JP2001011461A - Bromine-containing flame-retarded composition having resistance to iron oxide - Google Patents
Bromine-containing flame-retarded composition having resistance to iron oxideInfo
- Publication number
- JP2001011461A JP2001011461A JP18130399A JP18130399A JP2001011461A JP 2001011461 A JP2001011461 A JP 2001011461A JP 18130399 A JP18130399 A JP 18130399A JP 18130399 A JP18130399 A JP 18130399A JP 2001011461 A JP2001011461 A JP 2001011461A
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- composition
- iron oxide
- mixture
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 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 65
- 239000003063 flame retardant Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 8
- 238000004455 differential thermal analysis Methods 0.000 claims abstract description 6
- -1 Olefin epoxide Chemical class 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000004580 weight loss Effects 0.000 claims description 11
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052751 metal Chemical class 0.000 claims description 7
- 239000002184 metal Chemical class 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920005992 thermoplastic resin Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 3
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims description 2
- IGMYAFRPSRRXNA-UHFFFAOYSA-L 2-[dibutyl(carboxymethylsulfanyl)stannyl]sulfanylacetic acid Chemical compound [O-]C(=O)CS.[O-]C(=O)CS.CCCC[Sn+2]CCCC IGMYAFRPSRRXNA-UHFFFAOYSA-L 0.000 claims description 2
- QKZQKNCNSNZRFA-UHFFFAOYSA-N 2-hydroxyethyl 2-sulfanylacetate Chemical compound OCCOC(=O)CS QKZQKNCNSNZRFA-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- KALMIJKXWYFHIW-UHFFFAOYSA-N CC(C(C1=CC=CC=C1)(OC(C2=CC=CC=C2)(C(C)(C(Br)(Br)Br)Br)Br)Br)(C(Br)(Br)Br)Br Chemical compound CC(C(C1=CC=CC=C1)(OC(C2=CC=CC=C2)(C(C)(C(Br)(Br)Br)Br)Br)Br)(C(Br)(Br)Br)Br KALMIJKXWYFHIW-UHFFFAOYSA-N 0.000 claims description 2
- XDBQHXURPJGSJH-UHFFFAOYSA-K O-[butyl-di(ethanethioyloxy)stannyl] ethanethioate Chemical compound C(C)(=S)[O-].C(CCC)[Sn+3].C(C)(=S)[O-].C(C)(=S)[O-] XDBQHXURPJGSJH-UHFFFAOYSA-K 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- MMBVUVNQTGGVJS-UHFFFAOYSA-N [1,1,2,3,3-pentabromo-3-(1,1,2,3,3-pentabromo-3-phenylpropoxy)propyl]benzene Chemical compound C=1C=CC=CC=1C(Br)(Br)C(Br)C(Br)(Br)OC(Br)(Br)C(Br)C(Br)(Br)C1=CC=CC=C1 MMBVUVNQTGGVJS-UHFFFAOYSA-N 0.000 claims description 2
- YLFRJROMPGNJRP-UHFFFAOYSA-L [dibutyl(3-sulfanylpropanoyloxy)stannyl] 3-sulfanylpropanoate Chemical compound [O-]C(=O)CCS.[O-]C(=O)CCS.CCCC[Sn+2]CCCC YLFRJROMPGNJRP-UHFFFAOYSA-L 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 2
- RFAIKXASDCRKEP-UHFFFAOYSA-N dioctyl(sulfanylidene)tin Chemical compound CCCCCCCC[Sn](=S)CCCCCCCC RFAIKXASDCRKEP-UHFFFAOYSA-N 0.000 claims description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- 150000003606 tin compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000002950 deficient Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 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 6
- 239000003112 inhibitor Substances 0.000 description 6
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 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 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RMTMGXCQEXSWLI-UHFFFAOYSA-N (2-tert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(O)O RMTMGXCQEXSWLI-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- WEFMTVNJCFTOFQ-UHFFFAOYSA-N 6-decoxybenzo[c][2,1]benzoxaphosphinine Chemical compound C1=CC=C2P(OCCCCCCCCCC)OC3=CC=CC=C3C2=C1 WEFMTVNJCFTOFQ-UHFFFAOYSA-N 0.000 description 1
- LBSJFUFSEQQYFC-UHFFFAOYSA-N 8,8-diphenyloctyl dihydrogen phosphite Chemical compound C=1C=CC=CC=1C(CCCCCCCOP(O)O)C1=CC=CC=C1 LBSJFUFSEQQYFC-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- MYFPOWLHENHPTG-UHFFFAOYSA-L dioctyltin(2+);3-sulfanylpropanoate Chemical compound [O-]C(=O)CCS.[O-]C(=O)CCS.CCCCCCCC[Sn+2]CCCCCCCC MYFPOWLHENHPTG-UHFFFAOYSA-L 0.000 description 1
- 235000019820 disodium diphosphate Nutrition 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- RHPXYIKALIRNFA-UHFFFAOYSA-L disodium;2-[carboxylatomethyl(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CC([O-])=O RHPXYIKALIRNFA-UHFFFAOYSA-L 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical class C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【本発明の分野】本発明は耐酸化鉄性を有する難燃剤組
成物、詳しくは難燃剤を含む熱可塑性樹脂の成形時に、
その難燃剤が成形・加工装置に付着している酸化鉄(F
e2 O3,Fe3 O4 等)との反応に起因する不良成形
品の発生を防止することができる、難燃剤組成物に関す
る。FIELD OF THE INVENTION The present invention relates to a flame retardant composition having iron oxide resistance, and more particularly, to molding of a thermoplastic resin containing a flame retardant.
The iron oxide (F
The occurrence of defective molded articles due to the reaction with e 2 O 3, Fe 3 O 4 , etc.) can be prevented, it relates to a flame retardant composition.
【0002】[0002]
【本発明の背景および課題】電気および電子部品を含む
難燃性が要求されるプラスチック成形品を臭素系難燃剤
および三酸化アンチモンのような難燃助剤により難燃化
することは周知である。この目的に使用される臭素系難
燃剤を含む熱可塑性樹脂組成物は、樹脂の溶融温度以上
での難燃剤の熱分解により発生する臭素ラジカルや臭化
水素等の分解産物の発生抑制ないしそれをキャッチする
熱安定剤を一般に含んでおり、それによって樹脂の着色
や装置の腐食を防いでいる。BACKGROUND OF THE INVENTION It is well-known that plastic molded articles, including electric and electronic parts, which require flame retardancy, are made flame-retardant with a flame retardant and a flame retardant aid such as antimony trioxide. . The thermoplastic resin composition containing a bromine-based flame retardant used for this purpose suppresses the generation of decomposition products such as bromine radicals and hydrogen bromide generated by the thermal decomposition of the flame retardant at a temperature not lower than the melting temperature of the resin, or suppresses it. It generally contains catching heat stabilizers, thereby preventing resin coloration and equipment corrosion.
【0003】このような樹脂の溶融温度以上の温度にお
いて難燃剤の熱分解産物に起因する問題とは別に、押出
機や他の成形機を長らく使用していると含まれている難
燃剤によっては思わぬ成形不良品が発生することがあ
る。その原因はこれまで解明されていなかったので追求
したところ、ヤケや錆により装置の内部に酸化鉄が徐々
に沈着し、これが臭素系難燃剤と接解して臭化鉄が生成
するためであることがわかった。生成した臭化鉄が金型
表面に残ると成形品表面がくぼむシンクマークが顕出す
る成形不良となり、また臭化鉄が成形品に取り込まれる
と成形後の取扱中または使用中吸湿により表面に膨れ、
ボイド等の欠陥が発生する原因になる。この問題の解決
が本発明の課題である。[0003] Apart from the problem caused by the thermal decomposition products of the flame retardant at temperatures above the melting temperature of the resin, depending on the flame retardant included if the extruder or other molding machine has been used for a long time, An unexpected molding defect may occur. The cause was not clarified so far, and when pursued, iron oxide was gradually deposited inside the device due to burns and rust, which came into contact with the brominated flame retardant and produced iron bromide. I understand. If the formed iron bromide remains on the mold surface, the molded product surface will be depressed and sink marks will appear, resulting in molding failure.If the iron bromide is incorporated into the molded product, it will absorb moisture during handling or during use after molding. Swelling,
This may cause defects such as voids. The solution of this problem is the subject of the present invention.
【0004】[0004]
【解決方法】上に述べた成形装置内部に沈着した酸化鉄
と難燃剤の反応によって生成する臭化鉄に関連する問題
は、臭素を含んでいる難燃剤すべてではなく、特定のグ
ループの難燃剤に特異的にあるいは実用上許容できない
程度に出現する。そこでそのようなグループを特定でき
る基準が必要となる。The problems associated with the iron bromide formed by the reaction of the iron oxide and the flame retardant deposited inside the molding apparatus described above are not specific to all of the bromine-containing flame retardants, but to a specific group of flame retardants. Specifically or unacceptably practically. Therefore, a standard that can identify such a group is needed.
【0005】本発明では次の基準を用いて対象となる含
臭素難燃剤(a)を特定する。In the present invention, the target brominated flame retardant (a) is specified using the following criteria.
【0006】(1)当該難燃剤単独の130℃×2時間
の加熱減量試験において、加熱減量が0.1重量%以下
であること。(1) In the heat loss test of the flame retardant alone at 130 ° C. × 2 hours, the heat loss is 0.1% by weight or less.
【0007】(2)当該難燃剤と酸化鉄との重量比2
0:1の混合物を空気気流中で10℃/分の昇温速度で
示差熱分析により測定する時、当該難燃剤単独を用いて
同じ条件で示差熱分析により測定した1%および5%減
量温度よりも対応する減量温度がそれぞれ少なくとも3
0℃低いこと。(2) Weight ratio of the flame retardant to iron oxide: 2
When the mixture of 0: 1 is measured by differential thermal analysis in a stream of air at a heating rate of 10 ° C./min, the 1% and 5% weight loss temperatures measured by differential thermal analysis under the same conditions using the flame retardant alone. Each corresponding weight loss temperature is at least 3
0 ° C lower.
【0008】本発明の課題は、(a)上の基準を満たす
含臭素難燃剤、および(b)前記難燃剤の0.01〜5
0重量%のエポキシ当量1000以下を有するエポキシ
化合物、有機スズ化合物、キレート剤またはそれらの混
合物、を含んでいる難燃剤組成物を提供することによっ
て解決される。An object of the present invention is to provide (a) a bromine-containing flame retardant satisfying the above criteria, and (b) 0.01 to 5 of the flame retardant.
The problem is solved by providing a flame retardant composition comprising 0% by weight of an epoxy compound having an epoxy equivalent of 1000 or less, an organotin compound, a chelating agent or a mixture thereof.
【0009】[0009]
【具体的手段】先に述べた基準に合致する含臭素難燃剤
の例は、テトラブロモシクロオクタン、ヘキサブロモシ
クロドデカン(略号HBCD)、トリブロモフェニル−
ジブロモプロピルエーテル、トリブロモフェニル−1,
2−ジブロモ−2−メチルプロピルエーテル(略号TB
P−MDBPE)、テトラブロモビスフェノールA−ビ
スジブロモプロピルエーテル(略号TBBA−BDBP
E)、テトラブロモビスフェノールS−ビスジブロモプ
ロピルエーテル(略号TBBS−BDBPE)、トリス
ジブロモプロピルイソシアヌレート(略号TDBPI
C)を含むがこれらに限らない。Specific examples of brominated flame retardants meeting the above-mentioned criteria include tetrabromocyclooctane, hexabromocyclododecane (abbreviation HBCD), tribromophenyl-
Dibromopropyl ether, tribromophenyl-1,
2-dibromo-2-methylpropyl ether (abbreviation TB)
P-MDBPE), tetrabromobisphenol A-bisdibromopropyl ether (abbreviation: TBBA-BDBP)
E), tetrabromobisphenol S-bisdibromopropyl ether (abbreviation TBBS-BDBPE), trisdibromopropyl isocyanurate (abbreviation TDBPI)
C), but not limited thereto.
【0010】これに対し、例えばトリストリブロモネオ
ペンチルホスフェート(略号TTBNPP)およびトリ
ストリブロモフェノキシトリアジン(略号TTBPT
A)は、先に述べた基準(2)を満足しない。以下の表
1に難燃剤単独およびその酸化鉄混合物の1%および5
%減量温度の測定値を示す。On the other hand, for example, tristribromoneopentyl phosphate (abbreviation TTBNPPP) and tristribromophenoxytriazine (abbreviation TTBPT)
A) does not satisfy the criterion (2) described above. Table 1 below shows 1% and 5% of the flame retardant alone and its iron oxide mixture.
The measured value of% weight loss temperature is shown.
【0011】[0011]
【表1】 [Table 1]
【0012】本発明の難燃剤組成物は、上の難燃剤と酸
化鉄との反応によって生成する臭化鉄に起因して、添加
した熱可塑性樹脂の成形時に不良成形品が発生するのを
防止するインヒビター成分として、エポキシ当量100
0以下のエポキシ化合物、有機スズ化合物、キレート剤
またはそれらの混合物を含んでいる。個々のインヒビタ
ー成分の例を以下に示すがそれらに限らない。The flame retardant composition of the present invention prevents the occurrence of defective molded products during the molding of the thermoplastic resin added due to the iron bromide generated by the reaction between the above flame retardant and iron oxide. As an inhibitor component, an epoxy equivalent of 100
It contains 0 or less epoxy compounds, organotin compounds, chelating agents or mixtures thereof. Examples of individual inhibitor components are set forth below, but are not limited thereto.
【0013】(b−1)エポキシ化合物: 炭素数8〜30のα−オレフィンエポキシド:炭素数8
以上の1−アルケン例えば1−オクテンや、重合度2以
上のポリブタジエンオリゴマーの酸化によって得られ
る。(B-1) Epoxy compound: α-olefin epoxide having 8 to 30 carbon atoms: 8 carbon atoms
It is obtained by oxidation of the above 1-alkene such as 1-octene or polybutadiene oligomer having a degree of polymerization of 2 or more.
【0014】エポキシ化不飽和脂肪酸トリグリセリド:
エポキシ化大豆油、エポキシ化アマニ油などがこれに含
まれる。Epoxidized unsaturated fatty acid triglyceride:
This includes epoxidized soybean oil, epoxidized linseed oil and the like.
【0015】モノグリシジルエーテル:フェニルグリシ
ジルエーテル、o−フェニルフェニルグリシジルエーテ
ルなど。Monoglycidyl ether: phenylglycidylether, o-phenylphenylglycidylether and the like.
【0016】多価フェノールポリグリシジルエーテル:
一例はビスフェノール型エポキシ樹脂として知られてい
る。これらはビスフェノールA、ビスフェノールF、ビ
スフェノールS、これらの臭素化物にエピクロルヒドリ
ンを反応させることにより得られる。多価フェノールと
してノボラックフェノール樹脂、ノボラッククレゾール
樹脂、臭素化ノボラックフェノール樹脂等のノボラック
樹脂、または4,4’−ヒドロキシビフェニル化合物か
ら出発して得られるポリグリシジルエーテルおよび1,
1,2,2−テトラキス(p−2,3−エポキシプロピ
ルフェニル)エタンもこの例に含まれる。Polyglyceryl ether of polyhydric phenol:
One example is known as a bisphenol-type epoxy resin. These are obtained by reacting epichlorohydrin with bisphenol A, bisphenol F, bisphenol S, and their bromides. As polyhydric phenols, novolak phenol resins, novolak cresol resins, novolak resins such as brominated novolak phenol resins, or polyglycidyl ethers obtained by starting from 4,4′-hydroxybiphenyl compounds and 1,
1,2,2-Tetrakis (p-2,3-epoxypropylphenyl) ethane is also included in this example.
【0017】多価アルコールポリグリシジルエーテル:
脂肪族多価アルコールのポリグリシジルエーテル型エポ
キシ樹脂として知られている。出発多価アルコールの例
は、水添ビスフェノールA、1,4−ブタンジオール、
ネオペンチルグリコール、ポリオキシアルキレングリコ
ール、トリメチロールプロパンなどを含み、同様にエピ
クロルヒドリンとの反応によって得られる。Polyhydric alcohol polyglycidyl ether:
It is known as a polyglycidyl ether type epoxy resin of an aliphatic polyhydric alcohol. Examples of starting polyhydric alcohols are hydrogenated bisphenol A, 1,4-butanediol,
It contains neopentyl glycol, polyoxyalkylene glycol, trimethylolpropane and the like, and is similarly obtained by reaction with epichlorohydrin.
【0018】多価カルボン酸ポリグリシジルエステル:
このタイプのエポキシ化合物もエポキシ樹脂の1種とし
て知られている。フタル酸ジグリシジルエステル、水添
フタル酸ジグリジルエステルなどがその例である。Polyglycidyl polycarboxylic acid ester:
This type of epoxy compound is also known as one type of epoxy resin. Diglycidyl phthalate and hydrogenated diglycidyl phthalate are examples.
【0019】芳香族アミンのN,N−ジ−(2,3−エ
ポキシプロピル)誘導体:このタイプのエポキシ化合物
は、アニリン、トルイジン、メチレンビス(4−アミノ
ベンゼン)、m−アミノフェノールなどの芳香族アミン
にエピクロルヒドリンを反応させて得られる。N, N-di- (2,3-epoxypropyl) derivatives of aromatic amines: Epoxy compounds of this type include aromatic compounds such as aniline, toluidine, methylenebis (4-aminobenzene) and m-aminophenol. It is obtained by reacting an amine with epichlorohydrin.
【0020】イソシアヌル酸2,3−エポキシプロピル
エステル:モノ−,ジ−およびトリエステルが含まれ
る。トリエステルが好ましい。あまり高いエポキシ当量
を有する化合物は有効レベルのエポキシ基濃度を得るた
めに樹脂へ多量に添加する必要があり、そのため成形品
の難燃性や他の物性に悪影響する。2,3-Epoxypropyl isocyanurate: Includes mono-, di- and triesters. Triesters are preferred. Compounds with too high an epoxy equivalent need to be added in large amounts to the resin in order to obtain an effective level of epoxy group concentration, which adversely affects the flame retardancy and other physical properties of the molded article.
【0021】(b−2)有機スズ化合物:ジ−n−ブチ
ルスズマレエートポリマー、ジ−n−オクチルスズマレ
エートポリマー、ジ−n−ブチルスズ−3−メルカプト
プロピオネート、ジ−n−オクチルスズ−3−メルカプ
トプロピオネート、ジ−n−ブチルスズメルカプトアセ
テート、ジエチレングリコールビス(ブチルスズチオア
セテート)、ジブチルスズサルファイド、ジオクチルス
ズサルファイド、ジブチルスズジオクチルメルカプタイ
ド、ジメチルスズ(エチレングリコールモノチオグリコ
レート)など。(B-2) Organotin compounds: di-n-butyltin maleate polymer, di-n-octyltin maleate polymer, di-n-butyltin-3-mercaptopropionate, di-n-octyltin- 3-mercaptopropionate, di-n-butyltin mercaptoacetate, diethylene glycol bis (butyltin thioacetate), dibutyltin sulfide, dioctyltin sulfide, dibutyltin dioctylmercaptide, dimethyltin (ethylene glycol monothioglycolate) and the like.
【0022】(b−3)キレート剤:亜リン酸トリエス
テル:トリオクチルホスファイト、トリデシルホスファ
イト、トリドデシルホスファイトなどの脂肪族ホスファ
イト;トリフェニルホスファイト、トリスノニルフェニ
ルホスファイト、トリス−t−ブチルフェニルホスファ
イトなどの芳香族ホスファイト;ジフェニルオクチルホ
スファイト、ジフェニルイソデシルホスファイト等の脂
肪族と芳香族の混合ホスファイト;ビスフェノールA−
ビスジアルキルホスファイト、ジアルキルペンタエリス
リトールジホスファイト、2,2’−メチレンビス−ジ
−t−ブチルフェニルオクチルホスファイト、10−デ
シロキシ−9,10−ジヒドロ−9−オキサ−10−ホ
スファフェナントレン等の他のホスファイト。(B-3) Chelating agent: phosphite triester: aliphatic phosphite such as trioctyl phosphite, tridecyl phosphite, tridodecyl phosphite; triphenyl phosphite, trisnonyl phenyl phosphite, tris Aromatic phosphites such as t-butylphenyl phosphite; aliphatic and aromatic mixed phosphites such as diphenyloctyl phosphite and diphenylisodecyl phosphite; bisphenol A-
Bisdialkyl phosphite, dialkyl pentaerythritol diphosphite, 2,2'-methylenebis-di-t-butylphenyloctyl phosphite, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene and the like Other phosphites.
【0023】リン酸モノ−またはジエステルまたはその
金属塩:エステルのアルコール部分として炭素数1〜2
2の脂肪族アルコール、アルキル基のような置換基を有
してもよいフェノール、これらアルコールまたはフェノ
ールのエチレンオキシド付加物を有するリン酸のモノ−
またはジエステル、およびこれらリン酸エステルのL
i,Na,K,Mg,Cu,Ca,Sr,Ba,Zn,
Al等の金属塩。Phosphoric acid mono- or diesters or metal salts thereof: having 1 to 2 carbon atoms as the alcohol moiety of the ester
Aliphatic alcohols, phenols which may have a substituent such as an alkyl group, mono-phosphates of phosphoric acid having ethylene oxide adducts of these alcohols or phenols
Or diesters, and L of these phosphate esters
i, Na, K, Mg, Cu, Ca, Sr, Ba, Zn,
Metal salts such as Al.
【0024】縮合リン酸塩:ピロリン酸ナトリウム、ピ
ロリン酸カリウム、酸性ピロリン酸ナトリウム、酸性メ
タリン酸ナトリウム、トリポリリン酸ナトリウム、ヘキ
サメタリン酸ナトリウムなど。Condensed phosphates: sodium pyrophosphate, potassium pyrophosphate, sodium acid pyrophosphate, sodium acid metaphosphate, sodium tripolyphosphate, sodium hexametaphosphate and the like.
【0025】ジホスホン酸またはその金属塩:ヒドロキ
シエチリデン−1,1−ジホスホン酸、そのアルカリ金
属塩およびアルカリ土類金属塩。Diphosphonic acid or its metal salt: hydroxyethylidene-1,1-diphosphonic acid, its alkali metal salt and alkaline earth metal salt.
【0026】トリアゾール系キレート化合物:3−(N
−サリチロイル)アミノ−1,2,4−トリアゾール、
4−サリチリデンイミノ−3,5−ジフェニル−1,
2,4−トリアゾール、3,5−ビス(4−アミノ−
1,2,4−トリアゾール)など。Triazole chelate compound: 3- (N
-Salicyloyl) amino-1,2,4-triazole,
4-salicylideneimino-3,5-diphenyl-1,
2,4-triazole, 3,5-bis (4-amino-
1,2,4-triazole) and the like.
【0027】ヒドラジン系キレート化合物:N,N’−
ビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシ
フェニル)プロオニル〕ヒドラジン、デカンジカルボン
酸ジサリチロイルヒドラジド、デカンジカルボン酸ジ−
N’−ブチルサリチロイルヒドラジドなど。Hydrazine chelate compound: N, N'-
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) proonyl] hydrazine, decanedicarboxylic acid disalicyloyl hydrazide, decanedicarboxylic acid di-
N'-butylsalicyloyl hydrazide and the like.
【0028】多価カルボン酸またはその金属塩:コハク
酸、フマル酸、クエン酸、酒石酸、リンゴ酸、エチレン
ジアミン四酢酸、ニトリロ三酢酸、それらのアルカリ金
属塩およびアルカリ土類金属塩など。Polycarboxylic acids or metal salts thereof: succinic acid, fumaric acid, citric acid, tartaric acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, alkali metal salts and alkaline earth metal salts thereof.
【0029】上のエポキシ化合物、有機スズ化合物およ
びキレート剤は単独でも、または併用して含臭素難燃剤
へ添加することができる。添加量は含臭素難燃剤の0.
01〜50重量%、すなわち難燃剤100重量部あたり
0.01〜50重量部である。当然のことながら添加量
があまり少ないと酸化鉄との反応を阻害するのに十分で
はなく、過剰に添加すると所望の難燃度を達成するのに
必要な組成物の添加量が成形品の物性に悪影響するほど
多量になるので避けなければならない。The above epoxy compounds, organotin compounds and chelating agents can be added alone or in combination to the brominated flame retardant. The amount added is 0. 0 of brominated flame retardant.
01 to 50% by weight, that is, 0.01 to 50 parts by weight per 100 parts by weight of the flame retardant. Naturally, if the amount is too small, it is not enough to inhibit the reaction with iron oxide. It must be avoided because it is so large that it adversely affects
【0030】臭素系難燃剤とのブレンド方法は、乾式法
すなわち難燃剤とインヒビター成分とをヘンシェルミキ
サー、スピードミキサー、V型ブレンダー、ナウタミキ
サー、コニカルミキサー等の慣用の混合機を用いて均一
に混合する方法を採用することができる。インヒビター
成分の種類および添加量によって乾式法では均一な混合
物を得ることが困難な場合には湿式法を採用するのが好
ましい。例えばインヒビター成分を水または溶媒に溶
解、分散または乳化し、この液を難燃剤と混合した後乾
燥する方法、難燃剤の水または溶媒中のスラリーへイン
ヒビター成分を添加、混合した後、濾過して得られるケ
ーキを乾燥する方法などである。The method of blending with the brominated flame retardant is a dry method, that is, the flame retardant and the inhibitor component are uniformly mixed using a conventional mixer such as a Henschel mixer, a speed mixer, a V-type blender, a Nauta mixer, or a conical mixer. Can be adopted. If it is difficult to obtain a uniform mixture by the dry method depending on the type and amount of the inhibitor component, the wet method is preferably employed. For example, a method of dissolving, dispersing or emulsifying an inhibitor component in water or a solvent, mixing this liquid with a flame retardant and then drying the mixture, adding the inhibitor component to a slurry of the flame retardant in water or a solvent, mixing, and then filtering. For example, a method of drying the obtained cake.
【0031】本発明の難燃剤の使用対象となる熱可塑性
樹脂の典型例は、ポリエチレン、ポリプロピレン、ポリ
スチレン、ポリメタクリル酸メチル、HI−PS樹脂、
ABS樹脂、エチレン−酢酸ビニル樹脂(EVA)およ
びそれらのポリマーブレンドを含むがこれらに限られ
ず、他のすべての可燃性熱可塑樹脂が対象である。Typical examples of the thermoplastic resin for which the flame retardant of the present invention is used include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, HI-PS resin,
All other flammable thermoplastics, including but not limited to ABS resins, ethylene-vinyl acetate resins (EVA) and their polymer blends.
【0032】使用方法は、含まれている含臭素難燃剤を
単独に使用して熱可塑性樹脂を難燃化する場合と変わら
ない。The method of use is the same as the case of using the contained bromine-containing flame retardant alone to make the thermoplastic resin flame-retardant.
【0033】[0033]
【実施例】実施例1 テトラブロモビスフェノールA−ビスジブロモプロピル
エーテル(TBBA−BDBPE)1kgをスピードミ
キサーで混合しながら、ビスフェノールAジグリシジル
エーテル(旭電化工業(株)製アデカサイザーEP1
7;エポキシ当量190)の10%イソプロピルアルコ
ール溶液5gを加えてさらに10分間混合し、60℃の
送風乾燥機で6時間乾燥し、難燃剤組成物を得た。この
組成物の130℃×2時間の加熱減量は0.07%であ
った。この組成物と酸化鉄との重量比20:1の混合物
の1%および5%減量温度を測定し、表2に示す結果を
得た。Example 1 While mixing 1 kg of tetrabromobisphenol A-bisdibromopropyl ether (TBBA-BDBPE) with a speed mixer, bisphenol A diglycidyl ether (Adekaizer EP1 manufactured by Asahi Denka Kogyo KK) was used.
7; 10 g of a 10% isopropyl alcohol solution having an epoxy equivalent of 190) was added thereto, followed by mixing for further 10 minutes, followed by drying with a blow dryer at 60 ° C. for 6 hours to obtain a flame retardant composition. The loss on heating of this composition at 130 ° C. for 2 hours was 0.07%. The 1% and 5% weight loss temperatures of a 20: 1 weight ratio mixture of this composition and iron oxide were measured and the results shown in Table 2 were obtained.
【0034】次に以下の配合: 原料 重量部 ───────────────────── ──────── HI−PS樹脂(新日本製鉄化学(株)製 100 エスチレンH−65) 本発明の難燃剤組成物 7 三酸化アンチモン 2 イルガノックス1010 0.1 の混合物をヘンシェルミキサーで混合し、200℃に設
定した2軸押出機にて混練し、試験用樹脂ペレットを製
造し、このペレットを用いて難燃性および耐酸化鉄安定
性について試験した。結果を表2に示す。Next, the following composition: raw material parts by weight ───────────────────── HI-PS resin (Nippon Steel Chemical Co., Ltd.) (100 Estyrene H-65 manufactured by Co., Ltd.) The flame retardant composition of the present invention 7 A mixture of antimony trioxide 2 Irganox 1010 0.1 was mixed with a Henschel mixer and kneaded with a twin-screw extruder set at 200 ° C. The test resin pellets were manufactured, and the pellets were tested for flame retardancy and iron oxide stability. Table 2 shows the results.
【0035】実施例2 TBBA−BDBPE800gと、テトラブロモビスフ
ェノールAジグリシジルエーテル型エポキシ樹脂オリゴ
マー(エポキシ当量750)200gとをスピードミキ
サーを用いて10分間混合し、難燃剤組成物を得た。1
30℃×2時間の加熱減量は0.12%であった。Example 2 800 g of TBBA-BDBPE and 200 g of tetrabromobisphenol A diglycidyl ether type epoxy resin oligomer (epoxy equivalent: 750) were mixed for 10 minutes using a speed mixer to obtain a flame retardant composition. 1
The loss on heating at 30 ° C. for 2 hours was 0.12%.
【0036】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。ただし酸化鉄との混合物の
1%および5%減量温度の読みは、組成物中のTBBA
−BDBPE含有量に換算するためそれぞれ0.8%と
4%減量した値とした。This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained. However, the 1% and 5% weight loss temperature readings of the mixture with iron oxide are based on the TBBA in the composition.
-The values were reduced by 0.8% and 4%, respectively, for conversion to the BDBPE content.
【0037】実施例3 TBBA−BDBPE1kgをスピードミキサーで混合
しながら、テトラ(トリデシル)−4,4’−イソプロ
ピリデンジフェニルジホスファイト(城北化学工業
(株)製JA−805)2gを加え、30分間混合し、
難燃剤組成物を得た。Example 3 While 1 kg of TBBA-BDBPE was mixed with a speed mixer, 2 g of tetra (tridecyl) -4,4'-isopropylidenediphenyldiphosphite (JA-805 manufactured by Johoku Chemical Co., Ltd.) was added, and 30 Mix for a minute,
A flame retardant composition was obtained.
【0038】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【0039】実施例4 TBBA−BDBPE1kgと3−(N−サリチロイ
ル)アミノ−1,2,4−トリアゾール(旭電化工業
(株)製アデカスタブCDA−1M)10gをスピード
ミキサーを用いて混合し、難燃剤組成物を得た。Example 4 1 kg of TBBA-BDBPE and 10 g of 3- (N-salicyloyl) amino-1,2,4-triazole (Adeka Stab CDA-1M manufactured by Asahi Denka Kogyo KK) were mixed using a speed mixer. A flame retardant composition was obtained.
【0040】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【0041】実施例5 TBBA−BDBPE1kgをスピードミキサーで混合
しながら、ジスチレン化フェノールエチレンオキサイド
8モル付加物モノ−ジ混合リン酸エステルナトリウム塩
を50重量%含有する1:1水性メタノール溶液10g
をスプレーした。その後60℃の送風乾燥機で6時間乾
燥し、130℃×2時間の加熱減量が0.15%の難燃
剤組成物を得た。Example 5 10 g of a 1: 1 aqueous methanol solution containing 50% by weight of a mono-di-mixed phosphoric acid ester monoester salt of 8 mol of distyrenated phenol ethylene oxide while mixing 1 kg of TBBA-BDBPE with a speed mixer.
Was sprayed. Thereafter, the resultant was dried with a blow dryer at 60 ° C. for 6 hours to obtain a flame retardant composition having a loss on heating of 130 ° C. × 2 hours of 0.15%.
【0042】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。ただし1%および5%減量
温度の測定には、組成物を130℃×2時間の加熱減量
が0.08%になるまでさらに乾燥して用いた。This composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained. However, for the measurement of the 1% and 5% weight loss temperatures, the composition was further dried until the weight loss on heating at 130 ° C. × 2 hours became 0.08%.
【0043】実施例6 TBBA−BDBPE1kgをヘンシェルミキサー中で
攪拌しながら、ヒドロキシエチリデン−1,1−ジホス
ホン酸(四日市合成(株)製キレート101)の20%
水溶液(NaOHでpH6に調節)100gを添加し、
さらに3分間混合した後60℃の送風乾燥機にて乾燥
し、130℃×2時間の加熱減量が0.1%の難燃剤組
成物を得た。Example 6 While stirring 1 kg of TBBA-BDBPE in a Henschel mixer, 20% of hydroxyethylidene-1,1-diphosphonic acid (Chelate 101 manufactured by Yokkaichi Gosei Co., Ltd.) was added.
100 g of an aqueous solution (adjusted to pH 6 with NaOH) is added,
After further mixing for 3 minutes, the mixture was dried with a blow dryer at 60 ° C. to obtain a flame retardant composition having a heating loss of 0.1% at 130 ° C. × 2 hours.
【0044】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【0045】実施例7 TBBA−BDBPE1kgをイソプロピルアルコール
1L中にホモミキサーを用いて分散した。これにニトリ
ロ三酢酸ジナトリウム塩の10%水溶液100gを徐々
に滴下し、滴下終了後5B濾紙で濾過し、60℃の送風
機で乾燥し、難燃剤組成物を得た。Example 7 1 kg of TBBA-BDBPE was dispersed in 1 L of isopropyl alcohol using a homomixer. To this, 100 g of a 10% aqueous solution of nitrilotriacetic acid disodium salt was gradually added dropwise, and after completion of the addition, the mixture was filtered with a 5B filter paper and dried with a blower at 60 ° C. to obtain a flame retardant composition.
【0046】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【0047】実施例8 TBBA−BDBPE1kgとジブチルスズマレエート
ポリマー(mp.105〜125℃)10gをスピード
ミキサー中で混合し、難燃剤組成物を得た。Example 8 1 kg of TBBA-BDBPE and 10 g of dibutyltin maleate polymer (mp. 105-125 ° C.) were mixed in a speed mixer to obtain a flame retardant composition.
【0048】この組成物について実施例1と同様に試験
し、表2に示す結果を得た。The composition was tested in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【0049】実施例9 ヘキサブロモシクロドデカン(HBCD)1kgと、α
−オレフィン(炭素数18〜22)エポキシドのイソプ
ロパノール中10%溶液10gをスピードミキサー中で
混合し、60℃の送風乾燥機で乾燥し、130℃×2時
間の加熱減量が0.06%の難燃剤組成物を得た。Example 9 1 kg of hexabromocyclododecane (HBCD) and α
10 g of a 10% solution of olefin (C18-22) epoxide in isopropanol is mixed in a speed mixer, dried in a blast drier at 60 ° C., and has a loss on heating of 130 ° C. × 2 hours of 0.06%. A flame retardant composition was obtained.
【0050】この組成物を下記配合: 原料 重量部 ───────────────────── ──────── HI−PS樹脂(新日本製鉄化学(株)製 100 エスチレンH−65) 本発明の難燃剤組成物 3.5 イルガノックス1010 0.2 に従ってヘンシェルミキサー中で混合し、200℃に設
定した2軸押出機にて混練し、試験用樹脂ペレットを製
造した。This composition was formulated as follows: parts by weight of raw material ───────────────────── HI-PS resin (Nippon Steel Corporation) (100 Estyrene H-65 manufactured by Chemical Co., Ltd.) The flame retardant composition of the present invention 3.5 was mixed in a Henschel mixer according to Irganox 1010 0.2, kneaded with a twin screw extruder set at 200 ° C., and tested. Resin pellets were produced.
【0051】このペレットから成形した試験片について
実施例1と同様に難燃試験および耐酸化鉄安定性試験を
実施し、表3に示す結果を得た。ただし耐酸化鉄安定性
試験においては酸化鉄の混合量をペレットの5重量%へ
変更した。A test piece molded from the pellet was subjected to a flame retardancy test and an iron oxide resistance stability test in the same manner as in Example 1, and the results shown in Table 3 were obtained. However, in the iron oxide stability test, the mixing amount of iron oxide was changed to 5% by weight of the pellet.
【0052】実施例10 HBCD1kgと、セスキラウリルリン酸エステルの1
0%イソピルアルコール溶液200gをスピードミキサ
ー中で混合し、60℃の送風乾燥機で乾燥し、130℃
×2時間の加熱減量0.08%の難燃剤組成物を得た。Example 10 1 kg of HBCD and sesquilauryl phosphate 1
200 g of a 0% isopropyl alcohol solution was mixed in a speed mixer, dried with a blast dryer at 60 ° C, and dried at 130 ° C.
A flame retardant composition having a heat loss of 0.08% for 2 hours was obtained.
【0053】この組成物について実施例9と同様に試験
し、表2に示す結果を得た。The composition was tested in the same manner as in Example 9 and the results shown in Table 2 were obtained.
【0054】実施例11 HBCD1kgと、セスキフェニルリン酸エステルカル
シウム塩の30%水性スラリー100gをスピードミキ
サー中で混合した後、60℃の送風乾燥機にて乾燥し、
130℃×2時間の加熱減量が0.12%の難燃剤組成
物を得た。Example 11 After mixing 1 kg of HBCD and 100 g of a 30% aqueous slurry of calcium sesquiphenyl phosphate ester in a speed mixer, the mixture was dried with a blow dryer at 60 ° C.
A flame retardant composition having a loss on heating of 130 ° C. for 2 hours of 0.12% was obtained.
【0055】この組成物について実施例9と同様に試験
し、表3に示す結果を得た。ただし1%および5%減量
温度の測定には、組成物を130℃×2時間の加熱減量
が0.05%になるまでさらに60℃で乾燥して用い
た。This composition was tested in the same manner as in Example 9, and the results shown in Table 3 were obtained. However, for the measurement of the 1% and 5% weight loss temperatures, the composition was further dried at 60 ° C. until the weight loss on heating at 130 ° C. × 2 hours became 0.05%.
【0056】実施例12 HBCD1kgとジオクチルスズマレエートポリマー
(mp.91〜101℃)10gをスピードミキサーで
混合し、難燃剤組成物を得た。この組成物の130℃×
2時間の加熱減量は0.06%であった。Example 12 1 kg of HBCD and 10 g of dioctyltin maleate polymer (mp. 91 to 101 ° C.) were mixed with a speed mixer to obtain a flame retardant composition. 130 ° C. of the composition
The loss on heating for 2 hours was 0.06%.
【0057】この組成物について実施例9と同様に試験
し、表3に示す結果を得た。This composition was tested in the same manner as in Example 9, and the results shown in Table 3 were obtained.
【0058】比較例1 実施例1において、130℃×2時間の加熱減量が0.
05%のTBBA−BDBPE原末を用いたほかは実施
例1に同じ。Comparative Example 1 In Example 1, the loss on heating at 130 ° C. × 2 hours was 0.
Same as Example 1 except that 05% TBBA-BDBPE bulk powder was used.
【0059】比較例2 実施例9において、130℃×2時間の加熱減量が0.
08%のHBCD原末を用いたほかは実施例9に同じ。Comparative Example 2 In Example 9, the loss on heating at 130 ° C. for 2 hours was 0.
Same as Example 9 except that 08% HBCD bulk powder was used.
【0060】[0060]
【試験方法】難燃試験:試験用樹脂ペレットを200℃
に設定した射出成形機を用いてUL−94難燃テストピ
ース(1/8インチ厚み)に成形し、UL−94難燃試
験法によって試験した。[Test method] Flame retardancy test: Test resin pellets at 200 ° C
The test piece was molded into a UL-94 flame-retardant test piece (1/8 inch thick) using an injection molding machine set as described above, and tested by the UL-94 flame-retardant test method.
【0061】耐酸化鉄安定性試験:樹脂ペレット100
部とFe2 O3 2部(実施例1〜8、比較例1)または
5部(実施例9〜12、比較例2)をヘンシェルミキサ
ーで混合し、200kg/cm2 ,230℃×20分の
条件で1/16インチ厚みの試験片にプレス成形し、コ
ールドプレスで5分間冷却した。得られた試験片を2分
し、一方はシリカゲルデシケーター中室温で、他方はR
H80%,温度40℃の恒温恒湿オーブン中でそれぞれ
5日間保存し、表面状態を観察し、以下の基準に従って
評価した。 〇:両者ともに成形直後の表面状態との差がなかった。 △:デシケーター中で保存したものは変化がなく、恒温
恒湿オーブン中保存したものはふくれが生じた。 ×:成形直後に表面にボイドまたはシンクマークが発生
し、恒温恒湿オーブン中保存のものはふくれを生じた。Iron oxide resistance stability test: resin pellet 100
And 2 parts of Fe 2 O 3 (Examples 1 to 8 and Comparative Example 1) or 5 parts (Examples 9 to 12 and Comparative Example 2) were mixed with a Henschel mixer, and 200 kg / cm 2 , 230 ° C. × 20 minutes Was pressed into a test piece having a thickness of 1/16 inch under the conditions described in the above, and cooled by a cold press for 5 minutes. The obtained test piece was divided into two parts, one was at room temperature in a silica gel desiccator, and the other was R
Each was stored for 5 days in a constant temperature and humidity oven at 80% H and a temperature of 40 ° C., and the surface condition was observed and evaluated according to the following criteria. 〇: There was no difference between the two in the surface state immediately after molding. Δ: No change was observed in the sample stored in the desiccator, and blistering occurred in the sample stored in the constant temperature and humidity oven. ×: Voids or sink marks were generated on the surface immediately after molding, and those stored in a constant-temperature and constant-humidity oven blistered.
【0062】[0062]
【表2】 [Table 2]
【0063】[0063]
【表3】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4H028 AA07 AA28 AA29 AA30 AA35 4J002 AA011 BH022 CD042 CD082 CD132 CD142 EB096 EB136 EJ056 EL027 EQ027 EU167 EU196 EV066 EW067 EW127 EZ017 EZ067 FD136 FD202 FD207 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H028 AA07 AA28 AA29 AA30 AA35 4J002 AA011 BH022 CD042 CD082 CD132 CD142 EB096 EB136 EJ056 EL027 EQ027 EU167 EU196 EV066 EW067 EW127 EZ017 EZ067 FD136 FD202 FD
Claims (5)
て成形される熱可塑性樹脂のための耐酸化鉄性を有する
難燃剤組成物であって、 (a)当該難燃剤単独の130℃×2時間の加熱減量が
0.1重量%以下であり、当該難燃剤と酸化鉄との重量
比20:1の混合物の空気気流中の示差熱分析(昇温速
度10℃/分)により測定した1%および5%減量温度
が、当該難燃剤単独の同じ条件下の示差熱分析により測
定した1%および5%減量温度よりそれぞれ少なくとも
30℃低い含臭素難燃剤、および(b)前記難燃剤の
0.01〜50重量%のエポキシ当量1000以下を有
するエポキシ化合物、有機スズ化合物、キレート剤また
はそれらの混合物、を含んでいることを特徴とする難燃
剤組成物。1. A flame retardant composition having iron oxide resistance for a thermoplastic resin molded using a device which may come into contact with iron oxide, comprising: (a) 130 flame retardant alone. The heat loss at 2 ° C. × 2 hours was 0.1% by weight or less, and the mixture of the flame retardant and iron oxide at a weight ratio of 20: 1 was analyzed by differential thermal analysis (air-heating rate: 10 ° C./min) in an air stream. A bromine-containing flame retardant whose measured 1% and 5% weight loss temperatures are at least 30 ° C. respectively lower than the 1% and 5% weight loss temperatures measured by differential thermal analysis of the flame retardant alone under the same conditions; and A flame retardant composition comprising an epoxy compound, an organotin compound, a chelating agent or a mixture thereof having an epoxy equivalent of 1000 or less at 0.01 to 50% by weight of the flame retardant.
ロオクタン、ヘキサブロモシクロドデカン、トリブロモ
フェニル−ジブロモプロピルエーテル、トリブロモフェ
ニル−1,2−ジブロモ−2−メチルプロピルエーテ
ル、テトラブロモビスフェノールA−ビスジブロモプロ
ピルエーテル、テトラブロモビスフェノールS−ビスジ
ブロモプロピルエーテルおよびトリスジブロモプロピル
イソシアヌレートから選ばれる請求項1の組成物。2. The brominated flame retardant (a) is selected from tetrabromocyclooctane, hexabromocyclododecane, tribromophenyl-dibromopropyl ether, tribromophenyl-1,2-dibromo-2-methylpropyl ether, 2. The composition of claim 1 wherein the composition is selected from bisphenol A-bisdibromopropyl ether, tetrabromobisphenol S-bisdibromopropyl ether and trisdibromopropyl isocyanurate.
オレフィンエポキシド、エポキシ化不飽和脂肪酸トリグ
リセリド、多価フェノールのポリグリシジルエーテル、
多価アルコールのポリグリシジルエーテル、多価カルボ
ン酸のポリグリシジルエステル、芳香族アミンのN,N
−ジ−(2,3−エポキシプロピル)誘導体、およびイ
ソシアヌル酸2,3−エポキシプロピルエステルから選
ばれる請求項1または2の組成物。3. The epoxy compound according to claim 1, wherein said epoxy compound has 8 to 30 carbon atoms.
Olefin epoxide, epoxidized unsaturated fatty acid triglyceride, polyglycidyl ether of polyhydric phenol,
Polyglycidyl ether of polyhydric alcohol, polyglycidyl ester of polycarboxylic acid, N, N of aromatic amine
3. The composition according to claim 1, wherein the composition is selected from -di- (2,3-epoxypropyl) derivatives and isocyanuric acid 2,3-epoxypropyl ester.
レエートポリマー、ジ−n−オクチルスズマレエートポ
リマー、ジ−n−ブチルスズ−3−メルカプトプロピオ
ネート、ジ−n−オクチルスズ−3−メルカプトプロピ
オネート、ジ−n−ブチルスズメルカプトアセテート、
ジエチレングリコールビス(ブチルスズチオアセテー
ト)、ジブチルスズサルファイド、ジオクチルスズサル
ファイド、ジブチルスズジオクチルメルカプタイドおよ
びジメチルスズ(エチレングリコールモノチオグリコレ
ート)から選ばれる請求項1または2の組成物。4. The organic tin compound is di-n-butyltin maleate polymer, di-n-octyltin maleate polymer, di-n-butyltin-3-mercaptopropionate, di-n-octyltin-3-ion. Mercaptopropionate, di-n-butyltin mercaptoacetate,
3. The composition according to claim 1, wherein the composition is selected from diethylene glycol bis (butyltin thioacetate), dibutyltin sulfide, dioctyltin sulfide, dibutyltin dioctylmercaptide and dimethyltin (ethylene glycol monothioglycolate).
ン酸モノ−もしくはジエステルまたはそれらの金属塩、
縮合リン酸塩、ジホスホン酸またはその金属塩、トリア
ゾール系キレート化合物、ヒドラジン系キレート化合
物、および多価カルボン酸またはその金属塩から選ばれ
る請求項1または2の組成物。5. The chelating agent is a phosphite triester, a phosphate mono- or diester or a metal salt thereof,
The composition according to claim 1, wherein the composition is selected from condensed phosphate, diphosphonic acid or a metal salt thereof, a triazole chelate compound, a hydrazine chelate compound, and a polycarboxylic acid or a metal salt thereof.
Priority Applications (1)
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---|---|---|---|
JP18130399A JP2001011461A (en) | 1999-06-28 | 1999-06-28 | Bromine-containing flame-retarded composition having resistance to iron oxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18130399A JP2001011461A (en) | 1999-06-28 | 1999-06-28 | Bromine-containing flame-retarded composition having resistance to iron oxide |
Publications (1)
Publication Number | Publication Date |
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JP2001011461A true JP2001011461A (en) | 2001-01-16 |
Family
ID=16098327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18130399A Pending JP2001011461A (en) | 1999-06-28 | 1999-06-28 | Bromine-containing flame-retarded composition having resistance to iron oxide |
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Country | Link |
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JP (1) | JP2001011461A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006022285A (en) * | 2004-07-09 | 2006-01-26 | Kaneka Corp | Styrene-based resin foamed product and preparation of the same |
JP2014077030A (en) * | 2012-10-09 | 2014-05-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Granular flame-retardant composition and thermoplastic resin composition |
JP6262384B1 (en) * | 2016-10-03 | 2018-01-17 | 東洋スチレン株式会社 | Flame retardant resin composition and flame retardant resin molded article |
-
1999
- 1999-06-28 JP JP18130399A patent/JP2001011461A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006022285A (en) * | 2004-07-09 | 2006-01-26 | Kaneka Corp | Styrene-based resin foamed product and preparation of the same |
JP2014077030A (en) * | 2012-10-09 | 2014-05-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Granular flame-retardant composition and thermoplastic resin composition |
JP6262384B1 (en) * | 2016-10-03 | 2018-01-17 | 東洋スチレン株式会社 | Flame retardant resin composition and flame retardant resin molded article |
JP2018059041A (en) * | 2016-10-03 | 2018-04-12 | 東洋スチレン株式会社 | Flame-retardant resin composition and flame-retardant resin molded body |
US10920039B2 (en) | 2016-10-03 | 2021-02-16 | Toyo Styrene Co., Ltd. | Flame-retardant resin composition and flame-retardant resin molded article |
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