CN115885017A - 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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- CN115885017A CN115885017A CN202180046675.8A CN202180046675A CN115885017A CN 115885017 A CN115885017 A CN 115885017A CN 202180046675 A CN202180046675 A CN 202180046675A CN 115885017 A CN115885017 A CN 115885017A
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- thermoplastic resin
- resin composition
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 86
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 38
- 238000004898 kneading Methods 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 description 84
- 239000011347 resin Substances 0.000 description 84
- 229920001707 polybutylene terephthalate Polymers 0.000 description 29
- -1 Polyoxymethylene Polymers 0.000 description 28
- 229920006324 polyoxymethylene Polymers 0.000 description 28
- 239000004734 Polyphenylene sulfide Substances 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
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
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- 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
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- 125000000732 arylene group Chemical group 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
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- 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
- 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
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- 125000005907 alkyl ester 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
- 150000004820 halides Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000412 polyarylene Polymers 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
- 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003365 glass fiber Substances 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
- 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
- 239000000126 substance Substances 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
- 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
- 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
- 125000004432 carbon atom Chemical group C* 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
- 150000001732 carboxylic acid derivatives 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
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 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
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 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
- 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 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
- 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
Images
Classifications
-
- 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
- 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
-
- 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
The present invention relates to a thermoplastic resin composition obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin, a member obtained by molding the thermoplastic resin composition, a method for producing a conductive member, and a method for expressing the conductivity of the thermoplastic resin composition. Further, a method for manufacturing a conductive member includes: a step of preparing a resin composition obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin; and a step of molding the resin composition into a predetermined shape. The method for expressing the conductivity of the thermoplastic resin composition is a method for expressing the conductivity with respect to the thermoplastic resin composition, and the carbon nanostructure is added by at least 0.3 to 2.5 parts by mass to 100 parts by mass of the thermoplastic resin to perform melt kneading.
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 engineering 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 Kokai publication Hei-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 conductivity can be imparted by adding carbon black or carbon fiber, there is a problem that impact resistance and tensile elongation 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 melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin.
(2) A member obtained by molding the thermoplastic resin composition according to the above (1).
(3) A method of manufacturing an electrically conductive member, comprising:
a step for preparing a thermoplastic resin composition obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin; 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,
the melt kneading is carried out by adding at least 0.3 to 2.5 parts by mass of the carbon nanostructure to 100 parts by mass of the thermoplastic resin.
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 top view (A) and a rear view (B) 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 being obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure (hereinafter also referred to as "CNS") per 100 parts by mass of a thermoplastic resin.
The thermoplastic resin composition of the present embodiment is prepared by adding a predetermined amount of CNS to a thermoplastic resin and melt-kneading the mixture, and thereby carbon nanotubes are obtained without significantly reducing 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 thermoplastic resin is described below by way of example of a POM resin, a PAS resin, and a PBT resin, but the present embodiment is not limited thereto.
(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 copolyformaldehyde contains oxymethylene as main repeating unit and small amount of other structural units such as ethylene oxide, 1,3-dioxolane, 1,4-butanediol formalAnd the like. 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 a 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 according to the present embodiment are not impaired. The amount of terminal carboxyl groups of the PBT resin is preferably 30meq/kg or less, more preferably 25meq/kg or less.
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 PBT resins having different intrinsic viscosities to adjust the intrinsic viscosities. 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, 4,4' -diphenyletherdicarboxylic acid, and the like 8-14 The aromatic dicarboxylic acid of (a); 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 adipic acid, azelaic acid, sebacic acid, etc 6-12 An alkane dicarboxylic acid.
In the PBT resin, examples of the diol component (comonomer component) other than 1,4-butanediol include C such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,3-octanediol 2-10 An alkylene glycol of (a); 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 are more preferable 2-6 And a polyoxyalkylene glycol such as diethylene glycol, or an alicyclic glycol such as cyclohexanedimethanol.
As a means other than twoExamples of the comonomer component other than the carboxylic 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) - (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 sulfide group composed of the aryl group formed by different 2 or more combinations, but especially preferably use contains p-phenylene sulfide group 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) ]
In the thermoplastic resin composition of the present embodiment, as described above, by adding a predetermined amount of CNS to the thermoplastic resin and melt-kneading the mixture, electrical conductivity is imparted without significantly lowering impact resistance and tensile strain at break. The CNS used in the present embodiment is a structure that is 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 the CNS is explained with reference to the 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.
The CNS used in the present embodiment may be commercially available. For example, ATHLOS 200 and ATHLOS 100 manufactured by CABOT may be used.
The thermoplastic resin composition of the present embodiment contains 0.3 to 2.5 parts by mass of CNS relative to 100 parts by mass of the thermoplastic resin. When the content of CNS is less than 0.3 parts by mass, the electrical conductivity is poor, and when it exceeds 2.5 parts by mass, the impact resistance and tensile strain at break are lowered. The content of CNS is preferably 0.5 to 2.0 parts by mass, more preferably 0.6 to 1.8 parts by mass, and still more preferably 0.8 to 1.5 parts by mass.
[ other Components ]
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, colorants such as dyes and pigments, lubricants, nucleating agents, release agents, antistatic agents, surfactants, organic polymer materials, inorganic or organic fibrous, powdery, and plate-like fillers, 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 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 (hereinafter referred to as "step A") of preparing a thermoplastic resin composition obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin, and molding the thermoplastic 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 obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin is prepared.
Preferred products, preferred contents and other components of the respective components in the thermoplastic resin composition are as described above. The thermoplastic 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. The CNS is used as a master batch beforehand, which can be used in the case of addition of CNS. The master batch is a previously prepared thermoplastic resin composition containing CNS at a high concentration.
When melt-kneading is performed, it is preferable to take into consideration the temperature, shear rate and time during melt-kneading so that CNS can be sufficiently cut to exhibit the effects of conductivity, impact resistance and tensile strain at break.
[ 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 of the thermoplastic resin composition, and is characterized in that the carbon nanostructure is added by 0.3 to 2.5 parts by mass to 100 parts by mass of the thermoplastic resin, and the mixture is melt-kneaded.
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 preferable content of CNS components and other components relative 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 below with reference to examples, but the present embodiment is not limited to the following examples.
Examples 1 to 8 and comparative examples 1 to 7
In each of examples and comparative examples, the raw material components shown in tables 1 and 2 were 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): 9.0g/10 min) which was prepared by copolymerizing 96.7 mass% trioxane and 3.3 mass% 1,3-dioxolane
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 PPS resin is 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) Glass fiber
Chopped strand manufactured by Owens Corning Japan contract society
Fiber diameter: 10.5 μm, length 3mm
(4) Carbon fiber
HT C443 6mm, manufactured by Tenax, toho
(5) Carbon black
Shi Wang Zhushi, manufactured by Ketjen Black EC300J
(6) 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 evaluate the following test piece (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 measurement was carried out at room temperature for surface resistivity and volume resistivity, and at 23 ℃ and 50RH% for tensile strain at break and 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. 2 (a) was measured using a low resistivity measuring instrument (DIGITAL multi-meter R6450, manufactured by advance), and the resistance was regarded as the surface resistivity. Further, the resistance between C and D in FIG. 2 was measured and used as the volume resistivity. The measurement results are shown in tables 1 and 2.
The upper limit of the 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 determined 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 containing glass fibers.
(3) Impact resistance (Charpy impact strength)
The charpy impact strength (notch) of the long test piece obtained in the above manner was measured in accordance with ISO179/1 eA. The measurement results are shown in tables 1 and 2. The Charpy impact strength in the case of POM resins exceeds 5.5kJ/m 2 Can be said to be good, in the case of PBT resins, exceeding 3.5kJ/m 2 It can be said that it is good, in the case of PPS resin, more than 8kJ/m 2 It can be said to be good.
As is clear from table 1, examples 1 to 6 using the POM resin all showed low resistivity, and both tensile strain at break and impact resistance showed good results. In other words, in examples 1 to 6, the impact resistance and the tensile strain at break were not greatly reduced, and the conductivity was imparted. In contrast, comparative examples 1 and 2, which contained no or little CNS, had poor conductivity. In comparative example 3, which has a large CNS content, the electrical conductivity is excellent, but the tensile strain at break and impact resistance are poor. Further, comparative example 4 using carbon black instead of CNS and comparative example 5 using carbon fiber are excellent in conductivity, but poor in tensile strain at break and impact resistance.
On the other hand, it is found that in examples 7 and 8 in which the PBT resin and the PPS resin were used, respectively, the impact resistance and the tensile strain at break were not greatly reduced and the electrical conductivity was imparted. In contrast, comparative example 6, which used a PBT resin but did not contain CNS, was inferior in conductivity and impact resistance. In comparative example 7 in which the PPS resin was used but no CNS was contained, the conductivity was poor.
In examples 1 and 2, the surface resistivity was 5.0 × 10 9 Ω/sq, which is a measurement critical value and therefore differs from the actual value. The surface resistivity in comparative examples 1 and 2 containing no or little CNS was also 5.0X 10 9 Ω/sq, but the volume resistivity was higher than those of examples 1 and 2, and therefore it can be considered that the surface resistivity was lower in examples 1 and 2 than in comparative examples 1 and 2.
Claims (4)
1. A thermoplastic resin composition characterized by being obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin.
2. A member obtained by molding 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 obtained by melt-kneading at least 0.3 to 2.5 parts by mass of a carbon nanostructure per 100 parts by mass of a thermoplastic resin; 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,
the melt kneading is carried out by adding at least 0.3 to 2.5 parts by mass of the carbon nanostructure to 100 parts by mass of the thermoplastic resin.
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| JP2007112885A (en) * | 2005-10-19 | 2007-05-10 | Bussan Nanotech Research Institute Inc | Thermoplastic elastomer composition |
| JP2007119647A (en) * | 2005-10-28 | 2007-05-17 | Bussan Nanotech Research Institute Inc | Composite material |
| JP5596336B2 (en) * | 2009-12-24 | 2014-09-24 | ポリプラスチックス株式会社 | Method for producing polyacetal resin composition |
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