CN115916905A - Thermoplastic resin composition, part and method for producing same, and method for expressing conductivity of thermoplastic resin composition - Google Patents
Thermoplastic resin composition, part and method for producing same, and method for expressing conductivity of thermoplastic resin composition Download PDFInfo
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- CN115916905A CN115916905A CN202180047060.7A CN202180047060A CN115916905A CN 115916905 A CN115916905 A CN 115916905A CN 202180047060 A CN202180047060 A CN 202180047060A CN 115916905 A CN115916905 A CN 115916905A
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- thermoplastic resin
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- resin composition
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 95
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000006229 carbon black Substances 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- 238000004898 kneading Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 6
- 238000013329 compounding Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 84
- 239000011347 resin Substances 0.000 description 84
- 229920001707 polybutylene terephthalate Polymers 0.000 description 29
- 229920006324 polyoxymethylene Polymers 0.000 description 29
- -1 Polyoxymethylene Polymers 0.000 description 28
- 239000004734 Polyphenylene sulfide Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229920000069 polyphenylene sulfide Polymers 0.000 description 12
- 229930040373 Paraformaldehyde Natural products 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DCTMXCOHGKSXIZ-UHFFFAOYSA-N (R)-1,3-Octanediol Chemical compound CCCCCC(O)CCO DCTMXCOHGKSXIZ-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical group C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920013633 Fortron Polymers 0.000 description 1
- 239000004738 Fortron® Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
A thermoplastic resin composition obtained by compounding at least a thermoplastic resin, a carbon nanostructure, graphene or a BET specific surface area of 400m 2 And/g or more of carbon black, wherein the amount of the carbon nanostructure or the carbon black is 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of the thermoplastic resin, and the total amount of the carbon nanostructure and the graphene is more than 0.5 parts by mass and 2.5 parts by mass or less.
Description
Technical Field
The present invention relates to a thermoplastic resin composition, a member molded from the thermoplastic resin composition, a method for producing the member, and a method for expressing the conductivity of the thermoplastic resin composition.
Background
Polyoxymethylene resins (hereinafter also referred to as "POM resins") are widely used as process plastics because of their excellent physical and mechanical properties, chemical resistance, and sliding properties. However, POM resins are poor in electrical conductivity because they are electrical insulators as in most other resins. It is known that a conductive filler such as carbon black or carbon fiber is added to a POM resin to impart conductivity thereto (see patent documents 1 and 2). In this way, conductivity can be imparted by adding a conductive filler to the POM resin, and this is effective not only for the purpose of forming a conductive member but also for the addition of a conductive filler in antistatic properties.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 1978846
Patent document 2: japanese patent application laid-open No. 2004-526596
Disclosure of Invention
Problems to be solved by the invention
However, the present inventors confirmed that impact resistance and tensile strain at break are poor when carbon black or carbon fiber is added as a conductive filler to a POM resin composition. That is, although electrical conductivity can be imparted by adding carbon black or carbon fibers, there is a problem that impact resistance and tensile strain at break are greatly reduced. Such problems also occur in thermoplastic resin compositions including thermoplastic resins other than POM resins.
The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to provide a thermoplastic resin composition, a member and a method for producing the same, which are imparted with electrical conductivity without greatly lowering impact resistance and tensile strain at break, and a method for expressing the electrical conductivity of the thermoplastic resin composition.
Means for solving the problems
An aspect of the present invention to solve the above problems is as follows.
(1) A thermoplastic resin composition obtained by blending at least a thermoplastic resin, a carbon nanostructure, graphene or a thermoplastic resin having a BET specific surface area of 400m 2 A carbon black in an amount of at least one gram,
the amount of the carbon nanostructures mixed is 0.5 parts by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the total of the amount of the carbon nanostructures mixed and the amount of the graphene or the carbon black mixed is more than 0.5 parts by mass and 2.5 parts by mass or less.
(2) A member obtained by using the thermoplastic resin composition of the above (1).
(3) A method of manufacturing an electrically conductive member, comprising:
a step of preparing a thermoplastic resin composition in which the amount of carbon nanostructures mixed is 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of a thermoplastic resin, and the amount of the carbon nanostructures mixed and graphene or a BET specific surface area is 400m 2 At least one of a thermoplastic resin, a carbon nanostructure, graphene, and carbon black is melt-kneaded so that the total amount of carbon black is more than 0.5 parts by mass and not more than 2.5 parts by mass; and
and a step of molding the thermoplastic resin composition into a predetermined shape.
(4) A method for expressing the conductivity of a thermoplastic resin composition, which is a method for expressing the conductivity relative to the thermoplastic resin composition,
by mixing the amount of the carbon nano structure with the amount of the graphene or the BET specific surface area of 400m in an amount of 0.5 part by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin 2 At least a thermoplastic resin, a carbon nanostructure, graphene, or the carbon black is melt-kneaded in such a manner that the total amount of carbon black mixed in terms of/g is greater than 0.5 parts by mass and not more than 2.5 parts by mass.
Effects of the invention
According to the present invention, it is possible to provide a thermoplastic resin composition, a member and a method for producing the same, which are imparted with electrical conductivity without significantly reducing impact resistance and tensile strain at break, and a method for expressing the electrical conductivity of the thermoplastic resin composition.
Drawings
Fig. 1 is a schematic view showing a carbon nanostructure, in which (a) shows a state before melt-kneading, (B) shows a state immediately after start of melt-kneading, and (C) shows a state after melt-kneading.
FIG. 2 shows (A) a top view and (B) a rear view of a test piece used for measuring surface resistivity and volume resistivity in the examples.
Detailed Description
< thermoplastic resin composition >
The thermoplastic resin composition of the present embodiment is characterized by comprising at least a thermoplastic resin, a carbon nanostructure, graphene or a thermoplastic resin having a BET specific surface area of 400m 2 And/g or more of carbon black (hereinafter also referred to as "specific carbon black") in an amount of 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of the thermoplastic resin, and the sum of the amount of the carbon nanostructure and the amount of the graphene or the specific carbon black is 0.5 parts by mass or more and 2.5 parts by mass or less.
As the thermoplastic resin composition of the present embodiment, CNS, graphene, or a specific carbon black is mixed with a thermoplastic resin under a predetermined condition and melt-kneaded, whereby electrical conductivity is imparted without a significant decrease in impact resistance and tensile strain at break.
Hereinafter, each component of the thermoplastic resin composition of the present embodiment will be described.
[ thermoplastic resin ]
In the present embodiment, examples of the crystalline thermoplastic resin as the thermoplastic resin include a polyoxymethylene resin (hereinafter, also referred to as "POM resin"), a polyarylene sulfide resin (hereinafter, also referred to as "PAS resin"), a polybutylene terephthalate resin (hereinafter, also referred to as "PBT resin"), a polyethylene terephthalate resin, a polyamide resin, and the like. Among them, the thermoplastic resin is preferably one selected from the group consisting of a polyoxymethylene resin, a polyarylene sulfide resin, a polybutylene terephthalate resin, a polyethylene terephthalate resin, and a polyamide resin. The following description will be made by citing POM resin, PAS resin, and PBT resin as thermoplastic resin, but the present embodiment is not limited to this.
(polyoxymethylene resin (POM resin))
The polyformaldehyde resin is oxymethylene (-CH) 2 O-) is a main structural unit, including homo-polyformaldehyde and co-polyformaldehyde, which can be any one of them. The copolyformals contain, in addition to oxymethylene as a main repeating unit, a small amount of other structural units, for example, comonomer units such as ethylene oxide, 1, 3-dioxolane, and 1, 4-butanediol formal. In addition, as the other polymers, a terpolymer and a block polymer are also available, but any of them may be used. The molecule of the polyoxymethylene resin may have not only a linear structure but also a branched or crosslinked structure, and may be a known modified polyoxymethylene into which another organic group is introduced. The polymerization degree of the polyoxymethylene resin is not particularly limited as long as it has melt-moldability (for example, melt Flow Rate (MFR) at 190 ℃ under a load of 2160g is 1.0g/10 min or more and 100g/10 min or less).
The polyoxymethylene resin can be produced by a known production method.
(polybutylene terephthalate resin (PBT resin))
The PBT resin at least contains terephthalic acid or an ester-forming derivative thereof (C) 1-6 Alkyl ester, acid halide, etc.) and a diol component containing at least an alkylene glycol having 4 carbon atoms (1, 4-butanediol) or an ester-forming derivative thereof (an acetylate, etc.). The PBT resin is not limited to the homopolybutylene terephthalate, and may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
The amount of terminal carboxyl groups in the PBT resin is not particularly limited as long as the effects of the thermoplastic resin of the present embodiment are not impaired. The amount of terminal carboxyl groups in the PBT resin is preferably not more than 30meq/kg, more preferably not more than 25 meq/kg.
The intrinsic viscosity of the PBT resin is preferably 0.65 to 1.20dL/g. When a PBT resin having an intrinsic viscosity in the above-mentioned range is used, the obtained resin composition is excellent in mechanical properties and flowability. On the other hand, when the intrinsic viscosity is less than 0.65dL/g, excellent mechanical properties cannot be obtained, and when it exceeds 1.20dL/g, excellent fluidity cannot be obtained in some cases.
Further, the PBT resin having an intrinsic viscosity within the above range may be blended with a PBT resin having a different intrinsic viscosity to adjust the intrinsic viscosity. For example, a PBT resin having an inherent viscosity of 0.8dL/g can be prepared by mixing a PBT resin having an inherent viscosity of 0.9dL/g with a PBT resin having an inherent viscosity of 0.7 dL/g. The intrinsic viscosity of the PBT resin is, for example, a value measured under a condition of a temperature of 35 ℃ in o-chlorophenol.
In the PBT resin, examples of the dicarboxylic acid component (comonomer component) other than terephthalic acid and its ester-forming derivative include C such as isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, and 4,4' -diphenyletherdicarboxylic acid 8-14 The aromatic dicarboxylic acid of (1); c of succinic acid, adipic acid, azelaic acid, sebacic acid, etc 4-16 Alkane dicarboxylic acids of (a); c of cyclohexanedicarboxylic acid or the like 5-10 Cycloalkanedicarboxylic acids of (a); ester-forming derivatives (C) of these dicarboxylic acid components 1-6 Alkyl ester derivatives of (a), acid halides, etc.). These dicarboxylic acid components may be used alone or in combination of 2 or more.
Among these dicarboxylic acid components, C such as isophthalic acid is more preferable 8-12 And C of an aromatic dicarboxylic acid such as adipic acid, azelaic acid and sebacic acid 6-12 An alkane dicarboxylic acid.
Examples of the diol component (comonomer component) other than 1, 4-butanediol in the PBT resin include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, and 1, 6-hexanediolC of alcohol, neopentyl glycol, 1, 3-octanediol, etc 2-10 The alkylene glycol of (4); polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, and dipropylene glycol; alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol a; aromatic diols such as bisphenol a and 4,4' -dihydroxybiphenyl; bisphenol A C such as bisphenol A ethylene oxide 2 mol adduct and bisphenol A propylene oxide 3 mol adduct 2-4 Alkylene oxide adducts of (a); or ester-forming derivatives (acetylates, etc.) of these diols. These diol components may be used alone or in combination of 2 or more.
Among these diol components, C such as ethylene glycol and 1, 3-propanediol is more preferable 2-6 And a polyoxyalkylene glycol such as diethylene glycol, or an alicyclic glycol such as cyclohexanedimethanol.
Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the diol component include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 4-carboxy-4' -hydroxybiphenyl; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; c of propiolactone, butyrolactone, valerolactone, caprolactone (. Epsilon. -caprolactone, etc.), etc 3-12 A lactone; ester-forming derivatives (C) of these comonomer components 1-6 Alkyl ester derivatives, acid halides, acetylates, etc.).
(polyarylene sulfide resin (PAS resin))
PAS resins are characterized by excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties, and by good processability.
The PAS resin is a polymer compound mainly composed of- (Ar-S) - (wherein Ar is an arylene group) as a repeating unit, and a PAS resin having a generally known molecular structure can be used in the present embodiment.
Examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p '-diphenylene sulfone group, p' -biphenylene, p '-diphenylene ether group, p' -diphenylene carbonyl group, and naphthyl group. The PAS resin may be a homopolymer composed of only the above repeating units, and may be a copolymer including different kinds of repeating units described below in terms of processability and the like.
As the homopolymer, a polyphenylene sulfide resin (hereinafter, also referred to as "PPS resin") having a p-phenylene sulfide group as a repeating unit, in which a p-phenylene group is used as an arylene group, can be preferably used. In addition, as the copolymer, can use in the arylene composition composed of aromatic sulfide groups of different 2 or more combinations, but especially preferably use contains p-phenylene sulfide and m-phenylene sulfide group combination. Among them, a copolymer containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide group is preferable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties. Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization of a monomer mainly composed of a bifunctional halogenated aromatic compound can be particularly preferably used. In addition, the PAS resin used in the present embodiment may be used by mixing different PAS resins having a molecular weight of 2 or more.
In addition to the PAS resin having a linear structure, there are also included a polymer partially having a branched structure or a crosslinked structure by using a small amount of a monomer such as a polyhalogenated aromatic compound having 3 or more halogen substituents in the polycondensation, and a polymer having a low molecular weight linear structure which is heated at a high temperature in the presence of oxygen or the like and is increased in melt viscosity by oxidative crosslinking or thermal crosslinking to improve moldability.
The melt viscosity (310 ℃ C. Shear rate 1200 sec) of the PAS resin as the base resin used in the present embodiment -1 ) Preferably, 5 to 500 pas is used, including the case of the above-mentioned mixed system.
[ Carbon Nanostructures (CNS) ]
As described above, the thermoplastic resin composition of the present embodiment is obtained by mixing graphene together with a thermoplastic resin CNS under predetermined conditions and melt-kneading the mixture, whereby the mixture interacts with the graphene and specific carbon black used together, and thereby conductivity is imparted to the thermoplastic resin composition without reducing impact resistance and tensile strain at break. The CNS used in the present embodiment is a structure contained in a state where a plurality of carbon nanotubes are bonded, and the carbon nanotubes are bonded to other carbon nanotubes by a branched bond or a crosslinked structure. Details of such CNS are described in U.S. patent application publication No. 2013-0071565, U.S. patent No. 9,113,031, U.S. patent No. 9,447,259, and U.S. patent No. 9,111,658.
The morphology of CNS will be described with reference to the accompanying drawings. Fig. 1 schematically shows CNS used in the present embodiment, (a) shows a state before melt-kneading with a thermoplastic resin, (B) shows a state immediately after start of melt-kneading, and (C) shows a state after melt-kneading. As shown in fig. 1 (a), CNS10 before melt kneading exhibits a structure in which a plurality of branched carbon nanotubes 12 are entangled and bonded. When CNS10 is put into thermoplastic resin 20 and melt-kneaded, a plurality of CNS10 are cut as shown in fig. 1 (B). When the melt kneading is performed, the CNS10 is further cut, and 1 of the carbon nanotubes 12 are in a state of being in contact with each other via the contact 14 as shown in fig. 1 (C). That is, in the state of fig. 1 (C), the carbon nanotubes 12 in the thermoplastic resin are in a state of being in contact with each other in a large range to form a conductive path, and thus the conductivity is expressed. Further, it is considered that since the carbon nanotubes 12 are irregularly wound to form a three-dimensional mesh structure, the reduction of impact resistance and tensile strain at break can be suppressed.
As described above, by mixing the CNS resin composition with the thermoplastic resin composition, electrical conductivity can be imparted to the CNS resin composition without significantly reducing impact resistance and tensile strain at break. That is, expression of such effects CNS alone can also achieve expression of such effects. However, in the present embodiment, by using both CNS and graphene or specific carbon black, the amount of expensive CNS can be reduced, and the above-described effects can be achieved at a lower cost.
The CNS used in the present embodiment may be commercially available. For example, ATHLOS 200 and ATHLOS 100 manufactured by CABOT corporation can be used.
In the thermoplastic resin composition of the present embodiment, CNS is contained in an amount of 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of the thermoplastic resin. When the content of CNS is less than 0.5 parts by mass, the electrical conductivity is poor, and when it exceeds 2.0 parts by mass, the impact resistance and the tensile strain at break are lowered. The content of CNS is preferably 0.6 to 1.8 parts by mass, and more preferably 0.7 to 1.5 parts by mass.
[ graphene ]
Graphene is sp 2 A plate-like substance having a thickness of 1atom of carbon atoms and having bonded carbon atoms arranged in a hexagonal honeycomb lattice. In the present embodiment, the graphene may be one of single-layer graphene and multi-layer graphene. Alternatively, graphene derivatives may also be used.
In addition, although graphene may include carbon nanotubes and fullerenes in a broad sense, this embodiment does not include these.
The size of graphene is preferably 5 to 100 μm in terms of reduction in impact resistance and tensile elongation, and the 50% particle diameter (D50) measured by a laser diffraction/scattering method.
[ BET specific surface area 400m 2 Carbon black of more than g]
The carbon black has a BET specific surface area of 400m 2 Since carbon black having a high electrical conductivity per gram or more can be used together with the CNS, as with graphene. In contrast, the BET specific surface area is less than 400m 2 The carbon black/g has low conductivity, and thus, it is necessary to increase the amount of the carbon black to be mixed in order to sufficiently secure the conductivity, and thus, it is impossible to suppress the reduction of impact resistance and tensile strain at break. The BET specific surface area is preferably 500m 2 More preferably 600 m/g or more 2 (ii) at least g, the upper limit is not particularly limited, but is 2000m 2 And about/g.
Further, the BET specific surface area can be measured in accordance with ASTM D4820.
As the specific carbon Black, ketjen Black EC300J (BET specific surface area: 800 m), manufactured by lion corporation, is mentioned 2 /g), ketjen Black EC600JD (BET specific surface area: 1270m 2 ,/g), etc.
In the present embodiment, the amount of CNS is 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of the thermoplastic resin, and the total amount of CNS and graphene or specific carbon black is more than 0.5 parts by mass and 2.5 parts by mass or less.
When the total amount of the CNS and graphene or the specific carbon black is 0.5 parts by mass or less, the electrical conductivity is poor, and when it exceeds 2.5 parts by mass, the impact resistance and the tensile strain at break are greatly reduced. The total amount of these components is preferably 1.0 to 2.4 parts by mass, more preferably 1.2 to 2.2 parts by mass.
[ other ingredients ]
Various stabilizers selected as necessary may be mixed in the thermoplastic resin composition of the present embodiment. The stabilizer used in this case may be any 1 or 2 or more of a hindered phenol compound, a nitrogen-containing compound, a hydroxide of an alkali or alkaline earth metal, an inorganic salt, a carboxylate, and the like. Further, if necessary, 1 or 2 or more kinds of common additives to the thermoplastic resin, for example, a colorant such as a dye or a pigment, a lubricant, a nucleating agent, a release agent, an antistatic agent, a surfactant, an organic polymer material, an inorganic or organic fibrous, powdery or plate-like filler, and the like may be added as long as the above effects are not impaired.
The method for producing a molded article using the thermoplastic resin composition of the present embodiment is not particularly limited, and a known method can be used. For example, the plastic resin composition of the present embodiment can be produced by charging the plastic resin composition into an extruder, melt-kneading the composition into pellets, and charging the pellets into an injection molding machine equipped with a predetermined metal mold, followed by injection molding.
The thermoplastic resin composition of the present embodiment described above may be a conductive member described later, or may be a molded article having an antistatic function.
< parts >
The member of the present embodiment is formed by molding the thermoplastic resin composition of the present embodiment described above. Therefore, the member of the present embodiment has conductivity, and sufficient impact resistance and tensile strain at break, as in the thermoplastic resin composition of the present embodiment.
The member of the present embodiment can be suitably used for, for example, automobile components such as fuel pipe components and electric and electronic components such as printer components.
The member of the present embodiment can be manufactured by the method for manufacturing a conductive member of the present embodiment described below.
< method for manufacturing conductive Member >
The method for manufacturing a conductive member according to the present embodiment includes: a step of preparing a thermoplastic resin composition in which the amount of the carbon nanostructures to be mixed is 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of the thermoplastic resin, and the amount of the carbon nanostructures to be mixed and graphene or a BET specific surface area is 400m 2 At least a thermoplastic resin, a carbon nanostructure, graphene, or the carbon black is melt-kneaded so that the total amount of the carbon black is more than 0.5 parts by mass and not more than 2.5 parts by mass (hereinafter referred to as "step a"); and a step of molding the resin composition into a predetermined shape (hereinafter referred to as "step B").
The respective steps will be explained below.
[ Process A ]
In step a, a thermoplastic resin composition is prepared by melt-kneading at least a thermoplastic resin, a carbon nanostructure, graphene, or a specific carbon black in such a manner that the amount of the carbon nanostructure mixed is 0.5 parts by mass or more and less than 2.0 parts by mass relative to 100 parts by mass of the thermoplastic resin, and the total amount of the carbon nanostructure mixed and the amount of the graphene or the specific carbon black mixed is more than 0.5 parts by mass and 2.5 parts by mass or less. The preferred components of the respective components in the thermoplastic resin composition, their preferred contents, and other components are as described above. The POM resin composition is obtained by melt-kneading the above components and, if necessary, other components according to a conventional method. For example, the thermoplastic resin composition of the present embodiment can be obtained by charging the thermoplastic resin composition into an extruder, melt-kneading the composition, and granulating the composition. At least 1 of CNS, graphene and specific carbon black is put in advance as a master batch, and in the case of adding them, the master batch can be used.
The master batch is a previously prepared thermoplastic resin composition containing CNS at a high concentration.
In addition, when melt-kneading is performed, the CNS is sufficiently cut so as to exhibit the effects of conductivity, impact resistance and tensile strain at break, with preference given to the temperature, shear rate and time at the time of melt-kneading.
[ Process B ]
In step B, the thermoplastic resin composition is molded into a predetermined shape. For example, the pellets obtained as described above are put into an injection molding machine equipped with a predetermined metal mold and injection molded.
As described above, the conductive member having conductivity and sufficient impact resistance and tensile strain at break can be manufactured by the manufacturing method of the present embodiment.
< method for expressing conductivity of thermoplastic resin composition >
The method for expressing the conductivity of the thermoplastic resin composition of the present embodiment is a method for expressing the conductivity with respect to the thermoplastic resin composition, and is characterized by comprising mixing the carbon nanostructures in an amount of 0.5 parts by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and mixing the amount of the carbon nanostructures with graphene or a BET specific surface area of 400m 2 At least a thermoplastic resin, a carbon nanostructure, graphene, or the carbon black is melt-kneaded in such a manner that the total amount of carbon black mixed in terms of/g is greater than 0.5 parts by mass and not more than 2.5 parts by mass.
As described above, the conductive member obtained by molding the thermoplastic resin composition of the present embodiment has conductivity and sufficient impact resistance and tensile strain at break. That is, by using the thermoplastic resin composition of the present embodiment, the electrical conductivity of the thermoplastic resin composition can be expressed, and sufficient impact resistance and tensile strain at break can also be expressed. In the method for expressing the conductivity of the thermoplastic resin composition of the present embodiment, the CNS and the preferred content of graphene or specific carbon black and other components with respect to the thermoplastic resin are as described above for the thermoplastic resin composition of the present embodiment.
Examples
The present embodiment will be described more specifically with reference to the following examples, but the present embodiment is not limited to the following examples.
Examples 1 to 11 and comparative examples 1 to 11
In each of examples and comparative examples, each raw material component shown in tables 1 and 2 was dry-blended, and then put into a twin-screw extruder having a cylinder temperature of 200 ℃ to be melt-kneaded and pelletized. In tables 1 and 2, the numerical values of the respective components represent parts by mass.
The details of each raw material component used are shown below.
(1) Thermoplastic resin
Polyoxymethylene resin (POM resin)
A polyoxymethylene resin; a polyoxymethylene copolymer (melt flow rate (measured at 190 ℃ C. And a load of 2160g based on ISO 1133) which was prepared by copolymerizing 96.7 mass% trioxane and 3.3 mass% 1, 3-dioxolane was 9.0g/10 min)
Polybutylene terephthalate resin (PBT resin)
Polybutylene terephthalate resin manufactured by Baoli Plastic Ltd (inherent viscosity (measured at 35 ℃ C. In o-chlorophenol): 1.0 dL/g)
Polyphenylene sulfide resin (PPS resin)
Manufactured by KUREHA, fortron KPS (melt viscosity: 130 pas (shear rate: 1200 sec) -1 、310℃))
(measurement of melt viscosity of PPS resin)
The melt viscosity of the above PPS resin was measured in the following manner.
Capilograph manufactured by tokyo seiki was produced by tokyo seiki, and the calibers of capillaries were used as: 1mm, length:20mm flat die, shear rate 1200sec at barrel temperature 310 deg.C -1 The melt viscosity of (b) was measured.
(2) Carbon nanostructures
ATHLOS 200 manufactured by CABOT
(3) Graphene
Commercially available graphene (carbon content: 99.1atom%, particle diameter (D50): 12 μm, BET specific surface area: 19m 2 /g)
The carbon content is a measurement value measured by X-ray photoelectron spectroscopy (XPS), the particle diameter (D50) is a measurement value measured by a laser diffraction scattering method using water as a solvent, and the BET specific surface area is a measurement value measured by a gas adsorption method using nitrogen.
(4) Carbon black
Carbon Black 1
Ketjen Black EC300J (BET specific surface area: 800 m), manufactured by Shiwang corporation 2 /g)
Carbon Black 2
Lionite EC200L (BET specific surface area: 377 m), manufactured by King of lion corporation 2 /g)
(5) Carbon fiber
HT C443 6mm, manufactured by Tenax, toho
(6) Glass fiber
Chopped strand manufactured by Owens Corning Japan contract society
Fiber diameter: 10.5 μm, length 3mm
(7) Stabilizer (hindered phenol oxidation stabilizer)
Irganox1010 manufactured by BASF Japan K.K
[ Table 1]
[ Table 2]
[ evaluation ]
A test piece of ISO TYPE1A was injection-molded in an injection molding machine (EC 40, manufactured by Toshiba mechanical Co., ltd.) to perform the following evaluation (cylinder temperature of the molding machine: POM resin: 200 ℃, PBT resin: 260 ℃, PPS resin: 320 ℃, mold temperature: POM resin: 80 ℃, PBT resin: 80 ℃, PPS resin: 150 ℃). The measurements were carried out at room temperature for surface resistivity and volume resistivity, at 23 ℃ for tensile strain at break and at 50RH% for impact resistance.
(1) Surface resistivity and volume resistivity
Fig. 2 shows the appearance of the multi-purpose test piece obtained in the above manner. Fig. 2 (a) shows the front surface, and fig. 2 (B) shows the rear surface. A conductive paint (dot D500, manufactured by FUJIKURA KASEI co., LTD) was applied to a predetermined region (shaded region in fig. 2) of each surface of the test piece, and dried. Then, the resistance between A and B in FIG. 2A was measured using a low resistivity measuring device (DIGITAL MULTIMERER R6450, manufactured by ADVANTEST), and the measured resistance was regarded as the surface resistivity. In addition, the resistance between C-D of FIG. 2 was measured and taken as the volume resistivity. The measurement results are shown in tables 1 and 2.
In addition, the upper limit of measurement of the surface resistivity is 5.0X 10 9 Omega/sq, upper limit of volume resistivity measurement of 1.8X 10 11 Ω·cm。
(2) Strain at tensile break
The tensile strain at break was measured according to ISO527-1,2 using the multi-purpose test piece obtained in the above manner. The measurement results are shown in tables 1 and 2. The tensile strain at break is preferably 8% or more in the case of the POM resin and the PBT resin, and preferably 1.6% or more in the case of the PPS resin.
(3) Impact resistance (Charpy impact strength)
The charpy impact strength (notch) was measured according to ISO179/1eA using the long test piece obtained in the above manner. The measurement results are shown in tables 1 and 2. Charpy impact strength in excess of 5.5kJ/m in the case of POM-containing resins 2 Can be said to be good, in the case of PBT resins, exceeding 3.5kJ/m 2 Can be said to be good,More than 8kJ/m in the case of PPS resin 2 It can be said to be good.
As is clear from table 1, examples 1 to 9 using the POM resin showed good results in terms of both low surface resistivity and low volume resistivity, and tensile strain at break and impact resistance. In other words, in examples 1 to 6, the impact resistance and the tensile strain at break were not greatly reduced, and the electrical conductivity was imparted thereto. In contrast, comparative example 1, which does not contain any of CNS, graphene and specific carbon black, and comparative example 2, which contains CNS and graphene and contains a small amount of CNS, have poor conductivity. Further, comparative example 3 in which the amount of graphene mixed is large and comparative examples 4 to 6 in which the total amount of CNS and graphene mixed is large were inferior to comparative example 2 in impact resistance. In particular, comparative examples 5 and 6 were inferior in not only impact resistance but also tensile strain at break.
On the other hand, BET specific surface area of less than 400m is used 2 Comparative example 7, which is carbon black/g, is poor in conductivity. Furthermore, instead of graphene or specific carbon black, BET specific surface areas of less than 400m are used, respectively 2 Comparative examples 8 and 9, which are carbon black and carbon fiber per gram, have excellent conductivity but poor tensile strain at break and impact resistance.
It can also be known that: in examples 10 and 11 in which the PBT resin and the PPS resin were used, respectively, the impact resistance and the tensile strain at break were not significantly reduced, and conductivity was imparted thereto. In contrast, comparative example 10, which used a PBT resin and did not contain any of CNS, graphene, and specific carbon black, was inferior in conductivity and impact resistance. In addition, comparative example 11, which used a PPS resin and did not contain any of CNS, graphene, and specific carbon black, was poor in conductivity.
Claims (4)
1. A thermoplastic resin composition obtained by blending at least a thermoplastic resin, a carbon nanostructure, graphene or a thermoplastic resin having a BET specific surface area of 400m 2 A carbon black in an amount of at least one gram per gram, which is obtained by melt-kneading,
the amount of the carbon nanostructures mixed is 0.5 parts by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the total of the amount of the carbon nanostructures mixed and the amount of the graphene or the carbon black mixed is more than 0.5 parts by mass and 2.5 parts by mass or less.
2. A member obtained by using the thermoplastic resin composition according to claim 1.
3. A method for manufacturing a conductive member, comprising:
a step of preparing a thermoplastic resin composition in which the amount of carbon nanostructures mixed is 0.5 parts by mass or more and less than 2.0 parts by mass per 100 parts by mass of a thermoplastic resin, and the amount of the carbon nanostructures mixed and graphene or a BET specific surface area is 400m 2 At least a thermoplastic resin, a carbon nanostructure, graphene, or the carbon black is melt-kneaded so that the total amount of the carbon black is more than 0.5 parts by mass and not more than 2.5 parts by mass; and
and a step of molding the thermoplastic resin composition into a predetermined shape.
4. A method for expressing the conductivity of a thermoplastic resin composition, which is a method for expressing the conductivity of a thermoplastic resin composition,
by mixing the amount of the carbon nano structure with the amount of the graphene or the BET specific surface area of 400m in an amount of 0.5 part by mass or more and less than 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin 2 At least a thermoplastic resin, a carbon nanostructure, graphene, or the carbon black is melt-kneaded in such a manner that the total amount of carbon black mixed in terms of/g is greater than 0.5 parts by mass and not more than 2.5 parts by mass.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020112470 | 2020-06-30 | ||
| JP2020-112470 | 2020-06-30 | ||
| PCT/JP2021/020685 WO2022004236A1 (en) | 2020-06-30 | 2021-05-31 | Thermoplastic resin composition, member, manufacturing method therefor, and method for developing conductivity of thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115916905A true CN115916905A (en) | 2023-04-04 |
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| MX2023004042A (en) * | 2020-10-09 | 2023-08-31 | Polyplastics Co | Polyacetal resin composition and automobile component. |
| JP7217385B2 (en) * | 2020-12-23 | 2023-02-02 | ポリプラスチックス株式会社 | Polyacetal resin composition and fuel contactor |
| WO2022233674A1 (en) * | 2021-05-07 | 2022-11-10 | Basf Se | Polybutylene terephthalate composition and article |
| WO2024053535A1 (en) * | 2022-09-08 | 2024-03-14 | Dic株式会社 | Conductive resin composition, master batch, molded body, and production methods therefor |
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| CN103415571A (en) * | 2011-07-01 | 2013-11-27 | 奥林巴斯株式会社 | Thermoplastic resin composition |
| CN104136504A (en) * | 2012-02-21 | 2014-11-05 | 大日精化工业株式会社 | Production method for conductive resin composition, and conductive resin composition |
| CN104245852A (en) * | 2012-04-09 | 2014-12-24 | 理研科技株式会社 | Resin composition |
| CN104995245A (en) * | 2013-12-06 | 2015-10-21 | Lg化学株式会社 | Composite material with improved mechanical properties and molded article containing same |
| CN110325595A (en) * | 2017-02-28 | 2019-10-11 | 三井化学株式会社 | Conductive resin composition, its manufacturing method and formed body therefrom |
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| JP2007119647A (en) * | 2005-10-28 | 2007-05-17 | Bussan Nanotech Research Institute Inc | Composite material |
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| JP2012140482A (en) * | 2010-12-28 | 2012-07-26 | Hodogaya Chem Co Ltd | Polyacetal resin/carbon nanotube conductive resin composite material |
| WO2014052883A2 (en) * | 2012-09-28 | 2014-04-03 | Applied Nanostructured Solutions, Llc | Composite materials formed by shear mixing of carbon nanostructures and related methods |
| US9327969B2 (en) | 2012-10-04 | 2016-05-03 | Applied Nanostructured Solutions, Llc | Microwave transmission assemblies fabricated from carbon nanostructure polymer composites |
| KR20160026764A (en) * | 2014-08-29 | 2016-03-09 | 삼성에스디아이 주식회사 | Conductive thermoplastic composition |
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Patent Citations (5)
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| CN103415571A (en) * | 2011-07-01 | 2013-11-27 | 奥林巴斯株式会社 | Thermoplastic resin composition |
| CN104136504A (en) * | 2012-02-21 | 2014-11-05 | 大日精化工业株式会社 | Production method for conductive resin composition, and conductive resin composition |
| CN104245852A (en) * | 2012-04-09 | 2014-12-24 | 理研科技株式会社 | Resin composition |
| CN104995245A (en) * | 2013-12-06 | 2015-10-21 | Lg化学株式会社 | Composite material with improved mechanical properties and molded article containing same |
| CN110325595A (en) * | 2017-02-28 | 2019-10-11 | 三井化学株式会社 | Conductive resin composition, its manufacturing method and formed body therefrom |
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| JP7431970B2 (en) | 2024-02-15 |
| WO2022004236A1 (en) | 2022-01-06 |
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