JP7368391B2 - 成形材料、成形品、および、電動車両のバッテリーパック筐体 - Google Patents
成形材料、成形品、および、電動車両のバッテリーパック筐体 Download PDFInfo
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- JP7368391B2 JP7368391B2 JP2020571125A JP2020571125A JP7368391B2 JP 7368391 B2 JP7368391 B2 JP 7368391B2 JP 2020571125 A JP2020571125 A JP 2020571125A JP 2020571125 A JP2020571125 A JP 2020571125A JP 7368391 B2 JP7368391 B2 JP 7368391B2
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- 239000012778 molding material Substances 0.000 title claims description 55
- 239000000835 fiber Substances 0.000 claims description 166
- 239000000203 mixture Substances 0.000 claims description 110
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 107
- 238000002156 mixing Methods 0.000 claims description 101
- 150000007519 polyprotic acids Polymers 0.000 claims description 66
- 229920006305 unsaturated polyester Polymers 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 48
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- 239000011347 resin Substances 0.000 claims description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000011231 conductive filler Substances 0.000 claims description 32
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 31
- 239000012783 reinforcing fiber Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 26
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- 238000006116 polymerization reaction Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
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- 239000011118 polyvinyl acetate Substances 0.000 claims description 21
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- 239000002041 carbon nanotube Substances 0.000 claims description 17
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
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- 239000003112 inhibitor Substances 0.000 description 17
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
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- 239000003054 catalyst Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 229920001225 polyester resin Polymers 0.000 description 10
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- 125000003118 aryl group Chemical group 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 238000000034 method Methods 0.000 description 8
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
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- 238000005259 measurement Methods 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
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- 150000003839 salts Chemical class 0.000 description 6
- 239000002109 single walled nanotube Substances 0.000 description 6
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 5
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
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- 239000002562 thickening agent Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
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- 239000000779 smoke Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
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- 125000002723 alicyclic group Chemical group 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 3
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 2
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 2
- WAVTZYKJTMZICQ-UHFFFAOYSA-N 2-(2-methylbutan-2-ylperoxy)propan-2-yl hydrogen carbonate Chemical compound CCC(C)(C)OOC(C)(C)OC(O)=O WAVTZYKJTMZICQ-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 2
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
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- H01M50/222—Inorganic material
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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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
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Description
非臭素化ビスフェノール化合物として、例えば、ビスフェノールA、ビスフェノールF、ビスフェノールSなどが挙げられ、好ましくは、ビスフェノールAが挙げられる。
このような非臭素化エポキシ化合物として、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂などが挙げられる。
このような臭素化ビスフェノール化合物として、例えば、テトラブロモビスフェノールA([2,2-ビス(3,5-ジブロモ-4-ヒドロキシフェニル)プロパン)、ジブロモビスフェノールA、テトラブロモビスフェノールF、テトラブロモビスフェノールSなどが挙げられる。
このような臭素化エポキシ化合物として、例えば、テトラブロモビスフェノールA型エポキシ樹脂、ジブロモビスフェノールA型エポキシ樹脂、テトラブロモビスフェノールF型エポキシ樹脂、テトラブロモビスフェノールS型エポキシ樹脂などが挙げられる。
各実施例および各比較例で用いた各成分を以下に記載する。
ポリスチレン溶液:重量平均分子量が約250000のポリスチレンの35%スチレン溶液
ポリエチレン粉末:平均粒子径が約30μmのポリエチレン粉末
VULCAN XC72:カーボンブラック、Cabot社製
SWCNT:単層カーボンナノチューブ
ECP:ケッチェンブラック、ライオン・スペシャリティー・ケミカル社製
ドナカーボ・ミルドS-241:ピッチ系炭素繊維ミルドファイバー、平均繊維長0.14mm、導電性短繊維55質量%、導電性中長繊維45質量%(詳しくは、導電性中繊維45質量%、導電性長繊維0質量%)、大阪ガスケミカル社製
ドナカーボ・ミルドS-244:ピッチ系炭素繊維ミルドファイバー、平均繊維長0.68mm、導電性短繊維10質量%、導電性中長繊維90質量%(詳しくは、導電性中繊維90質量%、導電性長繊維0質量%)
CFMP-150R:PAN系炭素繊維ミルドファイバー、平均繊維長0.15mm、導電性短繊維15質量%、導電性中長繊維85質量%(詳しくは、導電性中繊維70質量%、導電性長繊維15質量%)、日本ポリマー産業株式会社製
150RE-P:PAN系炭素繊維ミルドファイバー、平均繊維長0.10mm、導電性短繊維60質量%、導電性中長繊維40質量%(詳しくは、導電性中繊維40質量%、導電性長繊維0質量%)、日本ポリマー産業株式会社製
炭酸カルシウム:平均粒子径約3μm
パーブチルI-75:t-ブチルパーオキシイソプロピルカーボネート、日油社製
BYK-W996:粘度低下剤、ビックケミー社製
BYK-P 9060:離型剤、ビックケミー社製
AP422:難燃剤、ポリリン酸アンモニウム、商品名:Exolit AP422、クラリアントケミカルズ社製、リン含量31%
FP-2500S:難燃剤、リン酸塩系、株式会社ADEKA社製
OP1230:難燃剤、ホスフィン酸金属塩、商品名:Exolit OP1230、クラリアントケミカルズ社製、リン含量23%
2.不飽和ポリエステル樹脂の調製
合成例1
温度計、窒素ガス導入管、還流冷却器および攪拌機を備えたフラスコに、無水マレイン酸10.0モル、プロピレングリコール6.5モル、ネオペンチルグリコール4.0モルを仕込み、窒素ガス雰囲気下で撹拌しながら200℃~210℃で重縮合反応させ、酸価が26.5mgKOH/gの不飽和ポリエステルを得た。なお、酸価の測定方法は、JIS K6901(2008年)に準拠した。得られた不飽和ポリエステル100質量部に対し、重合禁止剤としてハイドロキノンを0.01質量部、スチレンを66.7質量部添加し、これらを均一に混合して、不飽和ポリエステル樹脂(スチレン含有量40%)を得た。
温度計、窒素ガス導入管、還流冷却器および攪拌機を備えたフラスコに、イソフタル酸3.3モル、プロピレングリコール10.5モルを仕込み、窒素ガス雰囲気下で撹拌しながら200℃~210℃で重縮合反応させた。その後、反応生成物の酸価が20mgKOH/gになった時点で150℃まで冷却し、無水マレイン酸6.7モルを仕込み、再び210℃~220℃で反応させ、酸価27.5mgKOH/gの不飽和ポリエステルを得た。得られた不飽和ポリエステル100質量部に対し、重合禁止剤としてハイドロキノンを0.01質量部、スチレンを66.7質量部添加し、これらを均一に混合して、不飽和ポリエステル樹脂(スチレン含有率40%)を得た。
3.飽和ポリエステル樹脂の調製
合成例3
温度計、窒素ガス導入管、還流冷却器および攪拌機を備えたフラスコに、イソフタル酸4.0モル、ネオペンチルグリコール10.5モルを仕込み、窒素ガス雰囲気下で撹拌しながら200℃~210℃で重縮合反応させた。その後、反応生成物の酸価が10mgKOH/gになった時点で150℃まで冷却し、アジピン酸6.0モルを仕込み、再び210℃~220℃で反応させ、酸価9.5mgKOH/gの飽和ポリエステルを得た。得られた飽和ポリエステル100質量部に対し、重合禁止剤としてハイドロキノンを0.01質量部、スチレンを66.7質量部添加し、これらを均一に混合して、飽和ポリエステル樹脂(スチレン含有率40%)を得た。
4.ビニルエステル樹脂の調製
合成例4
攪拌機、還流冷却器、ガス導入管を備えたフラスコに、ビスフェノールA 114質量部(1.0当量)、ビスフェノールA型エポキシ樹脂(エポキシ当量185)555質量部(3.0当量)、触媒として、トリエチルベンジルアンモニウムクロライド 0.15質量部を仕込み、窒素を吹き込みながら、150℃で5時間反応させて、エポキシ当量が335の非臭素化エポキシ樹脂を得た。120℃まで冷却後、重合禁止剤としてハイドロキノン 0.10質量部、触媒としてトリエチルベンジルアンモニウムクロライド 1.50質量部、メタクリル酸 176質量部(2.05当量)を添加し、空気を吹き込みながら110℃で8時間反応させ、酸価8.5mgKOH/gのビニルエステルを得た。次いで、このビニルエステルにスチレン563質量部を加えることにより、スチレン40質量%含有のビニルエステル樹脂を得た。
5.不飽和ポリエステル樹脂組成物および成形材料の調製
実施例1
合成例1の不飽和ポリエステル樹脂75質量部(不飽和ポリエステル45質量部、スチレン30質量部)、低収縮化剤として、ポリ酢酸ビニル溶液(ポリ酢酸ビニルの40%スチレン溶液)8質量部、および、合成例3の飽和ポリエステル樹脂10質量部(飽和ポリエステル6質量部、スチレン4質量部)、重合性単量体として、スチレン7質量部、導電性フィラーとして、カーボンブラック(VULCAN XC72、Cabot社製)2.5質量部、PAN系炭素繊維ミルドファイバー(CFMP-150R) 20質量部、重合禁止剤として、p-ベンゾキノン0.05質量部、硬化剤として、t-ブチルパーオキシイソプロピルカーボネート(パーブチルI-75) 1.0質量部、離型剤として、ステアリン酸亜鉛5質量部、水酸化アルミニウム(平均粒子径8μm)160質量部、粘度低下剤として、BYK-W996 1質量部を混合して、不飽和ポリエステル樹脂組成物を得た。
配合処方を、表1~表4の記載に従って変更した以外は、実施例1と同様に処理して、成形材料を得た。
6.評価
(成形収縮率)
成形材料を、300mm×300mm平板金板を用いて、加熱圧縮成型して、厚み4mmの平板状の成形品を得た。
評価基準:
○:収縮率が、0未満であった。
△:収縮率が、0以上、0.10未満であった。
×:収縮率が、0.10以上であった。
成形収縮率測定平板作成と同様の手順で成形材料を成形し、厚み4mm、3mmおよび2.5mmの成形板を得た。成形板より試験片を切り出しUL規格(Underwriters Laboratories Inc.)のUL94規格(プラスチック材料燃焼性試験)に準拠して燃焼試験を実施した。厚さ4mm、厚さ3mm、厚さ2.5mmのそれぞれの試験片でV-0基準を満たすか評価した。その結果を表5~表8に示す。
評価基準:
○:V-0基準(厚み2.5mm)に適合した。
△:V-0基準(厚み3mm)に適合した。
×:V-0基準(厚み3mm)に適合しなかった。
上記難燃性試験で、厚み3mm試験片を使用した際のV-0判定試験において、燃焼時に黒煙が発生するか目視で観察した。
○:黒煙が発生しなかった。
×:黒煙が発生した。
(線膨張係数)
成形収縮率測定で用いた平板状の成形品(厚み4mm)から、試験片(4mm×4mm×5mm)を切削加工し、熱機械分析装置(日立ハイテクサイエンス社製、EXSTAR
TMA SS7100)で圧縮・膨張プローブを使用し、成形品の水平方向の線膨張係数を測定した。5℃/分の昇温速度で室温より100℃まで昇温し、50℃から80℃の範囲の線膨張係数を測定した。その結果を表5~表8に示す。
○:アルミニウムの線膨張係数との差の絶対値が、0以上5未満
×:アルミニウムの線膨張係数との差の絶対値が、5以上
(密度)
成形収縮率測定で用いた平板状の成形品(厚み4mm)から、試験片を切り出し、JIS K6911(1995年)に準拠し、密度を測定した。その結果を表5~表8に示す。
成形収縮率測定平板作成と同様の手順で成形材料を成形し、2.5mmの成形板を得た。この成形板を、KEC法による電磁波シールド効果測定装置のクローズセルに挟み、導電パターンを接地した状態で、電磁波の減衰率(dB)を測定した。測定周波数は1MHz、10MHz、100MHz、1000MHzで実施し、周波数1MHzでの減衰率(dB)を指標として、次の基準で優劣を評価した。その結果を表5~表8に示す。
◎:60dBを超過
○:40dB以上60dB以下
○-:30dB以上40dB未満
△:10dB以上30dB未満
×:10dB未満
(製造安定性)
<含浸状態の評価>
SMC製造直後にカッターナイフでキャリヤフィルムを剥ぎ取り、不飽和ポリエステル樹脂組成物とガラス繊維の含浸の程度を目視で評価した。
○:ガラス繊維が不飽和ポリエステル樹脂組成物で十分に濡らされ、不飽和ポリエステル樹脂組成物に含浸していないガラス繊維が観察されなかった。
×:部分的に、不飽和ポリエステル樹脂組成物に含浸していないガラス繊維が観察された。
熟成後の成形材料(SMC)のキャリヤフィルムをカッターナイフで剥がし、フィルム剥離性を評価した。
○:SMCにタックが少なくスムーズにフィルムが剥がれた。
×:SMCに強いタックが観察された。または、フィルム剥離時に一部成分の分離が観察された。
成形収縮率測定平板作成と同様の手順で成形材料を成形し、2.5mmの成形板を得た。この成形板を、JIS K6911(2006年)に準拠し、23℃および90℃において表面抵抗率を測定した。その結果を表5~表8に示す。
(曲げ特性)
成形収縮率測定で用いた平板状の成形品(厚み4mm)から、試験片(長さ80mm、幅10mm)を切り出し、JIS K7017(1999年)に準拠し、23℃および90℃において曲げ弾性率、曲げ強度を測定した。その結果を表5~表8に示す。
(引張特性)
成形収縮率測定で用いた平板状の成形品(厚み4mm)から、試験片を切り出し、JIS K7164(2005年)に準拠し、23℃において引張強さ、引張弾性率を測定した。その結果を表5~表8に示す。
2 トレイ部材
3 カバー部材
Claims (11)
- 不飽和ポリエステル樹脂組成物と、強化繊維(炭素繊維を除く)とを含み、
前記不飽和ポリエステル樹脂組成物は、不飽和ポリエステルと、重合性単量体と、低収縮化剤と、水酸化アルミニウムと、導電性フィラーと含み、かつ、強化繊維(炭素繊維を除く)を含まず、
前記不飽和ポリエステルは、多塩基酸と、多価アルコールとの重合生成物であり、
前記多塩基酸は、エチレン性不飽和二重結合を有する多塩基酸を含み、前記エチレン性不飽和二重結合を有する多塩基酸の配合割合は、前記多塩基酸100モル%に対して、80モル%以上であり、
前記低収縮化剤は、ポリ酢酸ビニルを含み、
前記ポリ酢酸ビニルの配合割合が、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、3質量部以上、10質量部以下であり、
前記水酸化アルミニウムの配合割合は、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、100質量部以上、200質量部以下であり、
前記導電性フィラーが、炭素繊維を含み、
前記炭素繊維が、0.01mm以上0.15mm以下の繊維長を有する導電性短繊維を含み、
前記導電性短繊維の配合割合が、前記炭素繊維に対して、12質量%以上50質量%以下であり、
前記エチレン性不飽和二重結合を有する多塩基酸は、無水マレイン酸を含み、
前記多価アルコールは、プロピレングリコールを含み、
前記重合性単量体は、スチレンであり、
前記不飽和ポリエステルの配合割合は、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤とを含む樹脂成分に対して、20質量%以上60質量%以下であり、
前記重合性単量体の配合割合は、前記樹脂成分に対して、20質量%以上60質量%以下であり、
前記導電性フィラーの配合割合が、前記樹脂成分に対して、0.2質量部以上25.1質量部以下であり、
前記強化繊維がガラス繊維を含み、
前記強化繊維の配合割合が、前記不飽和ポリエステル樹脂組成物および前記強化繊維の総量に対して、5質量%以上50質量%以下であることを特徴とする、成形材料。 - 不飽和ポリエステル樹脂組成物と、強化繊維(炭素繊維を除く)とを含み、
前記不飽和ポリエステル樹脂組成物は、不飽和ポリエステルと、重合性単量体と、低収縮化剤と、水酸化アルミニウムと、導電性フィラーとを含み、かつ、強化繊維(炭素繊維を除く)を含まず、
前記不飽和ポリエステルは、多塩基酸と、多価アルコールとの重合生成物であり、
前記多塩基酸は、エチレン性不飽和二重結合を有する多塩基酸を含み、前記エチレン性不飽和二重結合を有する多塩基酸の配合割合は、前記多塩基酸100モル%に対して、80モル%以上であり、
前記低収縮化剤は、ポリ酢酸ビニルを含み、
ポリ酢酸ビニルの配合割合が、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、3質量部以上、10質量部以下であり、
前記水酸化アルミニウムの配合割合は、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、100質量部以上、200質量部以下であり、
前記導電性フィラーが、カーボンナノチューブを含み、
前記エチレン性不飽和二重結合を有する多塩基酸は、無水マレイン酸を含み、
前記多価アルコールは、プロピレングリコールを含み、
前記重合性単量体は、スチレンであり、
前記不飽和ポリエステルの配合割合は、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤とを含む樹脂成分に対して、20質量%以上60質量%以下であり、
前記重合性単量体の配合割合は、前記樹脂成分に対して、20質量%以上60質量%以下であり、
前記導電性フィラーの配合割合が、前記樹脂成分に対して、0.2質量部以上25.1質量部以下であり、
前記強化繊維がガラス繊維を含み、
前記強化繊維の配合割合が、前記不飽和ポリエステル樹脂組成物および前記強化繊維の総量に対して、5質量%以上50質量%以下であることを特徴とする、成形材料。 - 前記導電性フィラーの配合割合が、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、8質量部以上、25質量部以下であることを特徴とする、請求項1または2に記載の成形材料。
- 前記炭素繊維の配合割合が、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、8質量部以上、21質量部以下であることを特徴とする、請求項1に記載の成形材料。
- 前記炭素繊維が、1.5mm以上、5mm以下の繊維長を有する導電性長繊維を含み、
前記導電性長繊維の配合割合が、前記炭素繊維に対して、10質量%以上30質量%以下であることを特徴とする、請求項1に記載の成形材料。 - 前記導電性フィラーが、カーボン粒子を含むことを特徴とする、請求項1または2に記載の成形材料。
- 前記カーボン粒子の配合割合が、前記不飽和ポリエステルと前記重合性単量体と前記低収縮化剤との総量100質量部に対して、1質量部以上、5質量部以下であることを特徴とする、請求項6に記載の成形材料。
- 請求項1~7のいずれか一項に記載の成形材料の硬化物を含むことを特徴とする、成形品。
- 線膨張係数が、17ppm/℃以上、25ppm/℃以下であることを特徴とする、請求項8に記載の成形品。
- 電動車両のバッテリーパック筐体用であることを特徴とする、請求項8または9に記載の成形品。
- アルミニウム部材、および、前記アルミニウム部材と組み合わされる請求項8~10のいずれか一項に記載の成形品を備えることを特徴とする、電動車両のバッテリーパック筐体。
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