TW202132450A - Polyol composition, fire resistant hard polyurethane foam and method for manufacturing same - Google Patents
Polyol composition, fire resistant hard polyurethane foam and method for manufacturing same Download PDFInfo
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- TW202132450A TW202132450A TW109144697A TW109144697A TW202132450A TW 202132450 A TW202132450 A TW 202132450A TW 109144697 A TW109144697 A TW 109144697A TW 109144697 A TW109144697 A TW 109144697A TW 202132450 A TW202132450 A TW 202132450A
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- Taiwan
- Prior art keywords
- polyol
- polyol composition
- flame
- polyurethane foam
- rigid polyurethane
- Prior art date
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- 229920005862 polyol Polymers 0.000 title claims abstract description 137
- 150000003077 polyols Chemical class 0.000 title claims abstract description 105
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 88
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 9
- 230000009970 fire resistant effect Effects 0.000 title 1
- 239000003063 flame retardant Substances 0.000 claims abstract description 100
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 59
- -1 polyol compound Chemical class 0.000 claims abstract description 55
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 30
- 229920001228 polyisocyanate Polymers 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 7
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 27
- 239000007788 liquid Substances 0.000 abstract description 26
- 239000000843 powder Substances 0.000 abstract description 23
- 230000002776 aggregation Effects 0.000 abstract description 22
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 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 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012970 tertiary amine catalyst Substances 0.000 description 5
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001737 promoting effect Effects 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
- 229910052725 zinc Inorganic materials 0.000 description 3
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 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 2
- 239000003086 colorant Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- IVJXXQSXKSRPIL-UHFFFAOYSA-N 2,4-bis[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1 IVJXXQSXKSRPIL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UNMUYUJQFADDAM-UHFFFAOYSA-N 2-N,2-N-diethyl-1-N-methylbenzene-1,2-diamine Chemical compound C(C)N(C1=C(C=CC=C1)NC)CC UNMUYUJQFADDAM-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- XDUZWPPSSHEDFK-VVXQKDJTSA-N C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O Chemical compound C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O XDUZWPPSSHEDFK-VVXQKDJTSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- 238000006683 Mannich reaction Methods 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 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
- OBNAOHSAPQWLGU-UHFFFAOYSA-N phthalic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OC(=O)C1=CC=CC=C1C(O)=O OBNAOHSAPQWLGU-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-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
- 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-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
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
提供一種多元醇組成物，其在含有包含指定之次膦酸(phosphinic acid)系金屬鹽及/或磷酸系金屬鹽之難燃劑之多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液中，可抑制液中的粉體之凝聚，且可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體；以及提供一種使用該多元醇組成物的難燃性硬質聚胺甲酸酯發泡體及其製造方法。本發明之多元醇組成物含有：多元醇化合物，其包含芳香族系聚酯多元醇；難燃劑，其包含1種以上選自包含指定之次膦酸系金屬鹽、及磷酸系金屬鹽的群組之化合物；及分散劑，其包含諾易堡矽土(Neuburg Siliceous Earth)粒子。A polyol composition is provided, which contains a polyol composition containing a designated phosphinic acid (phosphinic acid)-based metal salt and/or a phosphate-based metal salt of a flame retardant and a flame-retardant rigid polyurethane hair In the raw material liquid of the foam, the agglomeration of the powder in the liquid can be suppressed, and a rigid polyurethane foam with excellent flame retardancy can be obtained; and a flame retardancy using the polyol composition can be provided Rigid polyurethane foam and its manufacturing method. The polyol composition of the present invention contains: a polyol compound comprising an aromatic polyester polyol; a flame retardant comprising one or more selected from the group consisting of a designated phosphinic acid-based metal salt and a phosphoric acid-based metal salt Group of compounds; and dispersants, which include Neuburg Siliceous Earth particles.
Description
本發明係關於用於難燃性硬質聚胺甲酸酯發泡體之製造的多元醇組成物、以及使用其之難燃性硬質聚胺甲酸酯發泡體及其製造方法。The present invention relates to a polyol composition used for the production of a flame-retardant rigid polyurethane foam, a flame-retardant rigid polyurethane foam using the polyol composition, and a method for manufacturing the same.
硬質聚胺甲酸酯發泡體具有優異的隔熱性能，加工性及經濟性等亦為優異，由節能化及居住性的提升等之觀點來看，廣泛普遍用作建築物之隔熱材。Rigid polyurethane foam has excellent heat insulation performance, processability and economy, etc. It is widely used as heat insulation material in buildings from the viewpoint of energy saving and improvement of habitability. .
另一方面，硬質聚胺甲酸酯發泡體為有機高分子材料，具有所謂容易燃燒的特徵。由於建築施工及整修工程、拆除工程中之焊接熱割削作業中的火花，亦經常發生硬質聚胺甲酸酯發泡體延燒的火災事故。 已在檢討對硬質聚胺甲酸酯發泡體賦予難燃性的各式各樣的設想，作為降低此種火災事故的對策。On the other hand, rigid polyurethane foam is an organic polymer material and has a so-called easy to burn characteristic. Due to sparks from welding and hot cutting operations in construction and renovation projects, and demolition projects, fire accidents of rigid polyurethane foam prolonged burning often occur. Various ideas for imparting flame retardancy to rigid polyurethane foams have been reviewed as a countermeasure to reduce such fire accidents.
例如，已知於硬質聚胺甲酸酯發泡體中添加作為難燃劑之赤磷、磷酸酯而使其難燃化的技術。 然而，赤磷為具有引燃性的物質，於處理之際必須充分注意以確保安全。 又，赤磷、磷酸酯，對於硬質聚胺甲酸酯發泡體之難燃性的提升程度上有限度，而冀求可賦予更優異的難燃性，且可使硬質聚胺甲酸酯發泡體接近不燃性材料的難燃劑。For example, a technique of adding red phosphorus or phosphoric acid ester as a flame retardant to a rigid polyurethane foam to make it flame retardant is known. However, red phosphorus is a flammable substance, so it must be handled with sufficient care to ensure safety. In addition, red phosphorus and phosphoric acid esters have a limited degree of improvement in the flame retardancy of rigid polyurethane foams, and it is desired to provide more excellent flame retardancy and to make rigid polyurethane foams. The foam is close to the flame retardant of the non-combustible material.
對於此種課題，本發明人等已檢討應用例如，於專利文獻1中被作為合成皮革用之聚胺甲酸酯樹脂難燃劑使用之包含次膦酸(phosphinic acid)系金屬鹽的難燃劑，作為更有效的難燃劑。 [先前技術文獻] [專利文獻]For this problem, the present inventors have reviewed the application. For example, the flame retardant containing phosphinic acid-based metal salt used as a polyurethane resin flame retardant for synthetic leather in Patent Document 1 As a more effective flame retardant. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2016-79375號公報[Patent Document 1] JP 2016-79375 A
[發明欲解決之課題][The problem to be solved by the invention]
然而，上述專利文獻1所記載的包含次膦酸系金屬鹽的難燃劑，亦與赤磷等之以往的難燃劑同樣地難溶於為硬質聚胺甲酸酯發泡體之原料的多元醇化合物或聚異氰酸酯化合物中，且其為比重大的粉體狀之難燃劑，於硬質聚胺甲酸酯發泡體之原料液中容易發生凝聚。However, the flame retardant containing the phosphinic acid-based metal salt described in Patent Document 1 is also hardly soluble in the raw material of the rigid polyurethane foam like the conventional flame retardant such as red phosphorus. Among polyol compounds or polyisocyanate compounds, it is a powder-like flame retardant with a large specificity, and it is easy to aggregate in the raw material liquid of the rigid polyurethane foam.
於難燃性硬質聚胺甲酸酯發泡體之製造上，在製造現場摻合難燃劑，會增加現場作業的負擔，故一般而言係使用預先已添加難燃劑的多元醇組成物(多元醇預混物)或硬質聚胺甲酸酯發泡體之原料液。 如上述使粉體狀之難燃劑預先分散而調製成的多元醇組成物或硬質聚胺甲酸酯發泡體之原料液，於使用時，亦有分散物凝聚的情形，而為了再分散會需要很大的作業負擔，而且，亦會變得難以均勻的再分散。In the manufacture of flame-retardant rigid polyurethane foam, blending of flame-retardant at the manufacturing site will increase the burden of on-site operations. Therefore, generally, a polyol composition with flame-retardant added in advance is used (Polyol premix) or rigid polyurethane foam raw material liquid. As mentioned above, the polyol composition or the raw material liquid of the rigid polyurethane foam prepared by pre-dispersing the powdery flame retardant may also aggregate the dispersion during use, but for redispersion It will require a lot of work load, and it will become difficult to redistribute evenly.
因此，冀求在使用前述包含次膦酸系金屬鹽的粉體狀之難燃劑之際，可抑制於多元醇組成物或硬質聚胺甲酸酯發泡體之原料液中的粉體(固體)之凝聚，且在獲得均勻的原料組成物上的處理性優異者。關於包含磷酸系金屬鹽的粉體狀之難燃劑亦同。Therefore, it is desired to suppress the powder ( Solid) agglomerates and has excellent handling properties in obtaining a uniform raw material composition. The same applies to the powdery flame retardant containing phosphoric acid-based metal salt.
本發明係為了解決上述技術的課題而作成者，以提供一種多元醇組成物以及使用其之難燃性硬質聚胺甲酸酯發泡體及其製造方法為目的，該多元醇組成物在含有包含指定之次膦酸系金屬鹽及/或磷酸系金屬鹽之難燃劑之多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液中，可抑制液中之粉體之凝聚，且可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體。 [用以解決課題之手段]The present invention was made in order to solve the above-mentioned technical problems, and aims to provide a polyol composition, a flame-retardant rigid polyurethane foam using the same, and a method for producing the same. The polyol composition contains In the raw material liquid of the polyol composition containing the designated phosphinic acid metal salt and/or the flame retardant of the phosphoric acid metal salt and the flame-retardant rigid polyurethane foam, the powder in the liquid can be suppressed It is agglomerated, and a rigid polyurethane foam with excellent flame retardancy can be obtained. [Means to solve the problem]
本發明係基於發現下列事項而成者：在含有包含指定之次膦酸系金屬鹽的難燃劑的多元醇組成物中，藉由使用指定之分散劑，可有效地抑制粉體狀之難燃劑的凝聚，而且可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體。 又，發現：在含有包含磷酸系金屬鹽的難燃劑的多元醇組成物中，藉由使用包含諾易堡矽土(Neuburg Siliceous Earth)粒子的分散劑，亦可有效地抑制粉體狀之難燃劑的凝聚，而且可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體。The present invention is based on the discovery of the following: In a polyol composition containing a flame retardant containing a specified phosphinic acid-based metal salt, by using a specified dispersing agent, it is possible to effectively suppress the powdery difficulty Agglomeration of the inflammable agent, and a rigid polyurethane foam with excellent flame retardancy can be obtained. In addition, it has been found that in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, the use of a dispersant containing Neuburg Siliceous Earth particles can also effectively suppress powdery The flame retardant is agglomerated, and a rigid polyurethane foam with excellent flame retardancy can be obtained.
即，本發明係提供以下之[1]～[9]者。 [1]一種多元醇組成物，其係用於難燃性硬質聚胺甲酸酯發泡體之製造的多元醇組成物，其含有： 多元醇化合物，其包含芳香族系聚酯多元醇； 難燃劑，其包含1種以上選自包含下述式(1)所表示的次膦酸系金屬鹽、及磷酸系金屬鹽的群組之化合物；及 分散劑，其包含諾易堡矽土粒子。That is, the present invention provides the following [1] to [9]. [1] A polyol composition, which is a polyol composition used for the production of flame-retardant rigid polyurethane foam, and contains: Polyol compound, which includes aromatic polyester polyol; A flame retardant comprising one or more compounds selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1); and Dispersant, which contains Noibo silica particles.
(式(1)中，M為Mg、Al、Ca、Ti或Zn，R1 為氫原子、碳數1～6之直鏈狀烷基或苯基，n為2、3或4。) [2]如上述[1]記載之多元醇組成物，其中前述多元醇化合物包含曼尼希(Mannich)系多元醇。 [3]如上述[1]或[2]記載之多元醇組成物，其中相對於前述難燃劑中之固體含量的總計100質量份，包含1～50質量份前述諾易堡矽土粒子。 [4]如上述[1]～[3]中任一項記載之多元醇組成物，其包含發泡劑。 [5]如上述[4]記載之多元醇組成物，其中前述發泡劑包含氫氟烯烴及氫氯氟烯烴中之任一種以上。 [6]如上述[1]～[5]中任一項記載之多元醇組成物，其包含觸媒。 [7]如上述[1]～[6]中任一項記載之多元醇組成物，其包含泡沫穩定劑。(In formula (1), M is Mg, Al, Ca, Ti, or Zn, R 1 is a hydrogen atom, a linear alkyl group with 1 to 6 carbons or a phenyl group, and n is 2, 3 or 4.) [ 2] The polyol composition according to the above [1], wherein the polyol compound includes a Mannich-based polyol. [3] The polyol composition according to the above [1] or [2], which contains 1 to 50 parts by mass of the Noibble silica particles relative to the total 100 parts by mass of the solid content in the flame retardant. [4] The polyol composition according to any one of [1] to [3] above, which contains a foaming agent. [5] The polyol composition according to the above [4], wherein the blowing agent contains any one or more of hydrofluoroolefin and hydrochlorofluoroolefin. [6] The polyol composition according to any one of [1] to [5] above, which contains a catalyst. [7] The polyol composition according to any one of [1] to [6] above, which contains a foam stabilizer.
[8]一種難燃性硬質聚胺甲酸酯發泡體，其為如上述[1]～[7]中任一項記載之多元醇組成物、及聚異氰酸酯化合物之反應生成物。 [9]一種難燃性硬質聚胺甲酸酯發泡體之製造方法，其將如上述[1]～[7]中任一項記載之多元醇組成物、與聚異氰酸酯化合物進行混合，使其發泡及硬化，而獲得難燃性硬質聚胺甲酸酯發泡體。 [發明之效果][8] A flame-retardant rigid polyurethane foam which is a reaction product of the polyol composition described in any one of [1] to [7] above and a polyisocyanate compound. [9] A method for producing a flame-retardant rigid polyurethane foam by mixing the polyol composition as described in any one of [1] to [7] above with a polyisocyanate compound to make It is foamed and hardened to obtain a flame-retardant rigid polyurethane foam. [Effects of Invention]
依據本發明，可提供一種多元醇組成物，其於包含指定之次膦酸系金屬鹽之難燃劑的多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液中，可抑制液中的粉體之凝聚，且處理性優異。 又，藉由使用前述多元醇組成物，可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體。 又，依據本發明，於含有包含磷酸系金屬鹽的難燃劑的多元醇組成物中，亦可有效地抑制粉體狀之難燃劑的凝聚，而且可獲得具有優異的難燃性的硬質聚胺甲酸酯發泡體。According to the present invention, a polyol composition can be provided in the raw material liquid of a polyol composition containing a designated phosphinic acid-based metal salt of a flame retardant and a flame-retardant rigid polyurethane foam, It can suppress the aggregation of the powder in the liquid and has excellent handling properties. In addition, by using the aforementioned polyol composition, a rigid polyurethane foam having excellent flame retardancy can be obtained. In addition, according to the present invention, in a polyol composition containing a flame retardant containing a phosphoric acid-based metal salt, agglomeration of the powdered flame retardant can also be effectively suppressed, and a rigid material with excellent flame retardancy can be obtained. Polyurethane foam.
[用以實施發明的形態][Form to implement the invention]
以下，對於本發明之多元醇組成物、以及使用其之難燃性硬質聚胺甲酸酯發泡體及其製造方法，進行詳細地說明。Hereinafter, the polyol composition of the present invention, the flame-retardant rigid polyurethane foam using the same, and the production method thereof will be described in detail.
[多元醇組成物] 本發明之多元醇組成物為用於難燃性硬質聚胺甲酸酯發泡體之製造的多元醇組成物，其含有： 多元醇化合物，其包含芳香族系聚酯多元醇； 難燃劑，其包含1種以上選自包含下述式(1)所表示的次膦酸系金屬鹽、及磷酸系金屬鹽的群組之化合物；及 分散劑，其包含諾易堡矽土粒子。[Polyol composition] The polyol composition of the present invention is a polyol composition used for the production of flame-retardant rigid polyurethane foam, which contains: Polyol compound, which includes aromatic polyester polyol; A flame retardant comprising one or more compounds selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1); and Dispersant, which contains Noibo silica particles.
前述式(1)中，M為Mg、Al、Ca、Ti或Zn，R1 為氫原子、碳數1～6之直鏈狀烷基或苯基，n為2、3或4。In the aforementioned formula (1), M is Mg, Al, Ca, Ti, or Zn, R 1 is a hydrogen atom, a linear alkyl group having 1 to 6 carbons or a phenyl group, and n is 2, 3, or 4.
藉由摻合前述分散劑，於含有包含前述式(1)所表示的次膦酸系金屬鹽及/或磷酸系金屬鹽的難燃劑的難燃性硬質聚胺甲酸酯發泡體之原料液中，可有效地抑制液中之粉體的凝聚。據此，於難燃性硬質聚胺甲酸酯發泡體製造時，可減輕用以均勻地混合多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液的作業負擔，又，可提高前述原料液中之粉體的均勻分散性。又，亦可保持所獲得的難燃性硬質聚胺甲酸酯發泡體中的前述難燃劑所致的優異難燃性。By blending the above-mentioned dispersant, the flame-retardant rigid polyurethane foam containing a flame-retardant agent containing the phosphinic acid-based metal salt and/or phosphoric acid-based metal salt represented by the above formula (1) In the raw material liquid, the agglomeration of the powder in the liquid can be effectively inhibited. According to this, when the flame-retardant rigid polyurethane foam is manufactured, the work load for uniformly mixing the polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam can be reduced. In addition, the uniform dispersibility of the powder in the raw material liquid can be improved. In addition, the excellent flame retardancy due to the flame retardant in the obtained flame retardant rigid polyurethane foam can also be maintained.
＜多元醇化合物＞ 多元醇化合物為難燃性硬質聚胺甲酸酯發泡體之原料化合物，其構成本發明之多元醇組成物。前述多元醇化合物為具有2個以上羥基的醇化合物，藉由與聚異氰酸酯化合物之加成聚合反應，而生成聚胺甲酸酯樹脂。＜Polyol compound＞ The polyol compound is a raw material compound of the flame-retardant rigid polyurethane foam, which constitutes the polyol composition of the present invention. The aforementioned polyol compound is an alcohol compound having two or more hydroxyl groups, and a polyurethane resin is produced by an addition polymerization reaction with a polyisocyanate compound.
由良好的難燃性之觀點來看，就用於難燃性硬質聚胺甲酸酯發泡體之製造的多元醇化合物而言，主要使用芳香族系多元醇。與作為一般的聚胺甲酸酯發泡體原料被使用的聚丙二醇等相比，芳香族系多元醇可賦予更優異的難燃性。From the viewpoint of good flame retardancy, aromatic polyols are mainly used for the polyol compounds used for the production of flame-retardant rigid polyurethane foams. Compared with polypropylene glycol or the like used as a raw material of general polyurethane foam, the aromatic polyol can impart more excellent flame retardancy.
由獲得具有良好的難燃性及硬度等的難燃性硬質聚胺甲酸酯發泡體的觀點來看，前述芳香族系多元醇，其羥基價較佳為100～900mgKOH/g，更佳為150～800mgKOH/g，進一步較佳為180～700mgKOH/g。From the viewpoint of obtaining a flame-retardant rigid polyurethane foam having good flame retardancy and hardness, the aforementioned aromatic polyol preferably has a hydroxyl value of 100 to 900 mgKOH/g, more preferably It is 150-800 mgKOH/g, more preferably 180-700 mgKOH/g.
本發明中的多元醇化合物包含芳香族系聚酯多元醇，又，較佳為包含曼尼希系多元醇。 難燃性硬質聚胺甲酸酯發泡體之原料液中的粉體的凝聚，雖可藉由前述分散劑而良好地抑制，但藉由包含該分散劑，同時包含作為前述多元醇化合物之曼尼希系多元醇，可更有效地抑制粉體的凝聚。The polyol compound in the present invention includes an aromatic polyester polyol, and preferably includes a Mannich-based polyol. The agglomeration of the powder in the raw material liquid of the flame-retardant rigid polyurethane foam can be well suppressed by the aforementioned dispersant, but by including the dispersant, it also contains the polyol compound as the aforementioned polyol compound. Mannich series polyols can more effectively inhibit powder agglomeration.
由獲得具有良好的難燃性及硬度等的難燃性硬質聚胺甲酸酯發泡體的觀點來看，前述多元醇組成物100質量份中，前述多元醇化合物之總計含量較佳為10.0～60.0質量份，更佳為20.0～55.0質量份，進一步較佳為30.0～50.0質量份。From the viewpoint of obtaining a flame-retardant rigid polyurethane foam having good flame retardancy and hardness, the total content of the polyol compound in 100 parts by mass of the polyol composition is preferably 10.0 ~60.0 parts by mass, more preferably 20.0-55.0 parts by mass, still more preferably 30.0-50.0 parts by mass.
(芳香族系聚酯多元醇) 就芳香族系聚酯多元醇而言，可列舉例如，藉由芳香族系多元羧酸與多元醇之聚縮合而獲得的化合物。前述芳香族系聚酯多元醇可為單獨1種，亦可併用2種以上。 就芳香族系多元羧酸之具體例而言，可列舉酞酸、對酞酸、鄰酞酸、異酞酸、偏苯三甲酸、半蜜臘酸、焦蜜石酸等之芳香族系多元羧酸等。就多元醇之具體例而言，可列舉乙二醇、丙二醇、丁二醇、二乙二醇、二丙二醇、三亞甲基二醇、四亞甲基二醇、六亞甲基二醇、十亞甲基二醇、新戊二醇、3-甲基-1,5-戊二醇、甘油、三羥甲基丙烷、新戊四醇、山梨糖醇、雙酚A等。 又，就芳香族系聚酯多元醇而言，亦可列舉將聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等之聚對苯二甲酸烷二酯，以多元醇進行酯交換者。(Aromatic polyester polyol) The aromatic polyester polyol includes, for example, a compound obtained by polycondensation of an aromatic polycarboxylic acid and a polyol. The aforementioned aromatic polyester polyol may be used alone or in combination of two or more kinds. Specific examples of aromatic polycarboxylic acids include phthalic acid, terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, hemimelic acid, pyromellitic acid, etc. Carboxylic acid and so on. Specific examples of polyols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and tetramethylene glycol. Methylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, neopentylerythritol, sorbitol, bisphenol A, etc. In addition, for aromatic polyester polyols, polyalkylene terephthalate, such as polyethylene terephthalate and polybutylene terephthalate, can be esterified with polyols. Exchanger.
由獲得具有良好的難燃性的硬質聚胺甲酸酯發泡體的觀點來看，較佳為前述多元醇化合物中，以最多比率包含前述芳香族系聚酯多元醇。 前述多元醇化合物中之前述芳香族系聚酯多元醇的含量，於前述多元醇化合物100質量份中，較佳為50.0質量份以上，更佳為60.0～100質量份，進一步較佳為70.0～100質量份。From the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy, it is preferable that the aromatic polyester polyol is contained in the largest ratio among the polyol compounds. The content of the aromatic polyester polyol in the polyol compound is preferably 50.0 parts by mass or more in 100 parts by mass of the polyol compound, more preferably 60.0-100 parts by mass, and still more preferably 70.0- 100 parts by mass.
(曼尼希系多元醇) 本發明中的曼尼希系多元醇，係指使藉由酚化合物、醛化合物及胺化合物之曼尼希反應而獲得的生成物(曼尼希縮合物)的芳香族系多元醇，與環氧烷(alkylene oxide)進行加成聚合而成的芳香族系聚醚多元醇。前述曼尼希系多元醇可為單獨1種，亦可併用2種以上。 就前述酚化合物而言，一般使用例如，酚；甲酚、壬酚等之烷基酚等。 就前述醛化合物而言，一般使用例如，甲醛、乙醛等。 就前述胺化合物而言，可列舉例如，脂肪族一級或二級之單胺類，一般使用單乙醇胺、二乙醇胺、1-胺基-2-丙醇等之烷醇胺；甲基胺、二乙基胺等之烷基胺等。 就前述環氧烷而言，一般使用例如，環氧乙烷、環氧丙烷、環氧丁烷等。 前述曼尼希系多元醇，具體而言，可藉由國際公開第2010/147091號等所記載的製造方法而製造。(Mannich series polyol) The Mannich polyol in the present invention refers to an aromatic polyol of a product (Mannich condensate) obtained by Mannich reaction of a phenol compound, an aldehyde compound, and an amine compound, and epoxy Aromatic polyether polyol formed by addition polymerization of alkylene oxide. The aforementioned Mannich-based polyol may be used alone or in combination of two or more kinds. As for the aforementioned phenol compound, for example, phenol; alkylphenols such as cresol and nonanol are generally used. As for the aforementioned aldehyde compound, for example, formaldehyde, acetaldehyde, etc. are generally used. The aforementioned amine compounds include, for example, aliphatic primary or secondary monoamines. Generally, alkanolamines such as monoethanolamine, diethanolamine, 1-amino-2-propanol, etc. are used; methylamine, diethanolamine, etc. Alkyl amines such as ethyl amine, etc. As for the aforementioned alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, etc. are generally used. The aforementioned Mannich-based polyol can be specifically produced by the production method described in International Publication No. 2010/147091 and the like.
由抑制前述多元醇組成物中的粉體之凝聚，且獲得具有良好的難燃性的硬質聚胺甲酸酯發泡體的觀點來看，前述多元醇化合物中包含曼尼希系多元醇的情形，其含量，於前述多元醇組成物100質量份中，較佳為1.0～20.0質量份，更佳為2.0～15.0質量份，進一步較佳為3.0～10.0質量份。 又，由同樣的觀點來看，前述曼尼希系多元醇之含量之相對於前述芳香族系聚酯多元醇之含量的比率，較佳為0.10～1.00，更佳為0.15～0.90，進一步較佳為0.20～0.80。From the viewpoint of suppressing the aggregation of the powder in the aforementioned polyol composition and obtaining a rigid polyurethane foam with good flame retardancy, the aforementioned polyol compound contains Mannich-based polyols. In case, the content thereof is preferably 1.0 to 20.0 parts by mass, more preferably 2.0 to 15.0 parts by mass, and still more preferably 3.0 to 10.0 parts by mass in 100 parts by mass of the aforementioned polyol composition. Also, from the same viewpoint, the ratio of the content of the Mannich-based polyol to the content of the aromatic polyester polyol is preferably 0.10 to 1.00, more preferably 0.15 to 0.90, and furthermore Preferably, it is 0.20 to 0.80.
前述多元醇化合物，除了包含前述芳香族系聚酯多元醇及前述曼尼希系多元醇以外，亦可包含例如，前述曼尼希系多元醇以外之芳香族系聚醚多元醇等，而由獲得具有良好的難燃性的硬質聚胺甲酸酯發泡體的觀點來看，較佳為不包含脂肪族系多元醇。由同樣之觀點來看，前述多元醇化合物100質量份中之前述芳香族系聚酯多元醇及前述曼尼希系多元醇的總計含量，較佳為90質量份以上，更佳為95質量份以上，進一步較佳為100質量份。The polyol compound may include, in addition to the aromatic polyester polyol and the Mannich polyol, for example, aromatic polyether polyols other than the Mannich polyol, etc., and From the viewpoint of obtaining a rigid polyurethane foam having good flame retardancy, it is preferable not to include an aliphatic polyol. From the same viewpoint, the total content of the aromatic polyester polyol and the Mannich polyol in 100 parts by mass of the polyol compound is preferably 90 parts by mass or more, more preferably 95 parts by mass Above, it is more preferably 100 parts by mass.
＜難燃劑＞ 於本發明之多元醇組成物所使用的難燃劑包含1種以上選自包含下述式(1)所表示的次膦酸系金屬鹽、及磷酸系金屬鹽的群組之化合物。＜Flame Retardant＞ The flame retardant used in the polyol composition of the present invention includes one or more compounds selected from the group consisting of phosphinic acid-based metal salts and phosphoric acid-based metal salts represented by the following formula (1).
前述式(1)中，M為Mg、Al、Ca、Ti或Zn，較佳為Al或Zn，更佳為Al。M為Mg、Ca或Zn時，n＝2，M為Al時，n=3，M為Ti時，n=4。 R1 為氫原子、碳數1～6之直鏈狀烷基或苯基，較佳為氫原子、甲基、乙基或苯基。In the aforementioned formula (1), M is Mg, Al, Ca, Ti or Zn, preferably Al or Zn, more preferably Al. When M is Mg, Ca, or Zn, n=2, when M is Al, n=3, and when M is Ti, n=4. R 1 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a phenyl group, and preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.
前述難燃劑可為包含前述次膦酸系金屬鹽及磷酸系金屬鹽之任一者，亦可為包含兩者。由本發明之效果的觀點來看，前述難燃劑，較佳為包含前述次膦酸系金屬鹽者。The flame retardant may include any one of the phosphinic acid-based metal salt and the phosphoric acid-based metal salt, or may include both. From the viewpoint of the effects of the present invention, the flame retardant is preferably one containing the phosphinic acid-based metal salt.
前述次膦酸系金屬鹽為無機次膦酸鹽或有機次膦酸鹽，且為粉體狀。前述次膦酸系金屬鹽可為單獨1種，亦可併用2種以上。 前述包含次膦酸系金屬鹽的粉體狀之難燃劑，與以往之利用赤磷或磷酸酯等的難燃劑相比，可對硬質聚胺甲酸酯發泡體賦予更優異的難燃性。The aforementioned phosphinic acid-based metal salt is an inorganic phosphinate or an organic phosphinate, and is in powder form. The aforementioned phosphinic acid-based metal salt may be used alone or in combination of two or more kinds. The aforementioned powdered flame retardant containing phosphinic acid-based metal salt, compared with the conventional flame retardant using red phosphorus or phosphoric acid ester, can impart more excellent difficulty to rigid polyurethane foam. Flammability.
前述磷酸系金屬鹽為無機磷酸鹽或有機磷酸鹽，且為粉體狀。就前述磷酸系金屬鹽而言，較佳為磷酸酯金屬鹽。前述磷酸系金屬鹽中的金屬原子(離子)較佳為與前述次膦酸系金屬鹽同樣之金屬原子(離子)之鹽。前述磷酸系金屬鹽可為單獨1種，亦可併用2種以上。 前述磷酸系金屬鹽亦為粉體狀，藉由使用包含諾易堡矽土粒子的分散劑，獲得多元醇組成物中的良好的凝聚抑制效果。The aforementioned phosphoric acid-based metal salt is an inorganic phosphate or an organic phosphate, and is in the form of a powder. The aforementioned phosphoric acid-based metal salt is preferably a phosphoric acid ester metal salt. The metal atom (ion) in the aforementioned phosphoric acid-based metal salt is preferably a salt of the same metal atom (ion) as the aforementioned phosphinic acid-based metal salt. The aforementioned phosphoric acid-based metal salt may be used alone or in combination of two or more kinds. The aforementioned phosphoric acid-based metal salt is also in powder form, and by using a dispersant containing Noibble silica particles, a good aggregation inhibitory effect in the polyol composition can be obtained.
由更提升難燃性的觀點來看，前述難燃劑，除了含有前述次膦酸系金屬鹽或磷酸系金屬鹽之外，亦可含有能作用為難燃助劑的成分，較佳為例如，包含含有氮的化合物。
就前述含有氮的化合物而言，可列舉例如，三聚氰胺、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、酞酸三聚氰胺、三聚氰酸三聚氰胺、苯胍
惟，聚磷酸銨(ammonium polyphosphate)由於在製造硬質聚胺甲酸酯發泡體之際有延緩胺甲酸酯化反應的傾向，因而不佳。聚磷酸銨於多元醇組成物中容易膠化，於凝聚抑制的點為不佳。又，於多元醇組成物中，磷酸離子容易游離，游離酸會影響胺甲酸酯化反應中的觸媒活性，推測未充分促進胺甲酸酯化反應，會無法獲得具有良好的難燃性的硬質聚胺甲酸酯發泡體。However, ammonium polyphosphate has a tendency to delay the urethane reaction during the manufacture of rigid polyurethane foam, which is not preferable. Ammonium polyphosphate is easy to gel in the polyol composition, and it is not good at the point of aggregation inhibition. In addition, in the polyol composition, the phosphate ions are easily released, and the free acid will affect the catalyst activity in the urethane reaction. It is presumed that the urethane reaction is not fully promoted, and good flame retardancy cannot be obtained. Of rigid polyurethane foam.
於本發明中，作為包含前述次膦酸系金屬鹽及含有氮的化合物的粉體狀之難燃劑，可適合使用例如，大和化學工業股份有限公司製之「FRAN CM」系列等之市售品。In the present invention, as a powdery flame retardant containing the aforementioned phosphinic acid-based metal salt and a nitrogen-containing compound, for example, commercially available products such as the "FRAN CM" series manufactured by Daiwa Chemical Industry Co., Ltd. can be suitably used. Taste.
又，由獲得具有良好的難燃性的硬質聚胺甲酸酯發泡體的觀點來看，前述包含次膦酸系金屬鹽及/或磷酸系金屬鹽的粉體狀之難燃劑，於前述多元醇組成物中之難燃劑之總計100質量份中，較佳為50質量份以上，更佳為52～100質量份，進一步較佳為55～100質量份。 又，鑑於前述包含次膦酸系金屬鹽及/或磷酸系金屬鹽的粉體狀之難燃劑容易沉降及凝聚，該粉體狀之難燃劑，亦即前述難燃劑中之固體含量，於前述多元醇組成物100質量份中，較佳為10.0～40.0質量份，更佳為12.0～35.0質量份，進一步較佳為15.0～30.0質量份。In addition, from the viewpoint of obtaining a rigid polyurethane foam with good flame retardancy, the aforementioned powdered flame retardant containing a phosphinic acid-based metal salt and/or a phosphoric acid-based metal salt is In the total 100 parts by mass of the flame retardant in the aforementioned polyol composition, it is preferably 50 parts by mass or more, more preferably 52-100 parts by mass, and still more preferably 55-100 parts by mass. In addition, in view of the fact that the aforementioned powdered flame retardant containing phosphinic acid-based metal salt and/or phosphoric acid-based metal salt is easy to settle and agglomerate, the powdered flame retardant, that is, the solid content of the aforementioned flame retardant In 100 parts by mass of the aforementioned polyol composition, preferably 10.0-40.0 parts by mass, more preferably 12.0-35.0 parts by mass, and still more preferably 15.0-30.0 parts by mass.
前述難燃劑，由獲得硬質聚胺甲酸酯發泡體之加熱或燃燒時的初期之炭化抑制效果的觀點來看，可包含液體狀之磷酸酯，例如，一般使用含鹵素系磷酸酯的磷酸三(β-氯丙基)酯等。磷酸三(β-氯丙基)酯為液體，不會如粉體狀之前述次膦酸系金屬鹽或磷酸系金屬鹽、赤磷於硬質聚胺甲酸酯發泡體之原料液中發生凝聚等，但對硬質聚胺甲酸酯發泡體賦予難燃性的效果係以前述次膦酸系金屬鹽者較為優異。因此，前述難燃劑中包含液體狀之磷酸酯的情形，其含量，於該難燃劑100質量份中，較佳為50質量份以下，更佳為小於50質量份，進一步較佳為45質量份以下。The aforementioned flame retardant may contain liquid phosphoric acid ester from the viewpoint of obtaining the effect of inhibiting carbonization in the initial stage of heating or burning of rigid polyurethane foam. For example, a halogen-containing phosphoric acid ester is generally used. Tris (β-chloropropyl) phosphate and the like. Tris (β-chloropropyl) phosphate is a liquid, and will not occur in the raw material liquid of rigid polyurethane foam like the aforementioned phosphinic acid metal salt or phosphoric acid metal salt and red phosphorus in powder form. Aggregation, etc., but the effect of imparting flame retardancy to the rigid polyurethane foam is superior to the aforementioned phosphinic acid-based metal salt. Therefore, when the aforementioned flame retardant contains liquid phosphate ester, its content in 100 parts by mass of the flame retardant is preferably 50 parts by mass or less, more preferably less than 50 parts by mass, and still more preferably 45 parts by mass. Parts by mass or less.
＜分散劑＞ 前述多元醇組成物中之分散劑包含諾易堡矽土粒子。 本發明中的諾易堡矽土粒子係指粒子狀之隱微晶質(cryptomicrocrystalline)及非晶質矽石與板狀之高嶺土的天然結合物，亦稱為Sillitin或Sillikolloid。例如，可為Hoffman Minerals公司之作為SillitinV85、SillitinV88、SillitinN82、SillitinN85、SillitinN87、SillitinZ86、SillitinZ89、SillikolloidP87等之製品而取得。＜Dispersant＞ The dispersant in the aforementioned polyol composition contains Noibo silica particles. The Neuburg silica particles in the present invention refer to granular cryptomicrocrystalline and a natural combination of amorphous silica and plate-shaped kaolin, also known as Silitin or Silikolloid. For example, it can be obtained by Hoffman Minerals as products of SilitinV85, SilitinV88, SilitinN82, SilitinN85, SilitinN87, SilitinZ86, SilitinZ89, SilikolloidP87, etc.
諾易堡矽土粒子本身雖不溶於前述多元醇組成物中，但藉由將該諾易堡矽土粒子作為分散劑使用，即使於為粉體狀之難燃劑的前述次膦酸系金屬鹽及/或磷酸系金屬鹽沉降的情形，沉降的粉體亦難以凝聚，而可容易地再分散。 因此，難燃性硬質聚胺甲酸酯發泡體製造時，藉由於多元醇組成物中添加諾易堡矽土粒子，可減輕用以將多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液均勻混合之作業負擔，又，可提高前述原料液中之粉體之均勻分散性。Although the Noyborg silica particles themselves are not soluble in the aforementioned polyol composition, by using the Noyborg silica particles as a dispersing agent, even the phosphinic acid-based metal is a powdery flame retardant. When the salt and/or the phosphoric acid-based metal salt settle, the settled powder is also difficult to aggregate and can be easily redispersed. Therefore, when the flame-retardant rigid polyurethane foam is manufactured, the addition of Noibble silica particles to the polyol composition can reduce the use of the polyol composition and the flame-retardant rigid polyurethane foam. The work burden of uniform mixing of the raw material liquid of the ester foam can also improve the uniform dispersibility of the powder in the aforementioned raw material liquid.
由更有效地抑制前述多元醇組成物中的粉體之凝聚的觀點來看，前述分散劑，除了包含諾易堡矽土粒子之外，亦可包含發揮凝聚抑制作用的界面活性劑等。 由有效地抑制前述多元醇組成物中之粉體之凝聚，且對硬質聚胺甲酸酯發泡體賦予良好的難燃性的觀點來看，前述分散劑中之諾易堡矽土粒子之含量，於該分散劑100質量份中，較佳為90質量份以上，更佳為95～100質量份，進一步較佳為100質量份。 由同樣的觀點來看，諾易堡矽土粒子之含量，相對於前述難燃劑中之固體含量的總計100質量份，較佳為1～50質量份，更佳為5～40質量份，進一步較佳為10～20質量份。From the viewpoint of more effectively suppressing the aggregation of the powder in the polyol composition, the dispersant may include, in addition to Noibble silica particles, a surfactant or the like that exerts an aggregation inhibitory effect. From the viewpoint of effectively inhibiting the agglomeration of the powder in the polyol composition and imparting good flame retardancy to the rigid polyurethane foam, the Noibo silica particles in the dispersing agent The content in 100 parts by mass of the dispersant is preferably 90 parts by mass or more, more preferably 95-100 parts by mass, and still more preferably 100 parts by mass. From the same point of view, the content of Noibble silica particles is preferably 1-50 parts by mass, more preferably 5-40 parts by mass relative to the total 100 parts by mass of the solid content in the aforementioned flame retardant. More preferably, it is 10-20 mass parts.
＜其它之成分＞ 就難燃性硬質聚胺甲酸酯發泡體之製造原料而言，除了摻合為主原料之多元醇化合物、難燃劑及聚異氰酸酯化合物以外，亦可摻合發泡劑、觸媒、泡沫穩定劑等。此等之成分，可於難燃性硬質聚胺甲酸酯發泡體之製造時與多元醇組成物分開添加，但由減輕難燃性硬質聚胺甲酸酯發泡體之製造現場的作業負擔的觀點來看，較佳為摻合於前述多元醇組成物中。 再者，前述多元醇組成物中，因應必要，於不妨礙本發明之效果的範圍內，可含有溶劑、著色劑、抗氧化劑等之添加劑等。＜Other ingredients＞ As far as the raw materials for the production of flame-retardant rigid polyurethane foams, in addition to the polyol compounds, flame retardants and polyisocyanate compounds as the main raw materials, blowing agents, catalysts, Foam stabilizer, etc. These components can be added separately from the polyol composition during the manufacture of the flame-retardant rigid polyurethane foam, but they can reduce the work on the production site of the flame-retardant rigid polyurethane foam. From the viewpoint of burden, it is preferably blended with the aforementioned polyol composition. Furthermore, the aforementioned polyol composition may contain additives such as solvents, colorants, antioxidants, etc., as necessary, within a range that does not hinder the effects of the present invention.
(發泡劑) 發泡劑為具有藉由多元醇化合物與聚異氰酸酯化合物反應而形成胺甲酸酯鍵的樹脂化反應之發熱而使氣體產生，並使聚胺甲酸酯樹脂發泡的作用者。 就前述發泡劑而言，可列舉例如，氫氟烯烴(HFO)、氫氯氟烯烴(HCFO)、氫氟碳化物(HFC)、水等。此等可使用單獨1種，亦可併用2種以上。此等之中，由地球暖化抑制效果等之觀點來看，HFO及HCFO會取代HFC，而為今後預期需要增加的發泡劑，故使用此等為較佳。具體而言，可列舉反-1,3,3,3-四氟丙烯(trans-HFO-1234ze)、1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz)、反-1-氯-3,3,3-三氟丙烯(HCFO-1233zd)等。(Foaming agent) The foaming agent has a function of generating gas by the heat generated by the resinification reaction of forming a urethane bond by the reaction of the polyol compound and the polyisocyanate compound, and foaming the polyurethane resin. As the aforementioned foaming agent, for example, hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrofluorocarbon (HFC), water, and the like can be cited. These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of global warming suppression effect, etc., HFO and HCFO will replace HFC, and it is expected that there will be an increase in foaming agent in the future, so it is better to use these. Specifically, trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz ), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), etc.
聚異氰酸酯化合物之異氰酸酯基，亦與水反應而生成脲鍵及發生碳酸氣體的泡化反應。水成為硬質聚胺甲酸酯發泡體之生成反應的初期階段中的發泡誘因，又，由於可使製造的硬質聚胺甲酸酯發泡體之密度降低，較佳為包含水作為發泡劑。The isocyanate group of the polyisocyanate compound also reacts with water to form a urea bond and a foaming reaction of carbon dioxide gas occurs. Water becomes the foaming inducer in the initial stage of the formation reaction of the rigid polyurethane foam, and since the density of the rigid polyurethane foam produced can be reduced, it is preferable to include water as the hair Foaming agent.
由適度地使聚胺甲酸酯樹脂發泡的觀點來看，前述發泡劑之摻合量，相對於聚異氰酸酯化合物100質量份，總計較佳為5.0～40.0質量份，更佳為10.0～30.0質量份，進一步較佳為12.0～25.0質量份。 惟，水因有使芳香族系聚酯多元醇水解之虞，較佳為其含量較其它發泡劑少。相對於水以外之發泡劑的總計100質量份，較佳為20.0質量份以下，更佳為0.8～15.0質量份，進一步較佳為1.0～10.0質量份。From the viewpoint of appropriately foaming the polyurethane resin, the blending amount of the aforementioned blowing agent is preferably 5.0 to 40.0 parts by mass, more preferably 10.0 to 100 parts by mass of the polyisocyanate compound. 30.0 parts by mass, more preferably 12.0-25.0 parts by mass. However, since water may hydrolyze the aromatic polyester polyol, the content of water is preferably less than that of other foaming agents. It is preferably 20.0 parts by mass or less, more preferably 0.8 to 15.0 parts by mass, and still more preferably 1.0 to 10.0 parts by mass relative to the total 100 parts by mass of the foaming agent other than water.
(觸媒) 由促進前述樹脂化反應及泡化反應的觀點來看，於硬質聚胺甲酸酯發泡體之生成反應中，適合使用三級胺觸媒。又，由一部分三聚異氰酸酯化(nurate)所致的難燃性提升的觀點來看，亦可使用三聚異氰酸酯化觸媒(nurating catalyst)。就此等之觸媒而言，可使用於硬質聚胺甲酸酯發泡體之製造中習知的觸媒。此等可使用單獨1種，亦可併用2種以上。(catalyst) From the viewpoint of promoting the aforementioned resinification reaction and foaming reaction, it is suitable to use a tertiary amine catalyst in the formation reaction of the rigid polyurethane foam. In addition, from the viewpoint of the improvement of flame retardancy due to a part of nurate, a nurating catalyst can also be used. Regarding these catalysts, conventional catalysts used in the production of rigid polyurethane foams can be used. These may be used individually by 1 type, and may use 2 or more types together.
就前述三級胺觸媒而言，可列舉例如，二甲基乙醇胺、三乙二胺、甲基二環己基胺、二甲基環己基胺、五甲基二乙三胺、雙(2-二甲基胺基乙基)醚、二乙基甲基苯二胺、1,2-二甲基咪唑、1,4-二氮雜雙環[2.2.2]辛烷等。 由使適度促進硬質聚胺甲酸酯發泡體之樹脂化反應及泡化反應的觀點來看，前述三級胺觸媒之摻合量，相對於聚異氰酸酯化合物100質量份，較佳為0.1～10.0質量份，更佳為0.2～8.0質量份，進一步較佳為0.5～5.0質量份。Regarding the aforementioned tertiary amine catalyst, for example, dimethylethanolamine, triethylenediamine, methyldicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis(2- Dimethylaminoethyl)ether, diethylmethylphenylenediamine, 1,2-dimethylimidazole, 1,4-diazabicyclo[2.2.2]octane, etc. From the viewpoint of appropriately promoting the resinification reaction and foaming reaction of the rigid polyurethane foam, the blending amount of the aforementioned tertiary amine catalyst is preferably 0.1 relative to 100 parts by mass of the polyisocyanate compound ~10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, still more preferably 0.5 to 5.0 parts by mass.
就前述三聚異氰酸酯化觸媒而言，可列舉例如，參(二甲基胺基甲基)酚、2,4-雙(二甲基胺基甲基)酚、2,4,6-參(二烷基胺基烷基)六氫-S-三
(泡沫穩定劑) 由獲得均質的難燃性硬質聚胺甲酸酯發泡體的觀點來看，摻合泡沫穩定劑，可使用硬質聚胺甲酸酯發泡體之製造中的習知泡沫穩定劑。一般而言，適合使用矽酮系泡沫穩定劑，可列舉例如，矽氧烷-聚環氧烷共聚物(siloxane-polyalkylene oxide copolymer)等。 前述泡沫穩定劑之摻合量，因應生成的聚胺甲酸酯樹脂之種類而適當設定，但相對於聚異氰酸酯化合物100質量份，較佳為0.05～10.0質量份，更佳為0.1～8.0質量份，進一步較佳為0.2～5.0質量份。(Foam stabilizer) From the viewpoint of obtaining a homogeneous flame-retardant rigid polyurethane foam, a foam stabilizer can be blended, and a conventional foam stabilizer in the production of rigid polyurethane foam can be used. Generally speaking, a silicone-based foam stabilizer is suitable for use, for example, siloxane-polyalkylene oxide copolymer (siloxane-polyalkylene oxide copolymer) and the like can be cited. The blending amount of the aforementioned foam stabilizer is appropriately set according to the type of polyurethane resin to be produced, but it is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 8.0 parts by mass relative to 100 parts by mass of the polyisocyanate compound Parts, more preferably 0.2 to 5.0 parts by mass.
再者，於前述多元醇組成物中，因應必要，於不妨礙本發明之效果的範圍內，可含有溶劑、填料、著色劑、抗氧化劑等之添加劑。Furthermore, the aforementioned polyol composition may contain additives such as solvents, fillers, colorants, antioxidants, etc., as necessary, within a range that does not hinder the effects of the present invention.
[難燃性硬質聚胺甲酸酯發泡體] 本發明之難燃性硬質聚胺甲酸酯發泡體為前述多元醇組成物與聚異氰酸酯化合物反應而獲得的反應生成物。 使用非充分均勻的多元醇組成物的情形，難以獲得具有全體良好的難燃性的均質硬質聚胺甲酸酯發泡體。 相對於此，依據本發明之多元醇組成物，如上述，於使用包含容易凝聚的前述次膦酸系金屬鹽及/或磷酸系金屬鹽的粉體狀之難燃劑的情形，可於多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液中，有效地抑制粉體之凝聚。據此，於難燃性硬質聚胺甲酸酯發泡體製造時，可減輕用以使前述多元醇組成物及難燃性硬質聚胺甲酸酯發泡體之原料液均勻分散之作業負擔，又，可提高前述原料液中之粉體的均勻分散性。又，亦可保持所獲得的難燃性硬質聚胺甲酸酯發泡體中的前述難燃劑所致的良好難燃性。[Flame retardant rigid polyurethane foam] The flame-retardant rigid polyurethane foam of the present invention is a reaction product obtained by reacting the aforementioned polyol composition with a polyisocyanate compound. In the case of using an inadequately uniform polyol composition, it is difficult to obtain a homogeneous rigid polyurethane foam having good flame retardancy overall. On the other hand, the polyol composition according to the present invention, as described above, can be used in the polyol when a powdery flame retardant containing the aforementioned phosphinic acid-based metal salt and/or phosphoric acid-based metal salt that is easily aggregated is used. In the raw material liquid of the alcohol composition and the flame-retardant rigid polyurethane foam, the aggregation of the powder is effectively suppressed. According to this, when the flame-retardant rigid polyurethane foam is manufactured, the work load for uniformly dispersing the aforementioned polyol composition and the raw material liquid of the flame-retardant rigid polyurethane foam can be reduced , In addition, it can improve the uniform dispersibility of the powder in the raw material liquid. In addition, good flame retardancy due to the flame retardant in the obtained flame retardant rigid polyurethane foam can also be maintained.
＜聚異氰酸酯化合物＞ 聚異氰酸酯化合物為具有2個以上異氰酸酯基的異氰酸酯化合物，藉由與前述多元醇化合物之加成聚合反應而生成聚胺甲酸酯樹脂。 前述聚異氰酸酯化合物可為芳香族聚異氰酸酯或脂肪族聚異氰酸酯之任一者，可單獨使用此等之中之1種，亦可併用2種以上。＜Polyisocyanate compound＞ The polyisocyanate compound is an isocyanate compound having two or more isocyanate groups, and a polyurethane resin is produced by the addition polymerization reaction with the aforementioned polyol compound. The aforementioned polyisocyanate compound may be either an aromatic polyisocyanate or an aliphatic polyisocyanate, and one of these may be used alone, or two or more of them may be used in combination.
就芳香族聚異氰酸酯而言，可列舉例如，二苯基醚-2,4’-二異氰酸酯、二苯基醚-4,4’-二異氰酸酯、甲伸苯基-2,4-二異氰酸酯、甲伸苯基-2,6-二異氰酸酯、4,6-二甲基-1,3-伸苯基二異氰酸酯、2,2’-二苯基甲烷二異氰酸酯(2,2’-MDI)、2,4’-二苯基甲烷二異氰酸酯(2,4’-MDI)、4,4’-二苯基甲烷二異氰酸酯(4,4’-MDI)等之單體的MDI、聚亞甲基聚苯基聚異氰酸酯(粗製的MDI或聚合物的MDI)、3,3’-二甲基-4,4’-伸聯苯基二異氰酸酯、間-伸二甲苯異氰酸酯等。 就脂肪族聚異氰酸酯而言，可為非環式或脂環式之聚異氰酸酯之任一者，可例舉例如，四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、異佛酮二異氰酸酯、二環己基甲烷二異氰酸酯等。 此等之中，由反應性、及製造的硬質聚胺甲酸酯發泡體之難燃性等之觀點來看，較佳為2,2’-MDI、2,4’-MDI、4,4’-MDI等之單體的MDI、粗製的MDI或聚合物的MDI，又，其中由取得容易性、成本等之觀點來看，適合使用粗製的MDI或聚合物的MDI。As for the aromatic polyisocyanate, for example, diphenylether-2,4'-diisocyanate, diphenylether-4,4'-diisocyanate, tolylene-2,4-diisocyanate, Phenyl-2,6-diisocyanate, 4,6-dimethyl-1,3-phenyl-diisocyanate, 2,2'-diphenylmethane diisocyanate (2,2'-MDI), MDI and polymethylene of monomers such as 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and 4,4'-diphenylmethane diisocyanate (4,4'-MDI) Polyphenyl polyisocyanate (crude MDI or polymer MDI), 3,3'-dimethyl-4,4'-biphenyldiisocyanate, meta-xylene isocyanate, etc. As far as the aliphatic polyisocyanate is concerned, it can be either acyclic or alicyclic polyisocyanate, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Dicyclohexylmethane diisocyanate, etc. Among these, from the viewpoints of reactivity and the flame retardancy of the rigid polyurethane foam produced, 2,2'-MDI, 2,4'-MDI, 4, Monomer MDI such as 4'-MDI, crude MDI, or polymer MDI. Among them, crude MDI or polymer MDI is suitably used from the viewpoints of ease of availability and cost.
前述難燃性硬質聚胺甲酸酯發泡體之原料液中之聚異氰酸酯化合物的摻合量，雖因應聚異氰酸酯化合物之種類而適宜設定，但由與前述多元醇化合物之充分反應性、前述原料液之混合時之處理容易性等之觀點來看，相對於前述多元醇組成物100質量份，較佳為50～200質量份，更佳為70～150質量份，進一步較佳為80～120質量份。The blending amount of the polyisocyanate compound in the raw material liquid of the aforementioned flame-retardant rigid polyurethane foam is appropriately set according to the type of the polyisocyanate compound, but is determined by the sufficient reactivity with the aforementioned polyol compound and the aforementioned From the viewpoints of ease of handling during mixing of the raw material liquid, it is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and still more preferably 80 to 100 parts by mass of the aforementioned polyol composition. 120 parts by mass.
＜難燃性硬質聚胺甲酸酯發泡體製造方法＞ 前述難燃性硬質聚胺甲酸酯發泡體之製造方法中的成型發泡方法並非被特別限定者，可適用例如，模板成型(slab molding)、模具成型(mold-molding)、層壓成型、注入成型、噴霧發泡等之周知方法。於此等之各成型發泡方法，藉由將前述多元醇組成物、與前述聚異氰酸酯化合物混合，使其發泡及硬化，可製造具有全體良好的難燃性的均質的硬質聚胺甲酸酯發泡體。<Method for manufacturing flame-retardant rigid polyurethane foam> The molding foaming method in the manufacturing method of the aforementioned flame-retardant rigid polyurethane foam is not particularly limited. For example, slab molding, mold-molding, and laminate molding can be applied. , Injection molding, spray foaming and other well-known methods. In each of these molding and foaming methods, by mixing the aforementioned polyol composition with the aforementioned polyisocyanate compound, foaming and hardening, it is possible to produce a homogeneous rigid polyurethane with good flame retardancy. Ester foam.
如上述，因含有的粉體之凝聚被抑制，故前述多元醇組成物，其與聚異氰酸酯化合物混合之際的再分散，例如，使用利用攪拌槳葉等的一般的攪拌機，即可不需要大剪切力等，而容易地使均勻化。亦即，以少的作業負擔，即可容易地使均勻地再分散。因此，藉由使用前述多元醇組成物，可謀求難燃性硬質聚胺甲酸酯發泡體之製造的效率化。 [實施例]As described above, since the aggregation of the powder contained is suppressed, the polyol composition is redispersed when it is mixed with the polyisocyanate compound. For example, a general mixer using a stirring blade or the like is used, which eliminates the need for large shears. Shear force, etc., while easily homogenizing. That is, it is easy to uniformly redisperse with a small workload. Therefore, by using the aforementioned polyol composition, the production efficiency of the flame-retardant rigid polyurethane foam can be improved. [Example]
以下，藉由實施例而詳細地說明本發明，但本發明並未被限定於此等。Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these.
[多元醇組成物之調製] 以下呈示下述實施例及比較例之多元醇組成物之調製所使用的各原料的詳細內容。 ＜多元醇化合物＞ (聚酯多元醇) ・RFK-556：對酞酸系聚酯多元醇；「MAXIMOL(註冊商標) RFK-556」，川崎化成工業股份有限公司製，羥基價224mgKOH/g (曼尼希系多元醇) ・NB-622：「EXCENOL(註冊商標) NB-622」，AGC股份有限公司製，羥基價500mgKOH/g ＜難燃劑＞ (a1)CM-6R：包含次膦酸系金屬鹽的粉體狀之難燃劑；「FRAN CM -6R」，大和化學工業股份有限公司製 (a2)OP935：次膦酸金屬鹽；「Exolit(註冊商標) OP935」，Clariant Chemicals股份有限公司製 (a3)R098-5：磷酸酯金屬鹽(粉體狀)；「Nonnen(註冊商標) R098-5」，丸菱油化工業股份有限公司製 (a’1)・TK-1000：聚磷酸銨；「TK-1000」，MANAC股份有限公司製 ・TMCPP：磷酸三(β-氯丙基)酯；「TMCPP」，大八化學工業股份有限公司製 ＜分散劑＞ (諾易堡矽土粒子) (b1)P87：「Sillikolloid P87」，Hoffman mineral公司製 (b2)V85：「Sillitin V85」，Hoffman mineral公司製 (碳黑) ・MA220：「碳黑 MA220」，三菱化學股份有限公司製 ＜發泡劑＞ ・HCFO：反-1-氯-3,3,3-三氟丙烯(HCFO-1233zd)；「Solstice(註冊商標)LBA」，Honeywell International Inc.製 ・水 ＜觸媒＞ ・SX60：三級胺觸媒；「TOYOCAT(註冊商標)-SX60」，TOSOH股份有限公司製 ・DM70：三級胺觸媒；「TOYOCAT(註冊商標)-DM70」，TOSOH股份有限公司製 ・K-15：2-乙基己基酸鉀；「Dabco(註冊商標) K-15」，Evonik公司製，三聚異氰酸酯化觸媒 ＜泡沫穩定劑＞ ・L-6100：矽酮系泡沫穩定劑；「Niax(註冊商標) silicone L-6100」，Momentive Performance Materials Inc.製[Preparation of polyol composition] The details of each raw material used in the preparation of the polyol composition of the following examples and comparative examples are shown below. ＜Polyol compound＞ (Polyester polyol) ・RFK-556: Terephthalic acid polyester polyol; "MAXIMOL (registered trademark) RFK-556", manufactured by Kawasaki Chemical Industry Co., Ltd., hydroxyl value 224mgKOH/g (Mannich series polyol) ・NB-622: "EXCENOL (registered trademark) NB-622", manufactured by AGC Co., Ltd., hydroxyl value 500mgKOH/g ＜Flame Retardant＞ (a1) CM-6R: Powdered flame retardant containing phosphinic acid metal salt; "FRAN CM-6R", manufactured by Daiwa Chemical Industry Co., Ltd. (a2) OP935: phosphinic acid metal salt; "Exolit (registered trademark) OP935", manufactured by Clariant Chemicals Co., Ltd. (a3) R098-5: Phosphate metal salt (powder); "Nonnen (registered trademark) R098-5", manufactured by Marubi Oil Chemical Co., Ltd. (a’1)・TK-1000: Ammonium polyphosphate; "TK-1000", manufactured by MANAC Co., Ltd. ・TMCPP: Tris (β-chloropropyl) phosphate; "TMCPP", manufactured by Dahachi Chemical Industry Co., Ltd. ＜Dispersant＞ (Neubo Silica Particles) (b1) P87: "Sillikolloid P87", manufactured by Hoffman Mineral (b2) V85: "Sillitin V85", manufactured by Hoffman Mineral (Carbon black) ・MA220: "Carbon black MA220", manufactured by Mitsubishi Chemical Corporation ＜Blowing agent＞ ・HCFO: Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd); "Solstice (registered trademark) LBA", manufactured by Honeywell International Inc. ·water ＜Catalyst＞ ・SX60: Tertiary amine catalyst; "TOYOCAT (registered trademark)-SX60", manufactured by TOSOH Co., Ltd. ・DM70: Tertiary amine catalyst; "TOYOCAT (registered trademark)-DM70", manufactured by TOSOH Co., Ltd. ・K-15: Potassium 2-ethylhexyl acid; "Dabco (registered trademark) K-15", manufactured by Evonik, a trimeric isocyanate catalyst ＜Foam stabilizer＞ ・L-6100: Silicone foam stabilizer; "Niax (registered trademark) silicone L-6100", manufactured by Momentive Performance Materials Inc.
(實施例1) 於500mL聚乙烯瓶中，置入聚酯多元醇RFK-556 35.2質量份、觸媒(SX60、DM70及K-15)各1.6質量份、水(發泡劑)0.3質量份、TMCPP15.6質量份、及泡沫穩定劑1.6質量份，以安裝有籠型攪拌子的電動鑽機，以3000rpm攪拌20秒(以下，攪拌方法相同)。 於其中添加難燃劑(a1)20.0質量份、及諾易堡矽土粒子(b1)2.0質量份，攪拌20秒，接著，添加HCFO20.5質量份，再攪拌20秒後，於20℃之恆溫水槽中保溫，而調製多元醇組成物。(Example 1) In a 500mL polyethylene bottle, put 35.2 parts by mass of polyester polyol RFK-556, 1.6 parts by mass of each catalyst (SX60, DM70 and K-15), 0.3 parts by mass of water (foaming agent), and 15.6 parts by mass of TMCPP And 1.6 parts by mass of the foam stabilizer were stirred at 3000 rpm for 20 seconds with an electric drill equipped with a cage stirrer (hereinafter, the stirring method is the same). Add 20.0 parts by mass of flame retardant (a1) and 2.0 parts by mass of Noibo silica particles (b1), and stir for 20 seconds. Next, add 20.5 parts by mass of HCFO and stir for 20 seconds. Heat insulation in a constant temperature water tank to prepare a polyol composition.
(實施例2～6、比較例1～6) 摻合下述表1所示原料，與實施例1同樣地進行，各自調製多元醇組成物。 又，於比較例2，難燃劑為赤磷的情形，使用作為沉降防止劑之周知的碳黑，作為分散劑。(Examples 2 to 6, Comparative Examples 1 to 6) The raw materials shown in Table 1 below were blended in the same manner as in Example 1, and polyol compositions were prepared individually. In addition, in Comparative Example 2, when the flame retardant was red phosphorus, a well-known carbon black as a settling inhibitor was used as a dispersant.
[硬質聚胺甲酸酯發泡體之製造] 使用上述各實施例及各比較例之多元醇組成物，如以下方式，製造硬質聚胺甲酸酯發泡體。 又，就聚異氰酸酯化合物而言，使用聚亞甲基聚苯基聚異氰酸酯(聚合物的MDI)；「MILLIONATE(註冊商標) MR-200」，TOSOH股份有限公司製。 於500mL可回收量杯中，置入攪拌均勻的狀態之多元醇組成物100質量份、及聚異氰酸酯化合物102.5質量份，攪拌5秒鐘後，將所獲得的混合液(硬質聚胺甲酸酯發泡體之原料液)，流入至15cm見方的方形模具中，使靜置30分鐘後，脫模，獲得硬質聚胺甲酸酯發泡體。[Manufacturing of rigid polyurethane foam] Using the polyol composition of each of the foregoing Examples and Comparative Examples, a rigid polyurethane foam was produced in the following manner. In addition, as the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (MDI of polymer); "MILLIONATE (registered trademark) MR-200", manufactured by TOSOH Co., Ltd. was used. In a 500 mL recyclable measuring cup, 100 parts by mass of the polyol composition and 102.5 parts by mass of the polyisocyanate compound in a uniformly stirred state are placed, and after stirring for 5 seconds, the obtained mixture (hard polyurethane hair The raw material liquid of the foam body) was poured into a 15 cm square mold, allowed to stand for 30 minutes, and then demolded to obtain a rigid polyurethane foam.
[評價] 於上述各實施例及各比較例所調製的多元醇組成物及使用其而製造的硬質聚胺甲酸酯發泡體，針對下述之項目進行評價。將此等之評價結果，整理呈示於下述表1。[Evaluation] The polyol composition prepared in each of the above-mentioned Examples and Comparative Examples and the rigid polyurethane foam produced using the same were evaluated for the following items. These evaluation results are summarized and presented in Table 1 below.
＜凝聚性＞ 將置入多元醇組成物30g的50mL小瓶於室溫下(25℃)靜置21日後，將該小瓶側倒靜置5分鐘，再直立靜置5分鐘。以目視之外觀觀察，確認固體含量的沉降物的狀態。 基於下述之評價基準，評價此等之觀察結果。 (評價基準) AA：小瓶倒向側面時，沉降物流動，再次直立時，1分鐘以內回到原始的狀態。 A：小瓶倒向側面時，沉降物流動，再次直立時，緩緩地返回到其原始狀態。即使靜置5分鐘，沉降物完全不會返回到其原始狀態，但不會附著於小瓶的內壁面。 B：小瓶倒向側面時，沉降物流動，再次直立時，緩緩地返回到其原始狀態。即使靜置5分鐘，沉降物完全不會返回到其原始狀態，但於小瓶的內壁面有附著物殘留。 C：即使將小瓶側倒，沉降物亦不會流動。 D：固體含量會膠化。 評價AA或A的情形，可謂粉體之凝聚被良好地抑制，評價AA的情形，可謂凝聚抑制效果特別優異。另一方面，評價B～D的情形，判定未獲得充分的凝聚抑制效果，評價C及D的情形，判定不適於實用。＜Cohesion＞ After the 50 mL vial containing 30 g of the polyol composition was allowed to stand at room temperature (25° C.) for 21 days, the vial was left to stand upside down for 5 minutes, and then stood upright for 5 minutes. Observed by visual appearance, the state of the solid content sedimentation was confirmed. Based on the following evaluation criteria, evaluate these observation results. (Evaluation criteria) AA: When the vial is poured to the side, the sediment flows, and when it stands upright again, it returns to its original state within 1 minute. A: When the vial is poured to the side, the sediment flows, and when it stands upright again, it slowly returns to its original state. Even if it is left to stand for 5 minutes, the sediment will not return to its original state at all, but will not adhere to the inner wall surface of the vial. B: When the vial is poured to the side, the sediment flows, and when it stands up again, it slowly returns to its original state. Even if it is left for 5 minutes, the sediment will not return to its original state at all, but there will be adherents remaining on the inner wall of the vial. C: Even if the vial is poured on its side, the sediment does not flow. D: The solid content will gel. In the case of evaluating AA or A, it can be said that the aggregation of the powder is well suppressed, and in the case of evaluating AA, it can be said that the aggregation suppressing effect is particularly excellent. On the other hand, when evaluating B to D, it was judged that a sufficient aggregation suppression effect was not obtained, and when evaluating C and D, it was judged not to be suitable for practical use.
＜難燃性＞ 由上述製造的硬質聚胺甲酸酯發泡體，切出98mm×98mm×厚度(高度)25mm的試料。 依據ISO 5660-1，以錐形卡路里計(「Cone calorimeter III」、東洋精機製作所股份有限公司製；基材之不燃材：石膏板(厚度9.5mm))，藉由錐體對試料施加50KW/m2 之熱量，同時，藉由火星塞使點火10秒，測定加熱20分鐘時之總發熱量。 基於下述之評價基準，評價此等之測定值。 (評價基準) A：總發熱量不足8MJ/m2 B：總發熱量8MJ/m2 以上且不足11MJ/m2 C：總發熱量11MJ/m2 以上且不足20MJ/m2 D：總發熱量20MJ/m2 以上 評價A的情形，難燃性最高，可謂為不燃材料的程度。其次，評價B的情形難燃性亦充分高，可謂為準不燃材料的程度。<Flame retardancy> From the rigid polyurethane foam produced above, a sample of 98 mm×98 mm×thickness (height) 25 mm was cut out. According to ISO 5660-1, using a cone calorimeter ("Cone calorimeter III", manufactured by Toyo Seiki Seisakusho Co., Ltd.; non-combustible base material: gypsum board (thickness 9.5mm)), 50KW/ m 2 of heat, and at the same time, the spark plug is used to ignite for 10 seconds, and the total heat of heating for 20 minutes is measured. Evaluate these measured values based on the following evaluation criteria. (Evaluation criteria) A: Total heating value is less than 8MJ/m 2 B: Total heating value is 8MJ/m 2 or more and less than 11MJ/m 2 C: Total heating value is 11MJ/m 2 or more and less than 20MJ/m 2 D: Total heating value When the amount of 20MJ/m 2 or more is evaluated as A, the flame retardancy is the highest, which can be described as a non-combustible material. Secondly, in the case of evaluation B, the flame retardancy is also sufficiently high, which can be described as a quasi-non-combustible material.
[表1]
由表1所示結果可知，確認到藉由添加作為分散劑之諾易堡矽土粒子(實施例1～6)，抑制了包含1種以上選自包含指定之次膦酸系金屬鹽及磷酸系金屬鹽的群組之化合物的粉體狀之難燃劑的凝聚，且獲得了具有相當於準不燃材料以上之難燃性的硬質聚胺甲酸酯發泡體。併用作為多元醇化合物之曼尼希系多元醇的情形(實施例2～4)，確認到獲得了特別優異的凝聚抑制效果。 另一方面，未添加諾易堡矽土粒子的情形(比較例1、3及4)、添加作為分散劑之碳黑的情形(比較例2)，硬質聚胺甲酸酯發泡體之難燃性雖為良好，但多元醇組成物中的粉體之凝聚抑制效果不能稱為充分。 又，難燃劑包含聚磷酸銨的情形(比較例5及6)，多元醇組成物發生膠化或固化，硬質聚胺甲酸酯發泡體之難燃性亦差。From the results shown in Table 1, it was confirmed that the addition of Noibble silica particles as a dispersant (Examples 1 to 6) suppressed the inclusion of one or more selected from the group consisting of specified phosphinic acid-based metal salts and phosphoric acid It is the aggregation of the powdery flame retardant of the compound of the group of metal salts, and a rigid polyurethane foam with flame retardancy equal to or higher than that of a quasi-incombustible material is obtained. When a Mannich polyol as a polyol compound was used in combination (Examples 2 to 4), it was confirmed that a particularly excellent aggregation inhibitory effect was obtained. On the other hand, the case where Noibble silica particles are not added (Comparative Examples 1, 3, and 4), the case where carbon black is added as a dispersant (Comparative Example 2), hard polyurethane foam is difficult Although the flammability is good, the effect of suppressing aggregation of the powder in the polyol composition cannot be said to be sufficient. In addition, when the flame retardant contains ammonium polyphosphate (Comparative Examples 5 and 6), the polyol composition is gelled or cured, and the flame retardancy of the rigid polyurethane foam is also poor.
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