JP6837336B2 - Polyester resin composition - Google Patents
Polyester resin composition Download PDFInfo
- Publication number
- JP6837336B2 JP6837336B2 JP2017003561A JP2017003561A JP6837336B2 JP 6837336 B2 JP6837336 B2 JP 6837336B2 JP 2017003561 A JP2017003561 A JP 2017003561A JP 2017003561 A JP2017003561 A JP 2017003561A JP 6837336 B2 JP6837336 B2 JP 6837336B2
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- JP
- Japan
- Prior art keywords
- mass
- parts
- polyester resin
- resin composition
- fluororesin
- 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.)
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- 229920001225 polyester resin Polymers 0.000 title claims description 38
- 239000004645 polyester resin Substances 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 34
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 33
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 26
- 239000003365 glass fiber Substances 0.000 claims description 23
- 239000003063 flame retardant Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001463 antimony compounds Chemical class 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- -1 polybutylene terephthalate Polymers 0.000 description 47
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000002253 acid Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 239000010452 phosphate Substances 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 22
- 238000000465 moulding Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000012756 surface treatment agent 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- ZFYXTBYFHIVKEC-UHFFFAOYSA-N 1,2,4-tribromo-5-ethenylbenzene Chemical compound BrC1=CC(Br)=C(C=C)C=C1Br ZFYXTBYFHIVKEC-UHFFFAOYSA-N 0.000 description 2
- ICKFOGODAXJVSQ-UHFFFAOYSA-N 1,3,5-tribromo-2-ethenylbenzene Chemical compound BrC1=CC(Br)=C(C=C)C(Br)=C1 ICKFOGODAXJVSQ-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 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
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OQLRBFNNEQUJPK-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 OQLRBFNNEQUJPK-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GBRSUMKGOZKQCR-UHFFFAOYSA-N 1,2,3,5-tetrakis(2,4-dibutylphenyl)-4-phenylbenzene Chemical group C(CCC)C1=C(C=CC(=C1)CCCC)C=1C(=C(C(=C(C=1)C1=C(C=C(C=C1)CCCC)CCCC)C1=C(C=C(C=C1)CCCC)CCCC)C1=C(C=C(C=C1)CCCC)CCCC)C1=CC=CC=C1 GBRSUMKGOZKQCR-UHFFFAOYSA-N 0.000 description 1
- PAUFOHFMOYPVBY-UHFFFAOYSA-N 1,2,4-tribromo-5-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC(Br)=C(Br)C=C1Br PAUFOHFMOYPVBY-UHFFFAOYSA-N 0.000 description 1
- DXXGWBOAAMSTFR-UHFFFAOYSA-N 1,2,5-tribromo-3-ethenylbenzene Chemical compound BrC1=C(C=C)C=C(C=C1Br)Br DXXGWBOAAMSTFR-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- KXQRUSDQTREVCX-UHFFFAOYSA-N 1,3,5-tribromo-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=C(Br)C=C(Br)C=C1Br KXQRUSDQTREVCX-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- WXZMOAUBOXOPFV-UHFFFAOYSA-N 1,3-dibromo-2-ethenylbenzene Chemical compound BrC1=CC=CC(Br)=C1C=C WXZMOAUBOXOPFV-UHFFFAOYSA-N 0.000 description 1
- OITDEAXLQUVPQW-UHFFFAOYSA-N 1,3-dibromo-5-ethenylbenzene Chemical compound BrC1=CC(Br)=CC(C=C)=C1 OITDEAXLQUVPQW-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- KWVKCGGJLLNVSC-UHFFFAOYSA-N 1,4-dibromo-2-ethenylbenzene Chemical compound BrC1=CC=C(Br)C(C=C)=C1 KWVKCGGJLLNVSC-UHFFFAOYSA-N 0.000 description 1
- XZZWOTQMUOIIFX-UHFFFAOYSA-N 1-(2-diphenoxyphosphanyloxypropoxy)propan-2-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC(C)COCC(C)OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 XZZWOTQMUOIIFX-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- OGVFUFNUTOTCIA-UHFFFAOYSA-N 1-bromo-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(Br)C=C1 OGVFUFNUTOTCIA-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- NTHFKMZKTASAMH-UHFFFAOYSA-N 2,4-dibromo-1-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C(Br)=C1 NTHFKMZKTASAMH-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical compound [SiH3]CC=C DNAJDTIOMGISDS-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- BWPNIANVWARHPR-UHFFFAOYSA-N tridecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)O BWPNIANVWARHPR-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- SAAMKFBWYWFBNY-UHFFFAOYSA-N tris(4-tert-butylphenyl) phosphite Chemical compound C1=CC(C(C)(C)C)=CC=C1OP(OC=1C=CC(=CC=1)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1 SAAMKFBWYWFBNY-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリエステル樹脂組成物に関し、詳しくは、難燃性を維持しながら、流動性を損なうことなく、高い耐トラッキング性（ＣＴＩ）を有するポリエステル樹脂組成物に関する。 The present invention relates to a polyester resin composition, and more particularly to a polyester resin composition having high tracking resistance (CTI) while maintaining flame retardancy without impairing fluidity.
ポリブチレンテレフタレートやポリエチレンテレフタレートに代表される熱可塑性ポリエステル樹脂は、機械的強度、耐薬品性及び電気絶縁性等に優れており、また優れた耐熱性、成形性、リサイクル性を有していることから、電気電子部品、自動車部品その他の電装部品、機械部品等に広く用いられている。 Thermoplastic polyester resins typified by polybutylene terephthalate and polyethylene terephthalate are excellent in mechanical strength, chemical resistance, electrical insulation, etc., and also have excellent heat resistance, moldability, and recyclability. Therefore, it is widely used for electrical and electronic parts, automobile parts and other electrical parts, mechanical parts, and the like.
特に、電気電子機器分野では、火災に対する安全を確保するため難燃性が極めて重要であり、また電気的負荷による発火に対する安全性の確保のため、電気的特性の一つである耐トラッキング性に優れていることが必要である。
そして、近年、電気電子機器部品や電装部品は、機器自体の小型化傾向から薄肉小型化されてきており、その結果、絶縁距離が小さくなり、これら部品（成形品）の耐トラッキング性等への要求スペックは高度化している。絶縁材料は、通電中に装置から発生した熱により乾燥し帯電するため、絶縁材料の表面には埃が付着しやすい傾向がある。そのため、その絶縁材料から形成される部品は、装置停止中にその表面に埃が付着しやすく、その埃が空気中の水分を吸収し、吸収された水分により材料の表面抵抗が低下し、漏洩電流が増加する。一般に、電気部品は多かれ少なかれこのような状況にさらされており、絶縁材料の耐トラッキング特性が重要視されている。
In particular, in the field of electrical and electronic equipment, flame retardancy is extremely important to ensure safety against fire, and tracking resistance, which is one of the electrical characteristics, is required to ensure safety against ignition due to an electrical load. It needs to be good.
In recent years, electrical and electronic equipment parts and electrical component parts have become thinner and smaller due to the tendency of the equipment itself to become smaller, and as a result, the insulation distance has become smaller, and the tracking resistance of these parts (molded products) has been improved. The required specifications are becoming more sophisticated. Since the insulating material is dried and charged by the heat generated from the device during energization, dust tends to adhere to the surface of the insulating material. Therefore, the component formed from the insulating material tends to have dust attached to its surface while the device is stopped, and the dust absorbs the moisture in the air, and the absorbed moisture lowers the surface resistance of the material and leaks. The current increases. In general, electrical components are more or less exposed to this situation, and the tracking resistance properties of insulating materials are emphasized.
電気電子部品は、米国アンダーライターズ・ラボラトリーズ社のＵＬ９４規格の難燃性や比較トラッキング指数（ＣＴＩ：Ｃｏｍｐａｒａｔｉｖｅ Ｔｒａｃｋｉｎｇ Ｉｎｄｅｘ）等の要求事項を満たさねばならず、０．７５ｍｍ厚みにてＶ−０以上の難燃性と、ＣＴＩが３００Ｖ以上であることが望ましい。 Electrical and electronic components must meet the requirements such as flame retardancy and comparative tracking index (CTI) of UL94 standard of US Underwriters Laboratories, and V-0 or more at 0.75 mm thickness. It is desirable that the flame retardancy and CTI are 300V or more.
熱可塑性ポリエステル樹脂を難燃化するには、通常、ハロゲン系難燃剤や無機系難燃剤等が配合されるが、これらは熱可塑性ポリエステル樹脂の耐トラッキング性等の電気特性を低下させる傾向にある。例えば、ＣＴＩで３００Ｖ以上であるものが難燃剤を配合することにより３００Ｖ未満に悪化することはよく観察される。 In order to make a thermoplastic polyester resin flame-retardant, a halogen-based flame retardant, an inorganic flame retardant, or the like is usually blended, but these tend to reduce electrical characteristics such as tracking resistance of the thermoplastic polyester resin. .. For example, it is often observed that a CTI of 300 V or higher deteriorates to less than 300 V by adding a flame retardant.
耐トラッキング性の改良を試みた材料としては、例えば、特許文献１には、ポリブチレンテレフタレートにポリオレフィンを配合した樹脂組成物が、耐トラッキンング性を改善するとの提案がなされている。この方法では、配合したポリオレフィンの一部が表面に分散することで、炭化が抑制されて耐トラッキング性が改善される。しかしながら、ポリエチレンやポリプロピレンなどのポリオレフィンを多く配合すると耐熱性が低下するなどの弊害をもたらす。 As a material for which the tracking resistance has been improved, for example, Patent Document 1 proposes that a resin composition containing polybutylene terephthalate and polyolefin improves the tracking resistance. In this method, carbonization is suppressed and tracking resistance is improved by dispersing a part of the blended polyolefin on the surface. However, if a large amount of polyolefin such as polyethylene or polypropylene is blended, there will be an adverse effect such as a decrease in heat resistance.
本発明の目的（課題）は、難燃性を維持しながら、流動性を損なうことなく、高い耐トラッキング性（ＣＴＩ）を有するポリエステル樹脂組成物を提供することにある。 An object (problem) of the present invention is to provide a polyester resin composition having high tracking resistance (CTI) without impairing fluidity while maintaining flame retardancy.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、熱可塑性ポリエステル樹脂に、ガラス繊維と臭素系難燃剤、さらに分子量が高いフッ素樹脂と分子量が低いフッ素樹脂をそれぞれ特定の量を含有するポリエステル樹脂組成物が、難燃性を維持しながら、流動性を損なうことなく、高い耐トラッキング性（ＣＴＩ）を有することを見出し、本発明に到達した。
本発明は、以下のポリエステル樹脂組成物に関する。
As a result of diligent studies to solve the above problems, the present inventor has added specific amounts of glass fiber and brominated flame retardant to the thermoplastic polyester resin, as well as a fluorine resin having a high molecular weight and a fluorine resin having a low molecular weight. We have found that the polyester resin composition contained has high tracking resistance (CTI) without impairing fluidity while maintaining flame retardancy, and reached the present invention.
The present invention relates to the following polyester resin compositions.
［１］熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、ガラス繊維（Ｂ）０〜１２０質量部及び臭素系難燃剤（Ｃ）０〜５０質量部を含有し、（Ｂ）と（Ｃ）の含有量の合計は５〜１５０質量部であり、さらに、第１のフッ素樹脂（Ｄ１）と、第１のフッ素樹脂（Ｄ１）より質量平均分子量が低い第２のフッ素樹脂（Ｄ２）を併せて１〜２５質量部含有することを特徴とするポリエステル樹脂組成物。
［２］第１のフッ素樹脂（Ｄ１）の質量平均分子量が１，０００，０００〜１００，０００，０００である上記［１］に記載のポリエステル樹脂組成物。
［３］第２のフッ素樹脂（Ｄ２）の質量平均分子量が６０，０００〜８００，０００である上記［１］又は［２］に記載のポリエステル樹脂組成物。
［４］フッ素樹脂（Ｄ１）とフッ素樹脂（Ｄ２）の含有量の質量比が１／０．５〜１／１０である上記［１］〜［３］のいずれかに記載のポリエステル樹脂組成物。
[1] 100 parts by mass of the thermoplastic polyester resin (A) contains 0 to 120 parts by mass of the glass fiber (B) and 0 to 50 parts by mass of the bromine-based flame retardant (C), and (B) and (C) The total content of is 5 to 150 parts by mass, and the first fluororesin (D1) and the second fluororesin (D2) having a lower mass average molecular weight than the first fluororesin (D1) are combined. A polyester resin composition containing 1 to 25 parts by mass.
[2] The polyester resin composition according to the above [1], wherein the first fluororesin (D1) has a mass average molecular weight of 1,000,000 to 100,000,000.
[3] The polyester resin composition according to the above [1] or [2], wherein the second fluororesin (D2) has a mass average molecular weight of 60,000 to 800,000.
[4] The polyester resin composition according to any one of the above [1] to [3], wherein the mass ratio of the contents of the fluororesin (D1) and the fluororesin (D2) is 1 / 0.5 to 1/10. ..
本発明のポリエステル樹脂組成物は、難燃性と流動性を損なうことなく、高い耐トラッキング性（ＣＴＩ）を有し、強度に優れ、凝集異物の発生もなく、さらに生産性にも優れる。 The polyester resin composition of the present invention has high tracking resistance (CTI) without impairing flame retardancy and fluidity, is excellent in strength, does not generate agglomerated foreign matter, and is also excellent in productivity.
本発明のポリエステル樹脂組成物は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、ガラス繊維（Ｂ）０〜１２０質量部及び臭素系難燃剤（Ｃ）０〜５０質量部を含有し、（Ｂ）と（Ｃ）の含有量の合計は５〜１５０質量部であり、さらに、第１のフッ素樹脂（Ｄ１）と、第１のフッ素樹脂（Ｄ１）より質量平均分子量が低い第２のフッ素樹脂（Ｄ２）を併せて１〜２５質量部含有することを特徴とする。 The polyester resin composition of the present invention contains 0 to 120 parts by mass of glass fiber (B) and 0 to 50 parts by mass of bromine-based flame retardant (C) with respect to 100 parts by mass of the thermoplastic polyester resin (A). The total content of B) and (C) is 5 to 150 parts by mass, and further, the first fluorine resin (D1) and the second fluorine having a lower mass average molecular weight than the first fluorine resin (D1). It is characterized by containing 1 to 25 parts by mass of the resin (D2) in total.
以下、本発明について詳細に説明する。
以下に記載する各構成要件の説明は、本発明の代表的な実施態様や具体例に基づいてなされることがあるが、本発明はそのような実施態様や具体例に限定して解釈されるものではない。なお、本願明細書において、「〜」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
Hereinafter, the present invention will be described in detail.
The description of each constituent requirement described below may be based on a typical embodiment or specific example of the present invention, but the present invention is construed as being limited to such embodiment or specific example. It's not a thing. In the specification of the present application, "~" is used to mean that the numerical values described before and after the value are included as the lower limit value and the upper limit value.
［熱可塑性ポリエステル樹脂（Ａ）］
熱可塑性ポリエステル樹脂（Ａ）は、ジカルボン酸化合物とジヒドロキシ化合物の重縮合、オキシカルボン酸化合物の重縮合あるいはこれらの化合物の重縮合等によって得られるポリエステルであり、ホモポリエステル、コポリエステルのいずれであってもよい。
[Thermoplastic polyester resin (A)]
The thermoplastic polyester resin (A) is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, polycondensation of these compounds, etc., and is either a homopolyester or a copolyester. You may.
熱可塑性ポリエステル樹脂（Ａ）を構成するジカルボン酸化合物としては、芳香族ジカルボン酸又はそのエステル形成性誘導体が好ましく使用される。
芳香族ジカルボン酸としては、テレフタル酸、イソフタル酸、オルトフタル酸、１，５−ナフタレンジカルボン酸、２，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、ビフェニル−２，２’−ジカルボン酸、ビフェニル−３，３’−ジカルボン酸、ビフェニル−４，４’−ジカルボン酸、ジフェニルエーテル−４，４’−ジカルボン酸、ジフェニルメタン−４，４’−ジカルボン酸、ジフェニルスルフォン−４，４’−ジカルボン酸、ジフェニルイソプロピリデン−４，４’−ジカルボン酸、１，２−ビス（フェノキシ）エタン−４，４’−ジカルボン酸、アントラセン−２，５−ジカルボン酸、アントラセン−２，６−ジカルボン酸、ｐ−ターフェニレン−４，４’−ジカルボン酸、ピリジン−２，５−ジカルボン酸等が挙げられ、テレフタル酸が好ましく使用できる。
As the dicarboxylic acid compound constituting the thermoplastic polyester resin (A), an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably used.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, Biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulphon-4,4'-dicarboxylic acid , Diphenylisopropyridene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p Examples thereof include −terphenylene-4,4′-dicarboxylic acid and pyridine-2,5-dicarboxylic acid, and terephthalic acid can be preferably used.
これらの芳香族ジカルボン酸は２種以上を混合して使用しても良い。これらは周知のように、遊離酸以外にジメチルエステル等のエステル形成性誘導体として重縮合反応に用いることができる。
なお、少量であればこれらの芳香族ジカルボン酸と共にアジピン酸、アゼライン酸、ドデカンジオン酸、セバシン酸等の脂肪族ジカルボン酸や、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸および１，４−シクロヘキサンジカルボン酸等の脂環式ジカルボン酸を１種以上混合して使用することができる。
Two or more kinds of these aromatic dicarboxylic acids may be mixed and used. As is well known, these can be used in the polycondensation reaction as ester-forming derivatives such as dimethyl ester in addition to free acids.
In addition, if it is a small amount, along with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecandioic acid and sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 , 4-Cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids can be mixed and used.
熱可塑性ポリエステル樹脂（Ａ）を構成するジヒドロキシ化合物としては、エチレングリコール、プロピレングリコール、ブタンジオール、へキシレングリコール、ネオペンチルグリコール、２−メチルプロパン−１、３−ジオール、ジエチレングリコール、トリエチレングリコール等の脂肪族ジオール、シクロヘキサン−１、４−ジメタノール等の脂環式ジオール等、及びそれらの混合物等が挙げられる。これらの中でもエチレングリコール、ブタンジオールが好ましく、特にはブタンジオールが好ましい。
なお、少量であれば、分子量４００〜６，０００の長鎖ジオール、すなわち、ポリエチレングリコール、ポリ−１、３−プロピレングリコール、ポリテトラメチレングリコール等を１種以上共重合せしめてもよい。
また、ハイドロキノン、レゾルシン、ナフタレンジオール、ジヒドロキシジフェニルエーテル、２，２−ビス（４−ヒドロキシフェニル）プロパン等の芳香族ジオールも用いることができる。
Examples of the dihydroxy compound constituting the thermoplastic polyester resin (A) include ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol and triethylene glycol. Examples thereof include aliphatic diols, alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. Among these, ethylene glycol and butanediol are preferable, and butanediol is particularly preferable.
If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.
In addition, aromatic diols such as hydroquinone, resorcin, naphthalene diol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.
また、上記のような二官能性モノマー以外に、分岐構造を導入するためトリメリット酸、トリメシン酸、ピロメリット酸、ペンタエリスリトール、トリメチロールプロパン等の三官能性モノマーや分子量調節のため脂肪酸等の単官能性化合物を少量併用することもできる。 In addition to the bifunctional monomers as described above, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure, and fatty acids for adjusting the molecular weight, etc. A small amount of the monofunctional compound can also be used in combination.
熱可塑性ポリエステル樹脂（Ａ）としては、通常は主としてジカルボン酸とジオールとの重縮合からなるもの、即ち樹脂全体の５０質量％、好ましくは７０質量％以上がこの重縮合物からなるものを用いる。ジカルボン酸としては芳香族カルボン酸が好ましく、ジオールとしては脂肪族ジオールが好ましい。
なかでも好ましいのは、酸性分の９５モル％以上がテレフタル酸であり、アルコール成分の９５質量％以上が脂肪族ジオールであるポリアルキレンテレフタレート樹脂である。その代表的なものはポリブチレンテレフタレート樹脂及びポリエチレンテレフタレート樹脂である。これらはホモエステルに近いもの、即ち樹脂全体の９５質量％以上が、テレフタル酸成分及び１．４−ブタンジオール又はエチレングリコール成分からなるものであるのが好ましい。
As the thermoplastic polyester resin (A), a resin mainly composed of a polycondensation of a dicarboxylic acid and a diol, that is, a resin in which 50% by mass, preferably 70% by mass or more of the total resin is composed of this polycondensate is used. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.
Of these, a polyalkylene terephthalate resin in which 95 mol% or more of the acidic content is terephthalic acid and 95% by mass or more of the alcohol component is an aliphatic diol is preferable. Typical examples are polybutylene terephthalate resin and polyethylene terephthalate resin. It is preferable that these are close to homoesters, that is, 95% by mass or more of the total resin is composed of a terephthalic acid component and a 1.4-butanediol or ethylene glycol component.
本発明のポリエステル樹脂組成物は、主成分がポリブチレンテレフタレート樹脂であることが好ましい。 The polyester resin composition of the present invention preferably contains a polybutylene terephthalate resin as the main component.
熱可塑性ポリエステル樹脂（Ａ）の固有粘度は、０．５〜２ｄｌ／ｇであることが好ましい。成形性及び機械的特性の点からして、０．６〜１．５ｄｌ／ｇの範囲の固有粘度を有するものがより好ましい。固有粘度が０．５ｄｌ／ｇより低いものを用いると、得られる樹脂組成物が機械的強度の低いものとなりやすい。また２ｄｌ／ｇより高いものでは、樹脂組成物の流動性が悪くなり成形性が悪化する場合がある。
なお、熱可塑性ポリエステル樹脂の固有粘度は、１，１，２，２−テトラクロロエタンとフェノールとの１：１（質量比）の混合溶媒中、３０℃で測定するものとする。
The intrinsic viscosity of the thermoplastic polyester resin (A) is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If an intrinsic viscosity of less than 0.5 dl / g is used, the obtained resin composition tends to have low mechanical strength. If the value is higher than 2 dl / g, the fluidity of the resin composition may be deteriorated and the moldability may be deteriorated.
The intrinsic viscosity of the thermoplastic polyester resin shall be measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of 1,1,2,2-tetrachloroethane and phenol.
また、熱可塑性ポリエステル樹脂（Ａ）は、その末端カルボキシル基量は適宜選択して決定すればよいが、通常、６０ｅｑ／ｔｏｎ以下であり、５０ｅｑ／ｔｏｎ以下であることが好ましく、３０ｅｑ／ｔｏｎ以下であることがさらに好ましい。６０ｅｑ／ｔｏｎを超えると、樹脂組成物の溶融成形時にガスが発生しやすくなる。末端カルボキシル基量の下限値は特に定めるものではないが、ポリブチレンテレフタレート樹脂の製造の生産性を考慮し、通常、１０ｅｑ／ｔｏｎである。 The amount of the terminal carboxyl group of the thermoplastic polyester resin (A) may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and 30 eq / ton or less. Is more preferable. If it exceeds 60 eq / ton, gas is likely to be generated during melt molding of the resin composition. The lower limit of the amount of the terminal carboxyl group is not particularly determined, but is usually 10 eq / ton in consideration of the productivity of producing the polybutylene terephthalate resin.
なお、ポリエステル樹脂の末端カルボキシル基量は、ベンジルアルコール２５ｍＬにポリアルキレンテレフタレート樹脂０．５ｇを溶解し、水酸化ナトリウムの０．０１モル／ｌベンジルアルコール溶液を用いて滴定により測定して得られた値をいう。末端カルボキシル基量を調整する方法としては、重合時の原料仕込み比、重合温度、減圧方法などの重合条件を調整する方法や、末端封鎖剤を反応させる方法等、従来公知の任意の方法により行えばよい。 The amount of terminal carboxyl groups in the polyester resin was obtained by dissolving 0.5 g of a polyalkylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. The value. As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as a raw material charging ratio at the time of polymerization, a polymerization temperature, and a depressurization method, and a method of reacting a terminal blocking agent can be used. Just do it.
［ガラス繊維（Ｂ）］
本発明に用いるガラス繊維（Ｂ）としては、特に制限はないが、Ａガラス、Ｃガラス、Ｅガラス等の組成からなるものが好ましく、特に、Ｅガラス（無アルカリガラス）が熱可塑性ポリエステル樹脂の熱安定性に悪影響を及ぼさない点で好ましい。また一般的には、取り扱いの容易さや、高い強度・剛性および耐熱性を有する成形物を与える点などから、短繊維タイプ（チョップドストランド）のガラス繊維を使用することが好ましい。
[Glass fiber (B)]
The glass fiber (B) used in the present invention is not particularly limited, but one having a composition of A glass, C glass, E glass or the like is preferable, and in particular, E glass (non-alkali glass) is a thermoplastic polyester resin. It is preferable because it does not adversely affect the thermal stability. Further, in general, it is preferable to use a short fiber type (chopped strand) glass fiber from the viewpoint of ease of handling and providing a molded product having high strength / rigidity and heat resistance.
ガラス繊維（Ｂ）の平均繊維径は特に制限されないが、例えば１〜１００μｍの範囲で選ぶことが好ましく、より好ましくは２〜５０μｍ、更に好ましくは３〜３０μｍ、特に好ましくは５〜２０μｍである。平均繊維径が１μｍ未満のガラス繊維は、製造が容易でなく、コスト高になる恐れがあり、一方１００μｍを超えると、ガラス繊維の引張強度が低下する恐れがある。
また、ガラス繊維（Ｂ）の平均繊維長は特に限定されないが、例えば０．１〜２０ｍｍの範囲で選ぶことが好ましく、０．３〜５ｍｍであることがより好ましい。平均繊維長が０．１ｍｍ未満であると、補強効果が十分に発現しない恐れがあり、２０ｍｍを超えると、得られるポリエステル樹脂組成物の成形が困難になる恐れがある。
The average fiber diameter of the glass fiber (B) is not particularly limited, but is preferably selected in the range of, for example, 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 30 μm, and particularly preferably 5 to 20 μm. A glass fiber having an average fiber diameter of less than 1 μm is not easy to manufacture and may increase the cost, while if it exceeds 100 μm, the tensile strength of the glass fiber may decrease.
The average fiber length of the glass fiber (B) is not particularly limited, but is preferably selected in the range of, for example, 0.1 to 20 mm, more preferably 0.3 to 5 mm. If the average fiber length is less than 0.1 mm, the reinforcing effect may not be sufficiently exhibited, and if it exceeds 20 mm, it may be difficult to mold the obtained polyester resin composition.
ガラス繊維（Ｂ）は、収束剤又は表面処理剤と組み合わせて使用してもよい。このような収束剤又は表面処理剤としては、任意のものを使用でき、具体的には、例えば、アミノシラン系、エポキシシラン系、アリルシラン系、ビニルシラン系等のシラン系カップリング剤が好ましく挙げられる。
これらの中では、アミノシラン系表面処理剤が好ましく、具体的には例えば、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン及びγ−（２−アミノエチル）アミノプロピルトリメトキシシランが好ましい例として挙げられる。
また、ノボラック型等のエポキシ樹脂、ビスフェノールＡ型のエポキシ樹脂等も好ましく挙げられる。中でも、ノボラック型のエポキシ樹脂がより好ましい。
収束剤又は表面処理剤は、それぞれ単独で用いても複数種で用いてもよく、両者を併用することも好ましい。
The glass fiber (B) may be used in combination with a converging agent or a surface treatment agent. Any such converging agent or surface treatment agent can be used, and specific examples thereof include silane-based coupling agents such as aminosilane-based, epoxysilane-based, allylsilane-based, and vinylsilane-based coupling agents.
Among these, an aminosilane-based surface treatment agent is preferable, and specifically, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.
Further, a novolak type epoxy resin, a bisphenol A type epoxy resin and the like are also preferably mentioned. Of these, a novolak type epoxy resin is more preferable.
The converging agent or the surface treatment agent may be used alone or in a plurality of types, and it is also preferable to use both in combination.
ガラス繊維（Ｂ）は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、０〜１２０質量部であり、好ましくは１０質量部以上、より好ましくは２０質量部以上、さらに好ましくは３０質量部以上であり、また、好ましくは１００質量部以下、より好ましくは９０質量部以下、さらに好ましくは８０質量部以下、特には７０質量部以下であることが好ましい。ガラス繊維（Ｂ）の含有量が１２０質量部を上回ると、流動性が著しく損なわれ、好適に射出成形できなくなることがあるので好ましくない。 The glass fiber (B) is 0 to 120 parts by mass, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably 100 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. If the content of the glass fiber (B) exceeds 120 parts by mass, the fluidity is significantly impaired and injection molding may not be suitable, which is not preferable.
［臭素系難燃剤（Ｃ）］
本発明に用いる臭素系難燃剤（Ｃ）としては、従来公知の任意の、熱可塑性ポリエステル樹脂に使用される臭素系難燃剤を用いることができる。このような臭素系難燃剤としては、具体的には、例えば、テトラブロモビスフェノールＡのエポキシオリゴマー等の臭素化エポキシ、臭素化ポリスチレン、臭素化ポリカーボネート、ペンタブロモポリベンジルアクリレート等の臭素化ベンジルポリ（メタ）アクリレート、Ｎ，Ｎ’−エチレンビス（テトラブロモフタルイミド）等の臭素化イミド、臭素化ポリフェニレンエーテル、臭素化フェノキシ樹脂、臭素化ビスフェノールＡ、グリシジル臭素化ビスフェノールＡ等が挙げられる。
[Brominated flame retardant (C)]
As the brominated flame retardant (C) used in the present invention, any conventionally known brominated flame retardant used for thermoplastic polyester resins can be used. Specific examples of such a bromine-based flame retardant include brominated epoxy such as an epoxy oligomer of tetrabromobisphenol A, brominated benzyl poly (meth) such as brominated polystyrene, brominated polycarbonate, and pentabromopolybenzyl acrylate. ) Acrylate, brominated imide such as N, N'-ethylenebis (tetrabromophthalimide), brominated polyphenylene ether, brominated phenoxy resin, brominated bisphenol A, glycidyl brominated bisphenol A and the like.
これらの中でも、臭素化ベンジルポリ（メタ）アクリレート、臭素化ポリカーボネート、臭素化ポリスチレン、グリシジル臭素化ビスフェノールＡが、耐衝撃性の低下を抑制しやすい傾向にあり、好ましい。 Among these, brominated benzyl poly (meth) acrylate, brominated polycarbonate, brominated polystyrene, and glycidyl brominated bisphenol A tend to suppress a decrease in impact resistance and are preferable.
臭素化ベンジルポリ（メタ）アクリレートとしては、ペンタブロモベンジルポリアクリレートが特に好ましい。
臭素化ポリカーボネートとしては、臭素化ビスフェノールＡ、特にテトラブロモビスフェノールＡから得られる、臭素化ポリカーボネートであることが好ましい。その末端構造は４−ｔ−ブチルフェニル基や２，４，６−トリブロモフェニル基等が挙げられ、特に、末端基構造に２，４，６−トリブロモフェニル基を有するものが好ましい。
臭素化エポキシとしては、例えば、臭素化ビスフェノール、好ましくはテトラブロモビスフェノールＡを出発原料とし、その分子末端にエポキシ基を有する臭素化エポキシが代表的であり、オリゴマータイプやポリマータイプのものも好ましい。
As the bromide benzyl poly (meth) acrylate, pentabromobenzyl polyacrylate is particularly preferable.
The brominated polycarbonate is preferably a brominated polycarbonate obtained from brominated bisphenol A, particularly tetrabromobisphenol A. Examples of the terminal structure include a 4-t-butylphenyl group and a 2,4,6-tribromophenyl group, and those having a 2,4,6-tribromophenyl group in the terminal group structure are particularly preferable.
As the brominated epoxy, for example, a brominated epoxy using brominated bisphenol, preferably tetrabromobisphenol A as a starting material and having an epoxy group at the molecular terminal thereof is typical, and an oligomer type or a polymer type is also preferable.
臭素化ポリスチレンとしては、例えば、ポリ（４−ブロモスチレン）、ポリ（２−ブロモスチレン）、ポリ（３−ブロモスチレン）、ポリ（２，４−ジブロモスチレン）、ポリ（２，６−ジブロモスチレン）、ポリ（２，５−ジブロモスチレン）、ポリ（３，５−ジブロモスチレン）、ポリ（２，４，６−トリブロモスチレン）、ポリ（２，４，５−トリブロモスチレン）、ポリ（２，３，５−トリブロモスチレン）、ポリ（４−ブロモ−α−メチルスチレン）、ポリ（２，４−ジブロモ−α−メチルスチレン）、ポリ（２，５−ジブロモ−α−メチルスチレン）、ポリ（２，４，６−トリブロモ−α−メチルスチレン）およびポリ（２，４，５−トリブロモ−α−メチルスチレン）等が挙げられ、ポリ（２，４，６−トリブロモスチレン）、ポリ（２，４，５−トリブロモスチレン）および平均２〜３個の臭素基をベンゼン環中に含有するポリジブロモスチレン、ポリトリブロモスチレンが特に好ましく用いられる。 Examples of brominated polystyrene include poly (4-bromostyrene), poly (2-bromostyrene), poly (3-bromostyrene), poly (2,4-dibromostyrene), and poly (2,6-dibromostyrene). ), Poly (2,5-dibromostyrene), Poly (3,5-dibromostyrene), Poly (2,4,6-tribromostyrene), Poly (2,4,5-tribromostyrene), Poly ( 2,3,5-tribromostyrene), poly (4-bromo-α-methylstyrene), poly (2,4-dibromo-α-methylstyrene), poly (2,5-dibromo-α-methylstyrene) , Poly (2,4,6-tribromo-α-methylstyrene), poly (2,4,5-tribromo-α-methylstyrene) and the like, and poly (2,4,6-tribromostyrene), Poly (2,4,5-tribromostyrene) and polydibromostyrene and polytribromostyrene containing an average of 2 to 3 bromine groups in the benzene ring are particularly preferably used.
臭素系難燃剤（Ｃ）の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、０〜６０質量部である。６０質量部を超えると機械的強度が低下する。臭素系難燃剤（Ｂ）の好ましい含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、５質量部以上であり、より好ましくは８質量部以上、さらに好ましくは１０質量部以上であり、また好ましくは５０質量部以下であり、より好ましくは４０質量部以下、さらに好ましくは３０質量部以下、特に好ましくは２０質量部以下である。 The content of the brominated flame retardant (C) is 0 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If it exceeds 60 parts by mass, the mechanical strength decreases. The preferable content of the bromine-based flame retardant (B) is 5 parts by mass or more, more preferably 8 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.
ガラス繊維（Ｂ）と臭素系難燃剤（Ｃ）の含有量の合計は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、５〜１５０質量部である。本発明はガラス繊維（Ｂ）および／または臭素系難燃剤（Ｃ）の配合により強度向上および／または難燃性の機能が付与される代わりにＣＴＩが低下する現象を改善するものであるが、５質量部未満ではＣＴＩの低下が小さいが、強度向上および／または難燃性のいずれの機能も十分には発現しないので好ましくない。１５０質量部を超えると流動性が著しく悪化し、好適に射出成形できなくなることが ある。ガラス繊維（Ｂ）と臭素系難燃剤（Ｃ）の含有量の合計は、好ましくは１０質量部以上、より好ましくは２０質量部以上、さらに好ましくは３０質量部以上、特に好ましくは４０質量部以上であり、好ましくは１２０質量部以下、より好ましくは１００質量部以下、さらに好ましくは８０質量部以下である。 The total content of the glass fiber (B) and the brominated flame retardant (C) is 5 to 150 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). The present invention improves the phenomenon that the CTI is lowered at the cost of improving the strength and / or imparting the flame retardant function by blending the glass fiber (B) and / or the brominated flame retardant (C). If it is less than 5 parts by mass, the decrease in CTI is small, but it is not preferable because neither the function of improving strength and / or the function of flame retardancy is sufficiently exhibited. If it exceeds 150 parts by mass, the fluidity is significantly deteriorated, and injection molding may not be suitable. The total content of the glass fiber (B) and the brominated flame retardant (C) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more. It is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 80 parts by mass or less.
［フッ素樹脂（Ｄ１）及び（Ｄ２）］
本発明のポリエステル樹脂組成物は、第１のフッ素樹脂（Ｄ１）と、第１のフッ素樹脂（Ｄ１）より質量平均分子量が低い第２のフッ素樹脂（Ｄ２）を含有する。
高分子量の第１のフッ素樹脂（Ｄ１）を含有するだけの場合では、難燃性を向上させることはできるが耐トラッキング性（ＣＴＩ）は向上せず、さらに含有量を増加させるとＣＴＩを多少上げることはできるが、樹脂組成物ペレットの製造時にストランド切れが起きやすく、生産性が悪くなり、また品質の悪化（ペレット中に凝集異物発生等）が起きやすい。一方、低分子量の第２のフッ素樹脂（Ｄ２）だけを含有する場合、生産性や品質は悪化しないものの、ＣＴＩや難燃性の改善効果はみられない。
しかし、高分子量の第１のフッ素樹脂（Ｄ１）と低分子量の第２のフッ素樹脂（Ｄ２）を併せて含有することにより、ＣＴＩが顕著に向上し、難燃性、強度にも優れ、生産性や品質の問題も発生しないことが見いだされた。
[Fluororesin (D1) and (D2)]
The polyester resin composition of the present invention contains a first fluororesin (D1) and a second fluororesin (D2) having a lower mass average molecular weight than the first fluororesin (D1).
If only the high molecular weight first fluororesin (D1) is contained, the flame retardancy can be improved, but the tracking resistance (CTI) is not improved, and if the content is further increased, the CTI is slightly increased. Although it can be increased, strand breakage is likely to occur during the production of resin composition pellets, productivity is deteriorated, and quality is likely to be deteriorated (aggregated foreign matter is generated in the pellets, etc.). On the other hand, when only the second fluororesin (D2) having a low molecular weight is contained, the productivity and quality are not deteriorated, but the effect of improving CTI and flame retardancy is not observed.
However, by containing the high molecular weight first fluororesin (D1) and the low molecular weight second fluororesin (D2) together, the CTI is remarkably improved, and the flame retardancy and strength are excellent, and the production is excellent. It was found that there were no problems with sex or quality.
第１のフッ素樹脂（Ｄ１）の質量平均分子量は、１，０００，０００〜１００，０００，０００であることが好ましく、より好ましくは１，０００，０００〜５０，０００，０００である。また、第２のフッ素樹脂（Ｄ２）の質量平均分子量は、６０，０００〜８００，０００であることが好ましく、より好ましくは８０，０００〜７００，０００、さらに好ましくは１００，０００〜６００，０００である。 The mass average molecular weight of the first fluororesin (D1) is preferably 1,000,000 to 100,000,000, more preferably 1,000,000 to 50,000,000. The mass average molecular weight of the second fluororesin (D2) is preferably 60,000 to 800,000, more preferably 80,000 to 700,000, and even more preferably 100,000 to 600,000. Is.
なお、フッ素樹脂（Ｄ１）及び（Ｄ２）の質量平均分子量は、示差熱分析装置を用いて、フッ素樹脂試料を３７０℃から２０℃まで冷却したときの結晶化熱を測定し、下記式に従って算出される。
Ｍ＝２．１×１０１０×ΔＨｃ−５．１６
ここで、Ｍは質量平均分子量、ΔＨｃは結晶化熱（ｃａｌ／ｇ）である。
The mass average molecular weights of the fluororesins (D1) and (D2) are calculated according to the following formula by measuring the heat of crystallization when the fluororesin sample is cooled from 370 ° C. to 20 ° C. using a differential thermal analyzer. Will be done.
M = 2.1 × 10 10 × ΔHc- 5.16
Here, M is the mass average molecular weight, and ΔHc is the heat of crystallization (cal / g).
フッ素樹脂（Ｄ１）及び（Ｄ２）のフッ素樹脂としては、例えば、フルオロオレフィン樹脂が挙げられる。フルオロオレフィン樹脂は、通常フルオロエチレン構造を含む重合体あるいは共重合体であり、具体例としては、テトラフルオロエチレン重合体、ジフルオロエチレン重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／パーフルアルキルビニルエーテル共重合体、テトラフルオロエチレン／パーフルオロアルキル（メタ）アクリレート共重合体等が挙げられる。中でも好ましくはテトラフルオロエチレン重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体等が好ましい。 Examples of the fluororesin (D1) and (D2) fluororesin include fluoroolefin resins. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples thereof include a tetrafluoroethylene polymer, a difluoroethylene polymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and a tetrafluoroethylene. / Perflualkyl vinyl ether copolymer, tetrafluoroethylene / perfluoroalkyl (meth) acrylate copolymer and the like can be mentioned. Of these, a tetrafluoroethylene polymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and the like are preferable.
また、フッ素樹脂（Ｄ１）及び（Ｄ２）としては、有機重合体被覆フルオロオレフィン樹脂も好適に使用することができる。有機重合体被覆フルオロオレフィン樹脂を用いることで、分散性が向上し、成形品の表面外観が向上し、表面異物を抑制できる。有機重合体被覆フルオロオレフィン樹脂は、公知の種々の方法により製造でき、例えば、ポリフルオロエチレン粒子水性分散液と有機系重合体粒子水性分散液とを混合して、凝固またはスプレードライにより粉体化して製造する方法、ポリフルオロエチレン粒子水性分散液存在下で、有機系重合体を構成する単量体を重合した後、凝固またはスプレードライにより粉体化して製造する方法、ポリフルオロエチレン粒子水性分散液と有機系重合体粒子水性分散液とを混合した分散液中で、エチレン性不飽和結合を有する単量体を乳化重合した後、凝固またはスプレードライにより粉体化して製造する方法、等が挙げられる。 Further, as the fluororesins (D1) and (D2), organic polymer-coated fluoroolefin resins can also be preferably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and foreign substances on the surface can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and pulverized by coagulation or spray drying. Polyfluoroethylene particle aqueous dispersion, a method in which the monomers constituting the organic polymer are polymerized in the presence of an aqueous dispersion of polyfluoroethylene particles and then powdered by coagulation or spray drying. A method of emulsion-polymerizing a monomer having an ethylenically unsaturated bond in a dispersion liquid obtained by mixing the liquid and an aqueous dispersion of organic polymer particles and then powdering the monomer by coagulation or spray drying, etc. Can be mentioned.
第１のフッ素樹脂（Ｄ１）と第２のフッ素樹脂（Ｄ２）の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、（Ｄ１）と（Ｄ２）の合計で１〜２５質量部であり、好ましくは２質量部以上、より好ましくは３質量部以上であり、好ましくは２０質量部以下、より好ましくは１５質量部以下である。（Ｄ１）と（Ｄ２）の合計含有量が１質量部未満ではＣＴＩの向上効果が不十分になり、２５質量部を超えると機械強度が悪くなる。 The content of the first fluororesin (D1) and the second fluororesin (D2) is 1 to 25 parts by mass in total of (D1) and (D2) with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. If the total content of (D1) and (D2) is less than 1 part by mass, the effect of improving CTI is insufficient, and if it exceeds 25 parts by mass, the mechanical strength is deteriorated.
また、第１のフッ素樹脂（Ｄ１）の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、０．４〜３質量部であることが好ましく、より好ましくは０．５質量部以上、さらに好ましくは１質量部以上であり、より好ましくは２．７質量部以下、さらに好ましくは２．５質量部以下である。
また、第２のフッ素樹脂（Ｄ２）の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対し、０．２〜２０質量部であることが好ましく、より好ましくは０．５質量部以上、さらに好ましくは１質量部以上であり、より好ましくは１５質量部以下、さらに好ましくは１２質量部以下である。
さらに、フッ素樹脂（Ｄ１）とフッ素樹脂（Ｄ２）の含有量の質量比（Ｄ１／Ｄ２）は、１／０．５〜１／１０であることが好ましく、１／１〜１／５であることがより好ましい。
The content of the first fluororesin (D1) is preferably 0.4 to 3 parts by mass, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably 1 part by mass or more, more preferably 2.7 parts by mass or less, and further preferably 2.5 parts by mass or less.
The content of the second fluororesin (D2) is preferably 0.2 to 20 parts by mass, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the thermoplastic polyester resin (A). It is more preferably 1 part by mass or more, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less.
Further, the mass ratio (D1 / D2) of the contents of the fluororesin (D1) and the fluororesin (D2) is preferably 1 / 0.5 to 1/10, preferably 1/1 to 1/5. Is more preferable.
［難燃助剤］
さらに本発明のポリエステル樹脂組成物は、臭素系難燃剤（Ｃ）と共に、難燃助剤を含有することが好ましい。難燃助剤としては、例えば、アンチモン化合物、硼酸亜鉛、酸化銅、酸化マグネシウム、酸化亜鉛、酸化モリブデン、酸化ジルコニウム、酸化スズ、酸化鉄、酸化チタン、酸化アルミニウム等が挙げられ、２種以上併用してもよい。これらの中でも、難燃性がより優れる点からアンチモン化合物、硼酸亜鉛が好ましい。
アンチモン化合物としては、三酸化アンチモン（Ｓｂ２Ｏ３）、五酸化アンチモン（Ｓｂ２Ｏ５）、アンチモン酸ナトリウム等が挙げられる。特に、臭素系難燃剤（Ｃ）との相乗効果から、三酸化アンチモンを併用することが好ましい。
[Flame retardant aid]
Further, the polyester resin composition of the present invention preferably contains a flame retardant aid together with the brominated flame retardant (C). Examples of the flame retardant aid include antimony compounds, zinc borate, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, zirconium oxide, tin oxide, iron oxide, titanium oxide, aluminum oxide and the like, and two or more of them are used in combination. You may. Among these, an antimony compound and zinc borate are preferable from the viewpoint of being more excellent in flame retardancy.
Examples of the antimony compound include antimony trioxide (Sb 2 O 3 ), antimony pentoxide (Sb 2 O 5 ), sodium antimonate and the like. In particular, it is preferable to use antimony trioxide in combination because of the synergistic effect with the brominated flame retardant (C).
ポリエステル樹脂組成物中の臭素系難燃剤（Ｃ）由来の臭素原子と、アンチモン化合物由来のアンチモン原子の質量濃度が、両者の合計で５〜１６質量％であることが好ましく、６〜１５質量％であることがより好ましい。５質量％未満であると難燃性が低下する傾向にあり、１６質量％を超えると機械的強度や耐トラッキング特性が低下する場合がある。また、臭素原子とアンチモン原子の質量比（ハロゲン原子／アンチモン原子）は、０．３〜５であることが好ましく、０．３〜４であることがより好ましい。 The mass concentration of the bromine atom derived from the brominated flame retardant (C) and the antimony atom derived from the antimony compound in the polyester resin composition is preferably 5 to 16% by mass, preferably 6 to 15% by mass in total. Is more preferable. If it is less than 5% by mass, the flame retardancy tends to decrease, and if it exceeds 16% by mass, the mechanical strength and tracking resistance may decrease. The mass ratio of the bromine atom to the antimony atom (halogen atom / antimony atom) is preferably 0.3 to 5, and more preferably 0.3 to 4.
難燃助剤の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、好ましくは１〜２０質量部、より好ましくは３〜１５質量部、さらに好ましくは５〜１０質量部である。 The content of the flame retardant aid is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). ..
［無機充填材］
本発明のポリエステル樹脂組成物には、ガラス繊維（Ｂ）以外の無機充填材を含有することも好ましい。無機充填材としては常用のものをいずれも用いることができる。ガラス繊維（Ｂ）以外の無機充填材を含有する場合の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、好ましくは０．５〜５０質量部であり、より好ましくは１質量部以上であり、より好ましくは４０質量部以下、さらに好ましくは３０質量部以下である。ガラス繊維（Ｂ）以外の無機充填材の含有量が５０質量部を上回ると、流動性が低下するので好ましくない。
[Inorganic filler]
It is also preferable that the polyester resin composition of the present invention contains an inorganic filler other than the glass fiber (B). Any of the commonly used inorganic fillers can be used. When an inorganic filler other than the glass fiber (B) is contained, the content is preferably 0.5 to 50 parts by mass, and more preferably 1 part by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). It is more than a part, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less. If the content of the inorganic filler other than the glass fiber (B) exceeds 50 parts by mass, the fluidity decreases, which is not preferable.
ガラス繊維（Ｂ）以外の無機充填材としては、具体的には例えば、炭素繊維、ウォラストナイト、チタン酸カリウム繊維等の繊維状の充填材；炭酸カルシウム、酸化チタン、長石系鉱物、クレー、有機化クレー、ガラスビーズ等の粒状又は無定形の充填材；タルク等の板状の充填材；ガラスフレーク、マイカ、グラファイト等の鱗片状の充填材を用いることもできる。中でも、機械的強度、剛性及び耐熱性の点からタルクを用いるのが好ましい。 Specific examples of the inorganic filler other than the glass fiber (B) include fibrous fillers such as carbon fiber, wollastonite, and potassium titanate fiber; calcium carbonate, titanium oxide, pebbles mineral, clay, and the like. Granular or amorphous fillers such as organic clay and glass beads; plate-like fillers such as talc; scaly fillers such as glass flakes, mica and graphite can also be used. Above all, it is preferable to use talc from the viewpoint of mechanical strength, rigidity and heat resistance.
［離型剤］
本発明のポリエステル樹脂組成物は、更に、離型剤を含有することが好ましい。離型剤としては、ポリエステル樹脂に通常使用される既知の離型剤が利用可能であるが、中でも、離型性が優れる点で、ポリオレフィン系化合物、脂肪酸エステル系化合物及びシリコーン系化合物から選ばれる１種以上の離型剤が好ましい。
[Release agent]
The polyester resin composition of the present invention preferably further contains a mold release agent. As the release agent, a known release agent usually used for polyester resins can be used, and among them, a polyolefin-based compound, a fatty acid ester-based compound, and a silicone-based compound are selected because of their excellent releasability. One or more mold release agents are preferable.
ポリオレフィン系化合物としては、パラフィンワックス及びポリエチレンワックスから選ばれる化合物が挙げられ、中でも、質量平均分子量が、７００〜１０，０００、更には９００〜８，０００のものが好ましい。 Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax, and among them, those having a mass average molecular weight of 700 to 10,000, more preferably 900 to 8,000 are preferable.
脂肪酸エステル系化合物としては、グリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類等の脂肪酸エステル類やその部分鹸化物などが挙げられ、中でも、炭素数１１〜２８、好ましくは炭素数１７〜２１の脂肪酸で構成されるモノ又はジ脂肪酸エステルが好ましい。具体的には、グリセリンモノステアレート、グリセリンモノベヘネート、グリセリンジベヘネート、グリセリン−１２−ヒドロキシモノステアレート、ソルビタンモノベヘネート等が挙げられる。 Examples of the fatty acid ester-based compound include fatty acid esters such as glycerin fatty acid esters and sorbitan fatty acid esters, and partial saponified products thereof. Among them, the fatty acid is composed of fatty acids having 11 to 28 carbon atoms, preferably 17 to 21 carbon atoms. Mono or difatty acid esters to be produced are preferred. Specific examples thereof include glycerin monostearate, glycerin monobehenate, glycerin dibehenate, glycerin-12-hydroxymonostearate, and sorbitan monobehenate.
また、シリコーン系化合物としては、熱可塑性ポリエステル樹脂との相容性などの点から、変性されている化合物が好ましい。変性シリコーンオイルとしては、ポリシロキサンの側鎖に有機基を導入したシリコーンオイル、ポリシロキサンの両末端及び／又は片末端に有機基を導入したシリコーンオイルなどが挙げられる。導入される有機基としては、エポキシ基、アミノ基、カルボキシル基、カルビノール基、メタクリル基、メルカプト基、フェノール基などが挙げられ、好ましくはエポキシ基が挙げられる。変性シリコーンオイルとしては、ポリシロキサンの側鎖にエポキシ基を導入したシリコーンオイルが特に好ましい。 Further, as the silicone-based compound, a modified compound is preferable from the viewpoint of compatibility with the thermoplastic polyester resin and the like. Examples of the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, and silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane. Examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, a phenol group and the like, and an epoxy group is preferable. As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.
離型剤の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、０．０５〜２質量部であることが好ましい。０．０５質量部未満であると、溶融成形時の離型不良により表面性が低下する傾向があり、一方、２質量部を超えると、樹脂組成物の練り込み作業性が低下し、また成形品表面に曇りが見られる場合がある。離型剤の含有量は、好ましくは０．０７〜１．５質量部、更に好ましくは０．１〜１．０質量部である。 The content of the release agent is preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic polyester resin (A). If it is less than 0.05 parts by mass, the surface property tends to be deteriorated due to poor mold release during melt molding, while if it exceeds 2 parts by mass, the kneading workability of the resin composition is lowered and molding is performed. Cloudiness may be seen on the surface of the product. The content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass.
［安定剤］
本発明のポリエステル樹脂組成物は、さらに安定剤を含有することが、熱安定性改良や、機械的強度、透明性及び色相の悪化を防止する効果を有するという点で好ましい。安定剤としては、リン系安定剤およびフェノール系安定剤が好ましい。
リン系安定剤としては、亜リン酸、リン酸、亜リン酸エステル、リン酸エステル等が挙げられ、中でもホスファイト、ホスホナイトが好ましい。
[Stabilizer]
It is preferable that the polyester resin composition of the present invention further contains a stabilizer because it has an effect of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. As the stabilizer, a phosphorus-based stabilizer and a phenol-based stabilizer are preferable.
Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphorous acid ester, and phosphoric acid ester, and among them, phosphite and phosphonite are preferable.
ホスファイトとしては、例えば、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、ジラウリルハイドロジェンホスファイト、トリエチルホスファイト、トリデシルホスファイト、トリス（２−エチルヘキシル）ホスファイト、トリス（トリデシル）ホスファイト、トリステアリルホスファイト、ジフェニルモノデシルホスファイト、モノフェニルジデシルホスファイト、ジフェニルモノ（トリデシル）ホスファイト、テトラフェニルジプロピレングリコールジホスファイト、テトラフェニルテトラ（トリデシル）ペンタエリスリトールテトラホスファイト、水添ビスフェノールＡフェノールホスファイトポリマー、ジフェニルハイドロジェンホスファイト、４，４’−ブチリデン−ビス（３−メチル−６−ｔｅｒｔ−ブチルフェニルジ（トリデシル）ホスファイト）、テトラ（トリデシル）４，４’−イソプロピリデンジフェニルジホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ジラウリルペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリス（４−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、水添ビスフェノールＡペンタエリスリトールホスファイトポリマー、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト等が挙げられる。 Examples of phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilaurylhydrogen phosphite, triethylphosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl) phos. Fight, Tristearyl Phosphite, Diphenyl Monodecyl Phosphite, Monophenyl Didecyl Phosphite, Diphenyl Mono (Tridecyl) Phosphite, Tetraphenyl Dipropylene Glycol Diphosphite, Tetraphenyl Tetra (Tridecyl) Pentaerythritol Tetraphosphite, Water Additive bisphenol A phenol phosphite polymer, diphenylhydrogen phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4'- Isopropyridene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert- Butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2, 4-Dicumylphenyl) Pentaerythritol diphosphite and the like can be mentioned.
また、ホスホナイトとしては、テトラキス（２，４−ジ−ｉｓｏ−プロピルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｎ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｉｓｏ−プロピルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｎ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、およびテトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイトなどが挙げられる。 Examples of phosphonite include tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Nite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis 2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite and the like. ..
また、ホスフェートとしては、例えば、メチルアシッドホスフェート、エチルアシッドホスフェート、プロピルアシッドホスフェート、イソプロピルアシッドホスフェート、ブチルアシッドホスフェート、ブトキシエチルアシッドホスフェート、オクチルアシッドホスフェート、２−エチルヘキシルアシッドホスフェート、デシルアシッドホスフェート、ラウリルアシッドホスフェート、ステアリルアシッドホスフェート、オレイルアシッドホスフェート、ベヘニルアシッドホスフェート、フェニルアシッドホスフェート、ノニルフェニルアシッドホスフェート、シクロヘキシルアシッドホスフェート、フェノキシエチルアシッドホスフェート、アルコキシポリエチレングリコールアシッドホスフェート、ビスフェノールＡアシッドホスフェート、ジメチルアシッドホスフェート、ジエチルアシッドホスフェート、ジプロピルアシッドホスフェート、ジイソプロピルアシッドホスフェート、ジブチルアシッドホスフェート、ジオクチルアシッドホスフェート、ジ−２−エチルヘキシルアシッドホスフェート、ジオクチルアシッドホスフェート、ジラウリルアシッドホスフェート、ジステアリルアシッドホスフェート、ジフェニルアシッドホスフェート、ビスノニルフェニルアシッドホスフェート等が挙げられる。
リン系安定剤は、１種が含有されていてもよく、２種以上が任意の組み合わせ及び比率で含有されていても良い。
Examples of the phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl acid phosphate. , Stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, Dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc. Can be mentioned.
One type of phosphorus stabilizer may be contained, and two or more types may be contained in any combination and ratio.
フェノール系安定剤の具体例としては、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナミド］、２，４−ジメチル−６−（１−メチルペンタデシル）フェノール、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスフォエート、３，３’，３’’，５，５’，５’’−ヘキサ−ｔｅｒｔ−ブチル−ａ，ａ’，ａ’’−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔｅｒｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン，２，６−ジ−ｔｅｒｔ−ブチル−４−（４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ）フェノール等が挙げられる。 Specific examples of the phenolic stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-). 4-Hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl)- 4-Hydroxyphenyl] methyl] phosphate, 3,3', 3'', 5,5', 5''-hexa-tert-butyl-a, a', a''-(mesitylen-2,4,6 -Triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3, 5-Triazin-2-ylamino) phenol and the like can be mentioned.
中でも、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネートが好ましい。
なお、フェノール系安定剤は、１種が含有されていてもよく、２種以上が任意の組み合わせ及び比率で含有されていても良い。
Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. ..
In addition, 1 type may be contained in the phenol-based stabilizer, and 2 or more types may be contained in arbitrary combinations and ratios.
安定剤の含有量は、熱可塑性ポリエステル樹脂（Ａ）１００質量部に対して、通常０．００１質量部以上、好ましくは０．０１質量部以上であり、また、通常１．５質量部以下、好ましくは１質量部以下である。０．００１質量部未満では安定剤としての効果が不十分であり、成形時の分子量の低下や色相悪化が起こりやすく、また１．５質量部を超えると、過剰量となりシルバーの発生や、色相悪化が更に起こりやすくなる傾向がある。 The content of the stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1.5 part by mass or less, based on 100 parts by mass of the thermoplastic polyester resin (A). It is preferably 1 part by mass or less. If it is less than 0.001 part by mass, the effect as a stabilizer is insufficient, and the molecular weight at the time of molding is likely to decrease and the hue is likely to deteriorate. Deterioration tends to be more likely.
［その他成分］
本発明のポリエステル樹脂組成物は、本発明の効果を損なわない範囲で、上記した以外の種々の添加剤を含有していても良い。このような添加剤としては、紫外線吸収剤、染顔料、蛍光増白剤、帯電防止剤、防曇剤、滑剤、アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、抗菌剤等が挙げられる。
[Other ingredients]
The polyester resin composition of the present invention may contain various additives other than those described above as long as the effects of the present invention are not impaired. Examples of such additives include ultraviolet absorbers, dye pigments, fluorescent whitening agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improving agents, plasticizers, dispersants, antibacterial agents and the like. Be done.
また、本発明におけるポリエステル樹脂組成物には、熱可塑性ポリエステル樹脂（Ａ）以外の熱可塑性樹脂を、本発明の効果を損わない範囲で含有することができる。その他の熱可塑性樹脂としては、具体的には、例えば、ポリアセタール樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、ポリスチレン系樹脂、ポリフェニレンサルファイド樹脂、ポリサルホン樹脂、ポリエーテルサルホン樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂等が挙げられる。 Further, the polyester resin composition in the present invention may contain a thermoplastic resin other than the thermoplastic polyester resin (A) as long as the effects of the present invention are not impaired. Specific examples of other thermoplastic resins include polyacetal resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, polystyrene resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyetherimide resin, and the like. Examples thereof include polyether ketone resins.
［樹脂組成物の製造方法］
本発明のポリエステル樹脂組成物の製造方法としては、ポリエステル樹脂組成物調製の常法に従って行うことができる。通常は各成分及び所望により添加される種々の添加剤を一緒にしてよく混合し、次いで一軸又は二軸押出機で溶融混練する。なお、ガラス繊維は、押出機のシリンダー途中のサイドフィーダーから供給することが好ましい。また各成分を予め混合することなく、ないしはその一部のみを予め混合し、フィーダーを用いて押出機に供給して溶融混練し、本発明の樹脂組成物を調製することもできる。さらには、ポリエステル樹脂の一部に他の成分の一部を配合したものを溶融混練してマスターバッチを調製し、次いでこれに残りのポリエステル樹脂や他の成分を配合して溶融混練してもよい。
[Manufacturing method of resin composition]
The method for producing the polyester resin composition of the present invention can be carried out according to a conventional method for preparing a polyester resin composition. Usually, each component and various additives added as desired are mixed well together and then melt-kneaded in a uniaxial or twin-screw extruder. The glass fiber is preferably supplied from the side feeder in the middle of the cylinder of the extruder. Further, the resin composition of the present invention can also be prepared by premixing each component without premixing or only a part thereof, supplying the component to an extruder using a feeder and melt-kneading. Furthermore, even if a masterbatch is prepared by melt-kneading a part of a polyester resin mixed with a part of other components, and then melt-kneading the remaining polyester resin or other components. Good.
溶融混練に際しての加熱温度は、通常２２０〜３００℃の範囲から適宜選ぶことができる。温度が高すぎると分解ガスが発生しやすく、不透明化の原因になる場合がある。それ故、剪断発熱等に考慮したスクリュー構成の選定が望ましい。混練り時や、後行程の成形時の分解を抑制する為、酸化防止剤や熱安定剤の使用が望ましい。 The heating temperature for melt-kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation and the like. It is desirable to use an antioxidant or a heat stabilizer in order to suppress decomposition during kneading and molding in the subsequent process.
［成形体］
本発明のポリエステル樹脂組成物は、通常、任意の形状に成形して成形体として用いる。この成形体の形状、模様、色、寸法等に制限はなく、その成形体の用途に応じて任意に設定すればよい。
成形体の製造方法は、特に限定されず、ポリエステル樹脂組成物について一般に採用されている成形法を任意に採用できる。その例を挙げると、射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシスト等の中空成形法、断熱金型を使用した成形法、急速加熱金型を使用した成形法、発泡成形（超臨界流体も含む）、インサート成形、ＩＭＣ（インモールドコーティング成形）成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法、ブロー成形法等が挙げられ、中でも射出成形法が好ましい。
[Molded product]
The polyester resin composition of the present invention is usually molded into an arbitrary shape and used as a molded product. There are no restrictions on the shape, pattern, color, dimensions, etc. of this molded product, and it may be arbitrarily set according to the intended use of the molded product.
The method for producing the molded product is not particularly limited, and any molding method generally used for the polyester resin composition can be adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, Blow molding method and the like can be mentioned, and injection molding method is particularly preferable.
本発明のポリエステル樹脂組成物は、難燃性、流動性、高い耐トラッキング性を有し、強度にも優れるポリエステル樹脂材料であるので、電気電子機器あるいはそれ等の絶縁性部品として特に好適である。
絶縁性部品としては、金属接点、銅版などと組み合わせることにより、電気接点開閉部を有する電気電子機器部品、例えばリレー、スイッチ、ターミナルスイッチ、センサー、コネクター、アクチュエーター、マイクロスイッチ、マイクロセンサーおよびマイクロアクチュエーター等の有接点電気電子部品や、ブレーカー等の電気電子製品の筐体或いはカバー等として好ましく用いることができる。
The polyester resin composition of the present invention is a polyester resin material having flame retardancy, fluidity, high tracking resistance, and excellent strength, and is therefore particularly suitable as an insulating component for electrical and electronic equipment or the like. ..
Insulating parts include electrical and electronic equipment parts that have an electrical contact opening / closing part by combining with metal contacts, copper plates, etc., such as relays, switches, terminal switches, sensors, connectors, actuators, microswitches, microsensors, and microactors. It can be preferably used as a contact electric / electronic component, a housing or a cover of an electric / electronic product such as a breaker.
以下、実施例を示して本発明について更に具体的に説明する。ただし、本発明は以下の実施例に限定して解釈されるものではない。
なお、以下の説明において［部］とは、特に断りのない限り、質量基準に基づく「質量部」を表す。
以下の実施例および比較例において、使用した成分は、以下の表１の通りである。
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not construed as being limited to the following examples.
In the following description, [part] means "part by mass" based on the mass standard unless otherwise specified.
The components used in the following Examples and Comparative Examples are as shown in Table 1 below.
（実施例１〜３、比較例１〜８）
上記表１に記載の各成分を下記表２に記載の配合割合（質量部）になるように配合し、２軸押出機（日本製鋼所社製「ＴＥＸ−３０α」、スクリュー径３０ｍｍ）を用い、ガラス繊維はサイドフィーダーから供給し、バレル設定温度２５０℃、回転数２００ｒｐｍで溶融混練し、ストランド状に押出し、冷却後カッティングして、樹脂組成物のペレットを作った。
(Examples 1 to 3 and Comparative Examples 1 to 8)
Each component listed in Table 1 above is blended so as to have the blending ratio (parts by mass) shown in Table 2 below, and a twin-screw extruder (“TEX-30α” manufactured by Japan Steel Works, Ltd., screw diameter 30 mm) is used. , Glass fibers were supplied from a side feeder, melt-kneaded at a barrel set temperature of 250 ° C. and a rotation speed of 200 rpm, extruded into strands, cooled, and then cut to prepare pellets of a resin composition.
＜生産性評価＞
この際、ストランド切れを起こす等の問題点が発生するかどうかを観察し、生産性の評価を行った。
＜品質評価＞
また、凝集異物の評価のため、上記において、さらにカーボンブラックを０，５％配合した以外は同様にして、黒色のペレットを製造した。得られた黒色ペレットの表面をルーペで観察し、フッ素樹脂の凝集した白色の異物の有無を判定した。
<Productivity evaluation>
At this time, productivity was evaluated by observing whether problems such as strand breakage occurred.
<Quality evaluation>
Further, in order to evaluate the agglomerated foreign matter, black pellets were produced in the same manner as described above except that 0.5% of carbon black was further blended. The surface of the obtained black pellet was observed with a loupe to determine the presence or absence of agglomerated white foreign matter of the fluororesin.
＜物性評価＞
得られたペレットの特性は、射出成形機（日精樹脂工業社製「ＮＥＸ−８０」）を用いてシリンダー温度２６０℃で、下記（１）、（２）の形状の評価用試験片を射出成形した。なお、成形に際して、樹脂組成物はその直前まで１２０℃にて６〜８時間乾燥した。
（１）耐トラッキング特性（ＣＴＩ）
厚さ３．０ｍｍ、５０φの円板の試験片を用い、試験法ＵＬ７４６Ａ ２３項で規定されている耐トラッキング性試験方法はＡＳＴＭ Ｄ３６３８に準拠して測定した。装置のノズルから電解液（塩化アンモニウム０．１％水溶液、２３℃で抵抗率３８５Ω・ｃｍ）を３０秒間隔で滴下させ、両白金電極間に６００Ｖ以下（２５Ｖステップ）の電圧を印加し、トラッキングが発生するまでの電解液滴下数を測定し、５回の平均値が５０滴未満となる電圧（単位：Ｖ）を求めた。
ＣＴＩは、数値が高いほど耐トラッキング性が良好であることを意味し、３００Ｖ以上であるのが好ましい。
（２）難燃性（ＵＬ９４）
アンダーライターズ・ラボラトリーズのサブジェクト９４（ＵＬ９４）の方法に準じ、５本の試験片（厚み；０．８ｍｍ）を用いて難燃性を試験した。難燃性は、ＵＬ９４記載の評価方法に従って、Ｖ−０、Ｖ−１、Ｖ−２に分類した。さらに、５試料のうち、１つでも上記基準を満たさないものがある場合、Ｖ−２を満足しないとしてＮＲ（Ｎｏｔ Ｒａｔｅｄ）と評価した。
（３）曲げ強度
日本製鋼所社製射出成形機「Ｊ８５ ＡＤ」（型締め力８５トン）を用い、シリンダー温度２５０℃の条件でＩＳＯ試験片を射出成形し、ＩＳＯ１７８規格に準拠して曲げ強度（単位：ＭＰａ）を測定した。
以上の評価結果を、以下の表２に示す。
<Physical property evaluation>
The characteristics of the obtained pellets are that the test pieces for evaluation of the shapes (1) and (2) below are injection-molded at a cylinder temperature of 260 ° C. using an injection molding machine (“NEX-80” manufactured by Nissei Resin Industry Co., Ltd.). did. At the time of molding, the resin composition was dried at 120 ° C. for 6 to 8 hours until just before that.
(1) Tracking resistance (CTI)
Using a test piece of a disk having a thickness of 3.0 mm and a thickness of 50φ, the tracking resistance test method specified in the test method UL746A 23 was measured in accordance with ASTM D3638. An electrolytic solution (0.1% ammonium chloride aqueous solution, resistance 385 Ω · cm at 23 ° C.) was dropped from the nozzle of the device at intervals of 30 seconds, and a voltage of 600 V or less (25 V step) was applied between both platinum electrodes for tracking. The number of electrolytic droplets was measured until the occurrence of the above, and the voltage (unit: V) at which the average value of 5 times was less than 50 droplets was determined.
The higher the CTI value, the better the tracking resistance, and the CTI is preferably 300 V or higher.
(2) Flame retardant (UL94)
Flame retardancy was tested using five test pieces (thickness; 0.8 mm) according to the method of Subject 94 (UL94) of Underwriters Laboratories. Flame retardancy was classified into V-0, V-1, and V-2 according to the evaluation method described in UL94. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (Not Rated) as not satisfying V-2.
(3) Bending strength An ISO test piece is injection-molded under the condition of a cylinder temperature of 250 ° C. using an injection molding machine "J85 AD" (mold clamping force 85 tons) manufactured by Japan Steel Works, Ltd., and bending strength is compliant with ISO178 standard. (Unit: MPa) was measured.
The above evaluation results are shown in Table 2 below.
上記の比較例６では、ストランド切れが多発し、切れる度に対応し、サンプル採取したが、ストランド切れによるロス率３０％にも達した。
比較例８ではストランドが切れてしまい、全く引けずサンプル採取もできなかったため、物性は評価自体ができなかった。
In Comparative Example 6 described above, strand breakage occurred frequently, and a sample was taken corresponding to each break, but the loss rate due to strand breakage reached 30%.
In Comparative Example 8, the strands were cut, and the samples could not be taken because they could not be pulled at all, so that the physical properties could not be evaluated.
本発明のポリエステル樹脂組成物は、難燃性と耐トラキング性に優れるポリエステル樹脂材料なので、電気電子機器部品、例えばコネクター、リレー、スイッチ等や、電気電子機器部品の筐体・カバーなどの広範囲の部品に特に好適に利用できる。 Since the polyester resin composition of the present invention is a polyester resin material having excellent flame retardancy and trucking resistance, it has a wide range of electrical and electronic equipment parts such as connectors, relays, switches, and housings and covers of electrical and electronic equipment parts. It can be particularly preferably used for parts.
Claims (4)
第１のフッ素樹脂（Ｄ１）の質量平均分子量が１，０００，０００〜１００，０００，０００であり、第２のフッ素樹脂（Ｄ２）の質量平均分子量が６０，０００〜８００，０００であり、
フッ素樹脂（Ｄ１）とフッ素樹脂（Ｄ２）の含有量の質量比（Ｄ１）／Ｄ２）が１／１〜１／５であることを特徴とするポリエステル樹脂組成物。 100 parts by mass of the thermoplastic polyester resin (A) contains 0 to 120 parts by mass of the glass fiber (B) and 0 to 50 parts by mass of the bromine-based flame retardant (C), and the contents of (B) and (C). The total is 5 to 150 parts by mass, and further, the first fluororesin (D1) and the second fluororesin (D2) having a lower mass average molecular weight than the first fluororesin (D1) are combined to be 1 to 1 to 150 parts by mass. Contains 25 parts by mass,
The mass average molecular weight of the first fluororesin (D1) is 1,000,000 to 100,000,000, and the mass average molecular weight of the second fluororesin (D2) is 60,000 to 800,000.
A polyester resin composition characterized in that the mass ratio (D1) / D2) of the contents of the fluororesin (D1) and the fluororesin (D2) is 1/1 to 1/5.
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