JPS6214579B2 - - Google Patents
Info
- Publication number
- JPS6214579B2 JPS6214579B2 JP866378A JP866378A JPS6214579B2 JP S6214579 B2 JPS6214579 B2 JP S6214579B2 JP 866378 A JP866378 A JP 866378A JP 866378 A JP866378 A JP 866378A JP S6214579 B2 JPS6214579 B2 JP S6214579B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- group
- weight
- compound
- parts
- 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.)
- Expired
Links
- -1 aromatic halogen compound Chemical class 0.000 claims description 42
- 239000003063 flame retardant Substances 0.000 claims description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 36
- 239000011342 resin composition Substances 0.000 claims description 34
- 239000004952 Polyamide Substances 0.000 claims description 19
- 229920002647 polyamide Polymers 0.000 claims description 19
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 16
- 150000002736 metal compounds Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 11
- 229910052794 bromium Inorganic materials 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000410 antimony oxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 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 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 101000603877 Homo sapiens Nuclear receptor subfamily 1 group I member 2 Proteins 0.000 description 3
- 101001098529 Homo sapiens Proteinase-activated receptor 1 Proteins 0.000 description 3
- 101001098560 Homo sapiens Proteinase-activated receptor 2 Proteins 0.000 description 3
- 101000713170 Homo sapiens Solute carrier family 52, riboflavin transporter, member 1 Proteins 0.000 description 3
- 101000713169 Homo sapiens Solute carrier family 52, riboflavin transporter, member 2 Proteins 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 102100036863 Solute carrier family 52, riboflavin transporter, member 1 Human genes 0.000 description 3
- 102100036862 Solute carrier family 52, riboflavin transporter, member 2 Human genes 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 2
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 2
- LJDGJCNHVGGOFW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2-bromophenoxy)benzene Chemical compound BrC1=CC=CC=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br LJDGJCNHVGGOFW-UHFFFAOYSA-N 0.000 description 2
- FIAXCDIQXHJNIX-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-ethylbenzene Chemical compound CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br FIAXCDIQXHJNIX-UHFFFAOYSA-N 0.000 description 2
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 description 2
- YPPRYAOCSPGZMJ-UHFFFAOYSA-N 1,2,3-tribromo-4-[2-(2,3,4-tribromophenoxy)ethenoxy]benzene Chemical group BrC1=C(Br)C(Br)=CC=C1OC=COC1=CC=C(Br)C(Br)=C1Br YPPRYAOCSPGZMJ-UHFFFAOYSA-N 0.000 description 2
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 2
- 229910005965 SO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N monomethylhydroquinone Natural products CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- WRTIICUHQQXGCG-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenoxy)ethenoxy]benzene Chemical group BrC1=C(C(=C(C(=C1OC=COC1=C(C(=C(C(=C1Br)Br)Br)Br)Br)Br)Br)Br)Br WRTIICUHQQXGCG-UHFFFAOYSA-N 0.000 description 1
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 1
- VCNJVIWFSMCZPE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-prop-2-enoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(OCC=C)C(Br)=C1Br VCNJVIWFSMCZPE-UHFFFAOYSA-N 0.000 description 1
- CIPFDHFTBYJKQB-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-(2,3,4,5,6-pentachlorophenoxy)benzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CIPFDHFTBYJKQB-UHFFFAOYSA-N 0.000 description 1
- AVSIMRGRHWKCAY-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-methylbenzene Chemical compound CC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl AVSIMRGRHWKCAY-UHFFFAOYSA-N 0.000 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 description 1
- IXZVOZCULZBCDY-UHFFFAOYSA-N 1,2,3,4-tetrachloro-5-(2,3,4,5-tetrachlorophenoxy)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC(OC=2C(=C(Cl)C(Cl)=C(Cl)C=2)Cl)=C1Cl IXZVOZCULZBCDY-UHFFFAOYSA-N 0.000 description 1
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- VIHUMJGEWQPWOT-UHFFFAOYSA-N 1,2,3-tribromo-4-(3-bromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C(Br)=CC=2)Br)=C1 VIHUMJGEWQPWOT-UHFFFAOYSA-N 0.000 description 1
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 description 1
- ATIMVMORQPKRPC-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenoxy)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1OC1=CC=C(Cl)C(Cl)=C1Cl ATIMVMORQPKRPC-UHFFFAOYSA-N 0.000 description 1
- RSBUDFTVQYJNHK-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,4-dichlorophenoxy)benzene Chemical compound ClC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C(Cl)=C1Cl RSBUDFTVQYJNHK-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- BUQBQEYUVAKJQK-UHFFFAOYSA-N 1,2-dibromo-4-(2-bromophenoxy)benzene Chemical compound C1=C(Br)C(Br)=CC=C1OC1=CC=CC=C1Br BUQBQEYUVAKJQK-UHFFFAOYSA-N 0.000 description 1
- PLVQCZWYNUFLEB-UHFFFAOYSA-N 1,3-dichloro-5-[2-(3,5-dichloro-4-ethoxyphenyl)propan-2-yl]-2-ethoxybenzene Chemical compound C1=C(Cl)C(OCC)=C(Cl)C=C1C(C)(C)C1=CC(Cl)=C(OCC)C(Cl)=C1 PLVQCZWYNUFLEB-UHFFFAOYSA-N 0.000 description 1
- PGPNJCAMHOJTEF-UHFFFAOYSA-N 1-chloro-4-phenoxybenzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=CC=C1 PGPNJCAMHOJTEF-UHFFFAOYSA-N 0.000 description 1
- ZRWRPGGXCSSBAO-UHFFFAOYSA-N 2,4-dichloro-1-(2,4-dichlorophenoxy)benzene Chemical compound ClC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl ZRWRPGGXCSSBAO-UHFFFAOYSA-N 0.000 description 1
- PIORTDHJOLELKR-UHFFFAOYSA-N 2,4-dichloro-1-(4-chlorophenoxy)benzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl PIORTDHJOLELKR-UHFFFAOYSA-N 0.000 description 1
- YYDJTJGFHTVGGF-UHFFFAOYSA-N 2,6-dichloro-4-(3,5-dichloro-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1S(=O)(=O)C1=CC(Cl)=C(O)C(Cl)=C1 YYDJTJGFHTVGGF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- RVHUMFJSCJBNGS-UHFFFAOYSA-N 2-[2,6-dibromo-4-[2-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C(Br)=C(OCCO)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCCO)C(Br)=C1 RVHUMFJSCJBNGS-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-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
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- GXDIDDARPBFKNG-UHFFFAOYSA-N 4,4'-(Butane-1,1-diyl)diphenol Chemical compound C=1C=C(O)C=CC=1C(CCC)C1=CC=C(O)C=C1 GXDIDDARPBFKNG-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- LJHSHQLVJKWRKL-UHFFFAOYSA-N 4-(4-hydroxy-2-methylphenoxy)-3-methylphenol Chemical compound CC1=CC(O)=CC=C1OC1=CC=C(O)C=C1C LJHSHQLVJKWRKL-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- MIFGCULLADMRTF-UHFFFAOYSA-N 4-[(4-hydroxy-3-methylphenyl)methyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(CC=2C=C(C)C(O)=CC=2)=C1 MIFGCULLADMRTF-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- LCYRQNBSGYQLKY-UHFFFAOYSA-N 4-[2-(4-hydroxynaphthalen-1-yl)propan-2-yl]naphthalen-1-ol Chemical compound C1=CC=C2C(C(C)(C=3C4=CC=CC=C4C(O)=CC=3)C)=CC=C(O)C2=C1 LCYRQNBSGYQLKY-UHFFFAOYSA-N 0.000 description 1
- KBXXZTIBAVBLPP-UHFFFAOYSA-N 4-[[4-(diethylamino)-2-methylphenyl]-(4-methylphenyl)methyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=C(C)C=C1 KBXXZTIBAVBLPP-UHFFFAOYSA-N 0.000 description 1
- YZYGDZRBLOLVDY-UHFFFAOYSA-N 4-[cyclohexyl-(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1CCCCC1 YZYGDZRBLOLVDY-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、(A)テレフタル酸とイソフタル酸また
はこれらの機能誘導体とビスフエノール類または
これらの機能誘導体とより製造した芳香族ポリエ
ステル共重合体と(B)ポリアミドと(C)芳香族ハロゲ
ン化合物と(D)長周期型周期表第Ｂ、Ｂ、
Ｂ、Ａ、Ａ族および第Ａ族より選ばれた金
属の酸化物とハロゲン化物とよりなる群から選ば
れる少なくとも一種の化合物（以下、特定の金属
化合物という。）とよりなる優れた力学特性を有
する難燃性樹脂組成物に関するものである。
近年、金属材料に対するプラスチツクスによる
代替が各分野で急速に進んでいる。プラスチツク
スに対してはそのような事情から成形性、機械的
性質、化学的性質、電気的性質、耐熱性等の広範
な各種性質にすぐれることが要望されている。さ
らに、最近では特に難燃性を具備することがきわ
めて重要視されており、各種製品の火災事故に対
する安全性の観点からも社会的に強く要請されて
いる。
本出願人が先に出願した芳香族ポリエステル共
重合体とポリアミドとよりなる樹脂組成物は、ポ
リアミド単独の場合に比べて熱変形温度が著しく
向上し、また芳香族ポリエステル共重合体の欠点
であつた成形性、耐溶剤性も改善されている。そ
の程度は、両者の成分比から加成性によつて推定
されるよりもはるかに高いものであつて、組成物
を構成する単独成分からは思いもよらない驚くべ
き特性である。そして、かかる樹脂組成物は芳香
族ポリエステル共重合体が有するすぐれた引張強
度、曲げ回復特性、寸法安定性やポリアミドが有
するすぐれた耐クラツク性、耐摩耗性などもよく
維持していて誠に有用なる性質を保持する樹脂組
成物である（特開昭50−4146号、特開昭52−
98765号）。
しかるに、芳香族ポリエステル共重合体とポリ
アミドとよりなる樹脂組成物を、たとえば射出成
形法によつて各種成形品に成形し、その性質を詳
しく調べたところ以下のごとき欠点が判明した。
すなわち、各種成形品のゲート部のような肉薄部
や細長く突出した棒状部が特に絶乾時に折れやす
いので成形品を金型から離形する際に障害をきた
すばかりでなく、製品のデザインに制約を与える
など実用上の障害となり、さらには比較的肉厚の
成形品においても特に絶乾状態にある場合には落
下衝撃や落球衝撃などの衝撃的な力が加わつたと
きに割れを発生しやすいことが判明した。これら
の現象は、かかる樹脂組成物の用途を大巾に制限
するものである。
さらに、かかる樹脂組成物は難燃性においても
不十分であるため、先に述べたような事情により
その難燃性の向上が強く要請されるものである。
しかるに、このような力学特性に問題のある樹脂
組成物に大量の難燃剤を添加すればこれらの特性
がさらに劣化することは明らかであるので実用的
な面で大きな障害となつている。
本発明者らは、上記の問題を解決すべく鋭意研
究を続けた結果、特定の金属化合物を難燃剤とと
もに添加することにより力学特性、難燃性が大巾
に改善されることを見出し、本発明に到達したも
のである。
すなわち本発明は、(A)テレフタル酸とイソフタ
ル酸またはこれらの機能誘導体の混合物（ただ
し、テレフタル酸基とイソフタル酸基のモル比は
１：９ないし９：１）と一般式〔〕
で表わされるビスフエノール類（ただし、−Ｘ−
は、−Ｏ−、−Ｓ−、−SO2−、−CO−、アルキレ
ン基あるいはアルキリデン基よりなる群から選ば
れ、R1、R2、R3、R4、R′1、R′2、R′3、およびR′4
は水素原子および炭化水素からなる群より選ばれ
る）とから得られる芳香族ポリエステル共重合体
と、
(B)ポリアミドと、
(C)芳香族ハロゲン化合物と、
(D)成分の化合物が長周期型周期表第Ｂ、
Ｂ、Ｂ、Ａ、Ａ族および第Ａ族より選ば
れた金属の酸化物である場合には、該酸化物の含
有率が(A)、(B)および(C)成分の合計量の100重量部
に対して0.1〜25重量部であり、(D)成分の化合物
が長周期型周期表第Ｂ、Ｂ、Ｂ、Ａ、
Ａ族および第Ａ族より選ばれた金属のハロゲン
化物である場合には、該ハロゲン化物の含有率が
(A)、(B)および(C)成分の合計量の100重量部に対し
て0.005〜0.5重量部であることを特徴とする難燃
性樹脂組成物を要旨とするものである。
本発明の難燃性樹脂組成物の一成分である芳香
族ポリエステル共重合体は、テレフタル酸とイソ
フタル酸またはこれらの機能誘導体の混合物（た
だし、テレフタル酸基とイソフタル酸基のモル比
は９：１ないし１：９）と一般式〔〕で表わさ
れるビスフエノール類とから得られるものであ
る。
上記一般式〔〕で表わされるビスフエノール
類の例としては、４・4′−ジヒドロキシ−ジフエ
ニルエーテル、ビス（４−ヒドロキシ−２−メチ
ルフエニル）−エーテル、ビス（４−ヒドロキシ
フエニル）−サルフアイド、ビス（４−ヒドロキ
シフエニル）−スルホン、ビス（４−ヒドロキシ
フエニル）−ケトン、ビス（４−ヒドロキシフエ
ニル）−メタン、ビス（４−ヒドロキシ−３−メ
チルフエニル）−メタン、１・１−ビス（４−ヒ
ドロキシフエニル）−エタン、２・２−ビス（４
−ヒドロキシ−３−メチルフエニル）プロパン、
１・１−ビス（４−ヒドロキシフエニル）ｎ−ブ
タン、ビス（４−ヒドロキシフエニル）−フエニ
ルメタン、ビス（４−ヒドロキシフエニル）−ジ
フエニルメタン、ビス（４−ヒドロキシフエニ
ル）−4′−メチルフエニルメタン、１・１−ビス
（４−ヒドロキシフエニル）−シクロヘキサン、ビ
ス（４−ヒドロキシフエニル）−シクロヘキシル
メタン、２・２−ビス（４−ヒドロキシナフチ
ル）−プロパンなどがあげられるが、最も一般に
製造され代表的なものは、２・２−ビス（４−ヒ
ドロキシフエニル）−プロパンすなわちビスフエ
ノールＡと呼ばれているものである。もし必要な
らば、前記ビスフエノール類の混合物あるいはビ
スフエノール類と少量の他の２価の化合物、たと
えば、２・2′−ジヒドロキシジフエニル、２・６
−ジヒドロキシナフタレンの如きジヒドロキシナ
フタレン、ヒドロキノン、レゾルシノール、２・
６−ジヒドロキシトルエン、３・６−ジヒドロキ
シトルエンなどの混合物を使用することができ
る。
テレフタル酸またはイソフタル酸の機能誘導体
とは、これらの酸のジクロライドまたはアルキ
ル、アリールなどのジエステルである。
本発明に用いられるテレフタル酸またはイソフ
タル酸またはこれらの機能誘導体のフエニレン基
はアルキル基で置換されてもよい。
本発明においては芳香族ポリエステル共重合体
として、その一部が酸無水物結合によつておきか
えられているものを使用するとき、特に好ましい
力学特性を得ることができる。たとえばテレフタ
ル酸とイソフタル酸（１：１重量比）とビスフエ
ノールＡとよりなる樹脂に酸無水物結合が存在す
る場合は、たとえば赤外吸収スペクトルの1800cm
−１付近に吸収があらわれる。この酸無水物結合
の存在の効果はきわめて大であり、ごく少量の酸
無水物結合が存在しても好ましい力学特性が発現
される。
本発明に用いられる芳香族ポリエステル共重合
体は、たとえばエチレングリコールやネオペンチ
ルグリコールのようなアルキレングリコールなど
が主鎖の一部に組み込まれたものであつてもよい
し、主鎖の一部にたとえばカーボネート結合やア
ミド結合やエーテル結合などの異種の結合を含ん
だものであつてもよいが、その量は30モル％以
下、とくに10モル％以下であることが好ましい。
本発明に用いられる芳香族ポリエステル共重合
体は界面重合法、溶液重合法、溶融重合法などの
方法で合成される。
本発明の難燃性樹脂組成物の一成分として用い
られるポリアミドとは一般式〔〕
あるいは〔〕
で表わされるものである。ここで、R5、R6およ
びR7はアルキレン基を示す。本発明に用いられ
るポリアミドはジアミンと二塩基酸の縮合反応、
アミノ酸の自己縮合ならびにラクタムの重合反応
により形成された重合体を包含するものである。
また、これらアルキレン基の一部が芳香族環や脂
肪族環で置きかえられていてもよい。また、アミ
ド結合の一部がエステル結合などの他の結合で置
きかえられていてもよい。
本発明に用いられるポリアミドは上記一般式で
表わされるものなら如何なるものでもよく、たと
えばポリヘキサメチレンアジパミド、ポリカプロ
ラクタム、ポリヘキサメチレンセバカミド、ポリ
デカメチレンアジパミド、等があげられるが、と
くに好ましいものはポリカプロラクタムである。
また、本発明に用いられるポリアミドとしては96
％硫酸中、濃度１ｇ／100c.c.、25℃での相対粘度
が２以上、とくに2.8以上のものが高度な力学特
性を発現する上で好ましい。
本発明においては、難燃剤として芳香族ハロゲ
ン化合物を使用する。本発明に好適に用いられる
芳香族ハロゲン化合物は、芳香族ポリエステル共
重合体およびポリアミドからなる樹脂組成物の溶
融加工温度範囲において安定であり、樹脂組成物
の燃焼温度においてはじめて分解するものであ
る。かかる芳香族ハロゲン化合物としては、たと
えば下記一般式〔〕〜〔〕で示されるがごと
き化合物があげられる。
一般式〔〕
ただし、Z1〜Z10は水素、塩素または臭素を示
すが、Z1〜Z10のすべてが水素である場合を含ま
ない。
一般式〔〕で表わされるハロゲン化ジフエニ
ルエーテルの具体例としては、デカブロモジフエ
ニルエーテル、オクタブロモジフエニルエーテ
ル、ヘキサブロモジフエニルエーテル、ペンタブ
ロモジフエニルエーテル、テトラブロモジフエニ
ルエーテル、トリブロモジフエニルエーテル、ジ
ブロモジフエニルエーテル、モノブロモジフエニ
ルエーテル、デカクロロジフエニルエーテル、オ
クタクロロジフエニルエーテル、ヘキサクロロジ
フエニルエーテル、ペンタクロロジフエニルエー
テル、テトラクロロジフエニルエーテル、トリク
ロロジフエニルエーテル、ジクロロジフエニルエ
ーテル、モノクロロジフエニルエーテル等がある
が、難燃効果、熱安定性、などにより最も好まし
いのはデカブロモジフエニルエーテル、ついでヘ
キサブロモジフエニルエーテルである。
一般式〔〕
ただし、Ａは水素、塩素または臭素であり、Ａ
の少なくとも１個、好ましくは少なくとも２個は
塩素または臭素よりなる。一般式〔〕で表わさ
れる化合物としては、たとえばヘキサブロモベン
ゼン、ヘキサクロルベンゼン、テトラブロモベン
ゼン、テトラクロルベンゼン、トリブロモベンゼ
ン、トリクロロベンゼン等が挙げられるが、特に
耐熱性にすぐれ、しかもハロゲン含有量の多いヘ
キサブロモベンゼンが最も適している。
一般式〔〕
ただし、Ａは水素、塩素または臭素であり、Ａ
の少なくとも１個、好ましくは少なくとも２個は
塩素または臭素より成り、Ｒはアルキル基または
アルキレン基であり、その一部がハロゲン化され
るかまたはアルキル基置換されていてもよく、ま
たその一部にエーテル結合が含まれていてもよ
い。一般式〔〕で表わされる化合物としては、
たとえばペンタブロモトルエン、ペンタクロルト
ルエン、ペンタブロモエチルベンゼン、ペンタブ
ロモフエニルアリルエーテル、２・４・６−トリ
ブロモフエニルメタリルエーテル、２・４・６−
トリブロモフエニル−２−メチル−２・３−ジブ
ロモプロピルエーテル等が挙げられるが、特にペ
ンタブロモトルエンあるいはペンタブロモエチル
ベンゼンが熱安定性、難燃効果からみて好適であ
る。
一般式〔〕
ただし、ＡおよびＢは水素、塩素または臭素で
あり、ＡおよびＢともにその少なくとも１個は臭
素または塩素よりなり、ＲはＳ、SO2、アルキレ
ン基またはアルキリデン基であり、その一部がハ
ロゲン化されるかまたはアルキル基置換されてい
てもよく、またその一部にエーテル結合が含まれ
ていてもよい。一般式〔〕で表わされる化合物
としては、たとえばデカブロモジフエニルスルフ
イド、オクタブロモジフエニルスルフイド、テト
ラクロルジフエニルスルフイド、チトラクロルジ
フエニルスルホン、３・５−ジクロル−3′・5′−
ジブロモジフエニルスルホン、２・４−ジクロル
−3′・4′・5′−トリブロモジフエニルメタン、デ
カクロルジフエニルスルホン、デカブロモジフエ
ニルスルホン、ビス（トリブロモフエノキシ）メ
チレン、ビス（トリブロモフエノキシ）エチレ
ン、ビス（ペンタブロモフエノキシ）エチレン等
が挙げられるが、特にデカブロモジフエニルスル
ホン、ビス（トリブロモフエノキシ）エチレンが
熱安定性、難燃効果からみて好適である。
一般式〔〕
ただし、ＡおよびＢは水素、塩素または臭素であ
り、ＡおよびＢともにその少なくとも１個は臭素
または塩素よりなる。一般式〔〕で表わされる
化合物としては、たとえばヘキサクロルジフエニ
ル、ヘキサブロモジフエニル、オクタブロモジフ
エニル、オクタクロルジフエニル、デカブロモジ
フエニル、デカクロルジフエニル等が挙げられる
が、特にデカブロモジフエニル、オクタブロモジ
フエニルが熱安定性、難燃効果からみて好適であ
る。
一般式〔〕
ただし、ＡおよびＢは水素、塩素または臭素で
あり、ＡおよびＢともにその少なくとも１個は臭
素または塩素よりなり、R1はＯ、Ｓ、SO2、
CO、アルキレン基またはアルキリデン基であ
り、R2は水素、アルキル基またはヒドロキシア
ルキレン基であり、その一部がハロゲン化される
かまたはアルキル基置換されていてもよい。一般
式〔〕で表わされる化合物としては、たとえば
２・２−ビス（４−ヒドロキシ−３・５−ジブロ
モフエニル）プロパン、２・２−ビス（４−ヒド
ロキシエトキシ−３・５−ジブロモフエニル）プ
ロパン、２・２−ビス〔４（2′・3′−ジブロモプ
ロポキシ）−３・５−ジブロモフエニル〕プロパ
ン、ビス（４−ヒドロキシ−３・５−ジブロモフ
エニル）スルホン、２・２−ビス（４−エトキシ
−３・５−ジクロルフエニル）プロパン、ビス
（４−ヒドロキシ−３・５−ジクロルフエニル）
スルホン、２・２−ビス（４−エトキシ−３・５
−ジブロモフエニルプロパン等が挙げられるが、
特に２・２−ビス（４−ヒドロキシエトキシ−
３・５−ジブロモフエニル）プロパン、ビス（４
−ヒドロキシ−３・５−ジブロモフエニル）スル
ホンが熱安定性、難燃効果からみて好適である。
これら多くの芳香族ハロゲン化合物の中でもデ
カブロモジフエニルエーテルは熱安定性、難燃効
果、非移行性、樹脂組成物の熱変形温度に与える
影響、経済性などの各種の観点からみて特にすぐ
れている。
芳香族ハロゲン化合物は単独で使用することも
できるし、また２種類以上を併用することもでき
る。
(A)芳香族ポリエステル共重合体と(B)ポリアミド
とよりなる樹脂組成物を難燃化するに際して樹脂
組成物に含有せしめる(C)芳香族ハロゲン化合物の
量は、(A)成分、(B)成分および(C)成分の合計量に対
し0.5〜40重量％、難燃性と力学特性から特に好
ましくは２〜30重量％である。
また、本発明の難燃性樹脂組成物のうち、とく
に(A)成分、(B)成分および芳香族ハロゲン化合物の
含有量が(A)、(B)および芳香族ハロゲン化合物の合
計量に対してそれぞれ20〜78重量％20〜78重量
％、２〜30重量％であるものが、耐熱性、難燃
性、力学特性、耐薬品性あるいは耐ストレスクラ
ツク性などの多くの特性において極めてバランス
がとれており好ましいものである。
本発明の樹脂組成物の一成分として用いられる
特定の金属化合物は、長周期型周期表第Ｂ、
Ｂ、Ｂ、Ａ、Ａ族および第Ａ族より選ば
れた金属の酸化物とハロゲン化物とよりなる群か
ら選ばれる少なくとも一種の化合物であるが、か
かる特定の金属化合物に適した金属の具体例とし
てはチタン、ジルコニウム、銅、銀、亜鉛、カド
ミウム、水銀、アルミニウム、スズ、鉛、アンチ
モン、ビスマスなどがあげられる。かかる特定の
金属化合物の具体的に好ましい化合物の例をあげ
るならば酸化アンチモン、酸化チタン、酸化ジル
コニウム、酸化亜鉛、酸化スズ、酸化銅、酸化
銀、塩化銅、臭化銅、ヨウ化銅、臭化亜鉛、ヨウ
化亜鉛、塩化銀、臭化銀、ヨカ化銀、などがあげ
られる。これらの中でも酸化アンチモン、酸化ジ
ルコニウム、酸化亜鉛、酸化第２スズ、などは難
燃助剤としての性質をあわせもつので特に好まし
い。これらの中でも酸化アンチモンは難燃助剤と
しての効果と、本発明の樹脂組成物の力学特性を
改善する働きの両者のバランスにおいて特にすぐ
れている。また、本発明においては必要に応じて
上記の特定の金属化合物を組み合せて使用しても
よいし、上記の特定の金属化合物と他の難燃助剤
を組み合せて用いてもよい。本発明において金属
の酸化物と金属のハロゲン化物の併用、とくに酸
化アンチモンとハロゲン化銅の併用は、力学特
性、難燃性、耐熱耐久性などの改善効果において
とくに優れている。本発明において酸化アンチモ
ンを使用する場合、本発明の難燃性樹脂組成物に
含有せしめる芳香族ハロゲン化合物中のハロゲン
原子と酸化アンチモン中のアンチモン原子の当量
比は20：１〜２：１の範囲にあることが好まし
い。両者の当量比がこの範囲内にあるとき、その
難燃性付与効果はとくに顕著であり、すぐれた力
学特性を発揮することができる。
本発明に述べる効果のあらわれる特定の金属化
合物の添加量は通常、(A)成分と(B)成分の合計量
100重量部に対して0.001重量部以上であるが、特
定の金属化合物の種類によつて一様ではなく、酸
化物の場合は比較的大量の添加が効果的であり、
一方、塩化物の場合は比較的少量の添加で効果が
えられる。たとえば、力学特性の発現の上で好ま
しい添加量は(A)芳香族ポリエステル共重合体と(B)
ポリアミドと(C)芳香族ハロゲン化合物の合計量
100重量部に対して特定の金属化合物が酸化物の
場合は0.1〜25重量部、特に0.5〜15重量部程度で
あるのに対し、ハロゲン化合物の場合は0.005〜
0.5重量部程度である。本発明の難燃性樹脂組成
物においては、これらの特定の金属化合物を添加
することにより、力学特性の改善がはかられる。
一般に無機質を樹脂に充填する場合、特に射出
成形品の肉薄部などはもろくなつて折れやすくな
ることを考えると、本発明の難燃性樹脂組成物に
おけるように難燃剤や金属化合物を相当量含有し
ながら、これらを含有しない場合に比してかえつ
て力学特性が改善されるということは驚くべきこ
とである。どのような機構によつてこのような現
象が発現しているかは明らかでないが、押出しや
射出成形などの成形工程にて課される熟履歴によ
つて樹脂組成物が何らかの化学変化を生じている
のかもしれない。したがつて、本発明の難燃性樹
脂組成物にはこれらの加工工程における化学変化
の結果の反応物を含有するものも包含される。
本発明において(A)芳香族ポリエステル共重合体
と(B)ポリアミドと(C)芳香族ハロゲン化合物と(D)特
定の金属化合物の４成分を混合するには、(A)成分
と(B)成分を溶融押出しして混合した後に(C)成分と
(D)成分を加えてもよいし、また(A)成分か(B)成分の
いずれか一方、もしくは両方にその重合工程ある
いはチツプ化工程において(C)成分と(D)成分を添加
し、しかる後に最終樹脂組成物を得るために、再
押出ししてもよい。また、(C)成分や(D)成分を(A)成
分または(B)成分の一成分側に意識的に偏在させる
こともできる。たとえば、あらかじめ(A)成分と(C)
成分を溶融混合しておいて、しかる後に(B)成分と
(D)成分を加え再押出しする場合に比べ、(A)成分と
(B)成分を溶融混合しておいて、しかる後に(C)成分
や(D)成分を加えて再押出しする場合の方が成形品
の熱変形温度が高く、吸湿したときの寸法安定性
にすぐれている。さらに、(C)成分や(D)成分をあら
かじめ(B)成分に分散させておいて、しかる後(A)成
分を加えて溶融再押出しする場合には熱変形温度
や寸法安定性の面でさらにすぐれた結果が得られ
る。すなわち、(C)成分や(D)成分をなるべく(A)成分
側に偏在することを妨たげることによつて、熱変
形温度と水分に対する寸法安定性を向上させるこ
とができる。しかしながら、上記のごとき効果を
発現させるために(C)成分をあらかじめ(B)成分側に
偏在させようとして(C)成分を(B)成分と溶融押出し
しておき、しかる後に(A)成分と(D)成分を加える場
合には、あらかじめ(A)成分と(C)成分を加えておい
て、しかる後に(B)成分と(D)成分を加えて再押出し
する場合に比して、溶融押出時に分解しやすい傾
向が往々にしてみられる。この分解を防ぐには押
出し温度をさげればよいが、分散不良を生じやす
いという問題がある。この場合は(B)成分を二つに
分けてその一方と(A)成分とを溶融押出しし、さら
に残りの(B)成分に(C)成分の全量を加えて溶融押出
しし、ついで前２者に(D)成分を加えて再押出しす
る方法をとれば、(A)成分に(B)成分がブレンドされ
ることによつて押出温度を下げるので相対的に低
い温度で均一分散させうるようになるため分解を
防ぎながら良好な性質を維持することが可能であ
る。
(A)、(B)、(C)および(D)成分のすべてを混合した
後、一段階で溶融押出しする方法は生産性の面で
もつともすぐれている。しかしながら、(A)成分の
軟化温度が高いので必然的に押出し温度が高くな
り、そのために分解をともないやすいという問題
点があつた。この場合はベント付きの押出機を使
用して、なるべくホツパー側の温度を高く設定
し、早期に(A)成分と(B)成分を混練したのち先端部
の温度を下げて押出し機のバレルの先端近くにあ
るベント口より(C)成分と(D)成分を加えれば滞留時
間が短かくできるので分解しにくくなることが認
められた。さらに好ましい方法は、あらかじめ(C)
成分を溶融させておいて（この時(D)成分をこの中
に混合しておいてもよい）ベント口から滴下さす
かあるいは強制的にバレル先端近くに圧入すれば
均一に微粒子化させて、しかも熱分解を極力防ぎ
ながら分散させることができる。このような方法
をとることによつて難燃剤の使用量を同一の難燃
度を与えるのにより少なくすることができ、かつ
力学特性の上からも好ましい効果が得られる。上
記のごとく難燃剤をあらかじめ溶融させて押出機
のバレルへ直接滴下するかあるいは圧入する方法
は、さらにまた別の目的にも有効である。すなわ
ち、本発明の難燃性樹脂組成物において(C)成分や
(D)成分はできるだけ微粒子として存在させるのが
好ましい。たとえば熱安定性、非移行性、安全性
などの面ですぐれた難燃剤であるデカブロモジフ
エニルエーテル（以下DBDEと略称する。）は約
300℃の融点を有するのでDBDEをポリアミドに
偏在させる目的でポリアミド側にDBDEを均一分
散させようとすると300℃近傍で押出す必要があ
る。しかしながら、ポリアミドはもともと溶融粘
度が低い樹脂であり、かつ300℃付近では分解も
早いので単純に高温度で押出すのみでは良好な品
質のものを生産性よく得ることはきわめて困難で
ある。しかるに、前述したようなあらかじめ難燃
剤を溶融させておいてから押出機のバレルの中で
すでに溶融している樹脂の中へ滴下させるか、も
しくは圧入する方法をとることにより過激な温度
条件などを用いることなく、したがつて樹脂の分
解などを招くことなくして均一に難燃剤を微粒子
分散させることが可能となる。
本発明の難燃性樹脂組成物には、耐熱性や耐候
性を改良する目的でリン化合物、ヒンダードフエ
ノール化合物、アミン化合物、ベンゾトリアゾー
ル化合物等を含有せしめてもよい。
特に着色防止剤としては、正リン酸エステル、
酸性正リン酸エステル、正リン酸、亜リン酸エス
テル、酸性亜リン酸エステル、亜リン酸等を難燃
性樹脂組成物に対して0.01〜0.5重量％添加する
のが効果的である。また、この場合、エポキシ化
合物をリン化合物と併用してもよい。
また、必要に応じてガラス繊維、無機ケイ酸
塩、シリカゲルの蒸発により得られるシリカ、石
英、シリカゲル、炭素繊維、クリストバライト、
アスベスト、クレイ、タルク等のような通常の補
強充填材を含有せしめてもよい。
また、本発明の難燃性樹脂組成物には衝撃強
度、破断伸度などの機械的性質をさらに増大させ
る目的や耐熱劣化を向上させるなどの必要に応じ
てアクリロニトリル−ブタジエンゴム、スチレン
−ブタジエンゴム、ポリエステルゴム等のゴム
質、ABS、ポリカーボネート、ポリスルフオ
ン、ポリエーテルスルフオン、ポリエチレン、ポ
リプロピレン、ポリウレタン、ポリスチレン、
EVA、ポリアクリル酸エステル、ポリテトラフ
ルオロエチレン、イオノマー、メチルメタクリレ
ート、ポリアルキレンフエニレンエステル、ポリ
アルキレンフエニレンエステルエーテルを含有せ
しめてもよい。
本発明の難燃性樹脂組成物は、すぐれた難燃
性、耐熱性、機械的性質、成形性、水分に対する
寸法安定性を示すが、とくに得られた成形品が衝
撃を加えられても割れにくく、また成形品の肉薄
部が折れにくいという特徴も有する。
本発明の難燃性樹脂組成物は、粉末、チツプ、
その他の形状とし、このものを用いてプレス成
形、射出成形、押出成形など一般に知られている
プラスチツク成形法により各種の有用な製品を作
ることができる。このような製品の例としてはギ
ヤー、軸受け、電気部品容器その他広くあげられ
る。
このように、本発明の難燃性樹脂組成物はエン
ジニアリングプラスチツクスとして高い性能が要
求される製品として広範囲の用途に用いられる。
以下に実施例を挙げて本発明をさらに具体的に
説明する。なお、肉薄部の折り曲げ強度ならびに
衝撃強度は以下の方法で評価した。
〔1〕 肉薄部の折り曲げ強度の評価法
図を用いて説明すると、第１，２図において
１は射出成形品のスプレー、２はランナー、
３，３′はテストピース、４はゲート部であ
る。ランナーは８mmφ、ゲートは巾８mm、厚さ
１mm、ゲートランド（ゲートの長さ方向）の最
短距離２mm、テストピース３および３′はULの
燃焼試験に用いる長さ５インチ、巾1/2イン
チ、厚さ1/8インチおよび1/16インチの棒状試
験片である。テストピース３（厚さ1/8イン
チ）を所定の成形条件において成形したのちと
り出し、直ちにランナー２とテストピース３が
ゲート４を境いに直角方向になるように上下に
折り曲げ、上下に各１回折り曲げた時、完全に
ゲートが折れてテストピースがランナー部で離
れる場合を×と評価し、部分的にゲート部で折
れるが完全に離れない場合を△とし、折れを生
じない場合を〇として、〇が全体に占める割合
をゲート不折比として％で示した。
〔2〕 衝撃強度の評価法
実施的な射出成形品に衝撃的な力が加わる時
に発生する割れやすさにもつとも対応しやすい
評価法を各種検討した結果、一般的に衝撃強度
の評価法としてよく使用されるＶノツチアイゾ
ツト衝撃値よりもノツチなしアイゾツトに対応
するダインシユタツト衝撃強度の大きさ（イギ
リス規格B.S1330）が最も実用品の割れの発生
しやすさとよく対応することを確認した。使用
したサンプル形状は、第２図に示す1/2″×5″×
1/8″のテストピース３のエジエクターピン跡５
の間にはさまれた部分から樹脂の流れと平行ま
たは直角方向にB.S1330の試験片寸法を若干変
更して長さ1/2インチ、巾1/4インチ、厚さ1/8
インチの試験片を切り取り、ダインシユタツト
衝撃試験機により衝撃値を測定した。なお第２
図において、６の試験片にて測定した値を
ｙ、７の試験片にて測定した値をｘと表示し
た。ｙは樹脂の流動方向と直角方向の衝撃強
度、ｘは樹脂の流動方向と平行方向の衝撃強
度を示す。衝撃強度の測定は成形品を100℃に
おいて16時間乾燥後、行つた。測定結果は次の
式によりKg、cm／cm2で表わした。
測定値（Kg、cm／cm2）＝破壊エネルギー（Kg、cm）／
試料断面積（cm2）
また、本発明において燃焼試験は米国アンダー
ライターラボラトリーズのUL規格第94号に定め
る方法を用いた。
また、芳香族ハロゲン化合物の含有率の測定は
次のようにして行なつた。まず、(A)成分に対して
(B)成分が相対的に少ない場合は、成形品をできる
だけ薄く削り、１ｇ／1000c.c.の濃度になるような
量を採り、あらかじめ準備しておいた塩化メチレ
ン中に投入し、温湯で加熱し十分撹拌した。この
過程で(A)成分および(A)成分中に存在する(C)成分は
抽出されるが塩化メチレンに溶解性のない(C)成分
および(B)成分中に存在する(C)成分は抽出されな
い。十分撹拌したのち１号ガラスフイルターで固
形分と溶液とを分離し、ついで時計皿へ溶液を流
しこみ、塩化メチレンを蒸発させてフイルムを得
た。このフイルムには(A)成分と(A)成分中に含まれ
ていた(C)成分が入つていると考えられるので、こ
れを分析して(A)成分中の(C)成分の濃度を決めた。
この結果にもとづいて(B)成分中の(C)成分の濃度を
計算によつて求めた。また、(A)成分に対して(B)成
分が相対的に多い場合は塩化メチレンを使用して
も十分(A)成分およびそれに含まれている(C)成分を
抽出しにくいので一たん成形品を90％ギ酸に懸だ
く溶解させてのちギ酸の蒸発によつてフイルムを
作成し、このフイルムより前述の方法で塩化メチ
レンによつて(A)成分およびこの中に含まれている
(C)成分を抽出した。なお、ギ酸処理によつて(A)成
分中の(C)成分濃度が変化することもなく、この方
法を使用する時は(C)成分が塩化メチレンやギ酸に
対して十分溶解度が小さいことを確めた。(A)成分
および(C)成分よりなるフイルム中の(C)成分の濃度
の測定は酸素フラスコ燃焼法（分析化学、1963年
５月号、小野江、1964年４月号、小林、鈴木、荒
木）によりハロゲンを分離したのち、JIS Ｋ
0107のハロゲン分析法に準じて行なつた。
また、特定の金属化合物の含有率は上記と同様
の手順により、塩化メチレンに溶出してきた成分
を遠心分離法によつて分離秤量するかもしくは原
子吸光法によつて測定した。
実施例１〜８、比較例１〜10
テレフタル酸ジクロリドとイソフタル酸ジクロ
リドのモル比が１：１の混合酸クロリドの塩化メ
チレン溶液と、ビスフエノールＡのアルカリ水溶
液とより界面重合法によつて芳香族ポリエステル
共重合体（以下PARと称す）を製造した。これ
のフエノールテトラクロルエタン（重量比６／
４）中、25℃、濃度１ｇ／100c.c.の対数粘度は
0.75であつた。その他、原料としてナイロン６
（以下N6と称す）（ユニチカ製、96％硫酸中の相
対粘度は25℃、１ｇ／100c.c.で2.6）、DBDE、各
種金属化合物を使用した。
PARとN6を重量比で１：１の割合でスーパー
ミキサーで混合し、110℃で16時間熱風乾燥後、
高混練型押出機にてバレル温度280℃の設定で押
出し、均一なペレツトＵ−１を得た。
Ｕ−１とDBDEと各種金属化合物を表１の割合
で配合し、スーパーミキサーで混合後、110℃で
16時間熱風乾燥し、ついでバレル温度240℃の設
定で再押出しした。そのあと第１，２図に示した
形状の射出成形品を射出成形機を用いてシリンダ
ー温度240℃、金型温度80℃にて成形した。得ら
れた成形品について、各種特性を評価した結果は
表２に示すとおりであつた。
表２に示されるごとく、本発明の樹脂組成物は
難燃性が向上しているとともに実用的成形品。
The present invention comprises (A) an aromatic polyester copolymer produced from terephthalic acid, isophthalic acid or a functional derivative thereof, bisphenols or a functional derivative thereof, (B) a polyamide, and (C) an aromatic halogen compound. (D) Long-period periodic table B, B,
At least one compound (hereinafter referred to as a specific metal compound) selected from the group consisting of oxides and halides of metals selected from Groups B, A, A, and A, and excellent mechanical properties. The present invention relates to a flame-retardant resin composition having the following properties. In recent years, plastics are rapidly replacing metal materials in various fields. Under these circumstances, plastics are required to have a wide variety of excellent properties such as moldability, mechanical properties, chemical properties, electrical properties, and heat resistance. Furthermore, in recent years, it has become extremely important to have flame retardancy, and there is a strong social demand for various products from the viewpoint of safety against fire accidents. A resin composition made of an aromatic polyester copolymer and a polyamide, which the present applicant previously applied for, has a significantly higher heat distortion temperature than polyamide alone, and also overcomes the drawbacks of aromatic polyester copolymers. The moldability and solvent resistance have also been improved. This degree is much higher than that estimated from the additivity based on the ratio of both components, and is a surprising characteristic that could not be expected from the single component constituting the composition. In addition, such a resin composition maintains well the excellent tensile strength, bending recovery characteristics, and dimensional stability of the aromatic polyester copolymer, as well as the excellent crack resistance and abrasion resistance of the polyamide, making it extremely useful. It is a resin composition that maintains the properties (JP-A-50-4146, JP-A-52-
No. 98765). However, when resin compositions made of aromatic polyester copolymers and polyamides were molded into various molded products by, for example, injection molding, and their properties were investigated in detail, the following drawbacks were found.
In other words, thin parts such as the gates of various molded products and elongated rod-like parts that are elongated and protruding easily break, especially when completely dry, which not only causes problems when releasing the molded product from the mold, but also limits the design of the product. In addition, even relatively thick molded products are susceptible to cracking when subjected to shocking forces such as dropping or falling balls, especially when they are completely dry. It has been found. These phenomena greatly limit the uses of such resin compositions. Furthermore, since such resin compositions are insufficient in flame retardancy, there is a strong demand for improvement in their flame retardance due to the circumstances mentioned above.
However, it is clear that if a large amount of flame retardant is added to a resin composition having such problems in mechanical properties, these properties will further deteriorate, which is a major obstacle from a practical standpoint. As a result of intensive research to solve the above problems, the present inventors discovered that mechanical properties and flame retardance can be greatly improved by adding a specific metal compound together with a flame retardant. This invention has been achieved. That is, the present invention provides (A) a mixture of terephthalic acid and isophthalic acid or their functional derivatives (however, the molar ratio of terephthalic acid groups and isophthalic acid groups is 1:9 to 9:1) and the general formula [] Bisphenols represented by (however, -X-
is selected from the group consisting of -O-, -S-, -SO2- , -CO-, an alkylene group or an alkylidene group, and R1 , R2 , R3 , R4 , R'1 , R'2 , R′ 3 , and R′ 4
is selected from the group consisting of hydrogen atoms and hydrocarbons), (B) a polyamide, (C) an aromatic halogen compound, and (D) a long-period compound. periodic table B,
In the case of an oxide of a metal selected from B, B, A, Group A, and Group A, the content of the oxide is 100% of the total amount of components (A), (B), and (C). The amount is 0.1 to 25 parts by weight based on the weight part, and the compound of component (D) is a long-period type periodic table B, B, B, A,
In the case of a halide of a metal selected from Group A and Group A, the content of the halide is
The gist of the invention is a flame-retardant resin composition characterized in that the amount is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total amount of components (A), (B), and (C). The aromatic polyester copolymer, which is one component of the flame-retardant resin composition of the present invention, is a mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (however, the molar ratio of terephthalic acid groups to isophthalic acid groups is 9: 1 to 1:9) and a bisphenol represented by the general formula []. Examples of bisphenols represented by the above general formula [] include 4,4'-dihydroxy-diphenyl ether, bis(4-hydroxy-2-methylphenyl)-ether, and bis(4-hydroxyphenyl)-sulfide. , bis(4-hydroxyphenyl)-sulfone, bis(4-hydroxyphenyl)-ketone, bis(4-hydroxyphenyl)-methane, bis(4-hydroxy-3-methylphenyl)-methane, 1.1 -bis(4-hydroxyphenyl)-ethane, 2,2-bis(4
-hydroxy-3-methylphenyl)propane,
1,1-bis(4-hydroxyphenyl)n-butane, bis(4-hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4'- Examples include methylphenylmethane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)-cyclohexylmethane, 2,2-bis(4-hydroxynaphthyl)-propane, etc. The most commonly produced and typical one is called 2,2-bis(4-hydroxyphenyl)-propane, or bisphenol A. If necessary, mixtures of the bisphenols or bisphenols and small amounts of other divalent compounds, such as 2.2'-dihydroxydiphenyl, 2.6
- dihydroxynaphthalenes such as dihydroxynaphthalene, hydroquinone, resorcinol, 2.
Mixtures of 6-dihydroxytoluene, 3,6-dihydroxytoluene, etc. can be used. Functional derivatives of terephthalic acid or isophthalic acid are dichlorides or alkyl, aryl, etc. diesters of these acids. The phenylene group of the terephthalic acid or isophthalic acid or functional derivative thereof used in the present invention may be substituted with an alkyl group. In the present invention, when using an aromatic polyester copolymer in which a portion of the copolymer is replaced by acid anhydride bonds, particularly favorable mechanical properties can be obtained. For example, if an acid anhydride bond exists in a resin made of terephthalic acid, isophthalic acid (1:1 weight ratio), and bisphenol A, the infrared absorption spectrum
Absorption appears near -1. The effect of the presence of this acid anhydride bond is extremely large, and even if a very small amount of acid anhydride bond is present, favorable mechanical properties are exhibited. The aromatic polyester copolymer used in the present invention may be one in which an alkylene glycol such as ethylene glycol or neopentyl glycol is incorporated into a part of the main chain, or For example, it may contain different types of bonds such as carbonate bonds, amide bonds, and ether bonds, but the amount thereof is preferably 30 mol% or less, particularly 10 mol% or less. The aromatic polyester copolymer used in the present invention is synthesized by methods such as interfacial polymerization, solution polymerization, and melt polymerization. The polyamide used as a component of the flame-retardant resin composition of the present invention has the general formula [] or〔〕 It is expressed as Here, R 5 , R 6 and R 7 represent an alkylene group. The polyamide used in the present invention is produced by a condensation reaction of diamine and dibasic acid.
It includes polymers formed by self-condensation of amino acids and polymerization reactions of lactams.
Further, a part of these alkylene groups may be replaced with an aromatic ring or an aliphatic ring. Further, a part of the amide bond may be replaced with another bond such as an ester bond. The polyamide used in the present invention may be any polyamide as long as it is represented by the above general formula, and examples thereof include polyhexamethylene adipamide, polycaprolactam, polyhexamethylene sebacamide, polydecamethylene adipamide, etc. Especially preferred is polycaprolactam.
In addition, the polyamide used in the present invention is 96
% sulfuric acid, a concentration of 1 g/100 c.c., and a relative viscosity of 2 or more, particularly 2.8 or more at 25° C., is preferable in terms of exhibiting advanced mechanical properties. In the present invention, an aromatic halogen compound is used as a flame retardant. The aromatic halogen compound preferably used in the present invention is stable in the melt processing temperature range of the resin composition consisting of the aromatic polyester copolymer and polyamide, and decomposes only at the combustion temperature of the resin composition. Examples of such aromatic halogen compounds include compounds represented by the following general formulas [] to []. General formula [] However, although Z 1 to Z 10 represent hydrogen, chlorine, or bromine, the case where all of Z 1 to Z 10 are hydrogen is not included. Specific examples of the halogenated diphenyl ether represented by the general formula [] include decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, pentabromodiphenyl ether, tetrabromodiphenyl ether, and tribromodiphenyl ether. Diphenyl ether, dibromodiphenyl ether, monobromodiphenyl ether, decachlorodiphenyl ether, octachlorodiphenyl ether, hexachlorodiphenyl ether, pentachlorodiphenyl ether, tetrachlorodiphenyl ether, trichlorodiphenyl ether, dichloro There are diphenyl ether, monochlorodiphenyl ether, etc., but decabromodiphenyl ether is most preferred in terms of flame retardant effect, thermal stability, etc., followed by hexabromodiphenyl ether. General formula [] However, A is hydrogen, chlorine or bromine, and A
At least one, preferably at least two of these consist of chlorine or bromine. Examples of the compound represented by the general formula [] include hexabromobenzene, hexachlorobenzene, tetrabromobenzene, tetrachlorobenzene, tribromobenzene, and trichlorobenzene, which have particularly excellent heat resistance and low halogen content. Hexabromobenzene, which has a large amount of General formula [] However, A is hydrogen, chlorine or bromine, and A
at least one, preferably at least two of which are composed of chlorine or bromine, and R is an alkyl group or an alkylene group, a part of which may be halogenated or substituted with an alkyl group; may contain an ether bond. As a compound represented by the general formula [],
For example, pentabromotoluene, pentachlorotoluene, pentabromoethylbenzene, pentabromophenyl allyl ether, 2,4,6-tribromophenyl methallyl ether, 2,4,6-
Examples include tribromophenyl-2-methyl-2,3-dibromopropyl ether, and pentabromotoluene or pentabromoethylbenzene is particularly preferred in terms of thermal stability and flame retardant effect. General formula [] However, A and B are hydrogen, chlorine, or bromine, and at least one of both A and B is composed of bromine or chlorine, and R is S, SO 2 , an alkylene group, or an alkylidene group, some of which are halogenated. or may be substituted with an alkyl group, and a portion thereof may contain an ether bond. Examples of the compound represented by the general formula [] include decabromodiphenyl sulfide, octabromodiphenyl sulfide, tetrachlordiphenyl sulfide, titrachlordiphenyl sulfone, 3,5-dichloro-3'・5′−
Dibromodiphenyl sulfone, 2,4-dichloro-3',4',5'-tribromodiphenylmethane, decachlordiphenyl sulfone, decabromodiphenyl sulfone, bis(tribromophenoxy)methylene, bis( Examples include tribromophenoxy)ethylene, bis(pentabromophenoxy)ethylene, etc., but decabromodiphenyl sulfone and bis(tribromophenoxy)ethylene are particularly preferred in terms of thermal stability and flame retardant effect. It is. General formula [] However, A and B are hydrogen, chlorine or bromine, and at least one of both A and B consists of bromine or chlorine. Examples of the compound represented by the general formula [] include hexachlordiphenyl, hexabromodiphenyl, octabromodiphenyl, octachlordiphenyl, decabromodiphenyl, decachlordiphenyl, etc., but especially decabromodiphenyl, Diphenyl and octabromodiphenyl are preferred from the viewpoint of thermal stability and flame retardant effect. General formula [] However, A and B are hydrogen, chlorine or bromine, at least one of both A and B consists of bromine or chlorine, and R 1 is O, S, SO 2 ,
It is CO, an alkylene group, or an alkylidene group, and R 2 is hydrogen, an alkyl group, or a hydroxyalkylene group, and a part thereof may be halogenated or substituted with an alkyl group. Examples of the compound represented by the general formula [] include 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl) ) propane, 2,2-bis[4(2',3'-dibromopropoxy)-3,5-dibromophenyl]propane, bis(4-hydroxy-3,5-dibromophenyl)sulfone, 2,2 -Bis(4-ethoxy-3,5-dichlorophenyl)propane, bis(4-hydroxy-3,5-dichlorophenyl)
Sulfone, 2,2-bis(4-ethoxy-3,5
-dibromophenylpropane etc., but
Especially 2,2-bis(4-hydroxyethoxy-
3,5-dibromophenyl)propane, bis(4
-hydroxy-3,5-dibromophenyl) sulfone is preferred in terms of thermal stability and flame retardant effect. Among these many aromatic halogen compounds, decabromodiphenyl ether is particularly superior in terms of thermal stability, flame retardant effect, non-migration, influence on heat distortion temperature of resin compositions, and economic efficiency. There is. Aromatic halogen compounds can be used alone or in combination of two or more types. When making a resin composition consisting of (A) an aromatic polyester copolymer and (B) polyamide flame retardant, the amount of (C) aromatic halogen compound to be included in the resin composition is determined by the amount of (A) component, (B) The amount is preferably 0.5 to 40% by weight based on the total amount of component ) and component (C), and preferably 2 to 30% by weight from the viewpoint of flame retardancy and mechanical properties. In addition, in the flame-retardant resin composition of the present invention, the content of component (A), component (B), and aromatic halogen compound is particularly high relative to the total amount of (A), (B), and aromatic halogen compound. 20-78% by weight and 2-30% by weight, respectively, are extremely balanced in many properties such as heat resistance, flame retardance, mechanical properties, chemical resistance or stress crack resistance. It is preferable because it has the following properties. The specific metal compound used as a component of the resin composition of the present invention includes long-period type periodic table B,
At least one compound selected from the group consisting of oxides and halides of metals selected from Groups B, B, A, A, and A, and specific examples of metals suitable for such specific metal compounds. Examples include titanium, zirconium, copper, silver, zinc, cadmium, mercury, aluminum, tin, lead, antimony, and bismuth. Specific preferred examples of such specific metal compounds include antimony oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, copper oxide, silver oxide, copper chloride, copper bromide, copper iodide, and Examples include zinc chloride, zinc iodide, silver chloride, silver bromide, silver iodide, etc. Among these, antimony oxide, zirconium oxide, zinc oxide, stannic oxide, etc. are particularly preferred since they also have properties as flame retardant aids. Among these, antimony oxide is particularly excellent in its balance between the effect as a flame retardant aid and the function of improving the mechanical properties of the resin composition of the present invention. Further, in the present invention, the above-mentioned specific metal compounds may be used in combination as necessary, or the above-mentioned specific metal compounds and other flame retardant aids may be used in combination. In the present invention, the combination of a metal oxide and a metal halide, particularly the combination of antimony oxide and copper halide, is particularly effective in improving mechanical properties, flame retardance, heat resistance, and durability. When antimony oxide is used in the present invention, the equivalent ratio of the halogen atom in the aromatic halogen compound and the antimony atom in the antimony oxide to be contained in the flame retardant resin composition of the present invention is in the range of 20:1 to 2:1. It is preferable that the When the equivalent ratio of both is within this range, the effect of imparting flame retardance is particularly remarkable, and excellent mechanical properties can be exhibited. The amount of the specific metal compound added that produces the effects described in the present invention is usually the total amount of components (A) and (B).
The amount is 0.001 part by weight or more per 100 parts by weight, but it varies depending on the type of specific metal compound, and in the case of oxides, it is effective to add a relatively large amount.
On the other hand, in the case of chloride, the effect can be obtained by adding a relatively small amount. For example, in terms of developing mechanical properties, the preferred addition amounts are (A) aromatic polyester copolymer and (B)
Total amount of polyamide and (C) aromatic halogen compound
When the specific metal compound is an oxide, it is about 0.1 to 25 parts by weight, especially about 0.5 to 15 parts by weight, while in the case of a halogen compound, it is from 0.005 to 100 parts by weight.
It is about 0.5 part by weight. In the flame-retardant resin composition of the present invention, mechanical properties can be improved by adding these specific metal compounds. Generally speaking, when resin is filled with inorganic substances, thin parts of injection molded products in particular become brittle and break easily. However, it is surprising that the mechanical properties are improved compared to the case where they are not contained. Although it is not clear what mechanism causes this phenomenon, it is likely that the resin composition undergoes some chemical changes due to the aging process imposed during molding processes such as extrusion and injection molding. Maybe. Therefore, the flame-retardant resin compositions of the present invention also include those containing reactants as a result of chemical changes in these processing steps. In the present invention, in order to mix the four components of (A) aromatic polyester copolymer, (B) polyamide, (C) aromatic halogen compound, and (D) specific metal compound, (A) component and (B) After melt extruding and mixing the components, mix with component (C).
Component (D) may be added, or component (C) and (D) may be added to either component (A) or component (B), or both, in the polymerization step or chipping step, It may then be re-extruded to obtain the final resin composition. Furthermore, the component (C) or the component (D) can be intentionally unevenly distributed on the side of the component (A) or the component (B). For example, (A) component and (C)
The components are melted and mixed, and then mixed with component (B).
Compared to adding component (D) and re-extruding,
When component (B) is melt-mixed and then re-extruded by adding component (C) or (D), the heat distortion temperature of the molded product is higher and the dimensional stability when moisture is absorbed is lower. It is excellent. Furthermore, if components (C) and (D) are dispersed in component (B) in advance, and then component (A) is added and melted and re-extruded, there are concerns regarding heat distortion temperature and dimensional stability. Even better results can be obtained. That is, by preventing component (C) and component (D) from being unevenly distributed on the component (A) side as much as possible, the dimensional stability against heat distortion temperature and moisture can be improved. However, in order to achieve the above effects, component (C) is melt-extruded with component (B) in an attempt to make it unevenly distributed on the (B) component side, and then the (A) component is melt-extruded with component (B). When adding component (D), compared to adding components (A) and (C) in advance and then adding components (B) and (D) and re-extruding, the melt They often tend to decompose during extrusion. This decomposition can be prevented by lowering the extrusion temperature, but there is a problem that poor dispersion tends to occur. In this case, component (B) is divided into two parts, one of which is melt-extruded with component (A), and then the entire amount of component (C) is added to the remaining component (B) and melt-extruded, and then the first two components are melt-extruded. If component (D) is added to the extruder and extruded again, component (B) is blended with component (A) and the extrusion temperature is lowered, allowing for uniform dispersion at a relatively low temperature. Therefore, it is possible to maintain good properties while preventing decomposition. The method of mixing all components (A), (B), (C), and (D) and then melt-extruding them in one step is excellent in terms of productivity. However, since the softening temperature of component (A) is high, the extrusion temperature is inevitably high, which poses a problem in that it tends to cause decomposition. In this case, use an extruder with a vent, set the temperature on the hopper side as high as possible, knead components (A) and (B) early, and then lower the temperature at the tip of the extruder barrel. It was found that adding components (C) and (D) through the vent port near the tip shortened the residence time, making it difficult to decompose. A more preferable method is to use (C) in advance.
Melt the ingredients (at this time, you may also mix component (D) into the mixture) and drop them from the vent port or forcefully insert them near the tip of the barrel to make them uniformly atomized. Moreover, it can be dispersed while preventing thermal decomposition as much as possible. By adopting such a method, the amount of flame retardant used can be reduced while providing the same degree of flame retardancy, and favorable effects can also be obtained from the viewpoint of mechanical properties. The method of melting the flame retardant in advance and directly dropping or press-fitting the flame retardant into the barrel of the extruder as described above is also effective for other purposes. That is, in the flame retardant resin composition of the present invention, component (C) and
It is preferable that component (D) be present as fine particles as much as possible. For example, decabromodiphenyl ether (hereinafter abbreviated as DBDE), which is a flame retardant with excellent thermal stability, non-migration, and safety, has approximately
Since it has a melting point of 300°C, it is necessary to extrude at around 300°C in order to uniformly disperse DBDE in the polyamide in order to make it unevenly distributed in the polyamide. However, since polyamide is a resin that originally has a low melt viscosity and decomposes quickly at around 300°C, it is extremely difficult to obtain a product of good quality with good productivity simply by extruding it at a high temperature. However, by melting the flame retardant in advance and dropping or press-fitting it into the already molten resin in the extruder barrel, extreme temperature conditions can be avoided. It is therefore possible to uniformly disperse the flame retardant into fine particles without using a flame retardant or causing decomposition of the resin. The flame-retardant resin composition of the present invention may contain a phosphorus compound, a hindered phenol compound, an amine compound, a benzotriazole compound, etc. for the purpose of improving heat resistance and weather resistance. In particular, as a coloring preventive agent, orthophosphoric acid ester,
It is effective to add 0.01 to 0.5% by weight of acidic orthophosphoric acid ester, orthophosphoric acid, phosphite, acidic phosphite, phosphorous acid, etc. to the flame retardant resin composition. Moreover, in this case, an epoxy compound may be used in combination with a phosphorus compound. In addition, glass fiber, inorganic silicate, silica obtained by evaporation of silica gel, quartz, silica gel, carbon fiber, cristobalite,
Conventional reinforcing fillers such as asbestos, clay, talc, etc. may also be included. In addition, the flame-retardant resin composition of the present invention may be used to further increase mechanical properties such as impact strength and elongation at break, or to improve heat deterioration resistance, such as acrylonitrile-butadiene rubber or styrene-butadiene rubber. , rubber materials such as polyester rubber, ABS, polycarbonate, polysulfon, polyether sulfon, polyethylene, polypropylene, polyurethane, polystyrene,
It may contain EVA, polyacrylic acid ester, polytetrafluoroethylene, ionomer, methyl methacrylate, polyalkylene phenylene ester, and polyalkylene phenylene ester ether. The flame-retardant resin composition of the present invention exhibits excellent flame retardancy, heat resistance, mechanical properties, moldability, and dimensional stability against moisture. It also has the characteristic that the thin parts of the molded product are difficult to break. The flame-retardant resin composition of the present invention includes powder, chips,
Various useful products can be made into other shapes using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding. Examples of such products include gears, bearings, electrical parts containers, and a wide range of other products. As described above, the flame-retardant resin composition of the present invention can be used in a wide range of applications as a product requiring high performance as an engineering plastic. The present invention will be explained in more detail with reference to Examples below. The bending strength and impact strength of the thin portion were evaluated by the following methods. [1] Evaluation method of bending strength of thin wall part To explain using diagrams, in Figures 1 and 2, 1 is the spray of the injection molded product, 2 is the runner,
3 and 3' are test pieces, and 4 is a gate part. The runner is 8mmφ, the gate is 8mm wide, 1mm thick, the shortest distance of the gate land (in the longitudinal direction of the gate) is 2mm, and test pieces 3 and 3' are 5 inches long and 1/2 inch wide for use in UL combustion tests. , 1/8 inch and 1/16 inch thick bar specimens. After molding test piece 3 (1/8 inch thick) under the specified molding conditions, take it out, immediately bend it vertically so that runner 2 and test piece 3 are perpendicular to gate 4, and When bent once, if the gate completely breaks and the test piece separates at the runner part, it is evaluated as ×, if it partially breaks at the gate part but does not separate completely, it is evaluated as △, and if it does not break, it is evaluated as 〇. , the proportion of 〇 in the whole is shown as the gate refraction ratio in %. [2] Impact strength evaluation method As a result of examining various evaluation methods that are easy to deal with the susceptibility to cracking that occurs when an impact force is applied to practical injection molded products, we found that this is generally the best method for evaluating impact strength. It was confirmed that the magnitude of the impact strength of the V-notched isot (British standard B.S1330) corresponding to the V-notched isot which is used corresponds most closely to the susceptibility of cracking in practical products. The sample shape used is 1/2″ x 5″ x as shown in Figure 2.
Ejector pin trace 5 of 1/8″ test piece 3
The dimensions of the B.S1330 test piece were changed slightly from the sandwiched part in parallel or perpendicular to the resin flow to a length of 1/2 inch, a width of 1/4 inch, and a thickness of 1/8 inch.
An inch test piece was cut out and the impact value was measured using an in-situ impact tester. Furthermore, the second
In the figure, the value measured for test piece 6 is shown as y, and the value measured for test piece 7 is shown as x. y represents the impact strength in a direction perpendicular to the resin flow direction, and x represents the impact strength in a direction parallel to the resin flow direction. The impact strength was measured after drying the molded product at 100°C for 16 hours. The measurement results were expressed in kg and cm/cm 2 using the following formula. Measured value (Kg, cm/ cm2 ) = Fracture energy (Kg, cm)/
Sample cross-sectional area (cm 2 ) Furthermore, in the present invention, the method specified in UL Standard No. 94 of Underwriter Laboratories of the United States was used for the combustion test. Further, the content of aromatic halogen compounds was measured as follows. First, for component (A)
(B) If the component is relatively small, shave the molded product as thinly as possible, take an amount that will give a concentration of 1 g/1000 c.c., put it in methylene chloride prepared in advance, and boil it with hot water. Heat and stir thoroughly. In this process, component (A) and component (C) present in component (A) are extracted, but component (C) that is not soluble in methylene chloride and component (C) present in component (B) is extracted. Not extracted. After thorough stirring, the solid content and solution were separated using a No. 1 glass filter, and then the solution was poured into a watch glass to evaporate methylene chloride to obtain a film. This film is thought to contain component (A) and component (C) contained in component (A), so analyze this to determine the concentration of component (C) in component (A). decided.
Based on this result, the concentration of component (C) in component (B) was calculated. In addition, if there is a relatively large amount of component (B) compared to component (A), using methylene chloride will be sufficient, as it will be difficult to extract component (A) and component (C) contained in it, so once molded. After dissolving the product in 90% formic acid, a film is prepared by evaporating the formic acid, and from this film, component (A) and the components contained therein are dissolved using methylene chloride in the manner described above.
(C) Component was extracted. Note that the formic acid treatment does not change the concentration of component (C) in component (A), and when using this method, make sure that component (C) has a sufficiently low solubility in methylene chloride and formic acid. Confirmed. The concentration of component (C) in a film consisting of component (A) and component (C) can be measured using the oxygen flask combustion method (Analytical Chemistry, May 1963 issue, Onoe, April 1964 issue, Kobayashi, Suzuki, Araki ) after separating the halogen, JIS K
It was conducted according to the halogen analysis method of 0107. Further, the content of the specific metal compound was determined by separating and weighing the components eluted into methylene chloride by centrifugation or by atomic absorption spectrometry using the same procedure as above. Examples 1 to 8, Comparative Examples 1 to 10 Aromatic production using a methylene chloride solution of a mixed acid chloride with a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 and an alkaline aqueous solution of bisphenol A by an interfacial polymerization method. A polyester copolymer (hereinafter referred to as PAR) was produced. This phenoltetrachloroethane (weight ratio 6/
4) The logarithmic viscosity of medium, 25℃, concentration 1g/100c.c. is
It was 0.75. In addition, nylon 6 is used as a raw material.
(hereinafter referred to as N6) (manufactured by Unitika, relative viscosity in 96% sulfuric acid is 2.6 at 25° C., 1 g/100 c.c.), DBDE, and various metal compounds were used. PAR and N6 were mixed at a weight ratio of 1:1 using a super mixer, and after drying with hot air at 110℃ for 16 hours,
Extrusion was performed using a high kneading type extruder at a barrel temperature of 280°C to obtain uniform pellets U-1. Blend U-1, DBDE, and various metal compounds in the proportions shown in Table 1, mix in a super mixer, and then heat at 110℃.
It was dried with hot air for 16 hours, and then extruded again at a barrel temperature of 240°C. Thereafter, an injection molded product having the shape shown in Figures 1 and 2 was molded using an injection molding machine at a cylinder temperature of 240°C and a mold temperature of 80°C. The results of evaluating various properties of the obtained molded product are shown in Table 2. As shown in Table 2, the resin composition of the present invention has improved flame retardancy and can be used as a practical molded product.
【表】【table】
【表】【table】
【表】【table】
【表】
において、衝撃的特性の指標となるダインシユタ
ツト衝撃強度や肉薄部の強靭さの指標であるゲー
ト不折比において大巾に特性が改善されているこ
とが認められた。通常、比較例にみられるように
無機充填剤を添加した場合には、衝撃特性が一般
に低下することを考えあわせると、この現象はこ
のような樹脂組成物における驚くべき効果と考え
られる。
実施例９〜14、比較例11〜15
実施例１〜８において使用したＵ−１に、表３
に示す各種の難燃剤、Sb2O3、ヨウ化第１銅を表
３に示す割合でスーパーミキサーを用いて混合
し、実施例１〜８と同様にして乾燥、チツプ化、
射出成形したのち、性能評価をした。得られた結
果は表４に示すとおりであつた。In [Table], it was recognized that the properties were significantly improved in the in-shutt impact strength, which is an index of impact properties, and the gate refraction ratio, which is an index of the toughness of the thin wall part. This phenomenon is considered to be a surprising effect in such resin compositions, considering that the impact properties are generally reduced when inorganic fillers are added as seen in the comparative examples. Examples 9 to 14, Comparative Examples 11 to 15 Table 3 was added to U-1 used in Examples 1 to 8.
The various flame retardants shown in Table 3, Sb 2 O 3 and cuprous iodide were mixed using a super mixer in the proportions shown in Table 3, and dried, chipped and processed in the same manner as in Examples 1 to 8.
After injection molding, performance was evaluated. The results obtained were as shown in Table 4.
【表】【table】
【表】
表４からわかるごとく、比較例13〜17に比して
実施例９〜14は燃焼ランク、実用的な力学特性の
両方の面で大巾な改善が認められた。また、実施
例２と実施例９とを比較するとSb2O3とヨウ化第
１銅の組みあわされている後者の方がダインシユ
タツト衝撃強度が高かつた。
実施例 15〜18
実施例１〜８に使用したPARの赤外吸収を測
定したところ1800cm-1付近に吸収は認められなか
つた。一方、重合条件を変更して1800cm-1付近に
赤外吸収ピークが存在することにより酸無水物結
合の存在が確認されたPARを得た。前者と後者
を区別するため前者をPAR1と呼び後者をPAR2
と呼ぶ。PAR1とPAR2の原料配合比は全く同一
である。
実施例１〜８においてPAR1からＵ−１を得た
のと同一手順によりPAR2からＵ−２を得た。得
られたＵ−１およびＵ−２に表５に示す割合でビ
ス（トリブロモフエノキシ）エチレンとSb2O3を
添加し、乾燥後、240℃で押出し、ついで実施例
１〜８と同様にして射出成形して成形品を得、そ
の性能の評価を行なつた。得られた結果は表６に
示すとおりであつた。
表６からわかるごとく、実施例15、17に比して
実施例16、18は著しくすぐれた力学的特性を有し
ていた。[Table] As can be seen from Table 4, compared to Comparative Examples 13 to 17, Examples 9 to 14 were significantly improved in terms of both combustion rank and practical mechanical properties. Furthermore, when comparing Example 2 and Example 9, the latter, which was a combination of Sb 2 O 3 and cuprous iodide, had a higher in-situ bolt impact strength. Examples 15 to 18 When the infrared absorption of the PAR used in Examples 1 to 8 was measured, no absorption was observed near 1800 cm -1 . On the other hand, by changing the polymerization conditions, a PAR was obtained in which the presence of an acid anhydride bond was confirmed by the presence of an infrared absorption peak near 1800 cm -1 . To distinguish between the former and the latter, the former is called PAR1 and the latter is called PAR2.
It is called. The raw material mixing ratios of PAR1 and PAR2 are exactly the same. U-2 was obtained from PAR2 by the same procedure as that used to obtain U-1 from PAR1 in Examples 1 to 8. Bis(tribromophenoxy)ethylene and Sb 2 O 3 were added to the obtained U-1 and U-2 in the proportions shown in Table 5, and after drying, extrusion was carried out at 240°C, followed by Examples 1 to 8. A molded product was obtained by injection molding in the same manner, and its performance was evaluated. The results obtained were as shown in Table 6. As can be seen from Table 6, Examples 16 and 18 had significantly superior mechanical properties compared to Examples 15 and 17.
【表】【table】
【表】
実施例 19、20
N6として高粘度のN6（ユニチカ製、96％硫
酸、１ｇ／100c.c.、25℃の相対粘度3.4）を使用し
たほかは実施例１〜８と同様にしてペレツトＵ−
３を得た。Ｕ−１およびＵ−３に表７に示す難燃
剤と金属化合物を表７に示す割合で配合し、再押
出しし、チツプ化後、射出成形品を得、その性能
を評価した。得られた結果は表８に示すとおりで
あつた。
表８からわかるごとく、高粘度のN6を使用す
ることにより、ダインシユタツト衝撃強度が大巾
に改善されている。[Table] Examples 19, 20 Same as Examples 1 to 8 except that high viscosity N6 (manufactured by Unitika, 96% sulfuric acid, 1 g/100 c.c., relative viscosity at 25°C 3.4) was used as N6. Pellet U-
I got 3. The flame retardants and metal compounds shown in Table 7 were blended with U-1 and U-3 in the proportions shown in Table 7, and after re-extrusion and chipping, injection molded products were obtained and their performance was evaluated. The results obtained were as shown in Table 8. As can be seen from Table 8, the use of high viscosity N6 significantly improved the impact strength of the injection bolt.
【表】【table】
【表】
実施例 21、22
実施例１〜８にて使用したPAR42.5重量部と
DBDE15重量部をスーパーミキサーにて混合した
後、110℃で16時間乾燥して260℃で押出しチツプ
化した。これをＵ−４と呼ぶ。ついでＵ−４
57.5重量部と実施例１〜８に使用したN6 42.5重
量部とSb2O35重量部とを混合して230℃にて再押
出しした。これをＵ−５と呼ぶ。一方、同じ
PAR42.5重量部とN621.25重量部を290℃でブレン
ド、乾燥後、押出した。これをＵ−６と呼ぶ。ま
た、N6 21.25重量部をベント口付き押出機を用
いて230℃で押出しながら、ベント口よりSb2O35
重量部を懸だくさせた溶融DBDE15重量部を送入
してN6中にSb2O3とDBDEを均一に分散させた。
これをＵ−７と呼ぶ。次にＵ−６ 63.75重量部
とＵ−７ 41.25重量部を230℃で再押出しし、Ｕ
−８を得た。Ｕ−５とＵ−８を実施例１〜８と同
様の方法により射出成形し、その性能を評価し
た。得られた結果を表９に示す。（ここでＵ−５
とＵ−８はDBDEやSb2O3の分散状態や偏在状態
の相違のみで、平均した原料組成比は同一であ
る。）
表９からわかるごとく、燃焼ランクや力学特性
においてはＵ−５とＵ−８には大差ないが、Ｕ−
５に比してＵ−８は吸湿による寸法変化が少な
く、熱変形温度の高いことが認められた。[Table] Examples 21, 22 PAR42.5 parts by weight used in Examples 1 to 8
After mixing 15 parts by weight of DBDE in a super mixer, the mixture was dried at 110°C for 16 hours and extruded at 260°C to form chips. This is called U-4. Then U-4
57.5 parts by weight, 42.5 parts by weight of N6 used in Examples 1 to 8, and 5 parts by weight of Sb 2 O 3 were mixed and extruded again at 230°C. This is called U-5. On the other hand, the same
PAR42.5 parts by weight and N621.25 parts by weight were blended at 290°C, dried, and extruded. This is called U-6. In addition, while extruding 21.25 parts by weight of N6 at 230°C using an extruder with a vent, Sb 2 O 3 5
15 parts by weight of molten DBDE were introduced to uniformly disperse Sb 2 O 3 and DBDE in N6.
This is called U-7. Next, 63.75 parts by weight of U-6 and 41.25 parts by weight of U-7 were re-extruded at 230°C.
-8 was obtained. U-5 and U-8 were injection molded in the same manner as in Examples 1 to 8, and their performance was evaluated. The results obtained are shown in Table 9. (Here, U-5
and U-8 are different only in the dispersion state and uneven distribution state of DBDE and Sb 2 O 3 , but the average raw material composition ratio is the same. ) As can be seen from Table 9, there is not much difference between U-5 and U-8 in terms of combustion rank and mechanical properties, but U-5
It was found that U-8 had less dimensional change due to moisture absorption and higher heat distortion temperature than U-8.
【表】
実施例23、24、比較例16
実施例18に使用したＵ−２ 80重量部と
DBDE20重量部とSb2O37重量部とCu0.02重量
部TiO220重量部を混合して乾燥し、押出してＵ
−９を得た。別にTiO2量のみを30重量部にして
同様に押出してＵ−10を得た。
得られたＵ−９とＵ−10を射出成形し、燃焼テ
ストとゲート折り曲げ強度を測定した。一方、比
較のためにTiO2とほぼ同一粒度のCaCO3をＵ−
10におけるTiO2とSb2O3のかわりに37重量部使用
して押出し、Ｕ−11を得、同様の測定を行なつ
た。得られた結果を表10に示す。
表10からわかるごとく、比較例18では燃焼ラン
クが低いと同時に肉薄部がもろかつたが、実施例
23、24では大量の無機質が含まれているにもかか
わらず、肉薄部はもろくならなかつた。[Table] Examples 23, 24, Comparative Example 16 80 parts by weight of U-2 used in Example 18
20 parts by weight of DBDE, 7 parts by weight of Sb 2 O 3 and 0.02 parts by weight of Cu and 20 parts by weight of TiO 2 were mixed, dried, extruded and
-9 was obtained. Separately, only the amount of TiO 2 was changed to 30 parts by weight and extruded in the same manner to obtain U-10. The obtained U-9 and U-10 were injection molded, and a combustion test and gate bending strength were measured. On the other hand, for comparison, CaCO 3 with almost the same particle size as TiO 2 was
U-11 was obtained by extrusion using 37 parts by weight instead of TiO 2 and Sb 2 O 3 in No. 10, and the same measurements were performed. The results obtained are shown in Table 10. As can be seen from Table 10, Comparative Example 18 had a low combustion rank and was brittle at the same time, while the Example
In cases 23 and 24, the thin wall part did not become brittle despite the large amount of mineral content.
第１図はゲート不折比テスト、ダインシユタツ
ト衝撃試験およびUL94燃焼テスト用のテストピ
ースの正面図、第２図は同テストピースの平面図
を示す。
３，３′：テストピース、４：ゲート部。
Figure 1 shows a front view of a test piece for gate refraction ratio test, in-situ bolt impact test and UL94 combustion test, and Figure 2 shows a plan view of the same test piece. 3, 3': Test piece, 4: Gate part.
Claims (1)
の機能誘導体の混合物（ただし、テレフタル酸基
とイソフタル酸基のモル比は９：１ないし１：
９）と一般式〔〕 で表されるビスフエノール類（ただし、−Ｘ−
は、−Ｏ−、−Ｓ−、−SO2−、−CO−、アルキレ
ン基あるいはアルキリデン基よりなる群から選ば
れ、R1、R2、R3、R4、R′1、R′2、R′3およびR′4は
水素原子および炭化水素基からなる群より選ばれ
る）とから得られる芳香族ポリエステル共重合体
と、(B)ポリアミドと、(C)芳香族ハロゲン化合物
と、(D)長周期型周期表第Ｂ、Ｂ、Ｂ、
Ａ、Ａ族および第Ａ族より選ばれた金属の酸
化物とハロゲン化物とよりなる群から選ばれる少
なくとも一種の化合物とよりなり、(C)成分の含有
率が(A)、(B)および(C)成分の合計量に対して0.5〜
40重量％であり、(D)成分の化合物が長周期型周期
表第Ｂ、Ｂ、Ｂ、Ａ、Ａ族および第
Ａ族より選ばれた金属の酸化物である場合には、
該酸化物の含有率が(A)、(B)および(C)成分の合計量
の100重量部に対して0.1〜25重量部であり、(D)成
分の化合物が長周期型周期表第Ｂ、Ｂ、
Ｂ、Ａ、Ａ族および第Ａ族より選ばれた金
属のハロゲン化物である場合には、該ハロゲン化
物の含有率が(A)、(B)および(C)成分の合計量の100
重量部に対して0.005〜0.5重量部であることを特
徴とする難燃性樹脂組成物。[Scope of Claims] 1 (A) A mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (provided that the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:
9) and general formula [] Bisphenols represented by (however, -X-
is selected from the group consisting of -O-, -S-, -SO2- , -CO-, an alkylene group or an alkylidene group, and R1 , R2 , R3 , R4 , R'1 , R'2 , R′ 3 and R′ 4 are selected from the group consisting of a hydrogen atom and a hydrocarbon group); (B) a polyamide; (C) an aromatic halogen compound; D) Long-period periodic table number B, B, B,
A, at least one compound selected from the group consisting of oxides and halides of metals selected from Group A and Group A, and the content of component (C) is (A), (B) and (C) 0.5 to total amount of ingredients
40% by weight, and when the compound of component (D) is an oxide of a metal selected from Groups B, B, B, A, Group A, and Group A of the long period periodic table,
The content of the oxide is 0.1 to 25 parts by weight based on 100 parts by weight of the total amount of components (A), (B), and (C), and the compound of component (D) is found in the long periodic table. B, B,
In the case of a halide of a metal selected from B, A, Group A, and Group A, the content of the halide is 100% of the total amount of components (A), (B), and (C).
A flame-retardant resin composition characterized in that the amount is 0.005 to 0.5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP866378A JPS54101852A (en) | 1978-01-27 | 1978-01-27 | Flame retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP866378A JPS54101852A (en) | 1978-01-27 | 1978-01-27 | Flame retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54101852A JPS54101852A (en) | 1979-08-10 |
| JPS6214579B2 true JPS6214579B2 (en) | 1987-04-02 |
Family
ID=11699163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP866378A Granted JPS54101852A (en) | 1978-01-27 | 1978-01-27 | Flame retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54101852A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0299486U (en) * | 1989-01-26 | 1990-08-08 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4565850A (en) * | 1981-08-03 | 1986-01-21 | Allied Corporation | Thermoplastic composition containing nematic oligomer |
| JPS58103658A (en) * | 1981-12-16 | 1983-06-20 | Shimadzu Corp | Reference electrode |
-
1978
- 1978-01-27 JP JP866378A patent/JPS54101852A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0299486U (en) * | 1989-01-26 | 1990-08-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54101852A (en) | 1979-08-10 |
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