JP2008156401A - Mixture of electroconductive thermoplastic resin composition for molding, and molded article obtained by molding the same - Google Patents
Mixture of electroconductive thermoplastic resin composition for molding, and molded article obtained by molding the same Download PDFInfo
- Publication number
- JP2008156401A JP2008156401A JP2006344019A JP2006344019A JP2008156401A JP 2008156401 A JP2008156401 A JP 2008156401A JP 2006344019 A JP2006344019 A JP 2006344019A JP 2006344019 A JP2006344019 A JP 2006344019A JP 2008156401 A JP2008156401 A JP 2008156401A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- conductive
- weight
- molding
- mixture
- 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.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000000465 moulding Methods 0.000 title claims abstract description 28
- 239000011342 resin composition Substances 0.000 title claims description 14
- 239000000835 fiber Substances 0.000 claims abstract description 87
- 239000008188 pellet Substances 0.000 claims abstract description 65
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 6
- 238000007765 extrusion coating Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 239000006185 dispersion Substances 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 23
- -1 aromatic vinyl compound Chemical class 0.000 description 23
- 239000004917 carbon fiber Substances 0.000 description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 239000004793 Polystyrene Substances 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 229920000800 acrylic rubber Polymers 0.000 description 4
- 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 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 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
- 239000004711 α-olefin Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BXRXEOQDLYSFCZ-UHFFFAOYSA-N (2-bromophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1Br BXRXEOQDLYSFCZ-UHFFFAOYSA-N 0.000 description 1
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は電気・電子製造分野に好適な熱可塑性樹脂の成形品に関するものである。 The present invention relates to a molded article of a thermoplastic resin suitable for the electric / electronic manufacturing field.
熱可塑性樹脂は、その優れた機械的強度と成形加工性から様々な分野で用いられており、近年では熱可塑性樹脂に導電性、電磁波シールド性を付与して金属部品を代替する動きも活発である。その一つに、電極、スイッチ等の接点材料や抵抗体の部品が挙げられる。
熱可塑性樹脂に導電性を付与する方法としては、導電性繊維の短繊維やカーボンブラック等の導電性充填材を配合する方法が知られているが、目標とする導電性を得るためには多量の添加が必要であったため、得られた成形品は機械的強度に劣ったものであった。これを改良する目的で、連続導電性繊維を熱可塑性樹脂で被覆後、冷却・切断してペレット長と同じ長さの導電性繊維を含有する熱可塑性樹脂ペレットを得、これを成形に用いることで、成形品中の導電繊維を長く保ち、高い導電性と機械的強度を発現する方法が提案されている。（特許文献１〜６）
Thermoplastic resins are used in various fields because of their excellent mechanical strength and moldability, and in recent years there has been an active movement to replace metal parts by imparting conductivity and electromagnetic shielding properties to thermoplastic resins. is there. One of them is contact materials such as electrodes and switches, and resistor parts.
As a method for imparting conductivity to a thermoplastic resin, a method of blending conductive fillers such as short fibers of conductive fibers or carbon black is known. Therefore, the obtained molded product was inferior in mechanical strength. To improve this, after coating continuous conductive fibers with thermoplastic resin, cooling and cutting to obtain thermoplastic resin pellets containing conductive fibers of the same length as the pellet length, and using this for molding Thus, a method has been proposed in which the conductive fibers in the molded article are kept long and high conductivity and mechanical strength are exhibited. (
しかし、少量且つ繊維長の長い導電性繊維を用いて導電性を付与された成形品は、測定部位や成形品毎に表面抵抗率が大きくばらついてしまうという問題があった。このばらつきは、導電性繊維の添加量を増加することにより、ある程度は改善される。しかしながら、従来の手法を用いて製造された導電性繊維含有量の多い成形用ペレットは、ペレタイズ時、あるいはペレットの運搬中に導電性繊維に沿って割れ易く、その際導電性繊維の毛羽立ちが生じてしまう。この毛羽の成形品への混入が、成形品の外観不良、及び表面抵抗率のばらつきの原因となってしまうという問題があった。このため、信頼性を要する電極等の接点材料として使用するためには、接点部に導電ペーストを塗布する等、多大な手間とコストが必要であった。 However, a molded product imparted with conductivity using a small amount of conductive fibers having a long fiber length has a problem that the surface resistivity varies greatly between measurement sites and molded products. This variation is improved to some extent by increasing the amount of conductive fiber added. However, molding pellets with a high content of conductive fibers produced using conventional techniques are susceptible to cracking along the conductive fibers during pelletization or during transportation of the pellets, and the conductive fibers become fuzzy. End up. There is a problem that the mixture of the fluff into the molded product causes the appearance defect of the molded product and the variation in the surface resistivity. For this reason, in order to use as contact materials, such as an electrode which requires reliability, much effort and cost, such as apply | coating a conductive paste to a contact part, were required.
上述の通り、成形品中の導電性繊維長を長く保つことにより、高い機械的強度と導電性を同時に発現する方法は既にいくつか検討されている。しかしながら、高い導電性を発現し、且つ導電ペーストを塗布することなく導電性のばらつきの少ない信頼性の高い成形品を得ることは困難であった。 As described above, several methods have already been studied for maintaining high mechanical strength and conductivity simultaneously by keeping the length of the conductive fiber in the molded article long. However, it has been difficult to obtain a highly reliable molded product that exhibits high conductivity and has little variation in conductivity without applying a conductive paste.
本発明者等は、上述の問題を解決するために鋭意検討した結果、導電性繊維を特定方法を用いて、それぞれ特定量含有する熱可塑性樹脂ペレット二種以上を特定の比率で混合したものを成形に用いることにより、上述した課題を解決できることを見出し、本発明に到達した。
即ち本発明は、
［１］全混合物中における導電性繊維の含有量が２０〜４０重量％であって、下記［Ｉ
］および［ＩＩ］を主構成成分とすることを特徴とする導電性熱可塑性樹脂組成物の成形用混合物。
［Ｉ］熱可塑性樹脂（Ａ）にて導電性連続繊維束を押出被覆した後、所定の長さに切断して得られたペレットであって、導電性繊維の含有量が５〜２５重量％である熱可塑性樹脂ペレット。
［ＩＩ］熱可塑性樹脂（Ｂ）にて導電性連続繊維束を含浸被覆した後、所定の長さに切断して得られたペレットであって、導電性繊維の含有量が５０〜９５重量％である熱可塑性樹脂ペレット、
As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed two or more types of thermoplastic resin pellets each containing a specific amount of conductive fibers at a specific ratio using a specific method. The inventors have found that the above-mentioned problems can be solved by using the molding, and have reached the present invention.
That is, the present invention
[1] The content of the conductive fiber in the entire mixture is 20 to 40% by weight, and the following [I
] And [II] as main constituents, a molding mixture of a conductive thermoplastic resin composition.
[I] A pellet obtained by extrusion-coating a conductive continuous fiber bundle with the thermoplastic resin (A) and then cutting into a predetermined length, and the content of the conductive fiber is 5 to 25% by weight. Is a thermoplastic resin pellet.
[II] A pellet obtained by impregnating and coating a conductive continuous fiber bundle with a thermoplastic resin (B) and then cutting into a predetermined length, and the conductive fiber content is 50 to 95% by weight. Thermoplastic pellets, which is
［２］熱可塑性樹脂（Ａ）がスチレン系樹脂であることを特徴とする上記［１］記載の導電性熱可塑性樹脂組成物の成形用混合物、
［３］［Ｉ］が導電性連続繊維束を熱可塑性樹脂（Ｂ）にて含浸被覆した後、さらに熱可塑性樹脂（Ａ）にて押出被覆して、所定の長さに切断して得られたペレットであることを特徴とする上記［１］又は［２］に記載の導電性熱可塑性樹脂組成物の成形用混合物、
［４］熱可塑性樹脂（Ｂ）がゴム強化スチレン系樹脂であることを特徴とする上記［１］〜［３］いずれかに記載の導電性熱可塑性樹脂組成物の成形用混合物、
［５］全混合物を１００重量部とした時、［Ｉ］が５０〜９５重量部、且つ［ＩＩ］が５〜５０重量部であることを特徴とする上記［１］〜［４］いずれかに記載の導電性熱可塑性樹脂組成物の成形用混合物、
［６］上記［１］〜［５］のいずれかに記載の導電性熱可塑性樹脂組成物の成形用混合物を射出成形してなることを特徴とする成形品、
である。
[2] The molding mixture of the conductive thermoplastic resin composition according to the above [1], wherein the thermoplastic resin (A) is a styrene resin,
[3] [I] is obtained by impregnating and coating the conductive continuous fiber bundle with the thermoplastic resin (B), and further extrusion-coating with the thermoplastic resin (A) and cutting to a predetermined length. A molding mixture of the conductive thermoplastic resin composition according to the above [1] or [2], wherein the mixture is a pellet.
[4] The molding mixture of the conductive thermoplastic resin composition according to any one of the above [1] to [3], wherein the thermoplastic resin (B) is a rubber-reinforced styrene resin.
[5] Any of the above [1] to [4], wherein [I] is 50 to 95 parts by weight and [II] is 5 to 50 parts by weight when the total mixture is 100 parts by weight. A molding mixture of the conductive thermoplastic resin composition according to
[6] A molded article obtained by injection molding a molding mixture of the conductive thermoplastic resin composition according to any one of [1] to [5] above,
It is.
本発明により、導電性に優れ、成形条件、あるいは測定部位による導電性のばらつきが極めて少ない、電極等の接点材料に最適な成形品を得ることが出来る。 According to the present invention, it is possible to obtain a molded product that is excellent in electrical conductivity and has an extremely small variation in electrical conductivity depending on molding conditions or measurement sites, and that is optimal for contact materials such as electrodes.
本発明において、導電性連続繊維束とは、導電性を有する連続繊維のモノフィラメントが千本から数十万本の束になったものを言う。導電性連続繊維としては、例えば、炭素繊維、金属繊維、金属メッキを施した炭素繊維、あるいは金属メッキを施したガラス繊維等が挙げられるが、この中で導電性と比重のバランスを考慮すると、炭素繊維が好ましい。
連続炭素繊維としては、公知のものを使用することが出来、例えば、ポリアクリロニトリル系（以下、ＰＡＮ系と言う。）、ピッチ系、セルロース系が挙げられるが、この中で強度と導電性のバランスからＰＡＮ系が好ましい。炭素繊維のモノフィラメントの直径としては、導電性と取り扱いの容易さのバランスを考慮すると、３〜２０μｍ、好ましくは５〜１５μｍ、更に好ましくは５〜１０μｍである。また、炭素繊維束中のモノフィラメントの数としては、１，０００〜１００，０００本、好ましくは３，０００〜５０，０００本、更に好ましくは３，０００〜２０，０００本である。生産性の観点から１０００本以上が好ましい。１０００本未満であると、組成物中の導電性繊維含有量を調整するために、熱可塑性樹脂による被覆工程における生産性を著しく落として運転せざるを得ない。一方、射出成形工程における導電性繊維の分散性、成形品の外観や導電性、及び導電性の信頼性の観点から１００，０００本以下が好ましい。
連続金属繊維としては、公知の導電性金属繊維を使用することが出来、例えば、銅、鉄、ニッケル、金、銀、チタン、アルミニウムやこれらを主成分とするステンレス、真鍮等の合金製の繊維が挙げられる。
In the present invention, the conductive continuous fiber bundle refers to a bundle of thousands to hundreds of thousands of monofilaments of continuous fibers having conductivity. Examples of the conductive continuous fiber include carbon fiber, metal fiber, carbon fiber subjected to metal plating, or glass fiber subjected to metal plating, among them, considering the balance between conductivity and specific gravity. Carbon fiber is preferred.
As the continuous carbon fiber, known ones can be used, and examples thereof include polyacrylonitrile (hereinafter referred to as PAN), pitch, and cellulose. Among these, the balance between strength and conductivity is included. To PAN system is preferred. The diameter of the carbon fiber monofilament is 3 to 20 μm, preferably 5 to 15 μm, more preferably 5 to 10 μm in consideration of the balance between conductivity and ease of handling. In addition, the number of monofilaments in the carbon fiber bundle is 1,000 to 100,000, preferably 3,000 to 50,000, and more preferably 3,000 to 20,000. From the viewpoint of productivity, 1000 or more are preferable. When the number is less than 1000, in order to adjust the conductive fiber content in the composition, the productivity in the coating process with the thermoplastic resin must be remarkably reduced. On the other hand, 100,000 or less is preferable from the viewpoints of dispersibility of conductive fibers in the injection molding process, appearance and conductivity of the molded product, and reliability of conductivity.
As the continuous metal fiber, a known conductive metal fiber can be used, for example, copper, iron, nickel, gold, silver, titanium, aluminum, or a fiber made of an alloy such as stainless steel or brass mainly composed of these. Is mentioned.
連続炭素繊維に金属メッキを施したものあるいはガラス繊維に金属メッキを施したものとしては、公知の炭素繊維、ガラス繊維に上述した金属をメッキしたものが挙げられる。これら金属繊維、及び金属メッキ処理を施した炭素繊維、あるいは金属メッキ処理を施し
たガラス繊維のモノフィラメントの直径としては、導電性と取り扱いの容易さとのバランスを考慮すると３〜２０μｍ、好ましくは５〜１５μｍである。
また、これらの導電性連続繊維束には、これを配合した熱可塑性樹脂の力学的特性の向上、あるいは導電性の向上、及び連続繊維束の取り扱い性向上の目的で、カップリング剤やサイジング剤等の表面処理剤による処理を施してあっても良い。かかる表面処理剤としては、例えばシラン系、チタネート系等のカップリング剤、エポキシ系、ウレタン系、エーテル系、エステル系、アミド系、アクリル系、ポリビニルアルコール系のサイジング剤等が挙げられる。
Examples of the continuous carbon fiber plated with metal or the glass fiber plated with metal include known carbon fibers and glass fibers plated with the above-described metals. The diameter of monofilaments of these metal fibers and carbon fibers subjected to metal plating treatment or glass fibers subjected to metal plating treatment is 3 to 20 μm, preferably 5 to 5 in consideration of the balance between conductivity and ease of handling. 15 μm.
In addition, these conductive continuous fiber bundles include a coupling agent and a sizing agent for the purpose of improving the mechanical properties of a thermoplastic resin containing the conductive continuous fiber bundle, or improving the conductivity and handling of the continuous fiber bundle. You may give the process by surface treatment agents, such as. Examples of such surface treatment agents include silane-based and titanate-based coupling agents, epoxy-based, urethane-based, ether-based, ester-based, amide-based, acrylic-based, and polyvinyl alcohol-based sizing agents.
本発明に用いられる熱可塑性樹脂（Ａ）としては、特に制限されないが、スチレン系樹脂、ポリカーボネート、オレフィン系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、熱可塑性ポリエステル、ポリアセタール、ポリスルフォン、シリコーン樹脂、ポリエーテルエーテルケトン等が挙げられ、単独又は二種以上のアロイとしても使用することが出来る。
この中で、特に好ましいのは、スチレン系樹脂、ポリカーボネート、及びこれらのアロイである。
スチレン系樹脂としては、芳香族ビニル化合物の単一重合体、芳香族ビニル化合物、及びこれらと共重合可能な単量体とを共重合させてなる共重合体、ゴム質重合体に芳香族ビニル化合物、及びこれらと共重合可能な単量体とをグラフト共重合させてなるグラフト共重合体、及びこれらの混合物が挙げられる。
The thermoplastic resin (A) used in the present invention is not particularly limited, but styrene resin, polycarbonate, olefin resin, polyamide resin, vinyl chloride resin, thermoplastic polyester, polyacetal, polysulfone, silicone resin, Polyetheretherketone etc. are mentioned, It can use also as single or 2 or more types of alloys.
Among these, styrene resins, polycarbonates, and alloys thereof are particularly preferable.
Styrenic resins include aromatic vinyl compound single polymers, aromatic vinyl compounds, copolymers obtained by copolymerizing these with monomers, rubbery polymers and aromatic vinyl compounds. And a graft copolymer obtained by graft copolymerization with a monomer copolymerizable therewith, and a mixture thereof.
芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、エチルスチレン、ｐ−ｔ−ブチルスチレン、ビニルナフタレン、モノクロロスチレン、ジクロロスチレン、モノブロモスチレン、ジブロモスチレン等が挙げられ、これらは単独、又は二種以上を組み合わせて使用することが出来るが、この中で特に好ましいのは、スチレン、及びα−メチルスチレンである。
芳香族ビニル化合物と共重合可能な単量体としては、例えば、アクリロニトリル、メタアクリロニトリルなどのシアン化ビニル化合物、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステルや同様な置換体のメタクリル酸エステル、さらに、アクリル酸、メタクリル酸等のアクリル酸類やＮ−フェニルマレイミド、Ｎ−メチルマレイミド等のＮ−置換マレイミド系単量体、グリシジルメタクリレート等のグリシジル基含有単量体等が挙げられ、この中で特に好ましいのはアクリロニトリル、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸メチル、Ｎ−フェニルマレイミド、グリシジルメタクリレートである。これらは単独、又は二種以上を組み合わせて使用することが出来る。
Examples of aromatic vinyl compounds include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, ethyl styrene, pt-butyl styrene, vinyl naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, etc. These can be used singly or in combination of two or more. Among them, styrene and α-methylstyrene are particularly preferable.
Examples of the monomer copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and similar substituents. Examples include methacrylic acid esters, acrylic acids such as acrylic acid and methacrylic acid, N-substituted maleimide monomers such as N-phenylmaleimide and N-methylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. Of these, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N-phenylmaleimide, and glycidyl methacrylate are particularly preferable. These can be used alone or in combination of two or more.
スチレン系樹脂における還元粘度（ηｓｐ／ｃ）は０．２〜１．０ｄｌ／ｇ、好ましくは０．３〜１．０ｄｌ／ｇ、さらに好ましくは０．４〜１．０ｄｌ／ｇ、特に好ましくは０．４５〜１．０ｄｌ／ｇである。これがこの範囲にあると耐衝撃性、及び難燃性に優れた組成物を得ることが出来る。還元粘度は、樹脂０．５０ｇを２−ブタノン１００ｍｌにて溶解した溶液を、３０℃にてＣａｎｎｏｎ−Ｆｅｎｓｋｅ型毛細管中の流出時間を測定することにより得られる。 The reduced viscosity (ηsp / c) in the styrene-based resin is 0.2 to 1.0 dl / g, preferably 0.3 to 1.0 dl / g, more preferably 0.4 to 1.0 dl / g, particularly preferably. 0.45 to 1.0 dl / g. When this is in this range, a composition excellent in impact resistance and flame retardancy can be obtained. The reduced viscosity can be obtained by measuring the outflow time in a Cannon-Fenske type capillary tube at 30 ° C. with a solution obtained by dissolving 0.50 g of resin in 100 ml of 2-butanone.
スチレン系グラフト共重合体におけるゴム質重合体としては、例えば、ポリブタジエン、ブタジエン−スチレン共重合体、ブタジエン−アクリロニトリル共重合体、ブタジエン−アクリル共重合体、スチレン−ブタジエン−スチレンブロック共重合体、ポリイソプレン、スチレン−イソプレン共重合体等の共役ジエン系ゴム、及びこれらの水素添加物、アクリル酸エチル、アクリル酸ブチル等のアクリル系ゴム、エチレン−α−オレフィン−ポリエン共重合体、エチレン−α−オレフィン共重合体、シリコーンゴム、シリコーン−アクリルゴム等が挙げられ、これらは単独、又は二種以上を組み合わせて使用することが出来る。この中で特に好ましいのは、ポリブタジエン、ポリイソプレン、ブタジエン−スチ
レン共重合体、ブタジエン−アクリロニトリル共重合体、ブタジエン−アクリル共重合体、アクリル系ゴム、エチレン−α−オ
レフィン−ポリエン共重合体、エチレン−α−オレフィン共重合体、シリコーンゴム、シリコーン−アクリルゴムである。
スチレン系グラフト共重合体におけるゴム質重合体の重量平均粒子径は、耐衝撃性等の機械的強度、成形加工性、成形品外観のバランスから、好ましくは０．１〜１．２μｍ、より好ましくは０．１５〜０．８μｍ、さらに好ましくは０．１５〜０．６μｍ、特に好ましくは０．２〜０．４μｍである。
Examples of the rubbery polymer in the styrene-based graft copolymer include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, styrene-butadiene-styrene block copolymer, poly Conjugated diene rubbers such as isoprene and styrene-isoprene copolymers, and hydrogenated products thereof, acrylic rubbers such as ethyl acrylate and butyl acrylate, ethylene-α-olefin-polyene copolymers, ethylene-α- Examples include olefin copolymers, silicone rubber, silicone-acrylic rubber, and the like. These may be used alone or in combination of two or more. Of these, polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, acrylic rubber, ethylene-α-olefin-polyene copolymer, ethylene are particularly preferable. -Α-olefin copolymer, silicone rubber, silicone-acrylic rubber.
The weight average particle diameter of the rubbery polymer in the styrene-based graft copolymer is preferably 0.1 to 1.2 μm, more preferably from the balance of mechanical strength such as impact resistance, molding processability, and appearance of the molded product. Is 0.15 to 0.8 μm, more preferably 0.15 to 0.6 μm, and particularly preferably 0.2 to 0.4 μm.
また、スチレン系グラフト共重合体におけるグラフト率は、好ましくは１０〜１５０重量％、より好ましくは２０〜１１０重量％、更に好ましくは２５〜６０重量％である。グラフト率をこの範囲にすることで、耐衝撃性に優れ、成形加工性の良好な組成物を得ることが出来る。尚、グラフト率とは、ゴム質重合体にグラフト共重合した単量体の、ゴム質重合体に対する重量割合として定義される。その測定法は、重合反応により生成した重合体をアセトンに溶解し、遠心分離器によりアセトン可溶分と不溶分とに分離する。この時、アセトンに溶解する成分は重合反応した共重合体のうちグラフト反応しなかった成分（非グラフト成分）であり、アセトン不溶分はゴム質重合体、及びゴム質重合体にグラフト反応した成分（グラフト成分）である。アセトン不溶分の重量からゴム質重合体の重量を差し引いた値がグラフト成分の重量として定義されるので、これらの値からグラフト率を求めることが出来る。 Moreover, the graft ratio in a styrene-type graft copolymer becomes like this. Preferably it is 10 to 150 weight%, More preferably, it is 20 to 110 weight%, More preferably, it is 25 to 60 weight%. By setting the graft ratio within this range, a composition having excellent impact resistance and good moldability can be obtained. The graft ratio is defined as the weight ratio of the monomer graft copolymerized with the rubber polymer to the rubber polymer. In the measurement method, a polymer produced by a polymerization reaction is dissolved in acetone and separated into an acetone-soluble component and an insoluble component by a centrifuge. At this time, the component dissolved in acetone is a component that has not undergone a graft reaction (non-graft component) in the copolymer that has undergone a polymerization reaction, and the acetone insoluble component is a component that has undergone a graft reaction to the rubber polymer and the rubber polymer. (Graft component). Since the value obtained by subtracting the weight of the rubbery polymer from the weight of the acetone-insoluble component is defined as the weight of the graft component, the graft ratio can be determined from these values.
ポリカーボネート樹脂としては、ヒドロキシアリール化合物とホスゲンとの界面重縮合によって得られるもの、又はジヒドロキシアリール化合物とジフェニルカーボネートとのエステル交換反応（溶融重縮合）によって得られるもの等、公知の重合法によって得られるものが挙げられる。
オレフィン系樹脂としては、例えば、高密度、中密度、低密度ポリエチレン、ポリプロピレン、ポリブテン、４−メチルペンテン−１樹脂、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アルキル（メタ）アクリレート共重合体等が挙げられる。
ポリアミド系樹脂としては、例えば、ナイロン６、ナイロン１１、ナイロン６６、ナイロン６１０等が挙げられる。
The polycarbonate resin can be obtained by a known polymerization method such as one obtained by interfacial polycondensation between a hydroxyaryl compound and phosgene, or one obtained by transesterification (melt polycondensation) between a dihydroxyaryl compound and diphenyl carbonate. Things.
Examples of the olefin resin include high density, medium density, low density polyethylene, polypropylene, polybutene, 4-methylpentene-1 resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-alkyl (meta ) Acrylate copolymer and the like.
Examples of the polyamide-based resin include nylon 6, nylon 11, nylon 66, nylon 610, and the like.
塩化ビニル系樹脂としては、例えば、塩化ビニル、及びこれと共重合可能な単量体とを共重合させてなる共重合体が挙げられる。塩化ビニルと共重合可能な単量体としては、例えば、スチレン、α−メチルスチレン等の芳香族ビニル化合物、エチレン、プロピレン、１−ヘキセン等のα−オレフィン系単量体、酢酸ビニル、プロピオン酸ビニル等のエステル系単量体、ブチルビニルエーテル、セチルビニルエーテル、フェニルビニルエーテル等のエーテル系単量体、（メタ）アクリロニトリル等のシアン化ビニル化合物、塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル化合物、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステルや同様な置換体のメタクリル酸エステル、さらに、アクリル酸、メタクリル酸等のアクリル酸類やＮ−フェニルマレイミド、Ｎ−メチルマレイミド等のＮ−置換マレイミド系単量体等が挙げられる。 Examples of the vinyl chloride resin include a copolymer obtained by copolymerizing vinyl chloride and a monomer copolymerizable therewith. Examples of the monomer copolymerizable with vinyl chloride include aromatic vinyl compounds such as styrene and α-methylstyrene, α-olefin monomers such as ethylene, propylene, and 1-hexene, vinyl acetate, and propionic acid. Ester monomers such as vinyl, ether monomers such as butyl vinyl ether, cetyl vinyl ether and phenyl vinyl ether, vinyl cyanide compounds such as (meth) acrylonitrile, vinyl halide compounds such as vinylidene chloride and vinyl fluoride, acrylic Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and similar substituted methacrylic acid esters, acrylic acids such as acrylic acid and methacrylic acid, and N-phenylmaleimide and N-methylmaleimide N- Examples thereof include substituted maleimide monomers.
熱可塑性ポリエステルとしては、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート、ポリエチレンナフタレート等のジカルボン酸と脂肪族ジオールとから得られるポリエステルが挙げられる。
ジカルボン酸としては、テレフタル酸、アゼライン酸、セバシン酸、アジピン酸、デカンジカルボン酸等の脂肪族ジカルボン酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸等が挙げられ、
これらを単独、又は二種以上を組み合わせて使用することが出来る。
脂肪族ジオールとしては、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、トリメチレングリコール、１，４−シクロヘキサンジメタノール、ヘキサメチレングリコール等が挙げられる。
Examples of the thermoplastic polyester include polyesters obtained from dicarboxylic acids and aliphatic diols such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, and polyethylene naphthalate.
Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as terephthalic acid, azelaic acid, sebacic acid, adipic acid, and decanedicarboxylic acid, aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Etc.
These can be used alone or in combination of two or more.
Examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol, hexamethylene glycol and the like.
熱可塑性樹脂ペレット［Ｉ］を製造する方法としては、導電性連続繊維束を張力下で引き揃えながらクロスヘッドダイを通過させて熱可塑性樹脂（Ａ）にて押出被覆し、切断してペレット化する方法を用いることが出来る。この時、導電性連続繊維束に対する被覆量は、例えばクロスヘッドダイのダイス口径や樹脂の引き取り速度を適切に設定することで制御することが出来る。
熱可塑性樹脂ペレット［Ｉ］における導電性繊維の含有量は、５〜２５重量％、好ましくは１０〜２５重量％、さらに好ましくは１０〜２２重量％、特に好ましくは１２〜２２重量％である。これがこの範囲にあると、導電性繊維が成形品中により均一に分散し、且つペレット割れによる繊維の毛羽立ちを抑制することが出来るので、外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
As a method for producing the thermoplastic resin pellet [I], the conductive continuous fiber bundle is passed through a crosshead die while being aligned under tension, and is extrusion coated with the thermoplastic resin (A), cut and pelletized. Can be used. At this time, the coating amount with respect to the conductive continuous fiber bundle can be controlled, for example, by appropriately setting the die diameter of the crosshead die and the take-up speed of the resin.
The content of the conductive fiber in the thermoplastic resin pellet [I] is 5 to 25% by weight, preferably 10 to 25% by weight, more preferably 10 to 22% by weight, and particularly preferably 12 to 22% by weight. If this is in this range, the conductive fibers can be more uniformly dispersed in the molded product, and the fluffing of the fibers due to pellet cracking can be suppressed, so the appearance and conductivity are excellent, and reliability with little variation in conductivity is achieved. Can be obtained.
また、導電性連続繊維束を熱可塑性樹脂（Ａ）によって被覆する前に、予め熱可塑性樹脂（Ｂ）を含浸させ、繊維束中のモノフィラメント表面を被覆することにより、さらに導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。含浸被覆法としては、例えば連続繊維束に熱可塑性樹脂を溶融引き出し法により含浸被覆させる方法、連続繊維束を熱可塑性樹脂のエマルジョン、サスペンジョン、溶液、あるいは溶融物の入った含浸槽中を通過させた後に固化する方法、樹脂粉末等を振動や気体で分散させたところへ連続繊維束を通過させ、粉末を付着させた後に加熱して含浸被覆させる方法等が挙げられる。熱可塑性樹脂（Ｂ）がゴム強化スチレン系樹脂である時には、含浸被覆法としてエマルジョンを用いる方法が最も好ましい。 In addition, before coating the continuous conductive fiber bundle with the thermoplastic resin (A), impregnating the thermoplastic resin (B) in advance and covering the monofilament surface in the fiber bundle further reduces the variation in conductivity. A highly reliable molded product can be obtained. Examples of the impregnation coating method include a method in which a continuous fiber bundle is impregnated with a thermoplastic resin by a melt drawing method, and the continuous fiber bundle is passed through an impregnation tank containing an emulsion, suspension, solution, or melt of a thermoplastic resin. And a method of solidifying the resin powder and the like, a method in which a continuous fiber bundle is passed through a place where resin powder or the like is dispersed by vibration or gas, and the powder is attached, followed by heating and impregnation coating. When the thermoplastic resin (B) is a rubber-reinforced styrene resin, a method using an emulsion as the impregnation coating method is most preferable.
熱可塑性樹脂（Ｂ）としては、特に制限は無く、例えば上述した熱可塑性樹脂（Ａ）の例として挙げられたものを使用することが出来る。この中で好ましいのはスチレン系樹脂、特に好ましいのは、ゴム質重合体に芳香族ビニル化合物、及びこれらと共重合可能な単量体とをグラフト共重合させてなるグラフト共重合体を含有するゴム強化スチレン系樹である。
熱可塑性樹脂（Ｂ）は、必ずしも熱可塑性樹脂（Ａ）と組成、分子量、組成分布が同一である必要は無いが、機械的強度、及び分散性を考慮すると、熱可塑性樹脂（Ａ）と相溶性を示すか、公知のポリマーアロイとして用いられている組み合わせであることが好ましい。さらに、熱可塑性樹脂（Ｂ）の成形温度における流動性は、熱可塑性樹脂（Ａ）よりも優れている方が導電性繊維をより均一に分散させることが出来るので、外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
また、熱可塑性樹脂ペレット［Ｉ］における熱可塑性樹脂（Ｂ）と熱可塑性樹脂ペレット［ＩＩ］における熱可塑性樹脂（Ｂ）も、必ずしも同一である必要は無い。
There is no restriction | limiting in particular as a thermoplastic resin (B), For example, what was mentioned as an example of the thermoplastic resin (A) mentioned above can be used. Among these, a styrene resin is preferable, and a graft copolymer obtained by graft copolymerizing an aromatic vinyl compound and a monomer copolymerizable therewith with a rubbery polymer is particularly preferable. It is a rubber-reinforced styrene tree.
The thermoplastic resin (B) does not necessarily have the same composition, molecular weight, and composition distribution as the thermoplastic resin (A), but considering the mechanical strength and dispersibility, the thermoplastic resin (A) is compatible with the thermoplastic resin (A). It is preferable that the combination shows solubility or is used as a known polymer alloy. Furthermore, since the fluidity at the molding temperature of the thermoplastic resin (B) is more excellent than the thermoplastic resin (A), the conductive fibers can be more uniformly dispersed. A highly reliable molded product with little variation in conductivity can be obtained.
Further, the thermoplastic resin (B) in the thermoplastic resin pellet [I] and the thermoplastic resin (B) in the thermoplastic resin pellet [II] are not necessarily the same.
熱可塑性樹脂ペレット［ＩＩ］を製造する方法としては、導電性連続繊維束に熱可塑性樹脂（Ｂ）を含浸させ、繊維束中のモノフィラメント表面を被覆した後、所定の長さに切断する公知の方法を使用することが出来る。含浸被覆法としては、例えば連続繊維束に熱可塑性樹脂を溶融引き出し法により含浸被覆させる方法、連続繊維束を熱可塑性樹脂のエマルジョン、サスペンジョン、溶液、あるいは溶融物の入った含浸槽中を通過させた後に固化する方法、樹脂粉末等を振動や気体で分散させたところへ連続繊維束を通過させ、粉末を付着させた後に加熱して含浸被覆させる方法等が挙げられる。熱可塑性樹脂（Ｂ）がゴム強化スチレン系樹脂である時には、含浸被覆法としてエマルジョンを用いる方法が最も好ましい。
熱可塑性樹脂ペレット［ＩＩ］における導電性繊維の含有量は、５０〜９５重量％、好
ましくは５０〜９０重量％、さらに好ましくは５５〜９０重量％、特に好ましくは６０〜８５重量％である。これがこの範囲にあると、導電性繊維が成形品中により均一に分散し、且つペレット割れによる繊維の毛羽立ちを抑制することが出来るので、外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
As a method for producing the thermoplastic resin pellet [II], a conductive continuous fiber bundle is impregnated with a thermoplastic resin (B), the surface of the monofilament in the fiber bundle is coated, and then cut to a predetermined length. The method can be used. Examples of the impregnation coating method include a method in which a continuous fiber bundle is impregnated with a thermoplastic resin by a melt drawing method, and the continuous fiber bundle is passed through an impregnation tank containing an emulsion, suspension, solution, or melt of a thermoplastic resin. And a method of solidifying the resin powder and the like, a method in which a continuous fiber bundle is passed through a place where resin powder or the like is dispersed by vibration or gas, and the powder is attached, followed by heating and impregnation coating. When the thermoplastic resin (B) is a rubber-reinforced styrene resin, a method using an emulsion as the impregnation coating method is most preferable.
The content of the conductive fiber in the thermoplastic resin pellet [II] is 50 to 95% by weight, preferably 50 to 90% by weight, more preferably 55 to 90% by weight, and particularly preferably 60 to 85% by weight. If this is in this range, the conductive fibers can be more uniformly dispersed in the molded product, and the fluffing of the fibers due to pellet cracking can be suppressed, so the appearance and conductivity are excellent, and reliability with little variation in conductivity is achieved. Can be obtained.
本発明において、熱可塑性樹脂ペレット［Ｉ］、および熱可塑性樹脂ペレット［ＩＩ］の長さは３〜２０ｍｍが好ましく、より好ましくは５〜１５ｍｍ、特に好ましくは５〜１２ｍｍである。これがこの範囲にあると外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
熱可塑性樹脂ペレット［Ｉ］、および熱可塑性樹脂ペレット［ＩＩ］を混合する方法については、タンブラー等公知の方法を用いることが出来る。
少なくとも熱可塑性樹脂ペレット［Ｉ］および熱可塑性樹脂ペレット［ＩＩ］を構成成分とする全混合物中における導電性繊維の含有量は、２０〜４０重量％、好ましくは２０〜３５重量％、さらに好ましくは２２〜３５重量％、特に好ましくは２２〜３０重量％である。これがこの範囲にあると、成形性、外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
In the present invention, the length of the thermoplastic resin pellet [I] and the thermoplastic resin pellet [II] is preferably 3 to 20 mm, more preferably 5 to 15 mm, and particularly preferably 5 to 12 mm. When this is in this range, a highly reliable molded product having excellent appearance and conductivity and little variation in conductivity can be obtained.
About the method of mixing thermoplastic resin pellet [I] and thermoplastic resin pellet [II], well-known methods, such as a tumbler, can be used.
The content of the conductive fiber in the total mixture containing at least the thermoplastic resin pellet [I] and the thermoplastic resin pellet [II] as a constituent component is 20 to 40% by weight, preferably 20 to 35% by weight, more preferably It is 22 to 35% by weight, particularly preferably 22 to 30% by weight. When this is in this range, a highly reliable molded product having excellent moldability, appearance, and electrical conductivity and less variation in electrical conductivity can be obtained.
また、全混合物を１００重量部とした時の熱可塑性樹脂ペレット［Ｉ］は５０〜９５重量部、好ましくは６０〜９５重量部、さらに好ましくは６０〜９０重量部、特に好ましくは７０〜９０重量部、且つ熱可塑性樹脂ペレット［ＩＩ］は５〜５０重量部、好ましくは５〜４０重量部、さらに好ましくは１０〜４０重量部、特に好ましくは１０〜３０重量部である。これがこの範囲にあると、外観、導電性に優れ、導電性のばらつきの少ない信頼性の高い成形品を得ることが出来る。
本発明における成形法としては、射出成形、射出圧縮成形、ブロー成形、押出成形、真空成形、圧縮成形等の公知の方法が挙げられるが、この中では生産性に優れる射出成形が特に好ましい。
Further, the thermoplastic resin pellet [I] when the total mixture is 100 parts by weight is 50 to 95 parts by weight, preferably 60 to 95 parts by weight, more preferably 60 to 90 parts by weight, particularly preferably 70 to 90 parts by weight. Part and the thermoplastic resin pellet [II] are 5 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 40 parts by weight, and particularly preferably 10 to 30 parts by weight. When this is in this range, it is possible to obtain a highly reliable molded article having excellent appearance and conductivity and less variation in conductivity.
Examples of the molding method in the present invention include known methods such as injection molding, injection compression molding, blow molding, extrusion molding, vacuum molding, and compression molding. Among these, injection molding having excellent productivity is particularly preferable.
本発明において、その目的に応じて公知の添加剤、例えば、炭素繊維以外の導電性フィラー（例えば、アセチレンブラック、ケッチェンブラック等のカーボンブラック、ナノチューブカーボン、黒鉛等の炭素系フィラー、銅、鉄、ニッケル、金、銀、チタン、アルミニウム、及びステンレス、真鍮等の前述した金属を主成分とする合金等の金属系フィラー、酸化亜鉛、酸化チタン、酸化アルミニウム、酸化スズ、酸化インジウム等の金属酸化物系フィラー、ガラス表面に上記金属メッキ処理を施した複合系フィラー等）、可塑剤、滑剤（例えば、高級脂肪酸、及びその金属塩、高級脂肪酸アミド類等）、熱安定化剤、酸化防止剤（例えば、フェノール系、フォスファイト系、チオジブロプロピオン酸エステル型のチオエーテル等）、耐候剤（例えば、ベンゾトリアゾール系、ベンゾフェノン系、サリシレート系、シアノアクリレート系、蓚酸誘導体、ヒンダードアミン系等）、着色剤、顔料、染料、臭素系難燃剤（例えば、テトラブロモビスフェノールＡ及びその誘導体、テトラブロモビスフェノールＳ、テトラブロモ無水フタル酸、ヘキサブロモベンゼン、臭素化ジフェニルエーテル、臭素化ポリカーボネートオリゴマー及びその末端変性品、臭素化エポキシ樹脂（ビスフェノールＡタイプ、ノボラックタイプ）及びその末端変性品、臭素化フェノキシ樹脂、トリスブロモフェニルフォスフェート、臭素化ポリスチレン、臭素化フェニレンエーテルオリゴマー等）、リン系難燃剤（トリフェニルホスフェート、トリフェニルホスフェート、トリフェニルチオホスフェート、トリキシレニルホスフェート、トリキシレニルチオホスフェート、ハイドロキノンビス（ジフェニルホスフェート）、レゾルシノールビス（ジフェニルホスフェート）、ハイドロキノンビス（ジキシレニルホスフェート）等のホスフェート類、赤リン、ホスファゼン系化合物、ポリリン酸アンモニウム等）、難燃助剤（例えば、三酸化アンチモン、五酸化アンチモン等）、帯電防止剤（例えば、ポリアミドエーテルエステル等のポリアミドエラストマー、四級アンモニウム塩系、ピリジン誘導体、脂肪族スルホン酸塩、芳香族スルホン酸塩、硫酸エステル塩、多価アルコ
ール部分エステル、アルキルジエタノールアミン、アルクルジエタノールアミド、ポリアルキレングリコール誘導体、ベタイン系、イミダゾリン誘導体等）、抗菌剤、抗カビ剤、摺動性改良剤（例えば、低分子量ポリエチレン等の炭化水素系、高級アルコール、多価アルコール、ポリグリコール、ポリグリセロール、高級脂肪酸、高級脂肪酸金属塩、脂肪酸アミド、脂肪酸と脂肪族アルコールとのエステル、脂肪酸と多価アルコールとのフル、あるいは部分エステル、脂肪酸とポリグリコールとのフル、あるいは部分エステル、シリコーン系、フッ素樹脂系等）等をその目的に合わせて任意の割合で配合することが出来る。
In the present invention, known additives depending on the purpose, for example, conductive fillers other than carbon fiber (for example, carbon black such as acetylene black and ketjen black, carbon-based filler such as nanotube carbon and graphite, copper, iron Nickel, gold, silver, titanium, aluminum, and metal fillers such as alloys based on the aforementioned metals such as stainless steel and brass, metal oxides such as zinc oxide, titanium oxide, aluminum oxide, tin oxide, and indium oxide Physical fillers, composite fillers obtained by subjecting the glass surface to the above metal plating treatment, etc.), plasticizers, lubricants (for example, higher fatty acids and their metal salts, higher fatty acid amides, etc.), thermal stabilizers, antioxidants (For example, phenol-based, phosphite-based, thiodibropropionic acid ester type thioether, etc.), weathering agent ( For example, benzotriazole, benzophenone, salicylate, cyanoacrylate, oxalic acid derivatives, hindered amines, etc., colorants, pigments, dyes, brominated flame retardants (for example, tetrabromobisphenol A and its derivatives, tetrabromobisphenol S) , Tetrabromophthalic anhydride, hexabromobenzene, brominated diphenyl ether, brominated polycarbonate oligomer and its terminal modified product, brominated epoxy resin (bisphenol A type, novolak type) and its terminal modified product, brominated phenoxy resin, tris bromophenyl Phosphate, brominated polystyrene, brominated phenylene ether oligomers, etc.), phosphorus flame retardants (triphenyl phosphate, triphenyl phosphate, triphenylthiophosphate, trike) Phosphates such as rhenyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (dixylenyl phosphate), red phosphorus, phosphazene compounds, ammonium polyphosphate, etc.) Flame retardant aid (for example, antimony trioxide, antimony pentoxide, etc.), antistatic agent (for example, polyamide elastomer such as polyamide ether ester, quaternary ammonium salt system, pyridine derivative, aliphatic sulfonate, aromatic sulfonic acid Salts, sulfate esters, polyhydric alcohol partial esters, alkyldiethanolamines, alkuldiethanolamides, polyalkylene glycol derivatives, betaines, imidazoline derivatives, etc.), antibacterial agents, antifungal agents, slides Mobility improvers (for example, hydrocarbons such as low molecular weight polyethylene, higher alcohols, polyhydric alcohols, polyglycols, polyglycerols, higher fatty acids, higher fatty acid metal salts, fatty acid amides, esters of fatty acids and fatty alcohols, fatty acids And polyhydric alcohol full or partial ester, fatty acid and polyglycol full or partial ester, silicone-based, fluororesin-based, etc.) can be blended at any ratio according to the purpose.
本発明の成形品は、その優れた導電性、導電信頼性、および機械的強度から、電子・電気機器、精密機器、ＯＡ機器、及びその周辺機器のハウジング、カバー、及びこれらの部品搬送ケース、電磁波シールド部品、情報電子、自動車等の電気接点部品、電極部品等に用いることが出来る。 The molded product of the present invention has excellent electrical conductivity, conductive reliability, and mechanical strength, so that the housing and cover of electronic / electrical equipment, precision equipment, OA equipment, and peripheral equipment thereof, and their parts carrying cases, It can be used for electromagnetic shielding parts, information electronics, electrical contact parts such as automobiles, electrode parts and the like.
以下に実施例を示し、本発明を具体的に説明する。
［参考例１］熱可塑性樹脂（ａ−１）の製造
ポリブタジエンゴムラテックス（日機装（株）社製マイクロトラック粒度分析計「ｎａｎｏｔｒａｃ１５０」にて測定した体積平均粒子径＝０．２５μｍ、固形分量＝４９重量％）１１０重量部に、脱イオン水４５重量部を加え、気相部を窒素置換した後、脱イオン水２５重量部にナトリウムホルムアルデヒドスルホキシレート０．１５重量部、硫酸第一鉄０．００１重量部、エチレンジアミンテトラ酢酸２ナトリウム塩０．０９重量部を溶解してなる水溶液を加えて、５５℃に昇温した。続いて、１．５時間かけて７０℃まで昇温しながら、アクリロニトリル１５重量部、スチレンを３５重量部、ターシャリードデシルメルカプタン０．６重量部、クメンハイドロパーオキシド０．１重量部よりなる単量体混合液、及び脱イオン水１５重量部にナトリウムホルムアルデヒドスルホキシレート０．１３重量部を溶解してなる水溶液を５時間にわたり添加した。添加終了後１時間、反応槽を７０℃に制御しながら重合反応を完結させた。
このようにして得られたＡＢＳラテックスに、シリコーン樹脂製消泡剤、及びフェノール系酸化防止剤エマルジョンを添加した後、硫酸アルミニウム水溶液を加えて凝固させ、さらに、十分な脱水、水洗を行った後、乾燥させてグラフト共重合体（ａ−１）を得た。この時、グラフト率は５５重量％であり、非グラフト成分の還元粘度（０．５ｇ／１００ｍｌ、２−ブタノン溶液中、３０℃測定）は０．２６であった。
Hereinafter, the present invention will be specifically described with reference to examples.
[Reference Example 1] Production of thermoplastic resin (a-1) Polybutadiene rubber latex (volume average particle diameter measured by Microtrac Particle Size Analyzer “nanotrac 150” manufactured by Nikkiso Co., Ltd.) = 0.25 μm, solid content = 49 (Weight%) After adding 45 parts by weight of deionized water to 110 parts by weight and replacing the gas phase with nitrogen, 0.15 parts by weight of sodium formaldehyde sulfoxylate, 0.15 parts by weight of ferrous sulfate, 0.2 part by weight of deionized water. An aqueous solution obtained by dissolving 001 parts by weight and 0.09 part by weight of ethylenediaminetetraacetic acid disodium salt was added, and the temperature was raised to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, a single unit consisting of 15 parts by weight of acrylonitrile, 35 parts by weight of styrene, 0.6 parts by weight of terleaded decyl mercaptan, and 0.1 parts by weight of cumene hydroperoxide. An aqueous solution prepared by dissolving 0.13 parts by weight of sodium formaldehyde sulfoxylate in 15 parts by weight of a monomer mixture and deionized water was added over 5 hours. One hour after completion of the addition, the polymerization reaction was completed while controlling the reaction vessel at 70 ° C.
After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a graft copolymer (a-1). At this time, the graft ratio was 55% by weight, and the reduced viscosity of the non-grafted component (0.5 g / 100 ml, measured in 2-butanone solution at 30 ° C.) was 0.26.
［参考例２］熱可塑性樹脂（ａ−２）の製造
特許１９６０５３１号公報に記載の実施例１に記載の方法にて、アクリロニトリル、及びスチレンを、溶媒としてセカンダリーブチルアルコールを用い、重合反応器に上記混合液を連続的に添加し、重合計の温度を１４０から１６０℃にコントロールして重合反応を行った。その後、未反応のモノマーを真空下にて除去し、アクリロニトリル−スチレン共重合体の固形粉末を得た。該共重合体の組成は、フーリエ変換赤外分光光度計（ＦＲ−ＩＲ）（日本分光（株）製）を用いた組成分析の結果、アクリロニトリルは３０重量％、スチレンが７０重量％であった。また、還元粘度（０．５ｇ／１００ｍｌ、２−ブタノン溶液中、３０℃測定）は０．６５であった。
[Reference Example 2] Production of thermoplastic resin (a-2) In the method described in Example 1 described in Japanese Patent No. 1960531, acrylonitrile and styrene were used as solvents and secondary butyl alcohol was used as a polymerization reactor. The above mixture was continuously added, and the polymerization reaction was carried out by controlling the temperature of the polymerization meter from 140 to 160 ° C. Thereafter, unreacted monomers were removed under vacuum to obtain a solid powder of acrylonitrile-styrene copolymer. As a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR) (manufactured by JASCO Corporation), the composition of the copolymer was 30% by weight for acrylonitrile and 70% by weight for styrene. . The reduced viscosity (0.5 g / 100 ml, measured in a 2-butanone solution at 30 ° C.) was 0.65.
［参考例３］熱可塑性樹脂（Ａ−１）の製造
充分に乾燥し、水分の除去を行った熱可塑性樹脂（ａ−１）３０重量部、および熱可塑性樹脂（ａ−２）７０重量部をタンブラーにて混合した後、二軸押出機（東芝機械（株）製、ＴＥＭ−４８ＢＳ、Ｌ／Ｄ＝４６）にてシリンダー温度２５０℃で溶融混練し、熱可塑性樹脂（Ａ−１）のペレットを得た。
[Reference Example 3] Manufacture of thermoplastic resin (A-1) 30 parts by weight of thermoplastic resin (a-1) sufficiently dried and moisture-removed, and 70 parts by weight of thermoplastic resin (a-2) Were mixed with a tumbler and then melt-kneaded at a cylinder temperature of 250 ° C. with a twin-screw extruder (Toshiba Machine Co., Ltd., TEM-48BS, L / D = 46) to obtain a thermoplastic resin (A-1). Pellets were obtained.
［参考例４］熱可塑性樹脂（Ａ−２）
熱可塑性樹脂（Ａ−２）として以下のものを使用した。
ビスフェノールＡとジフェニルカーボネートから、溶融エステル交換法により製造された、ビスフェノールＡ系ポリカーボネートであり、ヒンダードフェノール系酸化防止剤としてオクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを３００ｐｐｍ、および、ホスファイト系熱安定剤としてトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトを１５０ｐｐｍ含むもの。
ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、テトラヒドロフランを溶媒として、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から下式による換算分子量較正曲線を用いて求められた重量平均分子量（Ｍｗ）は２２，８００であった。
ＭＰＣ＝０．３５９１ＭＰＳ１．０３８８
（ＭＰＣは芳香族ポリカーボネートの分子量、ＭＰＳはポリスチレンの分子量）
[Reference Example 4] Thermoplastic resin (A-2)
The following were used as the thermoplastic resin (A-2).
A bisphenol A polycarbonate produced from bisphenol A and diphenyl carbonate by a melt transesterification method, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) as a hindered phenol antioxidant ) One containing 300 ppm propionate and 150 ppm tris (2,4-di-t-butylphenyl) phosphite as a phosphite heat stabilizer.
Using gel permeation chromatography (GPC), using tetrahydrofuran as a solvent and polystyrene gel, the weight average molecular weight determined from the standard monodisperse polystyrene composition curve using the converted molecular weight calibration curve according to the following formula ( Mw) was 22,800.
M PC = 0.3591 M PS 1.0388
( MPC is the molecular weight of aromatic polycarbonate, MPS is the molecular weight of polystyrene)
［参考例５］熱可塑性樹脂Ｂラテックスの製造
ポリブタジエンゴムラテックス（日機装（株）社製、マイクロトラック粒度分析計「ｎａｎｏｔｒａｃ１５０」にて測定した体積平均粒子径＝０．２５μｍ、固形分量＝４９重量％）４３重量部に、脱イオン水９３重量部、アルケニルコハク酸カリウム（アルケニル基はＣ１３〜Ｃ１５）５．０重量部、ターシャリードデシルメルカプタン０．１重量部を加え、気相部を窒素置換した後、５５℃に昇温した。続いて、アクリロニトリル２４重量部、スチレン５６重量部、ターシャリードデシルメルカプタン０．７重量部、クメンハイドロパーオキシド０．１０重量部よりなる単量体混合液、及び脱イオン水２５重量部にナトリウムホルムアルデヒドスルホキシレート０．１５重量部、硫酸第一鉄０．００１重量部、エチレンジアミンテトラ酢酸２ナトリウム塩０．０４重量を溶解してなる水溶液を６時間にわたり添加しながら、１．５時間かけて７０℃まで昇温し、それ以降は反応槽を７０℃に制御しながら重合反応を完結させた。その後、これにフェノール系酸化防止剤エマルジョンを添加し、充分に攪拌し、さらに固形分４０重量％となるように脱イオン水にて希釈した。ラテックス中の未反応の全モノマー量はガスクロマトグラフィーによる定量分析の結果、１２０００ｐｐｍであった。また、樹脂分中のグラフト率は５３重量％であり、非グラフト成分の還元粘度（０．５ｇ／１００ｍｌ、２−ブタノン溶液中、３０℃測定）は０．２９であった。
Reference Example 5 Production of Thermoplastic Resin B Latex Polybutadiene rubber latex (manufactured by Nikkiso Co., Ltd., volume average particle size measured by Microtrac particle size analyzer “nanotrac 150” = 0.25 μm, solid content = 49 wt% ) To 43 parts by weight, 93 parts by weight of deionized water, 5.0 parts by weight of potassium alkenyl succinate (alkenyl group is C13 to C15) and 0.1 parts by weight of tarsiadedecyl mercaptan were added, and the gas phase part was substituted with nitrogen. Thereafter, the temperature was raised to 55 ° C. Subsequently, a monomer mixture consisting of 24 parts by weight of acrylonitrile, 56 parts by weight of styrene, 0.7 parts by weight of terresidic decyl mercaptan, and 0.10 parts by weight of cumene hydroperoxide, and 25 parts by weight of deionized water, sodium formaldehyde While adding 0.15 part by weight of sulfoxylate, 0.001 part by weight of ferrous sulfate and 0.04 part by weight of ethylenediaminetetraacetic acid disodium salt over 6 hours, 70 hours over 70 hours. The temperature was raised to 0 ° C., and thereafter the polymerization reaction was completed while controlling the reaction vessel at 70 ° C. Thereafter, a phenolic antioxidant emulsion was added thereto, stirred sufficiently, and further diluted with deionized water so as to have a solid content of 40% by weight. The total amount of unreacted monomers in the latex was 12000 ppm as a result of quantitative analysis by gas chromatography. The graft ratio in the resin component was 53% by weight, and the reduced viscosity of the non-grafted component (0.5 g / 100 ml, measured in 2-butanone solution at 30 ° C.) was 0.29.
［参考例６］導電性熱可塑性樹脂ペレット（Ｉ−１）の製造
下記導電性連続繊維束を５５℃に制御された熱可塑性樹脂（Ｂ）のラテックス槽中を通過させて含浸処理を行った後、乾燥機を通過させて水分を完全に除去した。この時、導電性連続繊維束に対する熱可塑性樹脂付着量は、重量測定の結果４２重量％であった。熱可塑性樹脂（Ａ−１）ペレットを単軸押出し機中にて溶融混練した後、押出し機先端に取り付けたクロスヘッドダイから押出しながら、前記の含浸処理を施した連続炭素繊維束をクロスヘッドダイ中に連続的に供給することで、熱可塑性樹脂（Ａ−１）にて連続炭素繊維束を被覆してストランドとし、冷却後にこれを回転刃からなるカッターにて切断し、５ｍｍのペレットを得た。
また、上記ストランドを５ｃｍ程度の長さに切断したものを１０本採取し、これらを２−ブタノンにて溶解して、熱可塑性樹脂（Ａ−１）、及び熱可塑性樹脂（Ｂ）を除去後、導電性連続繊維を取り出した。これを乾燥して重量を測定し、ストランド中における導電性連続繊維の含有量を求めた結果、１４．１重量％であった。
Reference Example 6 Production of Conductive Thermoplastic Resin Pellet (I-1) The following conductive continuous fiber bundle was passed through a latex tank of thermoplastic resin (B) controlled at 55 ° C. and impregnated. Thereafter, the water was completely removed by passing through a dryer. At this time, the amount of the thermoplastic resin attached to the conductive continuous fiber bundle was 42% by weight as a result of weight measurement. After melt-kneading the thermoplastic resin (A-1) pellets in a single screw extruder, the continuous carbon fiber bundle subjected to the impregnation treatment is extruded from the crosshead die attached to the tip of the extruder, and the crosshead die is used. By supplying continuously, a continuous carbon fiber bundle is coated with the thermoplastic resin (A-1) to form a strand, and after cooling, this is cut with a cutter comprising a rotary blade to obtain a 5 mm pellet. It was.
Further, after 10 strands of the above strands cut to a length of about 5 cm are collected and dissolved in 2-butanone, the thermoplastic resin (A-1) and the thermoplastic resin (B) are removed. The conductive continuous fiber was taken out. This was dried and weighed, and the content of the conductive continuous fiber in the strand was determined. As a result, it was 14.1% by weight.
［導電性連続繊維束］
三菱レイヨン（株）製「パイロフィルＣＦトウ ＴＲ３０Ｓ−１２Ｌ」
ＰＡＮ系炭素繊維、モノフィラメント径＝７μｍ、フィラメント数＝１２０００本
目付＝８００ｍｇ／ｍ、密度＝１．７９ｇ／ｃｍ３
引張強度＝４４１０ＭＰａ、引張弾性率＝２３５ＧＰａ
サイズ剤：エポキシ系樹脂、サイズ剤付着量＝０．８ｗｔ％
[Conductive continuous fiber bundle]
"Pyrofil CF tow TR30S-12L" manufactured by Mitsubishi Rayon Co., Ltd.
PAN-based carbon fiber, monofilament diameter = 7 μm, number of filaments = 12000, basis weight = 800 mg / m, density = 1.79 g / cm 3
Tensile strength = 4410 MPa, tensile modulus = 235 GPa
Sizing agent: Epoxy resin, sizing agent adhesion amount = 0.8 wt%
［参考例７］導電性熱可塑性樹脂ペレット（Ｉ−２）の製造
参考例６と同様にして、導電性熱可塑性樹脂ペレット（Ｉ−２）を製造した。ストランド中における導電性連続繊維の含有量を求めた結果、１９．８重量％であった。
［参考例８］導電性熱可塑性樹脂ペレット（Ｉ−３）の製造
参考例６と同様にして、導電性熱可塑性樹脂ペレット（Ｉ−２）を製造した。ストランド中における導電性連続繊維の含有量を求めた結果、３０．４重量％であった。
［参考例９］導電性熱可塑性樹脂ペレット（Ｉ−４）の製造
熱可塑性樹脂（Ａ−１）を熱可塑性樹脂（Ａ−２）とした以外は参考例６と同様にして、導電性熱可塑性樹脂ペレット（Ｉ−４）を製造した。ストランド中における導電性連続繊維の含有量を求めた結果、１４．２重量％であった。
[Reference Example 7] Production of Conductive Thermoplastic Resin Pellet (I-2) Conductive thermoplastic resin pellet (I-2) was produced in the same manner as in Reference Example 6. It was 19.8 weight% as a result of calculating | requiring content of the electroconductive continuous fiber in a strand.
Reference Example 8 Production of Conductive Thermoplastic Resin Pellet (I-3) Conductive thermoplastic resin pellet (I-2) was produced in the same manner as Reference Example 6. It was 30.4 weight% as a result of calculating | requiring content of the electroconductive continuous fiber in a strand.
Reference Example 9 Production of Conductive Thermoplastic Resin Pellet (I-4) Conductive heat was obtained in the same manner as Reference Example 6 except that the thermoplastic resin (A-1) was changed to the thermoplastic resin (A-2). A plastic resin pellet (I-4) was produced. It was 14.2 weight% as a result of calculating | requiring content of the electroconductive continuous fiber in a strand.
［参考例１０］導電性熱可塑性樹脂ペレット（ＩＩ−１）の製造
参考例６で用いたものと同様の導電性連続繊維束を５５℃に制御された熱可塑性樹脂（Ｂ）のラテックス槽中を通過させて含浸処理を行った後、乾燥機を通過させて水分を完全に除去した後、これを回転刃からなるカッターにて切断し、５ｍｍのペレットを得た。ストランド中における導電性連続繊維の含有量を求めた結果、６９．６重量％であった。
［参考例１１］導電性熱可塑性樹脂ペレット（ＩＩ−２）の製造
参考例１０と同様にして導電性熱可塑性樹脂ペレット（ＩＩ−２）を得た。ストランド中における導電性連続繊維の含有量を求めた結果、５５．２重量％であった。
［参考例１２］導電性熱可塑性樹脂ペレット（ＩＩ−３）
熱可塑性樹脂Ｂのラテックスを脱イオン水を加えて固形分量を２０ｗｔ％としたものを使用した以外は参考例１０と同様にして導電性熱可塑性樹脂ペレット（ＩＩ−３）を得た。ストランド中における導電性連続繊維の含有量を求めた結果、９７．１重量％であった。
Reference Example 10 Production of Conductive Thermoplastic Resin Pellet (II-1) In a latex tank of a thermoplastic resin (B) controlled at 55 ° C., the same conductive continuous fiber bundle as used in Reference Example 6 Then, after impregnation treatment was performed by passing through a dryer, moisture was completely removed by passing through a drier, and then this was cut with a cutter comprising a rotary blade to obtain 5 mm pellets. As a result of obtaining the content of the conductive continuous fiber in the strand, it was 69.6% by weight.
Reference Example 11 Production of Conductive Thermoplastic Resin Pellet (II-2) Conductive thermoplastic resin pellet (II-2) was obtained in the same manner as Reference Example 10. As a result of obtaining the content of the conductive continuous fiber in the strand, it was 55.2% by weight.
[Reference Example 12] Conductive thermoplastic resin pellet (II-3)
Conductive thermoplastic resin pellets (II-3) were obtained in the same manner as in Reference Example 10 except that the latex of thermoplastic resin B was used after adding deionized water to a solid content of 20 wt%. As a result of obtaining the content of the conductive continuous fiber in the strand, it was 97.1% by weight.
［実施例１］
８０℃にて３時間乾燥させた導電性熱可塑性樹脂ペレット（Ｉ−１）８０重部、および導電性熱可塑性樹脂ペレット（ＩＩ−１）２０重量部を、タンブラーにて３０分ブレンドした。これを射出成形機（東芝機械（株）製 ＩＳ１３０ＦＢ）のホッパーに投入し、下記成形条件にて直径２０ｍｍ、厚み１ｍｍの円盤を射出成形した。
［成形条件］
スクリュー径：４５ｍｍ
シリンダー温度：２６０℃
金型温度：６０℃
背圧：１００ｋｇｆ／ｃｍ３
射出速度：３０％
スクリュー回転数：１００ｒｐｍ
射出時間：１０秒
冷却時間：１０秒
ゲート形状：ピンゲート（φ＝２ｍｍ）
ゲート位置：円盤中心部
[Example 1]
80 parts by weight of conductive thermoplastic resin pellets (I-1) dried at 80 ° C. for 3 hours and 20 parts by weight of conductive thermoplastic resin pellets (II-1) were blended in a tumbler for 30 minutes. This was put into a hopper of an injection molding machine (IS130FB manufactured by Toshiba Machine Co., Ltd.), and a disk having a diameter of 20 mm and a thickness of 1 mm was injection molded under the following molding conditions.
[Molding condition]
Screw diameter: 45mm
Cylinder temperature: 260 ° C
Mold temperature: 60 ℃
Back pressure: 100 kgf / cm 3
Injection speed: 30%
Screw rotation speed: 100rpm
Injection time: 10 seconds Cooling time: 10 seconds Gate shape: Pin gate (φ = 2mm)
Gate position: disk center
この円盤の中心部に塩化銀を直径７ｍｍの円形に塗布して図１のように回路を繋ぎ、円盤の円周端から３ｍｍの部位に低抵抗率計（三菱化学（株）製、ロレスターＥＰ ＭＣＰ−Ｔ３６０）に接続したプローブ（ピン先０．２６Ｒ）を接触させ、抵抗値を測定した。さらに円盤を約３°回転させて同様に測定を行い、これを５００回繰り返した。表面抵抗率の平均は１２２Ω／□であり、標準偏差σは９０であった。また、ＩＳＯ１７９に準じて測定した該樹脂組成物の２３℃におけるノッチ付きシャルピー衝撃強さは５．１ｋＪ／
ｍ２、ＩＳＯ１７８に準じて測定した曲げ弾性率は１３３００ＭＰａであった。
また、この円盤を４７５℃にて電気炉にて加熱処理を施し、熱可塑性樹脂成分を燃焼させて炭素繊維を取り出し、これにクロロホルムを加えて炭素繊維を液中に充分分散させた後、スポイドにてスライドグラス上に数滴落とし、クロロホルムを乾燥させた。その後、これを１０〜１５倍の倍率で光学顕微鏡にて写真を撮影し、５００本以上の炭素繊維から各繊維長を求めたところ、成形品中の含有量が、１．５ｍｍを超える長さの炭素繊維は４．５ｗｔ％、０．５〜１．５ｍｍの長さの炭素繊維は９．２ｗｔ％、０．５ｍｍ未満の長さの炭素繊維は１１．５ｗｔ％であった。
A silver chloride is applied to the center of this disk in a circular shape with a diameter of 7 mm, and the circuit is connected as shown in FIG. 1. A low resistivity meter (Made by Mitsubishi Chemical Co., Ltd., Lorester EP) is placed 3 mm from the circumference of the disk. A probe (pin tip 0.26R) connected to MCP-T360) was brought into contact, and the resistance value was measured. Further, the disk was rotated about 3 °, and the same measurement was performed, and this was repeated 500 times. The average surface resistivity was 122 Ω / □, and the standard deviation σ was 90. Further, the Charpy impact strength with notch at 23 ° C. of the resin composition measured according to ISO 179 was 5.1 kJ /
The flexural modulus measured according to m 2 and ISO 178 was 13300 MPa.
In addition, the disk is heated in an electric furnace at 475 ° C., the thermoplastic resin component is burned to remove the carbon fiber, and chloroform is added thereto to sufficiently disperse the carbon fiber in the liquid. Drop several drops on the slide glass to dry the chloroform. Then, when this was photographed with an optical microscope at a magnification of 10 to 15 times and each fiber length was determined from 500 or more carbon fibers, the length in the molded product exceeded 1.5 mm. The carbon fiber was 4.5 wt%, the carbon fiber having a length of 0.5 to 1.5 mm was 9.2 wt%, and the carbon fiber having a length of less than 0.5 mm was 11.5 wt%.
［比較例１］
表１の割合で導電性熱可塑性樹脂ペレット（Ｉ−３）、導電性熱可塑性樹脂ペレット（ＩＩ−１）、および熱可塑性樹脂ペレット（Ａ−１）を混合する以外は実施例１と同様に成形、評価を行った。表面抵抗率の平均は４０５Ω／□であり、標準偏差σは１５０であった。また、ＩＳＯ１７９に準じて測定した該樹脂組成物の２３℃におけるノッチ付きシャルピー衝撃強さは５．０ｋＪ／ｍ２、ＩＳＯ１７８に準じて測定した曲げ弾性率は１３２００ＭＰａであった。
また、成形品中の炭素繊維の含有量は、１．５ｍｍを超える長さの炭素繊維は４．７ｗｔ％、０．５〜１．５ｍｍの長さの炭素繊維は１０．３ｗｔ％、０．５ｍｍ未満の長さの炭素繊維は１０．０ｗｔ％であった。
［実施例２〜５、および比較例２〜５］
導電性熱可塑性樹脂ペレット（Ｉ）、導電性熱可塑性樹脂ペレット（ＩＩ）、および熱可塑性樹脂ペレット（Ａ）を表１の割合で混合する以外は実施例１と同様に成形、評価を行った。評価結果を表１に示す。
[Comparative Example 1]
Except mixing conductive thermoplastic resin pellets (I-3), conductive thermoplastic resin pellets (II-1), and thermoplastic resin pellets (A-1) in the proportions shown in Table 1, the same as in Example 1. Molding and evaluation were performed. The average surface resistivity was 405Ω / □, and the standard deviation σ was 150. Further, the Charpy impact strength with notch at 23 ° C. of the resin composition measured according to ISO 179 was 5.0 kJ / m 2 , and the flexural modulus measured according to ISO 178 was 13200 MPa.
The carbon fiber content in the molded product is 4.7 wt% for carbon fibers having a length of more than 1.5 mm, 10.3 wt% for carbon fibers having a length of 0.5 to 1.5 mm, and 0.0. The carbon fiber having a length of less than 5 mm was 10.0 wt%.
[Examples 2 to 5 and Comparative Examples 2 to 5]
Molding and evaluation were performed in the same manner as in Example 1 except that the conductive thermoplastic resin pellet (I), the conductive thermoplastic resin pellet (II), and the thermoplastic resin pellet (A) were mixed at the ratio shown in Table 1. . The evaluation results are shown in Table 1.
実施例１〜５は、特定処理方法を用いて、導電性繊維の含有量が特定の範囲にある導電性熱可塑性樹脂ペレット（Ｉ）、および導電性熱可塑性樹脂ペレット（ＩＩ）を併用することにより、表面抵抗率が低く、且つ標準偏差σの値が小さい、すなわち表面抵抗率のばらつきが小さく信頼性の高い成形品を得ることが出来る。
比較例１は、導電性熱可塑性樹脂ペレット（Ｉ）中の導電性繊維含有量が範囲外であるため、ペレット割れに起因する導電性繊維の毛羽立ちが発生し、成形品中の導電性繊維の分散性に劣ったものとなる。その結果、実施例１と同等の導電性繊維含有量、および繊維長分布を持っているにも拘わらず、表面抵抗率が高く、また標準偏差σが大きい信頼性の劣ったものとなっている。
Examples 1-5 use together the conductive thermoplastic resin pellet (I) and conductive thermoplastic resin pellet (II) in which the content of conductive fibers is in a specific range, using a specific treatment method. Thus, a molded product having a low surface resistivity and a small standard deviation σ, that is, a small variation in surface resistivity and high reliability can be obtained.
In Comparative Example 1, since the conductive fiber content in the conductive thermoplastic resin pellet (I) is out of the range, fluffing of the conductive fiber due to pellet cracking occurs, and the conductive fiber in the molded product Dispersibility is inferior. As a result, in spite of having the same conductive fiber content and fiber length distribution as in Example 1, the surface resistivity is high and the standard deviation σ is large and the reliability is poor. .
比較例２は導電性熱可塑性樹脂ペレット（ＩＩ）単独であり導電性熱可塑性樹脂ペレット（Ｉ）を含有せず、成形品中の導電性繊維の分散性に劣るため、表面抵抗率が高く、また標準偏差σが大きい信頼性に劣ったものとなっている。
比較例３は導電性熱可塑性樹脂ペレット（ＩＩ）の導電性繊維含有量が範囲外であり、ペレット割れに起因する導電性繊維の毛羽立ちが発生し、成形品中の導電性繊維の分散性に劣ったものとなる。その結果、実施例１と同等の導電性繊維含有量、および繊維長分布を持っているにも拘わらず、表面抵抗率が高く、また標準偏差σが大きい信頼性に劣ったものとなっている。
Comparative Example 2 is a conductive thermoplastic resin pellet (II) alone and does not contain the conductive thermoplastic resin pellet (I), and is inferior in the dispersibility of the conductive fibers in the molded product, so the surface resistivity is high, Further, the standard deviation σ is large and the reliability is poor.
In Comparative Example 3, the conductive fiber content of the conductive thermoplastic resin pellet (II) is out of the range, the conductive fibers are fluffed due to pellet cracking, and the dispersibility of the conductive fibers in the molded product is increased. It will be inferior. As a result, despite having the same conductive fiber content and fiber length distribution as in Example 1, the surface resistivity is high and the standard deviation σ is large and the reliability is poor. .
比較例４は、導電性熱可塑性樹脂ペレット（Ｉ）中における導電性繊維の含有量が範囲外であり、また導電性熱可塑性樹脂ペレット（ＩＩ）を配合していないため、成形品中における導電性繊維の含有量が多いにも拘わらず表面抵抗率の標準偏差σが大きい信頼性の劣ったものとなっている。
比較例５は、成形品中の導電性繊維の含有量が範囲外であるため、表面抵抗率が高く、また標準偏差σが大きい信頼性に劣ったものとなっている。
In Comparative Example 4, the content of the conductive fiber in the conductive thermoplastic resin pellet (I) is out of the range, and the conductive thermoplastic resin pellet (II) is not blended. The surface resistivity has a large standard deviation σ in spite of a large content of the conductive fiber and is inferior in reliability.
In Comparative Example 5, since the content of the conductive fiber in the molded product is out of the range, the surface resistivity is high and the standard deviation σ is large and the reliability is poor.
本発明により、高い導電性を発現し、成形品の測定部位による導電性のばらつきの少ない信頼性の高い成形品を得ることができる。 According to the present invention, it is possible to obtain a highly reliable molded product that exhibits high conductivity and has little variation in conductivity depending on the measurement site of the molded product.
Claims (6)
［Ｉ］熱可塑性樹脂（Ａ）にて導電性連続繊維束を押出被覆した後、所定の長さに切断して得られたペレットであって、導電性繊維の含有量が５〜２５重量％である熱可塑性樹脂ペレット。
［ＩＩ］熱可塑性樹脂（Ｂ）にて導電性連続繊維束を含浸被覆した後、所定の長さに切断して得られたペレットであって、導電性繊維の含有量が５０〜９５重量％である熱可塑性樹脂ペレット。 The mixture for molding a conductive thermoplastic resin composition, wherein the content of the conductive fibers in the total mixture is 20 to 40% by weight, and the following [I] and [II] are the main constituent components .
[I] A pellet obtained by extrusion-coating a conductive continuous fiber bundle with the thermoplastic resin (A) and then cutting into a predetermined length, and the content of the conductive fiber is 5 to 25% by weight. Is a thermoplastic resin pellet.
[II] A pellet obtained by impregnating and coating a conductive continuous fiber bundle with a thermoplastic resin (B) and then cutting into a predetermined length, and the conductive fiber content is 50 to 95% by weight. Is a thermoplastic resin pellet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006344019A JP5224686B2 (en) | 2006-12-21 | 2006-12-21 | Mixture for molding conductive thermoplastic resin composition and molded article formed by molding the mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006344019A JP5224686B2 (en) | 2006-12-21 | 2006-12-21 | Mixture for molding conductive thermoplastic resin composition and molded article formed by molding the mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008156401A true JP2008156401A (en) | 2008-07-10 |
| JP5224686B2 JP5224686B2 (en) | 2013-07-03 |
Family
ID=39657696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006344019A Active JP5224686B2 (en) | 2006-12-21 | 2006-12-21 | Mixture for molding conductive thermoplastic resin composition and molded article formed by molding the mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5224686B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013216786A (en) * | 2012-04-09 | 2013-10-24 | Riken Technos Corp | Resin composition |
| JP2015203060A (en) * | 2014-04-14 | 2015-11-16 | 三菱レイヨン株式会社 | Carbon filament-containing resin material and method for producing the same |
| JPWO2013151022A1 (en) * | 2012-04-04 | 2015-12-17 | 信越ポリマー株式会社 | Substrate storage container |
| KR101811994B1 (en) * | 2016-04-28 | 2017-12-27 | 재단법인 한국탄소융합기술원 | Metal-plated glass fiber reinforced thermoplastic pellet for emi shielding and manufacturing method thereby |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297459A (en) * | 1987-05-29 | 1988-12-05 | Furukawa Electric Co Ltd:The | Electrically conductive polymer blend |
| JPH02199175A (en) * | 1989-01-27 | 1990-08-07 | Nippon G Ii Plast Kk | Conductive molding resin material |
| JPH05177630A (en) * | 1991-12-27 | 1993-07-20 | Ube Nitto Kasei Co Ltd | Pellet of long-fiber reinforced thermoplastic resin and preparation of the same |
| JPH10195311A (en) * | 1996-11-14 | 1998-07-28 | Kawasaki Steel Corp | Thermoplastic resin molding, material for molding and production of molding |
| JP2003062829A (en) * | 2001-08-30 | 2003-03-05 | Asahi Kasei Corp | Method for producing pellet containing carbon fiber, pellet containing carbon fiber, and resin composition for molding |
| JP2005225126A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Method for producing molding of conductive thermoplastic resin |
| JP2006181776A (en) * | 2004-12-27 | 2006-07-13 | Toray Ind Inc | Molding fiber-reinforced flame-retardant resin mixture and molded product |
-
2006
- 2006-12-21 JP JP2006344019A patent/JP5224686B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297459A (en) * | 1987-05-29 | 1988-12-05 | Furukawa Electric Co Ltd:The | Electrically conductive polymer blend |
| JPH02199175A (en) * | 1989-01-27 | 1990-08-07 | Nippon G Ii Plast Kk | Conductive molding resin material |
| JPH05177630A (en) * | 1991-12-27 | 1993-07-20 | Ube Nitto Kasei Co Ltd | Pellet of long-fiber reinforced thermoplastic resin and preparation of the same |
| JPH10195311A (en) * | 1996-11-14 | 1998-07-28 | Kawasaki Steel Corp | Thermoplastic resin molding, material for molding and production of molding |
| JP2003062829A (en) * | 2001-08-30 | 2003-03-05 | Asahi Kasei Corp | Method for producing pellet containing carbon fiber, pellet containing carbon fiber, and resin composition for molding |
| JP2005225126A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Method for producing molding of conductive thermoplastic resin |
| JP2006181776A (en) * | 2004-12-27 | 2006-07-13 | Toray Ind Inc | Molding fiber-reinforced flame-retardant resin mixture and molded product |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2013151022A1 (en) * | 2012-04-04 | 2015-12-17 | 信越ポリマー株式会社 | Substrate storage container |
| US10242896B2 (en) | 2012-04-04 | 2019-03-26 | Shin-Etsu Polymer Co., Ltd. | Substrate storage container |
| JP2013216786A (en) * | 2012-04-09 | 2013-10-24 | Riken Technos Corp | Resin composition |
| US9660271B2 (en) | 2012-04-09 | 2017-05-23 | Riken Technos Corporation | Resin composition |
| JP2015203060A (en) * | 2014-04-14 | 2015-11-16 | 三菱レイヨン株式会社 | Carbon filament-containing resin material and method for producing the same |
| KR101811994B1 (en) * | 2016-04-28 | 2017-12-27 | 재단법인 한국탄소융합기술원 | Metal-plated glass fiber reinforced thermoplastic pellet for emi shielding and manufacturing method thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5224686B2 (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2176335B1 (en) | Electro-conductive thermoplastic resin compositions and articles manufactured therefrom | |
| EP1367097B1 (en) | Carbon fiber reinforced resin composition, molding material and molded article therefrom | |
| US7026388B2 (en) | Conductive resin composition and process for producing the same | |
| JP2002088259A (en) | Molding material, its manufacturing method and its molded article | |
| JP4588155B2 (en) | Aromatic polycarbonate resin composition | |
| JP5224686B2 (en) | Mixture for molding conductive thermoplastic resin composition and molded article formed by molding the mixture | |
| EP0337487A1 (en) | Electroconductive polymer composition | |
| Ryu et al. | Improvements of the electrical conductivity and EMI shielding efficiency for the polycarbonate/ABS/carbon fiber composites prepared by pultrusion process | |
| JP2002231051A (en) | Conductive resin component, and molding product using the same | |
| JP3550255B2 (en) | Flame retardant resin composition and lithium ion battery case molded therefrom | |
| JP2001081318A (en) | Flame-retardant polyamide resin composition and its molded article | |
| CN102424720A (en) | Conduction-enhanced PC (Polycarbonate)/PBT (Polybutylece Terephthalate) composite material and preparation method thereof | |
| KR100700742B1 (en) | A composition of polycarbonate/styrenic copolymers with improved compatibility prepared by mixing carbon nanotube | |
| JP2001131426A (en) | Electrically conductive resin composition and its molded article | |
| JP2002317384A (en) | Electrically conductive fiber bundle for filament pellet, filament pellet made thereof, and formed article produced by using the same | |
| JP3960096B2 (en) | Conductive resin composition and method for producing the same | |
| JP2003012945A (en) | Conductive resin composition and its manufacturing method | |
| JP3634496B2 (en) | Conductive resin composition and molded article | |
| JP2002020606A (en) | Thermoplastic resin pellet composition and molded article obtained by injection molding | |
| JP2005225126A (en) | Method for producing molding of conductive thermoplastic resin | |
| JP2001129826A (en) | Conductive fiber-reinforced molding material and manufacturing method therefor | |
| JP2002146679A (en) | Carbon fiber bundle, resin composition, forming material and formed product using the same | |
| JP2002338794A (en) | Electrically conductive resin composition and molding material or molded part prepared from the composition | |
| JP2002256153A (en) | Electroconductive molded product and its manufacturing method | |
| JP2000198915A (en) | Flame retardant resin composition having good metal plating characteristics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091210 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110414 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121016 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121114 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121218 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121226 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130312 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130312 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5224686 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160322 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |