JP7400156B2 - Flame retardant polyurethane resin composition - Google Patents
Flame retardant polyurethane resin composition Download PDFInfo
- Publication number
- JP7400156B2 JP7400156B2 JP2019039171A JP2019039171A JP7400156B2 JP 7400156 B2 JP7400156 B2 JP 7400156B2 JP 2019039171 A JP2019039171 A JP 2019039171A JP 2019039171 A JP2019039171 A JP 2019039171A JP 7400156 B2 JP7400156 B2 JP 7400156B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- polyurethane resin
- flame retardant
- retardant
- melamine
- 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.)
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- 239000003063 flame retardant Substances 0.000 title claims description 110
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 105
- 229920005749 polyurethane resin Polymers 0.000 title claims description 44
- 239000011342 resin composition Substances 0.000 title claims description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 25
- 229920000877 Melamine resin Polymers 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 9
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 9
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229920000388 Polyphosphate Polymers 0.000 claims description 8
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001205 polyphosphate Substances 0.000 claims description 8
- 235000011176 polyphosphates Nutrition 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 4
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims 1
- 229920005862 polyol Polymers 0.000 description 26
- 150000003077 polyols Chemical class 0.000 description 22
- 239000000203 mixture Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 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 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- IRIAEMUUDSWZOX-UHFFFAOYSA-L 2,2-dibutyl-1,3,2-oxathiastanninan-6-one Chemical compound CCCC[Sn]1(CCCC)OC(=O)CCS1 IRIAEMUUDSWZOX-UHFFFAOYSA-L 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ACOQOLIJGGKILA-UHFFFAOYSA-N 2-methylpentane-1,1-diol Chemical compound CCCC(C)C(O)O ACOQOLIJGGKILA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- TVAYWUPSRJPZRS-UHFFFAOYSA-N [C](N=C=O)N=C=O Chemical compound [C](N=C=O)N=C=O TVAYWUPSRJPZRS-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ハロゲン化合物を用いないノンハロゲンタイプの難燃剤を含む難燃性ポリウレタン樹脂組成物であり、燃焼時にも溶融滴下がなく炭化層を容易に形成する難燃性ポリウレタン樹脂組成物及びその成形体並びに難燃性ポリウレタン樹脂組成物で使用するポリウレタン用難燃剤組成物に関する。 The present invention is a flame-retardant polyurethane resin composition containing a non-halogen type flame retardant that does not use a halogen compound, and a flame-retardant polyurethane resin composition that does not melt and drip even when burned and easily forms a carbonized layer, and its molding. The present invention relates to flame retardant compositions for polyurethane used in bodies and flame-retardant polyurethane resin compositions.
熱可塑性ポリウレタン樹脂は耐摩耗性弾性に優れるだけでなく、射出成形、押出成形などの成形性にも優れているので、自動車用部材、電線被覆、チューブなどの種々の分野で使用されている。しかし、熱可塑性ポリウレタン樹脂は難燃性に劣るため、難燃性が要求される分野での使用は避けられており、その点でまだ改善されるべき課題を有している。この課題を解決するため、熱可塑性ポリウレタン樹脂組成物の難燃性を改良する様々な方法がこれまで提案されている。 Thermoplastic polyurethane resins not only have excellent abrasion resistance and elasticity, but also have excellent moldability in injection molding, extrusion molding, etc., and are therefore used in various fields such as automobile parts, electric wire coatings, and tubes. However, thermoplastic polyurethane resins have poor flame retardancy, so their use in fields where flame retardancy is required is avoided, and there are still issues to be improved in this respect. To solve this problem, various methods have been proposed to improve the flame retardancy of thermoplastic polyurethane resin compositions.
具体例の一つとして、熱可塑性ポリウレタン樹脂組成物への難燃剤の添加が挙げられるが、この場合、熱可塑性ポリウレタン樹脂の優れた特性に悪影響を与えない程度の配合量で、かつ、難燃性能の向上が求められている。さらに、燃焼時の溶融物滴下を抑えることも要求されている。これらの要請にこたえるものとして、臭素などのハロゲン系元素を含有する難燃剤や赤燐などが有効な難燃剤として提案されている。しかし、ハロゲン系難燃剤は、優れた難燃効果が得られるものの、加工時に発生する腐食性ガスや環境に対する負荷の懸念があり、近年、ハロゲン系元素を用いずに高い難燃性を付与することが求められている。また、赤燐も優れた難燃効果を有するものの、配合された成形品が着色する問題、安全性の問題等もあり、必ずしも十分な解決策とはなっていない。 One specific example is the addition of flame retardants to thermoplastic polyurethane resin compositions. There is a need for improved performance. Furthermore, it is also required to suppress dripping of melt during combustion. To meet these demands, flame retardants containing halogen elements such as bromine, red phosphorus, and the like have been proposed as effective flame retardants. However, although halogen-based flame retardants can provide excellent flame-retardant effects, there are concerns about corrosive gases generated during processing and environmental impact, and in recent years, efforts have been made to provide high flame retardancy without using halogen-based elements. That is what is required. Further, although red phosphorus also has an excellent flame retardant effect, there are problems such as coloring of molded products containing it and safety problems, so it is not necessarily a sufficient solution.
そこで、特許文献１では、熱可塑性ポリウレタン、有機リン酸塩、特定のメラミン誘導体を含む混合物を溶融混錬した非ハロゲン系難燃性樹脂組成物が提案されている。この文献では、熱可塑性ポリウレタンとそれ以外の成分の配合比、有機リン酸塩配合量及び有機リン酸塩と特定のメラミン誘導体との配合割合を特定の範囲とすることで、タルクを使用せずに燃焼時の溶融物滴下を抑え、ＵＬ－９４Ｖ燃焼試験で「Ｖ－０」 レベルを達成できたことが報告されている。しかし、この例では有機リン酸塩と特定のメラミン誘導体の配合量が比較的多く、また難燃性能も必ずしも十分なものとは言えない。 Therefore, Patent Document 1 proposes a non-halogen flame-retardant resin composition obtained by melt-kneading a mixture containing a thermoplastic polyurethane, an organic phosphate, and a specific melamine derivative. In this document, talc is not used by setting the blending ratio of thermoplastic polyurethane and other components, the blending amount of organic phosphate, and the blending ratio of organic phosphate and a specific melamine derivative to specific ranges. It has been reported that the molten material dripping during combustion was suppressed and the "V-0" level was achieved in the UL-94V combustion test. However, in this example, the amounts of the organic phosphate and the specific melamine derivative are relatively large, and the flame retardant performance is not necessarily sufficient.
特許文献２では、熱可塑性ポリウレタンに、有機リン酸塩、タルク、ジペンタエリスリトール、メラミン誘導体を特定割合で配合することにより、難燃性、かつ燃焼時の溶融物滴下を抑制したポリウレタン樹脂組成物が提案されている。しかし、当該方法で得られる組成物は、高い難燃性を発揮するための必須成分が多く、種々の用途に適した材料設計がしにくいことから、より少ない成分で優れた難燃性を発揮することが求められている。また、タルクを使用する問題点もあり、タルクを必須成分とせずとも高い難燃性を付与することが求められている。
特許文献３では、ポリウレタン樹脂に無機酸メラミン塩、タルク及びゼオライトを所定量配合した切削加工用難燃性ポリウレタン樹脂形成性組成物が提案されている。しかし、この例でも、無機酸メラミン塩とタルク及びゼオライトの配合量が比較的多く、ポリウレタンの特性に対する影響は無視できるものではなく、また、前述のタルク配合の問題点も解決できていない。
Patent Document 2 discloses a polyurethane resin composition that is flame retardant and suppresses melt dripping during combustion by blending organic phosphate, talc, dipentaerythritol, and a melamine derivative in specific proportions with thermoplastic polyurethane. is proposed. However, the composition obtained by this method has many essential components to exhibit high flame retardancy, making it difficult to design materials suitable for various uses. is required to do so. Furthermore, there are also problems with the use of talc, and there is a need to provide high flame retardance without using talc as an essential component.
Patent Document 3 proposes a flame-retardant polyurethane resin-forming composition for cutting, which includes a polyurethane resin mixed with predetermined amounts of an inorganic acid melamine salt, talc, and zeolite. However, even in this example, the amount of inorganic acid melamine salt, talc, and zeolite blended is relatively large, and the influence on the properties of polyurethane cannot be ignored, and the above-mentioned problem of talc blending has not been solved.
そこで本発明が解決しようとする課題は、熱可塑性ポリウレタンを含む樹脂組成物において、ハロゲン系元素を必須成分として含まず、かつより少ない配合量でありながら、燃焼時の溶融滴下が無く、難燃性能にも優れた難燃性ポリウレタン樹脂組成物及びその成形体並びにそこで使用する難燃剤を提供することにある。 Therefore, the problem to be solved by the present invention is to create a resin composition containing thermoplastic polyurethane that does not contain halogen-based elements as an essential component and has a lower blending amount, yet does not cause melting and dripping during combustion, and is flame retardant. An object of the present invention is to provide a flame-retardant polyurethane resin composition with excellent performance, a molded article thereof, and a flame retardant used therein.
本発明者等は、上記の課題を解決するため、鋭意研究を重ねた結果、難燃性ポリウレタンに式（１）で表される難燃剤を特定量で配合することで上記課題を解決できることを見出し、また、式（１）で表される難燃剤に難燃助剤を組合わせることで望ましい難燃性能が得られることを見出し、本発明を解決するに至った。
すなわち、本発明は、
（１）ポリウレタン樹脂１００重量部に対し、下記式（１）で表される難燃剤（ａ）を１０～４０重量部含み、難燃性規格ＵＬ－９４Ｖ法で、溶融滴下がなく、Ｖ－０基準に適合する難燃性能を有し、炭化性能に優れることを特徴とする難燃性ポリウレタン樹脂組成物、
In order to solve the above problems, the present inventors have conducted extensive research and found that the above problems can be solved by blending a specific amount of a flame retardant represented by formula (1) into flame-retardant polyurethane. Furthermore, the present inventors have discovered that desirable flame retardant performance can be obtained by combining the flame retardant represented by formula (1) with a flame retardant auxiliary agent, and the present invention has been solved.
That is, the present invention
(1) Contains 10 to 40 parts by weight of a flame retardant (a) represented by the following formula (1) per 100 parts by weight of polyurethane resin, and according to the flame retardant standard UL-94V method, there is no melting and dripping, and V- A flame-retardant polyurethane resin composition characterized by having flame-retardant performance that meets the 0 standard and excellent carbonization performance,
（２）前記難燃性ポリウレタン樹脂組成物が、難燃助剤（ｂ）をポリウレタン樹脂１００重量部に対し０～３０重量部含むことを特徴とする（１）に記載の炭化性能に優れる難燃性ポリウレタン樹脂組成物、
（３）前記難燃助剤（ｂ）がリン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種以上を含む炭化性能に優れることを特徴とする（１）又は（２）に記載の難燃性ポリウレタン樹脂組成物、
(2) The flame retardant polyurethane resin composition has excellent carbonization performance according to (1), characterized in that the flame retardant polyurethane resin composition contains 0 to 30 parts by weight of the flame retardant aid (b) based on 100 parts by weight of the polyurethane resin. flammable polyurethane resin composition,
(3) The flame retardant aid (b) contains one or more selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate, and has excellent carbonization performance. The flame-retardant polyurethane resin composition according to (1) or (2), characterized in that
（４）前記難燃剤（ａ）と前記難燃助剤（ｂ）の重量比が、（ａ）／（ｂ）＝１００／０～５０／５０であることを特徴とする（１）～（３）のいずれかに記載の難燃性ポリウレタン樹脂組成物、
（５）前記難燃剤（ａ）の金属ＭがＡｌであり、前記難燃助剤（ｂ）がポリリン酸メラミン、メラミン、シアヌル酸メラミン又はポリリン酸アンモニウムであることを特徴とする（１）～（４）のいずれかに記載の難燃性ポリウレタン樹脂組成物、
（６）難燃性ポリウレタン樹脂組成物において使用される難燃剤組成物であって、該難燃剤組成物が下記式（１）で表される難燃剤（ａ）を含むことを特徴とするポリウレタン用難燃剤組成物、
(4) The weight ratio of the flame retardant (a) and the flame retardant aid (b) is (a)/(b) = 100/0 to 50/50 (1) to ( The flame-retardant polyurethane resin composition according to any one of 3),
(5) The metal M of the flame retardant (a) is Al, and the flame retardant aid (b) is melamine polyphosphate, melamine, melamine cyanurate, or ammonium polyphosphate (1) The flame-retardant polyurethane resin composition according to any one of (4),
(6) A flame retardant composition used in a flame retardant polyurethane resin composition, the flame retardant composition containing a flame retardant (a) represented by the following formula (1): flame retardant composition for
（７）前記ポリウレタン用難燃剤組成物が、難燃助剤（ｂ）としてリン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種または２種以上の難燃助剤を含み、前記難燃剤（ａ）と前記難燃助剤（ｂ）の重量比が（ａ）／（ｂ）＝１００／０～５０／５０であることを特徴とする（６）に記載のポリウレタン用難燃剤組成物、
（８）（１）～（５）のいずれかに記載の難燃性ポリウレタン樹脂組成物から成形されてなることを特徴とする難燃性ポリウレタン樹脂成形体。
(7) In the flame retardant composition for polyurethane, the flame retardant aid (b) is one selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate; It is characterized in that it contains two or more types of flame retardant aids, and the weight ratio of the flame retardant (a) and the flame retardant aid (b) is (a)/(b) = 100/0 to 50/50. The flame retardant composition for polyurethane according to (6),
(8) A flame-retardant polyurethane resin molded article, characterized in that it is molded from the flame-retardant polyurethane resin composition according to any one of (1) to (5).
本発明によれば、熱可塑性ポリウレタンを含む樹脂組成物において、ハロゲン系元素を含まず、かつより少ない難燃剤配合量で、燃焼時の溶融滴下が無い、優れた難燃性を有する難燃性ポリウレタン樹脂組成物およびその成形体並びにそこで使用する難燃剤を提供することができる。 According to the present invention, in a resin composition containing thermoplastic polyurethane, a flame retardant that does not contain halogen elements, has a lower amount of flame retardant, and has excellent flame retardancy without melting and dripping during combustion. A polyurethane resin composition, a molded article thereof, and a flame retardant used therein can be provided.
本発明の非ハロゲン系の難燃性ポリウレタン樹脂組成物は、熱可塑性のポリウレタン樹脂と式（１）で表される難燃剤（ａ）を含むものであり、難燃剤（ａ）はポリウレタン樹脂１００重量部に対し１０～４０重量部含み、難燃性規格ＵＬ－９４Ｖ法で、溶融滴下がなく、Ｖ－０基準に適合する難燃性能を有し、炭化性能に優れる難燃性ポリウレタン樹脂組成物である。さらに、前記難燃性ポリウレタン樹脂組成物は、必要に応じて、ポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウム等の難燃助剤（ｂ）を含んでもよい。 The non-halogen flame-retardant polyurethane resin composition of the present invention contains a thermoplastic polyurethane resin and a flame retardant (a) represented by formula (1), and the flame retardant (a) contains polyurethane resin 100%. A flame-retardant polyurethane resin composition that contains 10 to 40 parts by weight and has flame-retardant properties that meet V-0 standards without melting and dripping according to the flame-retardant standard UL-94V method, and has excellent carbonization performance. It is a thing. Furthermore, the flame retardant polyurethane resin composition may contain a flame retardant aid (b) such as melamine polyphosphate, melamine, melamine cyanurate, ammonium polyphosphate, etc., if necessary.
本発明に用いる熱可塑性のポリウレタン樹脂としては、公知のものを使用できるが、有機ジイソシアネート、鎖伸長剤および高分子ポリオールから合成して得られたものを用いることが好ましい。具体的には、有機ジイソシアネートとしては、芳香族ジイソシアネート、脂肪族ジイソシアネートおよび脂環族ジイソシアネートからなる群より選ばれる有機ジイソシアネートを用いることができ、鎖伸長剤としては炭素原子数が２～１０の低分子量ジオールを用いることができ、高分子ポリオールとしてはポリカーボネートポリオール、ポリエステルポリオール、ポリエーテルポリオールなどを用いることができる。いずれの成分も、単独で用いることも、２種類以上を併用して用いることもでき、また、触媒を使用することも可能である。 As the thermoplastic polyurethane resin used in the present invention, any known thermoplastic polyurethane resin can be used, but it is preferable to use one synthesized from an organic diisocyanate, a chain extender, and a polymer polyol. Specifically, as the organic diisocyanate, an organic diisocyanate selected from the group consisting of aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate can be used, and as the chain extender, a low carbon diisocyanate having 2 to 10 carbon atoms can be used. Molecular weight diols can be used, and as the polymer polyols, polycarbonate polyols, polyester polyols, polyether polyols, etc. can be used. Any of the components can be used alone or in combination of two or more, and it is also possible to use a catalyst.
本発明に用いる熱可塑性ポリウレタン樹脂の各構成成分について説明する。
（有機ジイソシアネート）
熱可塑性ポリウレタン樹脂の構成成分である有機ジイソシアネートとしては、前述のとおり、芳香族ジイソシアネート、脂肪族ジイソシアネートおよび脂環族ジイソシアネートを使用することができる。
芳香族ジイソシアネートとしては、４，４’－ジフェニルメタンジイソシアネート、１，４－フェニレンジイソシアネート、トリレンジイソシアネート、１，５－ナフチレンジイソシアネートなどを挙げることができる。
Each component of the thermoplastic polyurethane resin used in the present invention will be explained.
(Organic diisocyanate)
As the organic diisocyanate that is a component of the thermoplastic polyurethane resin, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates can be used, as described above.
Examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, and 1,5-naphthylene diisocyanate.
脂肪族ジイソシアネートとしては、メチレンジイソシアネート、エチレンジイソシアネート、１－メチルエチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、２－メチルブタン－１，４－ジイソシアネート、ヘキサメチレンジイソシアネート、オクタメチレンジイソシアネート、２，５－ジメチルヘキサン－１，６－ジイソシアネートなどを挙げることができる。 Examples of aliphatic diisocyanates include methylene diisocyanate, ethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and 2,5-dimethylhexane. -1,6-diisocyanate and the like can be mentioned.
また、脂環式ジイソシアネートとしては、シクロヘキサンジイソシアネート、Ｐ，Ｐ’－シクロヘキシルメタンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネートなどを挙げることができる。
これらのイソシアネートは、単独で用いることも、２種類以上を併用して用いることもできる。
Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, P,P'-cyclohexylmethane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.
These isocyanates can be used alone or in combination of two or more.
（鎖伸長剤）
熱可塑性ポリウレタン樹脂の構成成分である鎖伸長剤としては、前述のとおり、炭素原子数が２～１０の低分子量ジオールを使用することができ、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチルペンタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、オクタンジオール、ノナンジオール、デカンジオール、トリメチールプロパン、などの脂肪族グリコール類、それ以外に１，６－ヘキサンジオールなどの低分子の脂環族ジオール類などが挙げられる。これらのポリオールは、単独で用いることも、２種類以上を併用して用いることもできる。得られる成形品にゴム弾性が要求される場合には、上記ポリオールとして脂肪族ジオールを用いることが好ましい。
(chain extender)
As the chain extender which is a component of the thermoplastic polyurethane resin, as mentioned above, low molecular weight diols having 2 to 10 carbon atoms can be used, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol. , 1,3-butanediol, 1,4-butanediol, 2-methylpentanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, octanediol, nonanediol, decanediol, trimethyl Other examples include aliphatic glycols such as propane, and low-molecular alicyclic diols such as 1,6-hexanediol. These polyols can be used alone or in combination of two or more. When rubber elasticity is required for the resulting molded product, it is preferable to use an aliphatic diol as the polyol.
（高分子ポリオール）
熱可塑性ポリウレタン樹脂の構成成分である高分子ポリオールとしては、例えば、ポリカーボネートポリオール、ポリエステルポリオール、ポリエーテルポリオールなどが挙げられる。これらのポリオールは、単独で用いることも、２種類以上を併用して用いることもできる。これらの高分子ポリオールの単独または混合物の平均官能基数は２が好ましく、平均分子量は５００～３００００の範囲が好ましく、平均分子量は５００～５０００の範囲が特に好ましい。
(High molecular polyol)
Examples of the polymer polyol that is a component of the thermoplastic polyurethane resin include polycarbonate polyol, polyester polyol, and polyether polyol. These polyols can be used alone or in combination of two or more. The average number of functional groups of these polymeric polyols alone or as a mixture is preferably 2, the average molecular weight is preferably in the range of 500 to 30,000, and the average molecular weight is particularly preferably in the range of 500 to 5,000.
（ポリエステルポリオール）
ポリエステルポリオールは、少なくとも１種のジカルボン酸と、少なくとも１種のジオールとを反応させることによって製造することができる。例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、あるいはその他の低分子ジオール成分の１種または２種以上と、例えば、アジピン酸、ピメリン酸、スベリン酸、セバシン酸、テレフタル酸、イソフタル酸等の低分子ジカルボン酸の１種または２種以上との縮重合物やラクトンの開環重合で得たラクトンポリオール、例えば、ポリプロピオラクトンポリオール、ポリカプロラクトンポリオール、ポリパレロラクトンポリオールなどが挙げられるが、これらに限定されるものではない。
(Polyester polyol)
Polyester polyols can be produced by reacting at least one dicarboxylic acid and at least one diol. For example, one or more of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or other low molecular weight diol components, for example, adipic acid, Lactone polyols obtained by ring-opening polymerization of lactones or condensation products with one or more low-molecular-weight dicarboxylic acids such as pimelic acid, suberic acid, sebacic acid, terephthalic acid, and isophthalic acid, such as polypropiolactone polyol , polycaprolactone polyol, polyparerolactone polyol, etc., but are not limited to these.
（ポリエーテルポリオール）
ポリエーテルポリオールは、アルキレンオキシドの付加重合によって製造することができ、例えば、ポリプロピレンエーテルポリオール、ポリテトラメチレンエーテルポリオール、ヘキサメチレンエーテルポリオールなどが挙げられる。
(Polyether polyol)
Polyether polyols can be produced by addition polymerization of alkylene oxides, and include, for example, polypropylene ether polyols, polytetramethylene ether polyols, hexamethylene ether polyols, and the like.
（ポリカーボネートポリオール）
熱可塑性ポリウレタン樹脂に耐候性や耐熱性が要求される場合は、高分子ポリオールとして、ポリカーボネートポリオールを用いることが好ましい。ポリカーボネートポリオールは、例えば、低分子ポリオールとジアルキルカーボネートもしくはジアリールカーボネートとを縮合反応させることにより製造することができ、例えば、１，６－ヘキサンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、シクロヘキサンジメタノール、などが挙げられる。また、ジアルキルカーボネートもしくはジアリールカーボネートとしては、例えば、ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネートなどが挙げられる。
(Polycarbonate polyol)
When weather resistance and heat resistance are required for the thermoplastic polyurethane resin, it is preferable to use polycarbonate polyol as the polymer polyol. Polycarbonate polyols can be produced, for example, by condensation reaction of low-molecular polyols and dialkyl carbonates or diaryl carbonates, such as 1,6-hexanediol, 1,5-pentanediol, 3-methyl-1, Examples include 5-pentanediol, cyclohexanedimethanol, and the like. Examples of the dialkyl carbonate or diaryl carbonate include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and ethylene carbonate.
（触媒）
触媒を使用する場合、通常用いられているウレタン化触媒がいずれも使用できる。例えばトリエチルアミン、ジメチルシクロヘキシルアミン、Ｎ－メチルモルホリン、Ｎ，Ｎ’－ジメチルピペラジン、２－（ジメチルアミノエトキシ）エタノールおよびジアザビシクロ（２，２，２）－オクタンなどの三級アミン系触媒、オクタン酸第一錫、オレイン酸第一錫、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫マレート、ジブチル錫メルカプトプロピオネート、ジブチル錫ドデシルメルカプトなどの有機錫触媒などが挙げられる。使用する触媒の量は使用原料、反応条件、所望の反応時間などによって決定されるが、おおむね触媒は反応混合物全重量の０．０００１～５質量％、好ましくは０．０００１～２質量％の範囲で活性水素化合物側に混合して使用される。
熱可塑性ポリウレタン樹脂を調製するにあたって、イソシアネート基と活性水素との反応当量比は、好ましくは、０．９５～１．１０の範囲、より好ましくは、０．９６～１．０５、最も好ましくは、０．９７～１．０３の範囲である。
(catalyst)
When using a catalyst, any commonly used urethanization catalyst can be used. For example, tertiary amine catalysts such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol and diazabicyclo(2,2,2)-octane, octanoic acid Examples include organotin catalysts such as tin, stannous oleate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin mercaptopropionate, and dibutyltin dodecylmercapto. The amount of the catalyst to be used is determined depending on the raw materials used, reaction conditions, desired reaction time, etc., but the amount of the catalyst is generally in the range of 0.0001 to 5% by mass, preferably 0.0001 to 2% by mass of the total weight of the reaction mixture. It is used by mixing it with the active hydrogen compound side.
In preparing a thermoplastic polyurethane resin, the reaction equivalent ratio of isocyanate groups to active hydrogen is preferably in the range of 0.95 to 1.10, more preferably 0.96 to 1.05, and most preferably, It ranges from 0.97 to 1.03.
本発明の熱可塑性ポリウレタン樹脂の製造は、通常の熱可塑性ポリウレタンの製造方法を採用することができ、バッチ反応器または連続反応押出し成形機を使用することができる。上記バッチ反応器を使用する方法では、反応成分は反応器に導入後、ある程度まで反応に供され、次いで、外部のバット上に出され、続いて、８０～２００℃の範囲、好ましくは１２０～１８０℃の温度範囲での熱処理を経た後、粉砕して製造される。
一方、上記連続反応押出し成形機を使用する方法では、反応成分は、原材料貯蔵タンクから測定ユニットを介して押出し成形機に供給され、上記反応は押出し成形機内において完了し、押出ダイから押し出される。上記連続反応押し出し成形機を使用する方法は、上記バッチ反応器を使用する方法と比較して、熱移動が均一に行われるので、生成物の品質均一性が得られる点で好ましい。上記連続反応押出し成形機を用いる熱可塑性ポリウレタン樹脂の製造では、押出し成形機の温度は、好ましくは、１２０～２５０℃の範囲、より好ましくは、１７０～２１０℃の範囲である。
The thermoplastic polyurethane resin of the present invention can be manufactured by a conventional thermoplastic polyurethane manufacturing method, and a batch reactor or a continuous reaction extrusion molding machine can be used. In the above method using a batch reactor, the reaction components are introduced into the reactor and subjected to reaction to a certain extent, and then discharged onto an external vat and subsequently heated to a temperature in the range of 80-200°C, preferably 120-200°C. It is manufactured by undergoing heat treatment in a temperature range of 180°C and then pulverizing it.
On the other hand, in the method using the continuous reaction extruder, the reaction components are supplied from the raw material storage tank to the extruder through the measuring unit, the reaction is completed in the extruder, and then extruded from the extrusion die. Compared to the method using the batch reactor, the method using the continuous reaction extruder is preferable in that heat transfer is performed uniformly, so that uniform quality of the product can be obtained. In the production of thermoplastic polyurethane resin using the continuous reaction extrusion molding machine described above, the temperature of the extrusion molding machine is preferably in the range of 120 to 250°C, more preferably in the range of 170 to 210°C.
次に、本発明に用いる難燃剤成分について説明する。
（難燃剤）
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物に用いる難燃剤（ａ）としては、式(１)で表されるものを使用することができる。
Next, the flame retardant component used in the present invention will be explained.
(Flame retardants)
As the flame retardant (a) used in the flame retardant polyurethane resin composition with excellent carbonization performance of the present invention, those represented by formula (1) can be used.
本発明の式（１）で表される難燃剤（ａ）は、通常は無色または白色の粉体であるため、製品の着色性を阻害することなく使用可能である。これらの中では特にＡｌ塩又はＴｉ塩、中でもＡｌ塩が難燃性、炭化性能において優れた効果を有している。
上記式（１）で表される難燃剤（ａ）は、ホスフィン酸、またはホスフィン酸のアルカリ金属塩のいずれか一つと、マグネシウム、カルシウム、アルミニウム、チタン、亜鉛又はジルコニウムの硝酸塩、硫酸塩、塩酸塩、炭酸塩および水酸化物のいずれか一つとを、水溶液状態で、加熱、反応させることによって得られる無機系の難燃剤である。
本発明の難燃剤組成物に用いる難燃剤（ａ）の平均粒子径は１～５０μｍが好ましく、特に３～２０μｍが好ましい。平均粒子径が５０μｍを超えると、難燃性ポリウレタン樹脂組成物の機械物性が悪化するおそれがあり、平均粒子径が１μｍ未満だと、上記ポリウレタン樹脂組成物中での凝集物の発生または、極度の樹脂の溶融粘度の増加が起こるおそれがある。
Since the flame retardant (a) represented by formula (1) of the present invention is usually a colorless or white powder, it can be used without impairing the coloring properties of products. Among these, Al salts or Ti salts, especially Al salts, have excellent effects on flame retardancy and carbonization performance.
The flame retardant (a) represented by the above formula (1) is composed of phosphinic acid or an alkali metal salt of phosphinic acid, and a nitrate, sulfate, or hydrochloric acid of magnesium, calcium, aluminum, titanium, zinc, or zirconium. It is an inorganic flame retardant obtained by heating and reacting one of salt, carbonate, and hydroxide in an aqueous solution state.
The average particle diameter of the flame retardant (a) used in the flame retardant composition of the present invention is preferably 1 to 50 μm, particularly preferably 3 to 20 μm. If the average particle size exceeds 50 μm, the mechanical properties of the flame-retardant polyurethane resin composition may be deteriorated, and if the average particle size is less than 1 μm, the formation of aggregates in the polyurethane resin composition or extreme The melt viscosity of the resin may increase.
また、難燃剤（ａ）の配合量は、ポリウレタン樹脂１００重量部に対し、１０～４０重量部配合することが好ましく、より好ましくは、１５～３０重量部配合することが好ましい。難燃剤（ａ）の配合量がポリウレタン樹脂１００重量部に対し１０重量部未満の場合は目的とする難燃性能、燃焼時の溶融物滴下防止性能や炭化性能を得ることが難しく、また、４０重量部を超える場合は熱可塑性ポリウレタンの成形性や機械的性能に問題が生じる可能性がある。 The flame retardant (a) is preferably blended in an amount of 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, per 100 parts by weight of the polyurethane resin. If the blending amount of the flame retardant (a) is less than 10 parts by weight per 100 parts by weight of the polyurethane resin, it is difficult to obtain the desired flame retardant performance, performance to prevent melt dripping during combustion, and carbonization performance. If the amount exceeds parts by weight, problems may arise in the moldability and mechanical performance of the thermoplastic polyurethane.
（難燃助剤）
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物には、必要に応じ難燃助剤（ｂ）を配合することもでき、該難燃助剤（ｂ）としては、リン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種以上を使用することができる。上記難燃助剤（ｂ）の中では、ポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウムが好ましい。
(Flame retardant aid)
The flame retardant polyurethane resin composition of the present invention having excellent carbonization performance may contain a flame retardant auxiliary agent (b) as required. Examples of the flame retardant auxiliary agent (b) include melamine phosphate, One or more selected from the group consisting of melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate can be used. Among the flame retardant aids (b), melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate are preferred.
本発明の難燃助剤（ｂ）は、成形性、難燃性、燃焼時の溶融物滴下防止性能や炭化性能の点から,ポリウレタン樹脂１００重量部に対し０～３０重量部配合することが好ましく、より好ましくは０～２０重量部配合することが好ましい。
本発明の炭化性能に優れた難燃性ポリウレタン樹脂組成物において、難燃剤（ａ）と難燃助剤（ｂ）の重量比が（ａ）／（ｂ）＝１００／０～５０／５０であることが難燃性能、燃焼時の溶融物滴下防止性能や炭化性能の点から好ましく、より好ましくは（ａ）／（ｂ）＝９０／１０～６０／４０である。
The flame retardant aid (b) of the present invention is preferably blended in an amount of 0 to 30 parts by weight per 100 parts by weight of the polyurethane resin in terms of moldability, flame retardancy, performance in preventing melt dripping during combustion, and carbonization performance. Preferably, it is more preferably blended in an amount of 0 to 20 parts by weight.
In the flame retardant polyurethane resin composition with excellent carbonization performance of the present invention, the weight ratio of the flame retardant (a) and the flame retardant aid (b) is (a)/(b) = 100/0 to 50/50. It is preferable from the viewpoint of flame retardant performance, ability to prevent melt dripping during combustion, and carbonization performance, and more preferably (a)/(b) = 90/10 to 60/40.
本発明の難燃剤組成物に用いる式（１）の難燃剤（ａ）と難燃助剤（ｂ）の組合せの中では、難燃剤（ａ）がＡｌ塩であり、難燃助剤がポリリン酸メラミン、メラミン、シアヌル酸メラミン、ポリリン酸アンモニウムである場合が、最も好ましい結果が得られる。 Among the combinations of the flame retardant (a) of formula (1) and the flame retardant aid (b) used in the flame retardant composition of the present invention, the flame retardant (a) is an Al salt, and the flame retardant aid is polyphosphorus. The most favorable results are obtained when acid melamine, melamine, cyanuric acid melamine, and ammonium polyphosphate are used.
本発明の難燃性ポリウレタン樹脂組成物は、上記成分に加え、さらに必要に応じて、水酸化マグネシウム等の金属水和物、炭酸カルシウム、シリカ等の無機化合物、およびフェノール系、チオエーテル系等の酸化防止剤、ベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系、トリアジン系、ヒンダードアミン系等の紫外線吸収剤や安定剤類、シリコーン系、脂肪酸アマイド等の離型剤および滑剤、金属石鹸、脂肪酸アマイド等の分散剤、染料や有機系および無機系顔料等の着色剤および発泡剤、ｐ－トルエンスルホンアミド、安息香酸エステル系可塑剤、ポリエステル系可塑剤、また溶融滴下防止剤としてＰＴＦＥを添加することも可能であり、これら添加剤の種類と添加量を調整することにより、目的とする機能を調整することができる。 In addition to the above-mentioned components, the flame-retardant polyurethane resin composition of the present invention further contains metal hydrates such as magnesium hydroxide, inorganic compounds such as calcium carbonate and silica, and phenol-based, thioether-based, etc. Antioxidants, ultraviolet absorbers and stabilizers such as benzotriazole type, benzophenone type, benzoate type, triazine type and hindered amine type, mold release agents and lubricants such as silicone type and fatty acid amide, dispersion of metal soap, fatty acid amide, etc. It is also possible to add colorants such as dyes, organic and inorganic pigments, blowing agents, p-toluenesulfonamide, benzoic acid ester plasticizers, polyester plasticizers, and PTFE as a melt dripping prevention agent. By adjusting the type and amount of these additives, the desired function can be adjusted.
本発明の難燃性ポリウレタン樹脂組成物は、上記した各成分を所定量ずつ混合し、単軸押出型混錬機、オープンロールミキサー、加圧型ニーダー、バンバリーミキサー、二軸押出型混錬機等、既知の混合機を用い、樹脂設定温度を融点以上にして溶融混練する。このなかでも二軸押出型混練機は混練性、生産性の点で好ましい。溶融混練後、所望により粉砕して得た難燃性ポリウレタン樹脂組成物のペレットを、さらに成形機に供して押出成形法、射出成形法、圧縮成形法、吹込成形法、射出圧縮成形法などの公知の各種成形法に適用して、難燃性ポリウレタン樹脂成形体を製造する。 The flame-retardant polyurethane resin composition of the present invention can be prepared by mixing the above-mentioned components in predetermined amounts using a single-screw extrusion kneader, open roll mixer, pressure kneader, Banbury mixer, twin-screw extrusion kneader, etc. Using a known mixer, the resin is melted and kneaded at a temperature set at a temperature higher than the melting point. Among these, a twin-screw extruder kneader is preferred in terms of kneading performance and productivity. After melt-kneading, the pellets of the flame-retardant polyurethane resin composition obtained by crushing as desired are further subjected to a molding machine for extrusion molding, injection molding, compression molding, blow molding, injection compression molding, etc. A flame-retardant polyurethane resin molded article is manufactured by applying various known molding methods.
本発明の難燃性ポリウレタン樹脂組成物は、難燃性に極めて優れていることから少ない配合量で難燃効果が得られ、燃焼時および焼却時においてハロゲンガスの発生が無く、かつ熱可塑性ポリウレタンに見られる溶融滴下の発生をなくすことができ、高難燃性が求められる用途で使用することが可能である。このため、本発明の難燃性ポリウレタン樹脂組成物は、フィルム、電子部品成形材料等への適用が可能であるが、その中でも近年、特に高難燃性が求められている電線被覆材料、シート、チューブといった用途に好適に用いる
ことができる。
The flame-retardant polyurethane resin composition of the present invention has extremely excellent flame retardancy, so a flame-retardant effect can be obtained with a small amount of blending, no halogen gas is generated during combustion or incineration, and the composition is a thermoplastic polyurethane resin composition. It is possible to eliminate the occurrence of melt dripping that is seen in conventional methods, and it can be used in applications that require high flame retardancy. Therefore, the flame-retardant polyurethane resin composition of the present invention can be applied to films, electronic component molding materials, etc. Among these, in recent years, particularly high flame retardance has been required, such as wire coating materials and sheets. It can be suitably used for applications such as , tubes, etc.
以下、実施例により本発明を具体的に説明するが、本発明はこれら具体例に限定されるものではない。なお、実施例、比較例において、特に断りが無い場合は%表示、部表示は重量基準である。また、実施例１及び２は、その内容からみて参考例として扱う。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these specific examples. In Examples and Comparative Examples, unless otherwise specified, percentages and parts are based on weight. In addition, Examples 1 and 2 are treated as reference examples in view of their contents.
（実施例１～６、比較例１～７）
表１～３に記載した成分および配合割合で混合した後、二軸ベント式押出機（設定温度１５０～２００℃）で溶融混練後、ペレット化した。ペレットを射出成形機を用いて、長さ１２７ｍｍ×幅１２．７ｍｍ×厚３．０ｍｍの試験片を作成した。各特性の評価は以下の方法で実施し、評価結果は表１～３に併せて記載した。
(Examples 1 to 6, Comparative Examples 1 to 7)
After mixing the components and blending ratios listed in Tables 1 to 3, the mixture was melt-kneaded in a twin-screw vent extruder (temperature set at 150 to 200°C) and then pelletized. A test piece measuring 127 mm in length x 12.7 mm in width x 3.0 mm in thickness was prepared from the pellet using an injection molding machine. Evaluation of each characteristic was carried out by the following method, and the evaluation results are also listed in Tables 1 to 3.
（難燃性試験および滴りの有無の判定）
実施例１～６、比較例１～７で作製した試験片を用いて、ＵＬ－９４Ｖ燃焼試験に準拠して測定した。また、測定時の溶融滴下の有無を以下の基準に沿って評価した。
溶融滴下有り：有
溶融滴下無し：無
(Flame retardancy test and determination of presence or absence of dripping)
Using the test pieces prepared in Examples 1 to 6 and Comparative Examples 1 to 7, measurements were made in accordance with the UL-94V combustion test. In addition, the presence or absence of melt dripping during measurement was evaluated according to the following criteria.
With melt dripping: Yes Without melt dripping: No
Claims (3)
下記式（１）で表される難燃剤（ａ）を１０～３０重量部含み、
難燃助剤（ｂ）として、リン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、メラミン、シアヌル酸メラミン及びポリリン酸アンモニウムからなる群より選ばれる１種以上を、ポリウレタン樹脂１００重量部に対し１．１～２０重量部含み、
前記難燃剤（ａ）と前記難燃助剤（ｂ）の重量比が、（ａ）／（ｂ）＝９０／１０～６０／４０であり、
難燃性規格ＵＬ－９４Ｖ法で、溶融滴下がなく、Ｖ－０基準に適合する難燃性能を有し、炭化性能に優れることを特徴とする電線被覆用難燃性ポリウレタン樹脂組成物。
但し、上記難燃助剤（ｂ）以外のリン酸の誘導体又はホスホン酸の誘導体を含有する場合を除き、シリコーンポリエーテルグリコールとジイソシアネートから得られたウレタン樹脂を含有する場合を除き、シロキサンポリエーテルオールとジイソシアネートから得られたウレタン樹脂を含有する場合を除き、ポリテトラフルオロエチレンを含有する場合を除き、ペンタエリスリトール籠状ホスフェートを含有する場合を除き、ペンタエリスリトールを含有する場合を除き、更にピロリン酸ピペラジンを含有する場合を除く。 For 100 parts by weight of polyurethane resin,
Containing 10 to 30 parts by weight of a flame retardant (a) represented by the following formula (1),
As the flame retardant aid (b), one or more selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine, melamine cyanurate, and ammonium polyphosphate is added in an amount of 1.0% per 100 parts by weight of the polyurethane resin. Contains 1 to 20 parts by weight,
The weight ratio of the flame retardant (a) and the flame retardant aid (b) is (a)/(b) = 90/10 to 60/40,
A flame-retardant polyurethane resin composition for covering electric wires, which is characterized by no melting and dripping according to the flame-retardant standard UL-94V method, flame-retardant performance that meets the V-0 standard, and excellent carbonization performance.
However, except when it contains a derivative of phosphoric acid or a derivative of phosphonic acid other than the above flame retardant aid (b), and except when it contains a urethane resin obtained from silicone polyether glycol and diisocyanate, siloxane polyether Except when containing urethane resin obtained from ol and diisocyanate, except when containing polytetrafluoroethylene, except when containing pentaerythritol cage phosphate, except when containing pentaerythritol, and further containing pyrroline. Except when containing acid piperazine.
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