JPS62223257A - Flame-retardant thermoplastic polyester composition - Google Patents
Flame-retardant thermoplastic polyester compositionInfo
- Publication number
- JPS62223257A JPS62223257A JP61068135A JP6813586A JPS62223257A JP S62223257 A JPS62223257 A JP S62223257A JP 61068135 A JP61068135 A JP 61068135A JP 6813586 A JP6813586 A JP 6813586A JP S62223257 A JPS62223257 A JP S62223257A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- halogenated
- aromatic
- halogen
- vinyl
- 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 45
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- 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 25
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 24
- 150000002367 halogens Chemical class 0.000 claims abstract description 24
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 22
- 239000004417 polycarbonate Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000000806 elastomer Substances 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 5
- 239000004814 polyurethane Substances 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract 4
- 125000003118 aryl group Chemical group 0.000 claims description 42
- -1 alkylene glycol Chemical compound 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 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 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229920005992 thermoplastic resin Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 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
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-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
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- JWTDCPGVNRBTKT-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC=C1OCCO JWTDCPGVNRBTKT-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 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
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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）
本発明は耐衝撃性が著しく改善され、難燃剤のブリード
がなく、機械的強度や耐熱性の低下が少い離燃性のポリ
エステル系熱可塑性樹脂組成物に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a flame-retardant polyester heat treatment material with significantly improved impact resistance, no flame retardant bleed, and less deterioration in mechanical strength and heat resistance. The present invention relates to a plastic resin composition.
（従来の技術）
芳蕃族ポリエステルは耐溶剤性、耐水性、耐酸化性、耐
摩耗性及び電気特性など欅々の優れた特性を有し、フィ
ルムやＭ！２維として大分に使用されている。さらに近
年成形用としてもガラス繊維などで強化されたりあるい
は非強化で使われている。(Prior art) Aromatic polyester has excellent properties such as solvent resistance, water resistance, oxidation resistance, abrasion resistance, and electrical properties, and is used in films and M! It is used in Oita as a double fiber. Furthermore, in recent years, it has been used for molding either reinforced with glass fiber or unreinforced.
また耐熱性を改善する試みとして芳香族ポリカーボネー
トとのブレンド組成物が開示されている（例えば特公昭
８６−１４０８５号公報、特公昭５８−１２５８７号公
報）。しかし芳香族ポリエステル及び芳香族ポリエステ
ルと芳香族ポリカーボネートのブレンド組成物は共に耐
衝撃性が低く用途が制限されており、また多くの樹脂と
同様用燃性である。Further, as an attempt to improve heat resistance, blend compositions with aromatic polycarbonates have been disclosed (for example, Japanese Patent Publication No. 86-14085 and Japanese Patent Publication No. 58-12587). However, both aromatic polyesters and blend compositions of aromatic polyesters and aromatic polycarbonates have low impact resistance, which limits their use, and like many resins, they are flammable.
耐衝撃性を改善する試みとしては、所謂エラストマー成
分を加えた組成物（例えば特公昭４６−６２２７号公報
、特公昭５１−２５２５１号公報、特公昭５５−９４８
５号公報）が開示されている。一方、難燃性を付与する
方法としてはハロゲンやリン、窒素を含んだ難燃剤を添
加することが公知であり、中でもハロゲン含有難燃剤は
難燃効果が高い。しかしハロゲン含有難燃剤のうち低分
子量のものは機械的物性や耐熱性を著しく低下させ、ブ
リードし易い。そこでかかる欠点を改良するため、ハロ
ゲン化ビスフェノール系カーボネートオリゴマーを用い
ることが提案されているが（例えば特開昭４８−５２８
８４号公報）、ブリードは防止されるものの、機械的物
性（特に耐衝撃性）及び耐熱性の改善は不十分である。Attempts to improve impact resistance include compositions containing so-called elastomer components (for example, Japanese Patent Publication No. 46-6227, Japanese Patent Publication No. 51-25251, Japanese Patent Publication No. 55-948).
No. 5) is disclosed. On the other hand, as a method of imparting flame retardancy, it is known to add a flame retardant containing halogen, phosphorus, or nitrogen, and among them, halogen-containing flame retardants have a high flame retardant effect. However, among halogen-containing flame retardants, those with low molecular weights significantly reduce mechanical properties and heat resistance, and are prone to bleeding. In order to improve this drawback, it has been proposed to use halogenated bisphenol-based carbonate oligomers (for example, JP-A-48-528
No. 84), although bleeding is prevented, improvements in mechanical properties (particularly impact resistance) and heat resistance are insufficient.
（発明が解決しようとする問題点）
本発明の目的は、芳香族ポリエステルあるいは芳香族ポ
リエステルと芳香族ポリカーボネートのブレンド組成物
の耐衝−性を著しく改善すると同時に高度の難燃性を付
与した熱可塑性ポリエステル組成物を提供するにある。(Problems to be Solved by the Invention) An object of the present invention is to significantly improve the impact resistance of an aromatic polyester or a blend composition of an aromatic polyester and an aromatic polycarbonate, and to provide a thermal The present invention provides a plastic polyester composition.
（問題点を解決するための手段）
本発明は、（４）芳香族ポリエステルあるいは芳香族ポ
リエステルと芳香族ポリカーボネートのブレンド組成物
４５〜９４１量％、■）熱可塑性軟質樹脂４〜８０重量
％、（Ｃ）平均１５以上の繰り返し単位からなりハロゲ
ン含有率が４０重量％以上である高分子量ハロゲン含有
難燃剤２〜２５′Ｍ量％とからなることを特徴とする難
燃性熱可塑性ポリエステル組成物である。(Means for Solving the Problems) The present invention provides (4) 45 to 941% by weight of an aromatic polyester or a blend composition of aromatic polyester and aromatic polycarbonate, ■) 4 to 80% by weight of a thermoplastic soft resin, (C) A flame-retardant thermoplastic polyester composition comprising 2 to 25'M% of a high molecular weight halogen-containing flame retardant having an average of 15 or more repeating units and a halogen content of 40% by weight or more. It is.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いられる芳香族ポリエステルは、芳香環を重
合体の連鎖単位に有するポリエステルで、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。ジカルボン酸成分としては、例えばテレフタル酸
、イソフタル酸、ナフタレン−２，６−ジカルボン酸、
ナフタレン−２，７−ジカルボン酸、ジフェニル−４，
４−ジカルボン酸、ジフェノキシエタンジカルボン酸、
ジフェニルエーテルジカルボン酸等の芳香族ジカルボン
酸或いはそのエステル形成性誘導体がある。また酸成分
が２０モル％以下の脂肪族ジカルボン酸（例えば、アジ
ピン酸、セバシン酸）やこれらのエステル形成性誘導体
で置換されていてもよい。またジオール成分としては、
例えばエチレングリコール、１．４−ブタンジオール、
トリメチレングリコール、ペンタメチレングリコール、
ヘキサメチレングリコール、ネオペンチルグリコ−ル、
ジエチレングリコール、トリエチレングリコール、１．
１−シクロヘキサンジメタツール、１．４−シクロヘキ
サンジメタツール、キシリレングリコール、２．２−ビ
ス（４−ヒドロキシフェニル）プロパン、ビス（４−ヒ
ドロキシフェニル）スルホン、ビス（ヒドロキシエトキ
シ）ベンゼン、２．２−ビス（４−ヒドロキシフェニル
）プロパンのエチレンオキシド付加物、２．２−ビス（
４−ヒドロキシフェニル）プロパンのプロピレンオキシ
ド付加物等、及びこれらのエステル形成性誘導体が挙げ
られる。The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is mainly composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,
naphthalene-2,7-dicarboxylic acid, diphenyl-4,
4-dicarboxylic acid, diphenoxyethanedicarboxylic acid,
Examples include aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, and ester-forming derivatives thereof. Further, the acid component may be substituted with 20 mol % or less of aliphatic dicarboxylic acid (eg, adipic acid, sebacic acid) or an ester-forming derivative thereof. In addition, as a diol component,
For example, ethylene glycol, 1,4-butanediol,
trimethylene glycol, pentamethylene glycol,
hexamethylene glycol, neopentyl glycol,
Diethylene glycol, triethylene glycol, 1.
1-Cyclohexane dimetatool, 1.4-cyclohexane dimetatool, xylylene glycol, 2.2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(hydroxyethoxy)benzene, 2 .2-bis(4-hydroxyphenyl)propane ethylene oxide adduct, 2.2-bis(
Examples include propylene oxide adducts of 4-hydroxyphenyl)propane, and ester-forming derivatives thereof.
本発明に用いられる芳香族ポリエステルは２種以上の芳
香族ポリエステルの混合物であっても良い。特に好まし
い芳香族ポリエステルとしてはテレフタル酸、イソフタ
ル酸、ナフタレンジカルボン酸あるいはそのエステル形
成性誘導体とアルキレングリコールあるいはそのエステ
ル形成性誘導体より得られる重合体及び共重合体が挙げ
られる。The aromatic polyester used in the present invention may be a mixture of two or more aromatic polyesters. Particularly preferred aromatic polyesters include polymers and copolymers obtained from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or ester-forming derivatives thereof, and alkylene glycol or ester-forming derivatives thereof.
本発明に用いられる芳香族ポリカーボネートは、ホモも
しくはコポリカーボネート、またはそれらの混合物であ
り、公知のビスフェノール類とホスゲン、または炭酸ジ
エステルとの重縮合反応により得られる。ビスフェノー
ル類は、例えばヒドロキノン、レゾルシノール、ジヒド
ロキシシフエール、ビス（ヒドロキシフェニル）アルカ
ン、ビス（ヒドロキシフェニル）シクロアルカン、ビス
（ヒドロキシフェニル）スルフィド、ビス（ヒドロキシ
フェニル）エーテル、ビス（ヒドロキシフェニル）ケト
ン、ビス（ヒドロキシフェニル）スルホキシド、ビス（
ヒドロキシフェニル）スルホン、及ヒｔ１９ａ−ビス（
ヒドロキシフェニル）ジインプロピルベンゼン尋である
。特に好ましい芳香族ポリカーボネートは、ポリ−２，
２−ビス（４−ヒドロキシフェニル）プロパンカーボネ
ート及び／又はポリビス（４−ヒドロキシフェニル）ス
ルホンカーボネートである。The aromatic polycarbonate used in the present invention is a homo- or copolycarbonate, or a mixture thereof, and is obtained by a known polycondensation reaction of bisphenols and phosgene or carbonic acid diester. Bisphenols include, for example, hydroquinone, resorcinol, dihydroxycyphere, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, and bis(hydroxyphenyl)ketone. (hydroxyphenyl) sulfoxide, bis(
hydroxyphenyl) sulfone, and human t19a-bis(
Hydroxyphenyl) diimpropylbenzene. Particularly preferred aromatic polycarbonates are poly-2,
2-bis(4-hydroxyphenyl)propane carbonate and/or polybis(4-hydroxyphenyl)sulfone carbonate.
本発明に使用される熱可星性軟質樹脂（Ｂ）は常温でゴ
ム弾性を示す熱ＩｆＩｍ性樹脂であれば良く、例えばポ
リエステルエラストマー、ポリウレタン、ポリアミドエ
ラストマー及び０℃以下のガラス転移温度を有するビニ
ル系共重合体が挙げられ、２種類以上の熱可目性軟質樹
脂を用いてもかまわない０
ポリエステルエラストマーとしては芳香族ポリエステル
ブロックとポリエーテルブロック、または芳香族ポリエ
ステルブロックと脂肪族ポリエステルブロックよりなる
ブロック共重合体があり、好ましい例としてポリブチレ
ンテレフタレートとポリオキシテトラメチレンのブロッ
ク共重合体及びポリブチレンテレフタレートとポリカプ
ロラクトンのブロック共重合体が挙げられる。The thermoplastic soft resin (B) used in the present invention may be any thermal IfIm resin that exhibits rubber elasticity at room temperature, such as polyester elastomer, polyurethane, polyamide elastomer, and vinyl having a glass transition temperature of 0°C or lower. Polyester elastomers include aromatic polyester blocks and polyether blocks, or aromatic polyester blocks and aliphatic polyester blocks. There are block copolymers, and preferred examples include block copolymers of polybutylene terephthalate and polyoxytetramethylene and block copolymers of polybutylene terephthalate and polycaprolactone.
ポリウレタンとしては１分子中に２個以上の水酸基を有
するポリラクトンエステルポリオール、ポリアジピン酸
エステルポリオール、ポリ炭酸エステルポリオールある
いはポリエーテルに低分子址ポリオール類の存在下多官
能イソシアネートを付加重合した熱可盟性ポリウレタン
が挙げられる。Polyurethanes include polylactone ester polyols, polyadipate ester polyols, polycarbonate ester polyols, or polyethers having two or more hydroxyl groups in one molecule, and thermoplastic polymers obtained by addition-polymerizing polyfunctional isocyanates in the presence of low-molecular-weight polyols. Examples include polyurethane.
ポリアミドエラストマーとしてはポリカプロラクタムま
たはポリラウロラクタム等のポリアミドブロックとポリ
エステルブロック、またはポリアミドブロックとポリオ
キシエチレン、ポリオキシプロピレン、ポリオキシテト
ラメチレン等のポリエーテルブロックからなるブロック
共重合体がある。Examples of polyamide elastomers include block copolymers consisting of polyamide blocks such as polycaprolactam or polylaurolactam and polyester blocks, or polyamide blocks and polyether blocks such as polyoxyethylene, polyoxypropylene, and polyoxytetramethylene.
ビニル系重合体としては、公知のオレフィン単量体、ハ
ロゲン化ビニル単量体、ジエン単量体、芳香族ビニル単
量体、アクリル駿才たはメタアクリル酸誘導体（金腐塩
を含む）、ビニルエスチル単量体、ビニルエーテル単量
体、及び不飽和二塩基酸銹導体等のビニル単量体からな
るランダム、ブロック及びグラフト共重合体が挙げられ
る。好ましい例としてはエチレン−酢酸ビニル共重合体
、エチレン−プロピレン共重合体、エチレン−プロピレ
ン−ブタジェン共重合体、エチレン−エチルアクリレー
ト共重合体、スチレン−ブタジェンブロック共重合体、
部分水添スチレン−ブタジェンブロック共重合体、エチ
レン−プロピレン−スチレングラフト共重合体、エチレ
ン−プロピレン−スチレン−アクリロニトリルグラフト
共１合体、エチレンープロピレンーブタジエンースチレ
ングラフト共重合体、エチレン−プロピレン−ブタジェ
ン−スチレン−アクリロニトリルグラフト共重合体、ア
クリロニトリル−ブタジェン−スチレングラフト共重合
体、ブタジェン−スチレン−メチルメタクリレートグラ
フト共重合体、ブタジェン−アクリロニトリル共重合体
、ブタジェン−スチレン−アクリロニトリル−メチルメ
タクリレートグラフト共重合体、ブタジェン−アクリロ
ニトリル−メタクリル酸共重合体、スチレン−無水マレ
イン酸共重合体、エチレン−マレイン酸共重合体、スチ
レン−アクリル酸エチル−アクリル酸ｎ−ブチル−メタ
クリル酸アリルグラフト共重合体、エチレン−メタクリ
ル酸共重合体の亜鉛塩、エチレン−メタクリル酸共重合
体のマグネシウム塩などがある。Examples of vinyl polymers include known olefin monomers, halogenated vinyl monomers, diene monomers, aromatic vinyl monomers, acrylic or methacrylic acid derivatives (including metal salts), Examples include random, block, and graft copolymers of vinyl monomers such as vinyl ester monomers, vinyl ether monomers, and unsaturated dibasic acid salt conductors. Preferred examples include ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-butadiene copolymer, ethylene-ethyl acrylate copolymer, styrene-butadiene block copolymer,
Partially hydrogenated styrene-butadiene block copolymer, ethylene-propylene-styrene graft copolymer, ethylene-propylene-styrene-acrylonitrile graft copolymer, ethylene-propylene-butadiene-styrene graft copolymer, ethylene-propylene- Butadiene-styrene-acrylonitrile graft copolymer, acrylonitrile-butadiene-styrene graft copolymer, butadiene-styrene-methyl methacrylate graft copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile-methyl methacrylate graft copolymer , butadiene-acrylonitrile-methacrylic acid copolymer, styrene-maleic anhydride copolymer, ethylene-maleic acid copolymer, styrene-ethyl acrylate-n-butyl acrylate-allyl methacrylate graft copolymer, ethylene- Examples include zinc salts of methacrylic acid copolymers and magnesium salts of ethylene-methacrylic acid copolymers.
本発明に使用される高分子量ハロゲン含有難燃剤（Ｃ）
は、平均の繰り返し単位数が１５以上でハロゲンを４０
重量％以上含有するものであれば良く、好ましくは、芳
香環がハロゲン化されてなるハロゲン化ポリカーボネー
ト、ハロゲン化ポリフェニレンオキサイド、ハロゲン化
ビスフェノール系エポキシ樹脂、ハロゲン化ポリエステ
ル及びハロゲン化ポリスチレンなどである。High molecular weight halogen-containing flame retardant (C) used in the present invention
has an average repeating unit number of 15 or more and contains 40 halogens.
It may contain at least % by weight, and preferred examples include halogenated polycarbonate whose aromatic ring is halogenated, halogenated polyphenylene oxide, halogenated bisphenol-based epoxy resin, halogenated polyester, and halogenated polystyrene.
またより好ましい平均の繰り返し単位数は２５以上であ
る。さらに平均練り返し単位数が１５未満のハロゲン含
有難燃剤では、難燃剤のブリードが発生し易く、また熱
可塑性軟質樹脂（Ｉ３）を所定量配合しても耐衝撃性は
十分向上しない。一方、ハロゲン含有率が４０重量％未
満の高分子量ハロゲン含有難燃剤では難燃性を得るのに
多量の難燃剤を配合しなければならないため、耐ｋｍ性
を始めとする機械的強度が低下する。Furthermore, the average number of repeating units is more preferably 25 or more. Furthermore, in the case of a halogen-containing flame retardant having an average number of repeating units of less than 15, bleeding of the flame retardant is likely to occur, and even if a predetermined amount of the thermoplastic soft resin (I3) is blended, the impact resistance will not be sufficiently improved. On the other hand, with high molecular weight halogen-containing flame retardants with a halogen content of less than 40% by weight, a large amount of flame retardant must be added to achieve flame retardancy, resulting in a decrease in mechanical strength including km resistance. .
これらの高分子量ハロゲン含有難燃剤（Ｃは公知のいず
れの方法で得られたものでも良く、例えばます通常の方
法で高分子を重合し、次に７リ一デルクラフト反応餉媒
を用い、ジハロゲン化メタンやジハロゲン化エタンと反
応させハロゲン化して得ることができる。また他の方法
としては、ハロゲン化された各種単量体を単独であるい
は他の単量体を加え重合することより得ることができる
。These high molecular weight halogen-containing flame retardants (C) may be obtained by any known method; for example, a polymer is polymerized by a conventional method, and then dihalogen-containing flame retardant C is It can be obtained by halogenation by reacting with methane or dihalogenated ethane.Also, as another method, it can be obtained by polymerizing various halogenated monomers alone or by adding other monomers. can.
後者のハロゲン化された単量体を用いる方法は、より具
体的には例えばハロゲン化ビスフェノール類を炭酸エス
テルまたはホスゲン、ジカルボン酸、ジグリシジルエー
テルと反応させて各々ハロゲン化ポリカーボネート、ハ
ロゲン化ポリエステル、ハロゲン化ビスフェノール系エ
ポキシ樹脂を得る方法、ハロゲン化芳香族ジカルボン酸
とジオールを反応させてハロゲン化ポリエステルを得る
方法、及びハロゲン化フェノール、ハロゲン化スチレン
カラ各々ハロゲン化ポリフェニレンオキサイド、ハロゲ
ン化ポリスチレンを得る方法等がある。またハロゲンと
しては、塩素及び臭素が好ましい。The latter method using halogenated monomers is more specifically, for example, by reacting halogenated bisphenols with carbonate esters, phosgene, dicarboxylic acids, and diglycidyl ethers to produce halogenated polycarbonates, halogenated polyesters, and halogenated polyesters, respectively. A method for obtaining a halogenated bisphenol-based epoxy resin, a method for obtaining a halogenated polyester by reacting a halogenated aromatic dicarboxylic acid with a diol, a method for obtaining a halogenated phenol, a halogenated styrene color, a halogenated polyphenylene oxide, a halogenated polystyrene, etc. There is. Further, as the halogen, chlorine and bromine are preferable.
本発明の高分子量ハロゲン含有難燃剤（Ｃ）は、２種以
上を併用しても良く、さらにリン及び／又は窒素を含有
する難燃剤やアンチモン化合物、硼素化合物、モリブデ
ン化合物等の難燃助剤と併用することもでき、特に酸化
アンチモンとの併用が難燃性向上の面で好ましい。The high molecular weight halogen-containing flame retardant (C) of the present invention may be used in combination of two or more, and may further include flame retardants containing phosphorus and/or nitrogen, and flame retardant aids such as antimony compounds, boron compounds, and molybdenum compounds. It can also be used in combination with antimony oxide, and combination use with antimony oxide is particularly preferred in terms of improving flame retardancy.
本発明において、芳香族ポリエステルあるいは芳香族ポ
リエステルと芳香族ポリカーボネートのブレンド組成物
（１）、熱可塑性軟質樹脂ＣＢ）及び平均１６以上の繰
り返し単位からなりハロゲン含有率が４０重量％以上で
ある高分子量ハロゲン含有難燃剤（Ｃ）を配合する割合
は、各々（４）４５〜９４重量％ （Ｂ）４〜８０重量
％ （Ｃ２〜２５重量％である。In the present invention, an aromatic polyester or a blend composition (1) of an aromatic polyester and an aromatic polycarbonate, a thermoplastic soft resin CB) and a high molecular weight compound comprising an average of 16 or more repeating units and a halogen content of 40% by weight or more The proportions of the halogen-containing flame retardant (C) are (4) 45 to 94% by weight, (B) 4 to 80% by weight (C2 to 25% by weight).
（４）が４５重量％未満では芳香族ポリエステルや芳香
族ポリエステルと芳香族ポリカーボネートブレンド組成
物の優れた性能が発現せず、■が９４重量％を超える場
合は耐衝撃性が改善されず、難燃性も満足されない。（
Ｊ３）が４重量％未満では、耐衝撃性を改善することが
できず８０重量％を超えると＃衝撃性以外の機械的強度
が著しく低下する。If (4) is less than 45% by weight, the excellent performance of the aromatic polyester or aromatic polyester/aromatic polycarbonate blend composition will not be exhibited, and if (4) is more than 94% by weight, the impact resistance will not be improved, resulting in difficulty. The flammability is also not satisfactory. (
If J3) is less than 4% by weight, impact resistance cannot be improved, and if it exceeds 80% by weight, mechanical strength other than #impact resistance is significantly reduced.
（Ｃ）が２Ｍ量％未満では難燃性を付与することができ
ず、２５２！量％を超えると耐衝撃性を始め、機械的強
度が大きく低下する。If (C) is less than 2M%, flame retardancy cannot be imparted, and 252! If the amount exceeds %, impact resistance and mechanical strength will be greatly reduced.
また、耐衝撃性改善と難燃性付与の両方が十分達成され
る熱可塑性軟質樹脂ＣＢ）と高分子量ハロゲン含有矯燃
剤（Ｃ）の好ましい重量比は（Ｂ） ／ （Ｃ）＝ １
／２〜４／１の範囲である。In addition, the preferred weight ratio of the thermoplastic soft resin CB) and the high molecular weight halogen-containing flame retardant (C) to sufficiently achieve both impact resistance improvement and flame retardancy is (B) / (C) = 1.
The range is from /2 to 4/1.
成分（４）の芳香族ポリエステルと芳香族ポリカーボネ
ートのブレンド比は必要に応じて任意の値をとることが
司能で、芳香族ポリカーボネートの割合が増加すると、
耐溶剤性や成形時の流動性は低下するが、一方耐熱性及
び成形品の寸法安定性は向上する。The blending ratio of the aromatic polyester and aromatic polycarbonate of component (4) can be set to any value as required, and as the proportion of the aromatic polycarbonate increases,
Solvent resistance and fluidity during molding decrease, but heat resistance and dimensional stability of the molded product improve.
本発明において、芳香族ポリエステルあるいは芳香族ポ
リエステルと芳香族ポリカーボネートのブレンド組成物
（４）、熱可塑性軟質樹脂（２）及び平均１５以上の繰
り返し単位からなりハロゲン含有率が４０重量％以上で
ある高分子量ハロゲン含有難燃剤（Ｑを配合する方法は
、全て一度に溶融混練してペレット化する方法や全てを
配合と同時に成形する方法、あるいは２種類以上の成分
を予め溶融混練しマスターペレットを製造し、成形時に
残りの成分と混合し成形する方法など公知のいずれの方
法をも実施することができる。In the present invention, an aromatic polyester or a blend composition (4) of an aromatic polyester and an aromatic polycarbonate, a thermoplastic soft resin (2), and a high-density polymer comprising an average of 15 or more repeating units and a halogen content of 40% by weight or more are used. The molecular weight halogen-containing flame retardant (Q) can be blended by melt-kneading them all at once and forming them into pellets, by molding them all at the same time, or by melt-kneading two or more components in advance to produce master pellets. Any known method can be used, such as a method of mixing with the remaining components during molding and molding.
さらに本発明の組成物には必要に応じて、ガラス繊維、
炭素繊維、金属繊維等の繊維状充填剤、タルク、マイカ
等の無機充填剤、エポキシ化合物、アリール化合物等の
多官能性化合物、熱安定剤、結晶化促進剤、離型剤、滑
剤、着色剤などを添加することができる。Furthermore, the composition of the present invention may optionally contain glass fibers,
Fibrous fillers such as carbon fibers and metal fibers, inorganic fillers such as talc and mica, polyfunctional compounds such as epoxy compounds and aryl compounds, heat stabilizers, crystallization promoters, mold release agents, lubricants, and colorants. etc. can be added.
（発明の効果）
本願発明の難燃性熱可塑性ポリエステル組成物は、従来
公知のものに比べて、高度の難燃性に加え、優れた機絨
的物性、特に耐衝馨性を有している。これらの特性を生
かして各種内外装部品、ハウジングなどの材料に利用す
ることができる。(Effects of the Invention) The flame-retardant thermoplastic polyester composition of the present invention has not only a high degree of flame retardancy but also excellent mechanical properties, especially impact resistance, compared to conventionally known compositions. There is. Taking advantage of these properties, it can be used for materials such as various interior and exterior parts and housings.
（実施例）
以下実施例を用いて本発明をさらに詳細に説明する。な
お実施例中の％は全て重量％を意味する。(Example) The present invention will be described in further detail using Examples below. In addition, all % in an example means weight %.
実施例１〜８
成分囚としてボリ工手しンチレフタレート（カネボウ合
ｒｅ、 ｍｓ、ベルベットＥＦＧ−６）、成分（Ｂ）と
してポリエステルエラストマー（東洋紡償噛ペルプレン
Ｐ−１５０Ｍ）、スチレン−ブタジェンブロック共重合
体（１！気化学工業■ デンカ５ＴＲ１６０２）及び工
牛しンープロピレン共重合体（日本合成ゴム＠４ Ｅ
ＰＯＩＰＸ）、成分（ｃ）としてテトラブロムビスフェ
ノール人よりホスゲン法にて製造した臭素化ポリカーボ
ネート（平均繰り返し単位数＝２０、臭素含有率＝６４
％）、難燃助剤として三酸化アンチモン（日本精鉱■Ａ
ＴＯＸ−Ｂ）を用い各々表−１に示す割合で単軸スクリ
ュー押出機を用いて溶融混練しペレットを製造した。Examples 1 to 8 Polyester elastomer (Kanebo Gore, MS, Velvet EFG-6) as the component, polyester elastomer (Toyobo Co., Ltd. Pelprene P-150M) as the component (B), styrene-butadiene block Copolymer (1!Kikagaku Kogyo ■Denka 5TR1602) and engineered cowshin-propylene copolymer (Japan Synthetic Rubber @4 E
POIPX), brominated polycarbonate produced by the phosgene method from tetrabromobisphenol as component (c) (average number of repeating units = 20, bromine content = 64
%), antimony trioxide (Nippon Seiko ■A) as a flame retardant aid.
TOX-B) were melt-kneaded using a single screw extruder at the ratios shown in Table 1 to produce pellets.
次いで通常の条件で各種試験片を射出成形し、物性を測
定した。その結果を表−２に示す。Next, various test pieces were injection molded under normal conditions and their physical properties were measured. The results are shown in Table-2.
比較例１〜７
実施例１〜８で用いた成分く加え、難き剤としてホスゲ
ン法でテトラブロムビスフェノール人より製造した臭素
化ポリカーボネートオリゴマー（平均繰り返し単位数＝
１０、臭素含有率＝６５％）、テトラブロムビスフェノ
ール人とビスフェノール人より製造した臭素化コポリカ
ーボネート（平均繰り返し単位数＝２５、臭素含有率＝
８１％）及ヒデカプロムジフェニルエーテル（ｇ−工業
製薬■ ピロガード８Ｒ−２００ＡＷ）を表−１に示す
割合で実施例１〜８と同様の方法にて配合、成形し物性
を調べた。その結果を表−２に示す。Comparative Examples 1 to 7 In addition to the components used in Examples 1 to 8, brominated polycarbonate oligomers (average number of repeating units =
10, bromine content = 65%), brominated copolycarbonate made from tetrabromo bisphenol and bisphenol (average number of repeating units = 25, bromine content =
81%) and hidecaprom diphenyl ether (g-Kogyo Seiyaku ■ Pyroguard 8R-200AW) were blended and molded in the same manner as in Examples 1 to 8 in the proportions shown in Table 1, and the physical properties were investigated. The results are shown in Table-2.
実施例４，６
成分（４）をポリエチレンテレフタレート（カネボウ合
繊■ ベルベットＥＦＧ−６）と芳香族ポリカーボネー
ト（三菱瓦斯化学■ ニーピロ７ｆ３−１０００）のブ
レンド組成物とし、成分（Ｂ）を部分水添スチレン−ブ
タジェンブロック共重合体（シェル化学■ クレイトン
０１６５２）及びエチレン−酢酸ビニル共重合体（三井
ポリケミカル■ エバフレックス−１６０）とする以外
は実施例１〜８と同様の成分及び条件を用いて配合、成
形し物性を測定した。組成及び測定結果を表−８に示す
。Examples 4 and 6 Component (4) is a blend composition of polyethylene terephthalate (Kanebo Gosen ■ Velvet EFG-6) and aromatic polycarbonate (Mitsubishi Gas Chemical ■ Nipiro 7f3-1000), and component (B) is partially hydrogenated styrene. The same components and conditions as in Examples 1 to 8 were used, except for using -butadiene block copolymer (Shell Kagaku ■ Kraton 01652) and ethylene-vinyl acetate copolymer (Mitsui Polychemical ■ Evaflex-160). It was blended, molded, and its physical properties were measured. The composition and measurement results are shown in Table-8.
実施例６．７
成分（４）としてポリブチレンテレフタレート（三菱化
成■ ツバドール５０１０）、成分（Ｂ）としてスチレ
ン−ブタジェンブロック共重合体及びエチレン−酢酸ビ
ニル共重合体ブロック共重合体、成分（Ｑとして臭素化
ポリスチレン（日照フェロ有機化学化学■ パイロチェ
ック６８ＦＢ）、さらにガラス短繊維（日東紡績■ 日
東紡グラスファイバー〇！８６ＰＥ）を通常の強化ＰＢ
Ｔ樹脂の条件にて配合、成形を行い物性を調べた。その
結果を表−４に示す。Example 6.7 Component (4) was polybutylene terephthalate (Mitsubishi Kasei ■ Tubadol 5010), component (B) was styrene-butadiene block copolymer and ethylene-vinyl acetate copolymer block copolymer, component (Q Brominated polystyrene (Pyrocheck 68FB manufactured by Nissho Ferro Organic Chemistry) and short glass fiber (Nittobo Glass Fiber 〇! 86PE manufactured by Nissho Ferro Organic Chemical Industry Co., Ltd.) are used as regular reinforced PB.
Compounding and molding were performed under the conditions of T resin, and the physical properties were investigated. The results are shown in Table 4.
表−８ １）ム８ＴＭ ８６４８ 表−４Table-8 1) Mu8TM 8648 Table-4
Claims (8)
ステルと芳香族ポリカーボネートのブレンド組成物４５
〜９４重量％、 （Ｂ）熱可塑性軟質樹脂４〜３０重量％、 （Ｃ）平均１５以上の繰り返し単位からなりハロゲン含
有率が４０重量％以上である高分子量ハロゲン含有難燃
剤２〜２５重量％ とからなることを特徴とする難燃性熱可塑性ポリエステ
ル組成物。(1) (A) Aromatic polyester or blend composition of aromatic polyester and aromatic polycarbonate 45
~94% by weight, (B) 4 to 30% by weight of a thermoplastic soft resin, (C) 2 to 25% by weight of a high molecular weight halogen-containing flame retardant consisting of an average of 15 or more repeating units and having a halogen content of 40% by weight or more. A flame-retardant thermoplastic polyester composition comprising:
難燃剤（Ｃ）の重量比が（Ｂ）／（Ｃ）＝１／２〜４／
１である特許請求の範囲第１項記載の組成物。(2) The weight ratio of the thermoplastic soft resin (B) and the high molecular weight halogen-containing flame retardant (C) is (B)/(C) = 1/2 to 4/
1. The composition according to claim 1, which is
酸、ナフタレンジカルボン酸あるいはそのエステル形成
性誘導体とアルキレングリコールあるいはそのエステル
形成性誘導体より得られる重合体及び共重合体である特
許請求の範囲第１項記載の組成物。(3) Claim 1, wherein the aromatic polyester is a polymer or copolymer obtained from terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or an ester-forming derivative thereof, and alkylene glycol or an ester-forming derivative thereof. Composition of.
４−ヒドロキシフェニル）プロパンカーボネート及び／
又はポリビス（４−ヒドロキシフェニル）スルホンカー
ボネートである特許請求の範囲第１項記載の組成物。(4) Aromatic polycarbonate is poly-2,2-bis(
4-hydroxyphenyl)propane carbonate and/or
The composition according to claim 1, which is polybis(4-hydroxyphenyl)sulfone carbonate.
マー、ポリウレタン、ポリアミドエラストマー及び０℃
以下のガラス転移温度を有するビニル系共重合体から選
ばれた１種以上である特許請求の範囲第１項記載の組成
物。(5) Thermoplastic soft resin (B) is polyester elastomer, polyurethane, polyamide elastomer and 0°C
The composition according to claim 1, which is one or more vinyl copolymers selected from vinyl copolymers having the following glass transition temperatures.
化ビニル単量体、ジエン単量体、芳香族ビニル単量体、
アクリル酸またはメタアクリル酸誘導体（金属塩を含む
）、ビニルエスチル単量体、ビニルエーテル単量体、及
び不飽和二塩基酸誘導体からなるランダム、ブロック及
びグラフト共重合体である特許請求の範囲第５項記載の
組成物。(6) The vinyl copolymer is an olefin monomer, a halogenated vinyl monomer, a diene monomer, an aromatic vinyl monomer,
Claim 5, which is a random, block or graft copolymer consisting of an acrylic acid or methacrylic acid derivative (including a metal salt), a vinyl ester monomer, a vinyl ether monomer, and an unsaturated dibasic acid derivative Compositions as described.
ポリカーボネート、ハロゲン化ポリフェニレンオキサイ
ド、ハロゲン化ビスフェノール系エポキシ樹脂、ハロゲ
ン化ポリエステル及びハロゲン化ポリスチレンである特
許請求の範囲第１項記載の組成物。(7) The composition according to claim 1, wherein the high molecular weight halogen-containing flame retardant (C) is a halogenated polycarbonate, a halogenated polyphenylene oxide, a halogenated bisphenol-based epoxy resin, a halogenated polyester, and a halogenated polystyrene.
上の繰り返し単位からなる特許請求の範囲第１項記載の
組成物。(8) The composition according to claim 1, wherein the high molecular weight halogen-containing flame retardant (C) comprises an average of 25 or more repeating units.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068135A JPS62223257A (en) | 1986-03-25 | 1986-03-25 | Flame-retardant thermoplastic polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61068135A JPS62223257A (en) | 1986-03-25 | 1986-03-25 | Flame-retardant thermoplastic polyester composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62223257A true JPS62223257A (en) | 1987-10-01 |
Family
ID=13365000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61068135A Pending JPS62223257A (en) | 1986-03-25 | 1986-03-25 | Flame-retardant thermoplastic polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62223257A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62275156A (en) * | 1986-05-22 | 1987-11-30 | Daicel Chem Ind Ltd | Resin composition |
| JPH01234459A (en) * | 1987-12-24 | 1989-09-19 | General Electric Co <Ge> | Polymer blend consisting of polybutylene terephthalate and brominated polystyrene and article formed therefrom |
| DE3921029A1 (en) * | 1988-06-27 | 1989-12-28 | Daicel Chem | STYROLIC RESIN COMPOSITION WITH EXCELLENT FIRE-RESISTANT PROPERTIES |
| JPH02218740A (en) * | 1988-06-13 | 1990-08-31 | General Electric Co <Ge> | Compatible polyphenylene ether/linear polyester blend having improved impact strength |
| JPH0317150A (en) * | 1989-04-12 | 1991-01-25 | General Electric Co <Ge> | Polymer mixture of polybuty- leneterephthalate and thermo- plastic elastomer |
| JPH0331349A (en) * | 1989-06-28 | 1991-02-12 | Daicel Chem Ind Ltd | Styrene resin composition having high flame retardancy |
| JPH03259946A (en) * | 1990-03-12 | 1991-11-20 | Sumitomo Dow Ltd | Flame-retardant resin composition |
| JPH0413749A (en) * | 1990-05-02 | 1992-01-17 | Sumitomo Dow Ltd | Flame-retarding resin composition |
| CN102471565A (en) * | 2009-07-03 | 2012-05-23 | 帝斯曼知识产权资产管理有限公司 | Polymer composition and cable cover of that composition |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62275156A (en) * | 1986-05-22 | 1987-11-30 | Daicel Chem Ind Ltd | Resin composition |
| JPH01234459A (en) * | 1987-12-24 | 1989-09-19 | General Electric Co <Ge> | Polymer blend consisting of polybutylene terephthalate and brominated polystyrene and article formed therefrom |
| JPH02218740A (en) * | 1988-06-13 | 1990-08-31 | General Electric Co <Ge> | Compatible polyphenylene ether/linear polyester blend having improved impact strength |
| DE3921029A1 (en) * | 1988-06-27 | 1989-12-28 | Daicel Chem | STYROLIC RESIN COMPOSITION WITH EXCELLENT FIRE-RESISTANT PROPERTIES |
| JPH028234A (en) * | 1988-06-27 | 1990-01-11 | Daicel Chem Ind Ltd | Styrene resin composition having excellent flame retardance |
| DE3921029C2 (en) * | 1988-06-27 | 1998-07-02 | Daicel Chem | Styrene resin composition with excellent fire retardant properties |
| JPH0317150A (en) * | 1989-04-12 | 1991-01-25 | General Electric Co <Ge> | Polymer mixture of polybuty- leneterephthalate and thermo- plastic elastomer |
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| JPH0331349A (en) * | 1989-06-28 | 1991-02-12 | Daicel Chem Ind Ltd | Styrene resin composition having high flame retardancy |
| JPH03259946A (en) * | 1990-03-12 | 1991-11-20 | Sumitomo Dow Ltd | Flame-retardant resin composition |
| JPH0413749A (en) * | 1990-05-02 | 1992-01-17 | Sumitomo Dow Ltd | Flame-retarding resin composition |
| CN102471565A (en) * | 2009-07-03 | 2012-05-23 | 帝斯曼知识产权资产管理有限公司 | Polymer composition and cable cover of that composition |
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