JP5086575B2 - Polyol composition and method for producing rigid polyurethane foam - Google Patents
Polyol composition and method for producing rigid polyurethane foam Download PDFInfo
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- JP5086575B2 JP5086575B2 JP2006196264A JP2006196264A JP5086575B2 JP 5086575 B2 JP5086575 B2 JP 5086575B2 JP 2006196264 A JP2006196264 A JP 2006196264A JP 2006196264 A JP2006196264 A JP 2006196264A JP 5086575 B2 JP5086575 B2 JP 5086575B2
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- Prior art keywords
- polyurethane foam
- polyol
- rigid polyurethane
- polyol composition
- surfactant
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- 229920005862 polyol Polymers 0.000 title claims description 65
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 50
- 239000011496 polyurethane foam Substances 0.000 title claims description 50
- 150000003077 polyols Chemical class 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 polyol compound Chemical class 0.000 claims description 53
- 239000004094 surface-active agent Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000006260 foam Substances 0.000 description 14
- 238000009413 insulation Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 238000011156 evaluation Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 125000005263 alkylenediamine group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011491 glass wool Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- SVNWKKJQEFIURY-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyl)imidazole Chemical compound CC(C)CN1C=CN=C1C SVNWKKJQEFIURY-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 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
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002323 Silicone foam Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical class F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ILEDWLMCKZNDJK-UHFFFAOYSA-N esculetin Chemical class C1=CC(=O)OC2=C1C=C(O)C(O)=C2 ILEDWLMCKZNDJK-UHFFFAOYSA-N 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- NXHXNTAEDQTBLD-UHFFFAOYSA-N n,n-dimethyl-3-(triazinan-1-yl)propan-1-amine Chemical compound CN(C)CCCN1CCCNN1 NXHXNTAEDQTBLD-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000011493 spray foam Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 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 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、水を発泡剤とする硬質ポリウレタンフォーム用ポリオール組成物並びに該ポリオール組成物を使用した硬質ポリウレタンフォームの製造方法に関するものである。 The present invention relates to a polyol composition for rigid polyurethane foam using water as a foaming agent, and a method for producing a rigid polyurethane foam using the polyol composition.
従来、戸建住宅を中心とする建築用断熱材としては、従来はグラスウールが最も多く使用されていたが、壁体内に施工したグラスウールは年数経過により徐々に下方に沈み込んで壁の断熱性が低下するという問題を有するものであり、また近年要求される高い断熱性の要請を満たすためには施工厚さが厚くなるという問題も有する。 Conventionally, glass wool has been the most commonly used heat insulating material for buildings mainly in detached houses, but glass wool installed in the wall gradually sinks downward over the years, and the heat insulation of the wall In addition, there is a problem that the construction thickness is increased in order to satisfy the demand for high heat insulation required in recent years.
グラスウール断熱材と比較して高い断熱性を有し、しかも年数経過による沈み込みを起こさない建築物用の断熱材として外壁面又は内壁面の壁体内面にスプレーにより吹き付けるスプレー発泡法の硬質ポリウレタンフォームや外壁面と内壁面にて形成された壁体内に発泡原液を注入する注入法の硬質ポリウレタンフォームが公知である。硬質ポリウレタンフォームの発泡剤としては、古くはフロン化合物が使用されていたが、オゾン層の破壊という環境問題を起こす物質であることから製造が禁止され、現在使用可能な発泡剤は、ＨＦＣ化合物、ペンタン、炭酸ガス及び水である。これらの発泡剤の中でＨＦＣ化合物は高価であり、ペンタンは引火性の強い化合物であるためにスプレー発泡の硬質ポリウレタンフォームに使用することはできない。また炭酸ガスを発泡剤として使用する場合には、炭酸ガスをポリオール組成物に加圧混合する装置が必要であり、硬質ポリウレタンフォームを製造するための装置が高価なものとなる。これに対して水は低コストで取り扱いが容易であり、例えばスプレー発泡法用としても使用できる水発泡硬質ポリウレタンフォームは公知である（例えば特許文献１）。 Rigid polyurethane foam with spray foaming method that sprays on the inner wall of the outer wall or inner wall as a heat insulating material for buildings that has higher heat insulation than glass wool insulation and does not cause sinking over the years. In addition, a rigid polyurethane foam of an injection method in which a foaming stock solution is injected into a wall formed by an outer wall surface and an inner wall surface is known. As a foaming agent for rigid polyurethane foam, chlorofluorocarbon compounds have been used in the old days, but production is prohibited because it is a substance that causes environmental problems such as destruction of the ozone layer. Currently usable foaming agents are HFC compounds, Pentane, carbon dioxide and water. Among these foaming agents, HFC compounds are expensive, and pentane is a highly flammable compound and cannot be used for rigid polyurethane foams with spray foam. Further, when carbon dioxide is used as a foaming agent, an apparatus for pressurizing and mixing carbon dioxide with the polyol composition is necessary, and an apparatus for producing a rigid polyurethane foam becomes expensive. On the other hand, water is easy to handle at low cost, and for example, a water-foamed rigid polyurethane foam that can be used for spray foaming is known (for example, Patent Document 1).
特許文献１に開示された技術は、スプレー発泡によっても製造可能な、寸法安定性と難燃性に優れた水発泡硬質ポリウレタンフォームであり、エステルポリオールとフォームの気泡（セル）を連通化させる連通剤を原料成分として使用することを特徴とするものである。 The technology disclosed in Patent Document 1 is a water-foamed rigid polyurethane foam excellent in dimensional stability and flame retardancy that can be produced by spray foaming, and is a communication that connects ester polyol and foam cells (cells). An agent is used as a raw material component.
しかし、特許文献１開示の硬質ポリウレタンフォームは、寸法安定性は改善されてはいるものの、連通剤を使用しているために熱伝導率が高く、断熱性には問題を有するものである。 However, although the rigid polyurethane foam disclosed in Patent Document 1 has improved dimensional stability, it has a high thermal conductivity due to the use of a communicating agent and has a problem in heat insulation.
本発明は、上記公知技術の問題に鑑み、水を発泡剤とし、寸法安定性と断熱性に優れた硬質ポリウレタンフォーム用のポリオール組成物並びに該ポリオール組成物を使用した硬質ポリウレタンフォームの製造方法を提供することを目的とするものである。 In view of the above-mentioned problems of the known technology, the present invention provides a polyol composition for a rigid polyurethane foam excellent in dimensional stability and heat insulation using water as a foaming agent, and a method for producing a rigid polyurethane foam using the polyol composition. It is intended to provide.
上記課題を解決する本発明は以下のとおりである。
〔１〕ポリオール化合物、発泡剤として水、界面活性剤及び触媒を含有し、ポリイソシアネート成分と混合し、反応させて硬質ポリウレタンフォームを形成するポリオール組成物であり、
前記ポリオール化合物は芳香族エステルポリオールとポリエーテルポリオールとからなり、
前記界面活性剤はＨＬＢが１４．９以上であるポリオキシエチレンソルビタン脂肪酸エステルであり、前記界面活性剤の添加量がポリオール組成物全量中０．０１〜１０重量％であることを特徴とする硬質ポリウレタンフォーム用ポリオール組成物。
〔２〕前記ポリオキシエチレンソルビタン脂肪酸エステルは、ポリオキシエチレン基を構成するエチレンオキサイド単位の合計量が２０以上であることを特徴とする上記〔１〕の硬質ポリウレタンフォーム用ポリオール組成物。
〔３〕ポリオール化合物、発泡剤として水、界面活性剤及び触媒を含むポリオール組成物とポリイソシアネート成分とを混合し、反応させて硬質ポリウレタンフォームとする硬質ポリウレタンフォームの製造方法であって、
前記ポリオール化合物は芳香族エステルポリオールとポリエーテルポリオールとからなり、
前記界面活性剤はＨＬＢが１４．９以上であるポリオキシエチレンソルビタン脂肪酸エステルであり、前記界面活性剤の添加量をポリオール組成物全量中０．０１〜１０重量％とすることを特徴とする硬質ポリウレタンフォームの製造方法。
〔４〕前記ポリオキシエチレンソルビタン脂肪酸エステルは、ポリオキシエチレン基を構成するエチレンオキサイド単位の合計量が２０以上であることを特徴とする上記〔３〕の硬質ポリウレタンフォームの製造方法。
The present invention for solving the above problems is as follows.
[1] A polyol composition containing water, a surfactant and a catalyst as a polyol compound and a foaming agent, mixed with a polyisocyanate component, and reacted to form a rigid polyurethane foam,
The polyol compound comprises an aromatic ester polyol and a polyether polyol,
The surfactant is a polyoxyethylene sorbitan fatty acid ester having an HLB of 14.9 or more, and the amount of the surfactant added is 0.01 to 10% by weight in the total amount of the polyol composition Polyol composition for polyurethane foam.
[2] The polyoxyethylene sorbitan fatty acid esters, the total amount of ethylene oxide units constituting the polyoxyethylene group for rigid polyurethane foams polyol composition of [1], wherein a is 20 or more.
[3] A method for producing a rigid polyurethane foam comprising mixing a polyol composition containing a polyol compound, water as a foaming agent, a surfactant and a catalyst, and a polyisocyanate component and reacting them to form a rigid polyurethane foam,
The polyol compound comprises an aromatic ester polyol and a polyether polyol,
The surfactant is a polyoxyethylene sorbitan fatty acid ester having an HLB of 14.9 or more, and the amount of the surfactant added is 0.01 to 10% by weight based on the total amount of the polyol composition. A method for producing polyurethane foam.
[4] The polyoxyethylene sorbitan fatty acid ester, the method for producing a rigid polyurethane foam according to [3], wherein the total amount of ethylene oxide units constituting the polyoxyethylene group is 20 or more.
上記〔１〕の構成のポリオール組成物を使用して製造した硬質ポリウレタンフォームは、水のみを発泡剤として使用し、スプレー発泡法又は注入法により形成され、寸法安定性と断熱性に優れた硬質ポリウレタンフォームである。界面活性剤の添加量は、ポリオール組成物全量中０．０１〜１０重量％、好ましくは０．０１〜８重量％、さらに好ましくは０．０１〜５重量％である。界面活性剤の添加量がポリオール組成物全量中０．０１重量％未満の場合も１０重量％を超える場合も、いずれも形成される硬質ポリウレタンフォームの寸法安定性が満足できるものではない。 The rigid polyurethane foam produced using the polyol composition having the above-mentioned configuration [1] is formed by spray foaming or injection using only water as a foaming agent, and is rigid with excellent dimensional stability and heat insulation. Polyurethane foam. The addition amount of the surfactant is 0.01 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.01 to 5% by weight, based on the total amount of the polyol composition. When the addition amount of the surfactant is less than 0.01% by weight or more than 10% by weight in the total amount of the polyol composition, the dimensional stability of the rigid polyurethane foam to be formed is not satisfactory.
上記〔２〕の構成によれば、硬質ポリウレタンフォーム用ポリオール組成物に上記の界面活性剤を整泡剤と併用することによって、発泡剤として水のみを使用し、寸法安定性と断熱性に優れた硬質ポリウレタンフォームを得ることができる。ポリオキシエチレンソルビタン脂肪酸エステルとしては、ポリオキシエチレン基を構成するエチレンオキサイド単位の合計量が２０以上、ＨＬＢが１０以上、好ましくは１２以上、さらに好ましくは１４以上である。使用する界面活性剤であるポリオキシエチレンソルビタン脂肪酸エステルを構成するエチレンオキサイド単位の合計量が２０未満で、ＨＬＢが１０未満の場合は、形成される硬質ポリウレタンフォームの寸法安定性が満足できるものではない。 According to the configuration of [2], by using the surfactant in combination with the foam stabilizer in the polyol composition for rigid polyurethane foam, only water is used as a foaming agent, and the dimensional stability and heat insulation are excellent. A rigid polyurethane foam can be obtained. As the polyoxyethylene sorbitan fatty acid ester, the total amount of ethylene oxide units constituting the polyoxyethylene group is 20 or more, HLB is 10 or more, preferably 12 or more, more preferably 14 or more. When the total amount of ethylene oxide units constituting the polyoxyethylene sorbitan fatty acid ester which is the surfactant to be used is less than 20 and the HLB is less than 10, the dimensional stability of the formed rigid polyurethane foam is not satisfactory. Absent.
上記〔３〕の構成の製造方法によれば、水のみを発泡剤として使用し、寸法安定性と断熱性に優れた硬質ポリウレタンフォームをスプレー発泡法又は注入法により製造することができる。 According to the production method having the above-mentioned configuration [3], a rigid polyurethane foam excellent in dimensional stability and heat insulation can be produced by spray foaming or injection using only water as a foaming agent.
上記〔４〕の構成のスプレー発泡硬質ポリウレタンフォームの製造方法によれば、原料のポリオール組成物に上記の界面活性剤を整泡剤と併用することによって、発泡剤として水のみを使用し、寸法安定性と断熱性に優れた硬質ポリウレタンフォームを製造することができる。 According to the method for producing a spray-foamed rigid polyurethane foam having the above-mentioned configuration [4], by using the surfactant in combination with the foam stabilizer in the raw material polyol composition, only water is used as a foaming agent. A rigid polyurethane foam excellent in stability and heat insulation can be produced.
本発明のポリオール組成物は、ポリオール化合物、発泡剤として水、触媒を含む。本発明のポリオール組成物の粘度は、スプレー法による硬質ポリウレタンフォームの製造が容易に行える観点より１０００ｍＰａ・ｓ（２０℃）以下であることが好ましく、５００ｍＰａ・ｓ（２０℃）以下であることがより好ましい。 The polyol composition of the present invention contains a polyol compound, water as a foaming agent, and a catalyst. The viscosity of the polyol composition of the present invention is preferably 1000 mPa · s (20 ° C.) or less, and preferably 500 mPa · s (20 ° C.) or less, from the viewpoint of easily producing a rigid polyurethane foam by a spray method. More preferred.
本発明のポリオール組成物を構成するポリオール化合物としては、芳香族エステルポリオールとポリエーテルポリオールを使用する。 As the polyol compound constituting the polyol composition of the present invention, an aromatic ester polyol and a polyether polyol are used.
芳香族エステルポリオールは、エチレングリコール、ジエチレングリコール、１，６−ヘキサンジオール等から選択される少なくとも１種のグリコールとフタル酸、イソフタル酸、テレフタル酸等から選択される少なくとも１種の芳香族ジカルボン酸とのエステルポリオールである。 The aromatic ester polyol includes at least one glycol selected from ethylene glycol, diethylene glycol, 1,6-hexanediol, and the like, and at least one aromatic dicarboxylic acid selected from phthalic acid, isophthalic acid, terephthalic acid, and the like. The ester polyol.
ポリエーテルポリオールとしては、低分子量のアミンないし多価アルコールを開始剤としてエチレンオキサイド、プロピレンオキサイドの少なくとも１種を開環付加させた末端水酸基の公知のポリオール化合物を使用することができる。 As the polyether polyol, a known polyol compound having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using a low molecular weight amine or polyhydric alcohol as an initiator can be used.
開始剤としてアルキレンジアミン、アルカノールアミン、芳香族ジアミン等の低分子量アミンを開始剤とするポリオール化合物は、第３級アミノ基含有ポリオール化合物である。開始剤であるアルキレンジアミンとしては、公知の化合物が限定なく使用でき、具体的にはエチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ネオペンチルジアミン等の炭素数が２〜８のアルキレンジアミンの使用が好適である。これらの中でも、炭素数の小さなアルキレンジアミンの使用がより好ましく、特にエチレンジアミン、プロピレンジアミンを開始剤としたポリオール化合物の使用が好ましい。また芳香族ジアミンとしては、２，４−トルエンジアミン、２，６−トルエンジアミン、ジエチルトルエンジアミン、４，４’−ジアミノジフェニルメタン、ｐ−フェニレンジアミン、ｏ−フェニレンジアミン、ナフタレンジアミン等が例示される。モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミンを開始剤として使用した３官能の第３級アミノ基含有ポリオール化合物も使用可能である。 A polyol compound having a low molecular weight amine such as alkylene diamine, alkanolamine, or aromatic diamine as an initiator as an initiator is a tertiary amino group-containing polyol compound. As the alkylene diamine which is an initiator, known compounds can be used without limitation, specifically, use of alkylene diamine having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine and the like. Is preferred. Among these, the use of alkylenediamine having a small number of carbon atoms is more preferable, and the use of a polyol compound having ethylenediamine or propylenediamine as an initiator is particularly preferable. Examples of the aromatic diamine include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine and the like. . A trifunctional tertiary amino group-containing polyol compound using an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine as an initiator can also be used.
開始剤として低分子量の多価アルコールを使用したポリオール化合物は、脂肪族ポリエーテルポリオールであり、開始剤としては、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、シクロヘキシレングリコール、シクロヘキサンジメタノール等のグリコール類、トリメチロールプロパン、グリセリン等のトリオール類、ペンタエリスリトール等の４官能アルコール類、ソルビトール、シュークロース等の多価アルコール類などが例示される。 A polyol compound using a low molecular weight polyhydric alcohol as an initiator is an aliphatic polyether polyol. Examples of the initiator include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, , 6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol and other glycols, trimethylolpropane, glycerol and other triols, tetrafunctional alcohols such as pentaerythritol, polyhydric alcohols such as sorbitol and sucrose Examples are shown.
整泡剤成分として使用する界面活性剤成分であるポリオキシエチレンソルビタン脂肪酸エステルは、化学式（化１）にて表される化学構造を有する化合物である。 The polyoxyethylene sorbitan fatty acid ester which is a surfactant component used as a foam stabilizer component is a compound having a chemical structure represented by the chemical formula (Chemical Formula 1).
Ｒは炭素数８〜１８のアルキル基、アルケニル基又はアルカジエニル基であり、上述のように、ｍ＋ｎ＋ｐは２０以上、ＨＬＢは１０以上であることが好ましい。Ｒとしては、具体的にはオクチル基、ステアリル基、ラウリル基、オレイル基、パルミチル基などの公知の炭素数が８以上のアルキル基、アルケニル基、アルカジエニル基が例示される。 R is an alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkadienyl group, and as described above, m + n + p is preferably 20 or more and HLB is preferably 10 or more. Specific examples of R include octyl, stearyl, lauryl, oleyl, and palmityl groups, such as alkyl groups having 8 or more carbon atoms, alkenyl groups, and alkadienyl groups.
ポリオール組成物と混合、反応させて硬質ポリウレタンフォームを形成するポリイソシアネート化合物としては、取扱の容易性、反応の速さ、得られる硬質ポリウレタンフォームの物理特性が優れていること、低コストであることなどから、液状ＭＤＩを使用する。液状ＭＤＩとしては、クルードＭＤＩ（ｃ−ＭＤＩ）等が使用される。液状ＭＤＩに加えて、他のポリイソシアネート化合物を併用してもよい。併用するポリイソシアネート化合物としては、ポリウレタンの技術分野において公知のポリイソシアネート化合物は限定なく使用可能である。 The polyisocyanate compound that forms a rigid polyurethane foam by mixing and reacting with the polyol composition is easy to handle, fast in reaction, excellent in the physical properties of the resulting rigid polyurethane foam, and low in cost. For this reason, liquid MDI is used. As the liquid MDI, crude MDI (c-MDI) or the like is used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.
本発明の硬質ポリウレタンフォームの製造に際しては、上記成分の他に、当業者に周知の触媒、難燃剤、整泡剤、着色剤、酸化防止剤等が使用可能である。 In the production of the rigid polyurethane foam of the present invention, in addition to the above components, catalysts, flame retardants, foam stabilizers, colorants, antioxidants and the like well known to those skilled in the art can be used.
触媒としては、第３級アミン触媒、イミダゾール系触媒、脂肪酸アルカリ金属塩触媒等の公知の触媒を限定なく使用することができる。 As the catalyst, known catalysts such as tertiary amine catalysts, imidazole catalysts, and fatty acid alkali metal salt catalysts can be used without limitation.
第３級アミン触媒としては、具体的にはＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンやＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン（カオライザーＮｏ．１）、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ”−ペンタメチルジエチレントリアミン（カオライザーＮｏ．３）等のＮ−アルキルポリアルキレンポリアミン類、ジアザビシクロウンデセン（ＤＢＵ）、ビス（β−ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ−ジメチルアミノプロピルヘキサヒドロトリアジン等の第３級アミン触媒を例示できる。 As the tertiary amine catalyst, specifically, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine (Kaorizer No. 1), N, N-alkylpolyalkylenepolyamines such as N, N ′, N ′, N ″ -pentamethyldiethylenetriamine (Kaorizer No. 3), diazabicycloundecene (DBU), bis (β-dimethylaminoethyl) ether, N And tertiary amine catalysts such as N, N-dimethylaminopropylhexahydrotriazine.
イミダゾール系触媒としては、１−イソブチル−２−メチルイミダゾール、１−メチルイミダゾール、１，２−ジメチルイミダゾール等を例示でき、脂肪酸アルカリ金属塩触媒としてはオクチル酸カリウム、酢酸カリウム等を例示することができる。
触媒の添加量はポリオール化合物の合計１００重量部に対して０．１〜２０重量部であることが好ましく、さらには０．５〜１５重量部であることが好ましい。
Examples of the imidazole catalyst include 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, and examples of the fatty acid alkali metal salt catalyst include potassium octylate and potassium acetate. it can.
The addition amount of the catalyst is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the total polyol compound.
有機リン酸エステル類は、難燃剤と可塑剤の２つの作用を有する。有機リン酸エステル類としては、リン酸のハロゲン化アルキルエステル、アルキルリン酸エステルやアリールリン酸エステル、ホスホン酸エステル等が使用可能であり、具体的にはトリス（β−クロロエチル）ホスフェート、トリス（β−クロロプロピル）ホスフェート、トリブトキシエチルホスフェート、トリブチルホスフェート、トリエチルホスフェート、クレジルフェニルホスフェート、ジメチルメチルホスホネート等が例示でき、これらの１種以上が使用可能である。
有機リン酸エステル類の添加量はポリオール化合物の合計１００重量部に対して５０重量部以下であり、１０〜５０重量部であることが好ましい。この範囲を逸脱する場合には可塑化効果、難燃効果が十分に得られなかったり、フォームの機械的特性が低下するなどの問題が生じる場合ある。
Organophosphates have two functions of a flame retardant and a plasticizer. Examples of the organic phosphate esters include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, tris (β-chloroethyl) phosphate, tris (β -Chloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, cresylphenyl phosphate, dimethylmethylphosphonate and the like, and one or more of these can be used.
The addition amount of the organic phosphates is 50 parts by weight or less, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total polyol compound. When deviating from this range, problems such as insufficient plasticization effect and flame retardant effect and deterioration of the mechanical properties of the foam may occur.
整泡剤としては、公知の硬質ポリウレタンフォーム用シリコン整泡剤、即ちポリジメチルシロキサンとポリオキシエチレングリコール又はポリオキシエチレン−プロピレングリコールのグラフト共重合体を限定なく使用することができる。係る整泡剤としては、ＳＨ１９０，ＳＨ−１９２，ＳＨ−１９３，ＳＨ−１９４,Ｌ−５４２０，Ｌ−５３４０，ＳＺ−１６９８，ＳＺ−１７０４，ＳＺ−１９２３，ＳＺ−１９３２（東レダウコーニングシリコーン）等を例示することができる。 As the foam stabilizer, a known silicone foam stabilizer for rigid polyurethane foam, that is, a graft copolymer of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol can be used without limitation. Such foam stabilizers include SH190, SH-192, SH-193, SH-194, L-5420, L-5340, SZ-1698, SZ-1704, SZ-1923, SZ-1932 (Toray Dow Corning Silicone). Etc. can be illustrated.
整泡剤と界面活性剤は、予め混合して使用してもよく、別成分としてポリオール化合物と混合してもよい。
整泡剤と界面活性剤の比率は、整泡剤／界面活性剤重量比にて０／１００〜９０／１０であることが好ましく、５／９５〜８５／１５であることがより好ましく、１０／９０〜８０／２０であることがさらに好ましい。
The foam stabilizer and the surfactant may be mixed and used in advance, or may be mixed with a polyol compound as a separate component.
The ratio of the foam stabilizer to the surfactant is preferably 0/100 to 90/10, more preferably 5/95 to 85/15 in terms of the foam stabilizer / surfactant weight ratio. More preferably, it is / 90-80 / 20.
（ポリオール組成物）
表２上段に記載した組成にてポリオール組成物を調製した。使用した原料の内容、特性は表１に示した。
(Polyol composition)
A polyol composition was prepared with the composition described in the upper part of Table 2. The contents and characteristics of the raw materials used are shown in Table 1.
（実施例、比較例）
実施例、比較例は、表２の上段に記載した配合にて常法によりポリオール組成物を調整した。硬質ポリウレタンフォームの製造においては、市販の硬質ポリウレタンフォームのスプレー発泡装置を使用し、ポリオール組成物とポリイソシアネート成分とをイソシアネートインデックス（ＮＣＯ／ＯＨ当量比）が２．０となるように調整して試験面材に硬質ポリウレタンフォームを形成した。得られた硬質ポリウレタンフォームについて以下に記載の評価を行い、結果を表２の下段に示した。
(Examples and comparative examples)
In Examples and Comparative Examples, a polyol composition was prepared by a conventional method with the formulation described in the upper part of Table 2. In the production of rigid polyurethane foam, a commercially available rigid polyurethane foam spray foaming device is used, and the polyol composition and the polyisocyanate component are adjusted so that the isocyanate index (NCO / OH equivalent ratio) is 2.0. A rigid polyurethane foam was formed on the test face material. The obtained rigid polyurethane foam was evaluated as described below, and the results are shown in the lower part of Table 2.
（評価）
１）寸法安定性
硬質ポリウレタンフォームから７０ｍｍ×１００ｍｍ×３０ｍｍに裁断して作製した評価サンプルについて、２５℃及び５０℃にて３日間放置した後の収縮の有無を目視にて評価を行った。評価結果は、以下の基準により行った。
○ ：外観上の収縮なし。
× ：外観上の収縮発生。
(Evaluation)
1) Dimensional stability An evaluation sample prepared by cutting a rigid polyurethane foam into 70 mm × 100 mm × 30 mm was visually evaluated for the presence or absence of shrinkage after standing at 25 ° C. and 50 ° C. for 3 days. The evaluation results were performed according to the following criteria.
○: No shrinkage on appearance.
X: Shrinkage on appearance.
２）熱伝導率
硬質ポリウレタンフォームから７０ｍｍ×１００ｍｍ×３０ｍｍに裁断して作製した評価サンプルについて、２５℃にて３日間放置した後、迅速熱伝導率計ＱＴＭ−Ｄ３（京都電子工業製）を使用して熱伝導率を測定した。
2) Thermal conductivity An evaluation sample prepared by cutting a rigid polyurethane foam into 70 mm × 100 mm × 30 mm was allowed to stand at 25 ° C. for 3 days, and then a rapid thermal conductivity meter QTM-D3 (manufactured by Kyoto Electronics Industry) was used. The thermal conductivity was measured.
３）フォーム密度
硬質ポリウレタンフォームから７０ｍｍ×１００ｍｍ×３０ｍｍに裁断して作製した評価サンプルについて、２５℃にて３日間放置した後、重量測定を行って密度（ｋｇ／ｍ３）を算出した。
3) Foam density An evaluation sample prepared by cutting a rigid polyurethane foam into 70 mm × 100 mm × 30 mm was left at 25 ° C. for 3 days and then weighed to calculate the density (kg / m 3 ).
４）セルの均一性
硬質ポリウレタンフォームの切断面を電子顕微鏡にて観察し、セルの均一性を評価した。表結果は以下のように表示した。
○ ：セルサイズが均一である。
× ：セルサイズが不均一である。
4) Cell uniformity The cut surface of the rigid polyurethane foam was observed with an electron microscope to evaluate the cell uniformity. The table results were displayed as follows.
○: The cell size is uniform.
X: The cell size is not uniform.
表２の結果より、本発明のポリオキシエチレンソルビタン脂肪酸エステルを、整泡剤成分を構成する界面活性剤として使用したポリオール組成物を使用して製造した硬質ポリウレタンフォームは、寸法安定性、セルの均一性が良好であり、熱伝導率もグラスウールよりも小さく、建築物用には十分な断熱性能を有するものであった。これに対して界面活性剤を使用しなかった比較例１のフォームは収縮が大きく、比較例３のフォームは１セルの均一性が不良で断熱性能も満足できるものではなかった。界面活性剤のＨＬＢが本発明の範囲を逸脱する比較例２のフォームと本発明の界面活性剤を過剰に添加した比較例４のフォームも、共に寸法安定性が不良であり、他の評価が行えないものであった。 From the results in Table 2, the rigid polyurethane foam produced by using the polyol composition using the polyoxyethylene sorbitan fatty acid ester of the present invention as a surfactant constituting the foam stabilizer component is dimensional stability, cell The uniformity was good, the thermal conductivity was smaller than that of glass wool, and it had sufficient heat insulation performance for buildings. On the other hand, the foam of Comparative Example 1 which did not use a surfactant had a large shrinkage, and the foam of Comparative Example 3 had poor uniformity of one cell and was not satisfactory in heat insulation performance. Both the foam of Comparative Example 2 in which the HLB of the surfactant deviates from the scope of the present invention and the foam of Comparative Example 4 to which the surfactant of the present invention was excessively added had poor dimensional stability. It couldn't be done.
Claims (4)
前記ポリオール化合物は芳香族エステルポリオールとポリエーテルポリオールとからなり、
前記界面活性剤はＨＬＢが１４．９以上であるポリオキシエチレンソルビタン脂肪酸エステルであり、前記界面活性剤の添加量がポリオール組成物全量中０．０１〜１０重量％であることを特徴とする硬質ポリウレタンフォーム用ポリオール組成物。 A polyol composition containing water, a surfactant and a catalyst as a foaming agent, mixed with a polyisocyanate component, and reacted to form a rigid polyurethane foam,
The polyol compound comprises an aromatic ester polyol and a polyether polyol,
The surfactant is a polyoxyethylene sorbitan fatty acid ester having an HLB of 14.9 or more, and the amount of the surfactant added is 0.01 to 10% by weight in the total amount of the polyol composition Polyol composition for polyurethane foam.
前記ポリオール化合物は芳香族エステルポリオールとポリエーテルポリオールとからなり、
前記界面活性剤はＨＬＢが１４．９以上であるポリオキシエチレンソルビタン脂肪酸エステルであり、前記界面活性剤の添加量をポリオール組成物全量中０．０１〜１０重量％とすることを特徴とする硬質ポリウレタンフォームの製造方法。 A polyol compound, a polyol composition containing water, a surfactant and a catalyst as a foaming agent, and a polyisocyanate component are mixed and reacted to form a rigid polyurethane foam, which is a method for producing a rigid polyurethane foam,
The polyol compound comprises an aromatic ester polyol and a polyether polyol,
The surfactant is a polyoxyethylene sorbitan fatty acid ester having an HLB of 14.9 or more, and the amount of the surfactant added is 0.01 to 10% by weight based on the total amount of the polyol composition. A method for producing polyurethane foam.
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