JP2007277313A - Electroconductive resin composition - Google Patents
Electroconductive resin composition Download PDFInfo
- Publication number
- JP2007277313A JP2007277313A JP2006102490A JP2006102490A JP2007277313A JP 2007277313 A JP2007277313 A JP 2007277313A JP 2006102490 A JP2006102490 A JP 2006102490A JP 2006102490 A JP2006102490 A JP 2006102490A JP 2007277313 A JP2007277313 A JP 2007277313A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- mass
- resin composition
- conductive resin
- metal salt
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 41
- 239000004917 carbon fiber Substances 0.000 claims abstract description 41
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- 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 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims description 45
- 229920001955 polyphenylene ether Polymers 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 17
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011231 conductive filler Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 abstract description 22
- 238000000465 moulding Methods 0.000 abstract description 17
- 238000002156 mixing Methods 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract description 3
- -1 alkyl sulfonic acid Chemical compound 0.000 description 39
- 238000012360 testing method Methods 0.000 description 34
- 230000000704 physical effect Effects 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000004793 Polystyrene Substances 0.000 description 21
- 229920002223 polystyrene Polymers 0.000 description 21
- 239000004417 polycarbonate Substances 0.000 description 15
- 238000004898 kneading Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920005669 high impact polystyrene Polymers 0.000 description 13
- 239000004797 high-impact polystyrene Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000010998 test method 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
- 230000004580 weight loss Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- GBZVNKQWXLVYNG-UHFFFAOYSA-N (3-phosphonooxyphenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC(OP(O)(O)=O)=C1 GBZVNKQWXLVYNG-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000021189 garnishes Nutrition 0.000 description 1
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- 210000003127 knee Anatomy 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、炭素繊維やグラファイト、カーボンブラック等の炭素系導電性フィラーを配合した導電性樹脂組成物において、従来の導電性樹脂組成物に比べて、著しく導電性に優れ、また、耐熱性と流動性のバランス、耐衝撃性、引張伸度にも優れ、難燃化も容易で、さらに成形条件に左右されずに安定した導電性能を示す導電性樹脂組成物に関する。 The present invention is a conductive resin composition containing a carbon-based conductive filler such as carbon fiber, graphite, carbon black, etc., which is remarkably superior in electrical conductivity compared to conventional conductive resin compositions, and has heat resistance. The present invention relates to a conductive resin composition that is excellent in fluidity balance, impact resistance, and tensile elongation, is easily flame retardant, and exhibits stable conductive performance regardless of molding conditions.
近年、家電分野や事務機、情報機器分野において、パソコン、携帯電話、プリンターなどの電気・電子部品の構成部材には、導電性を有することに加えて、高耐熱性、高強度、また多くの場合、難燃性を有することが求められている。熱可塑性樹脂に導電性を付与する方法として、従来、炭素繊維やカーボンブラック、グラファイト等の炭素系フィラーを必要とされる導電レベルに応じて配合することが知られている。
しかし、熱可塑性樹脂にグラファイトやカーボンブラックを配合して十分な導電性を得るためには、多量に配合する必要があり、そのため機械強度や流動性、耐衝撃性等を著しく悪化させるため、好ましくなかった。一方、炭素繊維を使用した場合は、繊維を樹脂中に良好に分散させることによって、導電経路が形成されて良好な導電性が付与される反面、やはり十分な導電性を付与するためには、それなりの配合量が必要であり、そのため樹脂組成物の流動性や表面外観を悪化させ、難燃化の困難を招く等、必ずしも十分ではなかった。
In recent years, in the fields of home appliances, office machines, and information equipment, in addition to being conductive, the components of electrical and electronic parts such as personal computers, mobile phones, and printers have high heat resistance, high strength, and many In some cases, it is required to have flame retardancy. As a method for imparting conductivity to a thermoplastic resin, conventionally, it is known that a carbon-based filler such as carbon fiber, carbon black, or graphite is blended according to a required conductivity level.
However, in order to obtain sufficient conductivity by adding graphite or carbon black to the thermoplastic resin, it is necessary to add a large amount, and therefore, mechanical strength, fluidity, impact resistance, etc. are remarkably deteriorated. There wasn't. On the other hand, when carbon fiber is used, by dispersing the fiber in the resin well, a conductive path is formed and good conductivity is provided, but in order to give sufficient conductivity, Appropriate blending amount is necessary, and therefore, the fluidity and surface appearance of the resin composition are deteriorated, and it is not always sufficient, for example, causing difficulty in flame retardancy.
ところで、熱可塑性樹脂に有機スルホン酸金属塩を配合した樹脂組成物はすでに公知である。たとえば、ポリフェニレンエーテル系樹脂にアルキルスルホン酸金属塩を添加して、ポリフェニレンエーテル系樹脂の溶融体挙動を改善する技術が開示されている（例えば、特許文献１参照）。一般に熱可塑性樹脂にこのようなアルキルスルホン酸金属塩を添加することにより帯電防止性能が付与されることは既に広く知られている。しかしこのような樹脂成形品は水洗することによって成形品表面にブリードしたアルキルスルホン酸金属塩が洗い流され、帯電防止性能がたやすく消失してしまうため、長期帯電防止性能の持続の点で十分ではなかったといえる。 By the way, the resin composition which mix | blended the organic sulfonic acid metal salt with the thermoplastic resin is already well-known. For example, a technique for improving the melt behavior of a polyphenylene ether resin by adding an alkylsulfonic acid metal salt to the polyphenylene ether resin has been disclosed (for example, see Patent Document 1). In general, it is widely known that antistatic performance is imparted by adding such a metal salt of an alkyl sulfonic acid to a thermoplastic resin. However, such resin molded products are washed away with water and the alkyl sulfonic acid metal salt bleed on the surface of the molded product is washed away, and the antistatic performance is easily lost. It can be said that there was not.
芳香族ポリカーボネート樹脂に、無機質充填剤と有機スルホン酸金属塩を配合したポリカーボネート樹脂組成物に関する技術が開示されている（例えば、特許文献２参照）。この技術は、無機質充填剤を配合した芳香族ポリカーボネート系樹脂に、難燃剤としての有機スルホン酸金属塩を微量添加して、ブロム系やリン系の難燃剤を配合することなく難燃性を付与するための技術である。
カーボンブラック等の炭素生成物の表面を有機スルホン酸金属塩で予め表面改質したものを樹脂に配合したポリマー生成物に関する技術も開示されている（例えば、特許文献３参照）。しかしこの技術は、炭素生成物を配合したポリマー生成物の衝撃強さや引張強度を改善するための技術である。
A technique related to a polycarbonate resin composition in which an inorganic filler and an organic sulfonic acid metal salt are blended with an aromatic polycarbonate resin is disclosed (for example, see Patent Document 2). This technology adds a small amount of organic sulfonic acid metal salt as a flame retardant to an aromatic polycarbonate resin blended with an inorganic filler to give flame retardancy without blending a bromine or phosphorus flame retardant. It is a technique to do.
A technique relating to a polymer product in which a surface of a carbon product such as carbon black is previously surface-modified with an organic sulfonic acid metal salt is blended with a resin is also disclosed (for example, see Patent Document 3). However, this technique is a technique for improving the impact strength and tensile strength of a polymer product containing a carbon product.
有機ポリマーマトリックスと、カーボンフィブリル、カーボンブラック、炭素繊維などの導電性充填材からなる樹脂組成物に、導電性向上剤としてステアリン酸金属塩などの有機イオン種を比較的少量添加する技術もまた開示されている（例えば、特許文献４）。しかし、本願に示されるような物性バランスに優れ、なおかつ著しく導電性が改良された樹脂組成物に関しては、先の特許文献には十分な開示がなされておらず、またこれらの文献を元にして本願発明を想到することは極めて困難であるといえる。
本発明は、熱可塑性樹脂に配合する導電性フィラーの配合量を極力少なくして、なおかつ著しく良好な導電性能を付与すると同時に、成形品表面外観、耐熱性と成形流動性のバランス、耐衝撃性、引張伸度に優れ、安定した導電性能を示し、難燃化も容易な導電性樹脂組成物を提供することを目的とする。 The present invention reduces the blending amount of the conductive filler blended in the thermoplastic resin as much as possible, and gives remarkably good conductive performance, and at the same time, the molded product surface appearance, the balance between heat resistance and molding fluidity, and impact resistance. An object of the present invention is to provide a conductive resin composition that is excellent in tensile elongation, exhibits stable conductive performance, and is easily flame retardant.
本発明者は、環境に悪影響を及ぼさず、極力少なめの導電性フィラーの配合で熱可塑性樹脂に、従来にない良好で安定的な導電性能を発現させることを目的として鋭意検討した結果、導電助剤としてアルキルスルホン酸金属塩を用いることによって、驚くべきことに、従来の炭素系導電性フィラーのみを配合した導電性樹脂組成物に比べて導電性能が劇的に改良され、更に成形品を水洗してもアルキルスルホン酸金属塩の溶出による導電性能の低下が見られず逆に向上する傾向が見られること、成形条件等の変化による導電性能の変化のバラツキが極めて少ないこと、耐熱性と流動性のバランスが改良されること、剛性を低下させずに耐衝撃性や引張伸度等の靭性が改良されることを見出して、更に、配合する炭素系導電性フィラーとしてグラファイト単独又は、炭素繊維とグラファイトを特定の比率で併用して用いることによって、良好な導電性能、物性バランスを保持し、かつ成形体の表面外観に優れて、難燃化も容易な導電性樹脂組成物を作成することが可能であることを見出した。 The present inventor has conducted intensive studies for the purpose of causing thermoplastic resins to exhibit unprecedented good and stable conductive performance by adding as little conductive filler as possible without adversely affecting the environment. Surprisingly, the use of the alkylsulfonic acid metal salt as the agent dramatically improved the conductive performance compared to the conventional conductive resin composition containing only the carbon-based conductive filler, and the molded product was washed with water. However, there is no tendency to improve the conductive performance due to the elution of metal alkyl sulfonate, and there is a tendency to improve, the variation in the conductive performance due to changes in molding conditions etc. is extremely small, heat resistance and flow As a carbon-based conductive filler to be blended, the balance of properties is improved, and the toughness such as impact resistance and tensile elongation is improved without lowering the rigidity. By using phyto alone or in combination with carbon fiber and graphite at a specific ratio, the conductive resin maintains good conductive performance and physical property balance, has excellent surface appearance of the molded body, and is easily flame retardant. It has been found that a composition can be made.
即ち、本発明は、
１．熱可塑性樹脂（Ａ）１００質量部に対して、グラファイト（Ｂ１）５〜１００質量部、アルキルスルホン酸金属塩（Ｃ）０．５〜１５質量部、を含有してなる導電性樹脂組成物、
２．熱可塑性樹脂（Ａ）１００質量部に対して、グラファイト（Ｂ１）５〜９５質量％と炭素繊維（Ｂ２）９５〜５質量％からなる炭素系導電性フィラー（Ｂ）５〜１００質量部、アルキルスルホン酸金属塩（Ｃ）０．５〜１５質量部、を含有してなる導電性樹脂組成物、
３．前記１または２のいずれかにおいて、前記（Ｃ）成分が、アルキル芳香族スルホン酸金属塩である、導電性樹脂組成物、
４．前記３において、前記（Ｃ）成分のアルキル部分が、Ｃ７〜Ｃ１６成分である、導電性樹脂組成物、
５．前記３または４のいずれかにおいて、前記（Ｃ）成分の芳香族部分がベンゼン環である、導電性樹脂組成物、
That is, the present invention
1. A conductive resin composition comprising 5 to 100 parts by mass of graphite (B1) and 0.5 to 15 parts by mass of an alkylsulfonic acid metal salt (C) with respect to 100 parts by mass of the thermoplastic resin (A),
2. 5 to 100 parts by mass of carbon-based conductive filler (B) composed of 5 to 95% by mass of graphite (B1) and 95 to 5% by mass of carbon fiber (B2) with respect to 100 parts by mass of the thermoplastic resin (A), alkyl A conductive resin composition comprising 0.5 to 15 parts by mass of a sulfonic acid metal salt (C),
3. In either 1 or 2, the conductive resin composition, wherein the component (C) is an alkyl aromatic sulfonic acid metal salt,
4). In 3, the conductive resin composition, wherein the alkyl part of the component (C) is a C7 to C16 component,
5). In any one of 3 and 4, a conductive resin composition in which the aromatic moiety of the component (C) is a benzene ring,
６．前記３〜５のいずれかにおいて、前記（Ｃ）成分の主成分が、ドデシルベンゼンスルホン酸金属塩である、導電性樹脂組成物、
７．前記１〜６のいずれかにおいて、前記（Ｃ）成分の金属塩が、ナトリウム塩またはリチウム塩である、導電性樹脂組成物、
８．前記１〜７のいずれかにおいて、前記（Ａ）成分が、ポリフェニレンエーテル系樹脂である、導電性樹脂組成物、
９．前記１〜８のいずれかにおいて、前記（Ａ）、（Ｂ）、（Ｃ）成分の合計１００質量部に、更に、芳香族リン酸エステル系難燃剤（Ｄ）５〜４０質量部を含有してなる、導電性樹脂組成物、
１０．前記１〜８のいずれかにおいて、前記（Ａ）、（Ｂ）、（Ｃ）成分の合計１００質量部に、更に、フォスファゼン系難燃剤（Ｅ）５〜４０質量部を含有してなる、導電性樹脂組成物。
１１．前記１〜１０のいずれかに記載の導電性樹脂組成物によって得られた、成形体。
を提供するものである。
6). In any one of 3 to 5, a conductive resin composition, wherein the main component of the component (C) is a metal salt of dodecylbenzenesulfonic acid,
7). In any one of said 1-6, the conductive resin composition whose metal salt of said (C) component is a sodium salt or lithium salt,
8). In any one of 1 to 7, the conductive resin composition, wherein the component (A) is a polyphenylene ether-based resin,
9. In any one of the above 1 to 8, the total of 100 parts by mass of the components (A), (B), and (C) further contains 5 to 40 parts by mass of an aromatic phosphate ester flame retardant (D). A conductive resin composition,
10. Any one of 1 to 8 above, wherein the total of 100 parts by mass of the components (A), (B), and (C) further contains 5 to 40 parts by mass of a phosphazene flame retardant (E). Resin composition.
11. The molded object obtained by the conductive resin composition in any one of said 1-10.
Is to provide.
本発明によって、従来の導電性樹脂組成物に比べて、著しく導電性に優れ、また、耐熱性と流動性のバランス、耐衝撃性、引張伸度にも優れ、難燃化も容易で、さらに成形条件等に左右されずに安定した導電性能を示す導電性樹脂組成物が得られた。また、本発明によって得られた樹脂組成物は、成形加工性や成形品の表面外観にも優れ、家電ＯＡ機器、事務機、情報機器分野、自動車分野等に有効に使用することができる。 According to the present invention, compared with the conventional conductive resin composition, the conductivity is remarkably excellent, the balance between heat resistance and fluidity, impact resistance, tensile elongation is excellent, flame resistance is easy, A conductive resin composition showing stable conductive performance regardless of molding conditions and the like was obtained. In addition, the resin composition obtained by the present invention is excellent in molding processability and surface appearance of a molded product, and can be effectively used in home appliance OA equipment, office machines, information equipment fields, automobile fields, and the like.
本発明を更に詳細に説明する。
本発明の（Ａ）成分の熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン、あるいはポリスチレン、スチレン−アクリロニトリル共重合体、スチレン−アクリロニトリル−ブタジエン三元共重合体等の汎用樹脂、ポリアセタール、ポリカーボネート、ポリフェニレンエーテル樹脂、あるいは飽和ポリエステル等の汎用性のエンジニアリングプラスチック、ポリサルフォン、ポリエーテルサルフォン、ポリフェニレンサルファイド、ポリエーテルイミド、ポリエーテルエーテルケトンあるいはポリアリレート等の特殊エンジニアリングプラスチックが挙げられる。本発明においては、これら熱可塑性樹脂の中でも、導電性改良の度合いや成形加工性、十分な難燃性付与の観点から、ポリフェニレンエーテル系樹脂、ポリカーボネート、飽和ポリエステル樹脂が好適に用いられ、更にはポリフェニレンエーテル系樹脂が特に好適に用いられる。
The present invention will be described in further detail.
As the thermoplastic resin of the component (A) of the present invention, polyolefins such as polyethylene and polypropylene, general-purpose resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene terpolymer, polyacetal, polycarbonate, General engineering plastics such as polyphenylene ether resin or saturated polyester, and special engineering plastics such as polysulfone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyetheretherketone, and polyarylate. In the present invention, among these thermoplastic resins, polyphenylene ether-based resins, polycarbonates, saturated polyester resins are preferably used from the viewpoint of improving conductivity, molding processability, and sufficient flame resistance. Polyphenylene ether resins are particularly preferably used.
本発明のポリフェニレンエーテル系樹脂とは、ポリフェニレンエーテル樹脂単独、または必要に応じて、ポリフェニレンエーテル樹脂にスチレン系樹脂および／またはポリオレフィン系樹脂を配合した樹脂のことを示す。
本発明で使用されるポリフェニレンエーテル樹脂とは、次に示す一般式（１）を繰り返し単位とし、構成単位が一般式（１）の〔ａ〕または〔ｂ〕からなる単独重合体、あるいは共重合体が使用できる。
The polyphenylene ether resin of the present invention refers to a resin obtained by blending a polyphenylene ether resin alone or, if necessary, a polyphenylene ether resin with a styrene resin and / or a polyolefin resin.
The polyphenylene ether resin used in the present invention is a homopolymer having a repeating unit represented by the following general formula (1) and a structural unit consisting of [a] or [b] of the general formula (1), or a copolymer Combined can be used.
（式中、Ｒ1 ，Ｒ2 ，Ｒ3 ，Ｒ4 ，Ｒ5 ，Ｒ6 は炭素１〜４のアルキル基、アリール基、ハロゲン、水素等の一価の残基であり、Ｒ5 ，Ｒ6 は同時に水素ではない） (In the formula, R1, R2, R3, R4, R5 and R6 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen and hydrogen, and R5 and R6 are not hydrogen at the same time.)
ポリフェニレンエーテルの単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等のホモポリマーが挙げられ、その中でもポリ（２，６−ジメチル−１，４−フェニレン）エーテルが好ましい。 Representative examples of polyphenylene ether homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-) 1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenyle) ) Include homopolymers such as ether, poly (2,6-dimethyl-1,4-phenylene) ether is preferred among them.
ポリフェニレンエーテル共重合体としては、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体、２，６−ジメチルフェノールとｏ−クレゾールとの共重合体あるいは２，３，６−トリメチルフェノールとｏ−クレゾールとの共重合体等、ポリフェニレンエーテル構造を主体としてなるポリフェニレンエーテル共重合体を包含する。
また、本発明のポリフェニレンエーテルには、本発明の主旨に反しない限り、他の種々のフェニレンエーテルユニットを部分構造として含んでいても構わない。これらフェニレンエーテルユニットとしては、例えば、特開平０１−２９７４２８号公報及び特開昭６３−３０１２２２号公報に記載されている、２−（ジアルキルアミノメチル）−６−メチルフェニレンエーテルユニットや、２−（Ｎ−アルキル−Ｎ−フェニルアミノメチル）−６−メチルフェニレンエーテルユニット等が挙げられる。
また、ポリフェニレンエーテルの主鎖中にジフェノキノン等が少量結合したものも含まれる。
Examples of the polyphenylene ether copolymer include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,3,6. -Polyphenylene ether copolymers mainly composed of a polyphenylene ether structure, such as a copolymer of trimethylphenol and o-cresol, are included.
In addition, the polyphenylene ether of the present invention may contain other various phenylene ether units as a partial structure as long as it does not contradict the gist of the present invention. Examples of these phenylene ether units include 2- (dialkylaminomethyl) -6-methylphenylene ether units described in JP-A-01-297428 and JP-A-63-301222, and 2- ( N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit and the like.
Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of polyphenylene ether.
更に例えば、その一部または全部を不飽和カルボン酸或いはその官能的誘導体で変性した官能化ポリフェニレンエーテルで置き換えることも可能である。この場合、変性は不飽和カルボン酸やその官能的誘導体の中の１種により行われても良いし、２種以上の組み合わせによって行われても良い。
本発明に用いられるポリフェニレンエーテルの固有粘度（クロロホルム溶媒で３０℃にて測定）は０．３〜０．９の範囲が好ましく、より好ましくは０．４〜０．６の範囲にあることである。十分な物性付与の観点から０．３以上が好ましく、成形加工性の観点から０．９以下が好ましい。
Furthermore, for example, it is also possible to replace part or all of it with a functionalized polyphenylene ether modified with an unsaturated carboxylic acid or a functional derivative thereof. In this case, the modification may be performed with one of unsaturated carboxylic acids or functional derivatives thereof, or may be performed with a combination of two or more.
The intrinsic viscosity (measured with a chloroform solvent at 30 ° C.) of the polyphenylene ether used in the present invention is preferably in the range of 0.3 to 0.9, more preferably in the range of 0.4 to 0.6. . 0.3 or more is preferable from the viewpoint of imparting sufficient physical properties, and 0.9 or less is preferable from the viewpoint of molding processability.
本発明で使用されるスチレン系樹脂とは、スチレン系化合物、スチレン系化合物と共重合可能な化合物をゴム質重合体存在または非存在下に重合して得られる重合体である。
スチレン系化合物とは、一般式〔２〕で表される化合物を意味する。
The styrene resin used in the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.
The styrene compound means a compound represented by the general formula [2].
（式中、Ｒは水素、低級アルキルまたはハロゲンを示し、Ｚはビニル、水素、ハロゲン及び低級アルキルよりなる群から選択され、ｐは０〜５の整数である。） (In the formula, R represents hydrogen, lower alkyl, or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen, and lower alkyl, and p is an integer of 0-5.)
これらの具体例としては、スチレン、α−メチルスチレン、２，４−ジメチルスチレン、モノクロロスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、エチルスチレン等が挙げられる。また、スチレン系化合物と共重合可能な化合物としては、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル化合物類；無水マレイン酸等の酸無水物等が挙げられ、スチレン系化合物と共に使用される。また、ゴム質重合体としては共役ジエン系ゴムおよび共役ジエンと芳香族ビニル化合物のコポリマーまたはこれらの水添物あるいはエチレン−プロピレン共重合体系ゴム等が挙げられる。本発明のために特に好適なポリスチレン系樹脂はポリスチレンおよびゴム強化ポリスチレンである。 Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, or ethylene-propylene copolymer rubbers. Particularly preferred polystyrene resins for the present invention are polystyrene and rubber reinforced polystyrene.
本発明で使用されるポリオレフィン系樹脂とは、オレフィン化合物の少なくとも１種の重合体である。その具体例としては、エチレン、プロピレン、ブテン−１、ペンテン−１、ヘキセン−１、ヘプテン−１、オクテン−１等の直鎖状α−オレフィンや２−メチルプロペン−１、３−メチルペンテン−１、４−メチルペンテン−１、５−メチルヘキセン−１、４−メチルヘキセン−１、４，４−ジメチルペンテン−１等の分岐状α−オレフィン等の単独重合体または共重合体が挙げられる。これらの中で特に好適なのは、エチレン、プロピレン、ブテン−１、オクテン−１、４−メチルペンテン−１を過半重量含む共重合体または単独重合体である。 The polyolefin resin used in the present invention is at least one polymer of an olefin compound. Specific examples thereof include linear α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 2-methylpropene-1, 3-methylpentene- Examples include homopolymers or copolymers such as branched α-olefins such as 1,4-methylpentene-1,5-methylhexene-1,4-methylhexene-1,4,4-dimethylpentene-1. . Particularly preferred among these are copolymers or homopolymers containing a majority of ethylene, propylene, butene-1, octene-1, 4-methylpentene-1.
本発明で使用されるポリカーボネートは、４，４−ジヒドロキシジフェニル−２，２−プロパンをはじめとする４，４−ジオキシジアリルアルカン系ポリカーボネートである。本発明のために特に好適なのは４，４−ジヒドロキシジフェニル−２，２−プロパンのポリカーボネートである。
本発明で使用される飽和ポリエステル樹脂は、公知の熱可塑性ポリエステルである。その具体例として、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。
The polycarbonate used in the present invention is 4,4-dioxydiallylalkane-based polycarbonate including 4,4-dihydroxydiphenyl-2,2-propane. Particularly suitable for the present invention is polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane.
The saturated polyester resin used in the present invention is a known thermoplastic polyester. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.
本発明の（Ｂ）成分である、炭素系導電性フィラー成分は、グラファイト（Ｂ１）単独又は、特定比率のグラファイト（Ｂ１）と炭素繊維（Ｂ２）との組み合わせからなる。具体的にはグラファイト（Ｂ１）１００〜５質量％と炭素繊維０〜９５質量％の範囲より、グラファイト（Ｂ１）と炭素繊維（Ｂ２）との合計量が１００質量％となるような比率で選ばれる。本発明（Ｂ）成分である、炭素系導電性フィラー成分は、グラファイトを単独で用いても良いが、グラファイトと炭素繊維とをこのような特定の比率で併用した場合、導電性能が改良されるので、好ましい。 The carbon-based conductive filler component that is the component (B) of the present invention is composed of graphite (B1) alone or a combination of graphite (B1) and carbon fiber (B2) at a specific ratio. Specifically, the ratio is selected such that the total amount of graphite (B1) and carbon fiber (B2) is 100% by mass from the range of 100 to 5% by mass of graphite (B1) and 0 to 95% by mass of carbon fiber. It is. The carbon-based conductive filler component that is the component (B) of the present invention may use graphite alone, but when graphite and carbon fiber are used in combination at such a specific ratio, the conductive performance is improved. Therefore, it is preferable.
しかし、炭素繊維（Ｂ２）の比率が９５質量％を上回り、グラファイト（Ｂ１）の比率が５質量％を下回る場合は、導電性能は良好である反面、引張伸度の低下や成形品表面外観の悪化が顕著になり、また難燃化も困難になる。本発明を達成するためにより好ましい比率は、グラファイト（Ｂ１）９５〜５質量％と炭素繊維（Ｂ２）５〜９５質量％の組み合わせの範囲から選ばれ、更に好ましくはグラファイト（Ｂ１）９０〜１０質量％と炭素繊維（Ｂ２）１０〜９０質量％の組み合わせの範囲から選ばれ、特に好ましくはグラファイト（Ｂ１）７０〜３０質量％と炭素繊維（Ｂ２）３０〜７０質量％の組み合わせの範囲から選ばれる。 However, when the ratio of carbon fiber (B2) exceeds 95% by mass and the ratio of graphite (B1) is less than 5% by mass, the conductive performance is good, but the tensile elongation is reduced and the surface appearance of the molded product is low. Deterioration becomes noticeable and flame retardancy becomes difficult. A more preferable ratio for achieving the present invention is selected from a combination range of 95 to 5 mass% of graphite (B1) and 5 to 95 mass% of carbon fiber (B2), and more preferably 90 to 10 mass of graphite (B1). % And a combination of 10 to 90% by mass of carbon fiber (B2), particularly preferably selected from a range of a combination of 70 to 30% by mass of graphite (B1) and 30 to 70% by mass of carbon fiber (B2). .
本願（Ｂ）成分を構成するグラファイト（Ｂ１）は、人造品および天然品から、目的に応じて適宜選択することができる。本願で使用されるグラファイト粉末の形状は、鱗片状、塊状、球状等いずれでもよいが、より良好な導電性発現の観点から、鱗片状の天然グラファイトが最も好ましい。本願で使用されるグラファイト粉末の平均粒子径は、１〜１０００μｍの範囲が好ましい。より好ましくは５〜５００μｍ、更に好ましくは１０〜３００μｍの範囲より選ばれる。十分な導電性発現の観点から１μｍ以上が好ましく、取り扱い性と成形品表面外観の保持の観点から１０００μｍ以下が好ましい。 The graphite (B1) constituting the component (B) of the present application can be appropriately selected from artificial products and natural products according to the purpose. The shape of the graphite powder used in the present application may be any of scaly, massive, spherical, etc., but scaly natural graphite is most preferable from the viewpoint of better conductivity. The average particle diameter of the graphite powder used in the present application is preferably in the range of 1 to 1000 μm. More preferably, it is selected from the range of 5 to 500 μm, more preferably 10 to 300 μm. 1 μm or more is preferable from the viewpoint of sufficient conductivity, and 1000 μm or less is preferable from the viewpoint of handling and maintaining the appearance of the molded product surface.
本願（Ｂ）成分を構成する炭素繊維（Ｂ２）は、公知のものの中から目的に応じて適宜選択することができ、例えば、ＰＡＮ系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維、気相成長炭素繊維等から選ばれる。また、原糸をウレタン系あるいはエポキシ系等の収束剤で１０ｋ〜２０ｋの本数の範囲で収束した、カット長３〜６ｍｍ程度のチョップドストランドが取り扱い性の面から好適に用いられる。繊維径は０．５〜１５μｍの範囲が好ましく、特に好ましくは５〜１０μｍの範囲である。また、本願の導電性樹脂組成物（成形体中）の炭素繊維の繊維長は５０〜５００μｍの範囲が好ましく、より好ましくは２００〜４００μｍの範囲である。十分な導電性能発現の観点から５０μｍ以上が好ましく、成形品の表面外観保持と成形加工性等の観点から５００μｍ以下が好ましい。
本願の導電性樹脂組成物には、更なる導電性付与を目的としてニッケル等の金属で被覆した炭素繊維を配合することもできる。
The carbon fiber (B2) constituting the component (B) of the present application can be appropriately selected from known ones according to the purpose. For example, PAN-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber, gas phase Selected from grown carbon fiber. In addition, a chopped strand having a cut length of about 3 to 6 mm, in which the raw yarn is converged in a range of 10 k to 20 k with a sizing agent such as urethane or epoxy, is preferably used from the viewpoint of handleability. The fiber diameter is preferably in the range of 0.5 to 15 μm, particularly preferably in the range of 5 to 10 μm. Moreover, the fiber length of the carbon fiber of the conductive resin composition (in the molded body) of the present application is preferably in the range of 50 to 500 μm, more preferably in the range of 200 to 400 μm. The thickness is preferably 50 μm or more from the viewpoint of sufficient conductivity performance, and is preferably 500 μm or less from the viewpoint of maintaining the surface appearance of the molded product and molding processability.
Carbon fiber coated with a metal such as nickel can be added to the conductive resin composition of the present application for the purpose of imparting further conductivity.
本願（Ｃ）成分のアルキルスルホン酸金属塩は、化学式Ｒ−ＳＯ３Ｘ（Ｒ：炭素数Ｃ８〜Ｃ３４のアルキル基および／またはアリール基、Ｘ：アルカリ金属またはアルカリ土類金属）で示される化合物を示す。このようなアルキルスルホン酸金属塩の中でも、導電性改良および物性改良の観点から、アルキル芳香族スルホン酸金属塩が好ましい。
アルキル芳香族スルホン酸金属塩のアルキル部分は、樹脂との混和性の観点から、炭素数Ｃ７〜Ｃ１６の範囲の成分であることがより好ましく、最も好ましいのはドデシル基である。芳香族部分は、樹脂との混和性および導電性、物性改良の観点からベンゼン環であることがより好ましい。
本願のアルキルスルホン酸金属塩の金属塩部分は、具体的には、ナトリウム塩、リチウム塩、カリウム塩、ルビジウム塩、セシウム塩、ベリリウム塩、マグネシウム塩、カルシウム塩、ストロンチウム塩、バリウム塩が挙げられる。これらの中で、導電性発現の観点から特に好ましいのは、ナトリウム塩およびリチウム塩である。
The alkylsulfonic acid metal salt of the component (C) of the present application is a compound represented by the chemical formula R—SO 3 X (R: an alkyl group and / or aryl group having C8 to C34 carbon atoms, X: an alkali metal or an alkaline earth metal). Indicates. Among such alkyl sulfonic acid metal salts, alkyl aromatic sulfonic acid metal salts are preferable from the viewpoint of improving conductivity and improving physical properties.
The alkyl part of the alkyl aromatic sulfonic acid metal salt is more preferably a component having a carbon number of C7 to C16, and most preferably a dodecyl group, from the viewpoint of miscibility with the resin. The aromatic moiety is more preferably a benzene ring from the viewpoint of miscibility with the resin, electrical conductivity, and improvement of physical properties.
Specific examples of the metal salt portion of the alkylsulfonic acid metal salt of the present application include sodium salt, lithium salt, potassium salt, rubidium salt, cesium salt, beryllium salt, magnesium salt, calcium salt, strontium salt, and barium salt. . Among these, sodium salts and lithium salts are particularly preferable from the viewpoint of conductivity.
本願に用いるアルキルスルホン酸金属塩の形状は特に限定されるものではないが、取り扱い性の観点から、平均粒子径が２〜１０ｍｍのペレット形状のものが好ましい。尚、ここでいう平均粒子径とは、ペレット５０個を無作為に抽出して、その最長径と最短径を測定し、各々のペレットの最長径と最短径の和を２で割った値を合計した数値を５０で割って求めた値のことを示す。平均粒子径が２ｍｍ以下の粉体または顆粒状のものは、大気中の水分等で吸湿しやすく、生産条件によっては、二軸押出機等を利用した大量生産時に、吸湿したアルキルスルホン酸金属塩成分が、配合原料間に塊を生じさせたり、原料ホッパーから押出機の原料入り口までの搬送ライン間で原料のツマリによる搬送不良を引き起こす場合もある。本願において特に好ましいアルキルスルホン酸金属塩の平均粒子径は３〜７ｍｍの範囲である。 Although the shape of the alkylsulfonic acid metal salt used in the present application is not particularly limited, a pellet having an average particle diameter of 2 to 10 mm is preferable from the viewpoint of handleability. The average particle diameter here is a value obtained by randomly extracting 50 pellets, measuring the longest diameter and the shortest diameter, and dividing the sum of the longest diameter and the shortest diameter of each pellet by 2. Indicates the value obtained by dividing the total numerical value by 50. Powders or granules with an average particle size of 2 mm or less are easily absorbed by moisture in the atmosphere. Depending on the production conditions, the alkylsulfonic acid metal salt that has absorbed moisture during mass production using a twin screw extruder or the like. Ingredients may cause agglomeration between blended raw materials or cause poor conveyance due to raw material rounding between the conveying lines from the raw material hopper to the raw material inlet of the extruder. The average particle diameter of the alkylsulfonic acid metal salt particularly preferred in the present application is in the range of 3 to 7 mm.
本発明（Ｄ）成分の芳香族リン酸エステル系難燃剤は、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジキシレニルフェニルホスフェート、ヒドロキシノンビスフェノールホスフェート、レゾルシノールビスホスフェート、ビスフェノールＡビスフォスフェート等のトリフェニル置換タイプの芳香族リン酸エステル類が特に好適に用いられ、トリフェニルホスフェートとビスフェノールＡビスホスフェート がより好適に用いられる。これらは単独でも二種以上組み合わせて用いてもよい。
本発明（Ｅ）成分のフォスファゼン系難燃剤は、一般式〔３〕
The aromatic phosphate ester flame retardant of the component (D) of the present invention is, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, Triphenyl-substituted aromatic phosphates such as hydroxynon bisphenol phosphate, resorcinol bisphosphate, and bisphenol A bisphosphate are particularly preferably used, and triphenyl phosphate and bisphenol A bisphosphate are more preferably used. These may be used alone or in combination of two or more.
The phosphazene flame retardant of the component (E) of the present invention has the general formula [3]
〔式中、ＸはＰｈ（フェニル基）、又はＯＰｈ（フェニルオキシ基）を示す〕で表される構成単位を含有するものであれば特に制限されず、例えば、環状フォスファゼン化合物、鎖状フォスファゼン化合物、架橋基で架橋した架橋フォスファゼン化合物等が挙げられる。 [In the formula, X represents Ph (phenyl group) or OPh (phenyloxy group)]. The structural unit is not particularly limited, and examples thereof include cyclic phosphazene compounds and chain phosphazene compounds. And a crosslinked phosphazene compound crosslinked with a crosslinking group.
本発明においては、より良好な難燃性付与の観点から環状フォスファゼン化合物が好ましく、より好ましくは環状フェノキシフォスファゼン化合物である。また、本発明においては成型加工性、難燃性の観点から、三量体が７０質量％以上、特に好ましくは８５質量％以上を含有する環状フェノキシフォスファゼン化合物であることが望ましい。 In the present invention, a cyclic phosphazene compound is preferable from the viewpoint of imparting better flame retardancy, and a cyclic phenoxyphosphazene compound is more preferable. In the present invention, from the viewpoint of moldability and flame retardancy, it is desirable that the trimer is a cyclic phenoxyphosphazene compound containing 70% by mass or more, particularly preferably 85% by mass or more.
本発明の（Ｂ）成分である、グラファイト（Ｂ１）単独、又はグラファイト（Ｂ１）と炭素繊維（Ｂ２）とからなる炭素系導電性フィラー成分の配合量は、（Ａ）成分である熱可塑性樹脂１００質量部に対して、５〜１００質量部の範囲から選ばれる。好ましくは１０〜８０質量部の範囲であり、更に好ましくは２０〜６０質量部の範囲である。導電性付与の観点から５質量部以上、成形品の表面外観、成型加工性の観点から１００質量部以下の範囲となる。 The blending amount of the carbon-based conductive filler component consisting of graphite (B1) alone or graphite (B1) and carbon fiber (B2), which is the component (B) of the present invention, is the thermoplastic resin which is the component (A). It is selected from the range of 5 to 100 parts by mass with respect to 100 parts by mass. Preferably it is the range of 10-80 mass parts, More preferably, it is the range of 20-60 mass parts. It is 5 parts by mass or more from the viewpoint of imparting conductivity, and 100 parts by mass or less from the viewpoint of the surface appearance of the molded product and molding processability.
本発明（Ｃ）成分である、アルキルスルホン酸金属塩の配合量は、（Ａ）成分である熱可塑性樹脂１００質量部に対して、０．５〜１５質量部の範囲より選ばれる。好ましくは１〜１０質量部の範囲であり、更に好ましくは２〜６質量部の範囲である。導電性改良および物性改良の観点から０．５質量部以上、成形品の剥離や表面外観の悪化、機械物性低下等の観点から１５質量部以下の範囲となる。 The compounding quantity of the alkylsulfonic acid metal salt which is this invention (C) component is chosen from the range of 0.5-15 mass parts with respect to 100 mass parts of thermoplastic resins which are (A) components. Preferably it is the range of 1-10 mass parts, More preferably, it is the range of 2-6 mass parts. The range is 0.5 parts by mass or more from the viewpoint of improving conductivity and improving physical properties, and 15 parts by mass or less from the viewpoints of peeling of a molded product, deterioration of surface appearance, deterioration of mechanical properties, and the like.
本発明（Ｄ）成分である、芳香族リン酸エステル系難燃剤の配合量は、本願（Ａ）、（Ｂ）、（Ｃ）成分の合計量１００質量部に対して、５〜４０質量部の範囲が好ましい。より好ましくは１０〜３０質量部の範囲であり、更に好ましくは１５〜２５質量部の範囲である。十分な難燃性付与の観点から５質量部以上の配合が望ましく、耐熱性低下の観点から４０質量部以下の配合が望ましい。 The blending amount of the aromatic phosphate ester flame retardant which is the component (D) of the present invention is 5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C) of the present application. The range of is preferable. More preferably, it is the range of 10-30 mass parts, More preferably, it is the range of 15-25 mass parts. 5 mass parts or more of mixing | blending is desirable from a viewpoint of sufficient flame retardance provision, and 40 mass parts or less is desirable from a viewpoint of heat resistant fall.
本発明（Ｅ）成分である、フォスファゼン系難燃剤の配合量は、本願（Ａ）、（Ｂ）、（Ｃ）成分の合計量１００質量部に対して、５〜４０質量部の範囲が好ましい。より好ましくは１０〜３５質量部の範囲であり、更に好ましくは１５〜２５質量部の範囲である。十分な難燃性付与の観点から５質量部以上の配合が望ましく、耐熱性低下の観点から４０質量部以下の配合が望ましい。 The blending amount of the phosphazene-based flame retardant, which is the component (E) of the present invention, is preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), and (C). . More preferably, it is the range of 10-35 mass parts, More preferably, it is the range of 15-25 mass parts. 5 mass parts or more of mixing | blending is desirable from a viewpoint of sufficient flame retardance provision, and 40 mass parts or less is desirable from a viewpoint of heat resistant fall.
本発明の導電性樹脂組成物において、更なる耐衝撃性の付与が必要とされる場合には、熱可塑性エラストマーを配合することができる。
本発明に使用される熱可塑性エラストマーとしては、スチレン系熱可塑性エラストマー、オレフィン系熱可塑性エラストマー、ウレタン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ポリブタジエン系熱可塑性エラストマー、弗素系熱可塑性エラストマー等が挙げられる。これらの中でスチレン系熱可塑性エラストマーが本発明では特に好適に用いられる。スチレン系熱可塑性エラストマーとは、ポリスチレンブロックとゴム中間ブロックとを有するブロック共重合体であり、ゴム中間ブロックとしてはポリブタジエン、ポリイソプレン、ポリ（エチレン・ブチレン）、ポリ（エチレン・プロピレン）、ビニル−ポリイソプレン等が挙げられる。ゴム中間ブロックはこれらの組み合わせであっても良い。配列様式はリニアタイプでもラジアルタイプでも良い。またポリスチレンブロックとゴム中間ブロックにより構成されるブロック構造は二型、三型、四型の何れであっても良い。本発明の目的のために特に好適なのはポリスチレン−ポリ（エチレン・ブチレン）−ポリスチレン構造で構成される三型のリニアタイプのブロック共重合体であるが、ゴム中間ブロック中に３０質量％を超えない範囲でブタジエン単位が含まれたものであっても良い。
In the conductive resin composition of the present invention, a thermoplastic elastomer can be blended when further impact resistance is required.
Examples of the thermoplastic elastomer used in the present invention include styrene thermoplastic elastomer, olefin thermoplastic elastomer, urethane thermoplastic elastomer, polyester thermoplastic elastomer, polybutadiene thermoplastic elastomer, and fluorine thermoplastic elastomer. It is done. Of these, styrenic thermoplastic elastomers are particularly preferably used in the present invention. Styrenic thermoplastic elastomer is a block copolymer having a polystyrene block and a rubber intermediate block. As the rubber intermediate block, polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), vinyl- Examples include polyisoprene. The rubber intermediate block may be a combination of these. The arrangement pattern may be a linear type or a radial type. Further, the block structure constituted by the polystyrene block and the rubber intermediate block may be any of two types, three types, and four types. Particularly suitable for the purposes of the present invention are three linear type block copolymers composed of a polystyrene-poly (ethylene butylene) -polystyrene structure, but not exceeding 30% by weight in the rubber intermediate block. The range may include butadiene units.
本願において、熱可塑性エラストマーの配合量は（Ａ）、（Ｂ）、（Ｃ）成分の合計量１００質量部に対して、０．１〜１０質量部の範囲が好ましい。より好ましくは１〜５質量部、である。耐衝撃性改良の観点から０．１質量部以上の配合が好ましく、剛性、耐熱性保持の観点から１０質量部以下の配合が好ましい。
更に、本発明の導電性樹脂組成物には、必要に応じてガラス繊維、ガラスフレーク、シリカ、ワラストナイト、アルミナ、タルク、マイカ、クレー類、酸化チタン、亜鉛華、酸化鉄、炭酸カルシウム、硫酸バリウム等の無機質充填剤、酸化防止剤、紫外線吸収剤、熱安定剤等の安定剤類や着色剤、離型剤等も添加することができる。
本発明の製造方法によって製造された樹脂組成物を用いて成形体を成形する場合、特に成形法に制限は無いが、射出成形、押出成形、真空成形、圧空成形など既に広く知られた成形法が好適に用いられる。
In this application, the compounding quantity of a thermoplastic elastomer has the preferable range of 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A), (B), (C) component. More preferably, it is 1-5 mass parts. From the viewpoint of improving the impact resistance, 0.1 part by mass or more is preferable, and from the viewpoint of maintaining rigidity and heat resistance, 10 parts by mass or less is preferable.
Furthermore, in the conductive resin composition of the present invention, if necessary, glass fiber, glass flake, silica, wollastonite, alumina, talc, mica, clays, titanium oxide, zinc white, iron oxide, calcium carbonate, Inorganic fillers such as barium sulfate, stabilizers such as antioxidants, ultraviolet absorbers and heat stabilizers, colorants, release agents and the like can also be added.
When molding a molded body using the resin composition produced by the production method of the present invention, the molding method is not particularly limited, but already known molding methods such as injection molding, extrusion molding, vacuum molding, and pressure molding. Are preferably used.
本発明について、実施例に基づき以下具体的に説明する。本発明がこれらの例によって何ら限定されるものではない。尚、以下の用いる部は質量部である。
実施例および比較例中の各測定値は以下の方法によって求めた。
（１）荷重たわみ温度（ＨＤＴ）
ＡＳＴＭ Ｄ−６４８に準拠し、厚み０．６４ｃｍ、荷重１８．６ｋｇ／ｃｍ２で測定した。
（２）流動性（ＭＩ）
（株）東洋精機製作所製メルトインデクサーＰ−１１１を用いて、２５０℃、１０ｋｇ荷重にてメルトインデックスを測定した。
（３）引張伸度
ＡＳＴＭのＤ−６３８に定められた形状の引張試験片（形式Ｉ）を用いて、チャック間距離１１５ｍｍ、標点間距離５０ｍｍ、引張試験速度５ｍｍ／ｍｉｎの条件で引張試験を行い、引張伸度（破壊時歪％）を測定した。
（４）ノッチ付きアイゾッド衝撃値（耐衝撃性）
ＡＳＴＭのＤ−２５６に基づき２３℃にて測定した。
（５）曲げ強度、曲げ弾性率
ＡＳＴＭのＤ−７９０による曲げ試験法に基づいて三点曲げ試験を２３゜Ｃで測定した。
The present invention will be specifically described below based on examples. The present invention is not limited to these examples. In addition, the part used below is a mass part.
Each measured value in Examples and Comparative Examples was determined by the following method.
(1) Deflection temperature under load (HDT)
Based on ASTM D-648, the thickness was measured at 0.64 cm and the load was 18.6 kg / cm 2 .
(2) Fluidity (MI)
Using a Toyo Seiki Seisakusho melt indexer P-111, the melt index was measured at 250 ° C. and a load of 10 kg.
(3) Tensile test using a tensile test piece (Type I) with the shape specified in ASTM D-638 under the conditions of a chuck distance of 115 mm, a gauge distance of 50 mm, and a tensile test speed of 5 mm / min. The tensile elongation (strain at break%) was measured.
(4) Notched Izod impact value (impact resistance)
Measurements were made at 23 ° C. based on ASTM D-256.
(5) Bending strength and flexural modulus A three-point bending test was measured at 23 ° C based on the bending test method according to ASTM D-790.
（６）成形片剥離
ＡＳＴＭに定められた形状の引張試験片（形状Ｉ）を用いて、折り曲げ試験を行い、引っ張り試験片の表層剥離の有無を目視で判定した。判定は、折り曲げ試験によって表層剥離が認められないものを○とし、認められたものを×とした。
（７）表面外観
５０ｍｍ×９０ｍｍ×２．５ｍｍ（厚み）の平板試験片の表面外観を目視で観察し、判定を行った。判定は、導電性フィラー成分の試験片表層への浮きが目立ち難く、平滑で外観良好なものを○、導電性フィラー成分の試験片表層への浮きが目立ち、明らかに外観不良と判断されるものを×とした。
（８）導電性（表面抵抗値）
５０ｍｍ×９０ｍｍ×２．５ｍｍ（厚み）の平板成形片を用いて、前記成形片の９０ｍｍ辺の両端から２０ｍｍの所に、それぞれの線が平行になるように幅１〜２ｍｍの銀線を、銀ペーストを用いて引き、１０時間放置後、２３℃で、カスタム社製電気テスターＭ−０２を用いて表面抵抗値の測定を行った。水洗後の表面抵抗値の測定は、上記で作成した試験片を超音波洗浄機で３分間洗浄したのち、ペーパータオルで水滴を拭き取り、２３℃で３時間放置した後、上記と同様な方法で測定を行った。
(6) Molding piece peeling The bending test was done using the tensile test piece (shape I) of the shape defined by ASTM, and the presence or absence of surface layer peeling of the tensile test piece was visually determined. In the judgment, a case where surface peeling was not recognized by a bending test was evaluated as ◯, and a case where the surface layer was recognized was evaluated as x.
(7) Surface appearance The surface appearance of a flat test piece of 50 mm x 90 mm x 2.5 mm (thickness) was visually observed and judged. Judgment is that the float of the conductive filler component on the surface of the test piece is not conspicuous, the smooth and good appearance is ○, the float of the conductive filler component on the surface of the test piece is conspicuous, and it is clearly judged that the appearance is poor Was marked with x.
(8) Conductivity (surface resistance value)
Using a 50 mm × 90 mm × 2.5 mm (thickness) flat plate molded piece, 20 mm from both ends of the 90 mm side of the molded piece, a silver wire having a width of 1 to 2 mm so that each line is parallel, The surface resistance value was measured using a custom electric tester M-02 at 23 ° C. after being pulled using a silver paste and left for 10 hours. After measuring the surface resistance after washing with water, the test piece prepared above was washed with an ultrasonic cleaner for 3 minutes, then wiped off with a paper towel and left at 23 ° C. for 3 hours. Went.
（９）難燃性
１．６ｍｍ厚みの試験片を用いて、ＵＬ−９４試験法に基づいて測定した。
実施例および比較例に使用した原材料を以下に示す。
原材料１ 熱可塑性樹脂（Ａ）
（Ａ−１）固有粘度（クロロホルム溶媒で３０℃にて測定）が０．４３ｄｌ／ｇの、ポリマー片末端鎖がフェノール性水酸基を有するポリ（２，６−ジメチル−１，４−フェニレン）エーテル
（Ａ−２）住友ダウ社製のポリカーボネート（商品名：カリバー３０１−１０）
（Ａ−３）帝人化成社製のＰＣ／ＡＢＳ（商品名：マルチロンＴ−３０１１）
（Ａ−４）住友ダウ社製のＰＣ／ＰＥＴ（商品名：ＳＤポリカＣＲ−３２４１）
（Ａ−５）旭化成ケミカルズ社製のハイインパクトポリスチレン（商品名：Ｈ９４０５）
（Ａ−６）旭化成ケミカルズ社製のゼネラルパーパスポリスチレン（商品名：６８５）
（Ａ−７）旭化成ケミカルズ社製のスチレン−アクリロニトリル共重合体樹脂（商品名：Ｔ９７０１、ＡＮ約９ｗｔ％）
（Ａ−８）日本ポリプロピレン社製のポリプロピレン（商品名：ＳＡ５１０）
(9) Measurement was performed based on the UL-94 test method using a flame retardant 1.6 mm thick test piece.
The raw materials used in Examples and Comparative Examples are shown below.
Raw material 1 Thermoplastic resin (A)
(A-1) Poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity (measured with a chloroform solvent at 30 ° C.) of 0.43 dl / g and having one end chain of a polymer having a phenolic hydroxyl group (A-2) Sumitomo Dow Polycarbonate (trade name: Caliber 301-10)
(A-3) Teijin Chemicals PC / ABS (trade name: Multilon T-3011)
(A-4) PC / PET manufactured by Sumitomo Dow (trade name: SD Polycarbonate CR-3241)
(A-5) High impact polystyrene (trade name: H9405) manufactured by Asahi Kasei Chemicals Corporation
(A-6) General purpose polystyrene manufactured by Asahi Kasei Chemicals (trade name: 685)
(A-7) Styrene-acrylonitrile copolymer resin manufactured by Asahi Kasei Chemicals (trade name: T9701, AN about 9 wt%)
(A-8) Polypropylene manufactured by Nippon Polypropylene (trade name: SA510)
原材料２ 炭素系導電性フィラー（Ｂ）
（Ｂ−１）日本黒鉛工業社製の平均粒子径１３０μｍの鱗片状グラファイト粉末（商品名：Ｆ♯２）
（Ｂ−２）東レ社製の炭素繊維チョップドストランド（商品名：トレカＴＳ１２−００６−Ｃ） 繊維径７μｍ
Raw material 2 Carbon-based conductive filler (B)
(B-1) Scale-like graphite powder having an average particle size of 130 μm manufactured by Nippon Graphite Industries Co., Ltd. (trade name: F # 2)
(B-2) Carbon fiber chopped strand manufactured by Toray Industries, Inc. (trade name: Trading Card TS12-006-C) Fiber diameter 7 μm
原材料３ アルキルスルホン酸金属塩（Ｃ）
（Ｃ−１）日本油脂社製のアルキルスルホン酸ナトリウム（商品名：エレガンＡ２０００ＳＰ）平均粒子径約５ｍｍ
（Ｃ−２）竹本油脂社製のドデシルベンゼンスルホン酸ナトリウム（商品名：ＡＫＳ−５１８−２Ｍ）平均粒子径約５ｍｍ
（Ｃ−３）竹本油脂社製のドデシルベンゼンスルホン酸リチウム（商品名：ＡＫＳ−５３３）液状
Raw material 3 Alkyl sulfonic acid metal salt (C)
(C-1) Sodium alkyl sulfonate (trade name: Elegan A2000SP) manufactured by NOF Corporation, average particle diameter of about 5 mm
(C-2) Sodium dodecylbenzenesulfonate (trade name: AKS-518-2M) manufactured by Takemoto Yushi Co., Ltd. Average particle size of about 5 mm
(C-3) Lithium dodecylbenzenesulfonate (trade name: AKS-533) manufactured by Takemoto Yushi Co., Ltd.
原材料４ 芳香族リン酸エステル系難燃剤（Ｄ）
（Ｄ−１）大八化学社製のビスフェノールＡビスジフェニルホスフェート（商品名：ＣＲ７４１）
原材料５ フォスファゼン系難燃剤（Ｅ）
（Ｅ−１）下記化学式〔４〕において、
Raw material 4 Aromatic phosphate ester flame retardant (D)
(D-1) Bisphenol A bisdiphenyl phosphate manufactured by Daihachi Chemical Co., Ltd. (trade name: CR741)
Raw material 5 Phosphazene flame retardant (E)
(E-1) In the following chemical formula [4],
ｎ＝３が９３．６質量％、ｎ＝４が４．０質量％、ｎ≧５が２．４質量％であるフェノキシフォスファゼン。５％減量温度；３３６℃、５０％減量温度；３９８℃、５００℃残渣量；４．７質量％、酸価；０．１７、含有水分量；１８２ｐｐｍ Phenoxyphosphazene in which n = 3 is 93.6% by mass, n = 4 is 4.0% by mass, and n ≧ 5 is 2.4% by mass. 5% weight loss temperature: 336 ° C., 50% weight loss temperature; 398 ° C., 500 ° C. Residue amount: 4.7 mass%, acid value: 0.17, water content: 182 ppm
原材料６ 熱可塑性エラストマー（Ｆ）
（Ｆ−１）旭化成ケミカルズ社製の水添スチレン系熱可塑性エラストマー（商品名：タフテックＨ１０４３）
Raw material 6 Thermoplastic elastomer (F)
(F-1) Hydrogenated styrene thermoplastic elastomer (trade name: Tuftec H1043) manufactured by Asahi Kasei Chemicals Corporation
［実施例１］
ポリフェニレンエーテル（Ａ−１）３４部、ハイインパクトポリスチレン（Ａ−５）２０部、ゼネラルパーパスポリスチレン（Ａ−６）１３部、アルキルスルホン酸金属塩（Ｃ−２）１部、フォスファゼン系難燃剤（Ｅ−１）１２部とを、ＺＳＫ２５二軸押出機（独国Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製、バレル数１０）の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部を押出機溶融混練ゾーン途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−１に示す。
[Example 1]
34 parts of polyphenylene ether (A-1), 20 parts of high impact polystyrene (A-5), 13 parts of general purpose polystyrene (A-6), 1 part of alkylsulfonic acid metal salt (C-2), phosphazene flame retardant ( E-1) 12 parts are supplied to the extruder from the drive part side supply port (top feed port) of ZSK25 twin screw extruder (manufactured by Werner & Pfleiderer, Germany, number of barrels 10), and graphite (B-1) 10 And 10 parts of carbon fiber (B-2) were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 1 shows the physical property test results of the obtained conductive resin composition.
［実施例２］
実施例１のゼネラルパーパスポリスチレン（Ａ−６）１３部の内の２部を、アルキルスルホン酸金属塩（Ｃ−２）に置き換えて、アルキルスルホン酸金属塩（Ｃ−２）の配合量を３部にした以外は、実施例１を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−１に示す。
[Example 2]
2 parts of 13 parts of general purpose polystyrene (A-6) in Example 1 were replaced with alkylsulfonic acid metal salt (C-2), and the amount of alkylsulfonic acid metal salt (C-2) was 3 Example 1 was repeated except that it was part, and a conductive resin composition was obtained. Table 1 shows the physical property test results of the obtained conductive resin composition.
［実施例３］
実施例１のゼネラルパーパスポリスチレン（Ａ−６）１３部の内の４部を、アルキルスルホン酸金属塩（Ｃ−２）に置き換えて、アルキルスルホン酸金属塩（Ｃ−２）の配合量を５部にした以外は、実施例１を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−１に示す。
[Example 3]
By replacing 4 parts of 13 parts of general purpose polystyrene (A-6) of Example 1 with metal alkyl sulfonate (C-2), the amount of metal alkyl sulfonate (C-2) is 5 Example 1 was repeated except that it was part, and a conductive resin composition was obtained. Table 1 shows the physical property test results of the obtained conductive resin composition.
［実施例４］
ポリフェニレンエーテル（Ａ−１）３４部、ハイインパクトポリスチレン（Ａ−５）１７部、ゼネラルパーパスポリスチレン（Ａ−６）８部、スチレン−アクリロニトリル共重合体樹脂（Ａ−７）７部、アルキルスルホン酸金属塩（Ｃ−２）２部、フォスファゼン系難燃剤（Ｅ−１）１２部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−１に示す。
[Example 4]
34 parts of polyphenylene ether (A-1), 17 parts of high impact polystyrene (A-5), 8 parts of general purpose polystyrene (A-6), 7 parts of styrene-acrylonitrile copolymer resin (A-7), alkylsulfonic acid 2 parts of metal salt (C-2) and 12 parts of phosphazene flame retardant (E-1) are supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1. Then, 10 parts of graphite (B-1) and 10 parts of carbon fiber (B-2) were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 1 shows the physical property test results of the obtained conductive resin composition.
［実施例５］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１６部、ゼネラルパーパスポリスチレン（Ａ−６）１０部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）１１部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）５部および炭素繊維（Ｂ−２）２５部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−２に示す。
[Example 5]
30 parts of polyphenylene ether (A-1), 16 parts of high impact polystyrene (A-5), 10 parts of general purpose polystyrene (A-6), 3 parts of metal alkyl sulfonate (C-2), phosphazene flame retardant ( E-1) 11 parts is supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 5 parts of graphite (B-1) and carbon fiber (B- 2) 25 parts were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. The physical property test results of the obtained conductive resin composition are shown in Table-2.
［実施例６］
実施例５のグラファイト（Ｂ−１）の配合量を５部から２５部に増やし、逆に炭素繊維（Ｂ−２）の配合量を２５部から５部に減らした以外は、実施例５の操作を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−２に示す。
[Example 6]
The amount of graphite (B-1) in Example 5 was increased from 5 parts to 25 parts, and conversely, the amount of carbon fiber (B-2) was reduced from 25 parts to 5 parts. The operation was repeated to obtain a conductive resin composition. The physical property test results of the obtained conductive resin composition are shown in Table-2.
［実施例７］
実施例５のグラファイト（Ｂ−１）の配合量を５部から１５部に増やし、炭素繊維（Ｂ−２）の配合量を２５部から１５部に減らした以外は、実施例５の操作を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−２に示す。
[Example 7]
The operation of Example 5 was repeated except that the amount of graphite (B-1) in Example 5 was increased from 5 parts to 15 parts and the amount of carbon fiber (B-2) was reduced from 25 parts to 15 parts. The conductive resin composition was obtained by repeating. The physical property test results of the obtained conductive resin composition are shown in Table-2.
［実施例８］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１８部、ゼネラルパーパスポリスチレン（Ａ−６）１０部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）９部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）３０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−２に示す。
[Example 8]
30 parts of polyphenylene ether (A-1), 18 parts of high impact polystyrene (A-5), 10 parts of general purpose polystyrene (A-6), 3 parts of metal alkyl sulfonate (C-2), phosphazene flame retardant ( E-1) 9 parts are supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 30 parts of graphite (B-1) are supplied to the extruder melt kneading zone. Side feed from the barrel 6 was performed and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. The physical property test results of the obtained conductive resin composition are shown in Table-2.
［実施例９］
実施例１のアルキルスルホン酸金属塩（Ｃ−２）１部を、（Ｃ−１）１部に替えた以外は実施例１の操作を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−３に示す。
[Example 9]
The operation of Example 1 was repeated except that 1 part of the alkylsulfonic acid metal salt (C-2) of Example 1 was replaced with 1 part of (C-1) to obtain a conductive resin composition. Table 3 shows the physical property test results of the obtained conductive resin composition.
［実施例１０］
実施例１のアルキルスルホン酸金属塩（Ｃ−２）１部を、（Ｃ−３）１部に替えた以外は実施例１の操作を繰り返して、導電性樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−３に示す。
[Example 10]
The operation of Example 1 was repeated except that 1 part of the alkylsulfonic acid metal salt (C-2) of Example 1 was replaced with 1 part of (C-3) to obtain a conductive resin composition. Table 3 shows the physical property test results of the obtained conductive resin composition.
［実施例１１］
ポリフェニレンエーテル（Ａ−１）４５部、ハイインパクトポリスチレン（Ａ−５）１４部、ゼネラルパーパスポリスチレン（Ａ−６）７部、アルキルスルホン酸金属塩（Ｃ−２）２部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードし、更に、芳香族リン酸エステル系難燃剤（Ｄ−１）１２部をバレル９から液添して、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−３に示す。
[Example 11]
Example 1 45 parts of polyphenylene ether (A-1), 14 parts of high impact polystyrene (A-5), 7 parts of general purpose polystyrene (A-6), 2 parts of alkylsulfonic acid metal salt (C-2) The ZSK25 twin-screw extruder is supplied to the extruder from the drive part side supply port (top feed port), and 10 parts of graphite (B-1) and 10 parts of carbon fiber (B-2) are in the middle of the extruder melt kneading zone. Then, 12 parts of an aromatic phosphate ester flame retardant (D-1) was added from the barrel 9 and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 3 shows the physical property test results of the obtained conductive resin composition.
［実施例１２］
ポリフェニレンエーテル（Ａ−１）３４部、ハイインパクトポリスチレン（Ａ−５）２０部、ゼネラルパーパスポリスチレン（Ａ−６）９部、フォスファゼン系難燃剤（Ｅ−１）１２部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部、東邦テナックス社製のニッケルコート炭素繊維（商品名：ベスファイトＭＣ−ＨＴＡ−Ｃ６−ＵＳ）３部、アルキルスルホン酸金属塩（Ｃ−２）２部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−３に示す。
[Example 12]
34 parts of polyphenylene ether (A-1), 20 parts of high impact polystyrene (A-5), 9 parts of general purpose polystyrene (A-6), 12 parts of phosphazene flame retardant (E-1) ZSK25 twin-screw extruder is supplied to the extruder from the drive side supply port (top feed port), 10 parts of graphite (B-1) and 10 parts of carbon fiber (B-2), nickel-coated carbon manufactured by Toho Tenax Co., Ltd. Cylinder temperature was obtained by side-feeding 3 parts of fiber (trade name: Besfite MC-HTA-C6-US) and 2 parts of alkylsulfonic acid metal salt (C-2) from a barrel 6 in the middle of an extruder melt kneading zone. Extrusion was performed at 300 ° C. and a screw rotation speed of 250 rpm. Table 3 shows the physical property test results of the obtained conductive resin composition.
［実施例１３］
ポリフェニレンエーテル（Ａ−１）１５部、ハイインパクトポリスチレン（Ａ−５）１７部、熱可塑性エラストマー（Ｆ−１）６部、ポリプロピレン（Ａ−８）４０部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部、アルキルスルホン酸金属塩（Ｃ−２）２部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２７０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−４に示す。
[Example 13]
15 parts of polyphenylene ether (A-1), 17 parts of high impact polystyrene (A-5), 6 parts of thermoplastic elastomer (F-1), 40 parts of polypropylene (A-8) were added to ZSK25 biaxial of Example 1. Supplied to the extruder from the drive part side supply port (top feed port) of the extruder, 10 parts of graphite (B-1) and 10 parts of carbon fiber (B-2), metal alkyl sulfonate (C-2) 2 Were fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 270 ° C. and a screw rotation speed of 250 rpm. Table 4 shows the physical property test results of the obtained conductive resin composition.
［実施例１４］
ポリカーボネート（Ａ−２）７８部を、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部、アルキルスルホン酸金属塩（Ｃ−２）２部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２８０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−４に示す。
[Example 14]
78 parts of polycarbonate (A-2) is supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 10 parts of graphite (B-1) and carbon fiber (B -2) 10 parts and 2 parts of alkylsulfonic acid metal salt (C-2) were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 280 ° C and a screw rotation speed of 250 rpm. Table 4 shows the physical property test results of the obtained conductive resin composition.
［実施例１５］
ＰＣ／ＡＢＳ（Ａ−３）７８部を、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部、アルキルスルホン酸金属塩（Ｃ−２）２部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２８０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−４に示す。
[Example 15]
78 parts of PC / ABS (A-3) is supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, 10 parts of graphite (B-1) and carbon fiber (B-2) 10 parts and 2 parts of alkylsulfonic acid metal salt (C-2) were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 280 ° C. and a screw rotational speed of 250 rpm. . Table 4 shows the physical property test results of the obtained conductive resin composition.
［実施例１６］
ＰＣ／ＰＥＴ（Ａ−４）７８部を、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部、アルキルスルホン酸金属塩（Ｃ−２）２部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２８０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−４に示す。
[Example 16]
78 parts of PC / PET (A-4) is supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, 10 parts of graphite (B-1) and carbon fiber (B-2) 10 parts and 2 parts of alkylsulfonic acid metal salt (C-2) were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 280 ° C. and a screw rotational speed of 250 rpm. . Table 4 shows the physical property test results of the obtained conductive resin composition.
［比較例１］
実施例１のアルキルスルホン酸金属塩（Ｃ−２）１部を抜き、ゼネラルパーパスポリスチレン（Ａ−６）の配合量を１４部にした以外は、実施例１の操作を繰り返して、樹脂組成物を得た。得られた樹脂組成物の物性試験結果を表−５に示す。
[Comparative Example 1]
The procedure of Example 1 was repeated except that 1 part of the alkylsulfonic acid metal salt (C-2) of Example 1 was removed and the amount of general purpose polystyrene (A-6) was 14 parts. Got. Table 5 shows the physical property test results of the obtained resin composition.
［比較例２］
比較例１のゼネラルパーパスポリスチレン（Ａ−６）１４部を４部に減らし、替わりにアルキルスルホン酸金属塩（Ｃ−２）を１０部配合した以外は、実施例１の操作を繰り返して、樹脂組成物を得た。得られた樹脂組成物の物性試験結果を表−５に示す。
[Comparative Example 2]
The procedure of Example 1 was repeated except that 14 parts of General Purpose Polystyrene (A-6) in Comparative Example 1 were reduced to 4 parts, and 10 parts of alkylsulfonic acid metal salt (C-2) was blended instead. A composition was obtained. Table 5 shows the physical property test results of the obtained resin composition.
［比較例３］
ポリフェニレンエーテル（Ａ−１）３４部、ハイインパクトポリスチレン（Ａ−５）２０部、ゼネラルパーパスポリスチレン（Ａ−６）１０部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）１３部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、炭素繊維（Ｂ−２）２０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−５に示す。
[Comparative Example 3]
34 parts of polyphenylene ether (A-1), 20 parts of high impact polystyrene (A-5), 10 parts of general purpose polystyrene (A-6), 3 parts of alkylsulfonic acid metal salt (C-2), phosphazene flame retardant ( E-1) 13 parts are supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 20 parts of carbon fiber (B-2) is melt-kneaded in the extruder. Side feed was performed from the barrel 6 in the middle of the zone, and extrusion was performed at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 5 shows the physical property test results of the obtained conductive resin composition.
［比較例４］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１６部、ゼネラルパーパスポリスチレン（Ａ−６）１０部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）１１部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、炭素繊維（Ｂ−２）３０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−５に示す。
[Comparative Example 4]
30 parts of polyphenylene ether (A-1), 16 parts of high impact polystyrene (A-5), 10 parts of general purpose polystyrene (A-6), 3 parts of metal alkyl sulfonate (C-2), phosphazene flame retardant ( E-1) 11 parts are supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 30 parts of carbon fiber (B-2) is melt-kneaded in the extruder. Side feed was performed from the barrel 6 in the middle of the zone, and extrusion was performed at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 5 shows the physical property test results of the obtained conductive resin composition.
［比較例５］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１８部、ゼネラルパーパスポリスチレン（Ａ−６）１３部、フォスファゼン系難燃剤（Ｅ−１）９部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）３０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−６に示す。
[Comparative Example 5]
30 parts of polyphenylene ether (A-1), 18 parts of high impact polystyrene (A-5), 13 parts of general purpose polystyrene (A-6), 9 parts of phosphazene flame retardant (E-1) The ZSK25 twin screw extruder is supplied to the extruder from the drive part side supply port (top feed port), and 30 parts of graphite (B-1) is side-fed from the barrel 6 in the middle of the extruder melt kneading zone to obtain the cylinder temperature. Extrusion was performed at 300 ° C. and a screw rotation speed of 250 rpm. Table 6 shows the physical property test results of the obtained conductive resin composition.
［比較例６］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１６部、ゼネラルパーパスポリスチレン（Ａ−６）１０部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）１１部、デグサエンジニアードカーボン社製のカーボンブラック（商品名：Ｎ９９０）３０部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−６に示す。
[Comparative Example 6]
30 parts of polyphenylene ether (A-1), 16 parts of high impact polystyrene (A-5), 10 parts of general purpose polystyrene (A-6), 3 parts of metal alkyl sulfonate (C-2), phosphazene flame retardant ( E-1) 11 parts and 30 parts of carbon black (trade name: N990) manufactured by Degussa Engineered Carbon Co., Ltd. from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1 And extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 6 shows the physical property test results of the obtained conductive resin composition.
［比較例７］
ポリフェニレンエーテル（Ａ−１）３０部、ハイインパクトポリスチレン（Ａ−５）１６部、ゼネラルパーパスポリスチレン（Ａ−６）１３部、アルキルスルホン酸金属塩（Ｃ−２）３部、フォスファゼン系難燃剤（Ｅ−１）１１部、デグサエンジニアードカーボン社製のカーボンブラック（商品名：Ｎ９９０）２０部とを、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、炭素繊維（Ｂ−２）１０部を押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度３００℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−６に示す。
[Comparative Example 7]
30 parts of polyphenylene ether (A-1), 16 parts of high impact polystyrene (A-5), 13 parts of general purpose polystyrene (A-6), 3 parts of alkylsulfonic acid metal salt (C-2), phosphazene flame retardant ( E-1) 11 parts, 20 parts of carbon black (trade name: N990) manufactured by Degussa Engineered Carbon Co., Ltd. from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1 Then, 10 parts of carbon fiber (B-2) was side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 300 ° C. and a screw rotation speed of 250 rpm. Table 6 shows the physical property test results of the obtained conductive resin composition.
［比較例８］
実施例１０のアルキルスルホン酸金属塩を、日本油脂社製のステアリン酸カルシウム（商品名：カルシウムステアレートＳ）に置き換えた以外は、実施例１０の操作を繰り返して樹脂組成物を得た。得られた導電性樹脂組成物の物性試験結果を表−６に示す。
[Comparative Example 8]
The procedure of Example 10 was repeated to obtain a resin composition, except that the alkylsulfonic acid metal salt of Example 10 was replaced with calcium stearate (trade name: calcium stearate S) manufactured by NOF Corporation. Table 6 shows the physical property test results of the obtained conductive resin composition.
［比較例９］
ポリカーボネート（Ａ−２）８０部を、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２８０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−７に示す。
[Comparative Example 9]
80 parts of polycarbonate (A-2) is supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, and 10 parts of graphite (B-1) and carbon fiber (B -2) 10 parts were side-fed from the barrel 6 in the middle of the extruder melt kneading zone and extruded at a cylinder temperature of 280 ° C. and a screw rotation speed of 250 rpm. Table 7 shows the physical property test results of the obtained conductive resin composition.
［比較例１０］
ＰＣ／ＡＢＳ（Ａ−３）８０部を、実施例１のＺＳＫ２５二軸押出機の駆動部側供給口（トップフィード口）から押出機に供給し、グラファイト（Ｂ−１）１０部および炭素繊維（Ｂ−２）１０部とを押出機溶融混練ゾーンの途中のバレル６からサイドフィードして、シリンダー温度２８０℃、スクリュー回転数２５０ｒｐｍで押出した。得られた導電性樹脂組成物の物性試験結果を表−７に示す。
[Comparative Example 10]
80 parts of PC / ABS (A-3) are supplied to the extruder from the drive part side supply port (top feed port) of the ZSK25 twin-screw extruder of Example 1, 10 parts of graphite (B-1) and carbon fiber (B-2) 10 parts were side-fed from the barrel 6 in the middle of the extruder melt-kneading zone and extruded at a cylinder temperature of 280 ° C. and a screw rotation speed of 250 rpm. Table 7 shows the physical property test results of the obtained conductive resin composition.
本発明によって、導電性が従来のものに比べて著しく改善され、成形条件等の変化による導電性能のバラツキも極めて少なく、成形体の表面外観や、耐熱性と流動性のバランス、剛性、耐衝撃性等に優れ、難燃化も容易な導電性樹脂組成物を提供することが可能となった。家電ＯＡ機器、事務機、情報・通信機器、電気電子部品、ゲーム機器、自動車部品等に広く用いることができる。例えば、テレビハウジング、テレビシャーシ、デフレクションヨーク等のテレビ部品、ＡＣアダプター、電源ボックス、エアコン部品、オーディオ部品、照明カバー、ＴＶゲーム機部品、モニターハウジング、モニターシャーシ、ノート型ＰＣハウジング、ノート型ＰＣバッテリー、ＭＤシャーシ類、ＤＶＤシャーシ類、車載用ＣＤチェンジャートレー、車載用ＤＶＤデッキフレーム、モーターカバー、ギアボックス、液晶プロジェクターハウジング、ＰＤＡハウジング、アンテナカバー、プリンターハウジング、プリンターシャーシ、プリンター光学箱、トナーカートリッジ、インクタンク、給紙用トレー、スキャナーハウジング、スキャナーフレーム、携帯電話ハウジング、携帯電話バッテリー等の家電ＯＡ機器や電気電子部品、ポンプハウジング、空気清浄機部品、パイプ類、遮音壁、窓枠、サッシ、信号機部品、パチンコ部品、おもちゃ類、スポーツ用品、公園遊具、釣具、機械カバー、デジタルカメラ周辺部品、フラッシュメモリーカード部品等の情報通信機器、インストルメントパネル、センタークラスター、メータークラスター、グローブボックス、デフロスターガーニッシュ、エアーダクト、ヒーターコントロール、ステアリングコラムカバー、ニーボルスター、エアーデフロスター、ドアトリム、サンシェード、ルーフライナー、リアパーセルシェルフ、ピラーカバー、ピラーインパクトアブソーバー、ボンネットエアスコープ、ラジエターグリル、ヘッドランプ部品、シグナルランプ部品、フォグランプ部品、バンパー、ヘッドランプフィニッシャー、ライセンスプレートフィニシャー、フェンダー、ドアミラー、ドアパネル、リアクオーターパネル、リアコンビネーションランプ部品、テールゲートパネル、ラゲッジルームトリム、ホイールカバー、サイドリアカバー、センターキャップ、スポイラー、リアフィニシャー、バッテリートレイ、バッテリーハウジング、フロントエンドモジュール等の自動車部品の用途等が挙げられる。 According to the present invention, the conductivity is remarkably improved compared to the conventional ones, and there is very little variation in conductive performance due to changes in molding conditions, etc., the surface appearance of the molded body, the balance between heat resistance and fluidity, rigidity, impact resistance It has become possible to provide a conductive resin composition that is excellent in properties and the like and that is easily flame-retardant. It can be widely used for home appliance OA equipment, office machines, information / communication equipment, electrical / electronic parts, game equipment, automobile parts, and the like. For example, TV parts such as TV housings, TV chassis, deflection yokes, AC adapters, power boxes, air conditioner parts, audio parts, lighting covers, TV game machine parts, monitor housings, monitor chassis, notebook PC housings, notebook PCs Battery, MD chassis, DVD chassis, in-vehicle CD changer tray, in-vehicle DVD deck frame, motor cover, gear box, LCD projector housing, PDA housing, antenna cover, printer housing, printer chassis, printer optical box, toner cartridge , Home appliances such as ink tanks, paper feed trays, scanner housings, scanner frames, mobile phone housings, mobile phone batteries, electrical and electronic parts, pumps Information communication such as uzing, air purifier parts, pipes, sound insulation walls, window frames, sashes, traffic light parts, pachinko parts, toys, sports equipment, park play equipment, fishing gear, machine covers, digital camera peripheral parts, flash memory card parts, etc. Equipment, instrument panel, center cluster, meter cluster, glove box, defroster garnish, air duct, heater control, steering column cover, knee bolster, air defroster, door trim, sunshade, roof liner, rear parcel shelf, pillar cover, pillar impact Absorber, bonnet air scope, radiator grill, headlamp parts, signal lamp parts, fog lamp parts, bumper, headlamp finisher, lyse Splate finisher, fender, door mirror, door panel, rear quarter panel, rear combination lamp parts, tailgate panel, luggage compartment trim, wheel cover, side rear cover, center cap, spoiler, rear finisher, battery tray, battery housing, front Applications of automobile parts such as end modules are listed.
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| WO2012129276A1 (en) * | 2011-03-23 | 2012-09-27 | Sabic Innovative Plastics Ip B.V. | Polycarbonate composition with improved impact strength |
| JP2013043949A (en) * | 2011-08-25 | 2013-03-04 | Asahi Kasei Chemicals Corp | Thermoplastic resin composition |
| JP2014133842A (en) * | 2013-01-11 | 2014-07-24 | Yazaki Corp | Conductive resin composition |
| WO2017068834A1 (en) * | 2015-10-20 | 2017-04-27 | ソニー株式会社 | Flame-retardant resin composition, flame-retardant resin molded article, image-display device, battery adaptor, wearable terminal, and copier |
| JP2017179343A (en) * | 2016-03-28 | 2017-10-05 | 旭化成株式会社 | Polyphenylene ether resin composition |
| WO2019181828A1 (en) | 2018-03-20 | 2019-09-26 | 大日精化工業株式会社 | Electrically conductive resin composition and method for producing same |
| CN111100617A (en) * | 2019-11-22 | 2020-05-05 | 中国石油天然气股份有限公司 | Mineralization-sensitive shunt temporary plugging agent and preparation method and application thereof |
| CN114989552A (en) * | 2022-05-20 | 2022-09-02 | 江西江铜碳纳米材料有限公司 | Alloy prepared based on coating modified carbon method and preparation method thereof |
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| JP2011241257A (en) * | 2010-05-14 | 2011-12-01 | Asahi Kasei Chemicals Corp | Resin molded product for duct |
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| KR20200130397A (en) | 2018-03-20 | 2020-11-18 | 다이니치 세이카 고교 가부시키가이샤 | Conductive resin composition and manufacturing method thereof |
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| CN111100617B (en) * | 2019-11-22 | 2021-11-30 | 中国石油天然气股份有限公司 | Mineralization-sensitive shunt temporary plugging agent and preparation method and application thereof |
| CN114989552A (en) * | 2022-05-20 | 2022-09-02 | 江西江铜碳纳米材料有限公司 | Alloy prepared based on coating modified carbon method and preparation method thereof |
| CN114989552B (en) * | 2022-05-20 | 2023-06-27 | 江西江铜碳纳米材料有限公司 | Alloy prepared based on coating modified carbon method and preparation method thereof |
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