JP4674066B2 - Electromagnetic wave shielding thermoplastic resin composition - Google Patents
Electromagnetic wave shielding thermoplastic resin composition Download PDFInfo
- Publication number
- JP4674066B2 JP4674066B2 JP2004229557A JP2004229557A JP4674066B2 JP 4674066 B2 JP4674066 B2 JP 4674066B2 JP 2004229557 A JP2004229557 A JP 2004229557A JP 2004229557 A JP2004229557 A JP 2004229557A JP 4674066 B2 JP4674066 B2 JP 4674066B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- thermoplastic resin
- resin
- nickel metal
- coated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 61
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 55
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 139
- 239000004917 carbon fiber Substances 0.000 claims description 139
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 128
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 105
- 229910052751 metal Inorganic materials 0.000 claims description 82
- 239000002184 metal Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 81
- 229910052759 nickel Inorganic materials 0.000 claims description 64
- 229920005668 polycarbonate resin Polymers 0.000 claims description 32
- 239000004431 polycarbonate resin Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 238000004898 kneading Methods 0.000 claims description 22
- -1 polybutylene terephthalate Polymers 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 230000006872 improvement Effects 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- 238000004513 sizing Methods 0.000 description 22
- 239000000835 fiber Substances 0.000 description 20
- 238000011282 treatment Methods 0.000 description 19
- 238000000465 moulding Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 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 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical group CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical group CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229930003836 cresol Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 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
- 229920000642 polymer Polymers 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 150000003739 xylenols Chemical group 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 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
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical group CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 239000002134 carbon nanofiber Substances 0.000 description 1
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- 238000010000 carbonizing Methods 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 238000007772 electroless plating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
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- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Chemical group CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
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- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 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
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 239000002964 rayon Substances 0.000 description 1
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- 238000001175 rotational moulding Methods 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Description
本発明は、電磁波遮蔽性熱可塑性樹脂組成物、かかる樹脂組成物の製造方法、およびかかる樹脂組成物の電磁波遮蔽性向上方法に関する。より詳しくは、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、該樹脂組成物の製造方法、並びに該ニッケル金属被覆炭素繊維を用いることによる樹脂組成物の電磁波遮蔽性を向上する方法に関する。 The present invention relates to an electromagnetic wave shielding thermoplastic resin composition, a method for producing such a resin composition, and an electromagnetic wave shielding improvement method for such a resin composition. More specifically, heat containing nickel metal-coated carbon fibers obtained by adjusting O 1S / C 1S measured by the ESCA method on the carbon fiber surface of the nickel metal-coated carbon fibers before the nickel metal coating treatment to a specific range. The present invention relates to a plastic resin composition, a method for producing the resin composition, and a method for improving the electromagnetic wave shielding property of the resin composition by using the nickel metal-coated carbon fiber.
近年、コンピューターの如きＯＡ機器および情報端末機器等の電子機器において、そ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る場合がある。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、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必要が有る。
電磁波遮蔽効果を得る為には、電子機器筐体に導電性を付与する必要が有り、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。特に近年、中央演算処理装置の急速な高速化に伴い、より高い水準の電磁波遮蔽性が要求されてきている。
In recent years, in electronic equipment such as OA equipment and information terminal equipment such as computers, there is a problem in that electronic equipment causes malfunctions due to electromagnetic waves due to high integration and high density of circuits accompanying reduction in size and weight. There is. For this reason, it is necessary to provide an electromagnetic shielding effect for shielding the electromagnetic wave from the outside and preventing the leakage of the electromagnetic wave to the outside in the casing of the electronic device.
In order to obtain an electromagnetic wave shielding effect, it is necessary to impart electrical conductivity to the electronic device casing. Generally, the higher the electrical conductivity, the better the electromagnetic wave shielding property. In particular, in recent years, with the rapid increase in the speed of the central processing unit, a higher level of electromagnetic shielding has been required.
熱可塑性樹脂からなる成形品を導電化する方法としては、成形品表面に導電塗料の塗工、電磁波遮蔽メッキ処理、および亜鉛溶射等を施す表面処理による方法、並びに熱可塑性樹脂中に金属粉、カーボンブラック、金属フレーク、金属コートガラスフレーク、金属繊維、炭素繊維、および金属コート炭素繊維等の導電性充填材を添加して成形する方法が代表的な方法として例示される。
導電性充填材を添加した樹脂組成物から成形する方法は、従来より各種の提案がなされているが、それでもなお種々の問題がある。例えば、カーボンブラック、金属粉、および金属フレーク等の粒子状導電性充填材を添加した樹脂組成物は導電性が不十分である。しかもこれらは概してその添加量が多量になる為、樹脂組成物の機械的特性が著しく低下する欠点を有している。また、銅繊維、ステンレス繊維、炭素繊維、および金属コート炭素繊維等の繊維状導電性充填材を添加した樹脂組成物は、機械的および熱的特性が向上し、導電性が良好で電磁波遮蔽用樹脂組成物として有用である。しかしながら金属繊維類は折れ難いが故に成形加工性が悪化しやすく、一方炭素繊維類は溶融混練時の繊維の折れと共に導電性が低下する点で改良の余地がある。炭素繊維類の折れが抑制されると、少量で良好な導電性が得られるようになる。更に繰返しの溶融加工処理にも耐え得ることでリサイクル性に優れた樹脂材料が提供されるようになる。
かかる折れ抑制の効果は、樹脂の溶融粘度が高いほど効果的である。既にポリカーボネート樹脂、導電性繊維、密着性阻害成分、および特定の熱重量減少温度の有機リン化合物からなるリサイクル性に優れた電磁波遮蔽性樹脂組成物は公知である（特許文献１参照）。しかしながら該文献は、導電性繊維自体の特性が樹脂組成物の電磁波遮蔽性に与える影響については十分に開示していない。
As a method for making a molded article made of a thermoplastic resin conductive, a method by surface treatment for applying a conductive paint on the surface of the molded article, electromagnetic wave shielding plating treatment, zinc spraying, etc., and metal powder in the thermoplastic resin, Typical examples of the method include molding by adding a conductive filler such as carbon black, metal flake, metal-coated glass flake, metal fiber, carbon fiber, and metal-coated carbon fiber.
Various proposals have been made for methods of molding from a resin composition to which a conductive filler is added, but there are still various problems. For example, a resin composition to which particulate conductive fillers such as carbon black, metal powder, and metal flakes are added has insufficient conductivity. In addition, since these are generally added in a large amount, they have the disadvantage that the mechanical properties of the resin composition are significantly reduced. In addition, the resin composition to which fibrous conductive fillers such as copper fiber, stainless steel fiber, carbon fiber, and metal-coated carbon fiber are added has improved mechanical and thermal characteristics, good conductivity, and electromagnetic wave shielding. Useful as a resin composition. However, since metal fibers are not easily broken, the moldability is likely to be deteriorated, while carbon fibers have room for improvement in that the conductivity is lowered along with the bending of fibers during melt kneading. When the bending of the carbon fibers is suppressed, good conductivity can be obtained with a small amount. Furthermore, a resin material excellent in recyclability can be provided by withstanding repeated melt processing.
The effect of suppressing such folds is more effective as the melt viscosity of the resin is higher. An electromagnetic wave shielding resin composition excellent in recyclability comprising a polycarbonate resin, a conductive fiber, an adhesion inhibiting component, and an organophosphorus compound having a specific thermogravimetric decrease temperature is already known (see Patent Document 1). However, this document does not fully disclose the influence of the properties of the conductive fibers themselves on the electromagnetic wave shielding properties of the resin composition.
フッ素樹脂を除くマトリックス樹脂と、特定の比表面積あるいは炭素繊維表面の酸素含有量（Ｏ１ｓ／Ｃ１ｓ）が０．０５〜０．２０である酸化処理された炭素繊維とを含む樹脂組成物は公知である（特許文献２参照）。該文献は得られた樹脂組成物が良好な導電性を有することを示唆するが、具体的データは何ら開示していない。更に該文献は金属被覆炭素繊維について記載していない。
表面にしわを有する炭素繊維に金属被覆した金属被覆炭素繊維、並びに該炭素繊維は金属被覆のはがれやすさが改良されていることは公知である（特許文献３参照）。しかしながら該文献の知見にもかかわらず、電磁波遮蔽性の更に改良された金属被覆炭素繊維含有樹脂組成物が求められている。
ＥＳＣＡ法により測定されるＯ１Ｓ／Ｃ１Ｓのピーク比が０．１〜０．５であり、表面に生成する官能基であるカルボキシル基または水酸基の当量が０．６μｅｑ／ｇ以上でかつカルボキシル基／水酸基の比が１以上である金属酸化物コーティング用炭素繊維、並びに該炭素繊維は金属酸化物が均一かつ一定の付着量での強固な被覆を可能にすることは公知である（特許文献４参照）。しかしながら該文献は、電磁波遮蔽性の更に改良された樹脂組成物に関して十分な知見を開示していない。
炭素繊維束に電気メッキすることにより、金属被覆炭素繊維を製造する各種の方法は公知である（特許文献５〜８参照）。しかしながらいずれの文献においても電気メッキ前の炭素繊維の酸化処理の程度の重要性について教示したものはない。
It is known that metal-coated carbon fibers obtained by metal-coating carbon fibers having wrinkles on the surface, and that the carbon fibers have improved ease of peeling of the metal coating (see Patent Document 3). However, despite the knowledge of this document, there is a need for a metal-coated carbon fiber-containing resin composition with further improved electromagnetic shielding properties.
The peak ratio of O 1S / C 1S measured by the ESCA method is 0.1 to 0.5, and the carboxyl group or hydroxyl group equivalent which is a functional group generated on the surface is 0.6 μeq / g or more and the carboxyl group It is well known that carbon fiber for metal oxide coating having a ratio of / hydroxyl of 1 or more, and that the carbon fiber enables a strong coating with a uniform and constant adhesion amount of the metal oxide (Patent Document 4). reference). However, this document does not disclose sufficient knowledge regarding a resin composition having further improved electromagnetic wave shielding properties.
Various methods for producing metal-coated carbon fibers by electroplating a carbon fiber bundle are known (see Patent Documents 5 to 8). However, none of the documents teaches the importance of the degree of oxidation treatment of carbon fibers before electroplating.
本発明の目的は、ニッケル金属被覆炭素繊維を含有する電磁波遮蔽性熱可塑性樹脂組成物の電磁波遮蔽性を向上させる方法を提供すること、かかる電磁波遮蔽性の向上した熱可塑性樹脂組成物のペレットの製造方法および該ペレットを提供すること、並びに電磁波遮蔽性の向上したポリカーボネート樹脂組成物を提供することにある。 An object of the present invention is to provide a method for improving the electromagnetic wave shielding property of an electromagnetic wave shielding thermoplastic resin composition containing nickel metal-coated carbon fibers, and to improve the electromagnetic wave shielding property of the pellet of the thermoplastic resin composition with improved electromagnetic wave shielding property. It is in providing the manufacturing method and this pellet, and providing the polycarbonate resin composition which electromagnetic wave shielding property improved.
本発明者らは、上記目的を達成すべく、鋭意検討を重ねた結果、ポリカーボネート樹脂に代表される熱可塑性樹脂に、炭素繊維表面におけるＸ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）を０．１５〜０．１７の範囲に調整された炭素繊維にニッケル金属被覆を施したニッケル金属被覆炭素繊維を添加すると、上記目的に適う電磁波遮蔽性の向上が得られることを見出し、本発明に到達した。 As a result of intensive studies in order to achieve the above object, the inventors of the present invention have introduced a thermoplastic resin typified by polycarbonate resin with oxygen measured by X-ray photoelectron spectroscopy (ESCA method) on the surface of carbon fiber. the addition of the peak ratio (O 1S / C 1S) nickel metal-coated carbon fiber having been subjected to nickel metal-coated carbon fibers is adjusted to a range of from 0.15 to 0.17 of carbon, electromagnetic wave shielding that meets the above objects As a result, the present invention has been found.
より詳しくは、本発明者らは金属被覆炭素繊維自体の改良による樹脂組成物の電磁波遮蔽性の向上に関し鋭意検討をした。上述のとおり電磁波遮蔽性の低下の原因として溶融混練時の繊維の折れがあることから、当初折れにくい金属被覆炭素繊維に関して検討した。かかる検討において炭素繊維の強度と関連のある炭素繊維表面のＯ１Ｓ／Ｃ１Ｓの制御に着目した。しかしながらＯ１Ｓ／Ｃ１Ｓの値を従来より下げて炭素繊維の強度を向上させたものの樹脂組成物の電磁波遮蔽性は向上するどころか大きく低下することが判明した。かかる原因を鋭意究明したところ、炭素繊維表面から被覆された金属が脱落し、かかる脱落が電磁波遮蔽性の大幅な低下の原因となることを突き止めた。更にかかる知見に基づき精密にＯ１Ｓ／Ｃ１Ｓの制御を行なったところ、金属被覆が炭素繊維表面から脱落せず、かつ炭素繊維の折れにくい領域のあることが見出された。本発明者らはかかる知見に基づき更に研究をすすめ、本発明を完成するに至った。 More specifically, the present inventors have intensively studied on improving the electromagnetic shielding property of the resin composition by improving the metal-coated carbon fiber itself. As described above, since the fiber was broken at the time of melt kneading as a cause of the deterioration of the electromagnetic wave shielding property, the metal-coated carbon fiber which was difficult to break at first was examined. In such examination, attention was focused on the control of O 1S / C 1S on the surface of the carbon fiber which is related to the strength of the carbon fiber. However, although the value of O 1S / C 1S was lowered from the conventional value to improve the strength of the carbon fiber, it was found that the electromagnetic wave shielding property of the resin composition was greatly reduced rather than improved. As a result of earnest investigation of the cause, it was found that the metal coated from the surface of the carbon fiber dropped off, and that the dropping caused a significant decrease in electromagnetic shielding properties. Furthermore, when O 1S / C 1S was precisely controlled based on such knowledge, it was found that the metal coating did not fall off from the carbon fiber surface and there was a region where the carbon fiber was not easily broken. The present inventors have further studied based on such knowledge, and have completed the present invention.
本発明によれば、上記課題は、（Ｉ）熱可塑性樹脂１００重量部あたり、ニッケル金属被覆炭素繊維１〜１００重量部を含有する組成物であって、該ニッケル金属被覆炭素繊維は炭素繊維表面におけるＸ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）が、０．１５〜０．１７の範囲に調整された炭素繊維にニッケル金属被覆を施したニッケル金属被覆炭素繊維（Ｂ成分）であることを特徴とする電磁波遮蔽性熱可塑性樹脂組成物により達成される。
熱可塑性樹脂は、ポリカーボネート樹脂、ＡＢＳ樹脂およびポリブチレンテレフタレート樹脂からなる群より選ばれる少なくとも一種の樹脂であることが好ましい。
According to the present invention, the above-mentioned problem is (I) a composition containing 1 to 100 parts by weight of nickel metal-coated carbon fibers per 100 parts by weight of a thermoplastic resin, the nickel metal-coated carbon fibers having a carbon fiber surface. A carbon fiber having a peak ratio of oxygen to carbon (O 1S / C 1S ) measured by X-ray photoelectron spectroscopy (ESCA method) in the range of 0.15 to 0.17 is coated with a nickel metal coating. It is achieved by an electromagnetic wave shielding thermoplastic resin composition characterized by being applied nickel metal-coated carbon fiber (component B).
The thermoplastic resin is preferably a polycarbonate resin is at least one tree fat selected from the group consisting of ABS resin and polybutylene terephthalate resin.
本発明の好適な態様の１つは、（ＩＩ）上記熱可塑性樹脂は、ポリカーボネート樹脂を５０重量％以上含有する熱可塑性樹脂（Ａ成分）である上記構成（Ｉ）の電磁波遮蔽性熱可塑性樹脂組成物であり、更に好適な態様の１つは、（ＩＩＩ）更に、Ａ成分１００重量部あたり、有機リン化合物（Ｃ成分）１〜１００重量部を含む上記構成（ＩＩ）の電磁波遮蔽性熱可塑性樹脂組成物である。 One of the preferred embodiments of the present invention is: (II) The electromagnetic wave shielding thermoplastic resin having the above constitution (I), wherein the thermoplastic resin is a thermoplastic resin (component A) containing 50% by weight or more of a polycarbonate resin. One of the more preferable embodiments of the composition is (III) The electromagnetic wave shielding heat of the above-mentioned constitution (II) further comprising 1 to 100 parts by weight of an organophosphorus compound (component C) per 100 parts by weight of the component A It is a plastic resin composition.
また、本発明の別の態様によれば、（ＩＶ）（１）炭素繊維の表面を酸化処理して、Ｘ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）を０．１５〜０．１７の範囲に調整する工程（工程−Ｉ）、（２）該調整された炭素繊維束に電気メッキすることによりニッケル金属被覆炭素繊維を得る工程（工程−ＩＩ）、（３）該ニッケル金属被覆炭素繊維を集束剤を用いて集束処理し、集束されたニッケル金属被覆炭素繊維ロービングを得る工程（工程−ＩＩＩ）、（４）該ロービングを切断し、そのチョップドストランドを得る工程（工程−ＩＶ）、（５）熱可塑性樹脂を準備し、該熱可塑性樹脂１００重量部に対して、該チョップドストランド（Ｂ’成分）の割合が１〜１００重量部となるよう調整し、押出機に供給する工程（工程−Ｖ）、並びに（６）該熱可塑性樹脂とＢ’成分とを押出機中で溶融混練し樹脂組成物を得る工程（工程−ＶＩ）からなることを特徴とする電磁波遮蔽性熱可塑性樹脂組成物の製造方法が提供され、上記の課題が解決される。 Further, according to another aspect of the present invention, (IV) (1) the surface ratio of carbon fiber is oxidized, and the peak ratio of oxygen to carbon (O) measured by X-ray photoelectron spectroscopy (ESCA method) (O 1S / C 1S ) in the range of 0.15 to 0.17 (step-I), (2) step of obtaining nickel metal-coated carbon fibers by electroplating the adjusted carbon fiber bundle ( Step-II), (3) Step of bundling the nickel metal-coated carbon fiber with a sizing agent to obtain a bended nickel metal-coated carbon fiber roving (Step-III), (4) Cutting the roving The step of obtaining the chopped strand (step-IV), (5) preparing a thermoplastic resin, and the proportion of the chopped strand (B ′ component) is 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Tones And (6) a step of melt-kneading the thermoplastic resin and the B ′ component in the extruder to obtain a resin composition (step-VI). The manufacturing method of the electromagnetic shielding thermoplastic resin composition characterized by the above is provided, and said subject is solved.
また本発明の別の態様によれば、（Ｖ）熱可塑性樹脂１００重量部あたり、ニッケル金属被覆炭素繊維１〜１００重量部を含有する組成物の電磁波遮蔽性向上方法であって、該ニッケル金属被覆炭素繊維として炭素繊維表面におけるＸ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）が、０．１５〜０．１７の範囲に調整された炭素繊維にニッケル金属被覆を施したニッケル金属被覆炭素繊維（Ｂ成分）を用いることを特徴とする電磁波遮蔽性熱可塑性樹脂組成物の電磁波遮蔽性向上方法が提供され、上記の課題が解決される。 According to another aspect of the present invention, there is provided (V) a method for improving electromagnetic wave shielding of a composition containing 1 to 100 parts by weight of nickel metal-coated carbon fibers per 100 parts by weight of a thermoplastic resin, the nickel metal The peak ratio (O 1S / C 1S ) of oxygen and carbon measured by X-ray photoelectron spectroscopy (ESCA method) on the carbon fiber surface as the coated carbon fiber was adjusted to a range of 0.15 to 0.17. An electromagnetic wave shielding improvement method for an electromagnetic wave shielding thermoplastic resin composition characterized by using nickel metal coated carbon fiber (component B) in which nickel metal coating is applied to carbon fiber is provided, and the above-mentioned problems are solved. .
本発明の電磁波遮蔽性熱可塑性樹脂組成物は、従来の樹脂組成物から何らその組成や製造条件を変更することなく、電磁波遮蔽性が改良されたものである。かかる改良は折れ抑制剤を含有しない場合により顕著である。本発明の電磁波遮蔽性熱可塑性樹脂組成物の製造方法は、同様に組成や製造条件を変更することなく、電磁波遮蔽性が改良された樹脂組成物を製造するものであり、その結果電磁波遮蔽性の改良された樹脂成形品の提供を可能とする。本発明の電磁波遮蔽性の向上方法は上記樹脂組成物と同様の効果を有する。いずれも熱可塑性樹脂がポリカーボネート樹脂であると、上記の改良効果がより有効に発揮され、その機械特性、耐熱性、難燃性、および寸法安定性において従来どおりの特性を有しつつ、更に改良された電磁波遮蔽性を有する樹脂組成物が提供される。したがって、かかるポリカーボネート樹脂の電磁波遮蔽性熱可塑性樹脂組成物は、より高い水準の電磁波遮蔽性が要求される電子機器筐体に特に好適である。以上、本発明の方法並びに樹脂組成物は、電子機器の筐体を始め電磁波遮蔽を必要とする幅広い産業分野で好適であり、その奏する工業的効果は格別のものである。 The electromagnetic wave shielding thermoplastic resin composition of the present invention has improved electromagnetic wave shielding properties without changing the composition and production conditions of the conventional resin composition. Such an improvement is more conspicuous in the case of not containing a folding inhibitor. The method for producing an electromagnetic wave shielding thermoplastic resin composition of the present invention is to produce a resin composition having improved electromagnetic wave shielding properties without changing the composition and production conditions, and as a result, electromagnetic wave shielding properties. It is possible to provide improved resin molded products. The method for improving electromagnetic wave shielding properties of the present invention has the same effect as the above resin composition. In any case, when the thermoplastic resin is a polycarbonate resin, the above-mentioned improvement effect is more effectively exhibited, and further improvements are made while maintaining the mechanical properties, heat resistance, flame retardancy, and dimensional stability as usual. Provided is a resin composition having electromagnetic shielding properties. Therefore, the electromagnetic wave shielding thermoplastic resin composition of the polycarbonate resin is particularly suitable for an electronic device casing that requires a higher level of electromagnetic wave shielding. As described above, the method and the resin composition of the present invention are suitable in a wide range of industrial fields that require shielding of electromagnetic waves, including housings for electronic devices, and the industrial effects that they exhibit are exceptional.
以下、本発明の詳細について説明する。
＜熱可塑性樹脂＞
本発明で使用する熱可塑性樹脂は、基本的に限定されるものではなく、特に電子機器の筺体に用いられる熱可塑性樹脂が好ましく使用される。かかる熱可塑性樹脂としては、例えばポリプロピレン樹脂、ポリスチレン樹脂、変性ポリフェニレンオキサイド樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリフェニレンスルフィド樹脂、ポリエステル系樹脂等が挙げられる。特に好ましいものとしては、例えばＡＢＳ樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂およびこれらの二種以上の混合物が挙げられる。特にポリカーボネート樹脂を主体とする熱可塑性樹脂が好ましく、より好ましくはその１００重量％中ポリカーボネート樹脂を５０重量％以上含有する熱可塑性樹脂（Ａ成分）である。ポリカーボネート樹脂は機械的強度や寸法精度の点で良好である一方、溶融粘度が高くニッケル金属被覆炭素繊維の表面金属の脱落および折れが生じやすく、本発明の効果がより発揮されるためである。
Details of the present invention will be described below.
<Thermoplastic resin>
The thermoplastic resin used in the present invention is not basically limited, and in particular, a thermoplastic resin used for a casing of an electronic device is preferably used. Examples of such thermoplastic resins include polypropylene resins, polystyrene resins, modified polyphenylene oxide resins, polyamide resins, polycarbonate resins, polyphenylene sulfide resins, and polyester resins. Particularly preferable examples include ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and mixtures of two or more thereof. In particular, a thermoplastic resin mainly composed of a polycarbonate resin is preferable, and a thermoplastic resin (component A) containing 50% by weight or more of a polycarbonate resin in 100% by weight thereof is more preferable. This is because the polycarbonate resin is good in terms of mechanical strength and dimensional accuracy, but has a high melt viscosity, and the surface metal of the nickel metal-coated carbon fiber is likely to fall off and bend, and thus the effects of the present invention are more exerted.
＜ニッケル金属被覆炭素繊維＞
また、本発明で使用されるニッケル金属被覆炭素繊維（Ｂ成分）とは、炭素繊維にメッキ法および蒸着法などの公知の方法でニッケル、その合金などを被覆したものである。導電性、耐食性、生産性、および経済性の観点から、ニッケルが好ましい。更に本発明のニッケル金属被覆炭素繊維は、炭素繊維表面に電気メッキによりニッケル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ニッケル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。
ニッケル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。以上の中でも特にポリアクリロニトリルを出発原料とする高弾性率タイプの炭素繊維が好ましい。
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。
< Nickel metal coated carbon fiber>
Further, a nickel metal-coated carbon fibers used in the present invention (B component), nickel by a known method such as plating method and vapor deposition carbon fiber, Ru der those coated etc. its alloys. Conductivity, corrosion resistance, productivity, and in terms of economy, nickel is preferred. Furthermore, the nickel metal-coated carbon fiber of the present invention is preferably provided with a nickel metal coating on the surface of the carbon fiber by electroplating. A stronger nickel metal coating is formed by electroplating, and a resin composition having good electromagnetic shielding properties is provided.
Examples of the carbon fibers coated with nickel metal include carbon fibers starting from polymer fibers such as phenol resin, rayon, and polyacrylonitrile, and pitch fibers such as coal pitch, petroleum pitch, or liquid crystal pitch. A carbon fiber as a starting material is typically exemplified. Also, a method of spinning without forming an infusibilizing step represented by a method of spinning or molding a raw material composition comprising a solvent with a polymer having a methylene bond of aromatic sulfonic acids or salts thereof, and then carbonizing Carbon fibers obtained by the above can also be used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, high modulus type carbon fiber starting from polyacrylonitrile is particularly preferable.
For carbonization or graphitization of carbon fiber, it is preferable to sinter the fiber that can be carbonized in carbonization at a temperature of, for example, about 450 to 1,500 ° C. Baking treatment is preferably performed at a temperature of about 500 to 3,300 ° C. It is not always necessary to produce a graphite crystal structure by such heat treatment.
さらに、本発明のニッケル金属被覆前の炭素繊維は、炭素繊維表面におけるＸ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）が、０．１５〜０．１７の範囲に調整された炭素繊維である。炭素繊維表面におけるＸ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）を調整された炭素繊維は、炭素繊維を慣用の酸化処理に付すことにより得られる。酸化処理方法は特に限定されないが、例えば、（１）炭素繊維を酸もしくはアルカリまたはそれらの塩、あるいは酸化性気体により処理する方法、（２）炭素繊維化可能な繊維または炭素繊維を、含酸素化合物を含む不活性ガスの存在下、７００℃以上の温度で焼成する方法、および（３）炭素繊維を酸化処理した後、不活性ガスの存在下で熱処理する方法などが好適に例示される。
より具体的には、上記（１）の方法では、例えば硫酸および硝酸などの強酸並びにかかる強酸の塩、あるいは酢酸および次亜塩素酸などの弱酸並びにかかる弱酸の塩、あるいは水酸化ナトリウムおよび水酸化カリウムなどのアルカリ並びにかかるアルカリの塩などの溶液に原料炭素繊維を浸漬処理する方法が例示される。かかる方法において、例えば、５０〜１３０℃程度の温度で処理してもよい。もしくはかかる処理の際に炭素繊維に電流を流し、電解酸化を行わせる方法も有効である。特に炭素繊維に電流を流しながら炭素繊維を硫酸塩の水溶液中を通過させる方法は表面処理方法として好ましい。かかる場合に炭素繊維に通過させる電気量は、１〜１００ｃ／ｇ、特に５〜５０ｃ／ｇの範囲が好ましい。かかる方法によれば、炭素繊維表面におけるＯ１Ｓ／Ｃ１Ｓをより精密に制御することが可能となる。かかる方法における硫酸塩としては、硫酸ナトリウム、硫酸水素ナトリウム、硫酸アンモニウム、および硫酸水素アンモニウムなどが例示される。硫酸塩水溶液の濃度は１〜１５重量％が好適である。
Furthermore, the carbon fiber before nickel metal coating of the present invention has an oxygen to carbon peak ratio (O 1S / C 1S ) measured by X-ray photoelectron spectroscopy (ESCA method) on the carbon fiber surface of 0.15. Carbon fiber adjusted to a range of ˜0.17. The carbon fiber with the adjusted peak ratio of oxygen to carbon (O 1S / C 1S ) measured by X-ray photoelectron spectroscopy (ESCA method) on the surface of the carbon fiber is subjected to a conventional oxidation treatment. can get. The oxidation treatment method is not particularly limited. For example, (1) a method in which carbon fiber is treated with an acid or alkali or a salt thereof, or an oxidizing gas, and (2) a fiber or carbon fiber that can be converted into carbon fiber is oxygenated. Preferred examples include a method of firing at a temperature of 700 ° C. or higher in the presence of an inert gas containing a compound, and (3) a method of heat-treating in the presence of an inert gas after oxidizing the carbon fiber.
More specifically, in the above method (1), strong acids such as sulfuric acid and nitric acid and salts of such strong acids, weak acids such as acetic acid and hypochlorous acid and salts of such weak acids, or sodium hydroxide and hydroxide A method of immersing the raw carbon fibers in a solution of an alkali such as potassium and a salt of such an alkali is exemplified. In such a method, for example, the treatment may be performed at a temperature of about 50 to 130 ° C. Alternatively, a method in which an electric current is passed through the carbon fiber and electrolytic oxidation is performed during such treatment is also effective. In particular, a method of passing the carbon fiber through an aqueous solution of sulfate while passing an electric current through the carbon fiber is preferable as the surface treatment method. In such a case, the amount of electricity passed through the carbon fiber is preferably in the range of 1 to 100 c / g, particularly 5 to 50 c / g. According to such a method, O 1S / C 1S on the carbon fiber surface can be controlled more precisely. Examples of the sulfate in such a method include sodium sulfate, sodium hydrogen sulfate, ammonium sulfate, and ammonium hydrogen sulfate. The concentration of the aqueous sulfate solution is preferably 1 to 15% by weight.
上記（１）の方法における酸化性気体としては、オゾンおよびハロゲンなどが好適に例示される。その他酸素、水蒸気、一酸化炭素、二酸化炭素、および二酸化窒素などの含酸素気体が例示される。かかる処理は、例えば５００〜１，０００℃程度の範囲で行うことができる。
上記（２）の方法において、炭素繊維化可能な繊維としては、上記高分子繊維およびピッチ系繊維などが挙げられる。これらの繊維は少なくとも一種使用できる。含酸素化合物としては、上記（１）と同様の含酸素気体を使用できる。不活性ガスとしては、窒素、ヘリウム、ネオン、アルゴン、およびクリプトン等が挙げられる。不活性ガスは、二種以上の混合ガスとしても使用できる。不活性ガス中の含酸素化合物の含有量は、広い範囲で使用できるが、２０から５，０００ｐｐｍ程度である。
上記（３）の方法では、上記（１）および（２）と同様にして炭素繊維を酸化処理した後、不活性ガスの存在下で熱処理する。不活性ガス存在下での熱処理温度は、通常３００℃以上、好ましくは３００〜１，５００℃程度である。これらの酸化処理により、炭素繊維表面におけるＥＳＣＡ法により測定されるＯ１Ｓ／Ｃ１Ｓを調整された炭素繊維を得ることができる。
ニッケル金属被覆される炭素繊維の平均繊維径は、特に限定されるものではないが、通常３〜１５μｍのものが使用され、好ましくは５〜１３μｍである。またニッケル金属被覆層の厚みは好ましくは０．１〜１μｍ、より好ましくは０．１５〜０．５μｍである。更に好ましくは０．２〜０．３５μｍである。
Preferable examples of the oxidizing gas in the method (1) include ozone and halogen. Other examples include oxygen-containing gases such as oxygen, water vapor, carbon monoxide, carbon dioxide, and nitrogen dioxide. Such treatment can be performed, for example, in the range of about 500 to 1,000 ° C.
In the method (2), examples of the fiber that can be carbonized include the polymer fiber and the pitch fiber. At least one kind of these fibers can be used. As the oxygen-containing compound, an oxygen-containing gas similar to the above (1) can be used. Examples of the inert gas include nitrogen, helium, neon, argon, and krypton. The inert gas can also be used as a mixed gas of two or more. The content of the oxygen-containing compound in the inert gas can be used in a wide range, but is about 20 to 5,000 ppm.
In the method (3), the carbon fiber is oxidized in the same manner as in the above (1) and (2), and then heat-treated in the presence of an inert gas. The heat treatment temperature in the presence of an inert gas is usually 300 ° C. or higher, preferably about 300 to 1,500 ° C. By these oxidation treatments, carbon fibers adjusted to have O 1S / C 1S measured by the ESCA method on the carbon fiber surface can be obtained.
The average fiber diameter of the carbon fiber coated with nickel metal is not particularly limited, but is usually 3 to 15 μm, and preferably 5 to 13 μm. The thickness of the nickel metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2-0.35 micrometer.
酸化処理後、ニッケル金属被覆される炭素繊維は、必要に応じてニッケル金属被覆処理の際、炭素繊維束とされる。炭素繊維束とする方が取り扱いの容易な場合が多い。炭素繊維束は集束剤を用いて集束処理される。かかる集束剤はニッケル金属被覆する直前に除去されることが好ましい。かかる除去方法としては、酸化ガス雰囲気あるいは不活性ガス雰囲気中で焼成処理する方法が代表的に例示されかつ好適である。不活性ガス雰囲気中での焼成処理がより好ましい。かかる処理は炭素繊維表面の酸化が進行しないからである。
更に取り扱い性の点から、得られるニッケル金属被覆炭素繊維は好ましくは集束処理される。ニッケル金属被覆前の炭素繊維およびニッケル金属被覆炭素繊維の集束剤としては、オレフィン系樹脂、スチレン系樹脂、アクリル系樹脂、ポリエステル系樹脂、エポキシ系樹脂、およびウレタン系樹脂等が例示される。ニッケル金属被覆前の炭素繊維では、特にスチレン系樹脂、アクリル系樹脂、あるいはスチレン−アクリル共重合体樹脂が好適に例示され、ニッケル金属被覆炭素繊維では、特にエポキシ系樹脂やウレタン系樹脂が好適に例示される。これらの樹脂は、完全水溶性、部分水溶性、および水以外の有機・無機溶媒可溶性のいずれであってもよい。特に作業環境上部分水溶性または完全水溶性樹脂であるのが好ましい。これらの水溶性樹脂は、分子鎖中または末端基にポリアルキレンオキシド骨格、ピペラジンに代表される三級アミン骨格、スルホン酸基またはその塩、並びにアミノ基またはその塩などを分子鎖中に導入することにより得ることができる。その中でもポリアルキレンオキシドセグメント、スルホン酸基またはその塩の導入がより好ましい。またかかる塩はアルカリ金属塩が好ましい。更に集束された炭素繊維における１束当りのフィラメント数は、好ましくは３，０００〜３５０，０００本、より好ましくは６，０００〜７０，０００の範囲である。
After the oxidation treatment , the carbon fiber to be coated with nickel metal is made into a carbon fiber bundle during the nickel metal coating treatment as necessary. Carbon fiber bundles are often easier to handle. The carbon fiber bundle is subjected to sizing treatment using a sizing agent. Such sizing agent is preferably removed immediately before nickel metallization. As such a removal method, a method of firing in an oxidizing gas atmosphere or an inert gas atmosphere is typically exemplified and suitable. A baking treatment in an inert gas atmosphere is more preferable. This is because such treatment does not proceed with oxidation of the carbon fiber surface.
Further, from the viewpoint of handleability, the obtained nickel metal-coated carbon fiber is preferably subjected to a bundling treatment. Examples of the carbon fiber before nickel metal coating and the bundling agent for nickel metal coated carbon fiber include olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, and urethane resins. For carbon fibers before nickel metal coating, styrene resins, acrylic resins, or styrene-acrylic copolymer resins are particularly preferable examples. For nickel metal coated carbon fibers, epoxy resins and urethane resins are particularly preferable. Illustrated. These resins may be completely water-soluble, partially water-soluble, or soluble in organic / inorganic solvents other than water. In particular, a partially water-soluble or completely water-soluble resin is preferable in view of the working environment. These water-soluble resins introduce a polyalkylene oxide skeleton, a tertiary amine skeleton typified by piperazine, a sulfonic acid group or a salt thereof, and an amino group or a salt thereof into a molecular chain or a terminal group. Can be obtained. Among them, introduction of a polyalkylene oxide segment, a sulfonic acid group or a salt thereof is more preferable. Such a salt is preferably an alkali metal salt. Further, the number of filaments per bundle in the bundled carbon fibers is preferably in the range of 3,000 to 350,000, more preferably 6,000 to 70,000.
＜工程−Ｉ〜工程−ＶＩについて＞
本発明の別の態様は、上述のとおり工程−Ｉ〜工程−ＶＩからなることを特徴とする電磁波遮蔽性熱可塑性樹脂組成物、特に該組成物のペレットの製造方法にかかるものである。
工程−Ｉは、炭素繊維の表面を酸化処理して、Ｘ線光電子分光法（ＥＳＣＡ法）により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）を０．１５〜０．１７の範囲に調整する工程である。かかる工程−Ｉは上述のとおり、各種の酸化処理方法により炭素繊維表面を酸化処理する。Ｏ１Ｓ／Ｃ１Ｓが０．１５未満ではニッケル金属被覆の密着性が十分でないため、特に溶融粘度の高い樹脂との溶融混練においてかかる金属被覆が剥離し、樹脂組成物の電磁波遮蔽性が低下しやすい。一方、Ｏ１Ｓ／Ｃ１Ｓが０．１７を超えるとニッケル金属被覆の密着性は良好になるものの、特に溶融粘度の高い樹脂との溶融混練において炭素繊維が折れやすくなるために、電磁波遮蔽性が低下する傾向を示す。本発明のかかる効果は、従来本出願人が提案している折れ抑制剤を含有しない場合により顕著である。かかる折れ抑制剤は、良好な電磁波遮蔽性や良好な耐衝撃性を樹脂組成物に付与する。一方でかかる折れ抑制剤は、樹脂との密着性を低下させることから、強度が低下する。したがって、本発明の方法および該方法により得られる樹脂組成物やそのペレットは強度がより重視される用途においてより有効である。
<About Step-I to Step-VI>
Another aspect of the present invention relates to a method for producing an electromagnetic wave shielding thermoplastic resin composition, particularly a pellet of the composition, characterized by comprising Step-I to Step-VI as described above.
In Step-I, the surface of the carbon fiber is oxidized, and the peak ratio of oxygen to carbon (O 1S / C 1S ) measured by X-ray photoelectron spectroscopy (ESCA method) is 0.15 to 0.17. It is the process of adjusting to the range. In the step-I, as described above, the surface of the carbon fiber is oxidized by various oxidation methods. If the O 1S / C 1S is less than 0.15, the adhesion of the nickel metal coating is not sufficient, so that the metal coating peels off particularly during melt-kneading with a resin having a high melt viscosity, and the electromagnetic wave shielding property of the resin composition is lowered. Cheap. On the other hand, when O 1S / C 1S exceeds 0.17, the adhesion of the nickel metal coating is improved, but the carbon fiber is easily broken particularly in melt-kneading with a resin having a high melt viscosity. Shows a downward trend. Such an effect of the present invention is more conspicuous in the case where it does not contain a folding inhibitor proposed by the present applicant. Such a folding inhibitor imparts good electromagnetic wave shielding properties and good impact resistance to the resin composition. On the other hand, such a breakage inhibitor reduces the adhesiveness with the resin, so that the strength is reduced. Therefore, the method of the present invention and the resin composition and pellets obtained by the method are more effective in applications where strength is more important.
工程−ＩＩは、該調整された炭素繊維束に電気メッキすることによりニッケル金属被覆炭素繊維を得る工程である。かかる電気メッキの方法は、従来公知の各種の方法を採用することができる。例えば（ｉ）特開昭５９−２２６１９５号公報に開示された、多段で電気メッキを行うにあたり、後段ほど電流量を少なくして金属被覆による炭素繊維束の架橋を防止してメッキを施す方法、（ｉｉ）特開昭６０−２３８４９８号公報に開示された、多段で電気メッキを行うにあたり、２段目以降では炭素繊維束の開繊部だけで電気メッキし、非開繊部では電流を遮蔽して電気メッキしない方法、（ｉｉｉ）特開昭６３−２６４９６９号公報に開示された、上記（ｉ）とは逆に後段ほど電流量を多くしてメッキを施す方法、並びに（ｉｖ）特開平３−１０４９８４号公報に開示された、電気メッキを特定の張力範囲下で、エアーバブリングを行いながら行い、加えて多段で電気メッキを行うにあたり、１段目は特定の電流密度範囲で、それ以降は後段ほど電流密度を高くする方法などが例示される。炭素繊維束への電気メッキは、エアーバブリング、メッキ液の噴出、および炭素繊維の振動などの外力により、繊維束を開繊させて行うことが好ましい。特に炭素繊維束の本数が１０，０００本を超える場合には開繊のための外力を作用させることが好ましい。炭素繊維束は上記のとおり、集束剤で集束処理されていてもよい。かかる集束剤の好適な具体例としては、スチレン−アクリル共重合体樹脂と界面活性剤（ポリエチレン・オキサイド縮合物に代表される非イオン界面活性剤が好適）とからなる水性エマルジョン剤が例示される。 Step-II is a step of obtaining nickel metal-coated carbon fibers by electroplating the adjusted carbon fiber bundle. As the electroplating method, various conventionally known methods can be employed. For example, (i) disclosed in JP-A-59-226195, in performing electroplating in multiple stages, a method of performing plating by preventing the crosslinking of carbon fiber bundles due to metal coating by decreasing the amount of current in the subsequent stage, (Ii) When performing electroplating in multiple stages as disclosed in JP-A-60-238498, in the second and subsequent stages, electroplating is performed only at the opening portion of the carbon fiber bundle, and current is shielded at the non-opening portion. And (iii) a method of plating by increasing the amount of current in the subsequent stage, as disclosed in Japanese Patent Laid-Open No. 63-264969, and (iv) In the electroplating disclosed in Japanese Patent Laid-Open No. 3-104984, while performing air bubbling under a specific tension range and in addition to performing electroplating in multiple stages, the first stage is within a specific current density range. A method to increase the current density more subsequent is illustrated. The electroplating on the carbon fiber bundle is preferably performed by opening the fiber bundle by external force such as air bubbling, jetting of the plating solution, and vibration of the carbon fiber. In particular, when the number of carbon fiber bundles exceeds 10,000, it is preferable to apply an external force for opening. As described above, the carbon fiber bundle may be subjected to sizing treatment with a sizing agent. A specific example of such a sizing agent is an aqueous emulsion comprising a styrene-acrylic copolymer resin and a surfactant (preferably a nonionic surfactant typified by polyethylene oxide condensate). .
工程−ＩＩＩは、該ニッケル金属被覆炭素繊維を集束剤を用いて集束処理し、集束されたニッケル金属被覆炭素繊維ロービングを得る工程である。かかる集束処理における集束剤は、上記のとおりである。工程−ＩＩＩのロービングにおける集束剤は、乾燥された状態でも未乾燥の状態であってもよい。即ち集束剤が未乾燥のロービングを切断してチョップドストランドとし、かかる状態で乾燥することもできる。集束剤の炭素繊維への付着方法としては、該集束剤の水溶液または水性エマルジョン液を炭素繊維に付着させ、その後水分を除去する方法が好ましい。集束剤の炭素繊維への付着量は、液中の集束剤の濃度や液の粘度などにより調整することができる。かかる集束剤の液は、更に界面活性剤、有機溶媒、潤滑剤、および消泡剤などを含有することができる。また集束剤を付着させた後に更にこれら剤を付着させることができる。ニッケル金属被覆炭素繊維の集束剤は上記のとおり、エポキシ樹脂またはウレタン樹脂が好適である。特に集束がこれら樹脂の水性エマルジョン剤の処理により行われることが好ましい。
Step-III is a step of bundling the nickel metal-coated carbon fiber with a sizing agent to obtain a bended nickel metal-coated carbon fiber roving. The sizing agent in the sizing process is as described above. The sizing agent in the roving of step-III may be in a dried state or an undried state. That is, the roving with the sizing agent being undried can be cut into chopped strands and dried in such a state. As a method for attaching the sizing agent to the carbon fiber, a method in which an aqueous solution or an aqueous emulsion of the sizing agent is attached to the carbon fiber and then moisture is removed is preferable. The amount of the sizing agent attached to the carbon fiber can be adjusted by the concentration of the sizing agent in the liquid, the viscosity of the liquid, and the like. The sizing agent liquid may further contain a surfactant, an organic solvent, a lubricant, an antifoaming agent, and the like. Further, after the sizing agent is attached, these agents can be further attached. As described above, the sizing agent for nickel metal-coated carbon fibers is preferably an epoxy resin or a urethane resin. In particular, focusing is preferably performed by treatment with an aqueous emulsion of these resins.
工程−ＩＶは、該ロービングを切断し、そのチョップドストランドを得る工程である。上述のとおり、かかるロービングの集束剤は切断の際に必ずしも乾燥されている必要はなく、切断後に集束剤の乾燥をすることもできる。ロービングの切断は各種のカッターを用いて行うことができ、その切断長さは、１〜１５ｍｍ、より好ましくは４〜１０ｍｍの範囲で選択される。 Step-IV is a step of cutting the roving to obtain the chopped strand. As described above, the bundling agent for such roving does not necessarily have to be dried at the time of cutting, and the sizing agent can also be dried after cutting. The cutting of roving can be performed using various cutters, and the cutting length is selected in the range of 1 to 15 mm, more preferably 4 to 10 mm.
工程−Ｖは、熱可塑性樹脂を準備し、該熱可塑性樹脂１００重量部に対して、該チョップドストランド（Ｂ’成分）の割合が１〜１００重量部となるよう調整し、押出機に供給する工程である。かかる押出機は特に限定されず、熱可塑性樹脂組成物の製造に利用される押出機のいずれも利用できる。中でも二軸押出機に代表される多軸押出機が好ましい。かかる二軸押出機のスクリュー形状は２条ネジスクリューがより好ましく使用され、スクリューの長さ（Ｌ）と直径（Ｄ）との比（Ｌ／Ｄ）は、好ましくは２０〜４５、より好ましくは２８〜４２である。スクリューにはニーディングディスクセグメント（またはそれに相当する混練セグメント）から構成された混練ゾーンを１個所以上有することが必要であり、１〜３箇所有することが好ましい。押出機は、好ましくは原料中の水分や溶融混練樹脂から発生する揮発ガスを脱気できるベントを有する。
熱可塑性樹脂、チョップドストランドおよびその他の原材料は、各種の方法により押出機に供給することができる。熱可塑性樹脂を主供給口より主として供給し、チョップドストランドをサイドフィーダーを用いて押出機の途中段階に設けられた供給口から、溶融された樹脂に対して供給する方法が好適に採用される。熱可塑性樹脂とその他の原材料を予備混合する手段としては、例えばナウターミキサー、Ｖ型ブレンダー、メカノケミカル装置、および押出混合機などが例示される。
Step-V prepares a thermoplastic resin, adjusts the ratio of the chopped strands (B ′ component) to 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and supplies it to the extruder. It is a process. Such an extruder is not particularly limited, and any of the extruders used for producing a thermoplastic resin composition can be used. Of these, a multi-screw extruder represented by a twin-screw extruder is preferable. The screw shape of such a twin screw extruder is more preferably a double thread screw, and the ratio (L / D) of the length (L) to the diameter (D) of the screw is preferably 20 to 45, more preferably 28-42. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto), and preferably 1 to 3 kneading zones. The extruder preferably has a vent capable of degassing volatile gas generated from moisture in the raw material and melt-kneaded resin.
The thermoplastic resin, chopped strands and other raw materials can be supplied to the extruder by various methods. A method in which the thermoplastic resin is mainly supplied from the main supply port and the chopped strand is supplied to the molten resin from a supply port provided in the middle stage of the extruder using a side feeder is suitably employed. Examples of means for premixing the thermoplastic resin and other raw materials include a Nauta mixer, a V-type blender, a mechanochemical apparatus, and an extrusion mixer.
工程−ＶＩは、該熱可塑性樹脂とＢ’成分とを押出機中で溶融混練し樹脂組成物、殊にペレット形態の該樹脂組成物を得る工程である。上述のとおり、かかる溶融混練は熱可塑性樹脂とＢ’成分との混合物を１個所以上の混練ゾーンを通すことにより行われる。かかる混練ゾーンにおけるせん断作用があまりに強い場合には、金属被覆炭素繊維が折れやすくなり好ましくない。したがって溶融混練は、樹脂の溶融粘度をよく低くするために、対象樹脂において比較的高温のシリンダー温度を選択することが好ましい。更に混練ゾーンの構成として、例えばニーディングディスクセグメントの場合には、４５°位相の５枚１組のセグメント（Ｌ／Ｄ＝１）を使用し、トーピードリング、および正方向の組合せによる混練セグメントが好適に例示される（クリアランスはメーカー推奨値の場合）。
ダイスより吐出される溶融樹脂は、ストランド状またはシート状に冷却した後、ペレタイザーで切断しペレットを得ることができる。またダイスより吐出される溶融樹脂を直接切断してペレット化（いわゆるホットカット）することもできる。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２〜１５ｍｍ、さらに好ましくは２．５〜１０ｍｍである。
Step-VI is a step of melt-kneading the thermoplastic resin and the B ′ component in an extruder to obtain a resin composition, particularly a pellet form of the resin composition. As described above, such melt-kneading is performed by passing a mixture of the thermoplastic resin and the B ′ component through one or more kneading zones. When the shearing action in such a kneading zone is too strong, the metal-coated carbon fibers are easily broken, which is not preferable. Therefore, in melt kneading, it is preferable to select a relatively high cylinder temperature in the target resin in order to sufficiently lower the melt viscosity of the resin. Further, as the composition of the kneading zone, for example, in the case of a kneading disc segment, a set of five segments having a 45 ° phase (L / D = 1) is used, and a kneading segment by a torpedo ring and a positive direction combination is used. It is preferably exemplified (when the clearance is a manufacturer recommended value).
The molten resin discharged from the die can be cooled into a strand or sheet and then cut with a pelletizer to obtain pellets. Also, the molten resin discharged from the die can be directly cut into pellets (so-called hot cut). Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 15 mm, and still more preferably 2.5 to 10 mm.
＜ポリカーボネート樹脂について＞
本発明のより好適な熱可塑性樹脂は、ポリカーボネート樹脂を５０重量％以上含有する熱可塑性樹脂（Ａ成分）である。かかるポリカーボネート樹脂は、通常使用されるビスフェノールＡ型ポリカーボネート以外にも、他の二価フェノールを用いて重合された、高耐熱性または低吸水率の各種のポリカーボネート樹脂であってもよい。ポリカーボネート樹脂はいかなる製造方法によって製造されたものでもよく、界面重縮合の場合は通常一価フェノール類の末端停止剤が使用される。ポリカーボネート樹脂はまた３官能フェノール類を重合させた分岐ポリカーボネート樹脂であってもよく、更に脂肪族ジカルボン酸や芳香族ジカルボン酸、または二価の脂肪族または脂環族アルコールを共重合させた共重合ポリカーボネートであってもよい。ポリカーボネート樹脂の粘度平均分子量は、好ましくは１３，０００〜４０，０００、より好ましくは１５，０００〜３８，０００である。芳香族ポリカーボネート樹脂の粘度平均分子量（Ｍ）は塩化メチレン１００ｍｌにポリカーボネート樹脂０．７ｇを溶解した溶液から２０℃で求めた比粘度（ηｓｐ）を次式に挿入して求めたものである。かかるポリカーボネート樹脂の詳細については、特開２００２−１２９００３号公報に記載されている。
ηｓｐ／ｃ＝［η］＋０．４５×［η］２ｃ（但し［η］は極限粘度）
［η］＝１．２３×１０−４Ｍ０．８３
ｃ＝０．７
<About polycarbonate resin>
A more preferred thermoplastic resin of the present invention is a thermoplastic resin (component A) containing 50% by weight or more of a polycarbonate resin. Such a polycarbonate resin may be various polycarbonate resins having a high heat resistance or a low water absorption, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polycarbonate may be used. The viscosity average molecular weight of the polycarbonate resin is preferably 13,000 to 40,000, more preferably 15,000 to 38,000. The viscosity average molecular weight (M) of the aromatic polycarbonate resin is obtained by inserting the specific viscosity (η sp ) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation. Details of the polycarbonate resin are described in JP-A No. 2002-129003.
η sp /c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 −4 M 0.83
c = 0.7
他の二価フェノールを用いて重合された、高耐熱性または低吸水率の各種のポリカーボネート樹脂の具体例としては、下記のものが好適に例示される。
（１）該ポリカーボネートを構成する二価フェノール成分１００モル％中、４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール（以下“ＢＰＭ”と略称）成分が２０〜８０モル％（より好適には４０〜７５モル％、さらに好適には４５〜６５モル％）であり、かつ９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン（以下“ＢＣＦ”と略称）成分が２０〜８０モル％（より好適には２５〜６０モル％、さらに好適には３５〜５５モル％）である共重合ポリカーボネート。
（２）該ポリカーボネートを構成する二価フェノール成分１００モル％中、ビスフェノールＡ成分が１０〜９５モル％（より好適には５０〜９０モル％、さらに好適には６０〜８５モル％）であり、かつＢＣＦ成分が５〜９０モル％（より好適には１０〜５０モル％、さらに好適には１５〜４０モル％）である共重合ポリカーボネート。
（３）該ポリカーボネートを構成する二価フェノール成分１００モル％中、ＢＰＭ成分が２０〜８０モル％（より好適には４０〜７５モル％、さらに好適には４５〜６５モル％）であり、かつ１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン成分が２０〜８０モル％（より好適には２５〜６０モル％、さらに好適には３５〜５５モル％）である共重合ポリカーボネート。
これらの特殊なポリカーボネートは、単独で用いてもよく、２種以上を適宜混合して使用してもよい。また、これらを汎用されているビスフェノールＡ型のポリカーボネートと混合して使用することもできる。
これらの特殊なポリカーボネートの製法及び特性については、例えば、特開平６−１７２５０８号公報、特開平８−２７３７０号公報、特開２００１−５５４３５号公報及び特開２００２−１１７５８０号公報等に詳しく記載されている。
As specific examples of various polycarbonate resins polymerized using other dihydric phenols and having high heat resistance or low water absorption, the following can be suitably exemplified.
(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCF component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate.
These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.
＜有機リン化合物＞
上述のとおり本発明における樹脂組成物は、更に有機リン化合物（Ｃ成分）を特定割合で含有することが好ましい。かかる有機リン化合物としては、リン酸エステル、ホスホン酸エステル、およびホスファゼンオリゴマーなどが好適に例示される。これらの中でも、ＴＧＡによる、窒素ガス雰囲気中における２３℃から２０℃／分の昇温速度で６００℃まで昇温した時の５％重量減少温度が３００℃以上である有機リン化合物が好適である（上限は４００℃が好適である）。かかる好適な有機リン化合物は樹脂組成物のリサイクル性を向上させる。
更にリン酸エステルとしては、下記式（Ｉ）で示される化合物が好適である。
<Organic phosphorus compounds>
As described above, the resin composition in the present invention preferably further contains an organophosphorus compound (C component) at a specific ratio. Preferred examples of such organic phosphorus compounds include phosphate esters, phosphonate esters, and phosphazene oligomers. Among these, an organophosphorus compound having a 5% weight loss temperature of 300 ° C. or more when heated from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a rate of temperature increase of 20 ° C./min by TGA is preferable. (The upper limit is preferably 400 ° C.). Such a suitable organophosphorus compound improves the recyclability of the resin composition.
Further, as the phosphate ester, a compound represented by the following formula (I) is suitable.
上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導される二価の基であり、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ１１、Ｒ１２、Ｒ１３、およびＲ１４はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導される一価の基である。
更に好ましいものとしては、上記式中のＸが、ハイドロキノン、レゾルシノール、ビスフェノールＡ、およびジヒドロキシジフェニルから誘導される二価の基であり、ｎは１〜３の整数である成分を主成分として含み、またはｎ数の異なるリン酸エステルのブレンドの場合はその平均値であり、Ｒ１１、Ｒ１２、Ｒ１３、およびＲ１４はそれぞれ独立して１個以上のハロゲン原子を置換したもしくはより好適には置換していないフェノール、クレゾール、キシレノールから誘導される一価の基である。
X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4 -Hydroxyphenyl) divalent group derived from sulfide, n is an integer of 0-5, or an average value of 0-5 in the case of a mixture of phosphoric acid esters with different numbers of n, R 11 , R 12 , R 13 , and R 14 are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. Is a valent group.
More preferably, X in the above formula is a divalent group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and n includes a component having an integer of 1 to 3 as a main component, Or an average value in the case of a blend of phosphoric acid esters having different numbers of n, and R 11 , R 12 , R 13 , and R 14 are each independently substituted with one or more halogen atoms, or more preferably It is a monovalent group derived from unsubstituted phenol, cresol, and xylenol.
金属被覆炭素繊維の金属の中にはポリカーボネート樹脂の加水分解を助長するものがあるため（例えばニッケルなど）、かかるリン酸エステルの中でも耐加水分解性に優れるものが好適である。リン酸エステルの耐加水分解性に影響を与える因子として、残留触媒（金属）の如き不純物、酸価、および化学構造などが既に公知である。本発明においてもリ酸エステルの不純物や酸価は低いほど好ましい。化学構造上耐加水分解性の良好なリン酸エステルとしては、トリフェニルホスフェート、レゾルシノールビス（ジキシレニルホスフェート）およびビスフェノールＡビス（ジフェニルホスフェート）などが好適に例示され、特に上記ＴＧＡの条件を満足する後二者が好ましい。これら二者の市販品は、通常少量のモノリン酸エステル化合物を含む。更にビスフェノールＡビス（ジフェニルホスフェート）の市販品は、二量体以上のオリゴマーも少量含有する混合物である。かかる混合物中、トリフェニルホスフェートは０．１〜５重量％の範囲が好ましく、ビスフェノールＡビス（ジフェニルホスフェート）は８４〜９８．５重量％の範囲が好ましく、二量体以上のオリゴマーは１〜１１重量％の範囲が好ましい。
ホスファゼンオリゴマーとしては、フェノキシホスファゼンオリゴマーや環状フェノキシホスファゼンオリゴマーが好適に例示される。
Since some of the metals of the metal-coated carbon fibers promote the hydrolysis of the polycarbonate resin (for example, nickel), among these phosphate esters, those having excellent hydrolysis resistance are preferable. As factors affecting the hydrolysis resistance of phosphate esters, impurities such as residual catalyst (metal), acid value, and chemical structure are already known. Also in this invention, the impurity and acid value of a phosphoric acid ester are so preferable that it is low. Preferred examples of the phosphoric acid ester having good hydrolysis resistance in terms of chemical structure include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), and bisphenol A bis (diphenyl phosphate), and particularly satisfy the above TGA conditions. The latter two are preferred. These two commercial products usually contain a small amount of a monophosphate compound. Furthermore, a commercial product of bisphenol A bis (diphenyl phosphate) is a mixture containing a small amount of oligomers of dimer or higher. In such a mixture, the range of 0.1 to 5% by weight of triphenyl phosphate is preferable, the range of 84 to 98.5% by weight of bisphenol A bis (diphenyl phosphate) is preferable, and the oligomer of dimer or higher is 1 to 11%. A range of% by weight is preferred.
Preferable examples of the phosphazene oligomer include phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers.
＜折れ抑制剤について＞
特開２００２−１２９００３号公報には、熱可塑性樹脂と金属被覆炭素繊維との密着性を阻害する成分について記載されている。該成分は樹脂組成物製造時および樹脂組成物の溶融成形時に、金属被覆炭素繊維に加わる応力を低減しその折れを抑制する。その結果該成分の配合は樹脂組成物の電磁波遮蔽性を更に改良する。かかる折れ抑制剤の詳細については特開２００２−１２９００３号公報にポリカーボネート樹脂を主とする熱可塑性樹脂と導電性繊維との密着性を阻害する成分として記載されており、本発明においてもかかる記載の成分を利用できる。特に好適には、α−オレフィンと無水マレイン酸との共重合体、および炭素数４〜２０のアルキルアルコキシシラン化合物が例示される。
しかしながら上述のとおり、本発明では折れ抑制剤をその有効量含有しない場合に、その効果がより顕著に発揮される。したがって電磁波遮蔽性と共に強度がより重視される場合には折れ抑制剤をその有効量含有しないことが好ましい。
<About the folding inhibitor>
Japanese Patent Application Laid-Open No. 2002-129003 describes components that inhibit adhesion between a thermoplastic resin and metal-coated carbon fibers. The component reduces the stress applied to the metal-coated carbon fiber and suppresses its bending during the production of the resin composition and during the melt molding of the resin composition. As a result, the blending of the components further improves the electromagnetic shielding properties of the resin composition. The details of such a breakage suppressant are described in JP-A No. 2002-129003 as a component that inhibits the adhesion between a thermoplastic resin mainly composed of a polycarbonate resin and conductive fibers, and this description is also included in the present invention. Ingredients available. Particularly preferably, a copolymer of an α-olefin and maleic anhydride and an alkylalkoxysilane compound having 4 to 20 carbon atoms are exemplified.
However, as described above, in the present invention, when the breakage inhibitor is not contained in an effective amount, the effect is more remarkably exhibited. Therefore, when the strength is more important than the electromagnetic wave shielding property, it is preferable not to contain an effective amount of the folding inhibitor.
＜必要により配合し得る付加的成分について＞
本発明における樹脂組成物には、更には必要に応じ、離型剤（例えば、脂肪酸エステル、ポリオレフィンワックス、シリコーン化合物、およびフッ素オイルなど）、有機リン化合物以外の難燃剤（例えば、臭素化エポキシ樹脂、臭素化ポリスチレン、臭素化ポリカーボネート、臭素化ポリアクリレート、有機スルホン酸アルカリ（土類）金属塩、およびシリコーン系難燃剤など）、難燃助剤（例えば、アンチモン酸ナトリウム、および三酸化アンチモンなど）、滴下防止剤（フィブリル形成能を有するポリテトラフルオロエチレンに代表される）、酸化防止剤（例えば、ヒンダードフェノール系化合物、およびイオウ系酸化防止剤など）、紫外線吸収剤、光安定剤、離型剤、摺動剤（例えばＰＴＦＥ粒子および高分子量ポリエチレン粒子など）、着色剤（例えばカーボンブラックおよび酸化チタンなどの顔料、並びに染料）、光拡散剤（例えばアクリル架橋粒子、シリコン架橋粒子、極薄ガラスフレーク、および炭酸カルシウム粒子など）、無機系蛍光体（例えばアルミン酸塩を母結晶とする蛍光体）、帯電防止剤、導電剤（例えばカーボンブラック、気相成長炭素繊維、およびカーボンナノチューブなど）、流動改質剤（ポリカプロラクトン、およびスチレン系オリゴマーなど）、無機もしくは有機の抗菌剤、光触媒系防汚剤（微粒子酸化チタン、および微粒子酸化亜鉛など）、赤外線吸収剤（ＡＴＯ微粒子、ＩＴＯ微粒子、ホウ化ランタン微粒子、ホウ化タングステン微粒子、およびフタロシアニン系金属錯体など）、フォトクロミック剤、並びに蛍光増白剤などが配合できる。
<Additional ingredients that can be blended if necessary>
The resin composition in the present invention may further include a release agent (for example, fatty acid ester, polyolefin wax, silicone compound, and fluorine oil) and a flame retardant other than an organic phosphorus compound (for example, a brominated epoxy resin), if necessary. , Brominated polystyrene, brominated polycarbonate, brominated polyacrylates, organic sulfonate alkali (earth) metal salts, and silicone flame retardants), flame retardant aids (for example, sodium antimonate, and antimony trioxide) , Anti-dripping agents (typically represented by polytetrafluoroethylene having fibril-forming ability), antioxidants (for example, hindered phenolic compounds and sulfur-based antioxidants), UV absorbers, light stabilizers, release agents Molding agent, sliding agent (for example, PTFE particles and high molecular weight polyethylene particles) , Colorants (for example, pigments and dyes such as carbon black and titanium oxide), light diffusing agents (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, and calcium carbonate particles), inorganic phosphors (for example, alumina) Phosphors having acid salts as mother crystals), antistatic agents, conductive agents (such as carbon black, vapor-grown carbon fibers, and carbon nanotubes), flow modifiers (such as polycaprolactone and styrene oligomers), inorganic Or organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers (ATO fine particles, ITO fine particles, lanthanum boride fine particles, tungsten boride fine particles, phthalocyanine metal complexes, etc.) , Photochromic agent, fluorescent whitening agent, etc.
＜本発明の樹脂組成物からなる成形品について＞
本発明における樹脂組成物は、通常上述の方法で得られたペレットを射出成形して各種製品を製造することができる。かかる射出成形においては、通常の成形方法だけでなく、適宜目的に応じて、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（超臨界流体の注入によるものを含む）、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、サンドイッチ成形、および超高速射出成形などの射出成形法を用いて成形品を得ることができる。これら各種成形法の利点は既に広く知られるところである。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。
また本発明における樹脂組成物は、押出成形により各種異形押出成形品、シート、フィルムなどの形で使用することもできる。またシート、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、キャスティング法なども使用可能である。さら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などにより成形品とすることも可能である。
<About a molded product comprising the resin composition of the present invention>
The resin composition in the present invention can usually produce various products by injection molding the pellets obtained by the above-described method. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.
Moreover, the resin composition in this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product 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。表面処理としては、具体的には、ハードコート、撥水・撥油コート、紫外線吸収コート、赤外線吸収コート、並びにメタライジング（蒸着など）などの各種の表面処理が例示される。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。
本発明者らが現在最良と考える本発明の形態は、上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。
Furthermore, various surface treatments can be performed on the molded articles produced by the various methods described above. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor 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. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Furthermore, various transport containers, electromagnetic wave shielding covers, and the like can be produced by further subjecting sheet molded products (including ribbon-shaped molded products) to various vacuum forming, hot press forming, bending, and the like.
The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.
以下に実施例をあげて本発明を更に説明する。なお、評価は下記の方法により行った。
（Ｉ）電磁波遮蔽効果：一辺１５０ｍｍ、厚み３ｍｍの試験片を使用し、（株）アドバンテスト製のＴＲ−１７３０１ＡとＲ３３６１Ａを併用して電界波（周波数９００ＭＨｚ）について測定した。
（ＩＩ）引張破断強度：ＩＳＯ５２７−１および５２７−２に準拠して引張破断強度を測定した。試験形状は、長さ１７５ｍｍ×幅１０ｍｍ×４ｍｍであった。
The following examples further illustrate the present invention. The evaluation was performed by the following method.
(I) Electromagnetic wave shielding effect: A test piece having a side of 150 mm and a thickness of 3 mm was used, and an electric wave (frequency 900 MHz) was measured using TR-17301A and R3361A manufactured by Advantest Corporation.
(II) Tensile strength at break: The tensile strength at break was measured according to ISO 527-1 and 527-2. The test shape was 175 mm long × 10 mm wide × 4 mm wide.
［実施例１〜１０、比較例１〜４］
表１〜表２に記載の樹脂組成物を以下の要領で作成した。尚、説明は以下の表中の記号にしたがって説明する。
表１〜表２に記載の成分を以下の要領でベント式二軸押出機［日本製鋼所（株）製ＴＥＸ−３０ＸＳＳＴ］を用い、溶融混練して樹脂組成物のペレットを得た。原料は最後部の第１供給口および押出機途中の第２投入口（サイドフィーダー）より供給した。その他Ｃ成分の“リン酸−３”のみ、８０℃に加温し定量液注装置にて第１供給口直後の供給口より押出機に所定割合を供給した。第２供給口にはＢ成分の各種金属被覆炭素繊維を供給し、第１供給口からは樹脂、または樹脂とＣ成分とのドライブレンド物を供給した。第１供給口および第２供給口の供給量は、計量器［（株）クボタ製ＣＷＦ］により精密に計測された。第１供給口から第２供給口の間にニーディングディスクによる混練ゾーンがあり、その直後に開放されたベント口が設けられていた。サイドフィーダー以後に更にニーディングディスクによる混練ゾーンおよびそれに続くベント口が設けられていた。ベントの真空度は３ｋＰａであった。溶融樹脂組成物のストランドを押出し、水浴において冷却した後、ペレタイザーでストランドカットを行い、ペレット化した。
押出条件は、シリンダー温度２８０℃およびダイス温度２８０℃とした。但し、実施例９は２３０℃、実施例１０は２５０℃とした。
得られたペレットを１００℃で６時間乾燥した後、射出成形機［住友重機械工業（株）ＳＧ−１５０Ｕ］により、Ｃ成分を含有しないサンプルではシリンダー温度３００℃および金型温度１００℃、並びにＣ成分を含有するサンプルではシリンダー温度２８０℃および金型温度８０℃とした。実施例９のサンプルはシリンダ温度２３０℃および金型温度６０℃とし、実施例１０のサンプルはシリンダ温度２５０℃および金型温度４０℃とした。
[Examples 1 to 10, Comparative Examples 1 to 4]
The resin compositions described in Tables 1 and 2 were prepared as follows. The description will be made according to the symbols in the following table.
The components described in Tables 1 and 2 were melt-kneaded using a vented twin screw extruder [TEX-30XSST manufactured by Nippon Steel Works, Ltd.] in the following manner to obtain resin composition pellets. The raw material was supplied from the last first supply port and the second input port (side feeder) in the middle of the extruder. In addition, only “phosphoric acid-3” of component C was heated to 80 ° C., and a predetermined ratio was supplied to the extruder from the supply port immediately after the first supply port by a metering liquid injection device. Various metal-coated carbon fibers of component B were supplied to the second supply port, and a resin or a dry blend of resin and C component was supplied from the first supply port. The supply amounts of the first supply port and the second supply port were precisely measured by a measuring instrument [CWF manufactured by Kubota Corporation]. There was a kneading zone with a kneading disk between the first supply port and the second supply port, and a vent port opened immediately after that was provided. After the side feeder, a kneading zone with a kneading disk and a subsequent vent port were provided. The degree of vacuum of the vent was 3 kPa. After the strand of the molten resin composition was extruded and cooled in a water bath, the strand was cut with a pelletizer and pelletized.
The extrusion conditions were a cylinder temperature of 280 ° C. and a die temperature of 280 ° C. However, Example 9 was 230 degreeC and Example 10 was 250 degreeC.
After the obtained pellets were dried at 100 ° C. for 6 hours, the sample containing no C component was subjected to an injection molding machine [Sumitomo Heavy Industries, Ltd. SG-150U] with a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C., and In the sample containing component C, the cylinder temperature was 280 ° C. and the mold temperature was 80 ° C. The sample of Example 9 had a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the sample of Example 10 had a cylinder temperature of 250 ° C. and a mold temperature of 40 ° C.
原料は下記のものを使用した。
（樹脂成分）
ＰＣ：ポリカーボネート樹脂パウダー（帝人化成（株）製、パンライトＬ−１２５０ＷＰ（商品名）、粘度平均分子量は、２４，０００）
ＡＢＳ：ＡＢＳ樹脂ペレット（日本エイアンドエル（株）製、サンタックＵＴ−６１（商品名））
ＰＢＴ：ポリブチレンテレフタレート樹脂（ウィンテックポリマー（株）製、ジュラネックス５００ＦＰ（商品名））
（Ｂ成分）
ＮｉＣＦ−１：ＥＳＣＡ法により測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）が０．１６に調整された表面を有する炭素繊維にニッケル被覆を施したニッケル被覆炭素繊維（直径７．５μｍ、長さ６ｍｍ）
ＮｉＣＦ−２：Ｏ１Ｓ／Ｃ１Ｓが０．１４に調整された表面を有する炭素繊維にニッケル被覆を施したニッケル被覆炭素繊維（寸法ＮｉＣＦ−１に同じ）
ＮｉＣＦ−３：Ｏ１Ｓ／Ｃ１Ｓが０．１８に調整された表面を有する炭素繊維にニッケル被覆を施したニッケル被覆炭素繊維（市販製品に同じ、寸法ＮｉＣＦ−１に同じ）
（Ｂ成分の調整方法）
糸の太さが１．０デニールの単繊維フィラメントを１２，０００本集めて構成したアクリロニトリル繊維ストランドを空気中で２８０℃で耐炎化させた後、１，４００℃で炭素化処理を行った。引き続きこのストランドを５重量％の硫酸アンモニウム水溶液中に連続的に浸漬させながら、１５ｃ／ｇの電気量で通電して表面処理を施した。浸漬および通電の時間を６０秒前後で調整することにより、炭素繊維表面のＥＳＣＡ法で測定される酸素と炭素とのピーク比（Ｏ１Ｓ／Ｃ１Ｓ）の値を調整した。得られた炭素繊維は酸化処理後にイオン交換水で洗浄および乾燥した後、スチレン−メチルメタクリレート共重合体樹脂とポリエチレンオキサイドグリコール（重量比９／１）を含有するサイジング剤の水性エマルジョンに浸漬し乾燥することにより集束処理した。得られた炭素繊維束を次の一連の工程を連続して行いニッケル被覆された炭素繊維のチョップドストランドを得た。まず炭素繊維を窒素ガスを流通させた石英管中を通して焼成し（Ｏ１Ｓ／Ｃ１Ｓの値は変化していない）、次いで多段で電気メッキを行いニッケル被覆を施し、次いでイオン交換水で洗浄し、その後ウレタン樹脂の水性エマルジョン液中を通し乾燥することにより集束処理し、最後に集束された繊維をカッターにて６ｍｍに切断してチョップドストランドを得た。電気メッキは、特開昭５９−２２６１９５号公報に開示された条件に準じて行い、約０．２５μｍの膜厚のニッケル被覆を炭素繊維に施した。またウレタン集束剤の付着量は約３重量％であった。
（Ｃ成分）
リン酸−１：リン酸エステル（旭電化工業（株）製アデカスタブＦＰ５００（商品名））
リン酸−２：リン酸エステル（大八化学工業（株）製ＴＰＰ（商品名））
リン酸−３：リン酸エステル（大八化学工業（株）製ＣＲ−７４１（商品名））
（その他）
ＤＣ３０：無水マレイン酸とα−オレフィンとの共重合体からなる酸変性オレフィンワックス（三菱化学（株）製ダイヤカルナＰＡ３０Ｍ（商品名））
ＴＭＰ：トリメチルホスフェート（大八化学工業（株）製ＴＭＰ（商品名））
ＳＴ−１：ホスホナイト系抗酸化剤（サンド社製サンドスタブＰ−ＥＰＱ（商品名））
The following materials were used.
(Resin component)
PC: Polycarbonate resin powder (manufactured by Teijin Chemicals Ltd., Panlite L-1250WP (trade name), viscosity average molecular weight is 24,000)
ABS: ABS resin pellet (manufactured by Nippon A & L Co., Ltd., Santac UT-61 (trade name))
PBT: Polybutylene terephthalate resin (manufactured by Wintech Polymer Co., Ltd., DURANEX 500FP (trade name))
(B component)
NiCF-1: Nickel-coated carbon fiber (diameter 7 having a nickel coating on a carbon fiber having a surface in which the peak ratio of oxygen to carbon (O 1S / C 1S ) measured by the ESCA method is adjusted to 0.16 .5μm, length 6mm)
NiCF-2: Nickel-coated carbon fiber obtained by applying nickel coating to a carbon fiber having a surface in which O 1S / C 1S is adjusted to 0.14 (same as dimension NiCF-1)
NiCF-3: Nickel-coated carbon fiber obtained by applying nickel coating to carbon fiber having a surface with O 1S / C 1S adjusted to 0.18 (same as commercially available product, same as dimension NiCF-1)
(Method for adjusting component B)
An acrylonitrile fiber strand constituted by collecting 12,000 single fiber filaments having a thread thickness of 1.0 denier was flame-resistant in air at 280 ° C. and then carbonized at 1,400 ° C. Subsequently, the strand was subjected to a surface treatment by energizing with an electric quantity of 15 c / g while continuously immersing the strand in a 5 wt% aqueous ammonium sulfate solution. By adjusting the immersion and energization time around 60 seconds, the value of the peak ratio of oxygen to carbon (O 1S / C 1S ) measured by the ESCA method on the carbon fiber surface was adjusted. The obtained carbon fiber was washed with ion exchange water after the oxidation treatment and dried, then dipped in an aqueous emulsion of a sizing agent containing a styrene-methyl methacrylate copolymer resin and polyethylene oxide glycol (weight ratio 9/1) and dried. The focusing process was performed. The obtained carbon fiber bundle was continuously subjected to the following series of steps to obtain a chopped strand of nickel-coated carbon fiber. First, carbon fiber is fired through a quartz tube in which nitrogen gas is circulated (the value of O 1S / C 1S is not changed), then electroplating is performed in multiple stages, nickel coating is applied, and then it is washed with ion exchange water. Thereafter, the bundle was processed by passing through an aqueous emulsion solution of urethane resin and drying, and the finally bundled fibers were cut into 6 mm with a cutter to obtain chopped strands. The electroplating was performed according to the conditions disclosed in Japanese Patent Application Laid-Open No. 59-226195, and a nickel coating having a thickness of about 0.25 μm was applied to the carbon fiber. The adhesion amount of the urethane sizing agent was about 3% by weight.
(C component)
Phosphoric acid-1: Phosphate ester (Adeka Stub FP500 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.)
Phosphoric acid-2: Phosphate ester (TPP (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
Phosphoric acid-3: Phosphate ester (CR-841 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
(Other)
DC30: acid-modified olefin wax comprising a copolymer of maleic anhydride and α-olefin (Diacarna PA30M (trade name) manufactured by Mitsubishi Chemical Corporation)
TMP: Trimethyl phosphate (TMP (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
ST-1: Phosphonite-based antioxidant (Sand Stub P-EPQ (trade name) manufactured by Sand)
上記表から明らかなように、本発明の特定範囲のＯ１Ｓ／Ｃ１Ｓにおいては、改良された電磁波遮蔽性を有する樹脂組成物が得られることが分かる。更にかかる効果は折れ抑制剤（ＤＣ３０）を含有しないサンプルにおいてより顕著であることが分かる。更に電磁波遮蔽性は、リン酸エステルを含有するポリカーボネート樹脂組成物においてより良好である。 As is clear from the above table, it can be seen that a resin composition having improved electromagnetic shielding properties can be obtained with O 1S / C 1S in the specific range of the present invention. Furthermore, it turns out that this effect is more remarkable in the sample which does not contain a folding inhibitor (DC30). Furthermore, the electromagnetic wave shielding property is better in a polycarbonate resin composition containing a phosphate ester.
上述のとおり、本発明の方法並びに樹脂組成物は、電子機器の筐体を始め電磁波遮蔽を必要とする幅広い産業分野で好適であり、その奏する工業的効果は格別のものである。かかる樹脂組成物は、特に電子機器の筐体に好適であるが、その他その良好な導電性を活かして、スイッチ部品、電気メッキ用部材、発熱素子、および放熱用部材などにも利用可能である。
As described above, the method and the resin composition of the present invention are suitable in a wide range of industrial fields that require shielding of electromagnetic waves, including housings for electronic devices, and the industrial effects that they exhibit are exceptional. Such a resin composition is particularly suitable for a housing of an electronic device, but can also be used for a switch part, an electroplating member, a heat generating element, a heat radiating member, and the like by taking advantage of its good conductivity. .
Claims (8)
（２）該調整された炭素繊維束に電気メッキすることによりニッケル金属被覆炭素繊維を得る工程（工程−ＩＩ）、
（３）該ニッケル金属被覆炭素繊維を集束剤を用いて集束処理し、集束されたニッケル金属被覆炭素繊維ロービングを得る工程（工程−ＩＩＩ）、
（４）該ロービングを切断し、そのチョップドストランドを得る工程（工程−ＩＶ）、
（５）熱可塑性樹脂を準備し、該熱可塑性樹脂１００重量部に対して、該チョップドストランド（Ｂ’成分）の割合が１〜１００重量部となるよう調整し、押出機に供給する工程（工程−Ｖ）、並びに
（６）該熱可塑性樹脂とＢ’成分とを押出機中で溶融混練し樹脂組成物を得る工程（工程−ＶＩ）、
からなることを特徴とする電磁波遮蔽性熱可塑性樹脂組成物の製造方法。 (1) The surface ratio of carbon fiber is oxidized, and the peak ratio of oxygen to carbon (O 1S / C 1S ) measured by X-ray photoelectron spectroscopy (ESCA method) is in the range of 0.15 to 0.17. The step of adjusting to (step-I),
(2) Step of obtaining nickel metal-coated carbon fiber by electroplating the adjusted carbon fiber bundle (Step-II),
(3) A step of bundling the nickel metal-coated carbon fiber using a bundling agent to obtain a bended nickel metal-coated carbon fiber roving (step-III),
(4) cutting the roving and obtaining the chopped strand (step-IV),
(5) A step of preparing a thermoplastic resin, adjusting the ratio of the chopped strand (B ′ component) to 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and supplying it to the extruder ( Step-V), and (6) Step of melt-kneading the thermoplastic resin and the B ′ component in an extruder to obtain a resin composition (Step-VI),
A method for producing an electromagnetic wave shielding thermoplastic resin composition, comprising:
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| JP2009128933A (en) * | 2007-11-19 | 2009-06-11 | Toppan Printing Co Ltd | Laminate and storage implement |
| JP6087052B2 (en) * | 2011-05-16 | 2017-03-01 | ダイセルポリマー株式会社 | Flame retardant resin composition |
| JP6059903B2 (en) | 2012-08-06 | 2017-01-11 | ダイセルポリマー株式会社 | Thermoplastic resin composition |
| KR101558748B1 (en) * | 2014-03-19 | 2015-10-08 | 윈엔윈(주) | Electromagnetic wave shielding sheet and method for producing the same |
| KR20170116062A (en) * | 2015-09-02 | 2017-10-18 | (주)크린앤사이언스 | EMI shielding sheet and manufacturing method thereof |
| KR102162276B1 (en) * | 2016-12-28 | 2020-10-06 | 한국자동차연구원 | Conductive complex material using touch panel of vehicle |
| JP7166812B2 (en) * | 2017-07-05 | 2022-11-08 | 株式会社イノアックコーポレーション | vehicle battery case |
| JP7446127B2 (en) * | 2020-02-21 | 2024-03-08 | ポリプラスチックス株式会社 | Resin composition and molded product made from the resin composition |
| CN113878835B (en) * | 2021-12-08 | 2022-03-08 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
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