JPS63305161A - Flame-retarding polyphenylene ether resin composition - Google Patents
Flame-retarding polyphenylene ether resin compositionInfo
- Publication number
- JPS63305161A JPS63305161A JP14134987A JP14134987A JPS63305161A JP S63305161 A JPS63305161 A JP S63305161A JP 14134987 A JP14134987 A JP 14134987A JP 14134987 A JP14134987 A JP 14134987A JP S63305161 A JPS63305161 A JP S63305161A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- phosphate
- resin composition
- ether resin
- resin
- 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.)
- Granted
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- -1 phosphate compound Chemical class 0.000 claims abstract description 40
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 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 abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 229910001463 metal phosphate Inorganic materials 0.000 abstract 2
- 239000013032 Hydrocarbon resin Substances 0.000 abstract 1
- 229920006270 hydrocarbon resin Polymers 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920001971 elastomer Polymers 0.000 description 14
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000000806 elastomer Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- GWWBILGABMLVTN-UHFFFAOYSA-N 1-but-1-enyl-2,3-dimethylbenzene Chemical group CCC=CC1=CC=CC(C)=C1C GWWBILGABMLVTN-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical compound CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 description 1
- MFFHOTWDYMNSLG-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)phenol Chemical compound CC(C)C1=CC=C(O)C(C(C)C)=C1C(C)C MFFHOTWDYMNSLG-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- RLEWTHFVGOXXTN-UHFFFAOYSA-N 2,3-diethylphenol Chemical compound CCC1=CC=CC(O)=C1CC RLEWTHFVGOXXTN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NCVFZIASVZHSOI-UHFFFAOYSA-N 2-chloroethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCl)OC1=CC=CC=C1 NCVFZIASVZHSOI-UHFFFAOYSA-N 0.000 description 1
- OCKYMBMCPOAFLL-UHFFFAOYSA-N 2-ethyl-3-methylphenol Chemical compound CCC1=C(C)C=CC=C1O OCKYMBMCPOAFLL-UHFFFAOYSA-N 0.000 description 1
- XRSWLVYCXFHDDB-UHFFFAOYSA-N 2-ethyl-3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1CC XRSWLVYCXFHDDB-UHFFFAOYSA-N 0.000 description 1
- FBIRMMLBFOFVGU-UHFFFAOYSA-N 2-methyl-5-propylphenol Chemical compound CCCC1=CC=C(C)C(O)=C1 FBIRMMLBFOFVGU-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- JFAMOKKVRCODIC-UHFFFAOYSA-N 3-ethyl-2-propylphenol Chemical compound CCCC1=C(O)C=CC=C1CC JFAMOKKVRCODIC-UHFFFAOYSA-N 0.000 description 1
- FCUBUGPGVCEURB-UHFFFAOYSA-N 3-methyl-2-propylphenol Chemical compound CCCC1=C(C)C=CC=C1O FCUBUGPGVCEURB-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- ZXZYMQCBRZBVIC-UHFFFAOYSA-N bis(2-ethylhexyl) phenyl phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 ZXZYMQCBRZBVIC-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical class NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- YICSVBJRVMLQNS-UHFFFAOYSA-N dibutyl phenyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=CC=C1 YICSVBJRVMLQNS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- PDMLSWLQHBTLJF-UHFFFAOYSA-N trinaphthalen-2-yl phosphate Chemical compound C1=CC=CC2=CC(OP(OC=3C=C4C=CC=CC4=CC=3)(OC=3C=C4C=CC=CC4=CC=3)=O)=CC=C21 PDMLSWLQHBTLJF-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明Fi醸燃化ポリフェニレ/エーテル系樹脂組成物
に関し、更に詳しくはポリフェニレンエーテル系樹脂、
ビニル芳香族炭化水素樹脂。Detailed Description of the Invention [Industrial Application Field] The present invention relates to the Fi-breeding polyphenylene/ether resin composition, and more specifically to the polyphenylene ether resin,
Vinyl aromatic hydrocarbon resin.
リン酸の金属塩、及びホスフェート化合物を含有する難
燃化ポリフェニレンエーテル系樹脂組成物に関する。The present invention relates to a flame-retardant polyphenylene ether resin composition containing a metal salt of phosphoric acid and a phosphate compound.
ポリフェニレンエーテルは耐熱性、剛性、1!気時特性
諸性質に秀でた樹脂であり、有用な工/ジニアリングプ
ラスチックスとして広い用途に使用されている。しかし
ながら、ポリフェニレンエーテルは成形加工性および耐
衝撃性に劣り、さらには難燃性もそれ自体では十分とは
言い難い。Polyphenylene ether has heat resistance, rigidity, and 1! It is a resin with excellent weather properties and is used in a wide range of applications as a useful engineering/engineering plastic. However, polyphenylene ether is inferior in moldability and impact resistance, and furthermore, its flame retardance is not sufficient by itself.
成形加工性や耐衝撃性の改良を目的としてスチレン系樹
脂あるいは、エラストマー補強スイ・レン系w脂、さら
には各種エラスト7−類を配合する技術が、米I!!%
許第3.585.435号明刹妥等種々の文献KrA示
されている。しかしながら、スチレン系樹脂やエラスト
マー類を配合するととによってポリフェニレンエーテル
のq燃性を大きく損うこともよく知られている。The technology of blending styrene-based resins, elastomer-reinforced water resins, and various types of elastomers for the purpose of improving moldability and impact resistance is now available! ! %
Various documents such as No. 3,585,435 are listed. However, it is well known that the q-flammability of polyphenylene ether is greatly impaired when styrene resins and elastomers are added.
このため、難燃性を要求されろ用途にポリフェニレンエ
ーテル、あるいはポリフェニレンエーテルとスチレン系
樹脂および/またはエラストマー類とからなる樹脂組成
物を使用するためKは、難燃剤の配合が不可欠であるこ
ともよく知られている。そして、従来有効性の認められ
ている惜燃剤は主として含リン化合物と含ハロゲン化合
物である。For this reason, when polyphenylene ether or a resin composition consisting of polyphenylene ether and styrene resin and/or elastomer is used in applications that require flame retardancy, it is essential to include a flame retardant. well known. The retarding agents that have been recognized to be effective are mainly phosphorus-containing compounds and halogen-containing compounds.
例えば、特t′B昭49−52947号公報、特開昭5
5−75248号会報、1$開昭55−16081号公
報および特開昭57−30757号公報には芳香族す7
Ilエステル類の使用が提案されている。For example, Japanese Patent Publication No. 49-52947, Japanese Unexamined Patent Publication No. 5
Aromatic 7
The use of Il esters has been proposed.
リン酸エステル類は、ポリフエニシン二一テルに難燃剤
として配合した場合、優れた難燃効果を発揮し、さらに
可m化効果により成形加工性をも改良するが、その反面
、熱変形温度等の耐熱性あるいは引っ張り強度等の機械
的強度が大幅に低下することは避は難く、さら【大きな
問題点は、これらのす/酸エステルが成形加工時に樹脂
相から揮発し、金製を汚染し、ひいては成形品外観をも
損ねる事である。これはポリフェニレンエーテルを含有
する成形材料の成形加工温度が250〜300℃という
比較的高温を必要とすることに起因するものであり、実
用面で深刻な問題を提起している。例をトリフェニルホ
スフェートやトリクレジルホスフェートに取ろならば、
これらは樹脂相に練り込まれた後でさえも、300℃前
後に加熱した場合その20%程腹が揮発てろ場合がある
。このようなリン酸エステル類の揮発性の問題を解決す
る技術として、特開昭55−1189557号公報には
、芳香族す/酸エステル重合体の使用が提案されている
。When phosphoric acid esters are added as a flame retardant to polyphenycin 21-ter, they exhibit excellent flame retardant effects and also improve molding processability due to their plasticizing effect. It is unavoidable that mechanical strength such as heat resistance or tensile strength will be significantly reduced, and furthermore, [the major problem is that these acid esters volatilize from the resin phase during molding, contaminate the metal, Furthermore, the appearance of the molded product is also impaired. This is due to the fact that the molding material containing polyphenylene ether requires a relatively high temperature of 250 to 300° C., which poses a serious problem in practical terms. Taking triphenyl phosphate and tricresyl phosphate as an example,
Even after being kneaded into the resin phase, these substances may evaporate by about 20% when heated to around 300°C. As a technique for solving the problem of volatility of phosphoric acid esters, Japanese Patent Application Laid-Open No. 1189557/1983 proposes the use of an aromatic acid ester/acid ester polymer.
一方、含ハロゲン化合切に関しても多数の公知技術があ
り1例えば−a開昭48−7945号公報にはへキサブ
ロモペンゼ/と酸化アンチ七ンを配合する方法が提案さ
れ、特公昭48−39014号公報および*m昭52−
57255号公報にも類似の芳香族ハロゲン化合物を添
加する方法が開示されている。含ハロゲン化合物はポリ
フェニレンエーテルに対する可息化効果をほとんど有し
ておらず、ポリフェニレンエーテルに配合した場合、そ
の耐熱性をほとんど損なわない点はす/酸エステル類に
見られない優れた特徴であるが、その反面、成形加工性
が改良されないと言う点は欠点となる。さらには。On the other hand, there are many known techniques for cutting off halogen-containing compounds. For example, Japanese Patent Publication No. 48-7945 proposes a method of blending hexabromopense/and antiseptine oxide, and Japanese Patent Publication No. 48-39014 and *m1977-
No. 57255 also discloses a method of adding a similar aromatic halogen compound. Halogen-containing compounds have almost no breathability effect on polyphenylene ether, and when blended with polyphenylene ether, it hardly impairs its heat resistance, which is an excellent feature not found in acid esters. On the other hand, the disadvantage is that moldability is not improved. Furthermore.
含ハロゲン化合物な離燃剤として使用した場合には、含
ハロゲン化合物の成形品表面への移行性によるブルーム
の発生、含ハロゲン化合物の熱分解生成物による成形機
や金製等の腐食といった問題も生じろことはよ(知られ
ている。When a halogen-containing compound is used as a flame retardant, problems such as blooming due to the migration of the halogen-containing compound to the surface of the molded product and corrosion of molding machines and metal products due to thermal decomposition products of the halogen-containing compound may occur. Rokotohayo (known.
さらには、特公昭4B−38768号公報にはリン酸エ
ステルと芳香族ハロゲン化合物を併用する方法が開示さ
れているが、この方法においても、リン酸エステルと含
ハロゲン化合物の使用によりもたらされる本質的な欠点
を改良するに至っていない。Furthermore, Japanese Patent Publication No. 4B-38768 discloses a method of using a phosphoric acid ester and an aromatic halogen compound in combination, but even in this method, the essential The shortcomings have not been improved yet.
本発明者らは、従来公知の含リン化合物または含ハロゲ
ン化合物な難燃剤としてポリフェニレンエーテル系at
脂またはポリフェニレンエーテル系at脂とポリスチレ
ン系樹脂との樹脂組成物に配合した場合に見られろ前述
のごとき欠点を公知技術とは異なった手段で解消すべく
検討を行った結果、以下のことを見い出し1本発明の樹
脂組成物に到達した。即ち、 l) 後述のリン酸
の金属塩単独ではポリフェニレンニー f ル系樹脂組
成物に対する難燃化効果は認められない−n)vン酸金
属塩とホスフェート化合物を併用すると、相乗的な難燃
化効果が現れるので。The present inventors have discovered that polyphenylene ether-based at
As a result of our research to solve the above-mentioned drawbacks that occur when a resin composition of a polyphenylene ether-based AT fat or a polystyrene-based resin is blended with a polystyrene-based resin, we have discovered the following. Heading 1 The resin composition of the present invention has been reached. That is, l) The metal salt of phosphoric acid described below alone does not have a flame retardant effect on polyphenylene resin compositions; n) The combination of the metal salt of phosphoric acid and the phosphate compound produces a synergistic flame retardant effect. Because the effect of oxidation appears.
ホスフェート化合物を単独で使用する場合よりも、ホス
フェート化合物の使用量を減らせる。The amount of phosphate compound used can be reduced compared to when a phosphate compound is used alone.
++1)す7酸金属塩の加熱重量減少量はA常のホスフ
ェート化合物の場合より小さいので、併用に依るホスフ
ェート化合物の使用量の減少と相俣って−i燃剤全体と
しての加熱重量減少量を減らせる。++1) Since the amount of weight loss on heating of the heptaacid metal salt is smaller than that of ordinary phosphate compounds, the amount of weight loss on heating of the -i fuel as a whole can be reduced by reducing the amount of phosphate compound used in combination. Ru.
本発明の樹脂組成物は、(a)ポリフェニレンエーテル
系樹脂、(b1ビニル芳香族炭化水素樹脂。The resin composition of the present invention includes (a) a polyphenylene ether resin, and (b1 a vinyl aromatic hydrocarbon resin).
tel下記一般式+11で表わされろリン酸の金属塩。A metal salt of phosphoric acid represented by the following general formula +11.
および+dlホスフェート化合物を含有する無撚化ポリ
フェニレンエーテル系樹脂組成物である。and a non-twisted polyphenylene ether resin composition containing a +dl phosphate compound.
M : Ca e Ba + AAI
RI In21R31R4: C)〜3のアルキル基1
+ m * n * O: 0または1〜5の整数p
:MがCa、Baの時FiO
MがAJの時は1
本発明の樹脂組成物に葎)成分として用いられるポリフ
ェニレンエーテル系樹脂とは、一般式(IIで示される
単環式フェノール
H
(式中、 R5は炭素数1〜3の低級アルキル基。M: Ca e Ba + AAI RI In21R31R4: C) - 3 alkyl group 1
+ m * n * O: 0 or an integer p from 1 to 5
:FiO when M is Ca or Ba; 1 when M is AJ; polyphenylene ether resin used as a component in the resin composition of the present invention is a monocyclic phenol H represented by general formula (II); Among them, R5 is a lower alkyl group having 1 to 3 carbon atoms.
R6およびR7は水素原子または炭素数1〜6の低級ア
ルキル基であろ、)
の一種以上を酸化的に重縮合してイ0られるポリフエニ
レ/エーテル;このポリフェニレンエーテルにビニル芳
香族化合物をグラフト重合して得られる根幹にポリフェ
ニレンエーテルを有するグラフト共重合体を包含する。R6 and R7 are hydrogen atoms or lower alkyl groups having 1 to 6 carbon atoms; polyphenylene/ether obtained by oxidative polycondensation of one or more of the following; a vinyl aromatic compound is graft-polymerized to this polyphenylene ether; It includes graft copolymers having polyphenylene ether as the base obtained by
このポリフェニレンエーテルは、単独重合体であっても
共重合体であってもよい。This polyphenylene ether may be a homopolymer or a copolymer.
前記一般式(Irlで示されるI#環式フェノールとし
ては1例えば、2.6−ジメチルフェノール。The I# cyclic phenol represented by the general formula (Irl) is 1, for example, 2,6-dimethylphenol.
2.6−ジエチルフェノール、2.6−ジプロピルフェ
ノール、2−メチル−6−エチルフェノール、2−メチ
ル−6−ブロピルフエ/−ル。2.6-diethylphenol, 2.6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-bropylphenol.
2−エチル−6−ブロビルフエノールーm−クレゾーノ
i−2,3−ジメチルフェノール、2゜3−ジエチルフ
エ/−ル、2.3−ジプロピルフェノール−2−/チル
ロー3−エチルフエ/−ル、2−メチル−5−プロピル
フェノール、2−エチル−3−メチルフェノール+ 2
−エチル−3−プロピルフェノール、2−プロピル−3
−メチルフェノール、2−プロピル−3−エチルフェノ
ール+ 2.5.6−ドリメチルフエノール+ 2.
5.6−ドリエチル7エ/−ル、2゜3.6−1−リプ
ロピルフエ/−ル、2.6−シメチルー3−エチルフェ
ノール、2.6−ジメ千ルー3−プロビルフエ/−ル等
が挙げられる。2-Ethyl-6-brobylphenol, m-cresonol, 2,3-dimethylphenol, 2゜3-diethylphenol, 2,3-dipropylphenol-2-/chiro-3-ethylphenol. , 2-methyl-5-propylphenol, 2-ethyl-3-methylphenol + 2
-ethyl-3-propylphenol, 2-propyl-3
-Methylphenol, 2-propyl-3-ethylphenol + 2.5.6-drimethylphenol + 2.
Examples include 5.6-dryethyl 7 ethylphenol, 2゜3.6-1-lipropylpher/-l, 2.6-dimethyl-3-ethylphenol, 2.6-dimethyl-3-propylpher/-l, etc. It will be done.
モして−これらの単環式フェノールの一種以上の重縮合
により得られるポリフェニレンエーテルとしては1例え
ば、ポリ(2,6−シメチルー1.4−フェニレン)エ
ーテル、ポリ(2゜6−ジエチル−1,4−フエニレ/
)エーテル。Examples of polyphenylene ethers obtained by polycondensation of one or more of these monocyclic phenols include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2゜6-diethyl-1) ,4-Fenile/
)ether.
ポリ(2,6−ジプロビルー1.4−フェニレ/)エー
テル、ポリ(2−メチル−6−エチル−1,4−フエニ
レン)エーテル、ポリ(2−メチル−6−ブロピルー1
.4−)ユニしン)エーテル−ポリ(2−エチル−6−
プロピル−1,4−フェニレン)エーテル、2.6−シ
メチルフエノール/2.3.6−)リメチルフェノール
共11合体、 2 、 Is−ジメチルフェノール/
2−3−6− ) !jエチルフェノール共重合体。Poly(2,6-diprobyl-1,4-phenylene/)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2-methyl-6-bropylene/)ether
.. 4-) ether-poly(2-ethyl-6-)
Propyl-1,4-phenylene) ether, 2,6-dimethylphenol/2.3.6-)limethylphenol co-11 combination, 2, Is-dimethylphenol/
2-3-6-)! j Ethylphenol copolymer.
2.6−ジエチルフェノール/2.5.6−)リメゝチ
ルフェノール共重合体、2.6−ジプロビルフエノール
/2−3−6−)リメチルフェノール共重合体、ポリ(
2,6−シメチルー1゜4−)ユニしン)エーテルにス
チレンをグラフト重合したグラレト共重合体、2.6−
シメチルフエノール/2.5.6−)リメチルフェノー
ル共重合体にスチレンをグラフト重合したグラフト共重
合体等が挙げられろ、特に、ポリ(2,6−シメチルー
1.4−)ユニしン)エーテル、2.6−シメチルフエ
ノール/2,3豐6−ドリメチルフエノール共重合体、
および前二者にそれぞれスチレンをグラフト重合したグ
ラフト共重合体が本発明に用いるポリフェニレンエーテ
ル系樹脂として好ましいものである。2.6-diethylphenol/2.5.6-)limethylphenol copolymer, 2.6-diprobylphenol/2-3-6-)limethylphenol copolymer, poly(
Glareto copolymer obtained by graft polymerizing styrene to 2,6-dimethyl-1゜4-)unicine) ether, 2.6-
Examples include graft copolymers in which styrene is grafted onto a dimethylphenol/2.5.6-)limethylphenol copolymer. ) ether, 2,6-dimethylphenol/2,3-6-dimethylphenol copolymer,
A graft copolymer in which styrene is graft-polymerized to each of the former two is preferable as the polyphenylene ether resin used in the present invention.
本発明の樹脂組成物において前記ポリスユニレンエーテ
ル系樹脂と樹脂組成物を形成する(bl成分のビニル芳
香族炭化水素樹脂とは、下記一般式(肋
(式中、 Rg は水素原子または低級アルキル基。In the resin composition of the present invention, the vinyl aromatic hydrocarbon resin of the bl component is used to form a resin composition with the polysunilene ether resin described above (where Rg is a hydrogen atom or a lower alkyl Base.
2はハロゲン原子または低級アルキル基を示し、qは0
または1〜3の正の整数である。)で示される構造単位
をその重合体中和少なくとも25重量%以上含有する樹
脂をいう、かかるポリスチレン系樹脂を例示するならば
、ポリスチレン、ゴム変性ポリスチレン(耐衝撃性ポリ
スチレン)、ポリ−p−メチルスチレン、ゴム変性ポリ
−p−メチルスチレン、スチレン−ブタジェンコポリマ
ー、スチレン−ブタジェン−7クリロニトリルコポリマ
ー、スチレン−アクリル酸ゴム−アクリロニトリルコポ
リマー、スチレ/−α−メチルスチレンコポリマー、ス
チレン−ブタジェノフロックコポリマー、スチレン−無
水マレイノ酸コポリマー、ゴム変性ス+レンー無水マレ
イノ酸コポリマー等が挙げられ。2 represents a halogen atom or a lower alkyl group, and q is 0
Or a positive integer from 1 to 3. ) refers to a resin containing at least 25% by weight of the neutralized structural unit of the polymer. Examples of such polystyrene-based resins include polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), and poly-p-methyl. Styrene, rubber-modified poly-p-methylstyrene, styrene-butadiene copolymer, styrene-butadiene-7crylonitrile copolymer, styrene-acrylic acid rubber-acrylonitrile copolymer, styrene/-α-methylstyrene copolymer, styrene-butadiene floc copolymer , styrene-maleinoic anhydride copolymer, rubber-modified styrene-maleinoic anhydride copolymer, and the like.
これらFi211以上混合して用いてもよい。These Fi211 or more may be mixed and used.
本発明の樹脂組成物の(e)成分である前記一般式(I
lで表わされるリン酸の金属塩は特開昭59−1452
24号公報に開示されているリン酸エステル部分金属塩
の製造方法に準じて製造される。即ち、まず、フェノー
ル類をオキシ塩化リンまたは無水リン酸と反応(温度1
50〜200℃1反応時間2〜15時間)させた後、加
水分解して式:
で示されるリン酸エステルを得る。次に0通常の脂肪酸
金属塩の合成法に準じて該’)71!!エステルを強酸
両相当分の1.0〜1.1倍当量のアルカ゛す(例えば
水酸化ナトリウム等)で中和した後、カルシウム、バリ
ウム、アルミニウムの無機酸金属塩(例えば塩化カルシ
ウム、塩化バリウム−411酸アルミニウム等)を中和
に要した上記アルカリの当量もしくはその僅か危過剰分
で加え、複分解することにより、前記一般式111で表
わされる化合物が生成する。The general formula (I) which is the component (e) of the resin composition of the present invention
The metal salt of phosphoric acid represented by l is disclosed in JP-A-59-1452.
It is produced according to the method for producing a phosphate ester partial metal salt disclosed in Japanese Patent No. 24. That is, first, phenols are reacted with phosphorus oxychloride or phosphoric anhydride (at a temperature of 1
After heating at 50 to 200° C. for 2 to 15 hours, hydrolysis is performed to obtain a phosphoric acid ester represented by the formula: Next, according to the synthesis method of 0 ordinary fatty acid metal salts, ! After neutralizing the ester with an alkali (e.g., sodium hydroxide) in an amount equivalent to 1.0 to 1.1 times the amount of both strong acids, inorganic acid metal salts of calcium, barium, and aluminum (e.g., calcium chloride, barium chloride, etc.) are added. The compound represented by the general formula 111 is produced by adding aluminum 411 acid (aluminum 411 acid, etc.) in an equivalent amount of the alkali required for neutralization or a slight excess thereof and metathesis.
一般式111 において、 Ih、 R2,R3および
R4はそれぞれ独!して01〜3のフルキル基、即ち。In general formula 111, Ih, R2, R3 and R4 are each independent! and 01-3 furkyl group, ie.
メチル基、エチル基、プロピル基、イソプロピル基tあ
り、又+ l−m、n、oはそれぞれ独立しで0または
1〜5の整数である。従って。There is a methyl group, an ethyl group, a propyl group, an isopropyl group, and +lm, n, and o are each independently 0 or an integer of 1 to 5. Therefore.
一般式(I)で示されるリン酸の金属塩の製造に使用さ
れるフェノール類としては、具体的には。Specifically, the phenols used in the production of the metal salt of phosphoric acid represented by the general formula (I) include:
フェノール、クレゾール、キシレノール、トリメチルフ
ェノール、テトラメチルフェノール。Phenol, cresol, xylenol, trimethylphenol, tetramethylphenol.
ぺ/#メチルフェノール、エチルフェノール。P/# Methylphenol, ethylphenol.
プロピルフェノール、イソプロピルフェノール。Propylphenol, isopropylphenol.
ジエチルフェノール、トリイソプロピルフェノール、等
が挙げられ、これらは単独または混合して使用される。Examples include diethylphenol, triisopropylphenol, and the like, which may be used alone or in combination.
金属塩を形成する金属はカルシウム、バリウム、アルミ
ニウムであり、金属がアルミニウムの場合にはエステル
化されていない水酸基が1ケ残存していなければならな
い。The metals forming the metal salt are calcium, barium, and aluminum, and when the metal is aluminum, one unesterified hydroxyl group must remain.
本発明の樹脂組成物の(dl成分であるホスフェート化
合物としては以下の一般式■で示されるものが好ましい
、具体的には、フェニル−ビスRIIO/
(Re、RIG−RIIFi互いに独立してフルキル基
。As the phosphate compound (dl component) of the resin composition of the present invention, those represented by the following general formula (2) are preferred. Specifically, phenyl-bisRIIO/ (Re, RIG-RIIFi .
ジクロフルキル基、7リル基、フルキル置換7リル基、
7リル置換アルキル基、水素−等である。)
(ドデシル)ホスフェート、フェニル−ビス(ネオへエ
チル)ホスフェート、フェニル−エチル−ハイドロジエ
ンホスフェート、フェニル−ビス(5,5,5−)リメ
チルヘキシル)ホスフェート、エチル−ジフェニルホス
フェート。dichlorofurkyl group, 7lyl group, furkyl-substituted 7lyl group,
7lyl-substituted alkyl group, hydrogen, etc. ) (dodecyl) phosphate, phenyl-bis(neohethyl) phosphate, phenyl-ethyl-hydrodiene phosphate, phenyl-bis(5,5,5-)limethylhexyl) phosphate, ethyl-diphenyl phosphate.
ビス(2−エチルヘキシル)−P−)リルホス7w−ト
、トリトリルホスフェート、ビス(2−エチルヘキシル
)−フェニルホスフェート。Bis(2-ethylhexyl)-P-)lyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate.
トリ(ノニルフェニル)ホスフェート、フェニル−メチ
ル−ハイドロジェノホスフェート、ジ(ドデシル)−P
−トリルホスフェート、トリクレジルホスフェート、ト
リフェニルホスフニート、トリ(インプロピルフェニル
)ホスフェート、イソプロピルフェノールとフェノール
との混合物から得られるホスフェート、ジブチル−フェ
ニルホスフェート、P−トリル−ビス(2,5,5−ト
リメチルヘキシル)ホスフェート、2−エチルヘキシル
−ジフェニルホスフェート、ジフェニル−ハイドロジエ
ンホスフェート、ハロゲン化トリフェニルホスフェート
、2−クロロエチル−ジフェニルホスフェート、トリス
(β−ナフチル)ホスフェート、トリス(P−フェニル
フェニル)ホスフェート、等である。更に、一般式側で
表わされないホスフェート化合物としてはフェノールと
レゾルシンとの混合物から得られる1分子中に2ヶ以上
のりン原子を有するホスフェート重合体が挙げられる。Tri(nonylphenyl)phosphate, phenyl-methyl-hydrogenophosphate, di(dodecyl)-P
- tolyl phosphate, tricresyl phosphate, triphenylphosphinate, tri(impropylphenyl) phosphate, phosphate obtained from a mixture of isopropylphenol and phenol, dibutyl-phenyl phosphate, P-tolyl-bis(2,5,5 -trimethylhexyl) phosphate, 2-ethylhexyl-diphenyl phosphate, diphenyl-hydrodiene phosphate, halogenated triphenyl phosphate, 2-chloroethyl-diphenyl phosphate, tris(β-naphthyl) phosphate, tris(P-phenylphenyl) phosphate, etc. It is. Furthermore, examples of phosphate compounds not represented by the general formula include phosphate polymers having two or more phosphorus atoms in one molecule obtained from a mixture of phenol and resorcinol.
本発明の樹脂組成物において、一般式(Ilで表わされ
ろリン酸の金属塩およびホスフェート化合物の使用量は
樹脂成分の比率および/または樹脂組成物に要求されろ
難燃化度合によって異なるが、一般的には両者の合計量
が、樹脂成分(エラストマーも含む)1oo1量部に対
して。In the resin composition of the present invention, the amount of the metal salt of phosphoric acid and the phosphate compound represented by the general formula (Il) varies depending on the ratio of resin components and/or the degree of flame retardation required for the resin composition. Specifically, the total amount of both is based on 100 parts of the resin component (including the elastomer).
1〜50重量部、好ましくは2〜20重量部である。下
限量未滴であれば所定の離燃化度が達成され離<、上限
量を超えると、他の性能力を損なわれる。また、一般式
(Ilで表わされるリン酸の金属塩とホスフェート化合
物との比率(重量比)に関してはm一般的には10/’
10〜80720−好ましくは2 Q/B O〜70/
30−更に好ましくは40/60〜65/35である。The amount is 1 to 50 parts by weight, preferably 2 to 20 parts by weight. If the lower limit amount is not dropped, a predetermined degree of flammability is achieved, but if the upper limit amount is exceeded, other sexual performance will be impaired. In addition, the ratio (weight ratio) of the metal salt of phosphoric acid and the phosphate compound represented by the general formula (Il) is generally 10/'
10-80720-preferably 2 Q/B O-70/
30-more preferably 40/60 to 65/35.
一般式(I)で表わされる化合物の割合が多いと。When the proportion of the compound represented by general formula (I) is high.
所定の離燃化度が達成され離<、逆にホスフェート化合
物の割合が多いと、一般には加熱時に於ける樹脂組成物
からの揮発減量が多くなる。If a predetermined degree of flammability is achieved and the proportion of the phosphate compound is high, the amount of volatilization from the resin composition during heating will generally increase.
本発明の樹脂組成物におけるポリフェニレンエーテル系
樹脂とビニル芳香族縦比水素樹脂との割合(重象比ンに
関してはm一般的にFij799〜99/1−好ましく
は10/90〜90710、更に好ましくは20/80
〜80/20である。The ratio of the polyphenylene ether resin to the vinyl aromatic aspect ratio hydrogen resin in the resin composition of the present invention (with respect to the heavy ratio, m is generally 799 to 99/1 - preferably 10/90 to 90,710, more preferably 20/80
~80/20.
本発明の樹脂組成物には、目的に応じて各種添加剤、充
填材、エラストマー等の他の成分を配合することが可能
である。例えば、立体障害性フェノール、有機ホスファ
イト、ホスフォナイト、ホスフォナス酸、環状ホスフォ
ナイト2ヒドラジン誘導体、アミン誘導体、カーバメイ
ト誘導体、チオエーテル、ホスフォリックトリアミド−
ベンゾオキサゾール誘導体、金属の硫化物等の安定剤;
ぺ/シトリアゾール誘導体。Other components such as various additives, fillers, and elastomers may be added to the resin composition of the present invention depending on the purpose. For example, sterically hindered phenols, organic phosphites, phosphonites, phosphonasic acids, cyclic phosphonite dihydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phosphoric triamides.
Stabilizers such as benzoxazole derivatives and metal sulfides;
Pe/citriazole derivatives.
ぺ/シフエノン誘導体、サリシレート誘導体。Pe/siphenon derivatives, salicylate derivatives.
立体障害性アミン、しゆう酸ジアミド誘導体等の紫外線
吸収剤;ポリエチレンワックス、ポリプロビレ/ワック
ス等に代表される滑剤としてのオレフイ/ワックス;デ
カブロモビフェニル。Ultraviolet absorbers such as sterically hindered amines and oxalic acid diamide derivatives; Olefins/waxes as lubricants such as polyethylene wax and polypropylene/wax; decabromo biphenyl.
ぺ/タブクモトルエン。デカブロモビフェニルエーテル
、臭素化ポリエチレン等に代表されるJ4索系S燃剤;
酸化チタン、酸化亜鉛、カーボンブラック等に代表され
る頗科;ガラス繊維。Pe/Tab Kumotoluene. J4 cord type S refueling agent represented by decabromo biphenyl ether, brominated polyethylene, etc.;
Ceraminaceae represented by titanium oxide, zinc oxide, carbon black, etc.; Glass fiber.
ガラスピーズ、アスベスト、ウオラストナイト。glass peas, asbestos, and wollastonite.
マイカ、タルク、クレイ、炭酸カルシウム、シリカ等に
代表されろ無機充填材:銅、ニッケル。Inorganic fillers such as mica, talc, clay, calcium carbonate, silica, etc.: copper, nickel.
アルミニウム、亜鉛等のフレークに代表される金属フレ
ーク;アルミニウム#jI維、アルミニウム合金繊維、
黄銅繊維、ステンレス繊維等に代表される金属繊維、炭
素繊維、芳香族ポリアミド繊維に代表されろ存機充填材
等が挙げられる。Metal flakes represented by aluminum, zinc flakes, etc.; aluminum #jI fibers, aluminum alloy fibers,
Examples include metal fibers typified by brass fibers and stainless steel fibers, carbon fibers, filter fillers typified by aromatic polyamide fibers, and the like.
また前記エラストマーとは一般的な意味でのエラストマ
ーであり5例えば、 A、 V、 Tobolsky著
” Prop@rtl*s and 5tru
ctures of I”ol)rmers ”
(John WILEY & Songs Inc、
+ 1960年)71〜78ページに採用された定義を
引用でき。Further, the elastomer is an elastomer in a general sense.
tures of I”olmers”
(John WILEY & Songs Inc.
+ 1960) Please cite the definition adopted on pages 71-78.
エラストマーとは常温におけるヤング率が105〜10
’ dynes /a11(0、1〜1020KP/C
11)である重合体を意味する。エラストマーの具体例
としては+A−B−に屋エラストマー状ブロツク共重合
体、ポリブタジェン部分の二重結合が水素添加されたA
−B−A’型エラストマー状ブロック共重合体、ポリブ
タジェン、ポリイソプレ/、ジエン化合物とビニル化合
物との共重合体、ラジアルテレブロック共重合体、ニト
リルゴム、エチレン−プロピレン共重合体、エチレン−
プロピレン−ジエン共重合体(EPDM)。Elastomer has a Young's modulus of 105 to 10 at room temperature.
'dynes/a11 (0, 1~1020KP/C
11). Specific examples of elastomers include +A-B-Niya elastomeric block copolymer, and A in which the double bond in the polybutadiene portion is hydrogenated.
-B-A' type elastomeric block copolymer, polybutadiene, polyisopre/, copolymer of diene compound and vinyl compound, radial teleblock copolymer, nitrile rubber, ethylene-propylene copolymer, ethylene-
Propylene-diene copolymer (EPDM).
チオコールゴム、ポリスルフィドゴム、アクリル酸ゴム
、ポリウレタンゴム、ブチルゴムとポリエチレンとのグ
ラフト共重合体、ポリエステルエラストマー、ポリアミ
ドエラストマー、ポリウレタンエラストマー等が挙げら
れる。とりわけ、A−B−A’fiエラストマー状ブロ
ツブロック共重合体しい。このブロック共重合体の末端
ブロックAおよびA′は重合されたビニル芳香族炭化水
素ブロックであり、Bは重合された共役ジエンブロック
あるいは二重結合の大部分が水素添加された共役ジエン
ブロックであり、Bブロックの分子量FihおよびA′
ブロックの組み合わされた分子量より大であることが望
ましい・末端ブロックAおよびA′は同一でも異なって
もよく、且つ該ブロックは、芳香族部分が単環でも多環
でもよいビニル芳香族炭化水素から誘導された熱可塑性
単独重合体または共重合体である。かのするビニル芳香
族炭化水素の例はスチレ/、α−メチルスチレン、ビニ
ルトルエン、ビニルキシレン、エチルビニルキシレン、
ビニルナフタレンおよびそれらの混合物が挙げられろ。Examples include thiocol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, graft copolymer of butyl rubber and polyethylene, polyester elastomer, polyamide elastomer, polyurethane elastomer, and the like. In particular, A-B-A'fi elastomeric block copolymers. The terminal blocks A and A' of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated. , the molecular weight Fih of the B block and A'
It is desirable that the molecular weight is larger than the combined molecular weight of the blocks. The terminal blocks A and A' may be the same or different, and the block is made of a vinyl aromatic hydrocarbon in which the aromatic moiety may be monocyclic or polycyclic. A derived thermoplastic homopolymer or copolymer. Examples of such vinyl aromatic hydrocarbons are styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene,
Mention may be made of vinylnaphthalene and mixtures thereof.
中央ブロックBは共役ジエン系炭化水素1例えlf、
1 、3−ブタジェン、2.3−ジメチルブタジェン
、イソプレン、1.3−ぺ/タジエンおよびそれらの混
合物から誘導されたエラストマー状重合体である。各末
端ブロックAおよびA′の分子量は、好ましくけ約2.
000〜約100.000の範囲であり、−万一中央ブ
ロックBの分子量は、好ましくは約25.000〜約1
.000.000の範囲である。The central block B is a conjugated diene hydrocarbon, for example lf,
Elastomeric polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pe/tadiene and mixtures thereof. The molecular weight of each end block A and A' is preferably about 2.
000 to about 100,000, - should the molecular weight of the central block B preferably range from about 25,000 to about 1
.. The range is 000.000.
本梶明のポリフェニレンエーテル系樹脂組成物を調製す
るに際しては、従来公知の方法が採用されればよく1例
えば、各成分をターンプルミキサーやへ/シェルミキサ
ーで代表される高速ミキサーで混合した後、バンバリー
ミキサ−等で混合する方法が適宜選択される。When preparing the polyphenylene ether resin composition of the present invention, any conventionally known method may be used. For example, after mixing each component with a high-speed mixer such as a turnpull mixer or a shell/shell mixer, A mixing method using a Banbury mixer or the like is appropriately selected.
以下、参考例−実施例および比較例により本発明の樹脂
組成物を具体的に説明する。尚1部数は、特別のことわ
りがない限り1重量部である。Hereinafter, the resin composition of the present invention will be specifically explained using reference examples, examples, and comparative examples. Note that 1 part means 1 part by weight unless otherwise specified.
参考例
先に述べた方法に従って合成した以下のリン酸の金属塩
についてその加熱重量減少を測定した。Reference Example The following metal salts of phosphoric acid synthesized according to the method described above were measured for weight loss upon heating.
測定条件
装 R:TG−8110(ffJ学tm)昇 In:
10℃/ml口
雰囲気:加圧空気
室温から500℃に昇温するまでの、上記各物質の重量
減少nは以下の通りであった。比較の為に、トリフェニ
ルポスフェートの場合の値も示す。Measurement conditions Equipment R: TG-8110 (ffJ Gakutm) In:
10° C./ml Mouth atmosphere: pressurized air The weight loss n of each of the above substances until the temperature was raised from room temperature to 500° C. was as follows. For comparison, values for triphenyl phosphate are also shown.
TPP 79 %
A) q 、 4%
B) /) 、 q%
C) 9 、 a%
D) s 、 9%
上記の結果から明らかな如く1本発明の樹脂組成物に使
用されるリン酸の金属塩の加熱ii量減少は従来公知の
トリフェニルホスフェートの場合よりも遥かに小さい。TPP 79% A) q, 4% B) /), q% C) 9, a% D) s, 9% As is clear from the above results, 1. The metal phosphoric acid used in the resin composition of the present invention The reduction in the amount of salt on heating is much smaller than in the case of hitherto known triphenyl phosphate.
実施例 1〜3
固有粘度が0 、47 dl/jl (25℃、クロロ
ホルム中)の2.6−シメチルフエノール/2゜3.6
一ト!jメチルフエノール共重合体(2゜3.6−)リ
メチルフェノールの占めろ割合は5モル%)50部、耐
lI撃性ポリスチレ/(25℃でクロロホルムを溶媒と
して測定されたボリスチレ/マトリックスの固有粘度0
.80dA!/!!、ベンゼンを溶媒として得られたゲ
ル含有量22.4重量%)46部、ポリスチレ/−ポリ
ブタジェン−ポリスチレンブロック共重合体(ポリスチ
レン部分とポリブタンエン部分との重量比が50/70
であり、かつ当該共重合体の20%トルエノ溶液のブル
ックフィールドモデルR,VT粘度計を用いて25℃で
測定された粘度が1500cps)5部、エチレン−プ
ロピレン共重合体(デカリンを溶媒として濃度0゜1
y/1 o od、 温度135℃で測定された還元
比粘度2,0.ガラス転移点−49℃)1部。Examples 1-3 2.6-dimethylphenol/2°3.6 with an intrinsic viscosity of 0.47 dl/jl (25°C, in chloroform)
Itto! j Methylphenol copolymer (2゜3.6-) The proportion of methylphenol is 5 mol%) 50 parts, II impact-resistant polystyrene/(Boristyrene/matrix measured at 25°C using chloroform as a solvent) Intrinsic viscosity 0
.. 80dA! /! ! , gel content 22.4% by weight obtained using benzene as a solvent) 46 parts, polystyrene/-polybutadiene-polystyrene block copolymer (weight ratio of polystyrene part and polybutane part is 50/70)
and the viscosity of a 20% tolueno solution of the copolymer was 1500 cps as measured at 25°C using a Brookfield Model R, VT viscometer), 5 parts of ethylene-propylene copolymer (concentration using decalin as solvent) 0゜1
y/1 o od, reduced specific viscosity measured at a temperature of 135°C 2.0. Glass transition point -49°C) 1 part.
テトラキス(2,4−ジーtart−ブチルフェニル)
414’−ビフェニレンジ7オスフオナイト0.4
部、2,6−シーtert−ブチル−P−クレゾール0
.3部、酸化チタン5部、部分酸化型ポリエチレンワッ
クス(三洋化成:商品名rE 250pJ)1.5部、
及びトリフェニルホスフェート(TPP)と参考例のリ
ン酸の金属塩をそれぞれ表1に示されろ重量部、をラボ
プラストミル(東洋精機)で混練槽温度27ラボプラス
トミルより取り出し、290℃の金型を用いて、圧力2
001で10分間プレスして厚さ1/16”のシートを
作製した。このシートよりn”x s”の短冊状の試験
片を切り出し、これを用いてUT、94規格に準じた然
焼試験を行なった。結果を表1に示す。Tetrakis (2,4-di-tart-butylphenyl)
414'-biphenylene range 7 osphonite 0.4
parts, 2,6-tert-butyl-P-cresol 0
.. 3 parts, titanium oxide 5 parts, partially oxidized polyethylene wax (Sanyo Chemical: trade name rE 250pJ) 1.5 parts,
The weight parts of triphenyl phosphate (TPP) and the metal salt of phosphoric acid of the reference example shown in Table 1, respectively, were taken out of the Labo Plastomill (Toyo Seiki) at a kneading tank temperature of 27 and heated to 290°C. Using a mold, pressure 2
001 for 10 minutes to produce a sheet with a thickness of 1/16". N" x s" strip-shaped test pieces were cut from this sheet and used to perform a baking test according to UT and 94 standards. The results are shown in Table 1.
比較例 1〜4
実m例1〜5において、トリフェニルホスフェートとリ
ン酸の金属塩との併用に代えて、トリ1エニルホスフエ
ート、或いはす/a!の金属塩をそれぞれ単独で表1に
示される重量部使用する以外は実施例1〜3の操作を繰
り返した。Comparative Examples 1 to 4 In Examples 1 to 5, instead of the combined use of triphenyl phosphate and a metal salt of phosphoric acid, tri-1-enyl phosphate or Su/a! The operations of Examples 1 to 3 were repeated except that each of the metal salts was used individually in the parts by weight shown in Table 1.
結果を表1に示す。The results are shown in Table 1.
表1の結果から明ら力)な様に、多量のリン酸の金属塩
のみ(比較例2.3.4)では難燃化効果がないにも拘
わらず、少量のリン酸の金属塩でも少量のトリ7エニル
ホスフエートと併用することにより難燃化効果が顕れる
。尚、少量のトリフェニルホスフェートのみ(比ff例
1)でri難燃化効果が認められない。From the results in Table 1, it is clear that although a large amount of metal salt of phosphoric acid alone (Comparative Example 2.3.4) has no flame retardant effect, even a small amount of metal salt of phosphoric acid has no flame retardant effect. When used in combination with a small amount of tri-7enyl phosphate, the flame retardant effect becomes apparent. Note that the ri flame retardant effect is not observed with only a small amount of triphenyl phosphate (ratio FF example 1).
実施例 5
実施例1において、リン酸の金属塩として参考例のA)
をs、sN、、1部、トリフェニルホスフェートを8.
4重址部使用する以外は実施例1の操作を繰り返した。Example 5 In Example 1, reference example A) was used as the metal salt of phosphoric acid.
s, sN, 1 part, triphenyl phosphate 8.
The procedure of Example 1 was repeated except that a quadruple joint was used.
平均燃焼時間は4.9秒であった。因みに、トリフェニ
ルホスフェートのみを8.4重麓部使用した場合の平均
燃焼時間Fi8.5秒であった。The average burning time was 4.9 seconds. Incidentally, the average combustion time Fi was 8.5 seconds when only triphenyl phosphate was used in the 8.4-layer base.
実施例 6
実施例3において、す/酸の金属塩として参考例のC)
K代えてD)を8.5重量部、トリフェニルホスフェー
トを6.0重量部使用する以外は実施例3の操作を繰り
返した。平均燃焼時間は5.8秒であった。一方、参考
例のD)のみ12.6重量部使用した場合にはドロップ
が生じた。Example 6 In Example 3, reference example C) was used as the metal salt of sulphur/acid.
The operation of Example 3 was repeated except that K was replaced with D) in an amount of 8.5 parts by weight, and triphenyl phosphate was used in an amount of 6.0 parts by weight. The average burning time was 5.8 seconds. On the other hand, when only 12.6 parts by weight of D) in Reference Example was used, drops occurred.
本発明の樹脂組成物の構成成分であろり/酸の金属塩の
加熱重量減少量は小さく、従ってこれと少量のホスフェ
ート化合物とを含有する本発明の樹脂−組成物からの加
熱に基づくこれらの揮発量は対応するホスフェート化合
物のみを多量に含有する樹脂組成物の場合より少ない。The amount of weight loss on heating of the metal salt of the oxide/acid, which is a component of the resin composition of the present invention, is small, and therefore, the weight loss of the metal salt of the anolyte/acid, which is a component of the resin composition of the present invention, is small, and therefore, the weight loss of the metal salt of the anolyte/acid, which is a constituent component of the resin composition of the present invention, is small. The amount of volatilization is lower than in the case of a resin composition containing only a corresponding phosphate compound in a large amount.
更に、リン酸の金属塩とボス7ヱート化合物との併用は
ポリフェニレンエーテル系樹脂組成物に有効な難燃化効
果を特徴するFurthermore, the combined use of a metal salt of phosphoric acid and a Boss 7ite compound has an effective flame retardant effect on polyphenylene ether resin compositions.
Claims (1)
香族炭化水素樹脂、(c)下記一般式( I )で表わさ
れるリン酸の金属塩および(d)ホスフェート化合物を
含有する難燃化ポリフェニレンエーテル系樹脂組成物 ▲数式、化学式、表等があります▼( I ) M:Ca、Ba、Al R_1、R_2、R_3、R_4:C_1_〜_3のア
ルキル基l、m、n、o:0または1〜5の整数 p:MがCa、Baの時は0 MがAlの時は1[Claims] Contains (a) a polyphenylene ether resin, (b) a vinyl aromatic hydrocarbon resin, (c) a metal salt of phosphoric acid represented by the following general formula (I), and (d) a phosphate compound. Flame retardant polyphenylene ether resin composition▲Mathematical formulas, chemical formulas, tables, etc.▼(I) M: Ca, Ba, Al R_1, R_2, R_3, R_4: Alkyl groups of C_1_ to_3 l, m, n, o : 0 or an integer from 1 to 5 p: 0 when M is Ca or Ba 1 when M is Al
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14134987A JPH0826215B2 (en) | 1987-06-08 | 1987-06-08 | Flame-retardant polyphenylene ether resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14134987A JPH0826215B2 (en) | 1987-06-08 | 1987-06-08 | Flame-retardant polyphenylene ether resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63305161A true JPS63305161A (en) | 1988-12-13 |
JPH0826215B2 JPH0826215B2 (en) | 1996-03-13 |
Family
ID=15289901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14134987A Expired - Lifetime JPH0826215B2 (en) | 1987-06-08 | 1987-06-08 | Flame-retardant polyphenylene ether resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0826215B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6093760A (en) * | 1995-03-03 | 2000-07-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame retardant for styrene resin and resin composition comprising the same |
EP1304350A1 (en) * | 2001-10-17 | 2003-04-23 | Asahi Denka Co., Ltd. | Flame-retardant resin composition |
-
1987
- 1987-06-08 JP JP14134987A patent/JPH0826215B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6093760A (en) * | 1995-03-03 | 2000-07-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame retardant for styrene resin and resin composition comprising the same |
EP1304350A1 (en) * | 2001-10-17 | 2003-04-23 | Asahi Denka Co., Ltd. | Flame-retardant resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPH0826215B2 (en) | 1996-03-13 |
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