JPH021760A - Polyphenylene ether resin composition - Google Patents
Polyphenylene ether resin compositionInfo
- Publication number
- JPH021760A JPH021760A JP5715389A JP5715389A JPH021760A JP H021760 A JPH021760 A JP H021760A JP 5715389 A JP5715389 A JP 5715389A JP 5715389 A JP5715389 A JP 5715389A JP H021760 A JPH021760 A JP H021760A
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- polyphenylene ether
- parts
- ether 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 44
- 239000011342 resin composition Substances 0.000 title claims description 57
- 229920001971 elastomer Polymers 0.000 claims abstract description 125
- 239000005060 rubber Substances 0.000 claims abstract description 125
- 239000002131 composite material Substances 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- 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 23
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 18
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 12
- 229920005990 polystyrene resin Polymers 0.000 claims abstract 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 claims abstract description 11
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract 2
- 239000004793 Polystyrene Substances 0.000 claims description 17
- 229920002223 polystyrene Polymers 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- 241001385733 Aesculus indica Species 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 54
- 238000000034 method Methods 0.000 description 18
- 229920000126 latex Polymers 0.000 description 17
- -1 phosphate ester Chemical class 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 12
- 239000004816 latex Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- IGRYVRNQZARURF-UHFFFAOYSA-N 2-(dimethoxymethylsilyl)ethyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCOC(=O)C(C)=C IGRYVRNQZARURF-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- WUTSHINWYBIRDG-UHFFFAOYSA-N 3-[ethoxy(diethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](CC)(CC)CCCOC(=O)C(C)=C WUTSHINWYBIRDG-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- AIDAPOBEZDTRDC-UHFFFAOYSA-N 4-(diethoxymethylsilyl)butyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCCC[SiH2]C(OCC)OCC AIDAPOBEZDTRDC-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QZRFWQBUYGHLMU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.N#CC=CC=CC1=CC=CC=C1 QZRFWQBUYGHLMU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 241000282375 Herpestidae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 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 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 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
- 230000032798 delamination Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- OACSUWPJZKGHHK-UHFFFAOYSA-N tribenzyl phosphate Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)(=O)OCC1=CC=CC=C1 OACSUWPJZKGHHK-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- LFRFOEVCFVCHEV-UHFFFAOYSA-N tris(2-chlorophenyl) phosphate Chemical compound ClC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)Cl)OC1=CC=CC=C1Cl LFRFOEVCFVCHEV-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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〕
本発明は耐衝撃性、耐熱性、機械強度ならびに難燃性等
に優れたポリフェニレンエーテル樹脂組成物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene ether resin composition having excellent impact resistance, heat resistance, mechanical strength, flame retardance, etc.
本発明は、ポリフェニレンエーテル樹脂組成物において
、
ボIJ フェニレンエーテル樹脂組成物が、ポリフェニ
レンエーテル樹JI&ト1.Nリスチレン樹脂と、ポリ
オルガノシロキサンゴム成分とポリアルキル(メタ)ア
クリレートゴム成分とかう成る複合ゴムにビニル系単量
体を高効率でグラフト重合させて得た複合ゴム系グラフ
ト共重合体とからなる樹脂配合物にリン酸エステル系難
燃剤及び/又はガラス繊維と炭素繊維からなる群から選
ばれる少なくとも一種の無機繊維を配合することにより
耐衝撃性、耐熱性、機械強度ならびに難燃性等に優れた
組成物を提供することができるようにしたものである。The present invention provides a polyphenylene ether resin composition in which the polyphenylene ether resin composition is a polyphenylene ether resin composition. Consists of N-styrene resin and a composite rubber graft copolymer obtained by highly efficient graft polymerization of a vinyl monomer to a composite rubber consisting of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component. By blending a phosphate ester flame retardant and/or at least one type of inorganic fiber selected from the group consisting of glass fiber and carbon fiber into the resin compound, it has excellent impact resistance, heat resistance, mechanical strength, flame retardance, etc. This makes it possible to provide a composition that has the following properties.
〔従来の技術及び発明が解決しようとする課題〕ポリフ
ェニレンエーテル樹脂は耐熱性、剛性等に優れた成形物
を与えるためエンジニアリングプラスチックとしての用
途が拡大しているが、成形物の表面外観ならびに耐衝撃
性に若干劣ることからその用途が制限されている。[Prior art and problems to be solved by the invention] Polyphenylene ether resins are increasingly being used as engineering plastics because they provide molded products with excellent heat resistance and rigidity. Its use is limited due to its slightly inferior properties.
ポリフェニレンエーテル樹脂の成形物の耐衝撃性を改善
する方法として、ポリブタジェン系エラストマーを配合
する方法が特公昭47−32731号公報、特開昭46
−2345号公報等に開示されている。しかしながら、
かかる方法による場合はポリブタジェン系エラストマー
中に不飽和結合が残存するため熱的に不安定であり、実
用的に有用な熱安定性に優れたものが得られな込。As a method of improving the impact resistance of polyphenylene ether resin molded products, a method of blending a polybutadiene elastomer is disclosed in Japanese Patent Publication No. 47-32731 and Japanese Patent Application Laid-Open No. 1973-1989.
This is disclosed in Japanese Patent No.-2345 and the like. however,
When such a method is used, unsaturated bonds remain in the polybutadiene elastomer, making it thermally unstable, making it impossible to obtain a material with excellent thermal stability that is useful for practical purposes.
また、ポリフェニレンエーテル樹脂にポリオルガノシロ
キサン変性アルケニル芳香族樹脂を配合して耐衝撃性を
向上させる方法が特開昭55−75444号公報に、又
、ポリフェニレンエーテル樹脂にポリアルキル(メタ)
アクリレートを配合して樹脂成形物の強度改善を図る方
法が特公昭49−6579号公報にそれぞれ開示されて
いる。しかし、これらbずれの方法でも満足すべき成形
外観ならびに耐衝撃性を得る事が出来ないのが現状であ
る。Furthermore, a method of improving impact resistance by blending a polyorganosiloxane-modified alkenyl aromatic resin with a polyphenylene ether resin is disclosed in JP-A-55-75444.
Japanese Patent Publication No. 49-6579 discloses a method for improving the strength of resin molded products by blending acrylates. However, the current situation is that even with these methods with deviations from b, it is not possible to obtain satisfactory molded appearance and impact resistance.
そこで、ポリフェニレンエーテル樹脂成形物本来の優れ
た耐熱性及び機械的強度をそのまま保持しながら耐衝撃
性及び表面外観を改善するための樹脂組成について鋭意
検討した結果、ポリオルガノシロキサンゴム成分とポリ
アルキル(メタ)アクリレートゴム成分とから成る複合
ゴムにビニル系単量体を高効率でグラフト重合させて得
た複合ゴム系グラフト共重合体とポリフェニレンエーテ
ル樹脂とポリスチレン樹脂とを組合せることにより、こ
れら各樹脂間の相溶性が良好で、成形物とした場合に層
状剥離が生ずることがなく、しかも耐衝撃性ならびに表
面外観が著しく改善されかつ耐熱性及び機械的強度に優
れ、成形性ならびに流動性も優れた樹脂組成物が得られ
ることを見出し先に特許出願をしたが、難燃性の付与、
充分優れた機械強度の付与ができなかった。Therefore, as a result of intensive study on the resin composition to improve impact resistance and surface appearance while maintaining the excellent heat resistance and mechanical strength inherent to polyphenylene ether resin moldings, we found that polyorganosiloxane rubber components and polyalkyl ( By combining a composite rubber-based graft copolymer obtained by highly efficient graft polymerization of a vinyl monomer onto a composite rubber consisting of a meth)acrylate rubber component, a polyphenylene ether resin, and a polystyrene resin, each of these resins can be produced. The compatibility between the materials is good, and when molded, delamination does not occur, and the impact resistance and surface appearance are significantly improved, as well as excellent heat resistance and mechanical strength, as well as excellent moldability and fluidity. I applied for a patent after discovering that a resin composition with high flame retardance could be obtained.
It was not possible to provide sufficiently excellent mechanical strength.
本発明者らは上述した如き現状に鑑み鋭意検討した結果
上記複合ゴム系グラフト共重合体とポリフェニレンエー
テル樹脂トボリスチレン樹脂とを組合せた樹脂配合物に
はリン酸エステル系難燃剤が難燃性を付与するのに好ま
しいこと、又ガラス#&維および炭素I繊維の少なくと
も一種の無機繊維が優れた機械強度の付与が可能である
こと、さらにはこれらリン酸エステル系難燃剤と無機峻
維の組合使用が優れた機械強度と難燃性の付与が可能で
あることを見出し本発明に到達した。The present inventors conducted intensive studies in view of the current situation as described above, and found that a phosphate ester flame retardant imparts flame retardancy to a resin compound that combines the composite rubber graft copolymer and polyphenylene ether resin and tobolystyrene resin. In addition, at least one type of inorganic fiber such as glass #& fiber and carbon I fiber can provide excellent mechanical strength, and furthermore, the combination use of these phosphate ester flame retardants and inorganic fiber is preferred. The present invention was achieved by discovering that it is possible to impart excellent mechanical strength and flame retardancy to the material.
すなわち、本発明は
(A) rt!リフエニレンエーテル樹脂、(B)
ポリスチレン樹脂、
(C) ポリオルガノシロキサンゴム成分10〜90
重滑憾とポリアルキル(メタ)アクリレートゴム成分1
0〜qo7Ir量係とが分離できないように相互に絡み
合った構造を有し、かつポリオルガノシロキサンゴム成
分とポリアルキル(メタ)アクリレートゴム成分との合
計量が100重量部である平均粒子径0.08〜0.6
μmの複合ゴムに1種又は2種以上のビニル系単量体が
グラフト重合されてなる複合ゴム系グラフト共重合体及
び
(D) リン酸エステル系難燃剤
を構成成分として含有するポリフェニレンエーテル樹脂
組成物である。That is, the present invention is based on (A) rt! Lifuenylene ether resin, (B)
Polystyrene resin, (C) polyorganosiloxane rubber component 10-90
Heavy lubricant and polyalkyl (meth)acrylate rubber component 1
0 to qo7Ir have a structure in which they are intertwined with each other so that they cannot be separated, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 100 parts by weight. 08-0.6
A composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers to a μm-sized composite rubber, and (D) a polyphenylene ether resin composition containing a phosphate ester flame retardant as a constituent component. It is a thing.
さらには、本発明は上記成分(A)、成分(B)、成分
(C)及びガラスF繊維及び炭素繊維からなる群から選
ばれる少なくとも一種の無機繊維の成分(E!1をそれ
ぞれ構成成分として含有するポリフェニレンエーテル繊
樹組成分ならびに上記成分(A)、成分(B)、成分(
C)、成分(D)及び成分(捕をそれぞれ構成成分とし
て含有するポリフェニレンエーテル樹脂組成物を含むも
のである。Furthermore, the present invention provides the above component (A), component (B), component (C), and at least one inorganic fiber component (E!1) selected from the group consisting of glass F fibers and carbon fibers, respectively. Containing polyphenylene ether fiber components and the above components (A), (B), and (
It contains a polyphenylene ether resin composition containing component (C), component (D), and component (c) as constituent components, respectively.
本発明におりて用すられるポリフェニレンエーテル樹脂
(A)とは下記の式
(式中GLI 、、、Q4は水素及び炭化水素基からな
る群からそれぞれ独立に選択され、mは3o以上の数を
示す。)
で表わされる単独重合体または共重合体である。The polyphenylene ether resin (A) used in the present invention has the following formula: ) is a homopolymer or copolymer represented by
かかるポリフェニレンエーテル樹脂の具体例としてはポ
リ(2,15−ジメチル−1,4−7二二レン)エーテ
ル、ポリ(2,6−シエチルー1.4−フェニレン)エ
ーテル、ポリ(2,6−シプロビルー1.4−フェニレ
ン)エーテル、ポリ(2−メチル−6−エチル−1,4
−)ユニしン)エーテル、ポリ(2−メチル−6−プロ
ピル−1゜4−)ユニしン)エーテル、ポリ(2−エチ
ル−6−ブロビルー1.4−フェニレン)エーテル、(
2,6−シメチルー1.4−フェニレン)エーテルと(
2,3,6−ドリメチルー1.4−フェニレン)エーテ
ルとの共重合体、(2,6−ジニチルー1゜4−)ユニ
しン)ニーテルト(2,& 6− ) +7メチルー1
.4−フェニレン)エーテルとの共重合体、(2,6−
シメチルー1.4−フェニレン)エーテルと(Z&6−
ドリエチルー1.4−フェニレン)エーテルとの共重合
体等が挙げられる。Specific examples of such polyphenylene ether resins include poly(2,15-dimethyl-1,4-7dinilene) ether, poly(2,6-ethyl-1,4-phenylene) ether, and poly(2,6-cyprobylene) ether. 1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4
-) unicine) ether, poly(2-methyl-6-propyl-1゜4-)unicine) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, (
2,6-dimethyl-1,4-phenylene)ether and (
Copolymer with 2,3,6-dolimethyl-1,4-phenylene)ether, (2,6-dinityl-1゜4-)unisine)nietelt(2,&6-)+7methyl-1
.. Copolymer with 4-phenylene) ether, (2,6-
dimethyl-1,4-phenylene)ether and (Z&6-
Examples include copolymers with dryethyl-1,4-phenylene) ether.
特にポリ(2,6−シメチルー1.4−フェニレン)エ
ーテル、及び(2,6−シメチルー1.4−)ユニしン
)エーテルと(2,&6−ドリメチルーt4−フェニレ
ン)エーテルとの共重合体が好ましく、さらに好ましく
はポリ(2,6−シメチルー1.4−フェニレン)エー
テルでアル。コレラボリフ二二レンエーテル樹脂はあら
ゆる配合比率でポリスチレン樹脂に対して相溶性を有す
る。In particular, poly(2,6-dimethyl-1,4-phenylene) ether and copolymers of (2,6-dimethyl-1,4-)unicine) ether and (2,&6-drimethyl-t4-phenylene) ether is preferred, and poly(2,6-dimethyl-1,4-phenylene)ether is more preferred. Collaborif 22lene ether resin is compatible with polystyrene resin at all blending ratios.
本発明において用いられるポリフェニレンエーテル樹脂
の重合度は特に制限されるものではないが、25℃クロ
ロホルム溶媒下での還元粘度がα3〜CL 7 dt/
fのものが好ましく用いられる。α5 dt/を未満の
還元粘度のものでは熱安定性が悪くなる傾向があり、又
[L7 dt/fを超える還元粘度のものでは成形性が
損なわれる傾向がある。これらのポリフェニレンエーテ
ル樹脂は単独で又は2種以上混合して用−られる。The degree of polymerization of the polyphenylene ether resin used in the present invention is not particularly limited, but the reduced viscosity at 25° C. in a chloroform solvent is α3 to CL 7 dt/
f is preferably used. Those with a reduced viscosity of less than α5 dt/f tend to have poor thermal stability, while those with a reduced viscosity of more than [L7 dt/f tend to impair moldability. These polyphenylene ether resins may be used alone or in combination of two or more.
又、本発明において用いられるポリスチレン樹脂CB)
とは下記の式
(式中Yは水素原子又は炭素原子数1〜4のアルキル基
、2はハロゲン原子又炭素原子数1〜4のアルキル基、
Lは0又は1〜3の数を示す。)
で表わされる芳香族ビニル系単量体単位50重84以上
から構成される単独重合体又は共重合可能な他のビニル
系単量体との共重合体である。Moreover, polystyrene resin CB) used in the present invention
is the following formula (where Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 2 is a halogen atom or an alkyl group having 1 to 4 carbon atoms,
L represents 0 or a number from 1 to 3. ) is a homopolymer composed of 50 to 84 or more aromatic vinyl monomer units, or a copolymer with other copolymerizable vinyl monomers.
かかるポリスチレン樹脂の具体例としてはボリアゝ
スチレン、ホリクロルスチレン、ポリブロムスチレン、
ポリα−メチルスチレン、スチレン−アクリロニトリル
共重合体、スチレン−メチルメタクリレート共重合体、
スチレン−無水マレイン酸共重合体、スチレン−マレイ
ミド共重合体、スチレン−N−フェニルマレイミド共重
合体、スチレン−アクリロニトリル−α−メチルスチレ
ン三元共重合体等が挙げられ、ポリスチレンが特に好ま
しbo
さらに本発明において用いられる複合ゴム系グラフト共
重合体(C)とは、ポリオルガノシロキサンゴム成分1
0〜90重量部とポリアルキル(メタ)アクリレートゴ
ム成分90〜10重量部(各ゴム成分の合計量が100
重量部)から構成され両ゴム成分が相互に絡み合一実質
上分離出来ない構造を有しかつその平均粒子径がα08
〜α6μmである複合ゴムに11種又は2種以上のビニ
ル系単量体がグラフト重合された共重合体である。Specific examples of such polystyrene resins include boriastyrene, polychlorstyrene, polybromstyrene,
Poly α-methylstyrene, styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer,
Examples include styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-α-methylstyrene ternary copolymer, and polystyrene is particularly preferred. Furthermore, the composite rubber-based graft copolymer (C) used in the present invention refers to the polyorganosiloxane rubber component 1.
0 to 90 parts by weight and 90 to 10 parts by weight of the polyalkyl (meth)acrylate rubber component (the total amount of each rubber component is 100 parts by weight)
(parts by weight), both rubber components are intertwined with each other and have a structure that is virtually inseparable, and the average particle size is α08.
It is a copolymer in which 11 types or 2 or more types of vinyl monomers are graft-polymerized on a composite rubber having a diameter of ~α6 μm.
上記複合ゴムの代わりにポリオルガノシロキサンゴム成
分及びポリアルキル(メタ)アクリレートゴム成分のい
ずれか1種類ある込はこれらの単純混合物をゴム源とし
て使用しても本発明の樹脂組成物の有する特徴は得られ
ず、ポリオルガノシロキサンゴム成分トポリアルキル(
メタ)アクリレートゴム成分が相互に絡み合−複合一体
化されてはじめて優れた耐衝撃性と成形表面外観とを有
する成形物を与える樹脂組成物を得ることができる。Even if one of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component, or a simple mixture thereof, is used as a rubber source in place of the above-mentioned composite rubber, the characteristics of the resin composition of the present invention remain unchanged. Polyorganosiloxane rubber component topolyalkyl (
Only when the meth)acrylate rubber components are intertwined with each other and integrated into a composite body can a resin composition that provides a molded article with excellent impact resistance and molded surface appearance be obtained.
マタ複合ゴムを構成するポリオルガノシロキサンゴム成
分が90重量部を超えると、得られる樹脂組成物からの
成形物の成形表面外観が悪化し、又ポリアルキル(メタ
)アクリレートゴム成分が90重i4を超えると、得ら
れる樹脂組成物からの成形物の耐衝撃性が悪化する。こ
のため、複合ゴムを構成する2種のゴム成分はいずれも
10〜90重81(ただし、両ゴム成分の合計(i)J
−i100重84)の範囲であることが必要であり、さ
らに20〜80重Fk4の範囲であることが特に好まし
い。上記複合°ゴムの平均粒子径II″1108〜α6
μmの範囲にあることが必要である。平均粒子径がQ、
08μm未満になると得られる樹脂組成物からの成形物
の耐衝撃性が悪化し、又平均粒子径が[16μmを超え
ると得られる樹脂組成物からの成形物の耐衝撃性が悪化
すると共に、成形表面外観が悪化する。If the polyorganosiloxane rubber component constituting the mata composite rubber exceeds 90 parts by weight, the molded surface appearance of the molded product from the resulting resin composition will deteriorate, and the polyalkyl (meth)acrylate rubber component will exceed 90 parts by weight. If it exceeds this, the impact resistance of the molded product obtained from the resin composition will deteriorate. Therefore, the two rubber components constituting the composite rubber both have a weight of 10 to 90%81 (however, the total weight of both rubber components (i) J
-i 100 weight 84) is required, and it is particularly preferably in the range of 20 to 80 weight Fk4. Average particle diameter of the above composite ° rubber II''1108~α6
It is necessary to be in the μm range. The average particle diameter is Q,
If the average particle diameter is less than 0.8 μm, the impact resistance of the molded product obtained from the resin composition will deteriorate, and if the average particle size exceeds 16 μm, the impact resistance of the molded product obtained from the resin composition will deteriorate, and The surface appearance deteriorates.
この様な平均粒子径を有する複合ゴノ・を製造するには
乳化重合法が最適であり、まずポリオルガノシロキサン
ゴムのラテックスを調製t、、次にアルキル(メタ)ア
クリレートゴムの合成用単量体をポリオルガノシロキサ
ンゴムラテックスのゴム粒子に含浸させてから前記合成
用単量体を重合するのが好ましい。Emulsion polymerization is the most suitable method for producing composite rubber having such an average particle size. First, a latex of polyorganosiloxane rubber is prepared, and then a monomer for synthesis of alkyl (meth)acrylate rubber is prepared. Preferably, the body is impregnated with rubber particles of polyorganosiloxane rubber latex before polymerization of the synthetic monomer.
上記複合ゴムを構成するポリオルガノシロキサンゴム成
分は、以下に示すオルガノシロキサン及び架橋剤(I)
を用すて乳化重合によプ調製することかでき、その際、
さらにグラフト交叉剤(I)を併用することもできる。The polyorganosiloxane rubber components constituting the above composite rubber include the organosiloxane and crosslinking agent (I) shown below.
It can be prepared by emulsion polymerization using
Furthermore, a grafting agent (I) can also be used in combination.
オルガノシロキサンとしては、3員環以上の各種の環状
体が挙げられ、好ましく用いられるのは3〜6員環であ
る。例えばヘキサメチルシクロトリシロキサン、オクタ
メチルシクロテトランロキサン、デカメチルシクロペン
タシロキサン、ドデカメチルシクロヘキサシロキサン、
トリメチルトリフェニルシクロトリシロキサン、テトラ
メチルテトラフェニルシクロテトラシロキサン、オクタ
フェニルシクロテトラシロキサン等が挙げられ、これら
は単独で又は2種以上混合して用いられる。これらの使
用量はポリオルガノシロキサンゴム成分中50重量部以
上、好ましくは70重量J4以上である。The organosiloxane includes various cyclic bodies having 3 or more membered rings, and 3- to 6-membered rings are preferably used. For example, hexamethylcyclotrisiloxane, octamethylcyclotetranoxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane, which may be used alone or in combination of two or more. The amount of these used is 50 parts by weight or more, preferably 70 parts by weight or more in the polyorganosiloxane rubber component.
架橋剤(I)としては、5官能性又Fi4官能性のシラ
ン糸架橋剤、例えばトリメトキクメチルシラン、トリエ
トキシフェニルシラン、テトラエトキシシラン、テトラ
エトキシシラン、テトラ−n−プロポキシシラン、テト
ラブトキシシラン等が用すられる。特に4官能性の架橋
剤が好ましく、この中でもテトラエトキシシランが特に
好ましい。架橋剤の使用量はボリオルガノンロキサンゴ
ム成分中α1〜30重量%である。As the crosslinking agent (I), a penta-functional or Fi4-functional silane thread crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane can be used. etc. are used. Particularly preferred are tetrafunctional crosslinking agents, and among these, tetraethoxysilane is particularly preferred. The amount of the crosslinking agent used is α1 to 30% by weight in the polyorganone loxane rubber component.
グラフト交叉剤(I)としては、次式
0式%)
(各式中R1はメチル基、エチル基、プロピル基又はフ
ェニル基 Hlは水素原子又はメチル基、nは0.1又
は2、pは1〜6の数を示す。)で表わされる単位を形
成し得る化合物等が用いられる。式(I−1)の単位を
形成し得る(メタ)アクリロイルオキシシロキサンはグ
ラフト効率が高いため有効なグラフト鎖を形成すること
が可能であり耐衝撃性発現の点で有利である。The graft crossover agent (I) is the following formula 0%) (In each formula, R1 is a methyl group, ethyl group, propyl group, or phenyl group, H1 is a hydrogen atom or a methyl group, n is 0.1 or 2, and p is A compound or the like that can form a unit represented by (indicates a number from 1 to 6) is used. (Meth)acryloyloxysiloxane that can form the unit of formula (I-1) has a high grafting efficiency, so it is possible to form an effective graft chain and is advantageous in terms of impact resistance.
なお式(li)の単位を形成し得る本のとしてメタクリ
ロイルオキシシロキサンが特に好ましい。メタクリロイ
ルオキシシロキサンの具体例としてはβ−メタクリロイ
ルオキシエチルジメトキクメチルシラン、r−メタクリ
ロイルオキシプロピルメトキy9メチルシラン、γ−メ
タクリロイルオキシプロピルジメトキシメチルyラン、
γ−メタクリロイルオキシプロピルトリメトキシシラン
、γ−メタクリロイルオキシプロピルエトキシジエチル
シラン、γ−メタクリロイルオキシプロピルジェトキシ
メチルシラン、δ−メタクリロイルオキシブチルジエト
キVメチルシラン等が挙げられる。クラフト交叉剤の使
用量はポリオルガノシロキサンゴム成分中D〜10重量
部でちる。Note that methacryloyloxysiloxane is particularly preferred as a unit capable of forming the unit of formula (li). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, r-methacryloyloxypropylmethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylyran,
Examples include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyljethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, and the like. The amount of the kraft cross-agent used is D to 10 parts by weight in the polyorganosiloxane rubber component.
このポリオルガノシロキサンゴム成分のラテックスの製
造は、例えば米国特許第2891920号明細書、同第
3294725号明細書等に記載された方法を用するこ
とかできる。本発明の実施では、例えば、オルガノシロ
キサンと架橋剤(I)及び所望によりグラフト交叉剤(
I)の混合溶液とを、アルキルベンゼンスルホン酸、ア
ルキルスルホン酸等のスルホン酸系乳化剤の存在下で、
例えばホモジナイザー等を用いて水と剪断混合する方法
により製造することが好ましb0アルキルベンゼンスル
ホン酸ハオルガノシロキサンの乳化剤として作用すると
同時に重合開始剤ともなるので好適である。この際、ア
ルキルベンゼンスルホン酸金属塩、アルキルスルホン酸
金属塩等を併用するとグラフト重合を行う際にポリマー
を安定に維持するのに効果があるので好ましい。The latex of this polyorganosiloxane rubber component can be produced using, for example, the methods described in US Pat. No. 2,891,920 and US Pat. No. 3,294,725. In the practice of the present invention, for example, an organosiloxane and a crosslinking agent (I) and optionally a grafting agent (
I) in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid,
For example, it is preferably produced by a method of shear mixing with water using a homogenizer or the like, since it acts as an emulsifier for the b0 alkylbenzenesulfonic acid haorganosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use an alkylbenzenesulfonic acid metal salt, an alkylsulfonic acid metal salt, or the like in combination, since this is effective in maintaining the polymer stably during graft polymerization.
次に上記複合ゴムを構成するポリアルキル(メタ)アク
リレートゴム成分は以下に示すアルキル(メタ)アクリ
レート、架橋剤(II)及びグラフト交叉剤(n)を用
いて合成することができる。Next, the polyalkyl (meth)acrylate rubber component constituting the composite rubber can be synthesized using the alkyl (meth)acrylate, crosslinking agent (II), and grafting agent (n) shown below.
アルキル(メタ)アクリレートとしては、例えばメチル
アクリレート、エチルアクリレート、n−プロピルアク
リレート、n−ブチルアクリレート、2−エチルへキシ
ルアクリレート等のフルキルアクリレート及びヘキシル
メタクリレート、2−エチルへキシルメタクリレート、
n−ラウリルメタクリレート等のアルキルメタクリレー
トが挙げられ、特にn−ブチルアクリレートの使用が好
ましい。Examples of alkyl (meth)acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and other fulkyl acrylates, hexyl methacrylate, 2-ethylhexyl methacrylate,
Alkyl methacrylates such as n-lauryl methacrylate can be mentioned, with n-butyl acrylate being particularly preferred.
架橋剤(…)としては、例えばエチレングリコールジメ
タクリレート、プロピレングリコールジメタクリレート
、1.3−ブチレングリコールジメタクリレート、1.
4−ブチレングリコールジメタクリレート等が挙げられ
る。Examples of the crosslinking agent (...) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1.3-butylene glycol dimethacrylate, 1.
Examples include 4-butylene glycol dimethacrylate.
グラフト交叉剤(I0としては、例えばアリルメタクリ
レート、トリアリルシアヌレート、トリアリルイソシア
ヌレート等が挙げられる。アリルメタクリレートは架橋
剤として用いることもできる。これら架橋剤並びにグラ
フト交叉剤は単独又は2種以上併用して用いられる。こ
れら架橋剤及びグラフト交叉剤の合計の使用量はポリア
ルキル(メタ)アクリレートゴム成分中0.1〜20重
−に%である。Graft cross-linking agents (I0 include, for example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, etc. Allyl methacrylate can also be used as a cross-linking agent. These cross-linking agents and graft cross-agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and grafting agents used is 0.1 to 20% by weight in the polyalkyl (meth)acrylate rubber component.
ポリアルキル(メタ)アクリレートゴム成分の重合は、
水酸化ナトリウム、水酸化カリウム、炭酸す) +3ウ
ム等のアルカリの水溶液の添加により中和されたポリオ
ルガノシロキサンゴム成分のラテックス中へ上記アルキ
ル(メタ)アクリレート、架橋剤及びグラフト交叉剤を
添加し、ポリオルガノシロキサンゴム粒子へ含浸すせた
のち、通常のラジカル重合開始剤を作用させて行う。重
合の進行と共にポリオルガノシロキサンゴムの架橋網目
に相互に絡んだポリアルキル(メタ)アクリレートゴム
の架橋網目が形成され、実質上分離できないポリオルガ
ノシロキサンゴム成分とポリアルキル(メタ)アクリレ
ートゴム成分との複合ゴムのラテックスが得られる。な
お本発明の実施に際してはこの複合ゴムとしてポリオル
ガノシロキサンゴム成分の主骨格がジメチルシロキサン
の繰り返し単位を有し、ポリアルキル(メタ)アクリレ
ートゴム成分の主骨格がn−ブチルアクリレートの繰り
返し単位を有する複合ゴムが好ましく用すられる。The polymerization of the polyalkyl (meth)acrylate rubber component is
The above alkyl (meth)acrylate, crosslinking agent and grafting agent are added to the latex of the polyorganosiloxane rubber component which has been neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, carbonate, etc. After impregnating polyorganosiloxane rubber particles, a conventional radical polymerization initiator is applied. As the polymerization progresses, a crosslinked network of polyalkyl (meth)acrylate rubber is formed that is intertwined with the crosslinked network of polyorganosiloxane rubber, and the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are virtually inseparable. A composite rubber latex is obtained. In carrying out the present invention, this composite rubber is used in which the main skeleton of the polyorganosiloxane rubber component has repeating units of dimethylsiloxane, and the main skeleton of the polyalkyl (meth)acrylate rubber component has repeating units of n-butyl acrylate. Composite rubber is preferably used.
このようにして乳化重合により調製された複合ゴムは、
ビニル系単量体とグラフト共重合可能でアリ、又ポリオ
ルガノシロキサンゴム成分とポリアルキル(メタ)アク
リレートゴム成分とけ強固に絡み合っているためアセト
ン、トルエン等の通常の有機溶剤では抽出分離出来ない
。The composite rubber thus prepared by emulsion polymerization is
It can be graft copolymerized with vinyl monomers, and since the polyorganosiloxane rubber component and polyalkyl (meth)acrylate rubber component are tightly intertwined, they cannot be extracted and separated using ordinary organic solvents such as acetone and toluene.
この複合ゴムをトルエンにより90℃で12時間抽出し
て測定したゲル含量は80重−f41以上である。The gel content measured by extracting this composite rubber with toluene at 90° C. for 12 hours is 80 weight-f41 or more.
この複合ゴムにグラフト重合させるビニル系単1体とし
ては、スチレン、α−メチルスチレン、ビニルトルエン
等の芳香族アルケニル化合物;メチルメタクリレート、
2−エチルへキシルメタクリレート等のメタクリル酸エ
ステル;メチルアクリレート、エチルアクリレート、ブ
チルアクリレート等のアクリル酸エステル;アクリロニ
トリル、メタクリレートリル等のシアン化ビニル化合物
等の各種のビニル系単量体が挙げられ、これらは単独で
又は2種以上組合せて用いられる。これらビニル系単量
体のうち芳香族アルケニル化合物及びメタクリル酸エス
テルが好ましく、スチレン及びメチルメタクリレ−トが
特に好ましい。Examples of vinyl compounds to be graft-polymerized to this composite rubber include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyltoluene; methyl methacrylate;
Examples include various vinyl monomers such as methacrylic acid esters such as 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylaterile; may be used alone or in combination of two or more. Among these vinyl monomers, aromatic alkenyl compounds and methacrylic acid esters are preferred, and styrene and methyl methacrylate are particularly preferred.
複合ゴム系グラフト共重合体(C)における上記複合ゴ
ムと上記ビニル系単量体の割合は、このグラフト共重合
体(C)の重量を基準にして複合ゴム30〜95重量%
、好ましくは40〜90重量憾及び全幅ル系単量体5〜
70′M量憾、好ましくは10〜60重+Xl−係が好
ましい。ビニル系単量体が5重量壬未満では樹脂組成物
中でのグラフト共重合体(C)の分散が充分でなく、又
、70重i%を超えると衝撃強度発現性が低下するので
好ましくなり0
複合ゴム系グラフト共重合体(C)は、上記ビニル系単
量体を複合ゴムのラテックスに加えラジカル重合技術に
よって一段であるじは多段で重合させて得られる複合ゴ
ム系グラフト共重合体ラテックスを、塩化カルシウム又
は硫酸マグネシウム等の金属塩を溶解した熱水中に投入
し、塩析、凝固することにより分離、回収することがで
きる。The ratio of the composite rubber and the vinyl monomer in the composite rubber graft copolymer (C) is 30 to 95% by weight of the composite rubber based on the weight of the graft copolymer (C).
, preferably 40 to 90% by weight and full width monomer 5 to 90%
The amount is preferably 70'M, preferably 10 to 60 weight + Xl. If the vinyl monomer content is less than 5 weight %, the graft copolymer (C) will not be sufficiently dispersed in the resin composition, and if it exceeds 70 weight i%, impact strength development will decrease, so this is not preferred. 0 Composite rubber-based graft copolymer (C) is a composite rubber-based graft copolymer latex obtained by adding the above-mentioned vinyl monomer to composite rubber latex and polymerizing it in one step or in multiple stages using radical polymerization technology. It can be separated and recovered by pouring it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, and salting out and coagulating it.
本発明における樹脂配合物におりてポリフェニレンエー
テル樹脂(A)(以下、成分(A)と称する)ボリスチ
レ/樹脂(B)(以下、成分(B)と称する)及び複合
ゴム系グラフト共重合体(C)(以下成分(Cと称する
)は広い範囲の割合で組合わせることができる。なお本
発明における樹脂配合物は全樹脂配合物の重量を基準に
して、成分(A)が20〜80重を優、成分(I3)が
19〜75重を優及び成分(C)が1〜40重!4重量
るように構成されるのが好ましい。The resin composition of the present invention contains a polyphenylene ether resin (A) (hereinafter referred to as component (A)), a polystyrene/resin (B) (hereinafter referred to as component (B)), and a composite rubber-based graft copolymer (hereinafter referred to as component (B)). C) (hereinafter referred to as component (C)) can be combined in a wide range of proportions.The resin formulation in the present invention contains 20 to 80 parts by weight of component (A) based on the weight of the entire resin formulation. It is preferable that component (I3) weighs 19 to 75 weights, and component (C) weighs 1 to 40 weights!4.
成分(元が20重量部未満では耐熱性の付与が充分でな
り傾向があり、又、80重を係を超える場合には流動特
性が悪くなる傾向があり成形性が低下する傾向がある。If the weight of the component is less than 20 parts by weight, heat resistance tends to be insufficient, and if it exceeds 80 parts by weight, the flow characteristics tend to deteriorate and moldability tends to deteriorate.
又、成分(B)が19重量嗟未満では成形性と耐熱性と
のバランスをとることが困難となる傾向がおり、又、7
5yx量憾を超える場合には耐衝撃性と耐熱性とのバラ
ンスをとることが困難となる傾向がある。さらに、成分
<C)が1重量4未満では耐衝撃性能改善効果が不充分
となる傾向があり、又、40重量部を超えると複合ゴム
の含量が高くなり機械的強度が低下する傾向があり使用
に耐えにくくなる。In addition, if component (B) is less than 19 kg by weight, it tends to be difficult to balance moldability and heat resistance;
When the amount exceeds 5yx, it tends to be difficult to maintain a balance between impact resistance and heat resistance. Furthermore, if component <C) is less than 1 part by weight, the impact resistance performance improvement effect tends to be insufficient, and if it exceeds 40 parts by weight, the content of composite rubber tends to increase and mechanical strength tends to decrease. It becomes difficult to withstand use.
本発明における樹脂配合物自体は、耐熱性、耐衝撃性、
特に低温下での耐衝撃性に優れた成形物を与え、しかも
流動性にも優れ、又、上記成分(A)と成分(B)の配
合比率を変えることにより耐熱性のレベルを超耐熱樹脂
から通常の耐熱性樹脂の水準まで自由知設計することが
できる。The resin compound itself in the present invention has heat resistance, impact resistance,
A super heat-resistant resin that provides molded products with excellent impact resistance especially at low temperatures, and also has excellent fluidity, and by changing the blending ratio of component (A) and component (B), the level of heat resistance can be adjusted. It is possible to design freely up to the level of ordinary heat-resistant resin.
本発明においては上記成分(A)〜(C)を構成成分と
して含有する樹脂配合物に難燃性を与え得る量の難燃剤
を配合することによりUL−94燃焼試験に適合し得る
難燃性の樹脂組成物とすることができる。かかる難燃剤
の具体例としてはトリメチルホスフェート、トリエチル
ホスフェート、トリプロピルホスフェート、トリフチル
ホスフェート、トリベンジルホスフェート、トリへキシ
ルホスフェート、トリフェニルホスフェート、トリクレ
ジルホスフェート、トリキシリルホスフェート、トリス
(クロロエチル)ホスフェート、トリス(クロロフェニ
ル)ホスフェート、トリス(ジブロモプロピル)ホスフ
ェート等のリン酸エステル系難燃剤が挙げられ、これら
は単独でまたは組合せて用いられ、トリフェニルホスフ
ェートが特に好ましいものである。本発明の実施忙際し
ては上記リン酸エステル系)l ffi 剤と一諸にデ
カブロモビフェニルエーテル、臭素化エポキシ化合物、
臭素化ポリスチレン等を併用することは好ましいことで
ある。In the present invention, by blending a flame retardant in an amount capable of imparting flame retardance to a resin compound containing the above-mentioned components (A) to (C) as constituent components, flame retardance that can meet the UL-94 flame test is achieved. It can be made into a resin composition of. Specific examples of such flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphthyl phosphate, tribenzyl phosphate, trihexyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, tris(chloroethyl) phosphate, Phosphate ester flame retardants such as tris(chlorophenyl) phosphate and tris(dibromopropyl) phosphate may be mentioned, and these may be used alone or in combination, with triphenyl phosphate being particularly preferred. When carrying out the present invention, decabromo biphenyl ether, brominated epoxy compounds,
It is preferable to use brominated polystyrene or the like in combination.
特に臭素化ポリスチレンを併用することは好ましいこと
である。In particular, it is preferable to use brominated polystyrene in combination.
リン酸エステル系難燃剤の使用量は難燃剤の種類、成分
(に〜(C)の組成割合等により異なるが成分(A)〜
(C)からなる樹脂配合物100重量部に対して15〜
35重量部の範囲であることが好ましい。The amount of phosphate ester flame retardant used varies depending on the type of flame retardant, the composition ratio of the components (from component (A) to (C), etc.)
15 to 100 parts by weight of the resin compound consisting of (C)
A range of 35 parts by weight is preferred.
難燃性の樹脂組成物としては、成分(A)が20〜80
重量憾、成全幅B)が19〜75重量幅、成分(C)が
1〜40重量壬からなる樹脂配合物100重量部に上記
難燃剤が0.5〜35重量部配合してなるものが好まし
い。As a flame-retardant resin composition, component (A) is 20 to 80%
The flame retardant is blended with 0.5 to 35 parts by weight to 100 parts by weight of a resin compound having a weight range of 19 to 75 parts by weight and a complete width B) of 1 to 40 parts by weight of component (C). preferable.
さらに本発明におりては上記成分(A)〜(C)を構成
成分として含有する樹脂配合物にガラス繊維及び炭素繊
維からなる群から選ばれる少なくとも一種の無機繊維を
配合することにより強度補強効果を示す樹脂組成物とす
ることができると同時に樹脂組成物の線膨張係数を大巾
に低下させることができる。ガラス繊維は5〜50μm
の直径を有し、繊維長江2W以上のものが好ましい。さ
らにガラス繊維を配合するときに使用される表面処理剤
としてはアミノシラン、ビニルシラン、エポキシシラン
、その他シラン系処理剤、クロム系処理剤等を使用する
ことが好ましい。ガラス繊維の集束剤としてはポリエス
テル系、エポキシ系、ウレタン系、アクリルウレタン系
、エチレン−酢酸ビニル系等が挙げられる。又、炭素繊
維はポリアクリロニトリル系及びピッチ系等のものが使
用することができ、3〜30μmの直径を有し、繊維長
50μm以上のものが好ましい。これらガラス繊維及び
炭素maは単独で又は2種以上組合せてm−ることがで
きる。Furthermore, in the present invention, the strength reinforcing effect is achieved by blending at least one type of inorganic fiber selected from the group consisting of glass fiber and carbon fiber into the resin compound containing the above components (A) to (C) as constituent components. At the same time, the linear expansion coefficient of the resin composition can be significantly lowered. Glass fiber is 5-50μm
It is preferable that the fiber has a diameter of 2W or more. Furthermore, as the surface treatment agent used when blending glass fibers, it is preferable to use aminosilane, vinylsilane, epoxysilane, other silane type treatment agents, chromium type treatment agents, etc. Examples of the glass fiber sizing agent include polyester, epoxy, urethane, acrylic urethane, and ethylene-vinyl acetate. In addition, carbon fibers such as polyacrylonitrile type and pitch type can be used, and those having a diameter of 3 to 30 μm and a fiber length of 50 μm or more are preferable. These glass fibers and carbon ma can be used alone or in combination of two or more.
ガラス繊維及び炭素繊維から選ばれる無機繊維の使用量
は成分(A)〜(C)からなる樹脂配合物100重量部
に対して5〜100重景部、重量しくi!10〜70重
量部である。無機繊維の使用量が5重量部未満では樹脂
組成物に強度補強効果を与えることが困難であり、又、
100重量部を超えると本発明の特徴を示すことが困難
である。The amount of inorganic fibers selected from glass fibers and carbon fibers used is 5 to 100 parts by weight, based on 100 parts by weight of the resin compound consisting of components (A) to (C). It is 10 to 70 parts by weight. If the amount of inorganic fiber used is less than 5 parts by weight, it is difficult to impart a strength reinforcing effect to the resin composition;
If it exceeds 100 parts by weight, it will be difficult to exhibit the characteristics of the present invention.
強度補強効果を与える樹脂組成物としては、成分(A)
が20〜800〜80重量部B)が19〜759〜75
重量部c3が1〜40重量優からなる樹脂配合物100
重量部に上記少なくとも一種の無機繊維が5〜100重
量部配重量部外るものが好ましbo
さらに又、本発明においては上記成分(A)〜(C)を
構成成分として含有する樹脂配合物に上記リン酸エステ
ル系難燃剤と上記少なくとも一種の無機繊維を併用して
配合することによりUL−94燃焼試験に適合し得る難
燃性と強度補強効果を有する樹脂組成物とすることがで
きる。この場合のリン酸エステル系難燃剤及び少なくと
も一種の無機繊維の使用量は成分(A)〜(C)からな
る樹脂配合物100重量部に対してリン酸エステル系難
燃剤が15〜35重量部及び少々くとも一種の無機繊維
が5〜100重量部であることが好ましい。As a resin composition that provides a strength reinforcing effect, component (A)
is 20-800-80 parts by weight B) is 19-759-75
Resin blend 100 consisting of weight part c3 of 1 to 40 weight
Preferably, the above-mentioned at least one type of inorganic fiber is contained in 5 to 100 parts by weight.Furthermore, in the present invention, a resin compound containing the above-mentioned components (A) to (C) as constituent components is preferably used. By blending the above-mentioned phosphate ester flame retardant and at least one kind of inorganic fiber together, a resin composition can be obtained which has flame retardancy and strength reinforcing effect that can meet the UL-94 combustion test. In this case, the amount of the phosphate ester flame retardant and at least one inorganic fiber used is 15 to 35 parts by weight based on 100 parts by weight of the resin compound consisting of components (A) to (C). Preferably, the amount of at least one type of inorganic fiber is 5 to 100 parts by weight.
本発明の樹脂組成物を調製する方法としては成分(A)
〜(C)と難燃剤(D)及び/又は無機繊維(D)をバ
ンバリーミキサ−ロールミル、二軸押出機等の公知の装
置を用い機械的に混合しベレット状に賦形すればよい。As a method for preparing the resin composition of the present invention, component (A)
(C), the flame retardant (D) and/or the inorganic fiber (D) may be mechanically mixed using a known device such as a Banbury mixer roll mill or a twin screw extruder, and then shaped into a pellet.
さらに本発明の樹脂組成物には必要に応じて安定剤、可
塑剤、滑剤、顔料、充填剤等を配合し得る。具体的には
トリフェニルホスファイト等の安定剤;ポリエチレンワ
ックス、ポリプロピレンワックス等の滑剤;酸化チタン
、硫化亜鉛、酸化亜鉛等の顔料;アスベスト、ウオラス
トナイト、マイカ、タルク等の充填剤等が挙げられる。Furthermore, stabilizers, plasticizers, lubricants, pigments, fillers, etc. may be added to the resin composition of the present invention, if necessary. Specifically, stabilizers such as triphenyl phosphite; lubricants such as polyethylene wax and polypropylene wax; pigments such as titanium oxide, zinc sulfide, and zinc oxide; fillers such as asbestos, wollastonite, mica, and talc. It will be done.
以下本実施例により本発明を具体的に説明する。以下の
記載において「部」とあるのけすべて重量部を意味する
。The present invention will be specifically explained below with reference to Examples. In the following description, all "parts" mean parts by weight.
なお各実施例、比較例での諸物性の測定法は次の方法だ
よる。The various physical properties in each Example and Comparative Example were measured using the following methods.
曲げ強度: ASTM D790の方法による。Bending strength: According to the method of ASTM D790.
アイゾツト衝撃強度: As’I’M D256の方法による。Izotsu impact strength: According to the method of As'I'M D256.
(I/4“ ノツチ付) ビカー軟化温度: 1130 R306の方法による。(I/4" with notch) Vicat softening temperature: 1130 According to the method of R306.
メルトインデックス: ASTM D1238の方法に準拠した方法による。Melt index: By a method based on ASTM D1238 method.
(5kgの荷重下275℃での測定値)燃焼性: UL−94試験法による。(Measured value at 275℃ under 5kg load) Flammability: According to UL-94 test method.
線膨張率: ASTM D−696の方法に準拠した方法による。Linear expansion coefficient: By a method based on ASTM D-696 method.
参考例1
複合ゴム系グラフト共重合体(s−1)の製造:テトラ
エトキシシラン2部、r−メタクリロイルオキシプロピ
ルジメトキシメチルシラン15部及びオクタメチルシク
ロテトラシロキサン97.5部を混合し、シロキサン混
合物100部ヲ得た。ドデシルベンゼンスルホン酸ナト
リウム及びドデシルベンゼンスルホン酸をそhぞれ1部
を溶解した蒸留水200部に上記混合クロキサン100
部を加え、ホモミキサーにて10、 OOOrpmで予
備攪拌した後、ホモジナイザーにより500 kg/1
yn2の圧力で乳化、分散させ、オルガノシロキサンラ
テックスを得た。この混合液を、コンデンサー及び攪拌
翼を備えたセパラブルフラスコに移し、攪拌混合しなが
ら80℃で5時間加熱した後20℃で放置し、48時間
後に水酸化ナトリウム水溶液でこのラテックスのpHt
−&?に中和し、重合を完結しポリオルガノシロキサン
ゴムラテックス−1を得た。Reference Example 1 Production of composite rubber-based graft copolymer (s-1): 2 parts of tetraethoxysilane, 15 parts of r-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to form a siloxane mixture. I got 100 copies. 100 parts of the above mixed cloxane was added to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid were dissolved.
After pre-stirring with a homogenizer at 1000 rpm, 500 kg/1 with a homogenizer.
The mixture was emulsified and dispersed at a pressure of yn2 to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80°C for 5 hours while stirring and mixed, and then left at 20°C.After 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution.
-&? The polymerization was completed and polyorganosiloxane rubber latex-1 was obtained.
得られたポリオルガノシロキサンゴムの重合率Ir!
a q、 y 4であり、ポリオルガノシロキサンゴム
の平均粒子径は116μmであった。Polymerization rate Ir of the obtained polyorganosiloxane rubber!
a q and y 4, and the average particle diameter of the polyorganosiloxane rubber was 116 μm.
上記ポリオルガノシロキサンゴムラテックス−1を11
7部採取し、攪拌器を備えたセパラブルフラスコに入れ
、蒸留水57.5部を加え、窒素置換をしてから50℃
に昇温し、n−ブチルアクリレート3五95部、アリル
メタクリレ−) 1.05部及びtert−ブチルヒド
ロペルオキシド(I26部の混合液を仕込み30分間攪
拌し、この混合液をポリオルガノシロキサンゴム粒子に
浸透させた。次すで、硫酸第1鉄Q、002部、エチレ
ンジアミン四酢酸二ナトリウム塩α006部、ロンガリ
ット(lk26部及び蒸留水5部の混合液を仕込みラジ
カル重合を開始させ、その後内温70Cで2時間保持し
重合を完了して複合ゴムラテックスを得た。このラテッ
クスを一部採取し、複合ゴムの平均粒子径を測定したと
ころα19μmであった。又、このラテックスを乾燥し
固形物を得、トルエンで90℃、12時間抽出し、ゲル
含量を測定したところ97.5重量優であった。この複
合ゴムラテックスに、tart−ブチルヒドロペルオキ
シド0.12部とスチレン30部との混合液を70℃に
て15分間にわたり滴下し、その後70℃で4時間保持
し、複合ゴムへのグラフト重合を完了した。スチレンの
重合率は9 t 54であった。得られたグラフト共重
合体ラテックスを塩化カルシウム1.5重量優の熱水2
00部中に滴下し、凝固、分離し洗浄したのち75℃で
16時間乾燥し、複合ゴム系グラフト共重合体(以下、
S−1と称する)の乾粉を918部得九0
参考例2
参考例1で得た複合ゴムラテックス264部を攪拌器を
備えたセパラブルフラスコに入れ、窒素置換をしたのち
60Cに昇温し、その後メチルメタクリレート30部、
クメンヒドロペルオキシド[108部の混合液を1時間
にわたって滴下し、ラテックス温度を60℃に2時間維
持したのち重合を完結した。メチルメタクリレートの重
合率は9aO%であった。得られたグラフト共重合体ラ
テックスを塩化カルシウム1,5重量優の熱水200部
中処適下し、凝固、分離し洗浄したのち80℃で16時
間乾燥し、複合ゴムグラフト共重合体(以下、S−2と
称する)の乾粉を9部2部得た。11 of the above polyorganosiloxane rubber latex-1
Collect 7 parts, put in a separable flask equipped with a stirrer, add 57.5 parts of distilled water, replace with nitrogen, and heat at 50°C.
A mixture of 3595 parts of n-butyl acrylate, 1.05 parts of allyl methacrylate and 26 parts of tert-butyl hydroperoxide (I) was charged and stirred for 30 minutes. Next, a mixture of 002 parts of ferrous sulfate Q, 006 parts of ethylenediaminetetraacetic acid disodium salt α, 26 parts of Rongalit (lk) and 5 parts of distilled water was charged to start radical polymerization, and then the internal The polymerization was completed by holding at a temperature of 70C for 2 hours to obtain a composite rubber latex.A portion of this latex was sampled and the average particle size of the composite rubber was measured and found to be α19μm.Also, this latex was dried to form a solid The product was extracted with toluene at 90°C for 12 hours, and the gel content was measured to be 97.5% by weight.To this composite rubber latex, 0.12 parts of tart-butyl hydroperoxide and 30 parts of styrene were added. The mixed solution was added dropwise at 70°C for 15 minutes, and then maintained at 70°C for 4 hours to complete the graft polymerization to the composite rubber.The polymerization rate of styrene was 9t54.The resulting graft copolymerization Mix the combined latex with hot water containing 1.5% calcium chloride (2)
00 parts, solidified, separated, washed, and dried at 75°C for 16 hours to form a composite rubber-based graft copolymer (hereinafter referred to as
Reference Example 2 264 parts of the composite rubber latex obtained in Reference Example 1 was placed in a separable flask equipped with a stirrer, and after purging with nitrogen, the temperature was raised to 60C. , then 30 parts of methyl methacrylate,
A mixture of 108 parts of cumene hydroperoxide was added dropwise over 1 hour, and the latex temperature was maintained at 60° C. for 2 hours to complete the polymerization. The polymerization rate of methyl methacrylate was 9aO%. The obtained graft copolymer latex was poured into 200 parts of hot water containing 1.5% calcium chloride by weight, coagulated, separated, washed, and then dried at 80°C for 16 hours to form a composite rubber graft copolymer (hereinafter referred to as , referred to as S-2) was obtained in 9 parts and 2 parts.
実施例1〜4
参考例1及び2で得た複合ゴム系グラフト共重合体El
−1及びS−2を使用した難燃性ボリフエニレ/エーテ
ル樹脂組成物を次のように製造した。すなわち、複合ゴ
ム系グラフト共重合体E+−1及びS−2がそれぞれ8
4重量%、ポリ(2,6−シメチルー1.4−フェニレ
ン)エーテルが5瓜8重−in及び200℃荷t5ki
9でのメルトインデックスが51710分のポリスチレ
ン力2q、 sft、t%及ヒ) IJフェニルホスフ
ェートが5.5重i%となるようにそれぞれを配合して
2種類の樹脂組成物を調製した(実施例1〜2)。Examples 1 to 4 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Flame-retardant polyphenylene/ether resin compositions using -1 and S-2 were produced as follows. That is, the composite rubber graft copolymers E+-1 and S-2 each have 8
4% by weight, poly(2,6-dimethyl-1,4-phenylene) ether in 5 8-in and 200°C load t5ki
Polystyrene strength 2q, sft, t% and IJ phenyl phosphate having a melt index of 51,710 minutes at 9 was mixed to prepare two types of resin compositions. Examples 1-2).
さらに、複合ゴム系グラフト共重合体S−1及びE3−
2がそれぞれ8重量幅、上記ポリ(2゜6−シメチルー
1.4−フェニレン)エーテルが60@34、ポリスチ
レンが222重量%びトリフェニルホスフェートが10
重量嗟となるようにそれぞれを配合して2種類の樹脂組
成物を調製した(実施例3〜4)。Furthermore, composite rubber-based graft copolymers S-1 and E3-
2 each have a weight width of 8%, the above poly(2゜6-dimethyl-1,4-phenylene) ether is 60@34, polystyrene is 222% by weight, and triphenyl phosphate is 10% by weight.
Two types of resin compositions were prepared by blending each resin composition in such a manner that the weight of the resin compositions increased (Examples 3 and 4).
これら4種類の各樹脂組成物を二軸押出機(ウニルナ−
ファウドラー社製、Z8に一30型)にそれぞれ供給し
シリンダー温度280℃で溶融混練しそれぞれベレット
状に賦型した。Each of these four types of resin compositions was
The mixture was supplied to a Z8-130 (manufactured by Faudler Co., Ltd.), melted and kneaded at a cylinder temperature of 280°C, and shaped into a pellet shape.
得られたそれぞれのペレットを乾燥後、射出成形機(毛
様製作所製、8J−35型)に供給しシリンダー温度2
80℃、金型温度60℃で射出成形して各種試験片を得
た。これらの各試験片を用いて各種物性を評価した結果
を第1表にだ。After drying each of the obtained pellets, they were fed to an injection molding machine (Model 8J-35, manufactured by Keisyo Seisakusho) and the cylinder temperature was 2.
Various test pieces were obtained by injection molding at 80°C and a mold temperature of 60°C. Table 1 shows the results of evaluating various physical properties using each of these test pieces.
第1表の結果より複合ゴム系グラフト共重合体、ポリ(
2,6−シメチルー1.4−フェニレン)エーテル、ポ
リスチレン、トリフェニルホスフェートの組成をとれば
、優れた耐衝撃性能と、UL−94試験で1/16’厚
さでv−0、V−1のクラスに適合する難燃性を付与で
きることがわかる。From the results in Table 1, the composite rubber graft copolymer, poly(
The composition of 2,6-dimethyl-1,4-phenylene) ether, polystyrene, and triphenyl phosphate provides excellent impact resistance and UL-94 test results of V-0 and V-1 at 1/16' thickness. It can be seen that it is possible to impart flame retardancy that meets the class.
実施例5
参考例1で得た複合ゴムグラフト共重合休日−1を使用
した難燃性ポリフェニレンエーテル樹脂組成物を次のよ
うに製造した。すなわち、複合ゴム系グラフト共重合体
8−1が8重量%、実施例1で使用したボIJ(2,6
−シメチルー1゜4−)ユニレン)エーテルが60tf
%、Jll化ポリスチレン(パイロチエツクFB(商品
名)、日産フェロー■製)が100重量%実施例1で使
用したポリスチレンが177重量%びトリフェニルホス
フェートが5重を優となるようにそれぞれを配合して樹
脂組成物を調製した。Example 5 A flame-retardant polyphenylene ether resin composition using the composite rubber graft copolymerization holiday-1 obtained in Reference Example 1 was produced as follows. That is, 8% by weight of the composite rubber-based graft copolymer 8-1 and 8% by weight of the composite rubber-based graft copolymer 8-1,
-Simethyl-1゜4-)Unilene) ether is 60tf
%, Jllized polystyrene (Pyrocheck FB (trade name), manufactured by Nissan Fellow ■) was 100% by weight, the polystyrene used in Example 1 was 177% by weight, and triphenyl phosphate was 5% by weight. A resin composition was prepared.
この樹脂組成物を用い実施例1と同様の方法で各種試験
片を調製し、樹脂物性、難燃性を測定したところ、ピッ
カー軟化温度が143℃であり、アイゾツト衝撃強度(
I/a’ノツチ付23℃)が1 a9 kg ・cm/
cm テあり、UL−94試験は1/16#厚さで平均
燃焼時間28秒であす、v−〇クラスに適合する難燃性
を有していた。Various test pieces were prepared using this resin composition in the same manner as in Example 1, and the physical properties and flame retardance of the resin were measured. The picker softening temperature was 143°C, and the Izot impact strength (
I/a' notched 23℃) is 1 a9 kg・cm/
In the UL-94 test, it had a flame retardancy of 1/16# thickness and an average burning time of 28 seconds, meeting the V-○ class.
実施例6
実施例5において、臭素化ポリスチレンの代わりに臭素
化エボΦシ(F2400(商品名)、日立化成##)を
同量となるように使用する以外は実施例5と同様に実施
し、樹脂物性、難燃性を測定したところ、ピッカー軟化
温度が138℃であり、アイゾツト衝撃強度(I/4“
ノツチ付23℃)が1&5ゆ・(7)/αであり、UL
−94試験は1 /16’厚さで平均燃焼時間五6秒で
ありV−Oクラスに適合する難燃性を有していた。Example 6 The procedure was carried out in the same manner as in Example 5, except that the same amount of brominated ebo-shi (F2400 (trade name), Hitachi Chemical ##) was used instead of brominated polystyrene. When the physical properties and flame retardance of the resin were measured, the picker softening temperature was 138°C, and the Izot impact strength (I/4"
(23℃ with notch) is 1 & 5 Yu・(7)/α, and UL
-94 test had an average burning time of 56 seconds at a thickness of 1/16', and had flame retardancy meeting the V-O class.
実施例7〜12
参考例1及び2で得た複合ゴム系グラフト共重合体El
−1及び日−2を使用したガラス繊維強化ポリフェニレ
ンエーテル樹脂組成物を次のように製造した。Examples 7 to 12 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Glass fiber-reinforced polyphenylene ether resin compositions using Samples -1 and -2 were produced as follows.
すなわち、複合ゴム系グラフト共重合体S−1及び8−
2がそれぞれ64重量%、実施例1で用いたポリ(2,
6−’)メチル−1,4−フェニレン)エーテルが41
.6重−i%及び2CIO℃荷重5 kgでのメルトイ
ンデックスが69/10分のポリスチレンが32重量n
96及びガラス繊維(日本板ガラス■製、チョツプドス
トランドngs o3−Tp 68 (商品名))が2
oi量4となるようにそれぞれ配合して2種類の樹脂組
成物をI製した(実施例7〜8)。That is, composite rubber-based graft copolymers S-1 and 8-
2 was 64% by weight, respectively, and the poly(2,
6-') methyl-1,4-phenylene) ether is 41
.. Polystyrene with a melt index of 69/10 at 6wt-i% and 2CIOC load of 5kg is 32wtn
96 and glass fiber (manufactured by Nippon Sheet Glass ■, chopped strand NGS O3-Tp 68 (product name)) are 2
Two types of resin compositions were prepared by blending them so that the oi amount was 4 (Examples 7 and 8).
又、ガラス繊維添加量を第2表に示すように種々変えた
樹脂組成物を4種類調製した(実施例9〜12)。Additionally, four types of resin compositions were prepared in which the amount of glass fiber added was varied as shown in Table 2 (Examples 9 to 12).
これら、各種組成物を実施例1と同様に二軸押出機によ
りベレット状に賦形し、射出成形機により各種試験片を
得た。これらの各試験片を用いて各種物性を評価した結
果を第2表に示す。These various compositions were shaped into pellets using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine. Table 2 shows the results of evaluating various physical properties using each of these test pieces.
第2表の結果より、複合ゴム系グラフト共重合体、ポリ
(2,6−シメチルー1.4−フェニレン)エーテル、
ポリスチレン、ガラス繊維の組成をとれば、優れた機搬
強度と、高A耐熱性を付与できることがわかる。From the results in Table 2, the composite rubber graft copolymer, poly(2,6-dimethyl-1,4-phenylene) ether,
It can be seen that by using a composition of polystyrene and glass fiber, excellent transport strength and high A heat resistance can be imparted.
実施例13〜15
参考例1で得た複合ゴム系グラフト共重合体B−1を使
用した炭素繊維強化ポリフェニレンエーテル樹脂組成物
を次のように製造した。Examples 13 to 15 Carbon fiber-reinforced polyphenylene ether resin compositions using the composite rubber-based graft copolymer B-1 obtained in Reference Example 1 were produced as follows.
すなわち第3表に示す組成で複合ゴム系グラフト共重合
体、実施例1で用いたポ17 (2,6−ジメチル−1
,4−フェニレン)エーテル、実施例7で用いたポリス
チレン及び炭素繊維(三菱レイヨン■製、チョツプドス
トランド)を配合し樹脂組成物を調製した。これら各種
組成物を実施例1と同様に二軸押出機によりベレット状
釦賦形し、射出成形機により各種試験片を得た。That is, the composite rubber-based graft copolymer with the composition shown in Table 3, the poly-17 (2,6-dimethyl-1
, 4-phenylene) ether, the polystyrene used in Example 7, and carbon fiber (chopped strand manufactured by Mitsubishi Rayon ■) to prepare a resin composition. These various compositions were shaped into pellet-shaped buttons using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine.
これらの各試験片を用いて各種物性を評価した結果を第
3表に示す。Table 3 shows the results of evaluating various physical properties using each of these test pieces.
第3表の結果より、複合ゴム系グラフト共重合体、ポリ
(2,6−シメチルー1.4−)ユニレン)エーテル、
ポリスチレン、炭素繊維の組成をとれば、優れた機械強
度と高い耐熱性を付与できることがわかる。From the results in Table 3, the composite rubber-based graft copolymer, poly(2,6-dimethyl-1,4-)unilene)ether,
It can be seen that excellent mechanical strength and high heat resistance can be imparted by using a composition of polystyrene and carbon fiber.
実施例16〜21
参考例1及び2で得た複合ゴム系グラフト共重合体El
−1及びB−2を使用した難燃性ガラス繊維強化樹脂組
成物を次のように製造した。Examples 16-21 Composite rubber-based graft copolymer El obtained in Reference Examples 1 and 2
Flame-retardant glass fiber reinforced resin compositions using -1 and B-2 were manufactured as follows.
複合ゴム系グラフト共重合体S−1及び8−2がそれぞ
れ五2重量%、実施例1で用すたポリ(2,6−シメチ
ルー1.4−フェニレン)エーテルが56重量幅及び実
施例7で用いたポリスチレンが16重量%、トリフェニ
ルホスフェートが4.2重量部、実施例7で使用したガ
ラス繊維が20重量俤となるようにそれぞれを配合し−
C2種類の樹脂組成物を調製した(実施例16〜17)
。The composite rubber-based graft copolymers S-1 and 8-2 were each 52% by weight, the poly(2,6-dimethyl-1,4-phenylene) ether used in Example 1 was 56% by weight, and Example 7 The polystyrene used in Example 7 was 16% by weight, the triphenyl phosphate was 4.2 parts by weight, and the glass fiber used in Example 7 was 20% by weight.
C2 types of resin compositions were prepared (Examples 16 to 17)
.
又、トリフェニルホスフェートm 加量、jf 5ス繊
維添加量を第4表に示すように種々変えた組成物を調製
した(実施例18〜21)。Further, compositions were prepared in which the amount of triphenyl phosphate m and the amount of jf 5 fiber added were varied as shown in Table 4 (Examples 18 to 21).
これら各種組成物を、実施例1と同様に二軸押出機によ
シベレット状に賦形し、射出成形機により各種試験片を
得た。これらの各種試験片を用いて各種物性を評価した
結果を第4表に示す。These various compositions were shaped into civet shapes using a twin-screw extruder in the same manner as in Example 1, and various test pieces were obtained using an injection molding machine. Table 4 shows the results of evaluating various physical properties using these various test pieces.
第4表の結果より複合ゴム系グラフト共重合体、ポリ(
2,6−シメチルー1.4−)ユニレン)エーテル、ポ
リスチレン、ガラス繊維、トリフェニルホスフェートの
組成をとれば、優れた機械強度と難燃性を付与できるこ
とがわかる。From the results in Table 4, the composite rubber graft copolymer, poly(
It can be seen that excellent mechanical strength and flame retardance can be imparted by using a composition of 2,6-dimethyl-1,4-)unilene) ether, polystyrene, glass fiber, and triphenyl phosphate.
実施例22〜25
参考例1で得た複合ゴム系グラフト共重合体S−1を使
用しだ難燃性炭素繊維強化ポリフェニレンエーテル樹脂
組成物を次のように製造した。Examples 22 to 25 Flame-retardant carbon fiber-reinforced polyphenylene ether resin compositions using the composite rubber-based graft copolymer S-1 obtained in Reference Example 1 were manufactured as follows.
複合ゴム系グラフト共重合休日−1及び、実施例1で用
いたポl (2,6−シメチルー1.4−)ユニレン)
エーテル、実施例7で用t、−1ホlJスチレン、トリ
フェニルホスフェート、実施例13で用いた炭素繊維及
び実施例7で用すたガラス繊維を第5表に示す割合で配
合し樹脂組成物を調製した。Composite rubber-based graft copolymerization holiday-1 and poly (2,6-cymethyl-1,4-)unilene) used in Example 1
A resin composition was prepared by blending ether, t-1 styrene used in Example 7, triphenyl phosphate, the carbon fiber used in Example 13, and the glass fiber used in Example 7 in the proportions shown in Table 5. was prepared.
これら各組成物を実施例1と同様に二軸押出機、射出成
形機により成形し各種試験片を得た。Each of these compositions was molded using a twin-screw extruder and an injection molding machine in the same manner as in Example 1 to obtain various test pieces.
これらの各種試験片を用いて各植物性を評価した結果を
第5表に示す。第5表の結果より炭素繊維、場合によっ
てはガラス繊維を併用した組成物とすると、低い線膨張
率を有し、かつ優れた機械強度と難燃性を与える樹脂組
成物とすることができることがわかる。Table 5 shows the results of evaluating each vegetable quality using these various test pieces. The results in Table 5 indicate that a resin composition that uses carbon fiber, and in some cases glass fiber in combination, can have a low coefficient of linear expansion and provide excellent mechanical strength and flame retardancy. Recognize.
本発明はポリフェニレンエーテル樹脂、ポリスチレン樹
脂及び複合ゴム系グラフト共重合体から成るポリフェニ
レンエーテル樹脂配合物に、特定の難燃剤を配合するこ
とにより優れた難燃性ポリフェニレンエーテル樹脂組成
物を、又、ガラス繊維及び炭素繊維から選ばれる少なく
とも一種の無機繊維を配合するととだより優れた機械強
度を有したポリフェニレンエーテル樹脂組成物を、さら
に、特定の難燃剤と上記特定の無機繊維を配合すること
により難燃性であり、;つ島つ機械強度に優れたポリフ
ェニレンエーテル樹脂組成物を得ることができる等優れ
た効果を奏する。The present invention provides an excellent flame-retardant polyphenylene ether resin composition by blending a specific flame retardant into a polyphenylene ether resin composition consisting of a polyphenylene ether resin, a polystyrene resin, and a composite rubber-based graft copolymer. A polyphenylene ether resin composition that has superior mechanical strength when blended with at least one type of inorganic fiber selected from fibers and carbon fibers, and a polyphenylene ether resin composition that has superior mechanical strength when blended with a specific flame retardant and the above-mentioned specific inorganic fibers. It has excellent effects such as being able to obtain a polyphenylene ether resin composition that is flammable and has excellent mechanical strength.
特許出願人 三菱レイヨン株式会社 代理人 弁理士 吉 澤 敏 夫Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney Toshio Yoshizawa
Claims (1)
%とポリアルキル(メタ)アクリレートゴム成分10〜
90重量%とが分離できないように相互に絡み合つた構
造を有し、かつポリオルガノシロキサンゴム成分とポリ
アルキル(メタ)アクリレートゴム成分との合計量が1
00重量%である平均粒子径0.08〜0.6μmの複
合ゴムに1種又は2種以上のビニル系単量体がグラフト
重合されてなる複合ゴム系グラフト共重合体及び (D)リン酸エステル系難燃剤 を構成成分として含有するポリフエニレンエーテル樹脂
組成物。 2、成分(A)が20〜80重量%、成分(B)が19
〜75重量%、成分(C)が1〜40重量%からなる樹
脂配合物100重量部に成分(D)を0.5〜35重量
部配合してなる第1項記載のポリフエニレンエーテル樹
脂組成物。 3、(A)ポリフェニレンエーテル樹脂、 (B)ポリスチレン樹脂 (C)ポリオルガノシロキサンゴム成分10〜90重量
%とポリアルキル(メタ)アクリレートゴム成分10〜
90重量%とが分離できないように相互に絡み合つた構
造を有し、かつポリオルガノシロキサンゴム成分とポリ
アルキル(メタ)アクリレートゴム成分との合計量が1
00重量%である平均粒子径0.08〜0.6μmの複
合ゴムに1種又は2種以上のビニル系単量体がグラフト
重合されてなる複合ゴム系グラフト共重合体及び (E)ガラス繊維及び炭素繊維からなる群から選ばれる
少なくとも一種の無機繊維 を構成成分として含有するポリフエニレンエーテル樹脂
組成物。 4、成分(A)が20〜80重量%、成分(B)が19
〜75重量%、成分(C)が1〜40重量%からなる樹
脂配合物100重量部に成分(E)を5〜100重量部
配合してなる第5項記載のポリフェニレンエーテル樹脂
組成物。 5、(A)ポリフェニレンエーテル樹脂、 (B)ポリスチレン樹脂 (C)ポリオルガノシロキサンゴム成分10〜90重量
部とポリアルキル(メタ)アクリレートゴム成分10〜
90重量部とが分離できないように相互に絡み合つた構
造を有し、かつポリオルガノシロキサンゴム成分とポリ
アルキル(メタ)アクリレートゴム成分との合計量が1
00重量部である平均粒子径0.08〜0.6μmの複
合ゴムに1種又は2種以上のビニル系単量体がグラフト
重合されてなる複合ゴム系グラフト共重合体及び (D)リン酸エステル系難燃剤 (E)ガラス繊維及び炭素繊維からなる群から選ばれる
少なくとも一種の無機繊維 を構成成分として含有するポリフエニレンエーテル樹脂
組成物。 6、成分(A)が20〜80重量%、成分(B)が19
〜75重量%、成分(C)が1〜40重量部からなる樹
脂配合物100重量部に成分(D)を0.5〜35重量
部及び成分(E)を5〜100重量部配合してなる第5
項記載のポリフェニレンエーテル樹脂組成物。 7、成分(C)の複合ゴムが、オルガノシロキサンと架
橋剤( I )及び所望によりグラフト交叉剤( I )とを
用い乳化重合により得られたポリオルガノシロキサンゴ
ム成分と、このポリオルガノシロキサンゴム成分にアル
キル(メタ)アクリレート、架橋剤(II)及びグラフト
交叉剤(II)を含浸させてから重合させて得られたポリ
アルキル(メタ)アクリレートゴム成分とから成る第1
項、第2項、第3項、第4項、第5項又は第6項記載の
ポリフエニレンエーテル樹脂組成物。 8、成分(D)がトリフェニルホスフェートである第1
項、第2項、第5項又は第6項記載のポリフエニレンエ
ーテル樹脂組成物。 9、成分(D)のリン酸エステル系難燃剤が臭素化ポリ
スチレンを併用したものである第1項、第2項、第5項
又は第6項記載のポリフェニレンエーテル樹脂組成物。[Claims] 1. (A) polyphenylene ether resin, (B) polystyrene resin, (C) 10 to 90% by weight of a polyorganosiloxane rubber component and 10 to 90% by weight of a polyalkyl (meth)acrylate rubber component.
The polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component have a total amount of 1.
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (D) phosphoric acid. A polyphenylene ether resin composition containing an ester flame retardant as a constituent component. 2. Component (A) is 20-80% by weight, component (B) is 19% by weight.
The polyphenylene ether resin according to item 1, wherein 0.5 to 35 parts by weight of component (D) is blended to 100 parts by weight of a resin blend consisting of 1 to 40 parts by weight of component (C). Composition. 3. (A) polyphenylene ether resin, (B) polystyrene resin (C) 10 to 90% by weight of polyorganosiloxane rubber component and 10 to 90% by weight of polyalkyl (meth)acrylate rubber component
The polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component have a total amount of 1.
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (E) glass fiber. A polyphenylene ether resin composition containing as a constituent component at least one type of inorganic fiber selected from the group consisting of 4. Component (A) is 20-80% by weight, component (B) is 19% by weight.
6. The polyphenylene ether resin composition according to item 5, wherein 5 to 100 parts by weight of component (E) is blended to 100 parts by weight of a resin blend containing 1 to 40% by weight of component (C). 5. (A) polyphenylene ether resin, (B) polystyrene resin (C) 10 to 90 parts by weight of polyorganosiloxane rubber component and 10 to 90 parts by weight of polyalkyl (meth)acrylate rubber component
90 parts by weight are intertwined with each other so that they cannot be separated, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component is 1
A composite rubber graft copolymer obtained by graft polymerizing one or more vinyl monomers to a composite rubber having an average particle diameter of 0.08 to 0.6 μm and (D) phosphoric acid. Ester Flame Retardant (E) A polyphenylene ether resin composition containing as a constituent component at least one inorganic fiber selected from the group consisting of glass fibers and carbon fibers. 6. Component (A) is 20 to 80% by weight, component (B) is 19
~75% by weight, 0.5 to 35 parts by weight of component (D) and 5 to 100 parts by weight of component (E) are blended into 100 parts by weight of a resin blend consisting of 1 to 40 parts by weight of component (C). Naru no 5
The polyphenylene ether resin composition described in . 7. The composite rubber of component (C) is a polyorganosiloxane rubber component obtained by emulsion polymerization using an organosiloxane, a crosslinking agent (I), and optionally a grafting agent (I), and this polyorganosiloxane rubber component. a polyalkyl (meth)acrylate rubber component obtained by impregnating alkyl (meth)acrylate, a crosslinking agent (II), and a grafting agent (II) and then polymerizing the rubber component.
The polyphenylene ether resin composition according to item 1, 2, 3, 4, 5 or 6. 8. The first component (D) is triphenyl phosphate
The polyphenylene ether resin composition according to item 1, 2, 5 or 6. 9. The polyphenylene ether resin composition according to item 1, item 2, item 5, or item 6, wherein the phosphoric acid ester flame retardant of component (D) is used in combination with brominated polystyrene.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1057153A JP2707312B2 (en) | 1988-03-10 | 1989-03-09 | Polyphenylene ether resin composition |
US08/471,256 US5728321A (en) | 1988-09-30 | 1995-06-06 | Organic polymer, conducting organic polymer, production methods and uses of the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5704088 | 1988-03-10 | ||
JP63-57040 | 1988-03-10 | ||
JP1057153A JP2707312B2 (en) | 1988-03-10 | 1989-03-09 | Polyphenylene ether resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH021760A true JPH021760A (en) | 1990-01-08 |
JP2707312B2 JP2707312B2 (en) | 1998-01-28 |
Family
ID=26398039
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1057153A Expired - Lifetime JP2707312B2 (en) | 1988-03-10 | 1989-03-09 | Polyphenylene ether resin composition |
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Country | Link |
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JP (1) | JP2707312B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5042071A (en) * | 1990-01-18 | 1991-08-20 | Motorola, Inc. | Acoustic insulator for a telephone handset microphone |
US5210793A (en) * | 1990-11-07 | 1993-05-11 | Motorola, Inc. | Apparatus for mounting transducers |
JP2008291976A (en) * | 2007-05-28 | 2008-12-04 | Asahi Organic Chem Ind Co Ltd | Valve |
EP2987830A4 (en) * | 2013-04-17 | 2016-03-09 | Asahi Kasei Chemicals Corp | Resin composition and molded article |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60155260A (en) * | 1984-01-24 | 1985-08-15 | Mitsubishi Gas Chem Co Inc | Polyphenylene ether resin composition |
JPS62280210A (en) * | 1986-05-23 | 1987-12-05 | バイエル・アクチエンゲゼルシヤフト | Graft polymers having high notch impact strength |
-
1989
- 1989-03-09 JP JP1057153A patent/JP2707312B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60155260A (en) * | 1984-01-24 | 1985-08-15 | Mitsubishi Gas Chem Co Inc | Polyphenylene ether resin composition |
JPS62280210A (en) * | 1986-05-23 | 1987-12-05 | バイエル・アクチエンゲゼルシヤフト | Graft polymers having high notch impact strength |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5042071A (en) * | 1990-01-18 | 1991-08-20 | Motorola, Inc. | Acoustic insulator for a telephone handset microphone |
US5210793A (en) * | 1990-11-07 | 1993-05-11 | Motorola, Inc. | Apparatus for mounting transducers |
JP2008291976A (en) * | 2007-05-28 | 2008-12-04 | Asahi Organic Chem Ind Co Ltd | Valve |
WO2008146866A1 (en) * | 2007-05-28 | 2008-12-04 | Asahi Organic Chemicals Industry Co., Ltd. | Valve |
EP2987830A4 (en) * | 2013-04-17 | 2016-03-09 | Asahi Kasei Chemicals Corp | Resin composition and molded article |
US9617419B2 (en) | 2013-04-17 | 2017-04-11 | Asahi Kasei Kabushiki Kaisha | Resin composition and molded article |
US10174196B2 (en) | 2013-04-17 | 2019-01-08 | Asahi Kasei Kabushiki Kaisha | Resin composition and molded article |
Also Published As
Publication number | Publication date |
---|---|
JP2707312B2 (en) | 1998-01-28 |
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