JPH04258630A - Polyol composition for urethane and flexible urethane foam - Google Patents
Polyol composition for urethane and flexible urethane foamInfo
- Publication number
- JPH04258630A JPH04258630A JP3021030A JP2103091A JPH04258630A JP H04258630 A JPH04258630 A JP H04258630A JP 3021030 A JP3021030 A JP 3021030A JP 2103091 A JP2103091 A JP 2103091A JP H04258630 A JPH04258630 A JP H04258630A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- foam
- urethane
- polyol composition
- polyester polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 47
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 229920005862 polyol Polymers 0.000 title claims description 13
- 150000003077 polyols Chemical class 0.000 title claims description 12
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 150000002009 diols Chemical class 0.000 claims abstract description 13
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 4
- 230000006866 deterioration Effects 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 9
- 150000002148 esters Chemical class 0.000 abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000004619 high density foam Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- -1 lactone polyols Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WBSRHBNFOLDTGU-UHFFFAOYSA-N nonane-1,8-diol Chemical compound CC(O)CCCCCCCO WBSRHBNFOLDTGU-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 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
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は耐湿熱劣化性、耐アルカ
リ性、及び耐酸性に優れたウレタン用のポリエステル系
ポリオール組成物、及びそれを用いたエステル系軟質ウ
レタンフォームに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polyol composition for urethane which has excellent resistance to moisture and heat deterioration, alkali resistance and acid resistance, and a flexible ester urethane foam using the same.
【０００２】0002
【従来の技術】従来エステル系軟質ウレタンフォームの
製造方法としては、その主原料であるポリエステルポリ
オールとして、アジピン酸、ジエチレングリコール及び
トリメチロールプロパンの縮合反応より得られるポリエ
ステルポリオールを使用する方法が公知である。この方
法によって得られたエステル系軟質ウレタンフォームは
、エーテル系軟質ウレタンフォームに比べ、機械的強度
（特に引張強度、引裂強度、伸び率、及び耐摩耗性）が
優れ、セルがより均一であるために外観的にも優れるの
が特徴であるが、耐湿熱劣化性、耐アルカリ性、及び耐
酸性に劣る欠点がある。[Prior Art] As a conventional method for producing ester-based flexible urethane foam, a method is known in which a polyester polyol obtained from a condensation reaction of adipic acid, diethylene glycol, and trimethylolpropane is used as the main raw material polyester polyol. . The ester-based flexible urethane foam obtained by this method has superior mechanical strength (especially tensile strength, tear strength, elongation rate, and abrasion resistance) and more uniform cells than ether-based flexible urethane foam. Although it is characterized by its excellent appearance, it has the disadvantage of being inferior in moisture and heat deterioration resistance, alkali resistance, and acid resistance.
【０００３】エステル系軟質ウレタンフォームが耐湿熱
劣化性、耐アルカリ性、及び耐酸性に劣る原因は、ウレ
タン樹脂中に存在するエステル結合が水やアルカリ、酸
によって加水分解され、分子の切断が引き起こされる為
である。[0003] The reason why ester-based flexible urethane foam is inferior in resistance to moisture and heat deterioration, alkali resistance, and acid resistance is that the ester bonds present in the urethane resin are hydrolyzed by water, alkali, and acid, causing molecular scission. It is for this purpose.
【０００４】従来からの技術として、活性水素化合物と
してポリエステルポリオールを使用したウレタン樹脂の
耐加水分解性を向上させる手段としては、エステル結合
量を減らす為に長鎖の二塩基酸や長鎖のジオールをポリ
エステルポリオールの原料として使用する方法、あるい
はラクトン系のポリオール、ポリカーボネート系のポリ
オール、ポリブタジエン系のポリオールを使用する方法
がすでに報告されているが、これらの方法はいずれもエ
ラストマー、合成皮革、塗料、及び高密度フォーム等の
分野に関する報告であり、軟質ウレタンフォームの分野
に関する報告はなされていない。[0004] Conventional techniques have been used to improve the hydrolysis resistance of urethane resins that use polyester polyols as active hydrogen compounds. There have already been reports of methods using polyester polyols as raw materials for polyester polyols, or methods using lactone polyols, polycarbonate polyols, and polybutadiene polyols, but all of these methods are used for elastomers, synthetic leather, paints, and high-density foam, but no report has been made regarding the field of flexible urethane foam.
【０００５】また、特開昭６３−１０１４１２号公報に
３−メチル−１，５−ペンタンジオールとジカルボン酸
から得られるポリエステルポリオールを用いた靴底用発
泡ウレタンが報告されているが、この靴底用発泡ウレタ
ンは発泡体の比重が ０．４以上の高密度フォームであ
り、軟質ウレタンフォームに適用できる記載は全くない
。また、３官能性以上のポリオールを併用する記載もあ
るが、単に添加する旨を開示したにすぎない。[0005] Furthermore, urethane foam for shoe soles using a polyester polyol obtained from 3-methyl-1,5-pentanediol and dicarboxylic acid has been reported in JP-A-63-101412. Foamed urethane foam is a high-density foam with a specific gravity of 0.4 or more, and there is no description that it can be applied to flexible urethane foam. There is also a description of the use of trifunctional or higher-functionality polyols, but this merely discloses that they are added.
【０００６】[0006]
【発明が解決しようとする課題】軟質ウレタンフォーム
は発泡体の比重が通常０．１以下であり、良好なフォー
ムを得るには従来からの技術によって耐加水分解性を改
良したポリエステルポリオールを適用しても実質上不可
能である。軟質ウレタンフォームは発泡剤として水を多
量に用いており、フォーム製造時には、ポリオールとポ
リイソシアネートによる樹脂化反応に加えて水とイソシ
アネートによる泡化反応が同時に進行するという複雑な
過程を経て製造される。従って、良好なフォームを得る
にはこの樹脂化反応と泡化反応のバランスを適正に制御
しなければならないため、原料の種類、性状、処方に関
して、エラストマーや高密度フォームとは著しく異なっ
ており、より難度の高い対応が要求される。[Problems to be Solved by the Invention] Flexible urethane foam usually has a foam specific gravity of 0.1 or less, and in order to obtain a good foam, polyester polyol with improved hydrolysis resistance using conventional techniques must be used. However, it is virtually impossible. Flexible urethane foam uses a large amount of water as a blowing agent, and is manufactured through a complicated process in which a foaming reaction with water and isocyanate proceeds simultaneously in addition to a resin-forming reaction with polyol and polyisocyanate. . Therefore, in order to obtain a good foam, the balance between the resinization reaction and the foaming reaction must be properly controlled, so the type of raw materials, properties, and formulation are significantly different from those of elastomers and high-density foams. A more difficult response is required.
【０００７】特に主原料となるポリオールについては厳
しい対応が要求され、末端活性水素基の反応性、平均官
能基数、分子量、粘度、及び酸価等の特性を最適化させ
ることによってのみ良好なフォームを製造することが出
来る。[0007] Particularly strict measures are required for the polyol, which is the main raw material, and good foam can only be produced by optimizing properties such as the reactivity of the terminal active hydrogen group, the average number of functional groups, molecular weight, viscosity, and acid value. It can be manufactured.
【０００８】本発明は上述の製造方法の問題点を克服し
、従来のエステル系軟質ウレタンフォームと同等の機械
強度を有し、しかも耐湿熱劣化性、耐アルカリ性、及び
耐酸性に優れたウレタン用のポリエステル系ポリオール
組成物、及びそれを用いたエステル系軟質ウレタンフォ
ームを提供することを目的とする。The present invention overcomes the problems of the above-mentioned manufacturing method, and provides a urethane foam that has mechanical strength equivalent to that of conventional ester-based flexible urethane foams and has excellent resistance to moist heat deterioration, alkali resistance, and acid resistance. The present invention aims to provide a polyester-based polyol composition and an ester-based flexible urethane foam using the same.
【０００９】[0009]
【課題を解決するための手段】本発明は、有機二塩基酸
、ジオール及びトリオールの縮合反応によって得られる
水酸基価が３０乃至１２０ＫＯＨｍｇ／ｇであるポリエ
ステルポリオール組成物であって、該ジオールが分子中
に少なくとも１つのメチル基を有し、且つ１級のヒドロ
キシル基を有することを特徴とするウレタン用ポリオー
ル組成物、及びこの組成物を用いた軟質ウレタンフォー
ムに関する。[Means for Solving the Problems] The present invention provides a polyester polyol composition having a hydroxyl value of 30 to 120 KOHmg/g obtained by a condensation reaction of an organic dibasic acid, a diol, and a triol, wherein the diol is present in the molecule. The present invention relates to a polyol composition for urethane characterized by having at least one methyl group and a primary hydroxyl group, and a flexible urethane foam using this composition.
【００１０】本発明のポリエステルポリオールの製造方
法としては、二塩基酸とこの二塩基酸に対して過剰モル
のジオールもしくはトリオールとの脱水反応による従来
からの公知の方法が用いられる。The polyester polyol of the present invention can be produced by a conventionally known method involving a dehydration reaction between a dibasic acid and a molar excess of diol or triol relative to the dibasic acid.
【００１１】本発明に用いられる１分子中に少なくとも
１つのメチル基を有し、かつ１級のヒドロキシル基を有
するジオールの具体例としては、ネオペンチルグリコー
ル、３−メチル−１，５−ペンタンジオール、及び２−
メチル−１，８−オクタンジオール等が挙げられ、それ
ぞれ単独もしくは混合して用いられる。[0011] Specific examples of diols having at least one methyl group and a primary hydroxyl group in one molecule used in the present invention include neopentyl glycol, 3-methyl-1,5-pentanediol. , and 2-
Examples include methyl-1,8-octanediol, which can be used alone or in combination.
【００１２】ここに挙げた化合物以外のジオール、例え
ばエチレングリコール、ジエチレングリコール、１，３
−もしくは１，４−ブチレングリコール、１，６−ヘキ
サンジオール、及びトリエチレングリコール等の公知の
ジオールは、本発明の効果に著しく影響を与えない範囲
であれば、併用することが出来る。Diols other than those listed here, such as ethylene glycol, diethylene glycol, 1,3
- or known diols such as 1,4-butylene glycol, 1,6-hexanediol, and triethylene glycol can be used in combination as long as they do not significantly affect the effects of the present invention.
【００１３】本発明に用いられる有機二塩基酸の具体例
としては、マロン酸、コハク酸、グルタル酸、アジピン
酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカ
ン二酸、ドデカン二酸、及びダイマー酸等が挙げられ、
それぞれ単独もしくは混合して用いられる。これらの有
機二塩基酸のうち本発明の目的に対して好ましいものは
１分子中の炭素数が６〜１２の有機二塩基酸である。炭
素数が６未満のものを使用すると、ポリエステル中に存
在するエステル結合の量が多くなり、耐加水分解性が悪
くなる傾向があり、一方、炭素数が１２より大きいもの
を使用すると、得られた軟質ウレタンフォームの物性が
低下する傾向が認められる。特に好ましくは１分子中の
炭素数が８ないし１０の有機二塩基酸である。Specific examples of organic dibasic acids used in the present invention include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and dimer acid. etc. are mentioned,
Each can be used alone or in combination. Among these organic dibasic acids, preferred for the purpose of the present invention are organic dibasic acids having 6 to 12 carbon atoms in one molecule. If a polyester with less than 6 carbon atoms is used, the amount of ester bonds present in the polyester increases, and the hydrolysis resistance tends to deteriorate, whereas if a polyester with a carbon number of more than 12 is used, the polyester tends to have poor hydrolysis resistance. There is a tendency for the physical properties of flexible urethane foam to deteriorate. Particularly preferred are organic dibasic acids having 8 to 10 carbon atoms per molecule.
【００１４】本発明に用いられるトリオールの具体例と
しては、トリメチロールエタン、トリメチロールプロパ
ン、トリエタノールアミン、及びグリセリン等が挙げら
れ、それぞれ単独もしくは混合して用いられる。本発明
においてはトリオールとして、縮合反応により生成する
ポリエステルポリオールに対して、０．５ 〜１０重量
％使用するのが好ましい。０．５ 重量％未満では軟質
ウレタンフォームの製造時に樹脂の粘度上昇が遅くなり
、良好なフォームを得ることが出来なくなる可能性があ
る。また１０重量％以上では原料としての粘度が著しく
高くなり、製造時に問題になるばかりでなく、得られた
フォームの硬度が著しく高くなってしまう危険性がある
。Specific examples of the triol used in the present invention include trimethylolethane, trimethylolpropane, triethanolamine, and glycerin, each of which may be used alone or in combination. In the present invention, the triol is preferably used in an amount of 0.5 to 10% by weight based on the polyester polyol produced by the condensation reaction. If the amount is less than 0.5% by weight, the viscosity of the resin increases slowly during the production of flexible urethane foam, and it may become impossible to obtain a good foam. Moreover, if it exceeds 10% by weight, the viscosity of the raw material will become extremely high, which will not only cause problems during production, but also pose a risk that the hardness of the obtained foam will become extremely high.
【００１５】有機二塩基酸、ジオール及びトリオールの
併用割合は、特に限定されるものではないが、縮合反応
によって得られるポリエステルポリオールの水酸基価が
３０〜１２０ＫＯＨｍｇ／ｇ となる様に選ばれる。つ
まり、用いる有機二塩基酸、ジオール及びトリオールの
鎖長や配合割合及び反応による重合度を計算し、選定す
ることによって、前記の範囲の水酸基価を有するポリエ
ステルポリオールを得ることができる。この際トリオー
ルについては、縮合反応前のトリオールの量がポリエス
テルポリオールに対し０．５〜１０重量％用いることが
好ましい。The proportion of the organic dibasic acid, diol and triol used in combination is not particularly limited, but is selected so that the hydroxyl value of the polyester polyol obtained by the condensation reaction is from 30 to 120 KOHmg/g. That is, by calculating and selecting the chain lengths, blending ratios, and polymerization degrees of the organic dibasic acids, diols, and triols used, a polyester polyol having a hydroxyl value within the above range can be obtained. In this case, it is preferable to use the triol in an amount of 0.5 to 10% by weight based on the polyester polyol before the condensation reaction.
【００１６】本発明に用いられるポリエステルポリオー
ルの水酸基価は３０〜１２０ＫＯＨｍｇ／ｇであるが、
さらに好ましくは５０〜９０ＫＯＨｍｇ／ｇの範囲のも
のが用いられる。水酸基価が３０ＫＯＨｍｇ／ｇ以下で
あるとポリエステルポリオールの粘度が著しく高くなり
、フォーム製造時の作業性に問題が生じ、また水酸基価
が １２０ＫＯＨｍｇ／ｇ以上であると、フォーム製造
時の樹脂の粘度が不十分で良好なフォームを得ることが
困難になったり、得られたフォームの硬度が著しく硬く
なってしまうといった欠点が生じる。The hydroxyl value of the polyester polyol used in the present invention is 30 to 120 KOHmg/g,
More preferably, a range of 50 to 90 KOHmg/g is used. If the hydroxyl value is 30 KOHmg/g or less, the viscosity of the polyester polyol will become extremely high, causing problems in workability during foam production, and if the hydroxyl value is 120 KOHmg/g or more, the viscosity of the resin during foam production will increase. There are disadvantages that it becomes difficult to obtain an insufficiently good foam, and that the hardness of the obtained foam becomes extremely hard.
【００１７】さらに、本発明に用いられるポリエステル
ポリオールの粘度は２５℃の温度において５０００〜３
００００ＣＰＳ（センチポイズ）の範囲のものが好まし
い。粘度が５０００ｃｐｓ以下であると、軟質ウレタン
フォーム製造時の樹脂の粘度が不十分であり、３０００
０ ＣＰＳ以上であると製造時の作業に労力を要する。
さらに、酸価は１．５ＫＯＨｍｇ／ｇ以下が好ましい。Furthermore, the viscosity of the polyester polyol used in the present invention is 5000 to 3 at a temperature of 25°C.
A range of 0000 CPS (centipoise) is preferable. If the viscosity is less than 5,000 cps, the viscosity of the resin during the production of flexible urethane foam will be insufficient;
If the value is 0 CPS or more, it will require a lot of effort during manufacturing. Furthermore, the acid value is preferably 1.5 KOHmg/g or less.
【００１８】本発明の軟質ウレタンフォームは、有機ポ
リイソシアネートと上記ポリエステルポリオール組成物
とを、触媒、整泡剤、水及びその他の発泡剤、その他適
宜の助剤の存在下で常法により反応させて製造される。The flexible urethane foam of the present invention is obtained by reacting an organic polyisocyanate and the above polyester polyol composition in the presence of a catalyst, a foam stabilizer, water, other blowing agents, and other appropriate auxiliaries in a conventional manner. Manufactured by
【００１９】本発明の軟質ウレタンフォームの製造に用
いられるポリエステルポリオール以外の上記成分として
は、通常用いられるものが使用でき、特に限定されるも
のではない。またその配合量も通常と同程度でよい。The above-mentioned components other than the polyester polyol used in the production of the flexible urethane foam of the present invention may be those commonly used and are not particularly limited. Moreover, the amount added may be the same as usual.
【００２０】例えば、ポリイソシアネート化合物として
は、芳香族ポリイソシアネート（トリレンジイソシアネ
ート、ジフェニルメタンジイソシアネート、及びポリメ
チレンポリフェニルイソシアネート）、脂肪族ポリイソ
シアネート（ヘキサメチレンジイソシアネート）、脂環
式ポリイソシアネート（イソホロンジイソシアネート）
、そしてカルボジイミド変性イソシアネート、及びこれ
らと活性水素化合物との反応による末端イソシアネート
プレポリマーが挙げられる。これらのポリイソシアネー
ト化合物のうち好ましいものは、芳香族ポリイソシアネ
ートである。For example, the polyisocyanate compounds include aromatic polyisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylisocyanate), aliphatic polyisocyanates (hexamethylene diisocyanate), and alicyclic polyisocyanates (isophorone diisocyanate).
, carbodiimide-modified isocyanates, and terminal isocyanate prepolymers obtained by reacting these with active hydrogen compounds. Among these polyisocyanate compounds, aromatic polyisocyanates are preferred.
【００２１】触媒としては、アミン系触媒、有機金属系
触媒が挙げられる。アミン系触媒としては、例えばトリ
エチレンジアミン、トリエチルアミン、トリプロピルア
ミン、Ｎ −メチルモルフォリン、Ｎ −エチルモルフ
ォリン、Ｎ −メチルジエタノールアミン、Ｎ，Ｎ−ジ
メチルジエタノールアミン、ジエチレントリアミン、Ｎ
，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ
，Ｎ，Ｎ’，Ｎ’ −テトラメチルプロピレンジアミン
、Ｎ，Ｎ，Ｎ’，Ｎ’ −テトラメチルヘキサメチレン
ジアミン、Ｎ，Ｎ −ジメチルベンジルアミン、Ｎ，Ｎ
−ジメチルシクロヘキシルアミン、トリエチレンジア
ミンのギ酸塩及びその他の塩等がある。[0021] Examples of the catalyst include amine catalysts and organometallic catalysts. Examples of amine catalysts include triethylenediamine, triethylamine, tripropylamine, N-methylmorpholine, N-ethylmorpholine, N-methyldiethanolamine, N,N-dimethyldiethanolamine, diethylenetriamine, and
, N, N', N'-tetramethylethylenediamine, N
,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylbenzylamine, N,N
-Dimethylcyclohexylamine, triethylenediamine formate and other salts.
【００２２】有機金属系触媒しとては、酢酸錫、オクチ
ル酸錫、オレイン酸錫、ラウリル酸錫、ジブチル錫ジア
セテート、ジブチル錫ジラウレート、ジブチル錫ジクロ
ライド、オクタン酸鉛、ナフテン酸ニッケル、及びナフ
テン酸コバルト等がある。これらの触媒は１種以上の混
合物として使用される。Examples of the organometallic catalyst include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, nickel naphthenate, and naphthene. Cobalt acid etc. These catalysts are used as a mixture of one or more types.
【００２３】発泡剤は、水を必須として、他にトリクロ
ロフルオロメタン、ジクロロフルオロメタン、１，１，
１，２ −テトラフルオロエタン、２，２−ジクロロ−
１，１，１ −トリフルオロエタン、１，１ −ジクロ
ロ−１−フルオロエタン、メチレンクロライド、トリク
ロロエタン、及びｎ−ヘキサン等の１種以上の混合物で
ある。[0023] The blowing agent essentially includes water, and also trichlorofluoromethane, dichlorofluoromethane, 1,1,
1,2-tetrafluoroethane, 2,2-dichloro-
It is a mixture of one or more of 1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, methylene chloride, trichloroethane, n-hexane, and the like.
【００２４】整泡剤は、オルガノポリシロキサン共重合
体等の有機ケイ素系界面活性剤、またはアルキルフェノ
ールのアルキレノキサイドの付加物等の非ケイ素系界面
活性剤の１種以上の混合物として使用される。The foam stabilizer is used as a mixture of one or more organosilicon surfactants such as organopolysiloxane copolymers, or non-silicon surfactants such as alkylenoxide adducts of alkylphenols. Ru.
【００２５】又必要により染料、着色剤等を含有せしめ
ることができる。[0025] If necessary, dyes, coloring agents, etc. can be contained.
【００２６】本発明の軟質ウレタンフォームの製造には
、従来実施されているスラブ成形あるいはモールド成形
等の成形方法が採用できる。[0026]For producing the flexible urethane foam of the present invention, conventional molding methods such as slab molding or mold molding can be employed.
【００２７】[0027]
【実施例】次に本発明を参考例及び実施例に基づき更に
具体的に説明するが、本発明はこれらの実施例に限定さ
れるものではない。以下特に断らない限り、参考例及び
実施例中の部は重量部を示す。EXAMPLES Next, the present invention will be explained in more detail based on reference examples and examples, but the present invention is not limited to these examples. Unless otherwise specified below, parts in Reference Examples and Examples indicate parts by weight.
【００２８】参考例１〜４表１に示した配合表の数字の
各１０倍量（単位ｇ）の原料を用いて以下の手順でポリ
エステルポリオールを合成した。Reference Examples 1 to 4 Polyester polyols were synthesized according to the following procedure using raw materials in an amount ten times (unit: g) the numbers in the recipe shown in Table 1.
【００２９】脱水装置を取付けた２ｌの反応容器に各原
料及びエステル化触媒としてテトラブチルチタネート５
ｐｐｍ を仕込み、容器内の空気を窒素ガスで置換した
後、内容物を十分撹拌してスラリー化しながら昇温し、
副生する水を脱水装置で除去しながら反応温度を ２２
０℃に達せしめた。このまま約２時間反応させ、水の副
生が実質的に終了したことを確認した後、反応温度を
２３０℃まで上げ、反応容器内を徐々に減圧にし、約６
時間反応させた。酸価が１ＫＯＨｍｇ／ｇ以下になった
ことを確認した後、所定の水酸基価に調整を行いポリエ
ステルポリオールを得た。得られたポリエステルポリオ
ールの特性値を表２に示す。In a 2 liter reaction vessel equipped with a dehydrator, each raw material and 5 liters of tetrabutyl titanate were added as an esterification catalyst.
ppm, and after replacing the air in the container with nitrogen gas, the contents are sufficiently stirred to form a slurry while raising the temperature.
While removing by-product water with a dehydrator, the reaction temperature is increased to 22
The temperature was allowed to reach 0°C. Let the reaction continue as it is for about 2 hours, and after confirming that the by-product of water has substantially finished, the reaction temperature is lowered.
The temperature was raised to 230°C, and the pressure inside the reaction vessel was gradually reduced to about 6°C.
Allowed time to react. After confirming that the acid value was 1 KOHmg/g or less, the hydroxyl value was adjusted to a predetermined value to obtain a polyester polyol. Table 2 shows the characteristic values of the obtained polyester polyol.
【００３０】[0030]
【表１】[Table 1]
【００３１】[0031]
【表２】[Table 2]
【００３２】実施例１〜４
参考例１〜４で得られたポリエステルポリオール １０
０部、整泡剤Ｌ−５３２ １．０部、触媒 Ｎ−メチル
モルフォリン ２．０部、及び水 ３．０部をポリビー
カーに秤量し、ラボミキサーを用いて予備撹拌した。次
いで ＴＤＩ−６５をポリオールと水の活性水素に対し
１．０５倍当量添加し、すばやく撹拌した後底辺が１５
ｃｍ角のオープンモールドに注入し、軟質ウレタンフォ
ームを成形した。得られたフォームを６０℃で３０分硬
化し、その後１日放置した。得られたフォームの物性を
表３に示す。Examples 1 to 4 Polyester polyols obtained in Reference Examples 1 to 4 10
0 parts of foam stabilizer L-532, 2.0 parts of catalyst N-methylmorpholine, and 3.0 parts of water were weighed in a poly beaker and preliminarily stirred using a lab mixer. Next, TDI-65 was added in an equivalent amount of 1.05 times the active hydrogen of the polyol and water, and after stirring quickly, the base was 15
The mixture was poured into a cm square open mold to form flexible urethane foam. The resulting foam was cured at 60° C. for 30 minutes and then left for one day. Table 3 shows the physical properties of the obtained foam.
【００３３】耐湿熱劣化試験は、 １２０℃のオートク
レーブ中に９時間及び１８時間、試験片を吊した状態で
放置したものについて機械強度を測定し、未劣化品に対
する強度保持率を求めた。[0033] In the moisture and heat deterioration test, the mechanical strength of the test piece was measured after being left hanging in an autoclave at 120°C for 9 hours and 18 hours, and the strength retention rate was determined relative to the undegraded product.
【００３４】耐アルカリ性試験は、１％の水酸化ナトリ
ウム水溶液中に試験片を７日間及び１４日間、浸漬させ
たものについて湿熱劣化試験と同様に強度保持率を求め
た。[0034] In the alkali resistance test, the strength retention rate was determined in the same manner as the moist heat deterioration test for specimens immersed in a 1% sodium hydroxide aqueous solution for 7 and 14 days.
【００３５】耐酸性試験は、３％の硫酸水溶液中に試験
片を１５日間、浸漬させたものについて湿熱劣化試験と
同様に強度保持率を求めた。In the acid resistance test, a test piece was immersed in a 3% sulfuric acid aqueous solution for 15 days, and the strength retention rate was determined in the same manner as the moist heat deterioration test.
【００３６】各試験結果を表４に示す。Table 4 shows the results of each test.
【００３７】比較例−１
ポリエステルポリオールとして実施例で用いたポリエス
テルポリオールに代えて、アジピン酸、ジエチレングリ
コール、及びトリメチロールプロパンを原料として合成
したポリエステルポリオール（平均官能基数＝２．７５
水酸基価＝６１．０ ＫＯＨｍｇ／ｇ）を使用し、
実施例と同様の方法で軟質ウレタンフォームを成形した
。得られたフォームについて実施例と同様に各試験を行
った。その結果を表３及び表４に示す。Comparative Example 1 A polyester polyol synthesized using adipic acid, diethylene glycol, and trimethylolpropane as raw materials instead of the polyester polyol used in the examples (average number of functional groups = 2.75)
Using hydroxyl value = 61.0 KOHmg/g),
A flexible urethane foam was molded in the same manner as in the example. Each test was conducted on the obtained foam in the same manner as in the examples. The results are shown in Tables 3 and 4.
【００３８】[0038]
【表３】[Table 3]
【００３９】[0039]
【表４】[Table 4]
【００４０】表３及び表４の結果より、本発明品は比較
品と比較して、コア密度、引張強度、伸び率及び圧縮残
留歪の機械強度は同等であるが、耐湿熱劣化性、耐アル
カリ性及び耐酸性は優れていることが判る。According to the results in Tables 3 and 4, the products of the present invention have the same mechanical strength in terms of core density, tensile strength, elongation, and compressive residual strain as compared to the comparative products, but have lower resistance to moist heat deterioration and It can be seen that the alkalinity and acid resistance are excellent.
【００４１】[0041]
【発明の効果】本発明によれば従来のエステル系軟質ウ
レタンフォームと同等の機械強度を有し、さらに耐湿熱
劣化性、耐アルカリ性、及び耐酸性に優れたエステル系
軟質ウレタンフォームを得ることができ、耐加水分解性
を要求される分野への用途に用いることが可能となる。[Effects of the Invention] According to the present invention, it is possible to obtain an ester-based flexible urethane foam that has mechanical strength equivalent to that of conventional ester-based flexible urethane foam and also has excellent moist heat deterioration resistance, alkali resistance, and acid resistance. This makes it possible to use it in fields that require hydrolysis resistance.
Claims (4)
ルの縮合反応によって得られる水酸基価が３０乃至１２
０ＫＯＨｍｇ／ｇであるポリエステルポリオール組成物
であって、該ジオールが分子中に少なくとも１つのメチ
ル基を有し、且つ１級のヒドロキシル基を有することを
特徴とするウレタン用ポリオール組成物。Claim 1: A product with a hydroxyl value of 30 to 12 obtained by a condensation reaction of an organic dibasic acid, a diol, and a triol.
0 KOHmg/g, a polyester polyol composition for urethane, characterized in that the diol has at least one methyl group and a primary hydroxyl group in the molecule.
ステルポリオールに対して０．５乃至１０重量％である
ことを特徴とする請求項１記載のウレタン用ポリオール
組成物。2. The polyol composition for urethane according to claim 1, wherein the amount of triol before the condensation reaction is 0.5 to 10% by weight based on the polyester polyol.
ある請求項１又は２記載のウレタン用ポリオール組成物
。3. The polyol composition for urethane according to claim 1 or 2, wherein the organic dibasic acid has 6 to 12 carbon atoms.
レタン用ポリオール組成物と、有機ポリイソシアネート
から常法により製造された軟質ウレンタフォーム。4. A flexible urethane foam produced by a conventional method from the polyol composition for urethane according to any one of claims 1 to 3 and an organic polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3021030A JPH04258630A (en) | 1991-02-14 | 1991-02-14 | Polyol composition for urethane and flexible urethane foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3021030A JPH04258630A (en) | 1991-02-14 | 1991-02-14 | Polyol composition for urethane and flexible urethane foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04258630A true JPH04258630A (en) | 1992-09-14 |
Family
ID=12043594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3021030A Pending JPH04258630A (en) | 1991-02-14 | 1991-02-14 | Polyol composition for urethane and flexible urethane foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04258630A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303669B1 (en) | 1996-05-09 | 2001-10-16 | Inoac Corporation | Flexible polyurethane foam |
| JP2006233021A (en) * | 2005-02-25 | 2006-09-07 | Nippon Polyurethane Ind Co Ltd | Manufacturing process of flexible polyurethane foam |
| JP2007177172A (en) * | 2005-12-28 | 2007-07-12 | Kawasaki Kasei Chem Ltd | Polyester polyol, composition for isocyanurate-modified polyurethane foam using the same, and isocyanurate-modified polyurethane foam |
| JP2011213924A (en) * | 2010-03-31 | 2011-10-27 | Nhk Spring Co Ltd | Foamed polyurethane sheet |
-
1991
- 1991-02-14 JP JP3021030A patent/JPH04258630A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303669B1 (en) | 1996-05-09 | 2001-10-16 | Inoac Corporation | Flexible polyurethane foam |
| JP2006233021A (en) * | 2005-02-25 | 2006-09-07 | Nippon Polyurethane Ind Co Ltd | Manufacturing process of flexible polyurethane foam |
| JP2007177172A (en) * | 2005-12-28 | 2007-07-12 | Kawasaki Kasei Chem Ltd | Polyester polyol, composition for isocyanurate-modified polyurethane foam using the same, and isocyanurate-modified polyurethane foam |
| JP2011213924A (en) * | 2010-03-31 | 2011-10-27 | Nhk Spring Co Ltd | Foamed polyurethane sheet |
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