行った。次いで、この系に250℃で蒸留水509gを圧入し、255℃まで昇温してさらに2時間重合反応を行った。重合終了後、室温まで冷却し、重合スラリーを遠心濾過器で固液分離した。ケーキを窒素気流下でN-メチル-2-ピロリドン、アセトンで順次3回繰り返し洗浄し、さらに、窒素気流下で0.2%塩酸、及び温水で順次洗浄した。得られたポリ(p-フェニレンスルフィド)を105℃で一昼夜乾燥することによって、ポリアリーレンスルフィド樹脂(A-2)を得た。
A-2: Polyphenylene sulfide resin obtained by the following production method [manufacturing method]
1814 g of flaky sodium sulfide (Na 2 S.2.9H 2 O), 8.7 g of granular caustic soda (100% NaOH: special grade of Wako Pure Chemical) and N-methyl-2-pyrrolidone were placed in a 15-liter autoclave equipped with a stirrer. 3232 g was charged, and the temperature was gradually raised to 200° C. while stirring under a nitrogen stream, and 339 g of water was distilled off. After cooling to 190° C., 2129 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under nitrogen stream. The system was heated to 225° C. over 2 hours, polymerized at 225° C. for 1 hour, then heated to 250° C. over 25 minutes, and polymerized at 250° C. for 2 hours. Then, 509 g of distilled water was injected into this system at 250° C., the temperature was raised to 255° C., and the polymerization reaction was further carried out for 2 hours. After the polymerization was completed, the system was cooled to room temperature, and the polymer slurry was subjected to solid-liquid separation using a centrifugal filter. The cake was washed successively three times with N-methyl-2-pyrrolidone and acetone under a nitrogen stream, and further washed successively with 0.2% hydrochloric acid and warm water under a nitrogen stream. The resulting poly(p-phenylene sulfide) was dried at 105° C. for one day to obtain a polyarylene sulfide resin (A-2).
<B成分>
B-1:HT C923(帝人(株)製 繊維径:7.5μm、カット長:6mm、ニッケル金属被覆炭素繊維)
B-2:特開昭59-226195号公報に開示された条件に準じて銅めっき処理された銅金属被覆炭素繊維(繊維径:7.5μm、カット長:6mm、銅金属被覆炭素繊維)
B-3:HT P722(帝人(株)製 繊維系:7.0μm、カット長:3mm、PAN系炭素繊維)
<B component>
B-1: HT C923 (manufactured by Teijin Limited, fiber diameter: 7.5 μm, cut length: 6 mm, nickel metal coated carbon fiber)
B-2: Copper metal-coated carbon fiber (fiber diameter: 7.5 μm, cut length: 6 mm, copper metal-coated carbon fiber) plated with copper according to the conditions disclosed in JP-A-59-226195.
B-3: HT P722 (manufactured by Teijin Limited, fiber system: 7.0 μm, cut length: 3 mm, PAN-based carbon fiber)
<C成分>
C-1:LY1040(三井化学(株)製 リュブマー(商品名)、無水マレイン酸変性超高分子量ポリエチレン、重量平均分子量160,000)
C-2:ハイゼックス2200J((株)プライムポリマー製、ポリエチレン、重量平均分子量100,000未満)
C-3:ハイゼックスミリオン630M(三井化学(株)製 超高分子量ポリエチレン、重量平均分子量100,000以上)
<C component>
C-1: LY1040 (Lubmer (trade name) manufactured by Mitsui Chemicals, Inc., maleic anhydride-modified ultra-high molecular weight polyethylene, weight average molecular weight 160,000)
C-2: Hi-Zex 2200J (manufactured by Prime Polymer Co., Ltd., polyethylene, weight average molecular weight less than 100,000)
C-3: Hi-Zex Million 630M (Ultra-high molecular weight polyethylene manufactured by Mitsui Chemicals, Inc., weight average molecular weight of 100,000 or more)
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