JPH02160820A - Polyurethane resin composition - Google Patents
Polyurethane resin compositionInfo
- Publication number
- JPH02160820A JPH02160820A JP63315054A JP31505488A JPH02160820A JP H02160820 A JPH02160820 A JP H02160820A JP 63315054 A JP63315054 A JP 63315054A JP 31505488 A JP31505488 A JP 31505488A JP H02160820 A JPH02160820 A JP H02160820A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- polyhydroxy compound
- acid
- compound
- diol
- 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.)
- Granted
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims description 46
- 239000011342 resin composition Substances 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- -1 alicyclic hydrocarbon diol Chemical class 0.000 claims abstract description 21
- 150000002009 diols Chemical class 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 11
- 239000004417 polycarbonate Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 23
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005299 abrasion Methods 0.000 abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001361 adipic acid Substances 0.000 abstract description 4
- 235000011037 adipic acid Nutrition 0.000 abstract description 4
- 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 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 230000032050 esterification Effects 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- QJLYVCMEBJYLQD-UHFFFAOYSA-N 4-(1-hydroxyethyl)cyclohexan-1-ol Chemical compound CC(O)C1CCC(O)CC1 QJLYVCMEBJYLQD-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 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
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 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
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- GVVKYLZQTBWUBX-UHFFFAOYSA-N 3-(1-hydroxyethyl)cyclohexan-1-ol Chemical compound CC(O)C1CCCC(O)C1 GVVKYLZQTBWUBX-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YRGIDPVCOKABLX-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1(CO)CO YRGIDPVCOKABLX-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 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
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-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
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明（２、特定の線状ポリヒドロキシ化合物を用いた
新規なポリウレタン樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention (2) relates to a novel polyurethane resin composition using a specific linear polyhydroxy compound.
更に詳しくは、機械的強度、耐熱性、耐加水分解性、Ｍ
球性、耐摩耗性に優れたポリウレタン樹脂組成物に関す
る。More specifically, mechanical strength, heat resistance, hydrolysis resistance, M
This invention relates to a polyurethane resin composition with excellent sphericity and abrasion resistance.
高分子量の機状ノヒドロキシ化合物、有機ソイソシアネ
ート及び必要に応じイソシアネート基と反応する水素原
子を少なくとも２個有する低分子量化合物から成るポリ
ウレタン樹脂組成分はよく知られている。高分子量の線
状ヅヒドロキシ化合物としては、主としてヒドロキシル
基を有するジカルゲン酸ポリエステル、一般にアノピン
酸ポリエステルが使用される。アノピン酸ポリエステル
から得られるポリウレタン樹脂は、一般に優れた機械的
性質を有するが、アジピｙ酸ポリエステル中に存在する
グリコール成分によって多少の差はあるものの耐加水分
解性に劣る欠点を有する。アノピン酸ポリエステルに代
えてカ！ロラクトンＯ開環重合体が使用されたポリウレ
タン樹脂も提供されるが、耐加水分解に若干の改善が見
られるが充分満足し得るものではない。又、ポリウレタ
ン樹脂の耐加水分解性を改善する為にヒドロキシル基を
有するポリエーテル、一般にナト２ヒドロフランを開環
重合したポリテトラメチレンエーテルゾオールが高分子
の線状ジヒドロキシ化合物として使用されている。しか
しながら、このＩリテトラメチレンエーテルゾオール系
ポリウレタン樹脂は、機械的強度、耐熱性、耐摩耗性に
劣る欠点がある。ポリウレタン樹脂の機械的強度を保持
し耐加水分解性を改善する為に、例えばヒドロキシル基
を有する１、６−へキサメチレンジオール−ポリカーボ
ネートを高分子量の線状ジヒドロキシ化合物として使用
することが提案されているが、このＩリウレタン樹脂は
耐摩性に劣る欠点を有する。Polyurethane resin compositions comprising high molecular weight functional hydroxy compounds, organic isocyanates, and optionally low molecular weight compounds having at least two hydrogen atoms that react with isocyanate groups are well known. As the high molecular weight linear dihydroxy compound, dicargenic acid polyesters having hydroxyl groups, generally anopic acid polyesters, are used. Polyurethane resins obtained from anopic acid polyesters generally have excellent mechanical properties, but have the disadvantage of poor hydrolysis resistance, although this varies to some extent depending on the glycol component present in the adipic acid polyester. Instead of anopic acid polyester! Polyurethane resins using rolactone O ring-opening polymers are also provided, but although some improvement in hydrolysis resistance is seen, they are not fully satisfactory. Further, in order to improve the hydrolysis resistance of polyurethane resins, polyethers having hydroxyl groups, generally polytetramethylene ether zool obtained by ring-opening polymerization of nato-2hydrofuran, are used as polymeric linear dihydroxy compounds. However, this I-ritetramethylene ether zool polyurethane resin has the disadvantage of being inferior in mechanical strength, heat resistance, and abrasion resistance. In order to maintain the mechanical strength and improve the hydrolysis resistance of polyurethane resins, it has been proposed to use, for example, 1,6-hexamethylene diol-polycarbonate having hydroxyl groups as a high molecular weight linear dihydroxy compound. However, this I-urethane resin has a drawback of poor wear resistance.
又、１，６−へキサメチレ／ジオールＩリカーがネート
とアノピン酸ポリエステルとの混合物を線状ヒドロキシ
化合物として使用したポリウレタン樹脂も提案されてい
るが、耐寒性に若干の改善がみられる程度で、耐加水分
解性が極端に低下し充分満足し得るものではなか。Polyurethane resins have also been proposed in which a mixture of 1,6-hexamethylene/diol I liquor and anopic acid polyesters are used as the linear hydroxy compound, but the results show only a slight improvement in cold resistance. The hydrolysis resistance was extremely reduced and was not completely satisfactory.
本発明者らは、かかる欠点を改善し、機械的強度、耐熱
性、耐加水分解性、耐寒性、耐摩耗性のいずれの性質も
優れたポリウレタン樹脂組成物を提供することを目的と
して鋭意研究を重ねた結果、本発明を完成するに至った
。The present inventors have conducted extensive research with the aim of improving these drawbacks and providing a polyurethane resin composition that has excellent mechanical strength, heat resistance, hydrolysis resistance, cold resistance, and abrasion resistance. As a result of repeated efforts, the present invention was completed.
即ち、本発明は、線状ポリヒドロキシ化合物、有機ゾイ
ソクアナート及び必要に応じイソシアネート基と反応す
る水素原子を少なくとも２個有する低分子化合物から成
るポリウレタン樹脂組成物において、線状ポリヒドロキ
シ化合物として、ヒドロキシル基を有する脂肪族及び／
又は脂環族炭化水素ジオールのポリカーぎネートジオー
ルをアルコール成分の少なくとも一成分として得られる
ポリエステルポリカーゴネートポリオールを用イること
を特徴とするポリウレタン樹脂組成物を提供するもので
ある。That is, the present invention provides a polyurethane resin composition comprising a linear polyhydroxy compound, an organic zoisoquanate, and optionally a low molecular weight compound having at least two hydrogen atoms that reacts with an isocyanate group. aliphatic and/or
Alternatively, the present invention provides a polyurethane resin composition characterized in that a polyester polycargonate polyol obtained by using a polycarginate diol of an alicyclic hydrocarbon diol as at least one component of the alcohol component is used.
本発明に使用される線状ポリヒドロキシ化合物は、ポリ
エステルポリカー−ネートポリオールであ）、好ましく
は分子量１４５以上のヒドロキシル基を有する脂肪族及
び／又は脂環族炭化水素ジオールのポリカー？ネートを
単独でアルコール成分として用いるかもしくはこれとヒ
ドロキシ基を少なくとも２個有する低分子ポリヒドロキ
シ化合物を併用したものをアルコール成分とし、他方脂
肪族ノカルボン酸、芳香族ノカルがン酸及びそれらの無
水物、各種誘導体のうち少なくとも１つを酸成分として
、縮合することによって得られるものである。この数平
均分子量は、好ましくは５００〜１へ００Ω、よシ好ま
しくは５００〜５０００である・
ヒドロキシル基を有する脂肪族及び／又は脂環族炭化水
素ジオールの一すカーゴネートは、公知の方法で製造さ
れる。例えば、脂肪族及び／又は脂環族炭化水素ジオー
ルと炭酸シアリル又は炭酸ノアルキルを減圧反応するこ
とによって或は脂肪族及び／又は脂環族炭化水素ジオー
ルと環状のフルキレンカーボネートを減圧反応するとと
Ｋよって得られる。The linear polyhydroxy compound used in the present invention is a polyester polycarbonate polyol), preferably a polycarbonate of aliphatic and/or alicyclic hydrocarbon diol having a hydroxyl group with a molecular weight of 145 or more. The alcohol component is analyte alone or a combination of this and a low-molecular polyhydroxy compound having at least two hydroxy groups, and aliphatic nocarboxylic acids, aromatic nocarboxylic acids, and their anhydrides. , is obtained by condensing at least one of various derivatives as an acid component. The number average molecular weight is preferably from 500 to 100Ω, more preferably from 500 to 5000. The monocarponate of the aliphatic and/or alicyclic hydrocarbon diol having a hydroxyl group is produced by a known method. be done. For example, by reacting an aliphatic and/or alicyclic hydrocarbon diol with a sialyl carbonate or a noalkyl carbonate under reduced pressure, or by reacting an aliphatic and/or alicyclic hydrocarbon diol with a cyclic fullkylene carbonate under reduced pressure, K Therefore, it is obtained.
前記炭酸ノアリル（ノアリルカー？ネート）とは、例え
ばジフェニルカーボネート、ビスクロロフェニルカー２
ネート、ジグチルカーボネート、ゾトルイルカーゴネー
ト等が挙げられる。又炭酸ジアルキル（ノアルギルカー
ポネート）とは、例えば、ジメチルカーフネート、ジエ
チルカーがネート、ノプロピルカーゴネート、ソイソグ
ロピルカーがネート、ジグチルカーボネート等が挙げら
れる。更に前記環状のフルキレンカーボネートとは、例
えばエテレンカー〆ネート、トリメチレンカーゲネート
、ナト２メチレンカー？ネート、１．２−グロピレンカ
ーゴネート、１．２−プテレ／カー？ネート、１．３−
ｆチレンカーゴネート、２．３− ｆチレンカー〆ネ
ート、１．２−ベンチレンカーがネート、１．３−ベン
チレンカーボネート、１．４−ベンチレンカー’ ＊
） 、Ｌ５− ペンチレンカーポネー）、２．３−ベ
ンチレンカー＆ネ−）、２，４−ペンテレ／カーボネー
ト等が挙げられる。The above-mentioned noallyl carbonate (noallyl carbonate) is, for example, diphenyl carbonate, bischlorophenyl carbonate, etc.
carbonate, digtyl carbonate, zotolyl carbonate, and the like. Examples of the dialkyl carbonate (noargyl carbonate) include dimethyl carbonate, diethyl carbonate, nopropyl carbonate, soisoglopyl carbonate, digtyl carbonate, and the like. Further, the cyclic fullylene carbonate includes, for example, ethylene carnate, trimethylene cargenate, and di-methylene carbonate. nate, 1.2-glopyrene cargonate, 1.2-putele/car? Nate, 1.3-
f-tylene carbonate, 2.3-f-tylene cartonate, 1.2-benthylene carboxylate, 1.3-benthylene carbonate, 1.4-benthylene cartonate *
), L5-pentylene carbonate), 2,3-pentylene carbonate), 2,4-pentele/carbonate, and the like.
本発明に用いる脂肪族炭化水素ジオールとしては炭素数
が４〜１２のものが好ましく、例えば１．３−ブタンジ
オール、１．４−ブタンジオール、１．５−ペンタンジ
オール、１．６−へ中サンジオール、１，７−ヘグタン
ジオール、ｌ、８−オクタンジオール、工、１０−デカ
ンジオール、２．２−ツメチル−１，３−グロノ１ンジ
オール、２−エチル−１，６−ヘキサ／ジオール、２，
２．４−トリメチル−１，６−ヘキサ／ジオールなどが
挙げられ、脂環族炭化水素ジオールとしては、炭素数が
４〜１２のものが好ましく、例えば１．３−シクロヘキ
サンジオール、１．４−シクロヘキサンジオール、１．
３ツメチロールシクロヘキサン、１．４−ノメチロール
ンクロへ中サン、１．３−ノとドロキシエチルシクロヘ
キサン、１．４−ジヒドロキシエチルシクロヘキサンな
どが挙げられ、単一のジオールでも２橿以上のジオール
の混合物でもよい。The aliphatic hydrocarbon diol used in the present invention preferably has 4 to 12 carbon atoms, such as 1.3-butanediol, 1.4-butanediol, 1.5-pentanediol, 1.6-carbon diol, etc. Sandiol, 1,7-hegtanediol, 1,8-octanediol, 10-decanediol, 2,2-methyl-1,3-glono1diol, 2-ethyl-1,6-hex/diol, 2 ，
Examples include 2,4-trimethyl-1,6-hexa/diol, and the alicyclic hydrocarbon diol preferably has 4 to 12 carbon atoms, such as 1,3-cyclohexanediol, 1,4- Cyclohexanediol, 1.
Examples include 3-methylolcyclohexane, 1,4-nomethylolcyclohexane, 1,3-no-droxyethylcyclohexane, and 1,4-dihydroxyethylcyclohexane. A mixture may also be used.
ヒドロキシル基を有する脂肪族及び／又は脂環族炭化水
素ソオールポリカー？ネートの分子量は、反応する脂肪
族及び／又は脂環族炭化水素ジオールと炭酸ジアリル又
は炭酸シアル中ル或はアルΦレンカーゴネートとの反応
モル比によって制御される。そのモル比は、ジオール：
カー♂ネート■１：９〜９：１であるのが望ましい。又
その分子量は、３００〜４． ＯＯＯが好ましい。Aliphatic and/or alicyclic hydrocarbon sool polycarbons with hydroxyl groups? The molecular weight of the nate is controlled by the reaction molar ratio of the reacting aliphatic and/or cycloaliphatic hydrocarbon diol and the diallyl or sialyl carbonate or alkyl carbonate. The molar ratio is diol:
Carnate ■ It is desirable that the ratio is 1:9 to 9:1. Moreover, its molecular weight is 300 to 4. OOO is preferred.
本発明のアルコール成分として用いるヒドロキシル基を
少なくとも２個有する低分子ポリヒドロキシ化合物とし
ては、１，２グリコールを除く、宮能基数２〜４で、炭
素数３〜１２のものが好ましく、 Ｎ、ｔハ１，３−７
’ロノ々ンジオール１，３−ブタンジオール、１．４−
ｆタンジオール、１．５−ペンタ／ジオール、１，６
−ヘキサ／ジオール、１．７−へ！タンジオール、ｌ、
８−オクタンジオール、１．１０−デカツジオール、２
，２−ツメチル−１，３−ｆロノ臂ンゾオール、２，２
．４− ）リフチル−１，６−ヘキサンジオール、ビス
ヒドロキシエトキシベンゼン、Ｐ−キシレングリコール
、ネオペンチルグリコール、１，３−シクロヘキサンジ
オール、１，４−シクロヘキサンジオール、１．３−ジ
メチロールシクロヘキサン、１，４−ツメチロールシク
ロヘキサン、１．３−ジヒドロキシエチルシクロヘキサ
ン、１，４−ジヒドロキシエチルシクロヘキサン、グリ
セリン、トリメチロールグロノ量ン、ヘキサントリオー
ル、トリエタノールアミン、ペンタエリスリ） −ルな
どが挙げられ、これらは単独もしくは二種以上の混合物
として用いてもよい。ヒドロキシル基を少なくとも２個
有する低分子ポリヒドロキシ化合物として１．２−グリ
コール例えば、エチレングリコールを用いた場合ポリエ
ステルポリカー？ネートポリオールをエステル化によシ
製造する時、エチレンカーゲネートが多量に副生じて、
良好なポリウレタン樹脂原料が得られない。The low-molecular polyhydroxy compound having at least two hydroxyl groups used as the alcohol component of the present invention is preferably one having 2 to 4 functional groups and 3 to 12 carbon atoms, excluding 1,2 glycol, N, t Ha1, 3-7
'Lononanediol 1,3-butanediol, 1,4-
f tanediol, 1.5-penta/diol, 1,6
-Hexa/diol, to 1.7-! tandiol, l,
8-octanediol, 1.10-decatudiol, 2
,2-methyl-1,3-f lonozool, 2,2
．． 4-) riftyl-1,6-hexanediol, bishydroxyethoxybenzene, P-xylene glycol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-dimethylolcyclohexane, 1, Examples include 4-tumethylolcyclohexane, 1,3-dihydroxyethylcyclohexane, 1,4-dihydroxyethylcyclohexane, glycerin, trimethylolcyclohexane, hexanetriol, triethanolamine, pentaerythrol, etc., and these may be used alone. Alternatively, they may be used as a mixture of two or more. When 1,2-glycol, for example, ethylene glycol, is used as a low-molecular polyhydroxy compound having at least two hydroxyl groups, is it a polyester polycarbonate? When producing ester polyol by esterification, a large amount of ethylene cargenate is produced as a by-product.
Good polyurethane resin raw materials cannot be obtained.
本発明に用いる脂肪族ノカルーン酸としては、炭系数３
〜１４のものが好ましく、例えばマロン酸、コハク酸、
グルタル改、アノビン酸、ピメリン酸、スペリン歇、ア
ゼライン酸、セパシン酸、１．９−ノナメチレンカル？
ン酸、１．１０−デカメチレンヅ力ルゴン酸、１．１１
−ウンデカメチレンジカルダン峻、１．１２−ドデカメ
チレンゾカル♂ン酸などが挙げられる。又、芳香族ゾカ
ル？ン酸としては例えばオルソフタル酸、イソフタル酸
、テレフタル哉、ナフタレンジカル？ン酸、アントラセ
ンノカルボン酸もＬ＜はフェナンスレンジカルがン酸が
あるが、それらの無水物あるいは各種誘導体も使用出来
ることは熱論であシ、これらは単独もしくは二種以上の
混合物として用いてもよい。The aliphatic nocalonic acid used in the present invention has a carbon number of 3.
-14 are preferred, such as malonic acid, succinic acid,
Glutaric acid, anovic acid, pimelic acid, sperinic acid, azelaic acid, cepacic acid, 1.9-nonamethylenecal?
acid, 1.10-decamethyleneduric acid, 1.11
-undecamethylene dicardanate, 1,12-dodecamethylene dicarboxylic acid, and the like. Also, aromatic Zocal? Examples of acids include orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedical. For L<, phenanthlene dicarboxylic acid and anthracenocarboxylic acid include phenanthlene dicarboxylic acid, but it is a matter of course that their anhydrides and various derivatives can also be used, and these can be used alone or as a mixture of two or more. You can.
本発明の線状ポリヒドロキシ化合物に使用するアルコー
ル成分中の、ヒドロキシ基を有する脂肪族及パは脂環族
炭化水素ジオールの一すカーポネートジオールとヒドロ
キシ基を少なくとも２個有する低分子ポリヒドロキシ化
合物の混合割合は特に限定するものではないが、％に好
ましくは、９／１〜２／８の重量割合で用いられる。In the alcohol component used in the linear polyhydroxy compound of the present invention, an aliphatic compound having a hydroxy group and a monocarponate diol having an alicyclic hydrocarbon diol and a low molecular weight polyhydroxy compound having at least two hydroxy groups Although the mixing ratio is not particularly limited, it is preferably used in a weight ratio of 9/1 to 2/8.
本発明Ｏ線状ポリヒドロキシ化合物に使用される酸成分
とアルコール成分との割合は、アルコール成分及び酸成
分の遣類と線状ポリヒドロキシ化合物の分子量によｒ決
定され、特に制限するものではない。The ratio of the acid component and alcohol component used in the linear polyhydroxy compound of the present invention is determined by the type of alcohol component and acid component and the molecular weight of the linear polyhydroxy compound, and is not particularly limited. .
以上に揚げられたような諸原料を用いて前記線状ポリヒ
ドロキシ化合物を！４ｊＢするには、真空および／オた
は触媒を用いて行なう従来公知のエステル化技術が採用
できるものであシ、そのうちでも代表的なものとしては
、常圧下にグリコール類とゾカル？ン酸類とを反応させ
る方法とか、真空下でエステル化せしめる方法とか、ト
ルエンの如き不活性溶剤の存在下にエステル化を行なっ
九のち、縮合水と溶剤とを共沸させて反応系外に除去せ
しめる方法などがある。The linear polyhydroxy compound is made using the raw materials listed above! In order to obtain 4jB, conventionally known esterification techniques using vacuum and/or catalysts can be employed. Among these, a representative one is the esterification of glycols and zocal? under normal pressure. esterification in the presence of an inert solvent such as toluene, and then azeotroping the condensed water and the solvent to remove it from the reaction system. There are ways to force it.
触媒の存在しない系で反応を行なうことも熱論可能では
あるが、通常は、エステル化反応を円滑に進行させるた
めに、無＠酸または有機酸類；Ｌｌ ＋ Ｎａ ＋ Ｋ
＊ Ｒｂ ｒ Ｃａ ＋ Ｍｇ ｔ Ｓｒ 、 Ｚｎ
、 Ａｔｌ’ｒｉ ＊ Ｖ ｗ Ｃｒ ＋ Ｍｎ 、
Ｆ＊ 、 Ｃｏ 、 Ｎｉ ＋ Ｃｕ 、 Ｚｒ ｒ
Ｐｄ ｔ Ｓｎ ｔ Ｓｂもしくはｐｂなどの金属の塩
化物、は化物、水酸化物ｔたは酢酸、シ、つ酸、オクチ
ル酸、ラウリル酸もしくはナフテン葭などの脂肪酸項部
；ナトリウム・メチラート、ナトリウム・エチラート、
アルミニウム・トリイソプロポキサイド、イソプロピル
・チタネートもしくはｎ−ブチル・チタネートなどのア
ルコラード類；ナトリウム・フェノラートなどの７エノ
ラート類１あるいはＡｔ ＊ Ｔｌ ＋ Ｚｎ ９ Ｓ
ｎ ＋ Ｚｒもしくはｐｂなどの金属のその他の有機金
属化合物などの如き、通常のエステル化用およびエステ
ル交換用に使用されているすべての触媒を用いて行なう
のが望ましい。Although it is theoretically possible to carry out the reaction in a system without a catalyst, it is usually carried out without an acid or with an organic acid; Ll + Na + K in order to make the esterification reaction proceed smoothly.
* Rbr Ca + Mg t Sr, Zn
, Atl'ri * V w Cr + Mn ,
F*, Co, Ni + Cu, Zr r
Chlorides, halides, hydroxides of metals such as Pd t Sn t Sb or Pb or fatty acids such as acetic acid, citric acid, octylic acid, lauric acid or naphthenic acid; sodium methylate, sodium methylate, Ethilate,
Alcolades such as aluminum triisopropoxide, isopropyl titanate or n-butyl titanate; 7enolates such as sodium phenolate 1 or At*Tl+Zn9S
It is preferred to work with all the catalysts conventionally used for esterification and transesterification, such as n + Zr or other organometallic compounds of metals such as pb.
そのさいの触媒の使用量は前記ポリエステルジオール調
製用諸原料総量に対して０．００００１〜約５重′Ｊｊ
ｋ俤なる範囲内、好ましくは０．００１〜２７ＩＬ′ｊ
ｋ％なる範囲内が適当である。そして、このさいの反応
温度は通常、１００〜２５０℃の範囲である。The amount of catalyst used at that time is 0.00001 to about 5 parts by weight based on the total amount of raw materials for preparing the polyester diol.
within a range of k, preferably 0.001 to 27 IL'j
A range of k% is appropriate. The reaction temperature at this time is usually in the range of 100 to 250°C.
本発明に使用される有機ジイソシアネートとしては、脂
肪族、脂環族、及び芳香族ジイソシアネート例えば、テ
トラメチレンツイソシアネート、ヘキサメチレンジイソ
シアネート、リレンジイソシアネート、１．４−シクロ
ヘキサノイソシアネート、インホロンジイソシアネート
、１−メチル−２，４−シクロヘキサンジイソシアネー
ト、１−メチル−２，６−シクロヘキサンジイソシアネ
ート、キシリレンジイソシアネー）、４．４’−ジフェ
ニルノイソシアネート、２．４−）リレン・ジイソシア
ネート、２．６− ）リレンジイソシアネート、ｍ−フ
ェニレンジイソシアネート、ｐ−フェニレンジイソシア
ネート、４．４’−ソフェニルメタンノイソシアネート
、１．５−ナフチレンツイソシアネートなどの単独或は
２櫨以上の混合物が挙げられる。The organic diisocyanates used in the present invention include aliphatic, cycloaliphatic, and aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, lylene diisocyanate, 1,4-cyclohexanoisocyanate, inphorone diisocyanate, 1- Methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, xylylene diisocyanate), 4,4'-diphenylnoisocyanate, 2.4-) rylene diisocyanate, 2.6-) rylene Examples include diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-sophenylmethanoisocyanate, 1,5-naphthylene diisocyanate, etc. alone or in a mixture of two or more.
本発明に必要に応じて便用されるイソシアネートと反応
する水素原子を少なくとも２個有する低分子化合物とし
ては、通常ポリオール及びポリアミン例ｔ ハ、エチレ
ングリコール、ノエチレングリコール、１，３−プロピ
レングリコール、１，４−ブチレングリコール、１，５
−ペンタンジオール、２．２−ジメチル−１，３−グロ
パンジオール、１．６−ヘキサンジオール、１，４−シ
クロヘキサンジオール、１．４−ツメチロールヘキサン
、１，４−ノヒドロキシエチルシクロヘキサン、１，４
−ジヒドロキシニブルベンゼン、 ４２４’−メチレン
ビス（ヒドロキシエチルベンゼン）、グリセリン、トリ
メチロールグロノ９ノ、ペンタエリスリトール、Ｎ−メ
チルエタノールアミン、Ｎ−エチルエタノールアミン、
エチレンノアミン、１，３−ソアミノプロｉ４ノ、ヘキ
サメチレンジアミン、 ４．４’−ソフェニルメタンノ
アミン、メチレンビス（Ｏ−クロロアニリン）、ヒドラ
ジン、ノ辛ベラノン、 Ｎ、Ｎ’−ソアミノピベラノン
、水などの単独或は２ＰＪ以上の混合物が挙げられる。Examples of low-molecular compounds having at least two hydrogen atoms that react with isocyanates that are conveniently used in the present invention as needed include polyols and polyamines (c), ethylene glycol, noethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5
-pentanediol, 2,2-dimethyl-1,3-gropanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-tumethylolhexane, 1,4-nohydroxyethylcyclohexane, 1 ,4
-dihydroxynibblebenzene, 424'-methylenebis(hydroxyethylbenzene), glycerin, trimethylolglono9no, pentaerythritol, N-methylethanolamine, N-ethylethanolamine,
Ethylenenoamine, 1,3-soaminoproi4no, hexamethylene diamine, 4,4'-sophenylmethanoamine, methylenebis(O-chloroaniline), hydrazine, spicy veranone, N,N'-soaminopivera Examples include non-alcoholic acid, water, etc. alone, or a mixture of 2 PJ or more.
本発明のポリウレタン樹脂組成物は、公知の方法でポリ
ウレタン樹脂に製造される。例えば無溶剤系のポリウレ
タン樹脂を得るには、線状ポリヒドロキシ化合物と必要
に応じ使用されるイソシアネート基と反応する水素原子
を少なくとも２１’［ｉ！ｉｆ有する低分子化合物とを
混合しこれに有機ジイソシアネートを混合反応するか或
はイソシアネート基と反応する水素原子を少なくとも２
個有する低分子化合物を使用する場合には、線状ポリヒ
ドロキシ化合物と有機ジイソシアネートを反応して得ら
れるイソシアネート基を有するプレポリマーを得て更に
イソシアネート基と反応する水素原子を２個以上有する
低分子化合物を混合反応することによって得られる。更
に有機溶剤溶液のポリウレタン樹脂を得るには、線状ポ
リヒドロキシ化合物をイソシアネート基に対して不活性
の有機溶剤例えば、ツメチルフォルムアミド、ジエチル
フォルムアミド、ツメチルアセトアミド、ツメチルスル
ホキシド、テトラヒドロフラン、メチルエチルケトン、
メチルイソブチルケトン、酢酸メチル、酢酸エチル、酢
酸ブチル、トルエン、キシレンの単独或は２檀以上の混
合物に溶解し、必要に応じ使用されるイソシアネート基
と反応する水素原子を少なくとも２個有する低分子化合
物を混合した後有機ツイソシアネートを混合反応するか
、或はイソシアネート基と反応する水素原子を少なくと
も２個有する低分子化合物を使用する場合には、線状ポ
リヒドロキシ化合物を前記有機溶剤に浴解し有機ジイソ
シアネートと反応した後、イソシアネート基と反応する
水素原子を少なくとも２個有する低分子化合物を反応す
ることＫよりて得られる。The polyurethane resin composition of the present invention is manufactured into a polyurethane resin by a known method. For example, in order to obtain a solvent-free polyurethane resin, at least 21' [i! If the organic diisocyanate is mixed and reacted with the low molecular compound having the
When using a low-molecular compound having a linear polyhydroxy compound and an organic diisocyanate, a prepolymer having an isocyanate group is obtained by reacting a linear polyhydroxy compound with an organic diisocyanate, and then a low-molecular compound having two or more hydrogen atoms that reacts with the isocyanate group is obtained. Obtained by mixing and reacting compounds. Furthermore, to obtain a polyurethane resin in an organic solvent solution, the linear polyhydroxy compound can be dissolved in an organic solvent inert toward isocyanate groups, such as trimethylformamide, diethylformamide, trimethylacetamide, trimethylsulfoxide, tetrahydrofuran, methyl ethyl ketone. ,
A low-molecular compound that is dissolved in methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, toluene, or xylene alone or in a mixture of two or more, and has at least two hydrogen atoms that react with the isocyanate group used as necessary. When using a low molecular weight compound having at least two hydrogen atoms that react with isocyanate groups, the linear polyhydroxy compound is bath-dissolved in the organic solvent. It can be obtained by reacting with an organic diisocyanate and then reacting with a low molecular weight compound having at least two hydrogen atoms that react with the isocyanate group.
又、水分散液のポリウレタン樹脂として製造することも
できる。It can also be produced as an aqueous dispersion of polyurethane resin.
有機ジイソシアネートの使用量は得られる７ポリウレタ
ン樹脂の目的とする分子量によって限定されるものでは
ないが、エラストマーとして使用される場合は、通常線
状ポリヒドロキシ化合物と必要に応じて使用されるイソ
シアネート基と反応する水素原子を少なくとも２個有す
る低分子化合物との合計に対して化学理論的に０．９５
〜１．２である。従って本発明のポリウレタン樹脂は、
分子の末端がヒドロキシル基であってもイソシアネート
基であってもよく、またイソシアネート基と反応する水
素原子を少なくとも３個有する低分子化合物を使用する
ことによシ、或はウレタン結合及び／又はフレア結合と
イソシアネート基との反応により一部架橋構造を有して
もよい。また、本発明のポリウレタン樹脂を製造後、イ
ソシアネート基と反応する水素原子を少なくとも２個有
する低分子化合物はイソシアネート基を少なくとも２個
有する低分子化合物例えば、トリレンジイソシアネート
３壬ルトトリメチロールプロノ！フ１モルとの反応生成
物もしくは・Ｉ−オキシドと更に反応して高分子量化も
しくは網状化することができる。The amount of organic diisocyanate used is not limited by the desired molecular weight of the obtained 7 polyurethane resin, but when used as an elastomer, it is usually a linear polyhydroxy compound and an isocyanate group used as necessary. Chemically theoretically 0.95 with respect to the total of low molecular weight compounds having at least two reacting hydrogen atoms.
~1.2. Therefore, the polyurethane resin of the present invention is
The end of the molecule may be a hydroxyl group or an isocyanate group, and by using a low-molecular compound having at least three hydrogen atoms that react with the isocyanate group, or by forming a urethane bond and/or a flare. It may have a partially crosslinked structure due to the reaction between the bond and the isocyanate group. Further, after producing the polyurethane resin of the present invention, the low molecular compound having at least two hydrogen atoms that reacts with an isocyanate group is a low molecular compound having at least two isocyanate groups, such as tolylene diisocyanate, trimethylolprono! It is possible to further react with a reaction product with 1 mole of fluorine or .I-oxide to increase the molecular weight or form a network.
本発明のポリウレタン樹脂は、使用に際し各種添加剤例
えば着色剤、充填剤、安定剤（熱安定剤等）、紫外線吸
収剤、酸化防止剤、粘着防止剤、難燃剤、老化防止剤等
を添加混合することができる。When the polyurethane resin of the present invention is used, various additives such as colorants, fillers, stabilizers (thermal stabilizers, etc.), ultraviolet absorbers, antioxidants, anti-blocking agents, flame retardants, anti-aging agents, etc. are added and mixed. can do.
又本発明のポリウレタン樹脂には、各種重合体例えば、
ポリ塩化ビニル、塩化ビニルと他のビニル系重合性モノ
マーとの共重合体、アクリロニトリル−スチレン共重合
体、アクリロニトリル−ブタツエン共重合体、スチレン
−ブタノエン、ｔ１４合体、アクリロニトリル−ゲタツ
エン−スチレン共重合体、ニトロセルロース、セルロー
スアセテート、セルロースアテ−ト、セルロースアセテ
ートブチレート、他のポリウレタン樹脂例えば、ラクト
ン成分を含有しないポリ刀−ボネートジオールから得ら
れるポリウレタン樹脂、ポリエステルジオールから得ら
れるポリエステル系ポリウレタン樹脂、ポリエステル樹
脂、エポキシ樹脂、ビニルエステル樹脂、不飽和ポリエ
ステル樹脂、オレフィン系樹脂、フッ素樹脂、ポリアセ
タール樹脂、ポリカーボネート樹脂、ポリアミド樹脂等
が挙げられる。In addition, the polyurethane resin of the present invention includes various polymers such as
Polyvinyl chloride, copolymers of vinyl chloride and other vinyl polymerizable monomers, acrylonitrile-styrene copolymers, acrylonitrile-butatsuene copolymers, styrene-butanoene, t14 polymers, acrylonitrile-getatsuene-styrene copolymers, Nitrocellulose, cellulose acetate, cellulose acetate, cellulose acetate butyrate, other polyurethane resins, such as polyurethane resins obtained from polybonate diols containing no lactone component, polyester polyurethane resins obtained from polyester diols, polyester resins , epoxy resins, vinyl ester resins, unsaturated polyester resins, olefin resins, fluororesins, polyacetal resins, polycarbonate resins, polyamide resins, and the like.
本発明のポリウレタン樹脂は優れた機械的強度、耐熱性
、耐加水分解性、耐寒性、耐摩耗性を有することから、
機械部品、自動車部品、チェーン、ベルト類、フィルム
、ホース、チューブ、車輪、歯車、靴底、繊維被覆、を
線被覆、合成皮革素材、バイングー、接着剤などとして
有用である。Since the polyurethane resin of the present invention has excellent mechanical strength, heat resistance, hydrolysis resistance, cold resistance, and abrasion resistance,
It is useful as a wire coating for mechanical parts, automobile parts, chains, belts, films, hoses, tubes, wheels, gears, shoe soles, fiber coatings, synthetic leather materials, binders, adhesives, etc.
以下に、実施例を挙げて本発明を更に説明するが、これ
らは本発明を何ら制限するものではない。The present invention will be further explained below with reference to Examples, but these are not intended to limit the present invention in any way.
同、実施例中部及び・千−セントは全て重量部及び重量
・母−セントである。In the same example, all numbers in the middle part and 1,000 cents are parts by weight and weight/base cents.
実施例１
分子量１０００の１，６−へキサメチレンポリカーゴネ
ートジオール、４００部、１．４−プタンソオー＃２９
０部、７ジビン酸４２３ｓを２００℃で縮合させ九分子
蓋１９８５の線状ポリヒドロキシ化合物１００部をツメ
チルホルムアミド３３６部に溶解し、１．４−ｆタンジ
オール１８部を加え更にジフェニルメタンジイソシアネ
ート６３部を刃口え、次いでジプチル錫ノラウレー）
０．０１部加えて６０℃にて１２時間反応して樹脂濃度
３５％、粘度８２５ポイズの一すウレタン樹脂溶液を得
た。Example 1 1,6-hexamethylene polycargonate diol having a molecular weight of 1000, 400 parts, 1,4-butaneso #29
0 parts, 423s of 7 divic acid were condensed at 200°C, 100 parts of a linear polyhydroxy compound of Nine Molecule Lid 1985 was dissolved in 336 parts of dimethylformamide, 18 parts of 1.4-f tanediol were added, and further 63 parts of diphenylmethane diisocyanate was added. the cutting edge, then the dibutyl tin nolaure)
0.01 part was added and reacted at 60°C for 12 hours to obtain a monolithic urethane resin solution with a resin concentration of 35% and a viscosity of 825 poise.
このポリウレタン樹脂溶液を離型性のある支持体に塗布
し、１２０℃にて３０分間乾燥して約１５０ミクロンの
厚さの皮膜を得た。この皮膜の諸物性を測定した結果を
表−１に示した。This polyurethane resin solution was applied to a support with mold releasability and dried at 120°C for 30 minutes to obtain a film with a thickness of about 150 microns. Table 1 shows the results of measuring the physical properties of this film.
比較例１
実施例１の分子量１９８５の線状ポリヒドロキシ化合物
に代えて分子量１９８２の１．６−ヘキサメチレン４リ
カーゴネートゾオールを使用する以外は実施例１と同様
にして樹脂濃度３５チ、粘度８２２ポイズのポリウレタ
ン溶液を得、実施例１と同様にして皮膜を作成し、諸物
性を測定した結果を表−ＩＫ示した。Comparative Example 1 The resin concentration was 35% in the same manner as in Example 1 except that 1,6-hexamethylene 4-licargonate zool having a molecular weight of 1982 was used in place of the linear polyhydroxy compound having a molecular weight of 1985 in Example 1. A polyurethane solution with a viscosity of 822 poise was obtained, a film was prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table IK.
比較例２
実施例１の分子量１９８５の機状ポリヒドロヤシ化合物
１００部に代えて分子量１９８２の１，６−へキナメチ
レンカーボネートジオール５０部、分子ｆｉ２００５の
１．４−ブタンゾオールとアノピン酸を縮合して得られ
たポリエステルジオール５０部を使用する以外は実施例
１と同様にして樹脂濃度３５チ、粘度８１８デイズのポ
リウレタン樹脂溶液を得、実施例１と同様にして皮膜を
作成し、諸物性を測定した結果を表−１に示した。Comparative Example 2 In place of 100 parts of the mechanical polyhydrococonut compound with a molecular weight of 1985 in Example 1, 50 parts of 1,6-hexnameethylene carbonate diol with a molecular weight of 1982, 1,4-butanzool with a molecular fi of 2005, and anopic acid were condensed. A polyurethane resin solution with a resin concentration of 35 cm and a viscosity of 818 days was obtained in the same manner as in Example 1, except that 50 parts of the polyester diol prepared above was used.A film was prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table-1.
／
表 −１
諸物性測定法
抗張力・伸度：巾１０ｍ、長さ２０ｍの試片を２５℃に
て引張速度３００■／分の引張試験を行い、試片が切断
する時の負荷及び試片の長さからそれぞれ抗張力、伸度
を求めた。/ Table-1 Measurement method of various physical properties Tensile strength/elongation: A test specimen with a width of 10 m and a length of 20 m was subjected to a tensile test at a tensile rate of 300 cm/min at 25°C, and the load when the specimen was cut and the specimen The tensile strength and elongation were determined from the length of each.
耐熱性：皮膜を１２０℃の雰囲気中に３０日間放置した
後、引張試験を行い抗張力の耐熱性試験前の値に対する
割合を求めた。Heat resistance: After the film was left in an atmosphere at 120° C. for 30 days, a tensile test was conducted to determine the ratio of tensile strength to the value before the heat resistance test.
耐加水分解性：皮換金７０℃相対湿度９５慢の雰囲気中
に５０日間放置し九後、引張試験を行い抗張力の耐加水
分解性試験前の値に対する割合を求めた。Hydrolysis resistance: After 50 days in an atmosphere of 70°C and 95% relative humidity, a tensile test was conducted to determine the ratio of tensile strength to the value before the hydrolysis resistance test.
ガラス転位弧度：動的粘弾注を測定し、これよシガラス
転位温度を求めた。Glass transition arc degree: The glass transition temperature was determined by measuring the dynamic viscosity.
実施例２
分子ＪｉｌｌＯＯＯの１，６−へキサメチレンポリ刀−
メネートソオール５００部、１，６−ヘキサンフォール
２８３部、アゾビン［３０４部を２００℃で縮合させ九
分子童１５０５の機状ポリヒドロキシ化合物１００部に
１，４−ブタンジオール２０部を加、ｔ、＆Ｏ’ＣＫ加
熱し、５０℃のヅフェニルメタンノイソシアネート７３
部を加え１８０℃にて２時間反応し、２００℃における
溶融粘度ａＯＸ１０５ポイズのポリウレタン樹脂を得た
。このポリウレタン樹脂を約２箇厚の試片に射出成形し
、諸物性を測定した結果を表−２に示した。Example 2 1,6-hexamethylene polyester of molecule JillOOOO
500 parts of menatesool, 283 parts of 1,6-hexanephor, and 304 parts of azovin were condensed at 200°C, and 20 parts of 1,4-butanediol was added to 100 parts of a mechanical polyhydroxy compound of nine molecules 1505. 'CK heated to 50℃ duphenylmethanoisocyanate 73
The mixture was reacted at 180°C for 2 hours to obtain a polyurethane resin having a melt viscosity of aOX of 105 poise at 200°C. This polyurethane resin was injection molded into test pieces approximately two times thicker, and various physical properties were measured. The results are shown in Table 2.
比較例３
実施例２の分子ｆｉ１５０５の縁状ポリヒト゛ロキシ化
合物１００部に代えて分子量１５０３の１．６−ヘキサ
メチレン４リカーゴネートゾオール５０部、分子量１５
０８の１．６−ヘキサンジオールとアジピン酸を縮合し
て得られたポリエステルジオール５０部を使用する以外
は実施例２と同様にして２００℃における＃融粘度ａ５
Ｘ１０５ボイズのポリウレタン樹脂を得た。このポリウ
レタン樹脂を実施例２と同様にして約２鱈厚の試片を得
、実施例２と同様にして諸物性を測定した結果を表−２
に示した。Comparative Example 3 50 parts of 1,6-hexamethylene 4-licargonate zool having a molecular weight of 1503 and a molecular weight of 15 were used in place of 100 parts of the fringed polyhydroxy compound having the molecule fi1505 in Example 2.
Melt viscosity a5 at 200°C in the same manner as in Example 2 except that 50 parts of polyester diol obtained by condensing 1.6-hexanediol and adipic acid of No. 08 was used.
A polyurethane resin with X105 voids was obtained. A sample of approximately 2 mm thick was obtained from this polyurethane resin in the same manner as in Example 2, and its physical properties were measured in the same manner as in Example 2. The results are shown in Table 2.
It was shown to.
耐摩耗８：：テーパー摩耗試験機（摩耗輪Ｈ−２２、荷
重ＩＫｇ、１０００回）Ｋよシ摩耗減量を求めた。Wear resistance 8: Taper abrasion tester (wearing wheel H-22, load Ikg, 1000 times) K-yoshi wear loss was determined.
比較例４
分子量１０００の１．６−ヘキサメチレンポリカー＆ネ
ート−、ｙオール５００部、エチレングリコール１９５
部、アソピン＃Ｒ４１１部を２００℃で縮合させ７’ｔ
ＯＨＶ−７＆２（分子量１５２０）ＯｔＷ状ポリヒドロ
キシ化合物１００部に１．４−ｆタンジオール２０部を
加え、８０℃に加熱し、５０℃のジブエニルメタンソイ
ソシアネート７３部を加え１８０℃にて２時間反応した
が、２００″ｃＫおける溶融粘度が２．０ Ｘ １０３
ポイズのポリウレタン樹脂しか得られなかった。この
ポリウレタン樹脂を約２ｍ厚の試片に射出成形したが、
シートがもろく、物性が測定出来るものではなかった。Comparative Example 4 1.6-hexamethylene polycar & nate having a molecular weight of 1000, 500 parts of yol, 195 parts of ethylene glycol
7't by condensing 11 parts of Asopine #R4 at 200°C.
Add 20 parts of 1.4-f tanediol to 100 parts of OHV-7&2 (molecular weight 1520) OtW polyhydroxy compound, heat to 80°C, add 73 parts of dibutenylmethane soocyanate at 50°C, and heat at 180°C for 2 hours. It reacted, but the melt viscosity at 200"cK was 2.0 x 103
Only Poise polyurethane resin was obtained. This polyurethane resin was injection molded into a test piece approximately 2 m thick.
The sheet was brittle and its physical properties could not be measured.
そこで、本実験で使用したＯＨＭ −７＆２の婦状ポリ
ヒドロキシ化合物をＧＰＣにて分析したところ、１１３
％のエチレンカーゴネートが検出され九。Therefore, when the OHM-7&2 gynecological polyhydroxy compound used in this experiment was analyzed by GPC, it was found that 113
9% ethylene cargoes were detected.
実施例３
分子量１０００の１，４−シクロヘキサンポリカー？ネ
ートゾオール３００部、１，４−ブタソジオール３５９
部、７／ピア１８４６７部を２００℃で補合させた分子
量１０３０の線状ポリヒドロキシ化合物１００部をメチ
ルエチルケトン６０部とシクロへ中サノ７６０ｇとの混
合溶剤ＩＣ溶解し、２．２−ツメチル−１，３−ｆロノ
４ンジオール１０部及びノツデル錫ノラウレート０．０
１部を加え、更にＬ６−へ中テメチレンゾイソシアネー
ト３３部を加えて８０℃にて１８時間反応後、メチルエ
チルケト７２６７部を加えて樹脂濃度３５チ、粘度２２
５ポイズのポリウレタン樹脂溶液を得た。このポリウレ
タン樹脂溶液を実施例１と同様にして約１５０ミクロン
厚さの皮膜を得、実施例１と同様にして諸物性を測定し
た結果を表−３に示した。Example 3 1,4-cyclohexane polycarbonate with a molecular weight of 1000? 300 parts of natezool, 359 parts of 1,4-butasodiol
100 parts of a linear polyhydroxy compound with a molecular weight of 1030 prepared by combining 18,467 parts of 7/pia at 200°C was dissolved in a mixed solvent of 60 parts of methyl ethyl ketone and 760 g of cyclohexane, and 2.2-methyl-1 , 10 parts of 3-f lono-4 diol and 0.0 parts of Notsdel tin nolaurate.
1 part of temethylene diisocyanate was added to L6-, and after reaction at 80°C for 18 hours, 7267 parts of methyl ethyl keto was added to give a resin concentration of 35 cm and a viscosity of 22
A 5 poise polyurethane resin solution was obtained. This polyurethane resin solution was treated in the same manner as in Example 1 to obtain a film with a thickness of about 150 microns, and the various physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.
但し耐加水分解性は皮膜ｔ−７０℃相対湿度９５饅の雰
囲気中に１５日間放置した。However, the hydrolysis resistance was determined by leaving the film in an atmosphere at t-70°C and relative humidity of 95°C for 15 days.
比較例５
実施例３の分子量１０３０の線状ポリヒドロキシ化合物
に代えて、分子量１０５０の１．４−ｆタンジオールと
アジピン酸とを縮合して得られたポリエステルジオール
１００部を使用する以外は実施例３と同様にして樹脂ｍ
度３５チ、粘度２２８Ｉイズのポリウレタン樹脂溶液を
得九。このポリウレタン樹脂溶液を実施例３と同様にし
て皮膜を作成し、諸ｖｌＪ性を測定し九結果ｔ−表−３
に示した。Comparative Example 5 Example except that 100 parts of polyester diol obtained by condensing 1.4-f tanediol with a molecular weight of 1050 and adipic acid was used instead of the linear polyhydroxy compound with a molecular weight of 1030 in Example 3. Resin m in the same manner as in 3.
A polyurethane resin solution with a viscosity of 35 degrees and a viscosity of 228 degrees was obtained. A film was prepared from this polyurethane resin solution in the same manner as in Example 3, and various VlJ properties were measured.
It was shown to.
比較例６
実施例３０分子量１０３０の線状ポリヒドロキシ化合物
に代えて、分子量１０４０の１．６−ヘキサンジオール
とアゾピンばとを縮合して得られたポリエステルジオー
ル１００部を使用する以外は実施例３と同様にして樹脂
濃度３５％、粘度２２３ボイズのポリタレタン樹脂溶液
を得た。このポリウレタン樹脂溶液を実施例３と演様に
して皮膜を作成し、諸物性を測定した結果を表−３に示
し友。Comparative Example 6 Example 30 Example 3 except that 100 parts of a polyester diol obtained by condensing 1,6-hexanediol with a molecular weight of 1040 and azopine was used instead of the linear polyhydroxy compound with a molecular weight of 1030. In the same manner as above, a polytalethane resin solution having a resin concentration of 35% and a viscosity of 223 voids was obtained. A film was prepared from this polyurethane resin solution in the same manner as in Example 3, and the various physical properties were measured.The results are shown in Table 3.
本発明のポリウレタン樹脂組成物は、耐加水分解性、低
温での柔軟性、耐摩耗性等猪物在に優れ良ものでめった
。The polyurethane resin composition of the present invention was found to be excellent in terms of hydrolysis resistance, flexibility at low temperatures, and abrasion resistance.
代理人 弁理士 高 ａ ｍ 利Agent Patent Attorney Takashi Amri
Claims (1)
及び必要に応じイソシアネート基と反応する水素原子を
少なくとも２個有する低分子化合物から成るポリウレタ
ン樹脂組成物において、線状ポリヒドロキシ化合物とし
て、ヒドロキシル基を有する脂肪族及び／又は脂環族炭
化水素ジオールのポリカーボネートジオールをアルコー
ル成分の少なくとも一成分として得られるポリエステル
ポリカーボネートポリオールを用いることを特徴とする
ポリウレタン樹脂組成物。 ２、アルコール成分が、ポリカーボネートジオールとヒ
ドロキシル基を少なくとも２個有する低分子ポリヒドロ
キシ化合物からなる請求項１のポリウレタン樹脂組成物
。 ３、請求項２のヒドロキシル基を少なくとも２個有する
低分子ポリヒドロキシ化合物が１，２−グリコール以外
の化合物であることを特徴とするポリウレタン樹脂組成
物。[Scope of Claims] 1. A polyurethane resin composition comprising a linear polyhydroxy compound, an organic diisocyanate, and optionally a low molecular compound having at least two hydrogen atoms that reacts with an isocyanate group, wherein the linear polyhydroxy compound A polyurethane resin composition characterized in that a polyester polycarbonate polyol obtained by using a polycarbonate diol of an aliphatic and/or alicyclic hydrocarbon diol having a hydroxyl group as at least one component of the alcohol component is used. 2. The polyurethane resin composition according to claim 1, wherein the alcohol component comprises a polycarbonate diol and a low molecular weight polyhydroxy compound having at least two hydroxyl groups. 3. A polyurethane resin composition, wherein the low molecular weight polyhydroxy compound having at least two hydroxyl groups according to claim 2 is a compound other than 1,2-glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63315054A JP2712435B2 (en) | 1988-12-15 | 1988-12-15 | Polyurethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63315054A JP2712435B2 (en) | 1988-12-15 | 1988-12-15 | Polyurethane resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02160820A true JPH02160820A (en) | 1990-06-20 |
| JP2712435B2 JP2712435B2 (en) | 1998-02-10 |
Family
ID=18060883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63315054A Expired - Fee Related JP2712435B2 (en) | 1988-12-15 | 1988-12-15 | Polyurethane resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2712435B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001325A1 (en) * | 1993-06-29 | 1995-01-12 | The Dow Chemical Company | Polyols useful for preparing polyurethane foams having improved retention of insulative properties, polyurethane foams prepared therewith and methods for the preparation thereof |
| EP0673962A1 (en) * | 1994-03-22 | 1995-09-27 | Kuraray Co., Ltd. | Porous polyurethane sheet |
| JP2006124681A (en) * | 2004-09-30 | 2006-05-18 | Showa Denko Kk | Thermosetting resin composition using carboxyl-terminated urethane resin |
| US8524838B2 (en) | 2004-09-21 | 2013-09-03 | Showa Denko K.K. | Heat-curable urethane resin composition |
| WO2016039395A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and polyurethane resin film and synthetic leather obtained using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845220A (en) * | 1982-08-23 | 1983-03-16 | Dainichi Seika Kogyo Kk | Preparation of polyurethane elastomer |
| JPS62280214A (en) * | 1986-05-28 | 1987-12-05 | Dainippon Ink & Chem Inc | Polyurethane resin composition |
-
1988
- 1988-12-15 JP JP63315054A patent/JP2712435B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845220A (en) * | 1982-08-23 | 1983-03-16 | Dainichi Seika Kogyo Kk | Preparation of polyurethane elastomer |
| JPS62280214A (en) * | 1986-05-28 | 1987-12-05 | Dainippon Ink & Chem Inc | Polyurethane resin composition |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001325A1 (en) * | 1993-06-29 | 1995-01-12 | The Dow Chemical Company | Polyols useful for preparing polyurethane foams having improved retention of insulative properties, polyurethane foams prepared therewith and methods for the preparation thereof |
| EP0673962A1 (en) * | 1994-03-22 | 1995-09-27 | Kuraray Co., Ltd. | Porous polyurethane sheet |
| US5648151A (en) * | 1994-03-22 | 1997-07-15 | Kuraray Co., Ltd. | Porous polyurethane sheet |
| CN1046298C (en) * | 1994-03-22 | 1999-11-10 | 可乐丽股份有限公司 | Porous polyurethane sheet |
| US8524838B2 (en) | 2004-09-21 | 2013-09-03 | Showa Denko K.K. | Heat-curable urethane resin composition |
| JP2006124681A (en) * | 2004-09-30 | 2006-05-18 | Showa Denko Kk | Thermosetting resin composition using carboxyl-terminated urethane resin |
| JP4716416B2 (en) * | 2004-09-30 | 2011-07-06 | 昭和電工株式会社 | Thermosetting resin composition using terminal carboxyurethane resin |
| WO2016039395A1 (en) * | 2014-09-09 | 2016-03-17 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and polyurethane resin film and synthetic leather obtained using same |
| JPWO2016039395A1 (en) * | 2014-09-09 | 2017-06-22 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and polyurethane resin film and synthetic leather obtained using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2712435B2 (en) | 1998-02-10 |
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