JPH02245057A - Flame-retardant polyester composition - Google Patents
Flame-retardant polyester compositionInfo
- Publication number
- JPH02245057A JPH02245057A JP1066848A JP6684889A JPH02245057A JP H02245057 A JPH02245057 A JP H02245057A JP 1066848 A JP1066848 A JP 1066848A JP 6684889 A JP6684889 A JP 6684889A JP H02245057 A JPH02245057 A JP H02245057A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- weight
- parts
- compd
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 27
- 239000003063 flame retardant Substances 0.000 title claims abstract description 18
- 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 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims description 18
- 239000002253 acid Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- -1 phenol compound Chemical class 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 150000003606 tin compounds Chemical class 0.000 claims description 13
- 150000005526 organic bromine compounds Chemical class 0.000 claims description 12
- 150000001463 antimony compounds Chemical class 0.000 claims description 10
- 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 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 16
- 238000000465 moulding Methods 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- 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
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- VWSWIUTWLQJWQH-UHFFFAOYSA-N 2-butyl-6-[(3-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CC=2C(=C(CCCC)C=C(C)C=2)O)=C1O VWSWIUTWLQJWQH-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001553014 Myrsine salicina Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KTOCGRDHTCKGRC-UHFFFAOYSA-N [hydroxy(methoxy)phosphoryl] dimethyl phosphate Chemical compound COP(O)(=O)OP(=O)(OC)OC KTOCGRDHTCKGRC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Polymers C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000008188 pellet Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- OACSUWPJZKGHHK-UHFFFAOYSA-N tribenzyl phosphate Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)(=O)OCC1=CC=CC=C1 OACSUWPJZKGHHK-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-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
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- WOLVMJHAAKCIKN-UHFFFAOYSA-N tris(4-hydroxybutyl) phosphite Chemical compound OCCCCOP(OCCCCO)OCCCCO WOLVMJHAAKCIKN-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、成形性、機械的性質、電気特性とくに耐アー
ク性および広い温度領域における耐熱性が著しく改良さ
れた難燃性ポリエステル組成物に関するものである。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a flame-retardant polyester composition that has significantly improved moldability, mechanical properties, electrical properties, especially arc resistance and heat resistance over a wide temperature range. It is something.
〈従来の技術〉
ポリエチレンテレフタレートやポリブチレンテレフタレ
ートに代表される芳香族ポリエステルは、その優れた諸
特性を利用して、電気・電子部品、機械機構部品、およ
び自動車部品などに広く利用されている。それらのうち
、特にこれらの芳香族ポリエステルの電気特性を生かし
た用途はエレクトロニクス産業の発展とともに今後ます
ます増加するものと考えられる。<Prior Art> Aromatic polyesters represented by polyethylene terephthalate and polybutylene terephthalate are widely used in electrical and electronic parts, mechanical parts, automobile parts, etc. due to their excellent properties. Among these, applications that take advantage of the electrical properties of these aromatic polyesters are expected to increase in the future with the development of the electronics industry.
ところで、電気・電子部品に対して樹脂材料を使用する
際にはＵ乙規格に規定される離燃性を満足することが必
要であり、さらに電子コネクターなどの分野においては
、難燃性を付与した際にも良好な機械的性質を保有して
いるとともに難燃剤が成形品表面にブリードアウトしな
いことはもちろん成形品から絶縁不良を生ずるガスを発
生しないことが要求されている。By the way, when using resin materials for electrical and electronic parts, it is necessary to satisfy the flammability specified by the U-B standard, and in fields such as electronic connectors, it is necessary to provide flame retardant properties. It is also required that the flame retardant not bleed out onto the surface of the molded product, but also that the molded product not generate gases that would cause poor insulation.
そして、このような多様な要求に対応する芳香族ポリエ
ステル用の難燃剤としては、デカブロモジフェニルエー
テルなどの低分子量型の有機臭素化合物に代わり、比較
的分子量の高い臭素化ポリカーボネートや臭素化エポキ
シなどがその主体になりつつある。As flame retardants for aromatic polyesters that meet these diverse demands, relatively high molecular weight brominated polycarbonates and brominated epoxies are being used instead of low molecular weight organic bromine compounds such as decabromodiphenyl ether. It is becoming the main subject.
しかし、これらのオリゴマ型の難燃剤はブリードアウト
はしないものの、たとえば臭素化ポリカーボネートは芳
香族ポリエステルとの間にエステル交換反応を起こし、
芳香族ポリエステルの機械的性質を低下させること、成
形時の流動性が不良となることおよび成形品の熱処理時
に電気絶縁性のガスを発生しやすいことなどの間趙があ
り、また臭素化エポキシについてもその末端エポキシ基
の存在により成形滞留時に増粘して流動性が不良となる
ことおよび成形時に接点不良につながるようなガスを発
生しやすいことなどの問題があった。However, although these oligomeric flame retardants do not bleed out, for example, brominated polycarbonate undergoes a transesterification reaction with aromatic polyester.
There are some problems with aromatic polyesters, such as lowering their mechanical properties, poor fluidity during molding, and the tendency to generate electrically insulating gas during heat treatment of molded products, and brominated epoxy. However, due to the presence of the terminal epoxy group, there were problems such as thickening during molding retention, resulting in poor fluidity, and the tendency to generate gas that could lead to poor contact during molding.
そこで、難燃剤を高分子量化することによってこれらの
問題を解決しようという試みが種々なされており、たと
えば特開昭５４−８３０５３号公報には高重合度臭素化
ポリカーボネートを用いる方法が、特開昭５８−１１８
８４．９号公報には高重合度の臭素化エポキシ化合物を
用いる方法が開示されている。Therefore, various attempts have been made to solve these problems by increasing the molecular weight of flame retardants. 58-118
No. 84.9 discloses a method using a brominated epoxy compound with a high degree of polymerization.
〈発明が解決しようとする課題〉
しかしなから、前記の難燃剤を高重合度化する方法は若
干低ガス化などの効果か認められるものの、満足のいく
レベルになく、マた耐アーク性などの電気特性が低下し
やすいという問題があった。<Problems to be Solved by the Invention> However, although the above-mentioned method of increasing the degree of polymerization of flame retardants has some effects such as lower gas, it is not at a satisfactory level and has poor arc resistance etc. There was a problem in that the electrical characteristics of the metal tend to deteriorate.
したがって本発明の課題は、上述した従来の難燃性より
エステル組成物が有する問題点を解消することにある。Therefore, an object of the present invention is to solve the above-mentioned problems of conventional flame retardant ester compositions.
く課題を解決するための手段〉
そこで本発明者らは上記課題を解決すべく鋭意検討した
結果、芳香族ポリエステルに対して特定分子量の有機臭
素化合物、アンチモン化合物、特定のスズ化合物および
特定分子量のヒンダードフェノール化合物を特定量含有
せしめることによって、難燃性、機械的性質および難燃
剤のノンブルーミング性を満足するのみでなく、成形時
および成形品からのガス発生量が少なく、耐アーク性、
耐トラツキング性などの電気特性に優れ、しかも成形滞
留安定性などの成形性、耐熱性なども良好なポリエステ
ル組成物が得られることを見出し本発明に到達した。ま
た、さらに特定のリン化合物の併用により成形時の流動
性が向上するとともに、−層ガス発生量を低減できるこ
とも同時に見出した。Means for Solving the Problems> Therefore, the present inventors have made extensive studies to solve the above problems, and have found that aromatic polyesters are treated with organic bromine compounds of specific molecular weights, antimony compounds, specific tin compounds, and specific molecular weight compounds. By containing a specific amount of a hindered phenol compound, it not only satisfies flame retardancy, mechanical properties, and non-blooming properties of flame retardants, but also reduces the amount of gas generated during molding and from molded products, and provides arc resistance and
The present invention was achieved by discovering that a polyester composition can be obtained which has excellent electrical properties such as tracking resistance, as well as good moldability such as mold retention stability, and good heat resistance. Furthermore, we have also discovered that by using a specific phosphorus compound in combination, the fluidity during molding can be improved and the amount of negative layer gas generated can be reduced.
すなわち、本発明は、（Ａ）芳香族ポリエステル１００
重量部に対して、（Ｂ）平均分子量３０００以上の有機
臭素化合物１〜６０重量部、（Ｃ）アンチモン化合物１
〜５０重量部、（Ｄ）スズ酸、メタスズ酸およびそれら
の金属塩から選択されたスズ化合物の少なくとも１種０
０１〜１０重量部および、（［）分子量５００以上のヒ
ンダ−ドフェノール化合物０．０１〜５重量部を含有せ
しめてなる難燃性ポリエステル組成物およびさらには、
（Ｆ）リン酸、亜リン酸およびそれらのエステルから選
択されたリン化合物の少なくとも１種０．０１〜５重量
部を含有せしめてなる難燃性ポリエステル組成物を提供
するものである。That is, the present invention provides (A) aromatic polyester 100
Based on parts by weight, (B) 1 to 60 parts by weight of an organic bromine compound having an average molecular weight of 3000 or more, (C) 1 part by weight of an antimony compound
~50 parts by weight, (D) at least one tin compound selected from stannic acid, metastannic acid, and metal salts thereof
0.01 to 10 parts by weight, and ([) 0.01 to 5 parts by weight of a hindered phenol compound having a molecular weight of 500 or more, and further,
(F) A flame-retardant polyester composition containing 0.01 to 5 parts by weight of at least one phosphorus compound selected from phosphoric acid, phosphorous acid, and esters thereof.
本発明で用いる（＾）芳香族ポリエステル樹脂とは芳香
環を重合体の連鎖単位に有するポリエステルであり、具
体的には芳香族ジカルボン酸（あるいはそのエステル形
成性誘導体）とジオール（あるいはそのエステル形成性
誘導体）とを主成分とする縮合反応により得られる重合
体ないしは共重合体である。The (^) aromatic polyester resin used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and specifically, aromatic dicarboxylic acid (or its ester-forming derivative) and diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction mainly composed of
ここでいう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、１５−ナフタレンジカ
ルボン酸、２．５−ナフタレンカシカルボン酸、２，６
−ナフタレンジカルボン酸、４．４−一ビフエニルジカ
ルボン酸、３．３ビフエニルジカルボン酸、４，４゛−
ジフェニルエーテルジカルボン酸、４．４゛−ジフェニ
ルメタンジカルボン酸、４，４−−ジフェニルスルホン
ジカルボン酸、４，４−−ジフェニルイソプロピリデン
ジカルボン酸、１４２−ビス（フェノキシ）エタン−４
，４−−ジカルボン酸、２．５−アントラセンジカルボ
ン酸、２．６−アントラセンジカルボン酸、４．．４．
−−ｐ−ターフェニレンジカルボン酸および２，５−ピ
リジンジカルボン酸などが挙げられ、なかでもテレフタ
ル酸が好ましく使用できる。The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, 15-naphthalenedicarboxylic acid, 2.5-naphthalenecasicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 4.4-monobiphenyldicarboxylic acid, 3.3biphenyldicarboxylic acid, 4,4゛-
Diphenyl ether dicarboxylic acid, 4,4-diphenylmethane dicarboxylic acid, 4,4-diphenylsulfone dicarboxylic acid, 4,4-diphenylisopropylidene dicarboxylic acid, 142-bis(phenoxy)ethane-4
, 4-dicarboxylic acid, 2.5-anthracenedicarboxylic acid, 2.6-anthracenedicarboxylic acid, 4. ．． 4.
--p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and the like, among which terephthalic acid can be preferably used.
これらの芳香族ジカルボン酸は二種以上を混合して使用
してらよい。なお少量であれば、これらの芳香族ジカル
ボン酸とともにアジピン酸、アセライン酸、セバシン酸
およびドデカンジオン酸などの脂肪族ジカルボン酸およ
びシクロヘキサンジカルボン酸なとの脂環族ジカルボン
酸を一種以上混合使用することができる。Two or more of these aromatic dicarboxylic acids may be used in combination. If the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, acelaic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. I can do it.
またジオール成分としては、エチレングリコール、プロ
ピレングリコール、ネオペンチルグリコール、２−メチ
ル−１，３−プロパンジオール、ジエチレングリコール
およびトリエチレングリコールなどの脂肪族ジオール、
１．４−シクロヘキサンジメタツールなどの脂環族ジオ
ールなとおよびそれらの混合物などが挙げられる。Diol components include aliphatic diols such as ethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol;
Examples include alicyclic diols such as 1,4-cyclohexane dimetatool, and mixtures thereof.
なお少量であれは、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−プロピレンクリコールおよびポリテトラメチレング
リコールなどを一種以上共重合せしめてもよい。In addition, in small amounts, long-chain diols with a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,
One or more types of 3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.
芳香族ポリエステル樹脂（Ａ）の具体例としてはポリエ
チレンテレフタレート、ポリプロピレンテレフタレート
、ポリブチレンテレフタレート、ポリヘキシレンテレフ
タレート、ポリ−１゜４−シクロヘキサンジメチレンテ
レフタレート、ポリエチレンナフタレート、ポリブチレ
ンナフタレートおよびポリエチレン−１，２−ビス（フ
ェノキシ）エタン−４，４−−ジカルボキシレートなど
のほか、ポリエチレンイソフタレート／テレフタレート
、ポリブチレンチレフタレ−１〜／イソフタレートおよ
びポリブチレンテレフタレート／デカンジカルボキシレ
ートなどのような共重合ポリエステルが挙げられる。こ
れらのうち機械的性質および成形性などのバランスのと
れたポリブチレンテレフタレートが特に好ましく使用で
きる。Specific examples of the aromatic polyester resin (A) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, poly-1°4-cyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene-1 , 2-bis(phenoxy)ethane-4,4-dicarboxylate, etc., as well as polyethylene isophthalate/terephthalate, polybutylene terephthalate-1~/isophthalate, and polybutylene terephthalate/decanedicarboxylate. Examples include copolymerized polyesters. Among these, polybutylene terephthalate, which has well-balanced mechanical properties and moldability, can be particularly preferably used.
本発明において使用する芳香族ポリエステル樹脂（Ａ）
は０．５％の０−クロルフェノール溶液を２５℃で測定
した相対粘度が１．１５〜２．０、とくに１．３〜１．
８５のものが好適である。Aromatic polyester resin (A) used in the present invention
The relative viscosity of a 0.5% 0-chlorophenol solution measured at 25°C is 1.15 to 2.0, particularly 1.3 to 1.
85 is preferred.
本発明において（８）成分として用いられる平均分子量
３． ＯＯ０以上の有機臭素化合物とは、分子中に臭素
原子を有し、平均分子量が３．０００以上、好ましくは
５，０００以上であり、特に臭素含有量３０重量％以上
のものが好ましい。Average molecular weight used as component (8) in the present invention: 3. The organic bromine compound having OO0 or more has a bromine atom in the molecule and has an average molecular weight of 3,000 or more, preferably 5,000 or more, and particularly preferably has a bromine content of 30% by weight or more.
具体的には臭素化ポリカーボネート（たとえば臭素化ビ
スフェノールＡを原料として製造されたポリカーボネー
トオリゴマー）、臭素化エポキシあるいは臭素化フェノ
キシ化合物（たとえば臭素化ビスフェノールＡとエピク
ロルヒドリンとの反応によって製造されるジェポキシ化
合物や臭素化エポキシオリゴマー、臭素化エポキシポリ
マー、臭素化フェノキシポリマー）、ポリ（臭素化ベン
ジルアクリレート）、臭素化ポリフェニレンエーテル、
臭素化ビスフェノールＡ／塩化シアヌル／臭素化フェノ
ールの縮合物および臭素化ポリエチレン（線状タイプお
よび架橋タイプ）等のハロゲン化されたポリマーやオリ
ゴマーあるいは、これらの混合物で平均分子量３，００
０以上のものが挙げられる。なかでも臭素化エポキシオ
リゴマーおよびポリマー臭素化ポリスチレン、臭素化ポ
リフェニレンエーテル、臭素化ポリカーボネ−１・およ
び塩化シアヌル／臭素化ヒスフェノール／臭素化フェノ
ールの重縮合物が好ましく、特にｐ−ｔｅｒｔブチルフ
ェノール、トリブロムフェノールなど１価のフェノール
で末端封鎖したテトラブロモビスフェノールＡを原料と
する臭素化ポリカーボネートあるいはそのビスフェノー
ルＡボリカーホネートとの共重合体および臭素化フェノ
キシ樹脂が好ましく使用できる。Specifically, brominated polycarbonates (for example, polycarbonate oligomers produced using brominated bisphenol A as a raw material), brominated epoxy or brominated phenoxy compounds (for example, jepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and bromine) epoxy oligomer, brominated epoxy polymer, brominated phenoxy polymer), poly(brominated benzyl acrylate), brominated polyphenylene ether,
Halogenated polymers and oligomers such as brominated bisphenol A/cyanuric chloride/brominated phenol condensates and brominated polyethylene (linear type and crosslinked type), or mixtures thereof with an average molecular weight of 3.00
Examples include 0 or more. Among these, brominated epoxy oligomers and polymers such as brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate-1, and polycondensates of cyanuric chloride/brominated hisphenol/brominated phenol are preferred, particularly p-tert butylphenol, tribromine, etc. Brominated polycarbonate made from tetrabromobisphenol A end-capped with monohydric phenol such as phenol, a copolymer thereof with bisphenol A polycarbonate, and brominated phenoxy resin can be preferably used.
これらの分子量３． ＯＯ０以上の有機臭素化合物ＩＢ
）の添加量は、芳香族ポリニスデル（八）１００重量部
当り、１〜６０重量部、好ましくは５〜３０重量部であ
る。添加量が１重量部未満では、難燃性が十分でなく、
６０重量部を越えると組成物の物性が低下するため好ｔ
しくない。These molecular weights3. Organic bromine compound IB with OO0 or more
) is added in an amount of 1 to 60 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of aromatic polynisder (8). If the amount added is less than 1 part by weight, flame retardancy will not be sufficient,
If it exceeds 60 parts by weight, the physical properties of the composition will deteriorate, so it is preferable.
It's not right.
本発明において、使用する（Ｃ）アンチモン化合物は平
均分子量３． ＯＯ０以上の有機臭素化合物ｆＢ）と併
用添加することにより相乗的に難燃性を向上せしめると
ともに、（Ｄ）成分のスズ化合物および、（［）成分の
ヒンダードフェノール化合物と併用添加せしめることに
よりガス発生量を大幅に低下せしめる作用を奏する。In the present invention, the antimony compound (C) used has an average molecular weight of 3. By adding it in combination with an organic bromine compound fB) of OO0 or more, it synergistically improves flame retardancy, and by adding it in combination with the tin compound of component (D) and the hindered phenol compound of component ([), gas It has the effect of significantly reducing the amount generated.
かかるアンチモン化合物としては各種のものが使用でき
る。具体的には三酸化アンチモン、五酸化アンチモンな
どの酸化アンチモン、リン酸アンチモン、アンチモン酸
ソーダ、ＫＳｂ〈ｏＩ−■）６、酒石酸アンチモニルカ
リウム、Ｓｂ （ＯＣＨ２ＣＨ３）３、Ｓｂ ［ＯＣＨ
（ＣＨ３）ＣＨ２ＣＨ３）３およびｌ・リフェニルスチ
ビンなどが挙げられ、なかでも酸化アンチモンが好まし
く使用できる。Various types of antimony compounds can be used. Specifically, antimony oxides such as antimony trioxide and antimony pentoxide, antimony phosphate, sodium antimonate, KSb〈oI-■)6, antimonyl potassium tartrate, Sb (OCH2CH3)3, Sb [OCH
Examples include (CH3)CH2CH3)3 and l-rifhenylstibine, among which antimony oxide can be preferably used.
本発明におけるアンチモン化合ＴｈｆＣ）の添加量は芳
香族ポリエステル（Ａ）１００重量部に対し１〜５０重
量部、好ましくは３〜３０重量部であり、１重量部未満
ではアンチモン化合物の併用添加による難燃性改良効果
か十分ではなく、５０重量部を越えると芳香族ポリエス
テルの機械的性質が損なわれる。さらに好ましくは添加
した難燃剤中の臭素２〜５原子に対しアンチモン化合物
中のアンチモン原子１の割合で加えるのがよい。The amount of the antimony compound ThfC) added in the present invention is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, per 100 parts by weight of the aromatic polyester (A). The effect of improving flammability is not sufficient, and if the amount exceeds 50 parts by weight, the mechanical properties of the aromatic polyester will be impaired. More preferably, it is added in a ratio of 1 antimony atom in the antimony compound to 2 to 5 bromine atoms in the added flame retardant.
本発明において、（Ｄ）成分として用いるスズ化合物と
はスズ酸、メタスズ酸およびそれらの金属塩から選択さ
れた少なくとも１種である。In the present invention, the tin compound used as component (D) is at least one selected from stannic acid, metastannic acid, and metal salts thereof.
スズ酸とは４価の酸化スズの水和物であり、αスズ酸と
βスズ酸の両者とも使用することができる。また、メタ
スズ酸も４価の酸化スズの水和物である。これらの製法
としては、たとえばαスス酸はスズ酸アルカリ水溶液に
希酸を作用させる方法、βスズ酸およびメタスズ酸は酸
化スズに濃硝酸を作用させる方法が挙げられる。Stannic acid is a hydrate of tetravalent tin oxide, and both α-stannic acid and β-stannic acid can be used. Metastannic acid is also a hydrate of tetravalent tin oxide. As methods for producing these, for example, for α-stannic acid, a method in which a dilute acid is applied to an aqueous alkaline stannic acid solution, and for β-stannic acid and metastannic acid, a method in which concentrated nitric acid is applied to tin oxide can be mentioned.
さらにスズ酸およびメタスズ酸の金属塩としてはカリウ
ム、ナトリウムなどのアルカリ金属塩、マグネシウム、
カルシウム、ストロンチウムなどのアルカリ土類金属塩
、亜鉛塩、コバルト塙、鉛塩などが挙げられる。これら
のうち、スズ酸およびメタスズ酸が好ましく、なかでも
メタスズ酸が特に好ましく使用できる。Furthermore, metal salts of stannic acid and metastannic acid include alkali metal salts such as potassium and sodium, magnesium,
Examples include alkaline earth metal salts such as calcium and strontium, zinc salts, cobalt salts, and lead salts. Among these, stannic acid and metastannic acid are preferred, and among these, metastannic acid can be particularly preferably used.
これらのスズ化合物（Ｄ）の添加量は、芳香族ポリエス
テル（Ａ）１００ｉ量部当り、０．０１〜１０重量部、
好ましくは０，０５〜５重量部、より好ましくは０．１
〜３重量部である。添加量が０．０１重量部未満では耐
アーク性の改良および低ガス化の効果が十分でなく、１
０重量部を越えると機械的性質が低下するため好ましく
ない。The amount of these tin compounds (D) added is 0.01 to 10 parts by weight per 100 parts of aromatic polyester (A),
Preferably 0.05 to 5 parts by weight, more preferably 0.1
~3 parts by weight. If the amount added is less than 0.01 part by weight, the effect of improving arc resistance and reducing gas will not be sufficient, and 1
If it exceeds 0 parts by weight, mechanical properties will deteriorate, which is not preferable.
本発明の組成物に対して、（［）分子量５００以上のヒ
ンダードフェノール化合物を添加した場合には、他の特
性を低下させずに成形時の滞留安定性および得られた成
形品からのガス発生量を極めて減少させることができる
。When a hindered phenol compound ([) having a molecular weight of 500 or more is added to the composition of the present invention, retention stability during molding and gas release from the obtained molded product can be improved without deteriorating other properties. The amount generated can be significantly reduced.
本発明において使用する（［）分子量５００以上のヒン
ダードフェノール化合物とは、下記−服代（Ｉ）
（式中Ｒ１は、メチル、エチル、プロピル、第３ブチル
などの炭素数１〜１０のアルキル基である。）で表わさ
れる構造単位を含有するもののうち分子量５００以上の
化合物であり、分子量５００〜５． ＯＯＯのものが好
ましく、分子量６００〜２． ＯＯＯのものが特に好ま
しい。具体的には、トリス（β−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシ−フェニル）プロピオニルオキシ
エチルトンイソシアヌレート、２，４−ジ−ｔ−ブチル
−フェニル−３，５−ジ−ｔ−ブチル４−しドロキシベ
ンゾエート、１，１．３−１〜リス（２−メチル−４−
ヒドロキシ−５−ｔ−ブチル−フェニル）ブタン、２．
２−一メチレンビス（４−メチル−６−ブチル−フェノ
ール）、１．３．５−）リス＜３−．５−−ジ−ｔ−ブ
チル４−ヒドロキシベンゾイル）イソシアヌレート、テ
トラキス（メチレン−３（３，５−ジ−ｔ−ブチル−４
−ヒドロキシ−フェニル）プロピオネート）メタン、２
．２−チオ−くジメチルビス−３（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフェノール）プロピオネート）、
ｎ−オクタデシル−３−（４”−ヒドロキシ−３゛、５
ジー七−ブチルフェノール）プロピオネート、Ｎ、Ｎ−
一へキサメチレン−ビス＜３，５ジーｔ−ブチル−４−
ヒドロキシ−ヒドロシンアミド）、ビス（３，５−ジ−
ｔ−ブチル−４ヒドロキシベンゾイルホスポリツクアシ
ツド）モノメチルエステルのニッケル塩、１，３．５−
トリーメチル−２，４，６−１リス（３，５−ジ−ｔ−
ブチルー４−ヒドロキシ−ペンシル）ベンゼンおよび下
記構造の化合物
ｍ二５〜１５
などか挙げられ、なかでもテトラキス（メチレン−３（
３，５−ジ−ｔ−ブチル−４−ヒドロキシ−フェニル）
プロピオネート）メタンおよび１．３．５−）−リーメ
チル−２，４，６−ｈリス（３，５ジ〜ｔ−ブチル−４
−ヒドロキシ−ベンジル）ベンゼンなどが好ましく使用
できる。これらは単独もしくはエステルの型で用いても
よい。The hindered phenol compound ([) having a molecular weight of 500 or more used in the present invention is defined as the following (I) (wherein R1 is an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, tert-butyl, etc.). It is a compound with a molecular weight of 500 or more among those containing a structural unit represented by OOO is preferable, with a molecular weight of 600 to 2. Particularly preferred is OOO. Specifically, tris(β-(3,5-di-t-butyl-4-hydroxy-phenyl)propionyloxyethyltone isocyanurate, 2,4-di-t-butyl-phenyl-3,5-di -t-Butyl 4-droxybenzoate, 1,1.3-1-lis(2-methyl-4-
hydroxy-5-t-butyl-phenyl)butane, 2.
2-1 methylenebis(4-methyl-6-butyl-phenol), 1.3.5-)lis<3-. 5--Di-t-butyl 4-hydroxybenzoyl) isocyanurate, tetrakis(methylene-3(3,5-di-t-butyl-4)
-hydroxy-phenyl)propionate)methane, 2
．． 2-thio-dimethylbis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate),
n-octadecyl-3-(4”-hydroxy-3゛,5
di-7-butylphenol) propionate, N,N-
monohexamethylene-bis<3,5-di-t-butyl-4-
hydroxy-hydrocinamide), bis(3,5-di-
Nickel salt of t-butyl-4hydroxybenzoyl phosphoric acid) monomethyl ester, 1,3.5-
trimethyl-2,4,6-1lis(3,5-di-t-
Examples include butyl-4-hydroxy-pencyl)benzene and compounds m25-15 with the following structures, among which tetrakis(methylene-3(
3,5-di-t-butyl-4-hydroxy-phenyl)
propionate) methane and 1,3,5-)-lymethyl-2,4,6-hlis(3,5-di-t-butyl-4
-hydroxy-benzyl)benzene and the like can be preferably used. These may be used alone or in the form of an ester.
上記分子量５００以上のヒンダードフェノール化合物（
［）の添加量は、芳香族ポリエステル（Ａ）１００重量
部に対して０．０１〜５重量部、好ましくは０．０５〜
３重量部である。添加量が０．０１重量部未満ではガス
発生量の低減効果が認められず、５重量部を越えた場合
にはガスの発生量の低減効果が低下する上に、耐アーク
性の低下を生じるため好ましくない。また、ヒンダート
フェノール化合物の分子量が５００未満の場合には、ガ
ス発生量が多くなる傾向を示すため好ましくない。The above-mentioned hindered phenol compound with a molecular weight of 500 or more (
The amount of [) added is 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of aromatic polyester (A).
It is 3 parts by weight. If the amount added is less than 0.01 parts by weight, the effect of reducing the amount of gas generated will not be observed, and if it exceeds 5 parts by weight, the effect of reducing the amount of gas generated will be reduced and the arc resistance will be reduced. Therefore, it is undesirable. Moreover, when the molecular weight of the hindered phenol compound is less than 500, the amount of gas generated tends to increase, which is not preferable.
本発明においてはさらに（［）リン酸、亜リン酸および
それらのエステルから選択される一種以上のリン化合物
を併用添加することによって、−層ガス発生量の低下が
可能となり好ましい。In the present invention, it is preferable to additionally add one or more phosphorus compounds selected from ([) phosphoric acid, phosphorous acid, and esters thereof, since this makes it possible to reduce the amount of -layer gas generated.
このようなリン化合物としては、リン酸、リン酸ジメチ
ル、リン酸トリメチル、リン酸トリメチルエステル、リ
ン酸メチルジエヂル、リン酸トリエチル、リン酸トリイ
ソプロピル、リン酸トリブチル、リン酸トリフェニル、
リン酸トリベンジル、リン酸トリシクロヘキシル、亜リ
ン酸、亜リン酸トリメチル、亜リン酸トリエチル、亜リ
ン酸トリブチル、亜リン酸トリ（ヒドロキシブチル）、
亜リン酸トリフェニル、ビス（２，４−ジ−ｔ−ブチル
フェニル）ペンタエリスリトール−シフオスファイト、
ビス（２゜６−ジーｔ−ブチル−４−メチルフェニル）
ペンタエリスリ１−一ルージホスファイトおよびトロ
−
リス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト
などが挙げられ、なかでもリン酸トリメチルやリン酸ト
リフェニルなどが好ましく用いられる。これらのリン化
合物は１種のみを用いても２種以上を用いてもよい。Such phosphorus compounds include phosphoric acid, dimethyl phosphate, trimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate,
Tribenzyl phosphate, tricyclohexyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tri(hydroxybutyl) phosphite,
Triphenyl phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-shiphosphite,
Bis(2゜6-di-t-butyl-4-methylphenyl)
Pentaerythri 1-1 Rouge Phosphite and Toro
- Lis(2,4-di-t-butylphenyl) phosphite and the like are mentioned, among which trimethyl phosphate and triphenyl phosphate are preferably used. These phosphorus compounds may be used alone or in combination of two or more.
上記リン酸、亜リン酸およびそれらのエステルから選択
される一種以上のリン化合物（［）を添加する場合の添
加量は、芳香族ポリエステル（Ａ）１００重量部に対し
て０．０１〜５重量部、好ましくは０．０５〜１重量部
である。When adding one or more phosphorus compounds ([) selected from the above phosphoric acid, phosphorous acid, and their esters, the amount added is 0.01 to 5 parts by weight per 100 parts by weight of the aromatic polyester (A). part, preferably 0.05 to 1 part by weight.
なお、特に必須ではないが本発明の組成物に対してさら
に繊維状および／または粒状の充填剤を添加した場合、
他の特性を低下させずに開性を大幅に向上させることが
できる。このような充填剤としてはガラス繊維、炭素繊
維、金属繊維、アラミド繊維、セラミック繊維、アスベ
スト、チタン酸カリウィスカ、ワラステナイト、石コウ
繊維、セピオライト、ガラスピーズ、ガラスフレーク、
タルク、マイカ、クレー、炭酸カルシウム、硫酸バリウ
ム、酸化チタンおよび酸化アルミニウムなどが挙げられ
、なかでもチョツプドストランドタイプのガラス繊維が
好ましく使用できる。これらの添加量は通常芳香族ポリ
ニスデル１００重量部に対して３〜８０重量部である。Although not particularly essential, if fibrous and/or granular fillers are further added to the composition of the present invention,
Patency can be significantly improved without degrading other properties. Such fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, ceramic fibers, asbestos, potassium titanate whiskers, wollastenite, gypsum fibers, sepiolite, glass peas, glass flakes,
Examples include talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide, among which chopped strand type glass fiber is preferably used. The amount of these additives is usually 3 to 80 parts by weight per 100 parts by weight of the aromatic polynisdel.
さらに本発明の組成物は、本発明の目的を損なわない範
囲で、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、離
型剤、染料、顔料などの着色剤および核剤などの通常の
添加剤を１種以上含有することができる。また少量の他
の熱可塑性樹脂（たとえばポリカーボネート、ポリアミ
ド、ボリグロビレン、ポリエチレン、エチレン／プロピ
レン共重合体、エチレン／ブテン−１共重合体、エチレ
ン／プロピレン／非共役ジエン共重合体、エチレン／ア
クリル酸エチル共重合体、エチレン／メタクリル酸グリ
シジル共重合体、エチレン／＃酸ビニル／メタクリル酸
グリシジル共重合体およびエチレン／プロピレンｇ−無
水マレイン酸共重合体など）を含有することもできる。Furthermore, the composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants such as dyes and pigments, and nucleating agents, to the extent that the objects of the present invention are not impaired. It can contain one or more types of additives. Also small amounts of other thermoplastic resins (e.g. polycarbonate, polyamide, polyglobylene, polyethylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/ethyl acrylate) copolymers, ethylene/glycidyl methacrylate copolymers, ethylene/vinyl #acid/glycidyl methacrylate copolymers, and ethylene/propylene g-maleic anhydride copolymers).
本発明の組成物の製造方法は特に限定されるものではな
いが、芳香族ポリエステル（Ａ）、分子量５００以上の
有機臭素化合’ｔ！ｌ （Ｂ ）、アンチモン化合物［
Ｃ）、スズ化合物（Ｄ）および特定のヒンダードフェノ
ール化合！ｍ（Ｅ）さらに必要に応じてリン化合！ｔＪ
ＩＪ （Ｆ ）やガラス繊維などの他の添加剤を押出機
を使用して溶融混線する方法が好ましく挙げられる。The method for producing the composition of the present invention is not particularly limited, but includes aromatic polyester (A), an organic bromine compound having a molecular weight of 500 or more! l (B), antimony compound [
C), a tin compound (D) and a specific hindered phenol compound! m(E) Further phosphorus compounding if necessary! tJ
A preferred method is to melt and blend IJ (F) and other additives such as glass fiber using an extruder.
〈実施例〉 以下に実施例を挙げて本発明の効果をさらに詳述する。<Example> The effects of the present invention will be explained in further detail with reference to Examples below.
実施例１〜６、比較例１〜７
相対粘度１．６５のポリブチレンテレフタレート１００
重量部に対し、二酸化アンチモン８重量部、下記の有機
臭素化合物、スズ化合物およびヒンダードフェノール化
合物を表１に記載した量ヘンシェルミキサーで混合後、
４０關φ押出機を用いて２５０℃で溶融混練−ベレッｌ
〜化した。このベレットを１３０℃×４時間乾燥後、パ
ーフェクトオーブン中り８０℃×３０分熱処１つ −
理し揮発成分量を求めた。Examples 1 to 6, Comparative Examples 1 to 7 Polybutylene terephthalate 100 with a relative viscosity of 1.65
After mixing 8 parts by weight of antimony dioxide, the following organic bromine compounds, tin compounds and hindered phenol compounds in the amounts listed in Table 1 based on the weight part, using a Henschel mixer.
Melt kneading at 250℃ using a 40mm diameter extruder
It became ~. After drying this pellet at 130°C for 4 hours, it was heat-treated once at 80°C for 30 minutes in a perfect oven to determine the amount of volatile components.
また、２５０℃に設定した５オンスのスクリューインラ
イン型射出成形機を使用して金型温度８０℃、成形サイ
クル（射出時間／冷却時間）（イ）１０秒／１５秒で成
形し、ＡＳＴＭＩ号ダンベル、３關ｔＸ６０關φ円板、
１／８”ｔアイゾツト衝撃試験片および燃焼試験片（１
／１６″ｘｉ／２”ｘ５”）を各々得た。この時金型を
完全に充填するに必要な最小圧力である成形下限圧（ゲ
ージ圧）をＡＳＴＭＩ号ダンベル成形時に求めるととも
に成形サイクル（０）１０秒／６０秒での成形下限圧も
求めた。In addition, using a 5-ounce screw in-line injection molding machine set at 250°C, the mold temperature was 80°C, and the molding cycle (injection time/cooling time) (a) was 10 seconds/15 seconds. , 3mm x 60mm φ disc,
1/8”t Izot impact test piece and combustion test piece (1
/16"xi/2"x5") were obtained. At this time, the minimum molding pressure (gauge pressure), which is the minimum pressure required to completely fill the mold, was determined during molding of the ASTMI dumbbell, and the molding cycle (0 ) The lower limit pressure for molding at 10 seconds/60 seconds was also determined.
これらの試験片について、ＵＬ−９４規格に従い、垂直
燃焼試験を行うとともに、オーブン中１８０℃×５００
時間熱処理した試験片と未処理の試験片についてＡＳＴ
ＭＤ６３５に従い各々の引張試験を、さらにはＡＳＴＭ
Ｄ２５６に従いアイゾッ１〜衝撃試験を行なった。また
成形サイクル（イ）で成形した３ ｍｖＩｔ Ｘ ６０
＋ｕ＋φ円板を用いてＡＳＴＭＤ４９５に従い耐アー
ク性試験を行なった。These test pieces were subjected to a vertical combustion test in accordance with the UL-94 standard, and were also heated in an oven at 180℃ x 500℃.
AST for time heat treated and untreated specimens
Each tensile test according to MD635 and also ASTM
An Izod 1-impact test was conducted in accordance with D256. Also, 3 mvIt x 60 molded in molding cycle (a)
An arc resistance test was conducted using a +u+φ disk according to ASTM D495.
これらの結果を表１に併せて示す。These results are also shown in Table 1.
く難燃剤〉
Ａ−１：
Ｐ＝７
Ａ−２：上記Ａ
１の一般式においてＰ＝３
Ａ−３＝
Ａ−５：
くスズ化合物〉
Ｂ−１＝メタスズ酸
Ｂ−２：スズ酸
〈ヒンダードフェノール化合物〉
Ｃ−１，：４−メチル−２，６−ジーｔ−ブチルフェノ
ール
Ｃ−２：テ１〜ラキス（メチレン−３−＜３．５ジーｔ
−ブチル−４−ヒドロキシ
フェニル）プロピオネート）メタ
ン
くリン化合物〉
Ｄ−１ニリン酸トリメチル
表１の結果から明らかなように本発明の特定分子員の有
機臭素化合物、アンチモン化合物、スズ化合物およびヒ
ンダードフェノール化合物を併用した本発明の組成物は
成形時の滞留安定性および低ガス性に優れるのみならず
、得られた成形品は耐熱性か良好で、し７かも電気特性
とくに耐アーク性の著しく改良された樹脂成形品を与え
ることができる。Flame retardant> A-1: P=7 A-2: P=3 in the general formula of A1 above A-3= A-5: Tin compound> B-1 = Metastannic acid B-2: Stannic acid Hindered Phenol Compound> C-1,:4-Methyl-2,6-di-t-butylphenol C-2:te1-rakis (methylene-3-<3.5 di-t
-butyl-4-hydroxyphenyl) propionate) methane phosphorus compound> D-1 trimethyl diphosphate As is clear from the results in Table 1, organic bromine compounds, antimony compounds, tin compounds and hindered phenols with specific molecular members of the present invention The composition of the present invention in which the compound is used in combination not only has excellent retention stability and low gas properties during molding, but also the resulting molded products have good heat resistance and significantly improved electrical properties, especially arc resistance. It is possible to provide molded resin products.
一方、比較例２〜４の結果かられかるようにスズ化合物
、ビンタートフェノール化合物、三酸化アンチモンの添
加量が少ない場合、カスの発生量か増加し、さらに前２
者では耐熱性、耐アーク性も不良となる。また、比較例
５の結果かられかるように、ヒンダードフェノール化合
物の分子量が小さいとガス発生量か多く、耐熱性なども
不良となる。On the other hand, as can be seen from the results of Comparative Examples 2 to 4, when the amounts of tin compounds, vintate phenol compounds, and antimony trioxide added are small, the amount of scum generated increases, and
In this case, heat resistance and arc resistance are also poor. Furthermore, as can be seen from the results of Comparative Example 5, when the molecular weight of the hindered phenol compound is small, the amount of gas generated is large and the heat resistance is also poor.
実施例７〜８、比較例８〜１１
相対粘度１４５のポリブチレンテレフタレート１００重
量部、チョツプドストランドタイプのカラス繊維（径１
３μｍ、長さ３ｉ＋ｎ）５０重量部、三酸化アンチモン
８重量部、前記の有機臭素化合物に対して、スズ化合物
、ヒンダードフェノール化合物およびリン化合物を表２
に記載した１用いる他は、実施例１と同じ方法を用いて
、配合・押出し後成形、評価した。Examples 7-8, Comparative Examples 8-11 100 parts by weight of polybutylene terephthalate with a relative viscosity of 145, chopped strand type glass fiber (diameter 1
3 μm, length 3i+n) 50 parts by weight, 8 parts by weight of antimony trioxide, and the above organic bromine compound, tin compound, hindered phenol compound, and phosphorus compound were added in Table 2.
The same method as in Example 1 was used except that 1 described in 1 was used, followed by compounding, extrusion, molding, and evaluation.
結果を表２に示す。The results are shown in Table 2.
表２の結果から明らかなように、ガラス繊維を配合した
ときにおいても、本発明の組成物は、離燃性、耐アーク
性、成形性に優れていることがわかる。さらにリン化合
物を併用添加せしめた際には、カス発生量の低減、耐熱
性などに対して相乗的な改良効果か得られる。As is clear from the results in Table 2, it can be seen that even when glass fiber is blended, the composition of the present invention is excellent in flammability, arc resistance, and moldability. Furthermore, when a phosphorus compound is added in combination, a synergistic improvement effect can be obtained in reducing the amount of scum generated, heat resistance, etc.
〈発明の効果〉
芳香族ポリエステルに対して、特定分子量の有機臭素化
合物、アンチモン化合物、特定のスズ化合物、および特
定のヒンダードフェノール化合物を特定の割合で含有せ
しめてなる本発明の離燃性ポリエステル組成物は、成形
時の流動性、滞留安定性が良好でガス発生量が少なく、
しかも機械特性、耐熱性が優れるのみならず、耐アーク
性などの電気特性にも優れた成形品を与えることができ
るため、電子・電気部品、自動車部品などに対する適用
が期待できる。<Effects of the Invention> The flame retardant polyester of the present invention is made by containing an organic bromine compound, an antimony compound, a specific tin compound, and a specific hindered phenol compound of a specific molecular weight in an aromatic polyester in a specific ratio. The composition has good fluidity and retention stability during molding, and generates little gas.
In addition, it is possible to provide molded products that not only have excellent mechanical properties and heat resistance, but also excellent electrical properties such as arc resistance, so they can be expected to be applied to electronic/electrical parts, automobile parts, etc.
特許出願大東し株式会社Patent application Daitoshi Co., Ltd.
Claims (2)
、（Ｂ）平均分子量３０００以上の有機臭素化合物１〜
６０重量部、（Ｃ）アンチモン化合物１〜５０重量部、
（Ｄ）スズ酸、メタスズ酸およびそれらの金属塩から選
択されたスズ化合物の少なくとも１種０．０１〜１０重
量部および、（Ｅ）分子量５００以上のヒンダードフェ
ノール化合物０．０１〜５重量部を含有せしめてなるこ
とを特徴とする難燃性ポリエステル組成物。(1) (A) 1 to 100 parts by weight of aromatic polyester, (B) an organic bromine compound having an average molecular weight of 3000 or more
60 parts by weight, (C) 1 to 50 parts by weight of antimony compound,
(D) 0.01 to 10 parts by weight of at least one tin compound selected from stannic acid, metastannic acid, and metal salts thereof; and (E) 0.01 to 5 parts by weight of a hindered phenol compound having a molecular weight of 500 or more. A flame-retardant polyester composition comprising:
ステルから選択されたリン化合物の少なくとも１種０．
０１〜５重量部を含有せしめてなることを特徴とする請
求項（１）に記載の難燃性ポリエステル組成物。(2) Furthermore, (F) at least one phosphorus compound selected from phosphoric acid, phosphorous acid, and esters thereof.
The flame-retardant polyester composition according to claim 1, characterized in that it contains 01 to 5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066848A JPH02245057A (en) | 1989-03-16 | 1989-03-16 | Flame-retardant polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1066848A JPH02245057A (en) | 1989-03-16 | 1989-03-16 | Flame-retardant polyester composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02245057A true JPH02245057A (en) | 1990-09-28 |
Family
ID=13327679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1066848A Pending JPH02245057A (en) | 1989-03-16 | 1989-03-16 | Flame-retardant polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02245057A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996002591A1 (en) * | 1994-07-14 | 1996-02-01 | Raychem Corporation | Polyester compositions |
| WO1997045483A1 (en) * | 1996-05-31 | 1997-12-04 | Kanebo, Limited | Polyester resin composition and film made therefrom, polyester composite film and metal laminate made by using the same, and process for decreasing the content of low-molecular compounds present in polyester |
| JP2009537651A (en) * | 2006-05-15 | 2009-10-29 | ブロマイン コンパウンズ リミテッド | Flame retardant composition |
| JP2012512942A (en) * | 2008-12-18 | 2012-06-07 | ダウ グローバル テクノロジーズ エルエルシー | Stabilizers for polymers containing aliphatic bonded bromine |
-
1989
- 1989-03-16 JP JP1066848A patent/JPH02245057A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908887A (en) * | 1993-01-14 | 1999-06-01 | Raychem Corporation | Polyester compositions |
| WO1996002591A1 (en) * | 1994-07-14 | 1996-02-01 | Raychem Corporation | Polyester compositions |
| WO1997045483A1 (en) * | 1996-05-31 | 1997-12-04 | Kanebo, Limited | Polyester resin composition and film made therefrom, polyester composite film and metal laminate made by using the same, and process for decreasing the content of low-molecular compounds present in polyester |
| JP2009537651A (en) * | 2006-05-15 | 2009-10-29 | ブロマイン コンパウンズ リミテッド | Flame retardant composition |
| JP2012512942A (en) * | 2008-12-18 | 2012-06-07 | ダウ グローバル テクノロジーズ エルエルシー | Stabilizers for polymers containing aliphatic bonded bromine |
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