JP6780363B2 - Conductive resin composition, molded product and method for producing the same - Google Patents
Conductive resin composition, molded product and method for producing the same Download PDFInfo
- Publication number
- JP6780363B2 JP6780363B2 JP2016160972A JP2016160972A JP6780363B2 JP 6780363 B2 JP6780363 B2 JP 6780363B2 JP 2016160972 A JP2016160972 A JP 2016160972A JP 2016160972 A JP2016160972 A JP 2016160972A JP 6780363 B2 JP6780363 B2 JP 6780363B2
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- Prior art keywords
- resin
- carbon nanotubes
- carbon
- molded product
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 137
- 239000002041 carbon nanotube Substances 0.000 claims description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 114
- 229920005989 resin Polymers 0.000 claims description 89
- 239000011347 resin Substances 0.000 claims description 89
- 150000001336 alkenes Chemical class 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 30
- 229920005672 polyolefin resin Polymers 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 27
- 239000005977 Ethylene Substances 0.000 description 27
- 238000002844 melting Methods 0.000 description 24
- 230000008018 melting Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- 238000000465 moulding Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 150000001733 carboxylic acid esters Chemical class 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229920006026 co-polymeric resin Polymers 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- -1 4-methylpentene-1 Chemical compound 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000013585 weight reducing agent Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 239000000835 fiber Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
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- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
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- 239000000523 sample Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
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- 239000000945 filler Substances 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- VJGRFWVLROCEGS-UHFFFAOYSA-N cobalt;tetrahydrate Chemical compound O.O.O.O.[Co].[Co].[Co] VJGRFWVLROCEGS-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- DTGRQRFFKHYRJG-UHFFFAOYSA-N magnesium tetrahydrate Chemical compound O.O.O.O.[Mg+2] DTGRQRFFKHYRJG-UHFFFAOYSA-N 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
- B29K2105/167—Nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
- B29K2995/0005—Conductive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Description
本発明は、成形後も高い導電性及び熱伝導性を示す導電性樹脂組成物、成形体及びその製造方法に関する。 The present invention relates to a conductive resin composition, a molded product, and a method for producing the same, which exhibit high conductivity and thermal conductivity even after molding.
ＩＣやＬＳＩを用いた電子機器部品の包装材として、熱可塑性樹脂を成形したトレイ、エンボスキャリアテープなどが知られている。トレイやエンボスキャリアテープの基材は、一般的に樹脂シート等の樹脂成形品が使用されている。樹脂成形品は、導電性が無く、表面抵抗率や体積抵抗率が高いため、帯電による電子部品の絶縁破壊やゴミの付着による電子部品の機能低下などの問題を引き起こすことがある。そのため、樹脂成形品自体にカーボンブラックのような導電性粒子を練り混むことで、帯電防止能や静電気拡散能を付与している。さらに、電子部品分野や自動車分野では金属部分の代替として、樹脂成形品が使用されつつあり、カーボンブラックでは達成できない程度の導電性が求められている。また、金属代替材料として、熱伝導性が求められることも多い。 As a packaging material for electronic device parts using ICs and LSIs, trays formed of thermoplastic resins, embossed carrier tapes, and the like are known. As the base material of the tray and the embossed carrier tape, a resin molded product such as a resin sheet is generally used. Since the resin molded product has no conductivity and has high surface resistivity and volume resistivity, it may cause problems such as dielectric breakdown of electronic components due to electrification and functional deterioration of electronic components due to adhesion of dust. Therefore, by kneading conductive particles such as carbon black into the resin molded product itself, antistatic ability and static electricity diffusing ability are imparted. Further, in the fields of electronic parts and automobiles, resin molded products are being used as a substitute for metal parts, and there is a demand for conductivity that cannot be achieved with carbon black. In addition, thermal conductivity is often required as a metal substitute material.
特に電子部品分野では、携帯端末の小型化及び高性能化により身体に装着可能なサイズに小型したコンピュータ（ウェアラブルコンピュータ）が注目されており、ウェアラブルコンピュータに使われる電子デバイスは、カード、カバン、腕時計、衣服、靴のような、人体の身の回りのものに備わっていることが理想的であり、さらなる軽量化が要求されている。また、自動車分野でも更なる燃費の改善のために軽量化のニーズは高い。 In particular, in the field of electronic parts, computers (wearable computers) that are small enough to be worn on the body are attracting attention due to the miniaturization and higher performance of mobile terminals, and the electronic devices used in wearable computers are cards, bags, and wristwatches. Ideally, it should be installed in things around the human body, such as clothes and shoes, and further weight reduction is required. Also, in the automobile field, there is a strong need for weight reduction in order to further improve fuel efficiency.
カーボンナノチューブは、その特性からエレクトロニクス（トランジスター素子、配線など）、エネルギー（燃料電池用電極材料、太陽光発電装置、ガス貯蔵など）、電子放出（フラットパネル装置など）、化学（吸着剤、触媒、センサーなど）、複合材料（導電性プラスチック、強化材料、難燃ナノコンポジットなど）など様々な分野での応用が期待されており、その中でも特に導電性用途への応用が特に期待されており、カーボンブラックでは達成できない、高導電な成型体が実現できる可能性を秘めている。さらにカーボンナノチューブは素材としての熱伝導性も高く、導電性と熱伝導性を備えたまさに金属代替材料として高い可能性を有している。また、カーボンナノチューブは中に中空を有するという形状からカーボンブラックよりも真密度が低く、導電材料の軽量化という点では注目度が高い。しかし、カーボンナノチューブはアスペクト比が非常に大きく、複雑に絡み合った二次粒子の状態のものが多い。そのため樹脂成形品中に分散する難易度は非常に高い。 Due to their characteristics, carbon nanotubes are used for electronics (transistor elements, wiring, etc.), energy (electrode materials for fuel cells, solar power generation equipment, gas storage, etc.), electron emission (flat panel equipment, etc.), chemistry (adsorbents, catalysts, etc.) Applications are expected in various fields such as sensors), composite materials (conductive plastics, reinforced materials, flame-retardant nanocomposites, etc.), and among them, applications in conductive applications are particularly expected, and carbon It has the potential to realize a highly conductive molded body that cannot be achieved with black. Furthermore, carbon nanotubes have high thermal conductivity as a material, and have high potential as a metal substitute material having conductivity and thermal conductivity. In addition, carbon nanotubes have a lower true density than carbon black due to their hollow shape, and are attracting attention in terms of weight reduction of conductive materials. However, carbon nanotubes have a very large aspect ratio and are often in the state of secondary particles that are intricately intertwined. Therefore, the difficulty of dispersing in the resin molded product is very high.
カーボンナノチューブを樹脂中に分散させる技術としては、カーボンナノチューブをプラズマで処理することにより絡まりをほぐし樹脂へ分散させる方法が開示されている（特許文献１参照）。また、イオン性液体とカーボンナノチューブを主成分とし、導電性を発現させる技術（特許文献２参照）や、マトリックスポリマーと電子導電性繊維状充填剤とイオン性液体を成分とし、電子導電性繊維状充填剤の分散性に優れ、かつ、電気抵抗のばらつきが小さくする技術が開示されている（特許文献３参照）。 As a technique for dispersing carbon nanotubes in a resin, a method of untangling carbon nanotubes by treating them with plasma and dispersing them in a resin is disclosed (see Patent Document 1). In addition, a technique for expressing conductivity using an ionic liquid and carbon nanotubes as main components (see Patent Document 2) and an electron conductive fibrous form containing a matrix polymer, an electron conductive fibrous filler and an ionic liquid as components. A technique is disclosed in which the dispersibility of a filler is excellent and the variation in electrical resistance is reduced (see Patent Document 3).
一方、カーボンナノチューブを配合した樹脂組成物は、射出成型法による加工を行った場合、樹脂中に十分にカーボンナノチューブが分散した場合でも、十分な導電性が発現し難いという問題があった。その理由として、特に射出成形等のような成形方法においては、成形体表面に樹脂の存在比率が高い層（スキン層）が形成されてしまうことが主な要因の一つと考えられている。スキン層の形成を低減するためには、成形体中のカーボンナノチューブ濃度を高める方法があるが、コストアップや加工難度が増大するという懸念があり、成形条件（金型温度の高温化、成形温度の高温化、射出速度の低速度化等）による問題解決が試みられているものの、成形サイクルの長期化、成形体表面光沢の消失、成形体の物性が劣化するなどの問題点が挙げられる。一方、２種の樹脂を含むポリマーアロイを海島構造もしくは共連続状態の連続層へカーボンナノチューブを選択的に配合することで、カーボンナノチューブが低濃度でも導電性を発現する技術が開示されている（特許文献４、５）。しかし、これらの方法ではポリマーアロイを形成する２種以上の樹脂が非相溶である必要性があるため成形体の物性低下が著しいという問題があった。 On the other hand, the resin composition containing carbon nanotubes has a problem that it is difficult to exhibit sufficient conductivity even when the carbon nanotubes are sufficiently dispersed in the resin when the resin composition is processed by the injection molding method. The reason is considered to be one of the main factors that a layer (skin layer) having a high resin abundance ratio is formed on the surface of the molded body, particularly in a molding method such as injection molding. In order to reduce the formation of the skin layer, there is a method of increasing the concentration of carbon nanotubes in the molded product, but there is a concern that the cost will increase and the processing difficulty will increase, so the molding conditions (higher mold temperature, molding temperature) Although attempts have been made to solve the problem by increasing the temperature and lowering the injection speed, there are problems such as a longer molding cycle, loss of surface gloss of the molded product, and deterioration of the physical properties of the molded product. On the other hand, a technique has been disclosed in which a polymer alloy containing two types of resins is selectively blended with carbon nanotubes in a continuous layer having a sea-island structure or a co-continuous state to exhibit conductivity even at a low concentration of carbon nanotubes. Patent Documents 4 and 5). However, these methods have a problem that the physical properties of the molded product are significantly deteriorated because two or more kinds of resins forming the polymer alloy need to be incompatible with each other.
高い導電性と高い熱伝導性を両立させるためには、金属フィラーを充填させたり、電気伝導性の高い炭素材料と熱伝導性の高いセラミック材料を共存させるなどの方法が考えられるが、金属フィラーやセラミック材料は比重が大きいものが多く、軽量化という目的には適していない。 In order to achieve both high conductivity and high thermal conductivity, methods such as filling with a metal filler or coexisting a carbon material with high electrical conductivity and a ceramic material with high thermal conductivity can be considered. And ceramic materials have a large specific gravity and are not suitable for the purpose of weight reduction.
本発明は、軽量であり、高い導電性、高い熱伝導性および良好な外観の成形体を成形できる導電性樹脂組成物およびそれを用いた成形体の提供を目的とする。 An object of the present invention is to provide a conductive resin composition which is lightweight and capable of molding a molded product having high conductivity, high thermal conductivity and good appearance, and a molded product using the same.
本発明者らは、上記問題を解決するため、鋭意検討した結果、本発明に達した。
すなわち、本発明の実施態様は、融点５５℃以上１００℃未満、かつ真密度０．９２ｇ／ｍＬ以下であるポリオレフィン系樹脂（Ａ）、オレフィン・不飽和カルボン酸エステル共重合体樹脂（Ｂ）、カーボンナノチューブ（Ｃ）およびカーボンブラック（Ｄ）を含み、上記カーボンナノチューブ（Ｃ）の嵩密度が、０．００５〜０．１０ｇ／ｍＬである導電性樹脂組成物である。
The present inventors have reached the present invention as a result of diligent studies in order to solve the above problems.
That is, in the embodiment of the present invention, a polyolefin resin (A) having a melting point of 55 ° C. or higher and lower than 100 ° C. and a true density of 0.92 g / mL or less, an olefin / unsaturated carboxylic acid ester copolymer resin (B), A conductive resin composition containing carbon nanotubes (C) and carbon black (D) and having a bulk density of the carbon nanotubes (C) of 0.005 to 0.10 g / mL.
また、本発明の実施態様は、上記樹脂（Ａ）、上記樹脂（Ｂ）、上記カーボンナノチューブ（Ｃ）、および上記カーボンブラック（Ｄ）の合計１００質量部に対して、上記カーボンナノチューブ（Ｃ）５〜１５質量部および上記カーボンブラック（Ｄ）５〜２５質量部を含む上記導電性樹脂組成物である。 Further, in the embodiment of the present invention, the carbon nanotube (C) is based on 100 parts by mass of the resin (A), the resin (B), the carbon nanotube (C), and the carbon black (D) in total. The conductive resin composition containing 5 to 15 parts by mass and 5 to 25 parts by mass of carbon black (D).
また、本発明の実施態様は、上記カーボンナノチューブ（Ｃ）は、平均直径が５〜３０ｎｍ、かつ平均アスペクト比が１００〜１０００である上記導電性樹脂組成物である。 Further, in the embodiment of the present invention, the carbon nanotube (C) is the conductive resin composition having an average diameter of 5 to 30 nm and an average aspect ratio of 100 to 1000.
また、本発明の実施態様は、上記導電性樹脂組成物を用いて成形された成形体である。 Further, an embodiment of the present invention is a molded product molded by using the above-mentioned conductive resin composition.
また、本発明の実施態様は、上記導電性樹脂組成物を、８０〜１４０℃で成形する成形体の製造方法である。 Further, an embodiment of the present invention is a method for producing a molded product in which the conductive resin composition is molded at 80 to 140 ° C.
本発明により、軽量で高い導電性と高い熱伝導性および良好な外観の成形体を成形できる導電性樹脂組成物およびそれを用いた成形体を提供できるようになった。 INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a conductive resin composition capable of molding a molded product that is lightweight, has high conductivity, high thermal conductivity, and has a good appearance, and a molded product using the same.
以下、本発明について説明する。尚、本明細書において、「融点５５℃以上１００℃未満、かつ真密度０．９２ｇ／ｍＬ以下であるポリオレフィン系樹脂（Ａ）」を「ポリオレフィン系樹脂（Ａ）」または「樹脂（Ａ）」、「オレフィン・不飽和カルボン酸エステル共重合体樹脂（Ｂ）」を「樹脂（Ｂ）」と略記することがある。 Hereinafter, the present invention will be described. In the present specification, "polyolefin resin (A) having a melting point of 55 ° C. or higher and lower than 100 ° C. and a true density of 0.92 g / mL or less" is referred to as "polyolefin resin (A)" or "resin (A)". , "Olefin / unsaturated carboxylic acid ester copolymer resin (B)" may be abbreviated as "resin (B)".
＜導電性樹脂組成物＞
本発明の導電性樹脂組成物は、融点５５℃以上１００℃未満、かつ真密度０．９２ｇ／ｍＬ以下であるポリオレフィン系樹脂（Ａ）、オレフィン・不飽和カルボン酸エステル共重合体樹脂（Ｂ）、カーボンナノチューブ（Ｃ）およびカーボンブラック（Ｄ）とを含んでなる導電性樹脂組成物である。
<Conductive resin composition>
The conductive resin composition of the present invention is a polyolefin resin (A) having a melting point of 55 ° C. or higher and lower than 100 ° C. and a true density of 0.92 g / mL or less, and an olefin / unsaturated carboxylic acid ester copolymer resin (B). , A conductive resin composition comprising carbon nanotubes (C) and carbon black (D).
＜ポリオレフィン系樹脂（Ａ）＞
本発明に用いられるポリオレフィン系樹脂（Ａ）とは、オレフィン（単量体、モノマー）より構成される重合体であり、融点が５５℃以上１００℃未満、かつ真密度が０．９２ｇ／ｍＬ以下であるポリオレフィン系樹脂である。
<Polyolefin resin (A)>
The polyolefin-based resin (A) used in the present invention is a polymer composed of olefins (monomers, monomers), has a melting point of 55 ° C. or higher and lower than 100 ° C., and a true density of 0.92 g / mL or lower. It is a polyolefin-based resin.
樹脂（Ａ）を構成するオレフィンとしては、エチレン（エテン）、プロピレン（プロペン）、１−ブテン、２−ブテン、１−ヘキセン、４−メチルペンテン−１、１−デセン、１−ドデセン等が挙げられる。オレフィンとしては、炭素数２以上３０以下のオレフィンが好ましく、エチレンまたはプロピレンがより好ましく、エチレンがさらに好ましい。 Examples of the olefin constituting the resin (A) include ethylene (ethane), propylene (propene), 1-butene, 2-butene, 1-hexene, 4-methylpentene-1,1-decene, 1-dodecene and the like. Be done. As the olefin, an olefin having 2 to 30 carbon atoms is preferable, ethylene or propylene is more preferable, and ethylene is further preferable.
オレフィンより構成される重合体としては、重合体を構成するオレフィンは同一であっても異なっても良い。異なる場合は、２種類または３種類以上のオレフィンであっても良い。
同一である場合は、高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）等のポリエチレン樹脂（ＰＥ樹脂）、ポリプロピレン樹脂（ＰＰ樹脂）、炭素数４以上のオレフィンから構成される重合体等が挙げられる。異なる場合は、エチレンとプロピレンとの共重合体樹脂（エチレン／プロピレンの共重合比（質量比）＝０．５／９９．５〜３０／７０、好ましくは２／９８〜２０／８０）、エチレンまたはプロピレンと炭素数４以上のオレフィンとの共重合体樹脂（エチレンまたはプロピレン／炭素数４以上のオレフィン体の共重合比（質量比）＝３０／７０〜９９／１、好ましくは５０／５０〜９５／５）等が挙げられる。炭素数４以上のオレフィンとしては、炭素数４以上３０以下のオレフィンが好ましい。これらポリオレフィン系樹脂（Ａ）は、ポリオレフィンが部分的に酸化された酸化ポリオレフィンであっても構わない。
As the polymer composed of olefins, the olefins constituting the polymer may be the same or different. If they are different, they may be two or three or more types of olefins.
When they are the same, polyethylene resin (PE resin) such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene resin (PP resin), and carbon number 4 or more. Examples thereof include a polymer composed of olefin. If they are different, a copolymer resin of ethylene and propylene (copolymerization ratio (mass ratio) of ethylene / propylene = 0.5 / 99.5 to 30/70, preferably 2/98 to 20/80), ethylene Alternatively, a copolymer resin of propylene and an olefin having 4 or more carbon atoms (ethylene or propylene / copolymerization ratio (mass ratio) of an olefin having 4 or more carbon atoms) = 30/70 to 99/1, preferably 50/50 to 50. 95/5) and the like. As the olefin having 4 or more carbon atoms, an olefin having 4 or more carbon atoms and 30 or less carbon atoms is preferable. The polyolefin-based resin (A) may be an oxidized polyolefin in which the polyolefin is partially oxidized.
上記ポリオレフィン系樹脂の内、ＰＥ樹脂またはＰＰ樹脂が好ましく、ＰＥ樹脂がより好ましい。また、ＰＥ樹脂の中でも、特にメタロセン系触媒を用いて合成したＰＥ樹脂が、より好ましい。ポリオレフィン系樹脂（Ａ）は、単独または２種類以上を併用できる。 Among the above-mentioned polyolefin resins, PE resin or PP resin is preferable, and PE resin is more preferable. Further, among the PE resins, a PE resin synthesized by using a metallocene catalyst is particularly preferable. The polyolefin resin (A) can be used alone or in combination of two or more.
一般的なポリオレフィン系樹脂の内、比較的真密度の低いポリエチレン樹脂は、真密度や分岐量によってＨＤＰＥ、ＬＤＰＥ、ＬＬＤＰＥ等に分類され、融点や真密度が大きく異なるが、一般的なポリエチレン系樹脂の多くは、融点が１００℃を超え、真密度が０．９２より大きいのが実情である。しかし、本発明に用いられるポリオレフィン系樹脂（Ａ）は、融点５５℃以上１００℃未満であり、かつ真密度０．９２ｇ／ｍＬ以下であり、難分散性であるカーボンナノチューブに対して極めて良好な分散媒として働くことを本発明者らは見出した。したがって、ポリオレフィン系樹脂（Ａ）を用いることにより、効率よくカーボンナノチューブを分散し、カーボンナノチューブ由来の高い導電性を活かした導電性樹脂組成物を形成することができる。 Among general polyolefin resins, polyethylene resins with relatively low true density are classified into HDPE, LDPE, LLDPE, etc. according to the true density and the amount of branching, and the melting point and true density differ greatly, but general polyethylene resins. In reality, most of them have a melting point of more than 100 ° C. and a true density of more than 0.92. However, the polyolefin-based resin (A) used in the present invention has a melting point of 55 ° C. or higher and lower than 100 ° C. and a true density of 0.92 g / mL or less, which is extremely good for carbon nanotubes which are difficult to disperse. We have found that it acts as a dispersion medium. Therefore, by using the polyolefin resin (A), it is possible to efficiently disperse the carbon nanotubes and form a conductive resin composition utilizing the high conductivity derived from the carbon nanotubes.
また、カーボンナノチューブは、一般的には耐熱性のある材料ではあるが、高温で樹脂と混練する際にカーボンナノチューブ表面が傷つき、欠陥が生じることがある。カーボンナノチューブ表面の欠陥は、特に熱伝導性の著しい低下を引き起こす恐れがある。ポリオレフィン系樹脂（Ａ）を用いることで、カーボンナノチューブ表面の欠陥を可能な限り抑制することができるため、高い熱伝導性を維持することができる。
さらに樹脂自体の真密度が低い為、導電性樹脂組成物としても、さらにそれを成形した成形体としても、極めて軽量かつ高い導電性および熱伝導性を有する。
Further, although carbon nanotubes are generally a heat-resistant material, the surface of carbon nanotubes may be damaged when kneaded with a resin at a high temperature, resulting in defects. Defects on the surface of carbon nanotubes can cause a significant decrease in thermal conductivity, in particular. By using the polyolefin resin (A), defects on the surface of carbon nanotubes can be suppressed as much as possible, so that high thermal conductivity can be maintained.
Further, since the true density of the resin itself is low, it is extremely lightweight and has high conductivity and thermal conductivity both as a conductive resin composition and as a molded product obtained by molding the resin itself.
カーボンナノチューブ（Ｃ）は吸油量が大きく、分散が進むにつれ、加工時の粘度が著しく高くなる。しかしながら、粘度を下げるために加工温度を高くすると樹脂の劣化やカーボンナノチューブ（Ｃ）の劣化が促進されるため、成形体を製造する際の加工温度はできるだけ低いことが好ましく、結果として、ポリオレフィン系樹脂（Ａ）の融点が上記の範囲であることにより、加工温度を低く抑えることができ、高い導電性及び熱伝導性を持った成形体を得ることができる。尚、ポリオレフィン系樹脂（Ａ）の融点は、ＪＩＳ Ｋ７１２１に準拠し、示差走査熱量計（ＤＳＣ２２０、セイコーインスツルメンツ社製）を用いて測定した値である。 The carbon nanotube (C) has a large oil absorption amount, and as the dispersion progresses, the viscosity during processing becomes remarkably high. However, if the processing temperature is raised in order to reduce the viscosity, the deterioration of the resin and the deterioration of the carbon nanotube (C) are promoted. Therefore, it is preferable that the processing temperature at the time of producing the molded product is as low as possible, and as a result, the polyolefin-based When the melting point of the resin (A) is in the above range, the processing temperature can be kept low, and a molded product having high conductivity and thermal conductivity can be obtained. The melting point of the polyolefin resin (A) is a value measured using a differential scanning calorimeter (DSC220, manufactured by Seiko Instruments, Inc.) in accordance with JIS K7121.
真密度が低いことは、軽量な成形体を得る上で有益であるが、カーボンナノチューブ（Ｃ）の分散性にとっても好ましい。真密度が低いと、非晶性が高いため、カーボンナノチューブ（Ｃ）をより高効率で分散することができ、高い導電性と良好な外観の成形体を成形できる導電性樹脂組成物を形成することができる。ポリオレフィン系樹脂（Ａ）の真密度は、０．９２ｇ／ｍＬ以下であり、０．９０ｇ／ｍＬ以下であることが好ましい。真密度の下限値は特に制限はないが、一般に０．８５ｇ／ｍＬ未満のポリオレフィン系樹脂を作ることは難しいことから、実質的にポリオレフィン系樹脂（Ａ）真密度の下限値は０．８５ｇ／ｍＬ以上が好ましい。尚、真密度は、ＪＩＳ Ｋ７１１２に準拠し、水を用いて、ピクノメーターによる液相置換法により求めた。 The low true density is beneficial for obtaining a lightweight molded product, but is also preferable for the dispersibility of the carbon nanotube (C). When the true density is low, the amorphous property is high, so that the carbon nanotubes (C) can be dispersed with higher efficiency, and a conductive resin composition capable of forming a molded product having high conductivity and good appearance is formed. be able to. The true density of the polyolefin resin (A) is 0.92 g / mL or less, preferably 0.90 g / mL or less. The lower limit of the true density is not particularly limited, but since it is generally difficult to produce a polyolefin resin having a true density of less than 0.85 g / mL, the lower limit of the true density of the polyolefin resin (A) is 0.85 g / mL. mL or more is preferable. The true density was determined by a liquid phase substitution method using a pycnometer using water in accordance with JIS K7112.
＜オレフィン・不飽和カルボン酸エステル共重合体樹脂（Ｂ）＞
本発明に用いられるオレフィン・不飽和カルボン酸エステル共重合体樹脂（Ｂ）は、オレフィンおよび不飽和カルボン酸エステルを含む単量体より構成される共重合体樹脂である。樹脂（Ｂ）を構成する単量体は、オレフィンおよび不飽和カルボン酸エステルを必須とするが、その他単量体を含むことを除外するものではない。
<Olefin / unsaturated carboxylic acid ester copolymer resin (B)>
The olefin / unsaturated carboxylic acid ester copolymer resin (B) used in the present invention is a copolymer resin composed of a monomer containing an olefin and an unsaturated carboxylic acid ester. The monomer constituting the resin (B) requires an olefin and an unsaturated carboxylic acid ester, but does not exclude the inclusion of other monomers.
樹脂（Ｂ）を構成するオレフィンとしては、樹脂（Ａ）を構成するオレフィンと同じオレフィンが挙げられ、炭素数２以上３０以下のオレフィンが好ましく、エチレンまたはプロピレンがより好ましく、エチレンがさらに好ましい。 Examples of the olefin constituting the resin (B) include the same olefin as the olefin constituting the resin (A), preferably an olefin having 2 or more and 30 or less carbon atoms, more preferably ethylene or propylene, and even more preferably ethylene.
樹脂（Ｂ）を構成する不飽和カルボン酸エステルとは、オレフィンと共重合し得る不飽和カルボン酸エステルを意味する。オレフィンと共重合し得る不飽和カルボン酸エステルであれば良く、不飽和結合の位置や数は制限されないが、軽量な成形体を得るためには、不飽和脂肪族カルボン酸エステルが好ましく、（メタ）アクリル酸エステルおよび／または脂肪族カルボン酸ビニルがより好ましい。尚、「（メタ）アクリル」とは、「アクリルまたはメタクリル」を指すものとする。 The unsaturated carboxylic acid ester constituting the resin (B) means an unsaturated carboxylic acid ester that can be copolymerized with an olefin. An unsaturated carboxylic acid ester capable of copolymerizing with an olefin may be used, and the position and number of unsaturated bonds are not limited. However, in order to obtain a lightweight molded product, an unsaturated aliphatic carboxylic acid ester is preferable (meth). ) Acrylic ester and / or aliphatic vinyl carboxylate is more preferable. In addition, "(meth) acrylic" shall mean "acrylic or methacrylic".
（メタ）アクリル酸エステルとしては、（メタ）アクリル酸アルキルエステルが好ましく、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル等が挙げられる。これらの内、炭素数１〜３０のアルキル基を有する（メタ）アクリル酸アルキルエステルが好ましく、炭素数１〜４のアルキル基を有する（メタ）アクリル酸アルキルエステルがより好ましい。また、メタクリル酸エステルよりもアクリル酸アルキルエステルが好ましい。 As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester is preferable, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (. Examples thereof include hexyl acrylate (meth) and octyl (meth) acrylate. Of these, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 30 carbon atoms is preferable, and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is more preferable. Further, an acrylic acid alkyl ester is preferable to a methacrylic acid ester.
脂肪族カルボン酸ビニルとしては、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ヘキサン酸ビニル、オクタン酸ビニル等が挙げられる。これらの内、炭素数１〜４の脂肪族カルボン酸のビニルエステルが好ましく、酢酸ビニルがより好ましい。樹脂（Ｂ）を構成するオレフィンおよび不飽和カルボン酸エステルは、それぞれ単独または２種類以上を併用することが可能であり、必要に応じてその他単量体を含んでも良い。 Examples of the aliphatic vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanate and the like. Of these, vinyl esters of aliphatic carboxylic acids having 1 to 4 carbon atoms are preferable, and vinyl acetate is more preferable. The olefin and unsaturated carboxylic acid ester constituting the resin (B) can be used alone or in combination of two or more, and may contain other monomers as necessary.
上記オレフィンおよび不飽和カルボン酸エステル以外の、その他単量体としては、アクリル酸やメタクリル酸等の不飽和カルボン酸、無水マレイン酸等の不飽和カルボン酸無水物等が挙げられる。 Examples of other monomers other than the above-mentioned olefin and unsaturated carboxylic acid ester include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and unsaturated carboxylic acid anhydrides such as maleic anhydride.
したがって、樹脂（Ｂ）としては、オレフィン・（メタ）アクリル酸エステル共重合体またはオレフィン・脂肪族カルボン酸ビニル共重合体が好ましい。
オレフィン・（メタ）アクリル酸エステル共重合体としては、例えば、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・アクリル酸ブチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・メタクリル酸エチル共重合体、エチレン・メタクリル酸ブチル共重合体、プロピレン・アクリル酸メチル共重合体等が挙げられる。これらの内、エチレン・（メタ）アクリル酸エステル共重合体が好ましく、エチレン・（メタ）アクリル酸アルキルエステル共重合体がより好ましく、エチレン・アクリル酸アルキルエステル共重合体がさらに好ましい。中でも後述する融点や真密度を考慮すると、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・アクリル酸ブチル共重合体が好ましい。
Therefore, as the resin (B), an olefin / (meth) acrylic acid ester copolymer or an olefin / aliphatic carboxylic acid vinyl copolymer is preferable.
Examples of the olefin / (meth) acrylate copolymer include an ethylene / methyl acrylate copolymer, an ethylene / ethyl acrylate copolymer, an ethylene / butyl acrylate copolymer, and an ethylene / methyl methacrylate copolymer. Examples thereof include coalescence, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, and propylene / methyl acrylate copolymer. Of these, an ethylene / (meth) acrylic acid ester copolymer is preferable, an ethylene / (meth) acrylic acid alkyl ester copolymer is more preferable, and an ethylene / acrylic acid alkyl ester copolymer is further preferable. Among them, an ethylene / methyl acrylate copolymer, an ethylene / ethyl acrylate copolymer, and an ethylene / butyl acrylate copolymer are preferable in consideration of the melting point and the true density described later.
オレフィン・脂肪族カルボン酸ビニル共重合体としては、例えば、エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・酪酸ビニル共重合体、プロピレン・酢酸ビニル共重合体等が挙げられる。これらの内、エチレン・脂肪族カルボン酸ビニル共重合体が好ましく、エチレン・酢酸ビニル共重合体がより好ましい。 Examples of the olefin / aliphatic vinyl acetate copolymer include an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate copolymer, an ethylene / vinyl butyrate copolymer, and a propylene / vinyl acetate copolymer. Be done. Of these, an ethylene / aliphatic vinyl acetate copolymer is preferable, and an ethylene / vinyl acetate copolymer is more preferable.
樹脂（Ｂ）を構成する単量体は、生産性や機械物性を考慮すると、樹脂（Ｂ）中、オレフィン６０〜８５質量％含まれることが好ましく、不飽和カルボン酸エステル１５〜４０質量％含まれことが好ましい。樹脂（Ｂ）は、単独または２種類以上を併用できる。 The monomer constituting the resin (B) preferably contains 60 to 85% by mass of the olefin, and 15 to 40% by mass of the unsaturated carboxylic acid ester in the resin (B) in consideration of productivity and mechanical properties. This is preferable. The resin (B) can be used alone or in combination of two or more.
本発明に用いられる樹脂（Ｂ）は、融点が５０℃以上１００℃未満であることが好ましい。樹脂（Ｂ）もポリオレフィン系樹脂（Ａ）と同様、樹脂の劣化やカーボンナノチューブ（Ｃ）の劣化を抑制するために、成形体を製造する際の加工温度はできるだけ低いことが望ましいためである。樹脂（Ｂ）の融点が上記範囲内であることにより、加工温度を低く抑えることができ、高い導電性及び熱伝導性を持った成形体を得ることができる。尚、樹脂（Ｂ）の融点は、樹脂（Ａ）の融点と同じ方法による測定値である。 The resin (B) used in the present invention preferably has a melting point of 50 ° C. or higher and lower than 100 ° C. This is because it is desirable that the processing temperature at the time of producing the molded product of the resin (B) is as low as possible in order to suppress the deterioration of the resin and the deterioration of the carbon nanotubes (C) as in the polyolefin resin (A). When the melting point of the resin (B) is within the above range, the processing temperature can be kept low, and a molded product having high conductivity and thermal conductivity can be obtained. The melting point of the resin (B) is a measured value by the same method as the melting point of the resin (A).
本発明に用いられる樹脂（Ｂ）は、真密度が１．００ｇ／ｍＬ以下であることが好ましい。ポリオレフィン系樹脂（Ａ）と同様に真密度が低いことは、軽量な成形体を得る上で有益であり、更にカーボンナノチューブ（Ｃ）の分散性にとっても好ましい。真密度の下限値は特に制限はないが、０．９０ｇ／ｍＬ以上が好ましい。尚、樹脂（Ｂ）の真密度は、樹脂（Ａ）の真密度と同じ方法による測定値である。 The resin (B) used in the present invention preferably has a true density of 1.00 g / mL or less. Similar to the polyolefin resin (A), having a low true density is beneficial for obtaining a lightweight molded product, and is also preferable for the dispersibility of the carbon nanotube (C). The lower limit of the true density is not particularly limited, but is preferably 0.90 g / mL or more. The true density of the resin (B) is a measured value by the same method as the true density of the resin (A).
樹脂（Ａ）と樹脂（Ｂ）とを併用することにより、低温での加工性が向上し、成形後の導電性、熱伝導性が良化し、機械物性を強化することができる。樹脂（Ａ）と樹脂（Ｂ）の比率は適宜用途によって変えることができるが、両樹脂の長所を発現するためには、樹脂（Ａ）／樹脂（Ｂ）（質量比）＝２０／８０〜８０／２０の範囲内であることが好ましく、３０／７０〜７０／３０の範囲内であることがより好ましく、３０／７０〜５０／５０の範囲内であることがさらに好ましい。 By using the resin (A) and the resin (B) in combination, the workability at a low temperature is improved, the conductivity and thermal conductivity after molding are improved, and the mechanical properties can be enhanced. The ratio of the resin (A) to the resin (B) can be appropriately changed depending on the application, but in order to realize the advantages of both resins, the resin (A) / resin (B) (mass ratio) = 20/80 to It is preferably in the range of 80/20, more preferably in the range of 30/70 to 70/30, and even more preferably in the range of 30/70 to 50/50.
＜カーボンナノチューブ（C）＞
本発明に用いられるカーボンナノチューブは、グラフェンシートを丸めて円筒状にしたような構造をしており、単層の場合は単層カーボンナノチューブ（ＳＷＣＮＴ）、多層の場合は多層カーボンナノチューブ（ＭＷＣＮＴ）と呼ばれ、電子顕微鏡等で１本１本のカーボンナノチューブを観察することができる。カーボンナノチューブは、カーボンナノチューブ繊維同士が、一次凝集して絡み合ったり、バンドル状の一次凝集体を形成するが、一次凝集体が凝集して二次以上の凝集体を形成することもある。また、カーボンナノチューブの真密度は、概ね１．４ｇ／ｍＬであり、カーボンブラック（１．８〜１．９ｇ／ｍＬ）やグラファイト（真密度２．１〜２．３ｇ／ｍＬ）と比較して、炭素材料としては低く、また高い導電性を有するため、軽量な導電性材料として好適な性質を有する。
<Carbon nanotube (C)>
The carbon nanotubes used in the present invention have a structure in which a graphene sheet is rolled into a cylindrical shape, and in the case of a single layer, it is a single-walled carbon nanotube (SWCNT), and in the case of a multi-walled layer, it is a multi-walled carbon nanotube (MWCNT). It is called, and each carbon nanotube can be observed with an electron microscope or the like. In carbon nanotubes, carbon nanotube fibers are primarily aggregated and entangled with each other, or bundle-shaped primary aggregates are formed, but the primary aggregates may be aggregated to form secondary or higher aggregates. The true density of carbon nanotubes is approximately 1.4 g / mL, which is compared with carbon black (1.8 to 1.9 g / mL) and graphite (true density 2.1 to 2.3 g / mL). Since it is low as a carbon material and has high conductivity, it has properties suitable as a lightweight conductive material.
カーボンナノチューブ（Ｃ）の含有量は、樹脂（Ａ）、樹脂（Ｂ）、カーボンナノチューブ（Ｃ）およびカーボンブラック（Ｄ）の合計１００質量部に対して、カーボンナノチューブ（Ｃ）５〜１５質量部であることが好ましく、５〜１０質量部がより好ましい。５質量部以上含有することにより、十分な導電性を発現することができ、また１５質量部以下含有することにより、カーボンナノチューブの分散不良が生じ難くなり、押出時やフィルム成形時にカーボンナノチューブの未分散凝集塊の発生を抑制させることができる。 The content of the carbon nanotubes (C) is 5 to 15 parts by mass of the carbon nanotubes (C) with respect to 100 parts by mass of the total of the resin (A), the resin (B), the carbon nanotubes (C) and the carbon black (D). Is preferable, and 5 to 10 parts by mass is more preferable. Sufficient conductivity can be exhibited by containing 5 parts by mass or more, and poor dispersion of carbon nanotubes is less likely to occur by containing 15 parts by mass or less, and carbon nanotubes are not present during extrusion or film molding. The generation of dispersed agglomerates can be suppressed.
カーボンナノチューブ（Ｃ）は、平均直径が５〜３０ｎｍであることが好ましく、１０〜２０ｎｍであることがより好ましい。また、平均アスペクト比は、１００〜１０００であることが好ましい。このような物性を持ったカーボンナノチューブは、より高い導電性の成形体を得ることができる。なお、ここでいう平均直径とは、電子顕微鏡観察より求めた個々のカーボンナノチューブの短軸長の数平均値を意味し、平均アスペクト比とは、電子顕微鏡観察より求めた個々のカーボンナノチューブの短軸長（平均直径）と長軸長の数平均値の比であり、下記の式（１）により算出された値である。
式（１） 平均アスペクト比＝長軸長の数平均値÷平均直径
The carbon nanotube (C) preferably has an average diameter of 5 to 30 nm, more preferably 10 to 20 nm. The average aspect ratio is preferably 100 to 1000. Carbon nanotubes having such physical properties can obtain a molded product having higher conductivity. The average diameter referred to here means the number average value of the minor axis lengths of individual carbon nanotubes obtained by electron microscope observation, and the average aspect ratio is the shortness of individual carbon nanotubes obtained by electron microscope observation. It is the ratio of the shaft length (average diameter) to the number mean value of the major shaft length, and is a value calculated by the following formula (1).
Equation (1) Average aspect ratio = number average value of major axis length ÷ average diameter
カーボンナノチューブ（Ｃ）の嵩密度は、０．００５〜０．１０ｇ／ｍＬであり、０．０１〜０．０５ｇ／ｍＬであることが好ましい。上記範囲の嵩密度を有するカーボンナノチューブを使用した場合、ポリオレフィン系樹脂（Ａ）や樹脂（Ｂ）に対する分散性が良好となり、混練時の発熱を抑えられると共に、混練時のカーボンナノチューブ表面に発生する欠陥を抑制することができるため、熱伝導性の低下を抑制することができる。カーボンナノチューブ（Ｃ）の真密度は、ＪＩＳ−Ｒ７２２２に準拠し、ブタノールを用いて、ピクノメーターによる液相置換法により求めた。 The bulk density of the carbon nanotubes (C) is 0.005 to 0.10 g / mL, preferably 0.01 to 0.05 g / mL. When carbon nanotubes having a bulk density in the above range are used, the dispersibility in the polyolefin resin (A) and the resin (B) is improved, heat generation during kneading can be suppressed, and the carbon nanotubes are generated on the surface of the carbon nanotubes during kneading. Since defects can be suppressed, a decrease in thermal conductivity can be suppressed. The true density of the carbon nanotube (C) was determined by a liquid phase replacement method using a pycnometer using butanol in accordance with JIS-R7222.
カーボンナノチューブ（Ｃ）は、適度なバンドル構造を有するものが好ましい。ここで、バンドル構造とは、個々のカーボンナノチューブ繊維が一定方向に配向している構造を意味する。カーボンナノチューブは二次粒子で存在するのが一般的であり、例えば一般的な一次粒子であるカーボンナノチューブが複雑に絡み合っている状態でもよく、ほぐれ易くカーボンナノチューブを直線状にしたバンドル構造を有するものもある。バンドル構造を有するカーボンナノチューブは、カーボンナノチューブ一本一本が絡み合ったものではなく、束状になっているものである。このため、絡み合った一次凝集体と比較して、カーボンナノチューブ繊維が一次凝集体から解れ易く、ポリオレフィン系樹脂（Ａ）や樹脂（Ｂ）への分散が容易である。また、カーボンナノチューブがバンドル状であり、易分散性を有することは、高い熱伝導性を発現する上でも有利である。 The carbon nanotube (C) preferably has an appropriate bundle structure. Here, the bundle structure means a structure in which individual carbon nanotube fibers are oriented in a certain direction. Carbon nanotubes generally exist as secondary particles. For example, carbon nanotubes, which are general primary particles, may be intricately entangled, and have a bundle structure in which carbon nanotubes are easily loosened and linearized. There is also. The carbon nanotubes having a bundle structure are not entangled one by one, but are bundled. Therefore, as compared with the entangled primary aggregates, the carbon nanotube fibers are easily separated from the primary aggregates and easily dispersed in the polyolefin resin (A) and the resin (B). Further, it is advantageous that the carbon nanotubes are bundled and have easy dispersibility in order to exhibit high thermal conductivity.
カーボンナノチューブ（Ｃ）は、単層カーボンナノチューブ、２層またはそれ以上で巻いた多層カーボンナノチューブでも、これらが混在するものであっても良いが、コスト面および強度面から多層カーボンナノチューブであることが好ましい。また、カーボンナノチューブの側壁がグラファイト構造ではなく、アモルファス構造をもったカーボンナノチューブであっても構わない。 The carbon nanotube (C) may be a single-walled carbon nanotube, a multi-walled carbon nanotube wound with two or more layers, or a mixture of these, but it may be a multi-walled carbon nanotube from the viewpoint of cost and strength. preferable. Further, the side wall of the carbon nanotube may be a carbon nanotube having an amorphous structure instead of the graphite structure.
カーボンナノチューブ（Ｃ）は、一般にレーザーアブレーション法、アーク放電法、化学気相成長法（ＣＶＤ法）、燃焼法などで製造できるが、どのような方法で製造したカーボンナノチューブでも構わない。特にＣＶＤ法は、通常、４００〜１０００℃の高温下において、シリカ、アルミナ、酸化マグネシウム、酸化チタン、珪酸塩、珪藻土、アルミナシリカ、シリカチタニア、およびゼオライトなどの担体に鉄やニッケルなどの金属触媒を担持した触媒微粒子と、原料の炭素含有ガスとを接触させることにより、カーボンナノチューブを安価に、かつ大量に生産することができる方法であり、本発明に使用するカーボンナノチューブとして好ましい。 The carbon nanotube (C) can be generally produced by a laser ablation method, an arc discharge method, a chemical vapor deposition method (CVD method), a combustion method, or the like, but any carbon nanotube may be produced. In particular, the CVD method usually uses a metal catalyst such as iron or nickel on a carrier such as silica, alumina, magnesium oxide, titanium oxide, silicate, diatomaceous earth, alumina silica, silica titania, and zeolite at a high temperature of 400 to 1000 ° C. This is a method capable of producing carbon nanotubes in a large amount at low cost by contacting the catalyst fine particles carrying the above with the carbon-containing gas as a raw material, and is preferable as the carbon nanotubes used in the present invention.
＜カーボンブラック（Ｄ）＞
本発明に用いられるカーボンブラック（Ｄ）は、導電性を有する無定形炭素であり、油やガスを不完全燃焼させたり、 炭化水素を熱分解したりして製造できる。本発明におけるカーボンブラック（Ｄ）の役割は、射出成形や押出成形後、成形体内部に取り込まれたカーボンナノチューブ（Ｃ）表面との間に導電パスを形成することである。
導電性材料としてカーボンナノチューブのみを配合した導電性樹脂組成物は、射出成形をして成形体を製造した場合、組成物中に十分にカーボンナノチューブが分散された状態であっても、導電性が発現し難い場合がある。その理由としては、成形体表面に、樹脂の存在比率が高くカーボンナノチューブが低濃度の層（いわゆる「スキン層」）が形成されてしまうことが要因と考えられている。つまり、樹脂組成物中に、樹脂の存在比率が高くカーボンナノチューブが低濃度の部分と、樹脂の存在比率が低くカーボンナノチューブが高濃度の部分とが共存すると、各々の部分で溶融時の粘度（溶融粘度）が異なるため、例えば押出成型する場合、粘度が低く流動性の高い樹脂の存在比率が高い部分が成型時に先に押し出されることとなり、成形体表面がスキン層に覆われて、成型体の導電性が低下するものと考えられる。
<Carbon black (D)>
The carbon black (D) used in the present invention is an amorphous carbon having conductivity, and can be produced by incomplete combustion of oil or gas or thermal decomposition of hydrocarbons. The role of the carbon black (D) in the present invention is to form a conductive path with the surface of the carbon nanotube (C) taken into the molded body after injection molding or extrusion molding.
A conductive resin composition containing only carbon nanotubes as a conductive material has conductivity even when carbon nanotubes are sufficiently dispersed in the composition when a molded product is produced by injection molding. It may be difficult to develop. It is considered that the reason is that a layer having a high resin abundance ratio and a low concentration of carbon nanotubes (so-called “skin layer”) is formed on the surface of the molded product. That is, when a portion having a high resin abundance ratio and a low concentration of carbon nanotubes and a portion having a low resin abundance ratio and a high concentration of carbon nanotubes coexist in the resin composition, the viscosity at the time of melting in each portion ( Since the melt viscosity) is different, for example, in the case of extrusion molding, the portion having a low viscosity and a high presence ratio of the highly fluid resin is extruded first at the time of molding, and the surface of the molded body is covered with the skin layer to form the molded body. It is considered that the conductivity of the resin is reduced.
一方、カーボンブラックは、カーボンナノチューブと比較して、一般的に比表面積や吸油量が低いため、カーボンブラックを含む樹脂組成物は、カーボンナノチューブのみを含む樹脂組成物よりも、溶融粘度が高くなりにくく、成形体表面にスキン層が形成されにくい。また、カーボンブラックはカーボンナノチューブとの親和性も良好なため、カーボンナノチューブが成形体内部に取り込まれても、成形体表面に存在するカーボンブラックとの間に導電パスを形成できるため、本発明の成形体は高い導電性を発現することができる。 On the other hand, since carbon black generally has a lower specific surface area and oil absorption than carbon nanotubes, the resin composition containing carbon black has a higher melt viscosity than the resin composition containing only carbon nanotubes. It is difficult to form a skin layer on the surface of the molded product. Further, since carbon black has a good affinity with carbon nanotubes, even if the carbon nanotubes are taken into the molded body, a conductive path can be formed with the carbon black existing on the surface of the molded body. The molded product can exhibit high conductivity.
カーボンブラック（Ｄ）としては、気体若しくは液体の原料を反応炉中で連続的に熱分解し製造するファーネスブラック、特にエチレン重油を原料としたケッチェンブラック、原料ガスを燃焼させて、その炎をチャンネル鋼底面にあて急冷し析出させたチャンネルブラック、ガスを原料とし燃焼と熱分解を周期的に繰り返すことにより得られるサーマルブラック、及び、特にアセチレンガスを原料とするアセチレンブラック等の各種のものを単独で、若しくは２種類以上併せて使用することができる。又、通常行われている酸化処理されたカーボンブラックや、中空カーボン等も使用できる。 As carbon black (D), furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially acetylene black made from ethylene heavy oil, and the raw material gas are burned to burn the flame. Various types such as channel black that is rapidly cooled and precipitated on the bottom surface of channel steel, thermal black that is obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and acetylene black that uses acetylene gas as a raw material in particular. It can be used alone or in combination of two or more. In addition, normally oxidized carbon black, hollow carbon, and the like can also be used.
カーボンブラック（Ｄ）の含有量は、樹脂（Ａ）、樹脂（Ｂ）、カーボンナノチューブ（Ｃ）およびカーボンブラック（Ｄ）の合計１００質量部に対して、５〜２５質量部であることが好ましく、５〜１５質量部がより好ましい。５質量部以上含有することで、カーボンナノチューブ（Ｃ）と表面との間に十分な導電パスを形成することができ、成形時の導電性を向上させることができ、２５質量部以下の含有量にすることで、分散状態がより良好となり、また本発明の軽量化を実現することができる。 The content of carbon black (D) is preferably 5 to 25 parts by mass with respect to 100 parts by mass in total of the resin (A), the resin (B), the carbon nanotubes (C) and the carbon black (D). , 5 to 15 parts by mass is more preferable. By containing 5 parts by mass or more, a sufficient conductive path can be formed between the carbon nanotube (C) and the surface, the conductivity at the time of molding can be improved, and the content is 25 parts by mass or less. By doing so, the dispersed state becomes better, and the weight reduction of the present invention can be realized.
カーボンブラック（Ｄ）のＤＢＰ吸油量は、１００ｍＬ／１００ｇ〜４００ｍＬ／１００ｇであることが好ましく、更には１００ｍＬ／１００ｇ〜２００ｍＬ／１００ｇであることが好ましい。ＤＢＰ吸油量が、１００ｍＬ／１００ｇ〜４００ｍＬ／１００ｇの範囲内であることで、カーボンブラック（Ｄ）のポリオレフィン系樹脂（Ａ）に対する分散性をより向上できる。なおＤＢＰ吸油量とは、空隙容積を測定することでカーボンブラックのストラクチャーを間接的に定量化するもので、ＪＩＳ K ６２１７−４に準拠して測定した数値である。尚、「ＤＢＰ」とは、Ｄｉｂｕｔｙｌｐｈｔａｌａｔｅの略称である。 The amount of DBP oil absorbed by carbon black (D) is preferably 100 mL / 100 g to 400 mL / 100 g, and more preferably 100 mL / 100 g to 200 mL / 100 g. When the amount of DBP oil absorbed is in the range of 100 mL / 100 g to 400 mL / 100 g, the dispersibility of carbon black (D) with respect to the polyolefin resin (A) can be further improved. The DBP oil absorption amount indirectly quantifies the structure of carbon black by measuring the void volume, and is a numerical value measured in accordance with JIS K 6217-4. In addition, "DBP" is an abbreviation for Dibutyl phthalate.
カーボンブラック（Ｄ）の一次粒子径は、０．００５〜１μｍが好ましく、０．０１〜０．２μｍがより好ましい。ここでいう一次粒子径とは、電子顕微鏡等で測定された粒子２０個の平均値である。 The primary particle size of carbon black (D) is preferably 0.005 to 1 μm, more preferably 0.01 to 0.2 μm. The primary particle diameter referred to here is an average value of 20 particles measured by an electron microscope or the like.
市販のカーボンブラックとしては、例えば、ニテロン＃１０、＃２００及び＃３００等の新日化カーボン社製ファーネスブラック；
トーカブラック＃４３００、＃４４００、＃４５００、及び＃５５００等の東海カーボン社製ファーネスブラック；
プリンテックスＬ等のデグサ社製ファーネスブラック；
Ｒａｖｅｎ７０００、５７５０、５２５０、５０００ＵＬＴＲＡIII、５０００ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ＳＣ ＵＬＴＲＡ、９７５ ＵＬＴＲＡ、ＰＵＥＲ ＢＬＡＣＫ１００、１１５、及び２０５等のコロンビヤン社製ファーネスブラック；
＃２３５０、＃２４００Ｂ、＃２６００Ｂ、＃３００５０Ｂ、＃３０３０Ｂ、＃３２３０Ｂ、＃３３５０Ｂ、＃３４００Ｂ、及び＃５４００Ｂ等の三菱化学社製ファーネスブラック；
ＭＯＮＡＲＣＨ１４００、１３００、９００、ＶｕｌｃａｎＸＣ−７２Ｒ、及びＢｌａｃｋＰｅａｒｌｓ２０００等のキャボット社製ファーネスブラック；
Ｅｎｓａｃｏ２５０Ｇ、Ｅｎｓａｃｏ２６０Ｇ、Ｅｎｓａｃｏ３５０Ｇ、及びＳｕｐｅｒＰ−Ｌｉ等のＴＩＭＣＡＬ社製ファーネスブラック；
ケッチェンブラックＥＣ−３００Ｊ、及びＥＣ−６００ＪＤ等のアクゾ社製ケッチェンブラック、
デンカブラックＨＳ−１００、ＦＸ−３５等の電気化学工業社製アセチレンブラック等が挙げられるが、これらに限定されるものではない。
As commercially available carbon black, for example, Furnace Black manufactured by Shin Nikka Carbon Co., Ltd. such as Niteron # 10, # 200 and # 300;
Tokai Carbon Furnace Black such as Talker Black # 4300, # 4400, # 4500, and # 5500;
Furness Black manufactured by Degusa such as Printex L;
Colombian Furnace Black such as Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, Conductex SC ULTRA, 975 ULTRA, PUER BLACK 100, 115, 205;
Mitsubishi Chemical Furnace Black such as # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, and # 5400B;
Cabot Furnace Black such as MONARCH1400, 1300, 900, VulcanXC-72R, and BlackPearls2000;
TIMCAL Furnace Black such as Ensaco250G, Ensaco260G, Ensaco350G, and SuperP-Li;
Akzo's Ketjen Black, such as Ketjen Black EC-300J and EC-600JD,
Examples thereof include acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. such as Denka Black HS-100 and FX-35, but the present invention is not limited thereto.
本発明の導電性樹脂組成物には、必要に応じて、耐酸化安定剤、耐候安定剤、帯電防止剤、染料、顔料、分散剤、カップリング剤、結晶造核剤、樹脂充填材等の添加剤を含んでもよい。 The conductive resin composition of the present invention may contain, if necessary, an oxidation-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a dye, a pigment, a dispersant, a coupling agent, a crystal nucleating agent, a resin filler, and the like. Additives may be included.
本発明の導電性樹脂組成物の製造は、特に限定されるものではない。例えば、樹脂（Ａ）、樹脂（Ｂ）、カーボンナノチューブ（Ｃ）、カーボンブラック（Ｄ）、更に必要に応じて上記添加剤とを混合し、ヘンシェルミキサーやタンブラー、ディスパー等で混合し、ニーダー、ロールミル、スーパーミキサー、ヘンシェルミキサー、シュギミキサー、バーティカルグラニュレーター、ハイスピードミキサー、ファーマトリックス、ボールミル、スチールミル、サンドミル、振動ミル、アトライター、バンバリーミキサーのような回分式混練機、二軸押出機、単軸押出機、ローター型二軸混練機等で混合や溶融混練し、ペレット状、粉体状、顆粒状あるいはビーズ状等の形状の樹脂組成物を得ることができる。本発明では、二軸押出機を用いて溶融混錬することが好ましい。 The production of the conductive resin composition of the present invention is not particularly limited. For example, resin (A), resin (B), carbon nanotube (C), carbon black (D), and if necessary, the above additives are mixed, mixed with a Henshell mixer, tumbler, extruder, etc., and kneader. Roll mills, super mixers, henschel mixers, sugar mixers, vertical granulators, high speed mixers, fur matrices, ball mills, steel mills, sand mills, vibration mills, attritors, batch kneaders such as Banbury mixers, twin-screw extruders, A resin composition having a shape such as pellets, powders, granules or beads can be obtained by mixing or melt-kneading with a single-screw extruder, a rotor-type twin-screw kneader or the like. In the present invention, it is preferable to melt-knead using a twin-screw extruder.
＜成形体＞
本発明の成形体は、本発明の導電性樹脂組成物を成形することで製造することができる。成形時、必要に応じて希釈樹脂（樹脂（Ａ）および樹脂（Ｂ）以外の樹脂）を導電性樹脂組成物に配合してもよい。成形体は、導電性樹脂組成物を通常５０℃〜２００℃に設定した成形機にて溶融混合後に、所望とする成形体の形状に成形し、常温まで冷却して得ることができる。成形体の形状は、板状、棒状、繊維、チューブ、パイプ、ボトル、フィルムなどを得ることができる。
<Molded body>
The molded product of the present invention can be produced by molding the conductive resin composition of the present invention. At the time of molding, a diluted resin (resin other than the resin (A) and the resin (B)) may be blended with the conductive resin composition, if necessary. The molded product can be obtained by melting and mixing the conductive resin composition with a molding machine usually set at 50 ° C. to 200 ° C., molding the molded product into a desired molded product shape, and cooling to room temperature. The shape of the molded product can be plate-shaped, rod-shaped, fiber, tube, pipe, bottle, film or the like.
また、成形方法は、例えば、押出成形、射出成形、ブロー成形、圧縮成形、トランスファー成形、Ｔ−ダイ成形やインフレーション成形のようなフィルム成形、カレンダー成形、紡糸等を用いることができる。 Further, as the molding method, for example, extrusion molding, injection molding, blow molding, compression molding, transfer molding, film molding such as T-die molding and inflation molding, calendar molding, spinning and the like can be used.
成形体を製造する際、導電性樹脂組成物を、溶融混練し、８０℃〜１４０℃で成形することが好ましく、さらには９０℃〜１２０℃で成形することが好ましい。上記の範囲の加工温度（成形温度）であれば、加工温度を低く抑えることができ、ポリオレフィン系樹脂（Ａ）や、樹脂（Ｂ）、カーボンナノチューブ（Ｃ）の劣化を抑制することができ、高い導電性を有する成形体を製造することができる。 When producing the molded product, the conductive resin composition is preferably melt-kneaded and molded at 80 ° C. to 140 ° C., more preferably 90 ° C. to 120 ° C. If the processing temperature (molding temperature) is within the above range, the processing temperature can be suppressed low, and the deterioration of the polyolefin resin (A), the resin (B), and the carbon nanotube (C) can be suppressed. A molded product having high conductivity can be produced.
成形体の用途は、特に限定されるものではないが、半導体を搬送するトレーや半導体を梱包するのに用いられる保護材や袋等に好適に使用することができる。 The use of the molded product is not particularly limited, but it can be suitably used for trays for transporting semiconductors, protective materials and bags used for packing semiconductors, and the like.
以下に、実施例により、本発明をさらに詳細に説明するが、以下の実施例は、本発明を何ら制限するものではない。なお、実施例中、特に断りがない限り、「部」は「質量部」を、「%」は「質量%」を表す。以下に、カーボンナノチューブの製造例について説明する。 Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the present invention in any way. In the examples, unless otherwise specified, "parts" represents "parts by mass" and "%" represents "% by mass". An example of manufacturing carbon nanotubes will be described below.
（製造例１）
＜カーボンナノチューブ（Ｃ１）の作製＞
酢酸コバルト・四水和物２００ｇ及び担持成分としての酢酸マグネシウム・四水和物１７２ｇをビーカーに秤取った。秤取った材料を均一になるまで撹拌した。均一化された材料を耐熱性容器に移し替えた。電気オーブンを用いて、１９０±５℃の温度で３０分、容器内の材料を乾燥させ水分を蒸発させた。その後、乾燥させた材料を乳鉢で粉砕してカーボンナノチューブ合成用触媒(ａ)の前駆体を得た。得られた前駆体１００ｇを耐熱容器に秤取った。前駆体をマッフル炉にて、空気中５００℃±５℃雰囲気下で３０分焼成した。その後、焼成物を乳鉢で粉砕して触媒（ａ）を得た。
さらに、横型反応管の中央部に、カーボンナノチューブ合成用触媒(ａ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。横型反応管は加圧可能であり、かつ外部ヒーターで加熱可能であり、かつ内容積が１０リットルであった。横型反応管にアルゴンガスを注入しながら排気を行うことで、反応管内の空気をアルゴンガスで置換した。置換後の横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、横型反応管内の中心部温度が７００℃になるまで外部ヒーターにて反応管を加熱した。中心部温度が７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入することで、触媒を活性化する処理をした。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入することで、１時間接触反応を行った。反応終了後、反応管内のガスをアルゴンガスで置換することで、反応管内の温度が１００℃以下になるまで反応管を冷却した。冷却後、生成したカーボンナノチューブ（Ｃ１）を採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕するとともにろ過した。
(Manufacturing Example 1)
<Preparation of carbon nanotubes (C1)>
200 g of cobalt acetate / tetrahydrate and 172 g of magnesium acetate / tetrahydrate as a supporting component were weighed in a beaker. The weighed material was stirred until uniform. The homogenized material was transferred to a heat resistant container. Using an electric oven, the material in the container was dried and the water evaporated at a temperature of 190 ± 5 ° C. for 30 minutes. Then, the dried material was pulverized in a mortar to obtain a precursor of the catalyst (a) for synthesizing carbon nanotubes. 100 g of the obtained precursor was weighed in a heat-resistant container. The precursor was calcined in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes. Then, the calcined product was pulverized in a mortar to obtain a catalyst (a).
Further, a quartz glass bakeware sprayed with 1.0 g of a carbon nanotube synthesis catalyst (a) was installed in the central portion of the horizontal reaction tube. The horizontal reaction tube was pressurizable, could be heated by an external heater, and had an internal volume of 10 liters. The air in the reaction tube was replaced with argon gas by exhausting while injecting argon gas into the horizontal reaction tube. The atmosphere in the horizontal reaction tube after the replacement was set to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the temperature at the center of the horizontal reaction tube reached 700 ° C. After the core temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube for 1 minute at a flow rate of 0.1 liter per minute. Then, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to carry out a contact reaction for 1 hour. After completion of the reaction, the reaction tube was cooled until the temperature inside the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes (C1) were collected. The obtained carbon nanotubes were pulverized and filtered with an 80-mesh wire mesh.
（製造例２）
＜カーボンナノチューブ（Ｃ２）の作製＞
水酸化コバルト７４ｇ及び担持成分としての酢酸マグネシウム・四水和物１７２ｇをビーカーに秤取った。秤取った材料を均一になるまで撹拌した。均一化された材料を耐熱性容器に移し替えた。電気オーブンを用いて、１９０±５℃の温度で３０分、容器内の材料を乾燥させ水分を蒸発させた。その後、乾燥させた材料を乳鉢で粉砕してカーボンナノチューブ合成用触媒(ｂ)の前駆体を得た。得られた前駆体１００ｇを耐熱容器に秤取った。前駆体をマッフル炉にて、空気中５００℃±５℃雰囲気下で３０分焼成した。その後、乳鉢で焼成物を粉砕して触媒（ｂ）を得た。
さらに、横型反応管の中央部に、カーボンナノチューブ合成用触媒(ｂ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。横型反応管は加圧可能であり、かつ外部ヒーターで加熱可能であり、かつ内容積が１０リットルであった。横型反応管にアルゴンガスを注入しながら排気を行うことで、反応管内の空気をアルゴンガスで置換した。置換後の横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、横型反応管内の中心部温度が７００℃になるまで外部ヒーターにて反応管を加熱した。中心部温度が７００℃に到達した後、毎分０．１リットルの流速で１分間、水素ガスを反応管内に導入することで、触媒を活性化する処理をした。その後、炭素源としてエチレンガスを毎分１リットルの流速で反応管内に導入することで、２時間接触反応を行った。反応終了後、反応管内のガスをアルゴンガスで置換することで、反応管内の温度が１００℃以下になるまで反応管を冷却した。冷却後、生成したカーボンナノチューブ（Ｃ２）を採取した。得られたカーボンナノチューブは、８０メッシュの金網で粉砕するとともにろ過した。
(Manufacturing Example 2)
<Preparation of carbon nanotubes (C2)>
74 g of cobalt hydroxide and 172 g of magnesium acetate tetrahydrate as a supporting component were weighed in a beaker. The weighed material was stirred until uniform. The homogenized material was transferred to a heat resistant container. Using an electric oven, the material in the container was dried and the water evaporated at a temperature of 190 ± 5 ° C. for 30 minutes. Then, the dried material was pulverized in a mortar to obtain a precursor of the catalyst (b) for carbon nanotube synthesis. 100 g of the obtained precursor was weighed in a heat-resistant container. The precursor was calcined in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes. Then, the calcined product was pulverized in a mortar to obtain a catalyst (b).
Further, a quartz glass bakeware sprayed with 1.0 g of a carbon nanotube synthesis catalyst (b) was installed in the central portion of the horizontal reaction tube. The horizontal reaction tube was pressurizable, could be heated by an external heater, and had an internal volume of 10 liters. The air in the reaction tube was replaced with argon gas by exhausting while injecting argon gas into the horizontal reaction tube. The atmosphere in the horizontal reaction tube after the replacement was set to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the temperature at the center of the horizontal reaction tube reached 700 ° C. After the core temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube for 1 minute at a flow rate of 0.1 liter per minute. Then, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to carry out a contact reaction for 2 hours. After completion of the reaction, the reaction tube was cooled until the temperature inside the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes (C2) were collected. The obtained carbon nanotubes were pulverized and filtered with an 80-mesh wire mesh.
カーボンナノチューブ（Ｃ３）として、ナノシル社製のカーボンナノチューブＮＣ７０００（単に「ＮＣ７０００」と略記することがある）を用いた。以下に、カーボンナノチューブの体積抵抗率、嵩密度、真密度、構造、平均直径、平均アスペクト比の測定方法を示す。 As the carbon nanotube (C3), carbon nanotube NC7000 manufactured by Nanosil Co., Ltd. (sometimes simply abbreviated as “NC7000”) was used. The methods for measuring the volume resistivity, bulk density, true density, structure, average diameter, and average aspect ratio of carbon nanotubes are shown below.
（体積抵抗率）
粉体抵抗システムＭＣＰ−ＰＤ５１（三菱化学アナリティック社製）を用いて体積抵抗率（Ω・ｃｍ）を測定した。具体的にはカーボンナノチューブ粉末を１．２ｇ量り取り、２０ｋＮの荷重時の値を体積抵抗率とした。
(Volume resistivity)
The volume resistivity (Ω · cm) was measured using a powder resistivity system MCP-PD51 (manufactured by Mitsubishi Chemical Analytical Co., Ltd.). Specifically, 1.2 g of carbon nanotube powder was weighed, and the value under a load of 20 kN was taken as the volume resistivity.
（嵩密度）
測定装置としてスコットボリュームメータ（筒井理化学器機社製）を用いて嵩密度を測定した。カーボンナノチューブ粉末を測定装置上部より直円筒容器に流し入れ、山盛りになったところですり切った一定容積の試料質量を測定した。この質量と容器容積の比から下記の式（３）に基づいて算出した。
式（３） 嵩密度（ｇ／ｍＬ）＝
（すり切った一定容積のカーボンナノチューブの質量（ｇ））÷（容器容積（ｍＬ））
(The bulk density)
The bulk density was measured using a Scott volume meter (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) as a measuring device. The carbon nanotube powder was poured into a straight-cylindrical container from the upper part of the measuring device, and the mass of the sample with a constant volume was measured at the heap. It was calculated from the ratio of this mass to the volume of the container based on the following formula (3).
Equation (3) Bulk density (g / mL) =
(Mass (g) of carbon nanotubes with a constant volume worn) ÷ (Container volume (mL))
（真密度）
真密度は、ＪＩＳ−Ｒ７２２２に準拠し、ブタノールを用いたピクノメーター（比重びん）による液相置換法により求めた。
(True density)
The true density was determined by a liquid phase substitution method using a pycnometer (specific gravity bottle) using butanol in accordance with JIS-R7222.
（平均直径）
走査型電子顕微鏡（日本電子（ＪＥＯＬ）社製、ＪＳＭ−６７００Ｍ））を用いて加速電圧５ｋＶにてカーボンナノチューブを観察し、５万倍の画像（画素数１０２４×１２８０）を撮影した（図1ａ等）。次いで、撮影された画像にて任意のカーボンナノチューブ２０個について、各々の短軸長を測定し、それら短軸長の数平均値をカーボンナノチューブの平均直径とした。
(Average diameter)
Carbon nanotubes were observed at an accelerating voltage of 5 kV using a scanning electron microscope (JSM-6700M, manufactured by JEOL), and an image (pixel count 1024 x 1280) of 50,000 times was taken (Fig. 1a). etc). Next, the minor axis lengths of each of the 20 arbitrary carbon nanotubes were measured in the captured image, and the number average value of the minor axis lengths was taken as the average diameter of the carbon nanotubes.
（平均アスペクト比）
上述した平均直径と同様にしてカーボンナノチューブの画像を撮影した。次いで、撮影された画像にて任意のカーボンナノチューブ２０個について、各々の長軸長を測定し、それら長軸長の数平均値をカーボンナノチューブの平均長さとした。下記の式（４）により平均アスペクト比を算出した。
式（４） 平均アスペクト比＝長軸長の数平均値÷平均直径
(Average aspect ratio)
Images of carbon nanotubes were taken in the same manner as the average diameter described above. Next, the major axis lengths of each of the 20 arbitrary carbon nanotubes were measured in the captured image, and the number average value of the major axis lengths was taken as the average length of the carbon nanotubes. The average aspect ratio was calculated by the following formula (4).
Equation (4) Average aspect ratio = number average value of major axis length ÷ average diameter
表１〜表３に、実施例および比較例で使用したポリオレフィン系樹脂（Ａ１）〜（Ａ５）、樹脂（Ｂ１）〜（Ｂ３）、カーボンナノチューブ（Ｃ１）〜（Ｃ３）、カーボンブラック（Ｄ１）〜（Ｄ２）の物性値を示す。 Tables 1 to 3 show the polyolefin resins (A1) to (A5), resins (B1) to (B3), carbon nanotubes (C1) to (C3), and carbon black (D1) used in Examples and Comparative Examples. The physical property values of ~ (D2) are shown.
実施例で使用した原料は、以下のとおりである。
＜ポリオレフィン系樹脂（Ａ）＞
（Ａ１）ＰＥ樹脂１（メタロセン系プラストマー、カーネルＫＳ−２６０、日本ポリエチレン社製）融点：９２℃、真密度：０．９０ｇ／ｍＬ、熱伝導率：０．３２Ｗ／ｍ・Ｋ
（Ａ２）ＰＰ樹脂１（低密度ポリプロピレン、エルモーデュＳ４００、出光興産社製）融点：９３℃、真密度：０．８７ｇ／ｍＬ、熱伝導率：０．１５Ｗ／ｍ・Ｋ
（Ａ３）α―オレフィンＰＥ共重合体樹脂（α−オレフィンコポリマー、タフマーＤＦ−８４０、三井化学社製）融点：６６℃、真密度：０．８８ｇ／ｍＬ、熱伝導率：０．２８Ｗ／ｍ・Ｋ
＜ポリオレフィン系樹脂（Ａ）ではないポリオレフィン系樹脂（Ａ’）＞
（Ａ４）ＰＥ樹脂２（低密度ポリエチレン、ノバテックＬＤ ＬＪ８０２、日本ポリエチレン社製）融点：１０８℃、真密度：０．９２ｇ／ｍＬ、熱伝導率：０．３６Ｗ／ｍ・Ｋ
（Ａ５）ＰＰ樹脂２（ランダムポリプロピレン、プライムポリプロＪ２２６Ｔ、プライムポリマー社製）融点：１４０℃、真密度：０．９１ｇ／ｍＬ、熱伝導率：０．１８Ｗ／ｍ・Ｋ
The raw materials used in the examples are as follows.
<Polyolefin resin (A)>
(A1) PE resin 1 (metallocene plastomer, kernel KS-260, manufactured by Japan Polyethylene Corporation) Melting point: 92 ° C., true density: 0.90 g / mL, thermal conductivity: 0.32 W / m · K
(A2) PP resin 1 (low density polypropylene, Elmodu S400, manufactured by Idemitsu Kosan Co., Ltd.) Melting point: 93 ° C., true density: 0.87 g / mL, thermal conductivity: 0.15 W / m · K
(A3) α-olefin PE copolymer resin (α-olefin copolymer, Toughmer DF-840, manufactured by Mitsui Chemicals, Inc.) Melting point: 66 ° C., true density: 0.88 g / mL, thermal conductivity: 0.28 W / m・ K
<Polyolefin-based resin (A') that is not polyolefin-based resin (A)>
(A4) PE resin 2 (low density polyethylene, Novatec LD LJ802, manufactured by Japan Polyethylene Corporation) Melting point: 108 ° C., true density: 0.92 g / mL, thermal conductivity: 0.36 W / m · K
(A5) PP resin 2 (random polypropylene, prime polypro J226T, manufactured by Prime Polymer Co., Ltd.) Melting point: 140 ° C., true density: 0.91 g / mL, thermal conductivity: 0.18 W / m · K
＜樹脂（Ｂ）＞
（Ｂ１）ＥＭＡ樹脂（エチレン・アクリル酸メチル共重合体、ロトリル２４ＭＡ００５、アルケマ社製）アクリル酸メチル含有量：２４％ 融点：７０℃、真密度：０．９４ｇ／ｍＬ、熱伝導率：０．２１Ｗ／ｍ・Ｋ
（Ｂ２）ＥＢＡ樹脂（エチレン・アクリル酸ブチル共重合体、ロトリル１７ＢＡ０７Ｎ、アルケマ社製）アクリル酸ブチル含有量：１７％ 融点：９１℃、真密度：０．９３ｇ／ｍＬ、熱伝導率：０．１９Ｗ／ｍ・Ｋ
（Ｂ３）ＥＶＡ樹脂（エチレン・酢酸ビニル共重合体、エバフレックスＶ５２３、三井・デュポン社製）酢酸ビニル含有量：３３％ 融点：６３℃、真密度：０．９６ｇ／ｍＬ、熱伝導率：０．１７Ｗ／ｍ・Ｋ
<Resin (B)>
(B1) EMA resin (ethylene / methyl acrylate copolymer, Rotril 24MA005, manufactured by Arkema) Methyl acrylate content: 24% Melting point: 70 ° C., true density: 0.94 g / mL, thermal conductivity: 0. 21W / m ・ K
(B2) EBA resin (ethylene / butyl acrylate copolymer, Rotril 17BA07N, manufactured by Alchema) Butyl acrylate content: 17% Melting point: 91 ° C., true density: 0.93 g / mL, thermal conductivity: 0. 19W / m ・ K
(B3) EVA resin (ethylene-vinyl acetate copolymer, EVAFlex V523, manufactured by Mitsui-Dupont) Vinyl acetate content: 33% Melting point: 63 ° C., true density: 0.96 g / mL, thermal conductivity: 0 .17W / m ・ K
＜カーボンナノチューブ（Ｃ）＞
（Ｃ１）製造例１のカーボンナノチューブ
（Ｃ２）製造例２のカーボンナノチューブ
（Ｃ３）ＮＣ７０００（ナノシル社製）
<Carbon nanotube (C)>
(C1) Carbon Nanotube of Production Example 1 (C2) Carbon Nanotube of Production Example 2 (C3) NC7000 (manufactured by Nanosil)
＜カーボンブラック（Ｄ）＞
（Ｄ１）ＥＮＳＡＣＯ２５０Ｇ（ファーネスブラック粉、ＤＢＰ吸油量：１９０ｍＬ／１００ｇ、真密度：１．８１ｇ／ｍＬ、イメリス社製）
（Ｄ２）ニテロン♯１０（ファーネスブラック粉、ＤＢＰ吸油量：１２８ｍＬ／１００ｇ、真密度：１．８９ｇ／ｍＬ、新日化カーボン社製）
<Carbon black (D)>
(D1) ENSACO250G (Furness black powder, DBP oil absorption: 190 mL / 100 g, true density: 1.81 g / mL, manufactured by Imerys)
(D2) Niteron # 10 (Furness black powder, DBP oil absorption: 128 mL / 100 g, true density: 1.89 g / mL, manufactured by Shin Nikka Carbon Co., Ltd.)
［実施例１］
（導電性樹脂組成物１の製造）
ＰＥ樹脂１（Ａ１）４５部およびＥＭＡ樹脂（Ｂ１）４５部、カーボンナノチューブ（Ｃ１）５部、カーボンブラック（Ｄ１）５部をスーパーミキサー（カワタ社製）に投入し、２５℃にて３分間撹拌して混合物を得た。次いで前記混合物を二軸押出し機(日本プラコン社製)に投入し、２００℃で押し出し、ペレタイザーでカットすることで導電性樹脂組成物１を得た。
[Example 1]
(Manufacture of Conductive Resin Composition 1)
45 parts of PE resin 1 (A1), 45 parts of EMA resin (B1), 5 parts of carbon nanotubes (C1), and 5 parts of carbon black (D1) were put into a super mixer (manufactured by Kawata Co., Ltd.) for 3 minutes at 25 ° C. The mixture was obtained by stirring. Next, the mixture was put into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.), extruded at 200 ° C., and cut with a pelletizer to obtain a conductive resin composition 1.
（成形体１の作成）
導電性樹脂組成物１を、射出成形機（東芝機械社製ＩＳ−１００Ｆ型）を用いて１４０℃で射出成形を行い、縦３０ｍｍ×横４０ｍｍ×高さ３ｍｍの直方体の成形体１を作成した。
(Creation of molded body 1)
The conductive resin composition 1 was injection-molded at 140 ° C. using an injection molding machine (IS-100F type manufactured by Toshiba Machine Co., Ltd.) to prepare a rectangular parallelepiped molded body 1 having a length of 30 mm, a width of 40 mm, and a height of 3 mm. ..
＜成形体の体積抵抗率＞
抵抗率計「ロレスタＧＰ」（ロレスタＧＰ ＭＣＰ−Ｔ６１０型抵抗率計、ＪＩＳ−Ｋ７１９４準拠、４端子４探針法定電流印加方式、三菱化学アナリテック社製）（０．５ｃｍ間隔の４端子プローブ）を用い、成形体の体積抵抗率（Ω・ｃｍ）を測定した。
<Volume resistivity of molded product>
Resistor meter "Loresta GP" (Loresta GP MCP-T610 type resistivity meter, JIS-K7194 compliant, 4-terminal 4-probe method, Mitsubishi Chemical Analytech Co., Ltd.) (4-terminal probe at 0.5 cm intervals) The volume resistivity (Ω · cm) of the molded product was measured using.
＜成形体の熱伝導率＞
ホットディスク法熱物性測定装置（ＴＰＳ−５００ 京都電子工業製）を使用して、直径７ｍｍφのセンサーを用いて、熱伝導率（単位：Ｗ／ｍ・Ｋ）を測定した。
<Thermal conductivity of the molded product>
The thermal conductivity (unit: W / m · K) was measured using a sensor having a diameter of 7 mmφ using a hot disk method thermophysical property measuring device (TPS-500 manufactured by Kyoto Denshi Kogyo).
＜成形体の外観評価＞
成形体をビデオマイクロスコープ「ＶＨＸ−９００」（キーエンス社製）を用いて倍率５００倍にて表面観察を行い、成形体表面上の異物の数を計測し、下記の基準にて評価した。異物の数が少ないほど良好である。
○：５個未満（良好）
△：５個以上、１０個未満（使用可能）
×：１０個以上（不良）
<Appearance evaluation of molded product>
The surface of the molded product was observed using a video microscope "VHX-900" (manufactured by KEYENCE CORPORATION) at a magnification of 500 times, the number of foreign substances on the surface of the molded product was measured, and evaluation was performed according to the following criteria. The smaller the number of foreign substances, the better.
◯: Less than 5 (good)
Δ: 5 or more and less than 10 (usable)
×: 10 or more (defective)
［実施例２〜６］および［比較例１〜６］
（導電性樹脂組成物２〜１２の製造）
導電性樹脂組成物１のポリオレフィン系樹脂、カーボンナノチューブ及びカーボンブラックを、表５および表６の原料と配合量に変更した以外は、実施例１と同様な方法により、それぞれ導電性樹脂組成物２〜１２を得た。尚、表５および表６中の数値は、質量部を表し、空欄は使用していないことを表す。
[Examples 2 to 6] and [Comparative Examples 1 to 6]
(Manufacture of Conductive Resin Compositions 2-12)
The conductive resin composition 2 was produced by the same method as in Example 1 except that the polyolefin resin, carbon nanotubes, and carbon black of the conductive resin composition 1 were changed to the raw materials and blending amounts shown in Tables 5 and 6. ~ 12 was obtained. The numerical values in Tables 5 and 6 represent parts by mass, and blanks indicate that they are not used.
（成形体２〜１２の製造）
導電性樹脂組成物１を導電性樹脂組成物２〜１２にそれぞれ変更した以外は、実施例１と同様にして、成形体を作成し、体積抵抗率、熱伝導率及び比重の測定と外観評価を行った。評価結果を表７に示す。なお、実施例６にて作成した成形体６については、射出成形温度を１４０℃から１００℃に変更して射出成形を行った。
(Manufacturing of molded products 2 to 12)
A molded body was prepared in the same manner as in Example 1 except that the conductive resin composition 1 was changed to the conductive resin compositions 2 to 12, and the volume resistivity, thermal conductivity and specific gravity were measured and the appearance was evaluated. Was done. The evaluation results are shown in Table 7. The molded body 6 produced in Example 6 was injection-molded by changing the injection molding temperature from 140 ° C. to 100 ° C.
表７の結果から実施例１〜６の成形体１〜６は、比較例１〜６の成形体７〜１２よりも、低い体積抵抗率および良好な外観を示すとともに高い熱伝導性を示し、さらに軽量な成形体となり、良好な結果が得られることが明らかとなった。 From the results in Table 7, the molded products 1 to 6 of Examples 1 to 6 showed lower volume resistivity and better appearance and higher thermal conductivity than the molded products 7 to 12 of Comparative Examples 1 to 6. It was clarified that the molded product was lighter and good results were obtained.
［実施例２１］
＜導電性シートの作成＞
導電性樹脂組成物１を、Ｔ−ダイ押出機で１２０℃にて押出成形し、厚さ５００μｍの導電性シート１を作製した。
[Example 21]
<Creation of conductive sheet>
The conductive resin composition 1 was extruded at 120 ° C. with a T-die extruder to prepare a conductive sheet 1 having a thickness of 500 μm.
＜導電性シートの表面抵抗率＞
抵抗率計「ロレスタＧＰ」（０．５ｃｍ間隔の４端子プローブ）を用い、導電性シートの表面抵抗率（Ω／□）を測定した。
<Surface resistivity of conductive sheet>
The surface resistivity (Ω / □) of the conductive sheet was measured using a resistivity meter “Loresta GP” (4-terminal probe with 0.5 cm intervals).
＜導電性シートの熱伝導率＞
ホットディスク法熱物性測定装置（ＴＰＳ−５００ 京都電子工業製）を使用して、直径７ｍｍφのセンサーを用いて、熱伝導率（単位：Ｗ／ｍ・Ｋ）を測定した。
<Thermal conductivity of conductive sheet>
The thermal conductivity (unit: W / m · K) was measured using a sensor having a diameter of 7 mmφ using a hot disk method thermophysical property measuring device (TPS-500 manufactured by Kyoto Denshi Kogyo).
[実施例２２〜２６]、［比較例２１〜２６］
導電性樹脂組成物を変更した以外は、実施例２１と同様にして、導電性樹脂組成物２〜１２で導電性シート２〜１２を作成し、表面抵抗率、熱伝導率および比重を測定した。評価結果を表８に示す。
[Examples 22 to 26], [Comparative Examples 21 to 26]
Conductive sheets 2 to 12 were prepared from the conductive resin compositions 2 to 12 in the same manner as in Example 21 except that the conductive resin composition was changed, and the surface resistivity, thermal conductivity and specific gravity were measured. .. The evaluation results are shown in Table 8.
表８の結果から実施例２１〜２６の導電性シート１〜６は、比較例２１〜２６の導電性シート７〜１２よりも、低い表面抵抗率を示すとともに高い熱伝導性を示し、さらに軽量な導電シートとなり、良好な結果が得られることが明らかとなった。 From the results in Table 8, the conductive sheets 1 to 6 of Examples 21 to 26 show lower surface resistivity, higher thermal conductivity, and lighter weight than the conductive sheets 7 to 12 of Comparative Examples 21 to 26. It was clarified that a good conductive sheet was obtained and good results were obtained.
Claims (5)
前記樹脂（Ｂ）は、オレフィン・（メタ）アクリル酸エステル共重合体およびオレフィン・脂肪族カルボン酸ビニル共重合体の少なくともいずれかであって、
前記カーボンナノチューブ（Ｃ）の嵩密度が、０．００５〜０．１０ｇ／ｍＬである導電性樹脂組成物。 Mp temperatures above 55 ℃ below 100 ° C., and a true density of 0.92 g / mL or less is a polyolefin resin (A) (excluding the case where the resin (B)), dendritic fat (B), carbon nanotubes (C) And contains carbon black (D)
The resin (B) is at least one of an olefin / (meth) acrylic acid ester copolymer and an olefin / aliphatic vinyl acetate copolymer.
A conductive resin composition having a bulk density of the carbon nanotubes (C) of 0.005 to 0.10 g / mL.
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