JPS6329686B2 - - Google Patents
Info
- Publication number
- JPS6329686B2 JPS6329686B2 JP56102303A JP10230381A JPS6329686B2 JP S6329686 B2 JPS6329686 B2 JP S6329686B2 JP 56102303 A JP56102303 A JP 56102303A JP 10230381 A JP10230381 A JP 10230381A JP S6329686 B2 JPS6329686 B2 JP S6329686B2
- Authority
- JP
- Japan
- Prior art keywords
- glycol
- diol
- isocyanate groups
- diisocyanate
- thermoplastic polyurethane
- 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.)
- Expired
Links
- 150000002009 diols Chemical class 0.000 claims description 28
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 24
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- -1 etc. Chemical compound 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 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 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 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
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-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
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- XACKQJURAZIUES-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diol Chemical compound OCC(C)CC(C)(C)CCO XACKQJURAZIUES-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- VMNDRLYLEVCGAG-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-3-methylanilino]ethanol Chemical compound CC1=CC=CC(N(CCO)CCO)=C1 VMNDRLYLEVCGAG-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate 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
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-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
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003998 acyclic ketones Chemical class 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
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 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
- 229930188620 butyrolactone Natural products 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 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 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は熱可塑性ポリウレタン樹脂の製造法に
関する。更に詳しくは、本発明は有機溶剤に可溶
で、高い機械的物性を有し、分子中にペンダント
状及び／又は分子末端に活性水素を有する基をも
つ熱可塑性ポリウレタン樹脂の製造法に関する。
熱可塑性ポリウレタン樹脂（以下単にTPUと
かく）の用途には、溶剤に溶解して用いる分野が
ある。そのような分野では、塗布操作上の必要性
から溶剤に溶解している場合がほとんどであり、
塗布後、溶剤を除去する形で用いられるのが一般
的である。この場合、溶剤除去後は、耐溶剤性、
耐水性、耐熱性等を要求されることがあり、その
為には、TPU分子中に活性水素を導入し、塗布
時にポリイソシアネート等を併用して架橋硬化せ
しめるのが簡便かつ有効であることがよく知られ
ている。
一方、TPUの用途には、無機材料と混合して
用いる分野があるが、この分野では無機材料の分
散性が要求されることがあり、その為には、スル
ホン基、カルボキシル基、リン酸基等を分子中に
導入することも有効であるが、塗料化の際、ゲル
化を起す場合があるため、水酸基、アミノ基等の
活性水素を有する基の導入が一般的である。
しかも、これらの用途においても、TPU単独
でも充分な機械的物性を具備していることが望ま
しい。
そこで、本発明者らは、有機溶剤に可溶で、高
い機械的物性をそなえ、分子中に活性水素を有す
る基をもつ新規なTPUの製造法を検討した結果、
本発明に到達した。
すなわち本発明は平均分子量500〜5000の高分
子ジオール(A)、平均分子量500以下の低分子ジオ
ール(B)と有機ジイソシアネート(C)とを反応させて
熱可塑性ポリウレタンエラストマーを製造する方
法において、
(1) Ａ及びＢの活性水素の合計数とＣのイソシア
ネート基の数の比が１：1.02〜１：1.1の割合
で、Ａ，Ｂ及びＣを有機溶媒中で反応せしめて
末端にイソシアネート基を有するプレポリマー
(D)とし、
(2) 続いて活性水素３個以上有する架橋剤(E)を、
Ａ，Ｂ及びＥの活性水素の合計数に対するＣの
イソシアネート基の数との比が１：0.85〜１：
0.98の割合で加え、ＥでＤを鎖延長することに
より、得られた熱可塑性ポリウレタンエラスト
マーの分子構造が分子末端にOH基を少なくと
も２個持つことを特徴とする熱可塑性ポリウレ
タン樹脂の製造法、である。
本発明で用いる溶剤は、アミド系、スルホキサ
イド系、環状エーテル系、環状ケトン系ならびに
アセトン、メチルエチルケトン、メチルイソブチ
ルケトン等の非環状ケトン系溶剤の１種又は２種
以上、更には上記溶剤と酢酸エチル、酢酸ブチル
等のエステル系、ベンゼン、トルエン、キシレン
等の芳香族炭化水素系溶剤、メチレンクロライ
ド、パークロルエチレン、等の塩素系溶剤との混
合溶剤である。
本発明で用いる高分子ジオール(A)は平均分子量
500〜5000のものであり、公知のポリエーテルジ
オール、ポリエステルジオール、ポリカーボネー
トジオール等である。
ポリエーテルジオールは例えば、水、エチレン
グリコール、ジエチレングリコール、プロピレン
グリコール、ジプロピレングリコール、１，３―
又は１，４―ブチレングリコール、１，６―ヘキ
サメチレングリコール等にアルキレンオキサイド
たとえばエチレンオキサイド、プロピレンオキサ
イド、ブチレンオキサイド、テトラヒドロフラ
ン、スチレンオキサイド等を１種又は２種以上
（以下単にアルキレンオキサイドと略記する。）付
加せしめて得られるものである。ポリエステルジ
オールは例えば、エチレングリコール、ジエチレ
ングリコール、トリエチレングリコール、プロピ
レングリコール、ジプロピレングリコール、トリ
メチレングリコール、１，３―又は１，４―ブチ
レングリコール、ネオペンチルグリコール、１，
６―ヘキサメチレングリコール、デカメチレング
リコール等の１種又は２種以上と、マロン酸、マ
レイン酸、コハク酸、アジピン酸、グルタル酸、
ピメリン酸、セバシン酸、シユウ酸、フタル酸、
イソフタル酸、テレフタル酸、ヘキサヒドロフタ
ル酸等の１種又は２種以上とからのポリエステル
ジオール又はプロピオラクトン、ブチロラクト
ン、カプロラクトン等の環状エステルを開環重合
したジオール、更に上記グリコールと環状エステ
ルとから又は上記グリコール、二塩基酸、環状エ
ステルの３種からのポリエステルジオールであ
る。
ポリカーボネートジオールは、一般式Ｈ〔―Ｏ―
Ｒ―OCO〕―oROH（ｎ≧１）で表わされる化合物
でＲとしてはグリコール又は２価のフエノールの
残基であり、グリコール又は２価のフエノールは
例えばトリメチレングリコール、ジエチレングリ
コール、１，３―又は１，４―ブチレングリコー
ル、１，６―ヘキサメチレングリコール、デカメ
チレングリコール、ｐ―キシリレングリコール、
ビスフエノールＡ〔２，２―ビス（4′―ヒドロキ
シフエニル）プロパン〕、ビスフエノールＦ（４，
4′―ジヒドロキシジフエニルメタン）等である。
本発明の高分子ジオールとして、１，２―ポリ
ブタジエングリコール、１，４―ポリブタジエン
グリコール、ポリクロロプレンジオール、プタジ
エン―アクリロニトリル共重合体ジオール等も使
用される。
これら各種の高分子ジオールは単独又は２種以
上混合して用いられる。
本発明で用いる平均分子量500以下の低分子ジ
オール(B)は公知の脂肪族ジオール類、芳香族ジオ
ール類、Ｎ―アルキル又はＮ―アリールジアルカ
ノールアミン類等である。脂肪族ジオール類は例
えばエチレングリコール、プロピレングリコー
ル、１，３―又は１，４―ブチレングリコール、
１，５―ペンタンジオール、１，６―ヘキサメチ
レングリコール、ネオペンチルグリコール、２―
エチル―１，３―ヘキサンジオール、２，２，４
―トリメチル―１，３―ペンタンジオール、２，
２，４―又は２，４，４―トリメチル―１，６―
ヘキサンジオール、デカメチレングリコール、
１，４―シクロヘキサンジオール等である。芳香
族ジオール類は、例えば、ハイドロキノン、ビス
フエノールＡ、ビスフエノールＦ、ｐ―キシリレ
ングリコール等である。Ｎ―アルキル又はＮ―ア
リールジアルカノールアミン類は、例えば、メチ
ルジエタノールアミン、メチルジイソプロパノー
ルアミン、エチルジエタノールアミン、フエニル
ジエタノールアミン、ｍ―トリルジエタノールア
ミン等である。上記Ｂは前記脂肪族ジオール類、
芳香族ジオール類、Ｎ―アルキル又はＮ―アリー
ルジアルカノールアミン類にアルキレンオキサイ
ドを付加せしめて得られるものも用いられる。
これら各種の平均分子量500以下の低分子ジオ
ール(B)は単独又は２種以上混合して用いられる。
本発明で用いる活性水素を３個以上有する架橋
剤Ｅは公知のポリオール類、アルカノールアミン
類、ポリアミン類等である。ポリオール類は例え
ばトリメチロールプロパン、グリセリン、３―メ
チルペンタン―１，３，５―トリオール、ペンタ
エリスリトール、ソルビトール、シユークロー
ス、ポリグリセリン、トリス（β―ヒドロキシエ
チル）イソシアヌレート等又はこれらのアルキレ
ンオキサイド付加物もしくはε―カプロラクトン
付加物、ポリエステルポリオール等である。アル
カノールアミン類は、例えばモノエタノールアミ
ン、ジエタノールアミン、トリエタノールアミ
ン、モノイソプロパノールアミン、ジイソプロパ
ノールアミン、トリイソプロパノールアミン等で
ある。ポリアミン類は、例えばエチレンジアミ
ン、ジエチレントリアミン、トリレンジアミン、
ジフエニルメタンジアミン、イソホロンジアミ
ン、４，4′―メチレンビス（２―クロルアニリ
ン）等である。
これら各種の活性水素を３個以上有する架橋剤
は単独又は２種以上混合して用いられる。
本発明で用いる有機ジイソシアネート(C)は、例
えばトリレンジイソシアネート（各種異性体比の
もの）、ジフエニルメタン―４，4′―ジイソシア
ネート（以下MDIともかく。）、ナフチレン―１，
５―ジイソシアネート、３，3′―ジメチル―４，
4′―ビフエニレンジイソシアネート、キシリレン
ジイソシアネート、ジシクロヘキシルメタン―
４，4′―ジイソシアネート（水素化MDI）、イソ
ホロンジイソシアネート、ヘキサメチレンジイソ
シアネート、水素化キシリレンジイソシアネート
等である。
これら各種の有機ジイソシアネートは単独又は
２種以上混合して用いられても良い。
本発明の高分子ジオール(A)、低分子ジオール
(B)、架橋剤(E)、有機ジイソシアネート(C)は、
(1) Ａ，Ｂ及びＣからNCO末端のプレポリマー
(D)を製造するに際して、Ａ及びＢの活性水素の
合計数１に対してＣのイソシアネート基の数が
1.02〜1.1であること、
(2) ＤとＥからTPUを製造するに際しては、Ａ，
Ｂ及びＥの活性水素の合計数１に対してＣのイ
ソシアネート基の数が0.85〜0.98である。
ような量的関係で用いられる。
(1)の条件で、溶剤への溶解性の良好なTPUを
得るためには、イソシアネート基が過剰で鎖延長
を行い、NCO末端プレポリマー(F)を得るのが好
ましい。しかし、1.1を超えてイソシアネート基
が多いと鎖延長が不十分でポリマーの分子量が上
昇せず、物性が低下する。一方イソシアネート基
が1.02未満の場合、分子中に導入し得る活性水素
の数が少くなるので好ましくない。
(2)の条件で、イソシアネート基の数が0.85未満
の場合は未反応のＥの量が過多となり、硬化生成
物のブルーミングやブリードの原因となる。逆に
イソシアネート基の数が0.98を超えると、反応液
のゲル化の危険があり好ましくない。
なお(2)の条件で、反応後のイソシアネート基の
数が0.85未満の場合、或いは製品の粘度の調整等
必要に応じて、有機ポリイソシアネートを追加す
ることもできる。但しこの場合、追加される有機
ポリイソシアネートとＣとは合計イソシアネート
基数で0.85〜0.98の範囲内であり、追加される有
機ポリイソシアネートはＣと同種であつても異種
であつてもよい。
本発明においては反応の任意の段階で必要に応
じて従来公知のウレタン化触媒が用いられる。
又、本発明では必要に応じ酸化防止剤、紫外線
吸収剤、カルボジイミド等の各種添加剤が用いら
れる。
本発明のTPUの製造の概要を示すと、高分子
ジオール(A)と有機ジイソシアネート(C)、必要によ
りウレタン化触媒を溶剤中20〜80重量％（以下％
は重量％を表わす。）の固形分含有量で50〜90℃、
１〜３時間反応させる。さらに50〜90℃で低分子
ジオール(B)を一括又は分割装入により反応させ
る。反応液の増粘に伴ない、必要に応じ溶剤、触
媒を添加し反応させ、NCO末端プレポリマー溶
液(D)を得る。(D)に５〜90℃で架橋剤(E)、必要によ
り溶剤を一括装入により反応させる。１〜３時間
反応させた後、必要により５〜90℃で有機ジイソ
シアネートを一括又は分割装入により反応させ
る。（上記の条件は通常の条件を示したもので必
ずしもこれに限定されるものではない。）
得られたTPU溶液は、10〜40％の固形分含有
量とすることが好ましく、約30％溶液で25℃にお
ける粘度が1000センチポイズ以上であることが好
ましい。これより粘度が低いと良好な物性のもの
が得られない。
本発明では、有機溶剤に可溶で、高い機械的物
性をそなえ、少くとも分子末端１個当り２個以上
の活性水素及び又は分子中にペンダント状に活性
水素を有するTPUが得られる。又本発明の高分
子ジオール(A)、低分子ジオール(B)、有機ジイソシ
アネート(C)は、Ａ，Ｂ，Ｄの合計重量に対するＡ
の重量割合を変化させることにより、低モジユラ
ス品から高ヤング率品まで所望の物性を有する
TPUを得ることができる。更に本発明のTPU
は、トリメチロールプロパンと３モルのトリレン
ジイソシアネートの反応物、トリメチロールプロ
パンと３モルのヘキサメチレンジイソシアネート
の反応物、ビユーレツト基を導入して変性したヘ
キサメチレンジイソシアネート等のポリイソシア
ネート、NCO基含有プレポリマー、ブロツクポ
リイソシアネート等と組合せることにより、硬化
生成物を得ることができる。
本発明におけるTPUは、溶液の形又は常法に
より溶剤を除去した形で、樹脂、フイルム、各種
の被覆剤、含浸剤、接着剤、塗料、バインダー、
磁性塗料用バインダー、インキビヒクル等に用い
られる。
次に実施例を挙げて、本発明を具体的に説明す
る。
実施例 １
撹拌機および還流冷却器付反応器を窒素ガスで
置換後、メチルエチルケトン（以下単にMEKと
かく。）500部を仕込み、更にポリエステルジオー
ル（エチレングリコール及び１，４―ブチレング
リコールとアジピン酸からのポリエステルジオー
ル、平均分子量1600。以下単にPEBAとかく。）
100部、MDI（前出）291.3部、ジブチル錫ジラウ
レート（以下単にDBTDLとかく。）0.05部を加
え、80℃で２時間反応させた。上記溶液にネオペ
ンチルグリコール（以下単にNPGとかく。）
107.3部を加え、80℃で１時間反応させ、NCO末
端プレポリマー溶液を得た。このプレポリマー溶
液にNEK700部、トリメチロールプロパン（以下
単にTMPとかく。）
16.7部を加え、80℃で１時間反応せ、水酸基
（すなわち活性水素）含有のプレポリマー溶液を
得た。この水酸基含有プレポリマー溶液に80℃で
MDI（前出）10.9部を加え、80℃で１時間反応さ
せた。得られたTPU溶液は、固形分32.0％、粘
度、1900センチポイズ（25℃）であり、この溶液
から得られた樹脂はYs（降伏時応力）650Kg／cm2、
降伏時伸び4.3％、ヤング率23800Kg／cm2であつ
た。
Ys、降伏時伸び、ヤング率は巾５mmの短冊型
試料を標線間距離50mm、引張速度５mm／minで測
定した。
実施例 ２〜３
MDIを一度に添加した以外は実施例１と同様
の方法により、実施例２〜３の樹脂の製造を行つ
た。その組成、樹脂の性質を第１表に示した。
The present invention relates to a method for producing thermoplastic polyurethane resin. More specifically, the present invention relates to a method for producing a thermoplastic polyurethane resin that is soluble in organic solvents, has high mechanical properties, and has groups having active hydrogen pendantly and/or at the end of the molecule. Thermoplastic polyurethane resin (hereinafter simply referred to as TPU) is used in some fields by being dissolved in a solvent. In such fields, it is often dissolved in a solvent due to the necessity of coating operations.
Generally, the solvent is removed after application. In this case, after removing the solvent, the solvent resistance,
Water resistance, heat resistance, etc. may be required, and for this purpose, it is simple and effective to introduce active hydrogen into the TPU molecule and crosslink and harden it using polyisocyanate etc. at the time of application. well known. On the other hand, TPU is used in some fields where it is mixed with inorganic materials, but in this field, the dispersibility of inorganic materials is sometimes required, and for this purpose TPU has sulfonic, carboxyl, and phosphoric acid groups. It is also effective to introduce a group such as a hydroxyl group or an amino group into the molecule, but this may cause gelation when forming a paint, so it is common to introduce a group having active hydrogen such as a hydroxyl group or an amino group. Furthermore, even in these applications, it is desirable that TPU alone has sufficient mechanical properties. Therefore, the present inventors investigated a new method for manufacturing TPU that is soluble in organic solvents, has high mechanical properties, and has a group containing active hydrogen in its molecule.
We have arrived at the present invention. That is, the present invention provides a method for producing a thermoplastic polyurethane elastomer by reacting a high molecular diol (A) with an average molecular weight of 500 to 5000, a low molecular diol (B) with an average molecular weight of 500 or less, and an organic diisocyanate (C). 1) A, B, and C are reacted in an organic solvent at a ratio of the total number of active hydrogens of A and B to the number of isocyanate groups of C in a ratio of 1:1.02 to 1:1.1 to form isocyanate groups at the terminals. prepolymer with
(D), (2) followed by a crosslinking agent (E) having three or more active hydrogen atoms,
The ratio of the number of isocyanate groups in C to the total number of active hydrogens in A, B and E is 1:0.85 to 1:
A method for producing a thermoplastic polyurethane resin, characterized in that the molecular structure of the thermoplastic polyurethane elastomer obtained by adding at a ratio of 0.98 and chain-extending D with E has at least two OH groups at the molecular terminal. It is. The solvents used in the present invention include one or more of amide, sulfoxide, cyclic ether, cyclic ketone, and acyclic ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, as well as the above solvents and ethyl acetate. , ester-based solvents such as butyl acetate, aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene, and mixed solvents with chlorinated solvents such as methylene chloride and perchlorethylene. The polymer diol (A) used in the present invention has an average molecular weight of
500 to 5000, and include known polyether diols, polyester diols, polycarbonate diols, etc. Examples of polyether diols include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-
Alternatively, one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, etc. are added to 1,4-butylene glycol, 1,6-hexamethylene glycol, etc. (hereinafter simply referred to as alkylene oxide). ) is obtained by adding Polyester diols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3- or 1,4-butylene glycol, neopentyl glycol, 1,
One or more of 6-hexamethylene glycol, decamethylene glycol, etc., and malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid,
pimelic acid, sebacic acid, oxalic acid, phthalic acid,
Polyester diols from one or more of isophthalic acid, terephthalic acid, hexahydrophthalic acid, etc. or diols obtained by ring-opening polymerization of cyclic esters such as propiolactone, butyrolactone, caprolactone, etc., and further from the above glycols and cyclic esters. Alternatively, it is a polyester diol selected from the above three types of glycols, dibasic acids, and cyclic esters. Polycarbonate diol has the general formula H[-O-
R-OCO]- o In the compound represented by ROH (n≧1), R is a residue of glycol or divalent phenol, and glycol or divalent phenol is, for example, trimethylene glycol, diethylene glycol, 1,3- or 1,4-butylene glycol, 1,6-hexamethylene glycol, decamethylene glycol, p-xylylene glycol,
Bisphenol A [2,2-bis(4'-hydroxyphenyl)propane], bisphenol F (4,
4′-dihydroxydiphenylmethane), etc. As the polymer diol of the present invention, 1,2-polybutadiene glycol, 1,4-polybutadiene glycol, polychloroprene diol, putadiene-acrylonitrile copolymer diol, etc. can also be used. These various polymeric diols may be used alone or in combination of two or more. The low molecular weight diol (B) having an average molecular weight of 500 or less used in the present invention includes known aliphatic diols, aromatic diols, N-alkyl or N-aryldialkanolamines, and the like. Aliphatic diols include, for example, ethylene glycol, propylene glycol, 1,3- or 1,4-butylene glycol,
1,5-pentanediol, 1,6-hexamethylene glycol, neopentyl glycol, 2-
Ethyl-1,3-hexanediol, 2,2,4
-trimethyl-1,3-pentanediol, 2,
2,4- or 2,4,4-trimethyl-1,6-
hexanediol, decamethylene glycol,
1,4-cyclohexanediol and the like. Examples of aromatic diols include hydroquinone, bisphenol A, bisphenol F, and p-xylylene glycol. Examples of N-alkyl or N-aryl dialkanolamines include methyldiethanolamine, methyldiisopropanolamine, ethyldiethanolamine, phenyldiethanolamine, m-tolyldiethanolamine, and the like. The above B is the aliphatic diol,
Those obtained by adding alkylene oxide to aromatic diols, N-alkyl or N-aryl dialkanolamines are also used. These various low molecular weight diols (B) having an average molecular weight of 500 or less may be used alone or in combination of two or more. The crosslinking agent E having three or more active hydrogens used in the present invention includes known polyols, alkanolamines, polyamines, and the like. Examples of polyols include trimethylolpropane, glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, sorbitol, sucrose, polyglycerin, tris(β-hydroxyethyl)isocyanurate, and alkylene oxide adducts thereof. Or ε-caprolactone adduct, polyester polyol, etc. Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. Examples of polyamines include ethylenediamine, diethylenetriamine, tolylenediamine,
These include diphenylmethanediamine, isophoronediamine, 4,4'-methylenebis(2-chloroaniline), and the like. These various crosslinking agents having three or more active hydrogens may be used alone or in combination of two or more. The organic diisocyanate (C) used in the present invention is, for example, tolylene diisocyanate (various isomer ratios), diphenylmethane-4,4'-diisocyanate (hereinafter also referred to as MDI), naphthylene-1,
5-diisocyanate, 3,3'-dimethyl-4,
4'-Biphenylene diisocyanate, xylylene diisocyanate, dicyclohexylmethane-
These include 4,4'-diisocyanate (hydrogenated MDI), isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and the like. These various organic diisocyanates may be used alone or in combination of two or more. High molecular diol (A) and low molecular diol of the present invention
(B), crosslinking agent (E), and organic diisocyanate (C) are (1) NCO-terminated prepolymer from A, B, and C.
When producing (D), the number of isocyanate groups in C is 1 for the total number of active hydrogens in A and B.
1.02 to 1.1; (2) When manufacturing TPU from D and E, A,
The number of isocyanate groups in C is 0.85 to 0.98 relative to the total number of active hydrogens in B and E, which is 1. Used in quantitative relationships such as Under the conditions (1), in order to obtain TPU with good solubility in a solvent, it is preferable to carry out chain extension with an excess of isocyanate groups to obtain an NCO-terminated prepolymer (F). However, if the number exceeds 1.1 and there are many isocyanate groups, chain extension will be insufficient, the molecular weight of the polymer will not increase, and the physical properties will deteriorate. On the other hand, when the number of isocyanate groups is less than 1.02, the number of active hydrogens that can be introduced into the molecule decreases, which is not preferable. Under condition (2), if the number of isocyanate groups is less than 0.85, the amount of unreacted E will be excessive, causing blooming or bleeding of the cured product. On the other hand, if the number of isocyanate groups exceeds 0.98, there is a risk of gelation of the reaction solution, which is not preferable. Note that under the conditions (2), if the number of isocyanate groups after the reaction is less than 0.85, or if necessary to adjust the viscosity of the product, an organic polyisocyanate may be added. However, in this case, the total number of isocyanate groups of the added organic polyisocyanate and C is within the range of 0.85 to 0.98, and the added organic polyisocyanate may be the same type as C or different. In the present invention, a conventionally known urethanization catalyst is used as necessary at any stage of the reaction. Further, in the present invention, various additives such as antioxidants, ultraviolet absorbers, and carbodiimides are used as necessary. To outline the production of TPU of the present invention, polymer diol (A), organic diisocyanate (C), and if necessary urethanization catalyst are mixed in a solvent at 20 to 80% by weight (hereinafter %
represents weight %. ) 50-90℃, with solids content of
Allow to react for 1 to 3 hours. Furthermore, a low molecular weight diol (B) is reacted at 50 to 90°C by charging all at once or in portions. As the viscosity of the reaction solution increases, a solvent and a catalyst are added as necessary to cause a reaction, thereby obtaining an NCO-terminated prepolymer solution (D). (D) is reacted with the crosslinking agent (E) and, if necessary, a solvent, at 5 to 90°C by charging them all at once. After reacting for 1 to 3 hours, organic diisocyanate is reacted at 5 to 90° C., either all at once or in portions, if necessary. (The above conditions indicate normal conditions and are not necessarily limited to these.) The obtained TPU solution preferably has a solids content of 10 to 40%, and is approximately 30% solution. The viscosity at 25° C. is preferably 1000 centipoise or more. If the viscosity is lower than this, good physical properties cannot be obtained. The present invention provides TPU that is soluble in organic solvents, has high mechanical properties, and has at least two or more active hydrogens per molecule end and/or active hydrogens pendant in the molecule. In addition, the polymer diol (A), low molecular diol (B), and organic diisocyanate (C) of the present invention have an amount of A based on the total weight of A, B, and D.
By changing the weight ratio of
You can get TPU. Furthermore, the TPU of the present invention
is a reaction product of trimethylolpropane and 3 mol of tolylene diisocyanate, a reaction product of trimethylolpropane and 3 mol of hexamethylene diisocyanate, a polyisocyanate such as hexamethylene diisocyanate modified by introducing a Biuret group, and a preform containing an NCO group. By combining with polymers, blocked polyisocyanates, etc., cured products can be obtained. In the present invention, TPU can be used in resins, films, various coatings, impregnating agents, adhesives, paints, binders,
Used in binders for magnetic paints, ink vehicles, etc. Next, the present invention will be specifically explained with reference to Examples. Example 1 After purging the reactor with a stirrer and a reflux condenser with nitrogen gas, 500 parts of methyl ethyl ketone (hereinafter simply referred to as MEK) was charged, and polyester diol (produced from ethylene glycol, 1,4-butylene glycol, and adipic acid) was charged. Polyester diol, average molecular weight 1600.Hereafter simply referred to as PEBA)
100 parts of MDI (mentioned above), 291.3 parts of MDI (mentioned above), and 0.05 part of dibutyltin dilaurate (hereinafter simply referred to as DBTDL) were added, and the mixture was reacted at 80°C for 2 hours. Add neopentyl glycol (hereinafter simply referred to as NPG) to the above solution.
107.3 parts were added and reacted at 80°C for 1 hour to obtain an NCO-terminated prepolymer solution. To this prepolymer solution, 700 parts of NEK and 16.7 parts of trimethylolpropane (hereinafter simply referred to as TMP) were added and reacted at 80°C for 1 hour to obtain a prepolymer solution containing hydroxyl groups (that is, active hydrogen). Add to this hydroxyl group-containing prepolymer solution at 80℃.
10.9 parts of MDI (mentioned above) was added and reacted at 80°C for 1 hour. The obtained TPU solution has a solid content of 32.0% and a viscosity of 1900 centipoise (25°C), and the resin obtained from this solution has a Ys (stress at yield) of 650 Kg/cm 2 ,
The elongation at yield was 4.3%, and the Young's modulus was 23,800 Kg/cm 2 . Ys, elongation at yield, and Young's modulus were measured on a rectangular sample with a width of 5 mm at a distance between gauge lines of 50 mm and a tensile speed of 5 mm/min. Examples 2-3 The resins of Examples 2-3 were produced in the same manner as in Example 1 except that MDI was added all at once. The composition and properties of the resin are shown in Table 1.
【表】【table】
【表】【table】
Claims (1)
平均分子量500以下の低分子ジオール(B)と有機ジ
イソシアネート(C)とを反応させて熱可塑性ポリウ
レタンエラストマーを製造する方法において、 (1) Ａ及びＢの活性水素の合計数とＣのイソシア
ネート基の数の比が１：1.02〜１：1.1の割合
で、Ａ，Ｂ及びＣを有機溶媒中で反応せしめて
末端にイソシアネート基を有するプレポリマー
(D)とし、 (2) 続いて活性水素３個以上有する架橋剤(E)を、
Ａ，Ｂ及びＥの活性水素の合計数に対するＣの
イソシアネート基の数との比が１：0.85〜１：
0.98の割合で加え、ＥでＤを鎖延長することに
より、得られた熱可塑性ポリウレタンエラスト
マーの分子構造が分子末端にOH基を少なくと
も２個持つことを特徴とする熱可塑性ポリウレ
タン樹脂の製造法。[Claims] 1. A polymeric diol (A) having an average molecular weight of 500 to 5000,
In a method for producing a thermoplastic polyurethane elastomer by reacting a low molecular diol (B) with an average molecular weight of 500 or less and an organic diisocyanate (C), (1) the total number of active hydrogens in A and B and the number of isocyanate groups in C; A prepolymer having isocyanate groups at the terminals by reacting A, B and C in an organic solvent in a number ratio of 1:1.02 to 1:1.1
(D), (2) followed by a crosslinking agent (E) having three or more active hydrogen atoms,
The ratio of the number of isocyanate groups in C to the total number of active hydrogens in A, B and E is 1:0.85 to 1:
A method for producing a thermoplastic polyurethane resin, characterized in that the molecular structure of the thermoplastic polyurethane elastomer obtained by adding D at a ratio of 0.98 and chain-extending D with E has at least two OH groups at the molecular terminals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56102303A JPS585325A (en) | 1981-07-02 | 1981-07-02 | Production of thermoplastic polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56102303A JPS585325A (en) | 1981-07-02 | 1981-07-02 | Production of thermoplastic polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS585325A JPS585325A (en) | 1983-01-12 |
| JPS6329686B2 true JPS6329686B2 (en) | 1988-06-15 |
Family
ID=14323831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56102303A Granted JPS585325A (en) | 1981-07-02 | 1981-07-02 | Production of thermoplastic polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS585325A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3329775A1 (en) * | 1983-08-18 | 1985-02-28 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC POLYURETHANES OF HIGH HEAT RESISTANCE BASED ON NAPHTHYLENE DIISOCYANATE, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| JP6932026B2 (en) * | 2017-05-11 | 2021-09-08 | 日本パーカライジング株式会社 | A water-based metal surface treatment agent, a metal material having a base treatment layer, and a method for manufacturing the same. |
| JP6932025B2 (en) * | 2017-05-11 | 2021-09-08 | 日本パーカライジング株式会社 | Water-based metal surface treatment agent and metal material having a film and its manufacturing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064387A (en) * | 1973-10-08 | 1975-05-31 | ||
| JPS5151307A (en) * | 1974-09-06 | 1976-05-06 | Basf Ag | |
| JPS55110114A (en) * | 1979-02-17 | 1980-08-25 | Freudenberg Carl | Manufacture of low melting point polyurethane having improved strength property |
| JPS5610551A (en) * | 1979-07-06 | 1981-02-03 | Dainichi Seika Kogyo Kk | Pigment-colored polyurethane resin solution |
| JPS57111311A (en) * | 1980-12-29 | 1982-07-10 | Nippon Polyurethan Kogyo Kk | Thermoplastic polyurethane resin |
-
1981
- 1981-07-02 JP JP56102303A patent/JPS585325A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5064387A (en) * | 1973-10-08 | 1975-05-31 | ||
| JPS5151307A (en) * | 1974-09-06 | 1976-05-06 | Basf Ag | |
| JPS55110114A (en) * | 1979-02-17 | 1980-08-25 | Freudenberg Carl | Manufacture of low melting point polyurethane having improved strength property |
| JPS5610551A (en) * | 1979-07-06 | 1981-02-03 | Dainichi Seika Kogyo Kk | Pigment-colored polyurethane resin solution |
| JPS57111311A (en) * | 1980-12-29 | 1982-07-10 | Nippon Polyurethan Kogyo Kk | Thermoplastic polyurethane resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS585325A (en) | 1983-01-12 |
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