JP6894209B2 - Polyol-containing compositions, foamable polyurethane compositions and polyurethane foams - Google Patents
Polyol-containing compositions, foamable polyurethane compositions and polyurethane foams Download PDFInfo
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- JP6894209B2 JP6894209B2 JP2016205662A JP2016205662A JP6894209B2 JP 6894209 B2 JP6894209 B2 JP 6894209B2 JP 2016205662 A JP2016205662 A JP 2016205662A JP 2016205662 A JP2016205662 A JP 2016205662A JP 6894209 B2 JP6894209 B2 JP 6894209B2
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- parts
- polyol
- range
- phosphate
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- 229920005862 polyol Polymers 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 title claims description 80
- 150000003077 polyols Chemical class 0.000 title claims description 68
- 229920002635 polyurethane Polymers 0.000 title claims description 39
- 239000004814 polyurethane Substances 0.000 title claims description 39
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 30
- 239000011496 polyurethane foam Substances 0.000 title claims description 30
- 239000003063 flame retardant Substances 0.000 claims description 71
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 59
- -1 polyol compound Chemical class 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000005056 polyisocyanate Substances 0.000 claims description 29
- 229920001228 polyisocyanate Polymers 0.000 claims description 29
- 239000006260 foam Substances 0.000 claims description 17
- 239000004088 foaming agent Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- 229910019142 PO4 Inorganic materials 0.000 description 26
- 239000010452 phosphate Substances 0.000 description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 24
- 239000000047 product Substances 0.000 description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 150000003014 phosphoric acid esters Chemical class 0.000 description 14
- 238000005187 foaming Methods 0.000 description 12
- 238000005829 trimerization reaction Methods 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 229910000000 metal hydroxide Inorganic materials 0.000 description 9
- 150000004692 metal hydroxides Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000001205 polyphosphate Substances 0.000 description 5
- 235000011176 polyphosphates Nutrition 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 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 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- UCXOJWUKTTTYFB-UHFFFAOYSA-N antimony;heptahydrate Chemical compound O.O.O.O.O.O.O.[Sb].[Sb] UCXOJWUKTTTYFB-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000004712 monophosphates Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- BCMKHWMDTMUUSI-UHFFFAOYSA-N naphthalene-1,3,6,8-tetrol Chemical compound OC1=CC(O)=CC2=CC(O)=CC(O)=C21 BCMKHWMDTMUUSI-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- LYSTYSFIGYAXTG-UHFFFAOYSA-L barium(2+);hydrogen phosphate Chemical compound [Ba+2].OP([O-])([O-])=O LYSTYSFIGYAXTG-UHFFFAOYSA-L 0.000 description 1
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- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
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- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- FNILDPCCWMWNTE-UHFFFAOYSA-N dicyclohexylmethanediol Chemical compound C1CCCCC1C(O)(O)C1CCCCC1 FNILDPCCWMWNTE-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- AWROWLLGXAQBQF-UHFFFAOYSA-N dilithium hydrogen phosphite Chemical compound [Li+].[Li+].OP([O-])[O-] AWROWLLGXAQBQF-UHFFFAOYSA-N 0.000 description 1
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
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- 239000004872 foam stabilizing agent Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
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- 230000007774 longterm Effects 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
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- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
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- 229930187760 maximol Natural products 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- BZHCGFBZBPVRFE-UHFFFAOYSA-N monopotassium phosphite Chemical compound [K+].OP(O)[O-] BZHCGFBZBPVRFE-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- HDSZRJMNBCRATE-UHFFFAOYSA-N n-methyl-2-piperazin-1-ylethanamine Chemical compound CNCCN1CCNCC1 HDSZRJMNBCRATE-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 125000004433 nitrogen atom Chemical group 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
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- MTKRXXSLFWZJTB-UHFFFAOYSA-N oxo(oxoboranyl)borane Chemical compound O=BB=O MTKRXXSLFWZJTB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- RMNODSGCFHVNDC-UHFFFAOYSA-N phenyl bis(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1 RMNODSGCFHVNDC-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 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 description 1
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
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- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LYZXDRIYOSVZCW-UHFFFAOYSA-M potassium dioxidophosphanium Chemical class [K+].[O-][PH2]=O LYZXDRIYOSVZCW-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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- 239000004328 sodium tetraborate Substances 0.000 description 1
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- 150000003440 styrenes Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- CZMILNXHOAKSBR-UHFFFAOYSA-N tetraphenylazanium Chemical class C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CZMILNXHOAKSBR-UHFFFAOYSA-N 0.000 description 1
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- JDLDTRXYGQMDRV-UHFFFAOYSA-N tricesium;borate Chemical compound [Cs+].[Cs+].[Cs+].[O-]B([O-])[O-] JDLDTRXYGQMDRV-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、ポリイソシアネートと反応させてポリウレタン発泡体を得るためのポリオール含有組成物、発泡性ポリウレタン組成物及びポリウレタン発泡体に関する。 The present invention relates to a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam for reacting with polyisocyanate to obtain a polyurethane foam.
マンション等の集合住宅、戸建住宅、学校の各種施設、商業ビル等の建築物の断熱材として発泡ポリウレタン樹脂が用いられている。ウレタン樹脂は難燃性が低いため、断熱ウレタン材料に難燃性を付与することがある。 Polyurethane foam resin is used as a heat insulating material for buildings such as condominiums, detached houses, various school facilities, and commercial buildings. Since urethane resin has low flame retardancy, it may impart flame retardancy to the heat insulating urethane material.
例えば特許文献1及び2は、難燃性が高い硬質ポリウレタンフォームおよびその製造方法が開示されている。 For example, Patent Documents 1 and 2 disclose a rigid polyurethane foam having high flame retardancy and a method for producing the same.
しかしながら、特許文献1及び2のいずれの硬質ポリウレタンフォームも、建築基準法上の不燃性を満たすことは確認されていない。 However, it has not been confirmed that any of the rigid polyurethane foams of Patent Documents 1 and 2 satisfies the nonflammability under the Building Standards Act.
また、発泡ポリウレタン(ポリウレタンフォーム)に難燃性を付与するために一定量の固形分を用いる場合、溶液が高粘度になり、またケーキング(沈降凝集)が発生する。ケーキングが発生すると、ポリオール溶液静置後に難燃性能が低下することが問題となる。そのため、ポリオール溶液を長期間保管した場合の保管安定性を改善するための手段が必要である。 Further, when a certain amount of solid content is used to impart flame retardancy to polyurethane foam (polyurethane foam), the solution becomes highly viscous and caking (sedimentation and aggregation) occurs. When caking occurs, there is a problem that the flame retardant performance deteriorates after the polyol solution is allowed to stand. Therefore, a means for improving the storage stability when the polyol solution is stored for a long period of time is required.
特許文献1及び2には、長期間保管した場合の保管安定性を改善するための手段についての記載はない。 Patent Documents 1 and 2 do not describe means for improving storage stability when stored for a long period of time.
本発明の目的は、難燃性を有し、かつ、長期間保管後にも難燃性が維持される保管安定性に優れる発泡性ポリウレタン組成物およびポリウレタン発泡体を提供することである。 An object of the present invention is to provide a foamable polyurethane composition and a polyurethane foam having flame retardancy and excellent storage stability in which flame retardancy is maintained even after long-term storage.
本願発明者らは、上記の目的を達成すべく種々検討したところ、ポリオール含有組成物のチクソ性を高めることで、難燃性を有し、かつ、保管安定性に優れる発泡性ポリウレタン組成物が得られることを見出し、本発明を完成するに至った。 As a result of various studies to achieve the above object, the inventors of the present application have found a foamable polyurethane composition having flame retardancy and excellent storage stability by enhancing the thixophilicity of the polyol-containing composition. We have found that it can be obtained and have completed the present invention.
すなわち、本発明は以下の態様を包含する。 That is, the present invention includes the following aspects.
項1.ポリイソシアネートと反応させてポリウレタン発泡体を得るためのポリオール含有組成物であって、前記ポリオール含有組成物はポリオール化合物、整泡剤、触媒、発泡剤、および難燃剤を含み、
前記ポリオール含有組成物の25℃回転速度100rpmにおける粘度が105mPas以上であり、かつ、下記式により算出されるチクソ値が1.9以上であることを特徴とするポリオール含有組成物。
(チクソ値)=(25℃回転速度1rpmでの粘度)/(25℃回転速度10rpmでの粘度)
Item 1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, wherein the polyol-containing composition contains a polyol compound, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant.
A polyol-containing composition characterized in that the viscosity of the polyol-containing composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more, and the chixo value calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 °
項2.ポリオール化合物100重量部に対する固形成分が35重量部以上であることを特徴とする項1記載のポリオール含有組成物。 Item 2. Item 2. The polyol-containing composition according to Item 1, wherein the solid component is 35 parts by weight or more with respect to 100 parts by weight of the polyol compound.
項3.項1または2に記載のポリオール含有組成物と、ポリイソシアネートとを反応させてなることを特徴とする、発泡性ポリウレタン組成物。 Item 3. A foamable polyurethane composition, which comprises reacting the polyol-containing composition according to Item 1 or 2 with a polyisocyanate.
項4.項3に記載の発泡性ポリウレタン組成物が硬化したポリウレタン発泡体。 Item 4. A polyurethane foam obtained by curing the foamable polyurethane composition according to Item 3.
項5.成形体である項4に記載のポリウレタン発泡体。 Item 5. Item 2. The polyurethane foam according to Item 4, which is a molded product.
本発明の発泡性ポリウレタン組成物は、優れた難燃性と改善された保管安定性とを兼ね備えており、難燃性に優れている。 The foamable polyurethane composition of the present invention has both excellent flame retardancy and improved storage stability, and is excellent in flame retardancy.
本発明は、ポリイソシアネートと反応させてポリウレタン発泡体を得るためのポリオール含有組成物であって、前記ポリオール含有組成物はポリオール、整泡剤、触媒、発泡剤、および難燃剤を含み、前記ポリオール含有組成物の25℃回転速度100rpmにおける粘度が105mPas以上であり、かつ、下記式により算出されるチクソが1.9以上であることを特徴とするポリオール含有組成物を包含する。
(チクソ値)=(25℃回転速度1rpmでの粘度)/(25℃回転速度10rpmでの粘度)
The present invention is a polyol-containing composition for reacting with polyisocyanate to obtain a polyurethane foam, wherein the polyol-containing composition contains a polyol, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant, and the polyol. It includes a polyol-containing composition characterized in that the viscosity of the contained composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more and the chixo calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 °
なお、本明細書において「硬化した」とは、発泡性ポリウレタン組成物の主剤と硬化剤とを混合し、発泡および硬化させて反応が完了した後の状態を指す。 In the present specification, "cured" refers to a state after the main agent and the curing agent of the foamable polyurethane composition are mixed, foamed and cured to complete the reaction.
発泡性ポリウレタン組成物は、上記ポリオール含有組成物と、ポリイソシアネートとを反応させてなる。ウレタン樹脂の主剤としてのポリイソシアネートと、上記ポリオール含有組成物に含まれるウレタン樹脂の硬化剤としてのポリオールは、化学反応により硬化して、ウレタン樹脂を形成する。以下、各成分について説明する。 The foamable polyurethane composition is formed by reacting the above-mentioned polyol-containing composition with polyisocyanate. The polyisocyanate as the main component of the urethane resin and the polyol as the curing agent of the urethane resin contained in the above-mentioned polyol-containing composition are cured by a chemical reaction to form a urethane resin. Hereinafter, each component will be described.
1.ポリイソシアネート
ウレタン樹脂の主剤であるポリイソシアネートとしては、例えば、芳香族ポリイソシアネート、脂環族ポリイソシアネート、脂肪族ポリイソシアネート等が挙げられる。
1. 1. Polyisocyanate Examples of the polyisocyanate that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
芳香族ポリイソシアネートとしては、例えば、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、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、ジメチルジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.
脂環族ポリイソシアネートとしては、例えば、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ジメチルジシクロヘキシルメタンジイソシアネート等が挙げられる。 Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
脂肪族ポリイソシアネートとしては、例えば、メチレンジイソシアネート、エチレンジイソシアネート、プロピ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、ヘキサメチレンジイソシアネート等が挙げられる。 Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
ポリイソシアネートは一種もしくは二種以上を使用することができる。ウレタン樹脂の主剤は、使い易いこと、入手し易いこと等の理由から、芳香族ポリイソシアネートが好ましく、ジフェニルメタンジイソシアネートがより好ましい。 One type or two or more types of polyisocyanate can be used. As the main agent of the urethane resin, aromatic polyisocyanate is preferable, and diphenylmethane diisocyanate is more preferable, because it is easy to use and easily available.
2.ポリオール
ウレタン樹脂の硬化剤であるポリオールとしては、例えばポリラクトンポリオール、ポリカーポネートポリオール、芳香族ポリオール、脂環族ポリオール、脂肪族ポリオール、ポリエステルポリオール、ポリマーポリオール、ポリエーテルポリオール等が挙げられる。
2. Polyols Examples of polyols that are curing agents for urethane resins include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.
ポリラクトンポリオールとしては、例えば、ポリプロピオラクトングリコール、ポリカプロラクトングリコール、ポリバレロラクトングリコールなどが挙げられる。 Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
ポリカーボネートポリオールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオールなどの水酸基含有化合物と、ジエチレンカーボネート、ジプロピレンカーボネートなどとの脱アルコール反応により得られるポリオール等が挙げられる。 Examples of the polycarbonate polyol include a polyol obtained by dealcoholization of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. And so on.
芳香族ポリオールとしては、例えば、ビスフェノールA、ビスフェノールF、フェノールノボラック、クレゾールノボラック等が挙げられる。 Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac and the like.
脂環族ポリオールとしては、例えばシクロヘキサンジオール、メチルシクロヘキサンジオール、イソホロンジオール、ジシクロへキシルメタンジオール、ジメチルジシクロへキシルメタンジオール等が挙げられる。 Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
脂肪族ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール等が挙げられる。 Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
ポリエステルポリオールとしては、例えば、多塩基酸と多価アルコールとを脱水縮合して得られる重合体、ε−カプロラクトン、α−メチル−ε−カプロラクトン等のラクトンを開環重合して得られる重合体、ヒドロキシカルボン酸と上記多価アルコール等との縮合物が挙げられる。 Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and a polymer obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include a condensate of a hydroxycarboxylic acid and the above-mentioned polyhydric alcohol and the like.
ここで多塩基酸としては、具体的には、例えば、アジピン酸、アゼライン酸、セバシン酸、テレフタル酸、イソフタル酸、コハク酸等が挙げられる。また多価アルコールとしては、具体的には、例えば、ビスフェノールA、エチレングリコール、1,2−プロピレングリコール、1,4−ブタンジオール、ジエチレングリコール、1,6−ヘキサングリコール、ネオペンチルグリコール等が挙げられる。 Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol and the like. ..
またヒドロキシカルボン酸としては、具体的には、例えば、ひまし油、ひまし油とエチレングリコールの反応生成物等が挙げられる。 Specific examples of the hydroxycarboxylic acid include castor oil and reaction products of castor oil and ethylene glycol.
ポリマーポリオールとしては、例えば、芳香族ポリオール、脂環族ポリオール、脂肪族ポリオール、ポリエステルポリオール等に対し、アクリロニトリル、スチレン、メチルアクリレート、メタクリレート等のエチレン性不飽和化合物をグラフト重合させた重合体、ポリブタジエンポリオール、多価アルコールの変性ポリオールまたは、これらの水素添加物等が挙げられる。 Examples of the polymer polyol include polybutadiene, which is a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.
多価アルコールの変性ポリオールとしては、例えば、原料の多価アルコールにアルキレンオキサイドを反応させて変性したもの等が挙げられる。 Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.
多価アルコールとしては、例えば、グリセリンおよびトリメチロールプロパン等の三価アルコール;ペンタエリスリトール、ソルビトール、マンニトール、ソルビタン、ジグリセリン、ジペンタエリスリトール等、ショ糖、グルコース、マンノース、フルクト−ス、メチルグルコシドおよびその誘導体等の四〜八価のアルコール;フェノール、フロログルシン、クレゾール、ピロガロール、カテコ−ル、ヒドロキノン、ビスフェノールA、ビスフェノールF、ビスフェノールS、1−ヒドロキシナフタレン、1,3,6,8−テトラヒドロキシナフタレン、アントロール、1,4,5,8−テトラヒドロキシアントラセン、1−ヒドロキシピレン等のフェノールポリブタジエンポリオール;ひまし油ポリオール;ヒドロキシアルキル(メタ)アクリレートの(共)重合体およびポリビニルアルコール等の多官能(例えば官能基数2〜100)ポリオール、フェノールとホルムアルデヒドとの縮合物(ノボラック)が挙げられる。 Polyhydric alcohols include, for example, trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, sucrose, glucose, mannose, fructose, methylglucoside and Tetra-octavalent alcohols such as derivatives thereof; phenol, fluoroglycerin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene. , Anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene and other phenol polybutadiene polyols; castor oil polyol; (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional (eg, polyvinyl alcohol) such as polyvinyl alcohol. Examples thereof include polyols having a number of functional groups of 2 to 100) and condensates (novolac) of phenol and formaldehyde.
多価アルコールの変性方法は特に限定されないが、アルキレンオキサイド(以下、AOと略す)を付加させる方法が好適に用いられる。 The method for modifying the polyhydric alcohol is not particularly limited, but a method for adding an alkylene oxide (hereinafter abbreviated as AO) is preferably used.
AOとしては、炭素数2〜6のAO、例えば、エチレンオキサイド(以下、EOと略す)、1,2−プロピレンオキサイド(以下、POと略す)、1,3−プロピレオキサイド、1,2−ブチレンオキサイド、1,4−ブチレンオキサイド等が挙げられる。 Examples of AO include AO having 2 to 6 carbon atoms, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyleneoxide, 1,2-. Butylene oxide, 1,4-butylene oxide and the like can be mentioned.
これらの中でも性状や反応性の観点から、PO、EOおよび1,2−ブチレンオキサイドが好ましく、POおよびEOがより好ましい。AOを二種以上使用する場合(例えば、POおよびEO)の付加方法としては、ブロック付加であってもランダム付加であってもよく、これらの併用であってもよい。 Among these, PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable, from the viewpoint of properties and reactivity. When two or more types of AO are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.
ポリエーテルポリオ−ルとしては、例えば、活性水素を2個以上有する低分子量活性水素化合物等の少なくとも一種の存在下に、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等のアルキレンオキサイドの少なくとも1種を開環重合させて得られ
る重合体が挙げられる。
As the polyether polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened polymerized in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include a polymer obtained by subjecting the mixture.
活性水素を2個以上有する低分子量活性水素化合物としては、例えば、ビスフェノールA、エチレングリコール、プロピレングリコール、ブチレングリコール、1,6−ヘキサンジオ−ル等のジオール類、グリセリン、トリメチロールプロパン等のトリオール類、エチレンジアミン、ブチレンジアミン等のアミン類等が挙げられる。 Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , Ethylenediamine, amines such as butylene diamine and the like.
本発明に使用するポリオールは、燃焼した際の総発熱量の低減効果が大きいことからポリエステルポリオール、またはポリエーテルポリオールを使用することが好ましい。 As the polyol used in the present invention, it is preferable to use a polyester polyol or a polyether polyol because it has a large effect of reducing the total calorific value when burned.
その中でも分子量200〜800のポリエステルポリオールを用いることがより好ましく、分子量300〜500のポリエステルポリオールを用いることがさらに好ましい。 Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is further preferable to use a polyester polyol having a molecular weight of 300 to 500.
3.整泡剤
整泡剤としては、例えば、ポリオキシアルキレンアルキルエーテル等のポリオキシアルキレン整泡剤、オルガノポリシロキサン等のシリコーン整泡剤等の界面活性剤等が挙げられる。
3. 3. Defoaming agent Examples of the defoaming agent include a polyoxyalkylene defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone defoaming agent such as organopolysiloxane.
整泡剤の配合量は、ウレタン樹脂に応じて適宜設定することができる。一例を示すとすれば、整泡剤の配合量は、ポリオール化合物100重量部に対して、0.1重量部〜10重量部の範囲であれば好ましい。ウレタン樹脂100重量部に対しては、例えば、0.1重量部〜10重量部の範囲であれば好ましい。 The blending amount of the foam stabilizer can be appropriately set according to the urethane resin. As an example, the blending amount of the foam stabilizer is preferably in the range of 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the polyol compound. With respect to 100 parts by weight of the urethane resin, for example, the range of 0.1 parts by weight to 10 parts by weight is preferable.
整泡剤は一種もしくは二種以上を使用することができる。 One type or two or more types of foam stabilizers can be used.
4.触媒
触媒としては、例えば三量化触媒が挙げられる。
4. Catalyst Examples of the catalyst include a trimerization catalyst.
三量化触媒は、ポリウレタン樹脂の主剤であるポリイソシアネートに含まれるイソシアネート基を反応させて三量化させ、イソシアヌレート環の生成を促進する。 The trimerization catalyst reacts the isocyanate group contained in the polyisocyanate, which is the main component of the polyurethane resin, to tritrate it, and promotes the formation of an isocyanurate ring.
イソシアヌレート環の生成を促進するために、例えば、三量化触媒として、トリス(ジメチルアミノメチル)フェノール、2,4−ビス(ジメチルアミノメチル)フェノール、2,4,6−トリス(ジアルキルアミノアルキル)ヘキサヒドロ−S−トリアジン等の窒素含有芳香族化合物;酢酸カリウム、2−エチルヘキサン酸カリウム、オクチル酸カリウム等のカルボン酸アルカリ金属塩;トリメチルアンモニウム塩、トリエチルアンモニウム塩、トリフェニルアンモニウム塩等の3級アンモニウム塩;テトラメチルアンモニウム塩、テトラエチルアンモニウム、テトラフェニルアンモニウム塩等の4級アンモニウム塩等を使用することができる。 In order to promote the formation of the isocyanurate ring, for example, as a trimerization catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) Nitrogen-containing aromatic compounds such as hexahydro-S-triazine; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate; tertiary such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt. Ammonium salt; A quaternary ammonium salt such as tetramethylammonium salt, tetraethylammonium, or tetraphenylammonium salt can be used.
三量化触媒の量は、ポリオール化合物100重量部に対して、0.2重量部〜30重量部の範囲であることが好ましく、1.2重量部〜24重量部の範囲であることがより好ましく、1.2重量部〜18重量部の範囲であることが更に好ましく、1.2重量部〜9.0重量部の範囲であることが最も好ましい。0.2重量部以上の場合にポリイソシアネートの三量化が阻害される不具合が生じず、30重量部以下の場合は適切な発泡速度を維持することができ、取り扱いやすい。 The amount of the trimerization catalyst is preferably in the range of 0.2 parts by weight to 30 parts by weight, and more preferably in the range of 1.2 parts by weight to 24 parts by weight with respect to 100 parts by weight of the polyol compound. , 1.2 parts by weight to 18 parts by weight, more preferably 1.2 parts by weight to 9.0 parts by weight. When it is 0.2 parts by weight or more, there is no problem that the triglyceride of polyisocyanate is inhibited, and when it is 30 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.
三量化触媒の量は、ウレタン樹脂100重量部に対しては、0.1重量部〜10重量部の範囲であることが好ましく、0.6重量部〜8重量部の範囲であることがより好ましく、0.6重量部〜6重量部の範囲であることが更に好ましく、0.6重量部〜3.0重量部の範囲であることが最も好ましい。ウレタン樹脂100重量部に対しては、0.6重量部〜10重量部の範囲とすることもできる。上記下限値以上の場合にポリイソシアネートの三量化が阻害される不具合が生じず、10重量部以下の場合は適切な発泡速度を維持することができ、取り扱いやすい。 The amount of the trimerization catalyst is preferably in the range of 0.1 parts by weight to 10 parts by weight, and more preferably in the range of 0.6 parts by weight to 8 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 0.6 parts by weight to 6 parts by weight, and most preferably in the range of 0.6 parts by weight to 3.0 parts by weight. The range may be in the range of 0.6 parts by weight to 10 parts by weight with respect to 100 parts by weight of the urethane resin. When it is at least the above lower limit, there is no problem that the triglycerate of polyisocyanate is inhibited, and when it is 10 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.
また触媒として、三量化触媒以外に、下記の触媒が挙げられる:アルキル化ポリアルキレンポリアミン、トリエチルアミン、N”,N”−ペンタメチルジエチレントリアミン、N,N,N’−トリメチルアミノエチル−エタノールアミン、ウレタン触媒等のアミン;N−メチルモルホリンビス(2−ジメチルアミノエチル)エーテル、N,N,N’,ビス(2−ジメチルアミノエチル)エーテル、N−メチル−N’−ジ8メチルアミノエチルピペラジン、イミダゾール環中の第2級アミン官能基をシアノエチル基で置換したイミダゾール化合物等の窒素原子含有触媒等が挙げられる。 In addition to the trimerization catalyst, the following catalysts can be mentioned as catalysts: alkylated polyalkylene polyamine, triethylamine, N ", N" -pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, urethane. Amines such as catalysts; N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', bis (2-dimethylaminoethyl) ether, N-methyl-N'-di-8 methylaminoethyl piperazine, Examples thereof include nitrogen atom-containing catalysts such as imidazole compounds in which the secondary amine functional group in the imidazole ring is replaced with a cyanoethyl group.
かかる三量化触媒以外の触媒の添加量は、三量化触媒と三量化触媒以外の触媒の合計量で、ポリオール化合物100重量部に対して、0.6重量部〜30重量部の範囲であることが好ましく、1.2重量部〜24部の範囲であることがより好ましく、1.2重量部〜18重量部の範囲であることが更に好ましく、1.2重量部〜9.0重量部の範囲であることが最も好ましい。 The amount of the catalyst other than the trimerization catalyst added is the total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, and is in the range of 0.6 parts by weight to 30 parts by weight with respect to 100 parts by weight of the polyol compound. It is more preferably in the range of 1.2 parts by weight to 24 parts, further preferably in the range of 1.2 parts by weight to 18 parts by weight, and 1.2 parts by weight to 9.0 parts by weight. Most preferably it is in the range.
0.6重量部以上の場合はウレタン結合の形成が阻害される不具合が生じず、30重量部以下の場合は適切な発泡速度を維持することができ、取扱いやすい。 When it is 0.6 parts by weight or more, there is no problem that the formation of urethane bond is hindered, and when it is 30 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.
三量化触媒以外の触媒の添加量は、発泡性ポリウレタン組成物に含まれる場合は、三量化触媒と三量化触媒以外の触媒の合計量で、ウレタン樹脂100重量部に対して、0.3重量部〜10重量部の範囲であることが好ましく、0.6重量部〜8部の範囲であることがより好ましく、0.6重量部〜6重量部の範囲であることが更に好ましく、0.6重量部〜3.0重量部の範囲であることが最も好ましい。ウレタン樹脂100重量部に対して、0.6重量部〜10重量部の範囲とすることもできる。 When the foamable polyurethane composition contains a catalyst other than the trimerization catalyst, the amount of the catalyst added is the total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, which is 0.3 weight by weight based on 100 parts by weight of the urethane resin. The range is preferably in the range of 10 parts by weight, more preferably in the range of 0.6 parts by weight to 8 parts, still more preferably in the range of 0.6 parts by weight to 6 parts by weight, and 0. Most preferably, it is in the range of 6 parts by weight to 3.0 parts by weight. The range may be in the range of 0.6 parts by weight to 10 parts by weight with respect to 100 parts by weight of the urethane resin.
上記下限値以上の場合はウレタン結合の形成が阻害される不具合が生じず、10重量部以下の場合は適切な発泡速度を維持することができ、取扱いやすい。 When it is at least the above lower limit value, there is no problem that the formation of urethane bond is hindered, and when it is 10 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.
触媒は一種もしくは二種以上を使用することができる。 One type or two or more types of catalysts can be used.
5.発泡剤
発泡剤は、ウレタン樹脂の発泡を促進する。発泡剤としては、例えば、水;プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン等の低沸点の炭化水素;ジクロロエタン、プロピルクロリド、イソプロピルクロリド、ブチルクロリド、イソブチルクロリド、ペンチルクロリド、イソペンチルクロリド等の塩素化脂肪族炭化水素化合物;CHF3、CH2F2、CH3F等のフッ素化合物;トリクロルモノフルオロメタン、トリクロルトリフルオロエタン、ジクロロモノフルオロエタン、(例えば、HCFC141b(1,1−ジクロロ−1−フルオロエタン)、HCFC22(クロロジフルオロメタン)、HCFC142b(1−クロロ−1,1−ジフルオロエタン))等のハイドロクロロフルオロカーボン化合物;HFC−245fa(1,1,1,3,3−ペンタフルオロプロパン)、HFC−365mfc(1,1,1,3,3−ペンタフルオロブタン)等のハイドロフルオロカーボン;ジイソプロピルエーテル等のエーテル化合物、あるいはこれらの化合物の混合物等の有機系物理発泡剤、窒素ガス、酸素ガス、アルゴンガス、二酸化炭素ガス等の無機系物理発泡剤等が挙げられる。
5. Foaming agent The foaming agent promotes the foaming of urethane resin. Examples of the effervescent agent include water; low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptan; dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, etc. Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride, and isopentyl chloride; fluorine compounds such as CHF 3 , CH 2 F 2 , and CH 3 F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane, Hydrochlorofluorocarbon compounds such as (eg, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)); HFC-245fa (1, Hydrofluorocarbons such as 1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); ether compounds such as diisopropyl ether, or mixtures of these compounds, etc. Examples thereof include organic physical foaming agents, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and other inorganic physical foaming agents.
発泡剤の配合量は特に限定されないが、ポリオール化合物100重量部に対して、0.2重量部〜90重量部の範囲であることが好ましい。発泡剤は、ポリオール化合物100重量部に対して、0.2重量部〜54重量部の範囲であることがより好ましく、1重量部〜54重量部の範囲であることが更に好ましく、2重量部〜30重量部の範囲であることが最も好ましい。 The blending amount of the foaming agent is not particularly limited, but is preferably in the range of 0.2 parts by weight to 90 parts by weight with respect to 100 parts by weight of the polyol compound. The foaming agent is more preferably in the range of 0.2 parts by weight to 54 parts by weight, further preferably in the range of 1 part by weight to 54 parts by weight, with respect to 100 parts by weight of the polyol compound. Most preferably, it is in the range of ~ 30 parts by weight.
発泡剤の範囲が0.2重量部以上の場合は発泡が促進され、得られる成形体の密度を低減することができ、90重量部以下の場合は、発泡体が発泡せず発泡体が形成されないことを防ぐことができる。 When the range of the foaming agent is 0.2 parts by weight or more, foaming is promoted and the density of the obtained molded product can be reduced, and when it is 90 parts by weight or less, the foam does not foam and the foam is formed. It can be prevented that it is not done.
発泡剤の配合量は、ウレタン樹脂100重量部に対しては、0.1重量部〜30重量部の範囲であることが好ましい。発泡剤は、ウレタン樹脂100重量部に対して、0.1重量部〜18重量部の範囲であることがより好ましく、0.5重量部〜18重量部の範囲であることが更に好ましく、1重量部〜10重量部の範囲であることが最も好ましい。 The blending amount of the foaming agent is preferably in the range of 0.1 parts by weight to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The foaming agent is more preferably in the range of 0.1 parts by weight to 18 parts by weight, further preferably in the range of 0.5 parts by weight to 18 parts by weight, with respect to 100 parts by weight of the urethane resin. Most preferably, it is in the range of 10 parts by weight to 10 parts by weight.
発泡剤の範囲が0.1重量部以上の場合は発泡が促進され、得られる成形体の密度を低減することができ、30重量部以下の場合は、発泡体が発泡せず発泡体が形成されないことを防ぐことができる。 When the range of the foaming agent is 0.1 parts by weight or more, foaming is promoted and the density of the obtained molded product can be reduced, and when it is 30 parts by weight or less, the foam does not foam and the foam is formed. It can be prevented that it is not done.
発泡剤は一種もしくは二種以上を使用することができる。 One type or two or more types of foaming agents can be used.
6.難燃剤
難燃剤は、赤リン、リン酸エステル、リン酸塩含有難燃剤、臭素含有難燃剤、ホウ酸含有難燃剤、アンチモン含有難燃剤、および金属水酸化物から選ばれる少なくとも1つを含む。好ましくは、難燃剤は、赤リンと、リン酸エステル、リン酸塩含有難燃剤、臭素含有難燃剤、ホウ酸含有難燃剤、アンチモン含有難燃剤、および金属水酸化物から選ばれる少なくとも1つとを含む。
6. Flame Retardants The flame retardant comprises at least one selected from red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. Preferably, the flame retardant is red phosphorus and at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boric acid-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. Including.
難燃剤は、市販品を適宜選択して使用することができる。 As the flame retardant, a commercially available product can be appropriately selected and used.
また本発明に使用するリン酸エステルは特に限定されないが、モノリン酸エステル、縮合リン酸エステル等を使用することが好ましい。 The phosphoric acid ester used in the present invention is not particularly limited, but it is preferable to use a monophosphoric acid ester, a condensed phosphoric acid ester, or the like.
モノリン酸エステルとしては、特に限定はないが、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ(2−エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレ二ルホスフェート、トリス(イソプロピルフェニル)ホスフェート、トリス(フェニルフェニル)ホスフェート、トリナフチルホスフェート、クレジルジフェニルホスフェート、キシレ二ルジフェニルホスフェート、ジフェニル(2−エチルヘキシル)ホスフェート、ジ(イソプロピルフェニル)フェニルホスフェート、モノイソデシルホスフェート、2−アクリロイルオキシエチルアシッドホスフェート、2−メタクリロイルオキシエチルアシッドホスフェート、ジフェニル−2−アクリロイルオキシエチルホスフェート、ジフェニル−2−メタクリロイルオキシエチルホスフェート、メラミンホスフェート、ジメラミンホスフェート、メラミンピロホスフェート、トリフェニルホスフィンオキサイド、トリクレジルホスフィンオキサイド、メタンホスホン酸ジフェニル、フェニルホスホン酸ジエチル、レジルシノールビス(ジフェニルホスフェート)、ビスフェノールAビス(ジフェニルホスフェート)、ホスフアフエナンスレン、トリス(β−クロロプロピル)ホス
フェート等が挙げられる。
The monophosphoric acid ester is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, etc. Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-Acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, Examples thereof include tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resilsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.
縮合リン酸エステルとしては、特に限定はないが、例えば、トリアルキルポリホスフェート、レゾルシノールポリフェニルホスフェート、レゾルシノールポリ(ジ−2,6−キシリル)ホスフェート(大八化学工業社製、商品名PX−200)、ハイドロキノンポリ(2,6−キシリル)ホスフェートならびにこれらの縮合物等の縮合リン酸エステルを挙げられる。 The condensed phosphoric acid ester is not particularly limited, but for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, resorcinolpoly (di-2,6-kisilyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200). ), Hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphoric acid esters such as condensates thereof.
市販の縮合リン酸エステルとしては、例えば、レゾルシノールポリフェニルホスフェート(商品名CR−733S)、ビスフェノールAポリクレジルホスフェート(商品名CR−741)、芳香族縮合リン酸エステル(商品名CR747)、レゾルシノールポリフェニルホスフェート(ADEKA社製、商品名アデカスタブPFR)、ビスフェノールAポリクレジルホスフエ−ト(商品名FP−600、FP−700)等を挙げることができる。 Examples of commercially available condensed phosphoric acid esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycredyl phosphate (trade name CR-741), aromatic condensed phosphoric acid ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name Adecastab PFR), bisphenol A polycredyl phosphate (trade names FP-600, FP-700) and the like.
上記の中でも、硬化前の組成物中の粘度の低下させる効果と初期の発熱量を低減させる効果が高いためモノリン酸エステルを使用することが好ましく、トリス(β−クロロプロピル)ホスフェートを使用することがより好ましい。 Among the above, it is preferable to use a monophosphate ester because it has a high effect of reducing the viscosity of the composition before curing and the effect of reducing the initial calorific value, and tris (β-chloropropyl) phosphate should be used. Is more preferable.
リン酸エステルは一種もしくは二種以上を使用することができる。 One type or two or more types of phosphoric acid esters can be used.
リン酸エステルの添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の範囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。 The amount of the phosphoric acid ester added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
リン酸エステルの範囲が3重量部以上の場合には発泡性ポリウレタン組成物からなる成形品が火災の熟により形成される緻密残渣が割れることを防止でき、156重量部以下の場合には発泡性ポリウレタン組成物の発泡が阻害されない。 When the range of the phosphoric acid ester is 3 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the ripening of the fire from cracking, and when it is 156 parts by weight or less, it is foamable. Foaming of the polyurethane composition is not inhibited.
リン酸エステルの添加量は、ウレタン樹脂100重量部に対しては、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の範囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。 The amount of the phosphoric acid ester added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and preferably in the range of 1.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
リン酸エステルの範囲が1.5重量部以上の場合には発泡性ポリウレタン組成物からなる成形品が火災の熟により形成される緻密残渣が割れることを防止でき、52重量部以下の場合には発泡性ポリウレタン組成物の発泡が阻害されない。 When the range of the phosphoric acid ester is 1.5 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the ripening of the fire from cracking, and when it is 52 parts by weight or less, it can be prevented from cracking. Foaming of the foamable polyurethane composition is not inhibited.
また本発明に使用するリン酸塩含有難燃剤はリン酸を含むものである。リン酸塩含有難燃剤に使用されるリン酸は特に限定はないが、モノリン酸、ピロリン酸、ポリリン酸、およびそれらの組み合わせ等の各種リン酸が挙げられる。 The phosphate-containing flame retardant used in the present invention contains phosphoric acid. The phosphoric acid used in the phosphate-containing flame retardant is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and various phosphoric acids such as combinations thereof.
リン酸塩含有難燃剤としては、例えば、各種リン酸と周期律表IA族〜IVB族の金属、アンモニア、脂肪族アミン、芳香族アミンから選ばれる少なくとも一種の金属または化合物との塩からなるリン酸塩を挙げることができる。周期律表IA族〜IVB族の金属として、リチウム、ナトリウム、カルシウム、バリウム、鉄(II)、鉄(III)、アルミニウム等が挙げられる。 The phosphate-containing flame retardant is, for example, phosphorus composed of a salt of various phosphoric acids and at least one metal or compound selected from the metals of Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, and aromatic amines. Phosphate can be mentioned. Examples of the metals of Group IA to IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
また脂肪族アミンとして、メチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、ピペラジン等が挙げられる。 Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.
また芳香族アミンとして、ピリジン、トリアジン、メラミン、アンモニウム等が挙げられる。 Further, examples of the aromatic amine include pyridine, triazine, melamine, ammonium and the like.
なお、上記のリン酸塩含有難燃剤は、シランカップリング剤処理、メラミン樹脂で被覆する等の公知の耐水性向上処理を加えてもよく、メラミン、ペンタエリスリトール等の公知の発泡助剤を加えても良い。 The above-mentioned phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as a silane coupling agent treatment or coating with a melamine resin, or a known foaming aid such as melamine or pentaerythritol may be added. May be.
リン酸塩含有難燃剤の具体例としては、例えば、モノリン酸塩、ピロリン酸塩、ポリリン酸塩等が挙げられる。 Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate and the like.
モノリン酸塩としては特に限定されないが、例えば、リン酸アンモニウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム等のアンモニウム塩、リン酸−ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、亜リン酸−ナトリウム、亜リン酸二ナトリウム、次亜リン酸ナトリウム等のナトリウム塩、リン酸一カリウム、リン酸二カリウム、リン酸三カリウム、亜リン酸一カリウム、亜リン酸二カリウム、次亜リン酸カリウム等のカリウム塩、リン酸−リチウム、リン酸二リチウム、リン酸三リチウム、亜リン酸−リチウム、亜リン酸二リチウム、次亜リン酸リチウム等のリチウム塩、リン酸二水素バリウム、リン酸水素バリウム、リン酸三バリウム、次亜リン酸バリウム等のバリウム塩、リン酸一水素マグネシウム、リン酸水素マグネシウム、リン酸三マグネシウム、次亜リン酸マグネシウム等のマグネシウム塩、リン酸二水素カルシウム、リン酸水素カルシウム、リン酸三カルシウム、次亜リン酸カルシウム等のカルシウム塩、リン酸亜鉛、亜リン酸亜鉛、次亜リン酸亜鉛等の亜鉛塩等が挙げられる。 The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, sodium phosphate, disodium phosphate, trisodium phosphate, and phosphite. -Sodium, disodium phosphite, sodium hypophosphite and other sodium salts, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite Potassium salts such as potassium, dilithium phosphate, trilithium phosphate, trilithium phosphate, dilithium phosphite, lithium salts such as lithium hypophosphite, barium dihydrogen phosphate, phosphorus Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate , Calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite and other calcium salts, zinc phosphate, zinc phosphite, zinc hypophosphite and other zinc salts and the like.
またポリリン酸塩としては特に限定されないが、例えば、ポリリン酸アンモニウム、ポリリン酸ピペラジン、ポリリン酸メラミン、ポリリン酸アンモニウムアミド、ポリリン酸アルミニウム等が挙げられる。 The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
これらの中でも、リン酸塩含有難燃剤の自己消火性が向上するため、モノリン酸塩を使用することが好ましく、リン酸二水素アンモニウムを使用することがより好ましい。 Among these, monophosphate is preferably used, and ammonium dihydrogen phosphate is more preferable, because the self-extinguishing property of the phosphate-containing flame retardant is improved.
リン酸塩含有難燃剤は一種もしくは二種以上を使用することができる。 One or more types of phosphate-containing flame retardants can be used.
本発明に使用するリン酸塩含有難燃剤の添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の範囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。 The amount of the phosphate-containing flame retardant used in the present invention is preferably in the range of 3 parts by weight to 156 parts by weight, preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
本発明に使用するリン酸塩含有難燃剤の添加量は、ウレタン樹脂100重量部に対しては、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の範囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。 The amount of the phosphate-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The range is more preferably in the range of parts by weight, further preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
また本発明に使用する臭素含有難燃剤としては、分子構造中に臭素を含有する化合物であれば特に限定はないが、例えば、芳香族臭素化化合物等を挙げることができる。 The bromine-containing flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in its molecular structure, and examples thereof include aromatic brominated compounds.
芳香族臭素化化合物の具体例としては、例えば、ヘキサブロモベンゼン、ペンタブロモトルエン、ヘキサブロモビフェニル、デカブロモビフェニル、ヘキサブロモシクロデカン、デカブロモジフェニルエーテル、オクタブロモジフェニルエーテル、ヘキサブロモジフェニルエーテル、ビス(ペンタブロモフエノキシ)エタン、エチレンービス(テトラブロモフタルイミド)、テトラブロモビスフェノールA等のモノマー有機臭素化合物;臭素化ビスフェノールAを原料として製造されたポリカーボネートオリゴマー、ポリカ−ボネートオリゴマーとビスフェノールAとの共重合物等の臭素化ポリカーボネート;臭素化ビスフェノールAとエピクロルヒドリンとの反応によって製造されるジエポキシ化合物、臭素化フェノール類とエピクロルヒドリンとの反応によって得られるモノエポキシ化合物等の臭素化エポキシ化合物;ポリ(臭素化ベンジルアクリレート);臭素化ポリフェニレンエーテル;臭素化ビスフェノールA、塩化シアヌールおよび臭素化フェノールの縮合物;臭素化(ポリスチレン)、ポリ(臭素化スチレン)、架橋臭素化ポリスチレン等の臭素化ポリスチレン;架橋または非架橋臭素化ポリ(−メチルスチレン)等のハロゲン化された臭素化合物ポリマーが挙げられる。 Specific examples of the aromatic brominated compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, and bis (pentabromo). Fenoxy) Ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A and other monomeric organobromine compounds; polycarbonate oligomers produced from brominated bisphenol A as raw materials, copolymers of polycarbonate oligomers and bisphenol A, etc. Bromineed polycarbonate; diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin; poly (bromineed benzyl acrylate) Brominated polyphenylene ether; Condensate of brominated bisphenol A, cyanur chloride and brominated phenol; brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), crosslinked brominated polystyrene; crosslinked or non-crosslinked brominated Examples thereof include halogenated bromine compound polymers such as poly (-methylstyrene).
燃焼初期の発熱量を制御する観点から、臭素化ポリスチレン、ヘキサブロモベンゼン等が好ましく、ヘキサブロモベンゼンがより好ましい。 From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.
臭素含有難燃剤は一種もしくは二種以上を使用することができる。 One or more kinds of bromine-containing flame retardants can be used.
本発明に使用する臭素含有難燃剤の添加量は、ウレタン樹脂100重量部に対して、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の範囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。
本発明に使用する臭素含有難燃剤の添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の範囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。
The amount of the bromine-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The range is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
The amount of the bromine-containing flame retardant used in the present invention is preferably in the range of 3 parts by weight to 156 parts by weight, preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. Is more preferable, and it is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
また本発明に使用するホウ素含有難燃剤としては、ホウ砂、酸化ホウ素、ホウ酸、ホウ酸塩等が挙げられる。 Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate and the like.
酸化ホウ素としては、例えば、三酸化二ホウ素、三酸化ホウ素、二酸化二ホウ素、三酸化四ホウ素、五酸化四ホウ素等が挙げられる。 Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
ホウ酸塩としては、例えば、アルカリ金属、アルカリ土類金属、周期表第4族、第12族、第13族の元素およびアンモニウムのホウ酸塩等が挙げられる。 Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, borates of ammonium, and the like.
具体的には、ホウ酸リチウム、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸セシウム等のホウ酸アルカリ金属塩、ホウ酸マグネシウム、ホウ酸カルシウム、ホウ酸バリウム等のホウ酸アルカリ土類金属塩、ホウ酸ジルコニウム、ホウ酸亜鉛、ホウ酸アルミニウム、ホウ酸アンモニウム等が挙げられる。 Specifically, alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borate salts such as magnesium borate, calcium borate, and barium borate, borate. Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
本発明に使用するホウ素含有難燃剤は、ホウ酸塩であることが好ましく、ホウ酸亜鉛であればより好ましい。 The boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.
ホウ素含有難燃剤は、一種もしくは二種以上を使用することができる。 As the boron-containing flame retardant, one kind or two or more kinds can be used.
本発明に使用するホウ素含有難燃剤の添加量は、ウレタン樹脂100重量部に対して、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。
本発明に使用するホウ素含有難燃剤の添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。
The amount of the boron-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The enclosure is more preferably in the range of 2.0 parts by weight to 15 parts by weight, most preferably in the range of 2.0 parts by weight to 10 parts by weight.
The amount of the boron-containing flame retardant used in the present invention is preferably in the range of 3 parts by weight to 156 parts by weight with respect to 100 parts by weight of the polyol compound, and is surrounded by 3 parts by weight to 60 parts by weight. Is more preferable, and it is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
また本発明に使用するアンチモン含有難燃剤としては、例えば、酸化アンチモン、アンチモン酸塩、ピロアンチモン酸塩等が挙げられる。 Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, and pyroantimonate.
酸化アンチモンとしては、例えば、三酸化アンチモン、五酸化アンチモン等が挙げられる。 Examples of antimony oxide include antimony trioxide and antimony pentoxide.
アンチモン酸塩としては、例えば、アンチモン酸ナトリウム、アンチモン酸カリウム等が挙げられる。 Examples of the antimonate include sodium antimonate, potassium antimonate and the like.
ピロアンチモン酸塩としては、例えば、ピロアンチモン酸ナトリウム、ピロアンチモン酸カリウム等が挙げられる。 Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.
本発明に使用するアンチモン含有難燃剤は、酸化アンチモンであることが好ましい。 The antimony-containing flame retardant used in the present invention is preferably antimony oxide.
アンチモン含有難燃剤は、一種もしくは二種以上を使用することができる。 As the antimony-containing flame retardant, one kind or two or more kinds can be used.
アンチモン含有難燃剤の添加量は、ウレタン樹脂100重量部に対して、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の範囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。
アンチモン含有難燃剤の添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の範囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。
The amount of the antimony-containing flame retardant added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and preferably in the range of 1.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
The amount of the antimony-containing flame retardant added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
また本発明に使用する金属水酸化物としては、例えば、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム、水酸化鉄、水酸化ニッケル、水酸化ジルコニウム、水酸化チタン、水酸化亜鉛、水酸化銅、水酸化バナジウム、水酸化スズ等があげられる。 Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, and copper hydroxide. , Vanadium hydroxide, tin hydroxide and the like.
金属水酸化物は、一種もしくは二種以上を使用することができる。 As the metal hydroxide, one kind or two or more kinds can be used.
金属水酸化物の添加量は、ウレタン樹脂100重量部に対して、1.5重量部〜52重量部の範囲であることが好ましく、1.5重量部〜20重量部の範囲であることがより好ましく、2.0重量部〜15重量部の範囲であることが更に好ましく、2.0重量部〜10重量部の範囲であることが最も好ましい。
金属水酸化物の添加量は、ポリオール化合物100重量部に対して、3重量部〜156重量部の範囲であることが好ましく、3重量部〜60重量部の範囲であることがより好ましく、4.0重量部〜45重量部の範囲であることが更に好ましく、4.0重量部〜30重量部の範囲であることが最も好ましい。
The amount of the metal hydroxide added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and preferably in the range of 1.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.
The amount of the metal hydroxide added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.
本発明に使用する難燃剤の合計量はウレタン樹脂100重量部に対して4.5重量部〜70重量部の範囲であることが好ましく、4.5重量部〜40重量部の範囲であることがより好ましく、4.5重量部〜30重量部の範囲であることが更に好ましい。
本発明に使用する難燃剤の合計量はポリオール化合物100重量部に対して9重量部〜210重量部の範囲であることが好ましく、9重量部〜120重量部の範囲であることがより好ましく、9重量部〜90重量部の範囲であることが更に好ましい。
The total amount of the flame retardant used in the present invention is preferably in the range of 4.5 parts by weight to 70 parts by weight, preferably in the range of 4.5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the urethane resin. Is more preferable, and the range is further preferably in the range of 4.5 parts by weight to 30 parts by weight.
The total amount of the flame retardant used in the present invention is preferably in the range of 9 parts by weight to 210 parts by weight, more preferably in the range of 9 parts by weight to 120 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 9 parts by weight to 90 parts by weight.
難燃剤の合計量の範囲が4.5重量部以上の場合には発泡性ポリウレタン組成物からなる成形品が火災の熱により形成される緻密残渣が割れることを防止でき、70重量部以下の場合には発泡性ポリウレタン組成物の発泡が阻害されない。 When the total amount of the flame retardant is 4.5 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the heat of the fire from cracking, and when it is 70 parts by weight or less. Does not inhibit the foaming of the foamable polyurethane composition.
好ましい実施形態において、発泡性ポリウレタン組成物は、ポリイソシアネートとポリオールとからなるウレタン樹脂100重量部を基準として、そのうちポリイソシアネートが50〜85重量部であり、整泡剤を0.1重量部〜10重量部、触媒を3.5〜10重量部、発泡剤を0.1〜30重量部、難燃剤を4.5重量部〜70重量部、含有し、難燃剤のうち赤リンが3重量部〜18重量部の範囲であり、リン酸エステル、リン酸塩含有難燃剤、臭素含有難燃剤、ホウ素含有難燃剤、アンチモン含有難燃剤、および金属水酸化物から選ばれる少なくとも1つが1.5重量部〜52重量部である。この場合、難燃剤は好ましくは4.5重量部〜52重量部、より好ましくは4.5重量部〜30重量部である。リン酸エステル、リン酸塩含有難燃剤、臭素含有難燃剤、ホウ素含有難燃剤、アンチモン含有難燃剤、および金属水酸化物から選ばれる少なくとも1つはホウ素含有難燃剤であり、好ましい範囲は1.5重量部〜9重量部の範囲である。 In a preferred embodiment, the foamable polyurethane composition is based on 100 parts by weight of a urethane resin composed of a polyisocyanate and a polyol, of which 50 to 85 parts by weight is polyisocyanate and 0.1 parts by weight is a foam stabilizer. Contains 10 parts by weight, 3.5 to 10 parts by weight of catalyst, 0.1 to 30 parts by weight of foaming agent, 4.5 parts by weight to 70 parts by weight of flame retardant, and 3 parts by weight of red phosphorus among the flame retardants. In the range of parts to 18 parts by weight, at least one selected from phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide is 1.5. It is a part by weight to 52 parts by weight. In this case, the flame retardant is preferably 4.5 parts by weight to 52 parts by weight, more preferably 4.5 parts by weight to 30 parts by weight. At least one selected from phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide is a boron-containing flame retardant, and the preferred range is 1. The range is from 5 parts by weight to 9 parts by weight.
7.その他成分
無機充填材としては、特に限定はないが、例えば、シリカ、珪藻土、アルミナ、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト類、塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸バリウム、ドーソナイト、ハイドロタルサイト、硫酸カルシウム、硫酸バリウム、石膏繊維、ケイ酸カルシウム等のカリウム塩、タルク、クレー、マイカ、ウォラストナイト、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカパルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素パルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、アルミニウムポレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、各種磁性粉、スラグ繊維、フライアッシュ、シリカアルミナ繊維、アルミナ繊維、シリカ繊維、ジルコニア繊維等が挙げられる。
7. Other components The inorganic filler is not particularly limited, but for example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate. , Magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, active white clay, Sepiolite, Imogolite, Cerisite, Glass Fiber, Glass Beads, Silica Parun, Aluminum Nitride, Boron Nitride, Silicon Nitide, Carbon Black, Graphite, Carbon Fiber, Carbon Parun, Charcoal Powder, Various Metal Powders, Potassium Titanium, Magnesium Sulfate, Titanium Examples thereof include lead acid zirconate, aluminum porate, molybdenum sulfide, silicon carbide, stainless fibers, various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, and zirconia fibers.
無機充填材は、一種もしくは二種以上を使用することができる。 As the inorganic filler, one kind or two or more kinds can be used.
本発明の好ましい態様において、本発明のポリオール含有組成物には、保管安定性を向上させるために、微粉シリカが好適に用いられる。微粉シリカとは、ヒュームドシリカ、コロイダルシリカ等と呼ばれるものである。微粉シリカは、ポリオール含有組成物中でネットワーク構造を形成し、固形成分のケーキング(沈降凝集)を抑制する効果を発揮する。 In a preferred embodiment of the present invention, fine silica powder is preferably used in the polyol-containing composition of the present invention in order to improve storage stability. Fine silica is called fumed silica, colloidal silica, or the like. The fine silica powder forms a network structure in the polyol-containing composition and exerts an effect of suppressing caking (precipitation and aggregation) of solid components.
微粉シリカの添加量は、ポリオール化合物100重量部に対して、0.01重量部〜10重量部の範囲であることが好ましく、0.1重量部〜5重量部の範囲であることがより好ましく、0.50重量部〜2重量部の範囲であることが更に好ましい。 The amount of fine silica added is preferably in the range of 0.01 parts by weight to 10 parts by weight, more preferably in the range of 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of the polyol compound. , 0.50 parts by weight to 2 parts by weight is more preferable.
微粉シリカの範囲が0.01重量部以上の場合には、ポリオール含有組成物の保管安定性の効果を発揮することでき、10重量部以下とすることでポリウレタンフォーム形成に適した高すぎない流動性を達成することができる。 When the range of fine silica is 0.01 parts by weight or more, the effect of storage stability of the polyol-containing composition can be exhibited, and when it is 10 parts by weight or less, the flow is not too high and suitable for forming polyurethane foam. Sex can be achieved.
微粉シリカの添加量は、ウレタン樹脂100重量部に対して、0.005重量部〜4重量部の範囲であることが好ましく。0.05重量部〜2重量部の範囲であることがより好ましく、0.1重量部〜1重量部の範囲であることが更に好ましい。 The amount of fine silica added is preferably in the range of 0.005 parts by weight to 4 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 0.05 parts by weight to 2 parts by weight, and further preferably in the range of 0.1 parts by weight to 1 part by weight.
微粉シリカの範囲が0.005重量部以上の場合には、ポリオール含有組成物の保管安定性を発揮することができ、10重量部以下とすることでポリウレタンフォーム形成に適した高すぎない流動性を達成することができる。 When the range of fine silica is 0.005 parts by weight or more, the storage stability of the polyol-containing composition can be exhibited, and when it is 10 parts by weight or less, the fluidity is not too high and suitable for forming polyurethane foam. Can be achieved.
発泡性ポリウレタン組成物は、それぞれ本発明の目的を損なわない範囲で、必要に応じて、フェノール系、アミン系、イオウ系等の酸化防止剤、熱安定剤、金属害防止剤、帯電防止剤、安定剤、架橋剤、滑剤、軟化剤、顔料、粘着付与樹脂等の補助成分、ポリブテン、石油樹脂等の粘着付与剤を含むことができる。 The foamable polyurethane composition contains, as necessary, phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, etc., as long as the object of the present invention is not impaired. It can contain auxiliary components such as stabilizers, cross-linking agents, lubricants, softeners, pigments, antistatic resins, and antistatic agents such as polybutene and petroleum resins.
上記の1.〜7.の成分は混合されて発泡性ポリウレタン組成物は反応して硬化するため、その粘度は時間の経過と共に変化する。そこで発泡性ポリウレタン組成物を使用する前に、発泡性ポリウレタン組成物を二以上に分割して、発泡性ポリウレタン組成物が反応して硬化することを防止する。そして発泡性ポリウレタン組成物を使用する際に、二以上に分割しておいた発泡性ポリウレタン組成物を一つにまとめることにより、発泡性ポリウレタン組成物が得られる。 Above 1. ~ 7. The components of are mixed and the effervescent polyurethane composition reacts and cures, so its viscosity changes over time. Therefore, before using the effervescent polyurethane composition, the effervescent polyurethane composition is divided into two or more to prevent the effervescent polyurethane composition from reacting and curing. Then, when the foamable polyurethane composition is used, the foamable polyurethane composition can be obtained by combining the foamable polyurethane compositions divided into two or more into one.
なお発泡性ポリウレタン組成物を二以上に分割するときは、二以上に分割された発泡性ポリウレタン組成物のそれぞれの成分単独は硬化が始まらず、発泡性ポリウレタン組成物のそれぞれの成分を混合した後に硬化反応が始まるようにそれぞれの成分を分割すればよい。 When the effervescent polyurethane composition is divided into two or more, each component of the effervescent polyurethane composition divided into two or more does not start curing, and after mixing each component of the effervescent polyurethane composition. Each component may be divided so that the curing reaction starts.
発泡性ポリウレタン組成物の硬化は混合および常温で行なってもよいが、各成分を予め加熱しておいてもよい。 The effervescent polyurethane composition may be cured by mixing and at room temperature, but each component may be preheated.
本発明のポリオール含有組成物は、ポリイソシアネートと反応させてポリウレタン発泡体を得るためのポリオールプレミックスである。 The polyol-containing composition of the present invention is a polyol premix for reacting with polyisocyanate to obtain a polyurethane foam.
ポリイソシアネートと、ポリオール、整泡剤、触媒、発泡剤、および難燃剤を含有するポリオールプレミックスとが混合されて生じる発泡性ポリウレタン組成物は、発泡および硬化してポリウレタン発泡体となる。本発明は、上記の成分を含む発泡性ポリウレタン組成物から成形されたポリウレタン発泡体も包含する。 The foamable polyurethane composition produced by mixing a polyisocyanate with a polyol premix containing a polyol, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant is foamed and cured to form a polyurethane foam. The present invention also includes a polyurethane foam molded from an effervescent polyurethane composition containing the above components.
本発明のポリオール含有組成物は、25℃回転速度100rpmにおける粘度が105mPas以上、好ましくは105以上800mPas以下であり、かつ、下記式により算出されるチクソ値(チクソトロピー指数ともいう)が1.9以上であることを特徴とする。
(チクソ値)=(25℃回転速度1rpmでの粘度)/(25℃回転速度10rpmでの粘度)
The polyol-containing composition of the present invention has a viscosity of 105 mPas or more, preferably 105 or more and 800 mPas or less at a rotation speed of 100 rpm at 25 ° C., and a thixotropy value (also referred to as thixotropy index) calculated by the following formula is 1.9 or more. It is characterized by being.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 °
25℃回転速度100rpmにおける粘度を105mPas以上とすることで、液ダレの発生を抑制し、固形分量が少ない場合の難燃性低下が抑制される。また、25℃回転速度100rpmにおける粘度を800mPas以下とすることで、発泡性ポリウレタン組成物の流動性の低下を防止し、ポリウレタンフォーム形成能が優れるため、好ましい。 By setting the viscosity at a rotation speed of 100 rpm at 25 ° C. to 105 mPas or more, the occurrence of liquid dripping is suppressed, and the decrease in flame retardancy when the solid content is small is suppressed. Further, it is preferable that the viscosity at a rotation speed of 100 rpm at 25 ° C. is 800 mPas or less because the foamable polyurethane composition is prevented from being lowered in fluidity and the polyurethane foam forming ability is excellent.
本明細書において「粘度」とは、E型粘度計を用いた測定値をいう。 As used herein, the term "viscosity" refers to a measured value using an E-type viscometer.
また、本発明のポリオール含有組成物は、ポリオール化合物100重量部に対する固形成分が35重量部以上であることが好ましい。固形成分を35重量部以上とすることで、難燃性が改善されたポリウレタンフォームが得られる。 Further, the polyol-containing composition of the present invention preferably has a solid component of 35 parts by weight or more with respect to 100 parts by weight of the polyol compound. By setting the solid component to 35 parts by weight or more, a polyurethane foam having improved flame retardancy can be obtained.
「固形成分」とは、ポリオール含有組成物が含有する非溶解成分を意味する。「固形成分」は、赤リン;リン酸エステル、リン酸塩含有難燃剤等のリン酸化合物の難燃剤;臭素含有難燃剤等の有機ハロゲン化合物の難燃剤;ホウ酸含有難燃剤;アンチモン含有難燃剤、金属水酸化物等の金属化合物の難燃剤;シリカ化合物等の無機充填材などの難燃剤又は無機充填材であって非溶解成分であるものを包含する。好適な例としては、上記の6.難燃剤に記載の難燃剤または7.その他成分に記載の無機充填材であって非溶解成分であるものが挙げられる。 The "solid component" means an insoluble component contained in the polyol-containing composition. "Solid component" is red phosphorus; flame retardant of phosphoric acid compound such as phosphoric acid ester and phosphate-containing flame retardant; flame retardant of organic halogen compound such as bromine-containing flame retardant; boric acid-containing flame retardant; antimony-containing flame retardant Flame retardants of metal compounds such as fuel agents and metal hydroxides; include flame retardants such as inorganic fillers such as silica compounds or inorganic fillers that are insoluble components. As a preferable example, the above 6. The flame retardant described in the flame retardant or 7. Examples of the inorganic filler described in the other components include those which are insoluble components.
本発明の1つの態様では、本発明のポリオール含有組成物は、ポリオール化合物100重量部に対し、赤リン、ホウ酸含有難燃剤及び充填剤からなる群から選択される1種以上(好ましくはすべて)を、ポリオール化合物100重量部に対して35重量部含む。 In one aspect of the present invention, the polyol-containing composition of the present invention is one or more (preferably all) selected from the group consisting of red phosphorus, boric acid-containing flame retardants and fillers based on 100 parts by weight of the polyol compound. ) Is included in 35 parts by weight with respect to 100 parts by weight of the polyol compound.
本発明の発泡ウレタン組成物およびポリウレタン発泡体の難燃性(耐火性)は、ISO−5660の試験方法に準拠したコーンカロリーメーター試験により評価することができる。具体的には、この耐火試験では、発泡性ポリウレタン組成物からなるポリウレタン発泡体を縦10cm、横10cmおよび厚み5cmに切断して、コーンカロリーメーター試験用サンプルを準備する。次に、コーンカロリーメーター試験用サンプル用いて、ISO−5660の試験方法に準拠して、放射熱強度50kW/m2にて20分間加熱したときの総発熱量をコーンカロリーメーターにより測定する。 The flame retardancy (fire resistance) of the urethane foam composition and the polyurethane foam of the present invention can be evaluated by a cone calorimeter test based on the test method of ISO-5660. Specifically, in this fire resistance test, a polyurethane foam made of a foamable polyurethane composition is cut into a length of 10 cm, a width of 10 cm, and a thickness of 5 cm to prepare a sample for a corn calorimeter test. Next, using the corn calorimeter test sample, the total calorific value when heated at a radiant heat intensity of 50 kW / m 2 for 20 minutes is measured by the corn calorimeter according to the test method of ISO-5660.
本明細書において「不燃性」とは、(1)放射熱強度50kW/m2にて加熱開始後20分間の総発熱量が8MJ/m2以下である、(2)加熱開始後20分間に200kW/m2を超える発熱速度が10秒を超えて継続しない、(3)加熱開始後20分間に防火上有害な亀裂または穴等の変形が生じない、という(1)〜(3)の条件を全て具備するものをいう。 In the present specification, "nonflammable" means (1) a total calorific value of 8 MJ / m 2 or less for 20 minutes after the start of heating at a radiant heat intensity of 50 kW / m 2 , and (2) 20 minutes after the start of heating. Conditions (1) to (3) that the heat generation rate exceeding 200 kW / m 2 does not continue for more than 10 seconds, and (3) no deformation such as cracks or holes harmful to fire prevention occurs within 20 minutes after the start of heating. It means the one that has all of.
本発明の発泡性ポリウレタン組成物およびポリウレタン発泡体の用途は特に限定されないが、通常、建築物の開口部または隙間を充填するために用いられる。ここで「建築物」には、建築物を構成する任意の構造が含まれ、壁、天井、屋根、床などの建築物の構造材のみならず、窓(引き違い窓、開き窓、上げ下げ窓等を含む)、障子、扉(すなわちドア)、戸、ふすま、欄間などの建具も含まれる。なお「開口部」は、建築物の構造材の間に生じる目地や、一つの構造材中に生じる穴を含め、建築物に生じる任意の開口部を指すが、「隙間」とは開口部の中でも、構造材と構造材の間、構造材と建具の間、建具と建具の間、構造材または建具と家具(台所のシンク等)との間のように、向かい合う2つの部材または部分間に生じる開口部を指す。 The use of the foamable polyurethane composition and the polyurethane foam of the present invention is not particularly limited, but is usually used for filling openings or gaps in buildings. Here, "building" includes arbitrary structures that make up the building, and not only structural materials of the building such as walls, ceilings, roofs, and floors, but also windows (sliding windows, hinged windows, raising and lowering windows). , Etc.), obstacles, doors (that is, doors), doors, bran, windows, and other fittings are also included. The "opening" refers to any opening that occurs in the building, including joints that occur between the structural materials of the building and holes that occur in one structural material, but the "gap" refers to the opening. Among the two facing members or parts, such as between structural materials and structural materials, between structural materials and fittings, between fittings and fittings, and between structural materials or fittings and furniture (kitchen sinks, etc.). Refers to the resulting opening.
また、発泡性ポリウレタン組成物は、建築物の開口部または隙間に直接充填させるだけでなく、金型等に流し込んで建築物の開口部または隙間に適合する寸法(長さ、幅、及び厚み)に成形したり、混合容器から別の場所に吐出してポリウレタン発泡体として所定の寸法(長さ、幅、及び厚み)に切断したりした後に、ポリウレタン発泡体を建築物の開口部または隙間に装着してもよい。 In addition, the foamable polyurethane composition is not only directly filled in the opening or gap of the building, but also poured into a mold or the like to fit the opening or gap of the building (length, width, and thickness). The polyurethane foam is placed in the opening or gap of the building after being molded into a container or discharged from the mixing container to another location and cut to the specified dimensions (length, width, and thickness) as the polyurethane foam. It may be attached.
発泡性ポリウレタン組成物を発泡硬化したポリイソシアヌレート発泡体は、防水性、気密性、および防火性に優れているため、建築物の開口部または隙間からの水、煙や炎、燃焼により発生するガス等の侵入を効果的に遮断することができる。 Polyisocyanurate foams made by foaming and curing a foamable polyurethane composition are excellent in waterproofness, airtightness, and fire resistance, and are therefore generated by water, smoke, flames, and combustion through openings or gaps in buildings. It is possible to effectively block the intrusion of gas and the like.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
製造例1 発泡性ポリウレタン樹脂組成物および難燃性硬質ポリウレタン発泡体の製造
表1に示した配合により、実施例1〜3及び比較例1〜3に係る発泡性ポリウレタン樹脂組成物を、(1)ポリオールプレミックスおよび(2)ポリイソシアネートの2つに分けて準備した。なお表中の各成分の詳細は次の通りである。
Production Example 1 Production of Foamable Polyurethane Resin Composition and Flame Retardant Rigid Polyurethane Foam The foamable polyurethane resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Table 1 (1). ) Polyol premix and (2) Polyisocyanate were prepared separately. The details of each component in the table are as follows.
(1)ポリオールプレミックス
・ポリオール
p−フタル酸ポリエステルポリオール(川崎化成工業社製、製品名:マキシモールRLK−087、水酸基価=200mgKOH/g)
・整泡剤
ポリアルキレングリコール系整泡剤(東レダウコーニング社製、製品名:SH−193)
・触媒
3量化触媒(東ソー社製、製品名:TOYOCAT(登録商標)−TRX)
3量化触媒(サンアプロ株式会社製、製品名:U−CAT 18X)
アルキル化ポリアルキレンポリアミン(三級アミン)(東ソー社製、製品名:TOYOCAT(登録商標)−TT)
三級アミンのウレタン触媒(イミダゾール系化合物、サンアプロ株式会社製、製品名:U−CAT 202)
三級アミン(1,2−ジメチルイミダゾールとエチレングリコールの混合物、東ソー社製、製品名:TOYOCAT(登録商標)−DM70)
・発泡剤
水
HFC HFC−365mfc(1,1,1,3,3−ペンタフルオロブタン、セントラル硝子社製)及びHFC−245fa(1,1,1,3,3−ペンタフルオロプロパン、日本ソルベイ社製)、混合比率 HFC−365mfc:HFC−245fa = 7:3、以下「HFC」という)
・難燃剤
トリス(β−クロロプロピル)ホスフェート(大八化学社製、製品名:TMCPP、「TMCPP」という。)
赤リン (燐化学工業社製、製品名:ノーバエクセル140)
ホウ酸亜鉛(早川商事株式会社製、製品名:FIRebrake ZB)
・無機充填材
ウォラストナイト(SiO2・CaO)(キンセイマテック社製、製品名:SH−1250)
微粉シリカ(日本アエロジル社製、製品名:アエロジルR976S)。
(1) Polyol premix polyol p-phthalate polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
・ Defoaming agent Polyalkylene glycol-based defoaming agent (manufactured by Toray Dow Corning, product name: SH-193)
-Catalyst triad catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -TRX)
Quantifier catalyst (manufactured by Sun Appro Co., Ltd., product name: U-CAT 18X)
Alkylated polyalkylene polyamine (tertiary amine) (manufactured by Tosoh Corporation, product name: TOYOCAT®-TT)
Urethane catalyst of tertiary amine (imidazole compound, manufactured by San-Apro Co., Ltd., product name: U-CAT 202)
Tertiary amine (mixture of 1,2-dimethylimidazole and ethylene glycol, manufactured by Tosoh Corporation, product name: TOYOCAT®-DM70)
・ Foaming agent water HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.) and HFC-245fa (1,1,1,3,3-pentafluoropropane, Nippon Solvay Co., Ltd.) ), Mixing ratio HFC-365mfc: HFC-245fa = 7: 3, hereinafter referred to as "HFC")
-Flame retardant Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, called "TMCPP")
Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)
Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: FIRebreak ZB)
-Inorganic filler Wollastonite (SiO 2 · CaO) (manufactured by Kinsei Matek, product name: SH-1250)
Fine silica (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil R976S).
(2)ポリイソシアネート
4,4’−ジフェニルメタンジイソシアネート(4,4’−MDI)(万華化学ジャパン株式会社製、製品名:PM200)。
(2) Polyisocyanate 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Kagaku Japan Co., Ltd., product name: PM200).
下記の表1の配合に従い、ポリオールプレミックス(ポリオール含有組成物)600Lを適切な容器と適切なホモミキサーを用いて調製した。実施例1〜3及び比較例1、3については、固形成分1原料添加毎に回転速度3600rpmにて40分間攪拌分散を行った(「十分攪拌」)。比較例2については、全原料添加後に回転速度3600rpmにて20分間攪拌分散を行った(「不十分攪拌」)。 According to the formulation in Table 1 below, 600 L of polyol premix (polyol-containing composition) was prepared using a suitable container and a suitable homomixer. For Examples 1 to 3 and Comparative Examples 1 and 3, each time the solid component 1 raw material was added, stirring and dispersion were performed at a rotation speed of 3600 rpm for 40 minutes (“sufficient stirring”). In Comparative Example 2, after all the raw materials were added, stirring and dispersion were performed at a rotation speed of 3600 rpm for 20 minutes (“insufficient stirring”).
攪拌直後の若しくは2週間(2w)静置後の(1)ポリオールプレミックスを、ホモミキサーを用いて30分間撹拌した後に、(1)ポリオールプレミックスの成分の混練物を必要量取り出した。このポリオールプレミックスに(2)ポリイソシアネートを加え、ハンドミキサーで約10秒間撹拌し発泡性ポリウレタン樹脂組成物を作成した。得られた発泡性ポリウレタン樹脂組成物は時間の経過と共に流動性を失い、難燃性硬質ポリウレタン発泡体を得た。前記ポリオールプレミックス及び前記発泡体を下記の基準により評価し、結果を表1に示した(各成分の割合をウレタン樹脂100重量部に対する重量部で示す)。 The (1) polyol premix immediately after stirring or after standing for 2 weeks (2w) was stirred for 30 minutes using a homomixer, and then the required amount of the kneaded mixture of the components of the (1) polyol premix was taken out. (2) Polyisocyanate was added to this polyol premix, and the mixture was stirred with a hand mixer for about 10 seconds to prepare a foamable polyurethane resin composition. The obtained foamable polyurethane resin composition lost its fluidity with the passage of time, and a flame-retardant rigid polyurethane foam was obtained. The polyol premix and the foam were evaluated according to the following criteria, and the results are shown in Table 1 (the ratio of each component is shown in parts by weight with respect to 100 parts by weight of urethane resin).
試験例1 粘度測定
攪拌直後のポリオールプレミックス(ポリオール含有組成物)の粘度を、Viscometer/TV-22(東機産業社製)を用いて25℃で測定を行った。回転速度を0.5rpm、1rpm、5rpm、10rpm、20rpm、50rpm、100rpmの順に設定し安定化した時点で数値を読み取った。
Test Example 1 Viscosity measurement The viscosity of the polyol premix (polypoly-containing composition) immediately after stirring was measured at 25 ° C. using a Viscometer / TV-22 (manufactured by Toki Sangyo Co., Ltd.). The rotation speed was set in the order of 0.5 rpm, 1 rpm, 5 rpm, 10 rpm, 20 rpm, 50 rpm, and 100 rpm, and the numerical value was read when it became stable.
チクソ値は回転速度1rpmでの粘度と回転速度10rpmでの粘度の比によって求めた。 The chixo value was determined by the ratio of the viscosity at a rotation speed of 1 rpm to the viscosity at a rotation speed of 10 rpm.
粘度及びチクソ値の測定結果を表1及び図1のグラフに示す。 The measurement results of the viscosity and the thixo value are shown in Table 1 and the graph of FIG.
表1に示すように、実施例1〜3の25℃での回転速度100rpmでの粘度はそれぞれ136、109、154であり、比較例1〜3の25℃での回転速度100rpmでの粘度はそれぞれ218、102、143であった。 As shown in Table 1, the viscosities of Examples 1 to 3 at a rotation speed of 100 rpm at 25 ° C. are 136, 109, and 154, respectively, and the viscosities of Comparative Examples 1 to 3 at a rotation speed of 100 rpm at 25 ° C. are They were 218, 102, and 143, respectively.
表1に示すように、実施例1〜3のチクソ値はそれぞれ2.9、2.7及び2.1であり、比較
例1〜3のチクソ値はそれぞれ1.5、2.3、1.8であった。
As shown in Table 1, the chixo values of Examples 1 to 3 were 2.9, 2.7 and 2.1, respectively, and the chixo values of Comparative Examples 1 to 3 were 1.5, 2.3 and 1.8, respectively.
試験例2 難燃性試験
発泡性ポリウレタン樹脂組成物の硬化発泡体から10cm×10cm×5cmになるようにコーンカロリーメーター試験用サンプルを切り出し、ISO−5660に準拠し、放射熱強度50kW/m2にて20分間加熱したときの最大発熱速度、総発熱量を測定した。
Test Example 2 Flame Retardant Test A sample for corn calorimeter test was cut out from the cured foam of the foamable polyurethane resin composition so as to have a size of 10 cm × 10 cm × 5 cm, and a radiant heat intensity of 50 kW / m 2 was obtained in accordance with ISO-5660. The maximum heat generation rate and the total heat generation amount when heated for 20 minutes were measured.
この測定方法は、建築基準法施行令第108条の2に規定される公的機関である建築総合試験所にて、コーンカロリーメーター法による基準に対応するものとして規定された試験法であり、ISO−5660の試験方法に準拠したものである。 This measurement method is a test method specified by the Building Comprehensive Laboratory, which is a public institution stipulated in Article 108-2 of the Building Standards Law Enforcement Ordinance, as corresponding to the standard by the corn calorimeter method. It conforms to the ISO-5660 test method.
20分間加熱でコーンカロリーメーターの総発熱量が8MJ/m2以下の場合に合格であるが、本試験では20分間加熱で8MJ/m2を超えるものを×、20分間加熱で8MJ以下のものを○とした。 It passed when the total calorific value of the corn calorimeter was 8 MJ / m 2 or less after heating for 20 minutes, but in this test, those exceeding 8 MJ / m 2 after heating for 20 minutes were x, and those exceeding 8 MJ / m 2 after heating for 20 minutes. Was marked as ○.
表1に示すように、実施例1〜3は、(1)ポリオールプレミックスとして製造直後のもの及び2週間静置後のもののいずれを用いた場合においても、合格であった。比較例1及び3は、(1)ポリオールプレミックスとして製造直後のものを用いた場合には合格であったが、2週間静置後のものを用いた場合には不合格であった、比較例2は、(1)ポリオールプレミックスとして製造直後のもの及び2週間静置後のもののいずれを用いた場合においても、不合格であった。 As shown in Table 1, Examples 1 to 3 passed the test regardless of whether (1) the polyol premix immediately after production or after standing for 2 weeks was used. Comparative Examples 1 and 3 were (1) passed when the polyol premix immediately after production was used, but failed when the one after standing for 2 weeks was used. Example 2 was unacceptable when either (1) the polyol premix immediately after production or the one after standing for 2 weeks was used.
Claims (5)
前記ポリオール含有組成物はポリオール化合物、整泡剤、触媒、発泡剤、微粉シリカおよび難燃剤を含み、
前記ポリオール化合物100重量部に対して、前記難燃剤を9〜210重量部の範囲で含有し、
前記ポリオール化合物100重量部に対して、固形成分の含有量が35重量部以上であり、
前記ポリオール含有組成物の25℃回転速度100rpmにおける粘度が105mPas以上であり、かつ、下記式により算出されるチクソ値が1.9以上であることを特徴とするポリオール含有組成物。
(チクソ値)=(25℃回転速度1rpmでの粘度)/(25℃回転速度10rpmでの粘度) A polyol-containing composition for reacting with polyisocyanate to obtain a polyurethane foam.
The polyol-containing composition contains a polyol compound, a foam stabilizer, a catalyst, a foaming agent, fine silica powder and a flame retardant.
The flame retardant was contained in the range of 9 to 210 parts by weight with respect to 100 parts by weight of the polyol compound.
The content of the solid component is 35 parts by weight or more with respect to 100 parts by weight of the polyol compound.
A polyol-containing composition characterized in that the viscosity of the polyol-containing composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more, and the chixo value calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 ° C. rotation speed 10 rpm)
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