CN116783245A - Polyacetal resin composition and fuel contact - Google Patents
Polyacetal resin composition and fuel contact Download PDFInfo
- Publication number
- CN116783245A CN116783245A CN202180086478.9A CN202180086478A CN116783245A CN 116783245 A CN116783245 A CN 116783245A CN 202180086478 A CN202180086478 A CN 202180086478A CN 116783245 A CN116783245 A CN 116783245A
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- Prior art keywords
- mass
- carbon
- resin composition
- parts
- polyacetal resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 96
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims description 54
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000006229 carbon black Substances 0.000 claims abstract description 28
- -1 fatty acid ester Chemical class 0.000 claims abstract description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 24
- 239000000194 fatty acid Substances 0.000 claims abstract description 24
- 229930195729 fatty acid Natural products 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- 239000002482 conductive additive Substances 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims description 19
- 150000003077 polyols Chemical class 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 239000002041 carbon nanotube Substances 0.000 description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 description 17
- 239000002245 particle Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004898 kneading Methods 0.000 description 9
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- 239000002657 fibrous material Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000014692 zinc oxide Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 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 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JHYLOZKQMTWGPP-UHFFFAOYSA-N 2,9-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]decanedioic acid Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC(CCCCCCC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(O)=O)C(O)=O)=C1 JHYLOZKQMTWGPP-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- CVQKYABDDFNVSM-UHFFFAOYSA-N COCOC.C(COCCO)O Chemical compound COCOC.C(COCCO)O CVQKYABDDFNVSM-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- JYSSGQITKNFRQE-UHFFFAOYSA-N [3-(4-anilinoanilino)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound C1=CC(NCC(O)COC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 JYSSGQITKNFRQE-UHFFFAOYSA-N 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- HSAGRKXNQXYOCG-UHFFFAOYSA-N butane-1,4-diol dimethoxymethane Chemical compound COCOC.C(CCCO)O HSAGRKXNQXYOCG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
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- 229940009714 erythritol Drugs 0.000 description 1
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- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
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- 238000001175 rotational moulding Methods 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
A polyacetal resin composition comprising (A) 100 parts by mass of a polyacetal resin, (B) 0.1 to 1.0 part by mass of an antioxidant, (C) 0.3 to 2.0 parts by mass of at least 1 of magnesium oxide and zinc oxide, (D) 0.5 to 3.0 parts by mass of a polyalkylene glycol, (E) 0.01 to 1.0 parts by mass of a fatty acid ester of a polyhydric alcohol having an esterification rate of 80% or more, and (F) 0.3 to 2.5 parts by mass of a carbon-based conductive additive selected from the group consisting of (F1) carbon nanostructures alone and (F1) carbon nanostructures and having a BET specific surface area of 300m 2 One of the combinations of the above (F2) carbon black.
Description
Technical Field
The present application relates to a polyacetal resin composition and a fuel contact body obtained by molding the polyacetal resin composition.
Background
Polyacetal resins (hereinafter also referred to as "POM resins") are excellent in drug resistance, and molded articles using POM resins as raw materials are widely used as automobile parts. For example, the present application is used as a large-sized component such as a fuel delivery unit represented by a fuel pump module or the like that is in direct contact with fuel oil.
In recent years, low-sulfur fuel has been advanced in order to cope with environmental regulations in various countries. However, since desulfurization facilities require a large amount of power, there are also high sulfur fuel streams in some countries. These high sulfur fuels tend to degrade POM resins more easily than low sulfur fuels.
In addition, an injection molded article made of POM resin has residual stress inside the molded article due to cooling at the time of injection molding. When the injection molded product is brought into contact with a high sulfur fuel or the like, cracks are generated at a portion where residual stress is large, which may cause problems such as fuel leakage. For this reason, resin materials having high resistance to high sulfur fuels are required as raw materials for various countries in which high sulfur fuels are circulated.
In order to solve these problems, the present inventors have reported that the polyacetal resin can be significantly improved by containing an alkali metal oxide, a polyalkylene glycol, and a specific ester (see patent document 1). Particularly for parts such as fuel delivery units that are in contact with high sulfur fuels, significant improvements have been found.
On the other hand, as a molded article used around the fuel pump, it is demanded to impart conductivity to the molded article without electrification in order to prevent ignition of fuel due to static electricity. As a countermeasure for imparting conductivity to the POM resin, it is known to add a conductive filler such as carbon black or carbon fiber (see patent documents 2 and 3).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5814419
Patent document 2: japanese patent publication No. 07-002891
Patent document 3: japanese patent application laid-open No. 2004-526596
Disclosure of Invention
Problems to be solved by the application
However, when an alkaline earth metal oxide is added to the POM resin composition to impart durability to fuel and a conductive filler such as carbon black is added to exhibit antistatic effect, there is a problem that toughness is greatly lowered. That is, in the POM resin composition, if the performance of the antistatic effect and the performance of the durability against the acid component are to be simultaneously achieved, the toughness is significantly reduced.
The present application has been made in view of the above-described conventional problems, and an object thereof is to provide a POM resin composition and a fuel contact body which do not significantly deteriorate toughness and impart durability to high sulfur fuel and antistatic effect.
Means for solving the problems
One aspect of the present application to solve the above-described problems is as follows.
(1) A polyacetal resin composition comprising:
(A) 100 parts by mass of polyacetal resin;
(B) 0.1 to 1.0 mass portion of antioxidant;
(C) 0.3 to 2.0 parts by mass of at least 1 kind of magnesium oxide and zinc oxide;
(D) 0.5 to 3.0 parts by mass of polyalkylene glycol;
(E) 0.01 to 1.0 parts by mass of a fatty acid ester of a polyhydric alcohol having an esterification rate of 80% or more; and
(F) 0.3 to 2.5 parts by mass of carbon conductive additive,
the (F) carbon-based conductive additive is selected from (F1) carbon nanostructures only, and (F1) carbon nanostructures and (F2) BET specific surface area of 300m 2 One of the combinations of carbon black above/g.
(2) The polyacetal resin composition according to the item (1) above, which is a copolymer comprising a cyclic oligomer of formaldehyde as a main monomer and a compound selected from a cyclic ether and/or cyclic methylal having at least 1 carbon-carbon bond as a comonomer.
(3) The polyacetal resin composition according to the item (1) or (2), wherein the BET specific surface area of the magnesium oxide (C) is 100m 2 And/g.
(4) The polyacetal resin composition according to any one of (1) to (3) above, wherein the mass ratio ((F2)/(F1)) of the (F1) carbon nanostructure to the (F2) carbon black is 10 or less.
(5) The polyacetal resin composition according to any one of (1) to (4) above, wherein the fatty acid ester of the polyol (E) is an ester compound of a polyol having 3 or more carbon atoms and a fatty acid.
(6) A fuel contact comprising a molded article of the polyacetal resin composition according to any one of (1) to (5) above.
Effects of the application
According to the present application, it is possible to provide a POM resin composition and a fuel contact body which impart durability and antistatic effect to a high sulfur fuel without significantly deteriorating toughness.
Drawings
Fig. 1 is a diagram schematically showing a state of the carbon nanostructure (a) before melt-kneading, (B) immediately after start of melt-kneading, and (C) after melt-kneading.
Fig. 2 is a top view (a) and a rear view (B) of a test piece for measuring surface resistivity and volume resistivity in the example.
Detailed Description
Polyacetal resin composition
The POM resin composition of the present embodiment contains: 100 parts by mass of (A) polyacetal resin, (B) 0.1 to 1.0 part by mass of antioxidant, (C) 0.3 to 2.0 parts by mass of at least 1 of magnesium oxide and zinc oxide, (D) 0.5 to 3.0 parts by mass of polyalkylene glycol, 0.01 to 1.0 parts by mass of fatty acid ester of (E) polyhydric alcohol with an esterification rate of 80% or more, and (F) 0.3 to 2.5 parts by mass of carbon-based conductive additive. And is characterized in that the (F) carbon-based conductive additive is selected from the group consisting of (F1) carbon nanostructures alone, and (F1) carbon nanostructures and BET specific surface area of 300m 2 (F2) carbon black of/g or moreIs one of the combinations of (a).
In the POM resin composition of the present embodiment, durability against high sulfur fuel can be provided by mixing (C) at least 1 of magnesium oxide and zinc oxide with the POM resin. Further, by mixing (F) the carbon-based conductive additive, conductivity can be imparted, and an antistatic effect can be exhibited. In the conventional method, when carbon black or the like is added to exhibit an antistatic effect, the carbon black or the like is bonded to magnesium oxide or the like, and toughness is significantly lowered. However, in the present embodiment, since conductivity is imparted by the (F) carbon-based conductive additive, a significant decrease in toughness can be suppressed. The mechanism thereof will be described later. The "high sulfur fuel" refers to a fuel having a sulfur component concentration of 0.1 mass% or more.
The components of the POM resin composition according to the present embodiment will be described below.
[ (A) polyacetal resin (POM resin) ]
The POM resin (A) used in the present embodiment means a resin obtained by reacting a resin with an oxymethylene group (-CH) 2 Examples of the polymer compound having a structural unit mainly composed of O-) include polyoxymethylene polymers substantially composed of only repeating units of oxymethylene groups, polyacetal copolymers having a small amount of structural units other than oxymethylene groups, and the like. Although these can be used, polyacetal copolymers are preferable as the base resin from the viewpoint of fuel resistance.
(A) When the component (b) is a polyacetal copolymer, the polyacetal copolymer is preferably a polyacetal copolymer obtained by copolymerizing 0.5 to 30% by mass of the comonomer component, and particularly preferably a polyacetal copolymer obtained by copolymerizing 0.5 to 10% by mass of the comonomer component. The polyacetal copolymer obtained by copolymerizing the comonomer component is excellent in acid resistance and can maintain excellent thermal stability, mechanical strength and the like. The polyacetal copolymer is not only a substance having a linear structure in the molecule but also a substance having a branched structure or a crosslinked structure.
In the production of such polyacetal copolymers, cyclic oligomers of formaldehyde represented by trioxymethylene can be used as the main monomer. Furthermore, as comonomer component, compounds selected from cyclic ethers and/or cyclic formals having at least 1 carbon-carbon bond can be used. Examples of such a comonomer include ethylene oxide, 1, 3-dioxolane, diethylene glycol methylal, 1, 4-butanediol methylal, 1, 3-dioxane, propylene oxide, and the like.
In the POM resin (A), particularly the polyacetal copolymer, the polymerization degree and the like thereof are not particularly limited, and the polymerization degree and the like may be adjusted according to the purpose of use and molding means. However, from the viewpoint of both acid resistance and moldability, the Melt Flow Rate (MFR) measured at a measurement temperature of 190℃under a load of 2.16kg according to ISO1133 is preferably 1 to 100g/10 min, particularly preferably 5 to 30g/10 min.
[ (B) antioxidant ]
The antioxidant (B) used in the present embodiment includes an aromatic amine antioxidant, a hindered phenol antioxidant, and the like. Examples of the aromatic amine antioxidant include N-phenyl-1-naphthylamine, bis (4-octylphenyl) amine, 4' -bis (. Alpha.,. Alpha. -dimethylbenzyl) diphenylamine, p- (p-toluenesulfonamide) diphenylamine, N ' -di-2-naphthalene-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N-phenyl-N ' - (1, 3-dimethylbutyl) -p-phenylenediamine, and N-phenyl-N ' - (3-methacryloxy-2-hydroxypropyl) -p-phenylenediamine. Among them, 4' -bis (. Alpha.,. Alpha. -dimethylbenzyl) diphenylamine is preferable.
Examples of the hindered phenol-based antioxidant include 2,2 '-methylenebis (4-methyl-6-t-butylphenol), hexamethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tetrakis [ methylenebis (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane, triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], 1,3, 5-trimethyl-2, 4, 6-tris (3', 5 '-di-t-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- (4' -hydroxy-3 ',5' -di-t-butylphenyl) propionate, 4 '-methylenebis (2, 6-di-t-butylphenol), 4' -butylidenebis (6-t-butyl-3-methyl-phenol), distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 2-t-butyl-6- (3-t-butyl-5-hydroxy-benzyl) -2- (3, 5-di-t-butyl-4-hydroxy-benzyl) -2- [3, 5-di-t-butylphenyl ] -3- (3-hydroxy-3-methylphenyl) propionate, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [ 5,5 ] undecane and the like, of which triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, hexamethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] are preferred.
In this embodiment, at least one or two or more antioxidants selected from these antioxidants may be used.
The amount of the antioxidant (B) to be mixed in the present embodiment is 0.1 to 1.0 parts by mass, more preferably 0.2 to 0.8 parts by mass, based on 100 parts by mass of the POM resin (a).
[ (C) magnesia, zinc oxide ]
At least 1 kind of magnesium oxide (hereinafter also referred to as "component (C)") among zinc oxides is mixed in the POM resin composition of the present embodiment. The component (C) used in the present embodiment is preferable because of excellent balance between improvement in high sulfur fuel resistance (durability against high sulfur fuel (hereinafter also referred to as "fuel resistance")) and performance such as mechanical physical properties and moldability.
As for magnesium oxide, it is preferable that BET specific surface area is 100m 2 And/or more and has an average particle diameter of 1.5 μm or less. By satisfying these conditions, the decrease in toughness is suppressed and fuel resistance can be obtained. The BET specific surface area of the magnesium oxide is preferably 100 to 500m 2 Preferably 120 to 300m 2 And/g. The average particle diameter of the magnesium oxide is preferably 0.2 to 1.3. Mu.m, more preferably 0.3 to 1.0. Mu.m. The average particle diameter is determined by the particle diameter of 50% of the cumulative value of the particle size distribution (volume basis) measured by the laser diffraction/scattering method.
The amount of the component (C) to be mixed in the present embodiment is 0.3 to 2.0 parts by mass, preferably 1.0 to 1.8 parts by mass, based on 100 parts by mass of the POM resin (A). (C) The blending amount of the components is 0.3 parts by mass or more, whereby the fuel resistance is particularly excellent, and stable production can be realized by 2.0 parts by mass or less, and the balance of mechanical properties is particularly excellent within 1.8 parts by mass. In this case, if the component (C) is increased, the decomposition of the unstable terminal in the POM resin may be accelerated, but if the component (a) of the present embodiment is the POM resin, the decomposition thereof can be suppressed, and thus the fuel resistance improvement property due to the increase of the component (C) can be exhibited.
[ (D) polyalkylene glycol ]
The type of the polyalkylene glycol (D) used in the present embodiment is not particularly limited, and is preferably polyethylene glycol and/or polypropylene glycol, more preferably polyethylene glycol, from the viewpoint of affinity with the POM resin.
The number average molecular weight (Mn) of the polyalkylene glycol is not particularly limited, but is preferably 1,000 to 50,000, more preferably 5,000 to 30,000, from the viewpoint of dispersibility in the POM resin. In the present specification, the number average molecular weight is a molecular weight in terms of polystyrene obtained by Size Exclusion Chromatography (SEC) using Tetrahydrofuran (THF) as a solvent.
The content of the polyalkylene glycol (D) in the present embodiment is 0.5 to 3.0 parts by mass, more preferably 1.0 to 2.0 parts by mass, based on 100 parts by mass of the POM resin (a). When the mixing amount of the (D) polyalkylene glycol is small, there is a possibility that sufficient stress relaxation cannot be performed. (D) If the amount of the polyalkylene glycol to be mixed is excessive, there is a possibility that the mechanical physical properties of the molded article may be lowered.
[ (E) fatty acid esters of polyols ]
The fatty acid ester of the polyol (E) used in the present embodiment is one having an esterification rate of 80% or more. When the esterification rate is less than 80%, fuel resistance is poor. (E) The esterification rate of the fatty acid ester of the polyol is preferably 85% or more.
The polyol may be aliphatic or aromatic, but is preferably aliphatic in terms of affinity with (a) the POM resin.
The valence of the polyhydric alcohol is not particularly limited, but is preferably 3 to 4. The number of carbon atoms of the polyol is not particularly limited, but is preferably 3 to 10, more preferably 3 to 5, in terms of affinity with (a) the POM resin.
Preferred polyols for forming the ester of component (E) include, for example, glycerin, trimethylolpropane, pentaerythritol, erythritol, pentose alcohol, hexanol, sorbitol, etc., but pentaerythritol is preferred in that the mass reduction of the POM resin composition after impregnation with sulfur fuel is controlled to be low.
The type of fatty acid is not particularly limited, but is preferably a fatty acid having 10 to 30 carbon atoms, more preferably an aliphatic carboxylic acid having 10 to 20 carbon atoms, in terms of affinity with (a) the POM resin.
Preferable fatty acids for forming the ester of component (E) include, for example, stearic acid, palmitic acid, lauric acid, and the like, and preferable fatty acids are stearic acid.
The component (E) is preferably an ester compound of a polyol having 3 or more carbon atoms and a fatty acid. Specifically, glycerol tristearate and pentaerythritol tetrastearate are preferably used, and pentaerythritol tetrastearate is more preferably used. The component (E) may be used in combination of 2 or more kinds of polyols, esters having different fatty acids, and esters having different esterification rates.
The content of the fatty acid ester of the (E) polyol in the present embodiment is 0.01 to 1.0 parts by mass, more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the (a) POM resin. (E) If the mixing amount of the fatty acid full ester of the polyol is less than 0.01 parts by mass, the releasability of the molded article may be deteriorated. (E) If the mixing amount of the fatty acid ester of the polyol exceeds 1.0 part by mass, there is a possibility that the processability of the molded article may be lowered.
[ (F) carbon-based conductive additive ]
The POM resin composition of the present embodiment contains a prescribed amount of (F) a carbon-based conductive additive relative to the (a) POM resin. (F) The carbon-based conductive additive is selected from the group consisting of (F1) carbon nanostructures alone (hereinafter also referred to as "CNS"), and (F1) carbon nanostructures having a BET specific surface area of 300m 2 One of the combinations of the above (F2) carbon black. Further, the antistatic effect can be exerted by adding (F) a carbon-based conductive additive to the POM resin composition to impart conductivity. Furthermore, when aloneWhen carbon black is added, the toughness of the obtained molded article is reduced, but the reduction in toughness can be suppressed by adding (F) the carbon-based conductive additive.
The following applies to (F1) carbon nanostructures and BET specific surface area of 300m 2 The above (F2) carbon black is described.
((F1) Carbon Nanostructures (CNS))
The CNS used in the present embodiment is a structure including a plurality of carbon nanotubes bonded to each other, and the carbon nanotubes are bonded to each other by a branched bond or a crosslinked structure. Details of such CNS are described in us patent application publication No. 2013-00715575, us patent No. 9,113,031, 9,447,259, 9,111,658.
The morphology of the CNS is described with reference to the accompanying drawings. Fig. 1 schematically shows the CNS used in the present embodiment, (a) shows a state before melt-kneading with the POM resin, (B) shows a state immediately after the start of melt-kneading, and (C) shows a state after melt-kneading. As shown in fig. 1 (a), CNS10 before melt-kneading is formed into a structure in which a plurality of branched carbon nanotubes 12 are entangled. Then, when the CNS10 is put into the POM resin 20 and melt kneaded, the CNS10 is divided into a plurality of parts as shown in fig. 1 (B). When the molten and kneaded mixture advances, the CNS10 is further divided, and 1 carbon nanotube 12 is in contact with 1 through a joint 14 as shown in fig. 1 (C). That is, the state (C) of fig. 1 is a state in which the carbon nanotubes 12 are in contact with each other over a wide range in the POM resin, and thus a conductive path is formed, and thus conductivity is exhibited. Further, it is considered that the carbon nanotubes 12 form a three-dimensional network structure by being entangled together in disorder, and therefore, the decrease in toughness can be suppressed.
In order to obtain CNS of the morphology shown in fig. 1 (C), the CNS shown in fig. 1 (a) is preferably in a predetermined sheet form. The platy CNS shown in FIG. 1 (A) contains a plurality of carbon nanotubes that are branched, cross-linked, and share a common wall with each other. In this case, the plurality of carbon nanotubes may have at least 1 of the structural features as a whole, instead of all having the structural features such as being branched, cross-linked, and sharing a common wall. The use of the sheet-like CNS described above results in the form shown in fig. 1 (C) by melt kneading.
The flaky CNS is obtained by growing on a growth substrate such as a fibrous material and removing the grown CNS from the growth substrate. In the CNS growth process, a growth substrate such as a fiber, vine, filament, fabric, nonwoven fabric, sheet, tape, or ribbon may be used. That is, the growth substrate may be a fibrous material of a size that enables the formation of CNS to be performed continuously while the growth substrate is being transported.
More specifically, the catalyst can be coated on a growth substrate and CNS growth can be achieved by a fine pore CVD process. The CNS-forming growth substrate is then preserved, after which it may be rolled to remove the CNS.
When the CNS is grown on a growth substrate, it is preferable to use a catalyst comprising a plurality of transition metal nanoparticles. For coating the growth substrate with the catalyst, for example, particle adsorption may be performed by direct catalyst coating or the like using vapor deposition by a liquid or gel-like precursor substance. As the transition metal nanoparticle catalyst, d-block transition metal or d-block transition metal salt is contained. The transition metal salt may be coated on the growth substrate without heat treatment, or the transition metal salt may be converted to a zero-valent transition metal on the growth substrate by heat treatment.
Although the CNS contains carbon nanotubes in a network with a complex architecture, the complex architecture is believed to result from the formation of CNS on a growth substrate under growth conditions of carbon nanotubes generated at rapid growth rates on the order of a few microns per second.
Various techniques for forming carbon nanotubes can be employed in synthesizing carbon nanotubes on a fibrous material, including those disclosed in U.S. patent application publication No. 2004/0245088. The CNS grown on the fiber can be formed, for example, by microcavity, thermal and plasma enhanced CVD techniques, laser ablation, arc discharge, and high pressure carbon monoxide (HiPCO) techniques. The acetylene gas may be ionized to generate a low-temperature carbon plasma for synthesizing carbon nanotubes. At this time, the plasma faces the fibrous material with the catalyst. In this way, in order to synthesize CNS on the fiber material, it is preferable to include two conditions, i.e., (a) formation of carbon plasma and (b) orientation of the carbon plasma to the catalyst disposed on the fiber material. The diameter of the grown carbon nanotubes may be dictated by the size of the carbon nanotube forming catalyst. In addition, CNS synthesis can be readily performed by heating the sized fibrous material to a temperature of 550 to 800 ℃.2 gases were flowed into the reactor in order to initiate the growth of carbon nanotubes. Namely, a process gas such as argon, helium or nitrogen, and a carbon-containing gas such as acetylene, ethylene, ethanol or methane. Further, the carbon nanotubes are grown at the positions where the carbon nanotubes form the catalyst.
The CNS used in this embodiment can be commercially available. For example, ATHLOS 200, ATHLOS 100, etc. manufactured by CABOT corporation may be used.
(BET specific surface area of 300 m) 2 Carbon black of (F2) above/g
In the present embodiment, carbon black may be used having a BET specific surface area of 300m 2 Carbon black of/g or more. However, the carbon black is not used alone, but in combination with the CNS. Since the POM resin composition containing the carbon black has high conductivity, the POM resin composition can maintain conductivity even when used together with CNS. In contrast, BET specific surface area of less than 300m is mixed 2 The POM resin composition of carbon black per gram has low conductivity, and the mixing amount needs to be increased to sufficiently secure conductivity, so that the decrease in toughness cannot be suppressed. The BET specific surface area is preferably 310m 2 Preferably at least/g, more preferably at least 350m 2 The upper limit of the ratio of the catalyst to the catalyst is not particularly limited, but the ratio is 2000m 2 Degree/g.
In addition, the BET specific surface area can be determined according to ASTM D4820.
As the specific carbon BLACK, there may be mentioned KETJEN BLACK EC300J (BET specific surface area: 800m 2 /g), KETJEN BLACK EC600JD (BET specific surface area: 1270m 2 /g)、LioniteEC200L (BET specific surface area: 377 m) 2 /g), and the like.
In the POM resin composition of the present embodiment, 0.3 to 2.5 parts by mass of the (F) carbon-based conductive additive is mixed with 100 parts by mass of the POM resin. When the mixing amount of the (F) carbon-based conductive additive is less than 0.3 parts by mass, the conductivity is poor, and when it exceeds 2.5 parts by mass, the toughness is lowered. The mixing amount of the 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.
In the case where (F1) CNS is used in combination with (F2) carbon black, the mass ratio of (F1) CNS to (F2) carbon black ((F2)/(F1)) is preferably 10 or less, more preferably more than 0 and 5 or less. When the mass ratio is 10 or less, the balance between conductivity and toughness can be ensured. Furthermore, although the closer the value of F2/F1 is to 0, the more means that CNS is excessively mixed, CNS may be excessively mixed as such. However, if the CNS price is high, the lower limit of the value of F2/F1 is preferably 0.1 from the viewpoint of cost performance.
[ other Components ]
The POM resin composition of the present embodiment may contain other components as needed. As long as the purpose and effect of the POM resin composition of the present embodiment are not impaired, 1 or 2 or more known stabilizers can be added to the POM resin composition.
The method for producing a molded article using the POM resin composition of the present embodiment is not particularly limited, and a known method may be used. For example, the POM resin composition of the present embodiment can be produced by charging the POM resin composition into an extruder, melt-kneading the POM resin composition, granulating the POM resin composition, and injection molding the granulated POM resin composition in an injection molding machine equipped with a predetermined mold.
The POM resin composition according to the present embodiment described above may be used as an automobile part described later, or may be used as a molded article having resistance to antistatic function and fuel.
< Fuel contact body >)
The fuel contact body of the present embodiment includes a molded article of the POM resin composition. The molded article can be obtained by using the POM resin composition and molding the composition by a conventional molding method, such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, and the like.
The fuel contact body of the present embodiment is not limited to the high sulfur fuel, and may be a fuel contact body that contacts a low sulfur fuel.
Examples
Hereinafter, the present embodiment will be described more specifically by way of examples, but the present embodiment is not limited to the following examples.
Examples 1 to 20 and comparative examples 1 to 14
In each example and comparative example, each raw material component shown in tables 1 to 4 was dry-blended, and then fed into a twin-screw extruder having a cylinder temperature of 200℃to melt-knead, and pelletized. In tables 1 to 4, the numerical values of the respective components represent parts by mass.
The details of the raw material components used are shown below.
(A) Polyacetal resin (POM resin)
A-1: 96.7 mass% of trioxymethylene and 3.3 mass% of 1, 3-dioxolane were copolymerized to obtain a polyacetal copolymer. MFR (measured at 190 ℃ c. Under load 2160g based on ISO 1133): 9g/10 min)
(B) Antioxidant agent
B-1: tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane (Irganox 1010, manufactured by BASF corporation)
B-2:4,4' -bis (. Alpha.,. Alpha. -dimethylbenzyl) diphenylamine (crack-free CD available from Dain New chemical industry Co., ltd.)
(C) Magnesium oxide and the like
C-1: magnesium oxide, BET specific surface area 135m 2 Per gram, average particle diameter 0.9 μm (KYOWAMAG MF150, manufactured by Kyowa chemical Co., ltd.)
C-2: magnesium oxide, BET specific surface area 30m 2 Per g, average particle diameter 0.6 μm (KYOWAMAG MF30, manufactured by Kyowa chemical Co., ltd.)
C-3: magnesium oxide, BET specific surface area155m 2 /g, average particle diameter 7 μm (KYOWAAG 150, manufactured by Kyowa chemical Co., ltd.)
C-4: zinc oxide (BET specific surface area 60-90 m) 2 /g) (AZO active zinc white manufactured by chemical industry Co., ltd.)
(measurement of average particle diameter)
The particle size distribution was measured by a laser diffraction/scattering method under the following measurement conditions using a laser diffraction/scattering particle size distribution measuring apparatus LA-920 manufactured by horiba, ltd, to obtain an average particle size (50% d) having an integrated value of 50%.
Measurement conditions of over-
Circulation speed: 5
Laser light source: 632.8nmHe-Ne laser 1mW, tungsten lamp 50 W.Detector: ring 75 divides silicon photodiode x1, silicon photodiode x 12
Dispersion medium: distilled water
Ultrasonic wave: has the following components
Transmittance: 75 to 90 percent
Relative refractive index with water: 1.32
Particle size benchmark: volume of
(D) Polyalkylene glycol
D-1: polyethylene glycol (PEG 6000S manufactured by Sanyo chemical industry Co., ltd.)
(E) Fatty acid esters of polyols
E-1: pentaerythritol tetrastearate (fatty acid ester of polyol having an esterification ratio of 80% or more, manufactured by Nipple Co., ltd., unister H476)
E-2: tristearate (fatty acid ester of polyol with esterification rate of 80% or more, POEM S-95 manufactured by Living Co., ltd.)
E-3: glycerol monostearate (fatty acid ester of polyol with esterification rate lower than 80%, manufactured by LikeMAL S-100A)
(F) Carbon nanostructures, carbon black
F-1: carbon nanostructures (ATHLOS 200 manufactured by CABOT Co., ltd.)
F-2: carbon black (KET made by lion king Co., ltd.)JEN BLACK EC300J, BET specific surface area: 800m 2 /g)
F-3: carbon black (specific surface area of Lionite EC200L, BET, manufactured by lion king Co., ltd.: 377 m) 2 /g)
F-4: carbon BLACK (Denka BLACK, manufactured by Denka Co., ltd., BET specific surface area: 65 m) 2 /g)
< evaluation >
The following evaluations were performed using the POM resin compositions prepared from examples and comparative examples.
(1) Evaluation of Fuel resistance
Pellets of the prepared POM resin composition were used, and ASTM No. 4 dumbbell test pieces having a thickness of 1mm were produced by injection molding. Furthermore, in order to evaluate the fuel resistance of the POM resin composition, the dumbbell test pieces were immersed in diesel fuel (product name: CEC RF at 100 DEG C
90-a-92, manufactured by Halterman corporation) for 14 days, the mass reduction rate due to the fuel impregnation was calculated from the mass of the test pieces before and after the test pieces, and evaluated according to the following evaluation criteria. The evaluation results are shown in tables 1 to 4.
[ evaluation criterion ]
A:20% or less
B: more than 20%
Next, using the POM resin compositions prepared in examples and comparative examples, multipurpose test pieces described in ISO294-1 were produced by injection molding using an injection molding machine (EC 40, manufactured by toshiba machinery co., ltd.) under the conditions of ISO9988-1,2, and used for the evaluations of (2) and (3) below.
(2) Evaluation of tensile failure nominal Strain (toughness)
The tensile failure nominal strain according to ISO527-1, 2 was measured using the above-described multi-purpose test piece, and evaluated according to the following evaluation criteria. The evaluation results are shown in tables 1 to 4.
[ evaluation criterion ]
A: more than 10 percent
B: less than 10%
(3) Conductivity of conductive material
The following evaluation was performed using the above-described multi-purpose test piece.
(surface resistivity/volume resistivity)
The appearance of the multipurpose test piece obtained in the above manner is shown in fig. 2. Fig. 2 (a) shows the front surface, and fig. 2 (B) shows the back surface. Conductive paint (DOTITE D500, manufactured by rattan warehouse chemical company, ltd.) was applied to a predetermined region (hatched 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 device (DIGITAL MULTIMETER R6450, manufactured by ADVANTEST), and this was used as the surface resistivity. The resistance between C and D in FIG. 2 was measured and used as the volume resistivity. The surface resistivity and the volume resistivity were evaluated according to the following evaluation criteria. The evaluation results are shown in tables 1 to 4.
[ evaluation criterion of surface resistivity ]
A：1.0×10 4 Omega/≡ (++omega/sq) or below
B: exceeding 1.0X10 4 Ω/≡and 1.0X10 7 Omega/≡below
C: exceeding 1.0X10 7 Ω/□
[ evaluation criterion of volume resistivity ]
A：1.0×10 4 Omega cm or less
B: exceeding 1.0X10 4 Omega cm and 1.0X10 7 Omega cm or less
C: exceeding 1.0X10 7 Omega cm [ Table 1 ]]
TABLE 2
TABLE 3
TABLE 4
As is clear from tables 1 to 4, good results were obtained in any of the evaluations of examples 1 to 20. In contrast, in comparative examples 1 to 14, all the evaluations could not be made as good results at the same time.
Comparative example 1 differs from example 2 in that the components (C) to (F) are not mixed, and is poor in fuel resistance and electrical conductivity. Comparative example 2 differs from example 2 in that the component (F) is not mixed, and the conductivity is poor. Comparative example 3 is different from example 2 in that the component (C) is not mixed, and fuel resistance is poor. Comparative example 4 is different from example 2 in that the component (D) is not mixed, and fuel resistance is poor. Comparative example 5 is different from example 2 in that the component (C) is too small and fuel resistance is poor. Comparative example 6 differs from example 2 in that the component (C) is excessive and the component (F) is slightly increased, and the toughness is poor. Comparative example 7 is different from example 2 in that the component (D) is too small and fuel resistance is poor. Comparative example 8 differs from example 2 in that the component (D) is excessive and the component (F) is slightly increased, and the toughness is poor. Comparative example 9 is different from example 2 in that the component (E) is excessive and fuel resistance is poor. Comparative example 10 differs from example 2 in that the fuel resistance was poor in using the (E) component having an esterification rate of less than 80%. Comparative examples 11 and 12 are different from example 2 in that the component (F) is too small or too large, respectively, and comparative example 11 is poor in conductivity and comparative example 12 is poor in toughness. Comparative example 13 differs from example 20 in that the (F) component used in the combination of the carbon nanostructure and the carbon black is excessive and the toughness is poor. Comparative example 14 differs from example 18 in that carbon black having too small BET specific surface area is used, and the conductivity is poor.
From the above, it is clear that when the components (a) to (F) are not mixed in a predetermined content, the results of good toughness, fuel resistance and antistatic effect cannot be obtained.
Claims (6)
1. A polyacetal resin composition comprising:
(A) 100 parts by mass of polyacetal resin;
(B) 0.1 to 1.0 mass portion of antioxidant;
(C) 0.3 to 2.0 parts by mass of at least 1 kind of magnesium oxide and zinc oxide;
(D) 0.5 to 3.0 parts by mass of polyalkylene glycol;
(E) 0.01 to 1.0 parts by mass of a fatty acid ester of a polyhydric alcohol having an esterification rate of 80% or more; and
(F) 0.3 to 2.5 parts by mass of carbon conductive additive,
the (F) carbon-based conductive additive is selected from (F1) carbon nanostructures alone, and (F1) carbon nanostructures and (F2) BET specific surface area of 300m 2 One of the combinations of carbon black above/g.
2. The polyacetal resin composition according to claim 1, wherein,
the polyacetal resin is a copolymer comprising a cyclic oligomer of formaldehyde as a main monomer and a compound selected from a cyclic ether and/or cyclic methylal having at least 1 carbon-carbon bond as a comonomer.
3. The polyacetal resin composition according to claim 1 or 2, wherein,
the BET specific surface area of the (C) magnesium oxide is 100m 2 And/g.
4. The polyacetal resin composition according to claim 1 to 3, wherein,
the mass ratio ((F2)/(F1)) of the (F1) carbon nanostructure to the (F2) carbon black is 10 or less.
5. The polyacetal resin composition according to any one of claim 1 to 4, wherein,
the fatty acid ester of the polyol (E) is an ester compound of a polyol having 3 or more carbon atoms and a fatty acid.
6. A fuel contact body comprising the molded article of the polyacetal resin composition according to any one of claims 1 to 5.
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