JPH02263817A - Curable urethane modified polyester resin - Google Patents
Curable urethane modified polyester resinInfo
- Publication number
- JPH02263817A JPH02263817A JP1085602A JP8560289A JPH02263817A JP H02263817 A JPH02263817 A JP H02263817A JP 1085602 A JP1085602 A JP 1085602A JP 8560289 A JP8560289 A JP 8560289A JP H02263817 A JPH02263817 A JP H02263817A
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- polyester resin
- modified polyester
- curable urethane
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229920001225 polyester resin Polymers 0.000 title claims description 20
- 239000004645 polyester resin Substances 0.000 title claims description 20
- 239000000178 monomer Substances 0.000 claims abstract description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 2
- 125000004031 fumaroyl group Chemical group C(\C=C\C(=O)*)(=O)* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000007259 addition reaction Methods 0.000 abstract description 6
- 239000001361 adipic acid Substances 0.000 abstract description 6
- 235000011037 adipic acid Nutrition 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- -1 adipic acid) Chemical class 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 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 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 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 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint 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
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- HABAXTXIECRCKH-UHFFFAOYSA-N bis(prop-2-enyl) butanedioate Chemical compound C=CCOC(=O)CCC(=O)OCC=C HABAXTXIECRCKH-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硬化性並びに硬化物の物性が優れた新規なウ
レタン変性ポリエステル樹脂に関し、特にその硬化物は
柔軟性及び耐衝撃性が優れているため、本発明樹脂は単
独又はラジカル重合性モノマーと併用して、ラジカル硬
化性樹脂の改質剤、塗料、注型硬化物、ライ÷ング材、
積層材、成形材料などの広範囲の用途に大変有用なもの
である。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel urethane-modified polyester resin that has excellent curability and physical properties of a cured product, and in particular, the cured product thereof has excellent flexibility and impact resistance. Therefore, the resin of the present invention can be used alone or in combination with a radically polymerizable monomer to be used as a modifier for radically curable resins, paints, cast cured products, lining materials,
It is very useful for a wide range of applications such as laminated materials and molding materials.
ウレタン変性ポリエステル樹脂は、ポリエステルポリマ
ー分子鎖の末端にラジカル重合性の二重結合を存在させ
、それと重合性単量体（例；スチレン）とを共重合させ
ることによって、硬化物を得ている。その場合ポリマー
分子鎖内の束縛点が末端部だけのため、生成ポリマー分
子鎖は線状となり、柔軟なゴム弾性体が得られている。Urethane-modified polyester resin has a radically polymerizable double bond present at the end of a polyester polymer molecular chain, and a cured product is obtained by copolymerizing this with a polymerizable monomer (eg, styrene). In this case, since the binding point within the polymer molecular chain is only at the terminal end, the resulting polymer molecular chain becomes linear and a flexible rubber elastic body is obtained.
従来の方法では、ポリマー分子鎖の末端に二重結合を付
与する手段として、アクリル系の特殊な重合性単量体を
使用しなければならない。例えばエポキシ基を持つアク
リル単量体（例；グリシジルメタクリレート）をエステ
ル結合を介して付与する方法、及びヒドロキシ基を持つ
アクリル単量体（例；２−ヒドロキシエチルメタクリレ
ート）をウレタン結合を介して付与する方法が知られて
いる。エポキシ基を持つアクリル単量体を使用する方法
は、エポキシ基とポリマー分子鎖の末端のカルボキシ基
とのエステル化反応を利用する方法であり、ヒドロキシ
基を持つアクリル単量体を使用する方法は、ジイソシア
ナート（例；イソホロンジイソシアナート）を間に介し
て、ポリマー分子鎖の末端のヒドロキシ基とのウレタン
化反応を利用する方法である。以下に代表例を一般的な
反応式で示す。Conventional methods require the use of special acrylic polymerizable monomers as a means of attaching double bonds to the ends of polymer molecular chains. For example, an acrylic monomer having an epoxy group (e.g. glycidyl methacrylate) is added via an ester bond, and an acrylic monomer having a hydroxy group (e.g. 2-hydroxyethyl methacrylate) is attached via a urethane bond. There are known ways to do this. The method using an acrylic monomer with an epoxy group utilizes an esterification reaction between the epoxy group and the carboxy group at the end of the polymer molecular chain, and the method using an acrylic monomer with a hydroxy group This is a method that utilizes a urethanization reaction with a hydroxyl group at the end of a polymer molecular chain via a diisocyanate (eg, isophorone diisocyanate). Representative examples are shown below using a general reaction formula.
（Ｉ）エポキシ基を持つアクリル単量体（例；グリシジ
ルメタクリレート）の場合ポリエステル
−Ｈ０−Ｘ’ −Ｃｏ−０−ＣＭ、 −ＣＨ−ＣＭ、
−０−Ｃｏ−ＣＨ−ＣＨ！０ＨＣＭ。(I) In the case of an acrylic monomer having an epoxy group (e.g. glycidyl methacrylate), polyester -H0-X' -Co-0-CM, -CH-CM,
-0-Co-CH-CH! 0HCM.
（以下余白）
（２）ＯＣＮ−Ｒ’ ＋ＮＨ−Ｃｏ−０−Ｘ’ −０−
Ｃｏ−ＮＨ−Ｒ’＋ ＮＧＯ触謀
ＣＨ。(Left below) (2) OCN-R'+NH-Co-0-X' -0-
Co-NH-R'+ NGO conspiracy CH.
ＯＨ
−ＣＨ，−０−Ｃｏ−Ｘ’ −０−Ｃｏ−ＮＨ）、 Ｒ
’ＣＨ，ＣＭ。OH -CH, -0-Co-X' -0-Co-NH), R
'CH, CM.
−Ｏ＋ＣＨ，）、 Ｏ・ＣＯ・ＮＨ−Ｒ’ ４ＮＨ・ｃ
ｏ−ｏ・ｘ’−ｏ−ｃｏ・〔■〕 ヒドロキシ基を持つ
アクリル単量体（例；２−ヒドロキシエチルメタクリレ
ート）の場合ヒドロキシポリエステル
触媒
（１） ａＨｏ・Ｘ’ −ＯＨ÷ （ｎ＋１）ＯＣ
Ｎ−Ｒ’ −ＮＣＯ−＋ＯＣＮ・−Ｒ’４８Ｈ−Ｃｏ−
０−Ｘ’ −０−Ｃｏ−ＮＨ−Ｒ’） ＮＧＯ（以下
余白）
【但し Ｘ ／ 、 Ｘ ｊはポリエステル鎖から末端
のヒドロキシ基及びカルボキシル基を除いた残基である
。またＲ’ 、Ｒ’はジイソシアナートからイソシアナ
ート基を除いた残基を表わす。ｎは１以上の整数を示す
。〕
しかしながら、〔ｌ〕の方法では、エポキシ基とポリマ
、−分子鎖の末端のカルボキシル基が反応してエステル
結合を形成すると同時に、エステル結合の隣にヒドロキ
シ基も生成され、次に行なうウレタン化反応の時に、生
成した水酸基も反応に関与し、二重結合がポリマー分子
鎖の末端のみならず側鎖にも生成することになり、十分
なゴム弾性を示す硬化物が得られなくなるという不都合
が生ずる。-O+CH,), O・CO・NH−R' 4NH・c
o-o.
N-R'-NCO-+OCN・-R'48H-Co-
0-X'-0-Co-NH-R') NGO (hereinafter blank) [However, X / and X j are residues obtained by removing the terminal hydroxy group and carboxyl group from the polyester chain. Further, R' and R' represent a residue obtained by removing an isocyanate group from a diisocyanate. n represents an integer of 1 or more. However, in method [l], the epoxy group and the carboxyl group at the end of the polymer chain react to form an ester bond, and at the same time, a hydroxyl group is also generated next to the ester bond, which leads to the formation of a urethane. During the reaction, the generated hydroxyl groups also participate in the reaction, and double bonds are generated not only at the ends of the polymer molecular chain but also at the side chains, which causes the inconvenience that a cured product that exhibits sufficient rubber elasticity cannot be obtained. arise.
また（ｎ）の方法では、ウレタン化反応が多く起るため
、ジイソシアナートの添加量が多くなり、価格の面でも
割高となり、また活性なイソシアナート基が消失するま
での反応時間が長くなるという不都合が生じ晶い。In addition, in method (n), since a large amount of urethanization reaction occurs, the amount of diisocyanate added increases, making it relatively expensive, and the reaction time until the active isocyanate group disappears becomes long. This inconvenience arises.
さらに、アクリル単量体及びジイソシアナートを多めに
添加する場合は、急激な発熱を避けるために、滴下装置
を使って徐々に添加しなければならないという不都合が
ある。更にエポキシ基やヒドロキシ基を持つアクリル単
量体は特殊性が高く、現在かなり入手し易くなって来た
といえ、従来より使用されている不飽和ポリエステル樹
脂の原料の不飽和酸（例；無水マレイン酸、フマル酸）
と比較すると価格において不利であり、それゆえ、より
一般的な広範囲の用途に利用することを目的とするには
、不都合がある。Furthermore, when adding a large amount of acrylic monomer and diisocyanate, there is the disadvantage that they must be added gradually using a dropping device in order to avoid rapid heat generation. Furthermore, acrylic monomers with epoxy and hydroxyl groups are highly specialized and are now quite easy to obtain. acid, fumaric acid)
It is disadvantageous in terms of price compared to , and is therefore inconvenient for use in more general and wide-ranging applications.
本発明は、従来の方法において不都合となっていたエポ
キシ基またはヒドロキシ基を持つ特殊なアクリル単量体
を使用しないで、ポリマー分子鎖の末端にラジカル重合
性の二重結合を付与された、優れた硬化物物性を与える
ウレタン変性ポリエステル樹脂の提供を課題とするもの
である。The present invention is an excellent method in which radically polymerizable double bonds are added to the terminals of polymer molecular chains without using special acrylic monomers having epoxy groups or hydroxyl groups, which were disadvantageous in conventional methods. The object of the present invention is to provide a urethane-modified polyester resin that provides cured product physical properties.
本発明者らは、前記課題を解決すべく鋭意検討した結果
、例えば２価アルコール（例；エチレングリコール）と
２価カルボン酸（例；アジピン酸）とをエステル化して
得られる分子鎖の両末端にヒドロキシ基を有するジヒド
ロキシオリゴマーの一端のヒドロキシ基に無水マレイン
酸を開環付加反応させて、二重結合を部分的に付与し、
さらにこの反応生成物を重合性単量体（例；スチレン）
に溶解し、ウレタン触媒の存在下で、ジイソシアネート
（例、 ４．４’−ジフェニルメタンジイソシアナー
ト）と付加反応させて、オリゴマーの他端に残っている
ヒドロキシ基をジイソシアナートの両イソシアナート基
とウレタン化させて末端にフマロイル基を有するウレタ
ン変性ポリエステル樹脂を得ることにより、エポキシ基
またはヒドロキシ基を持つ特殊なアクリル単量体を使用
せず、従来法よりも簡単な方法によってゴム弾性を有す
る硬化物が得られることを見い出し、本発明に至った。As a result of intensive studies to solve the above problems, the present inventors found that both ends of a molecular chain obtained by esterifying a dihydric alcohol (e.g., ethylene glycol) and a dihydric carboxylic acid (e.g., adipic acid), for example, A ring-opening addition reaction of maleic anhydride is performed on the hydroxyl group at one end of the dihydroxy oligomer having a hydroxyl group to partially impart a double bond,
Furthermore, this reaction product is converted into a polymerizable monomer (e.g. styrene).
The remaining hydroxy group at the other end of the oligomer is converted into both isocyanate groups of the diisocyanate by addition reaction with a diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate) in the presence of a urethane catalyst. By urethanizing the resin to obtain a urethane-modified polyester resin with a fumaroyl group at the end, it has rubber elasticity using a simpler method than conventional methods without using special acrylic monomers with epoxy or hydroxyl groups. It was discovered that a cured product can be obtained, leading to the present invention.
本発明の理解を助けるために好適な実施態様によって説
明する。２価アルコール（例；エチレングリコール）と
２価カルボン酸（例；アジピン酸）とを２価アルコール
を過剰にして、酸価がゼロ近くになるまでエステル化し
、分子鎖の末端がヒドロキシ基であるジヒドロキシオリ
ゴマーが得られる。次にこのジヒドロキシオリゴマーに
計算量の無水マレイン酸を添加し、通常のポリエステル
樹脂の反応温度より低い温度約１４０〜１８０℃で反応
を行なう。この反応においては、無水マレイン酸が開環
して、オリゴマーの末端のヒドロキシ基に付加する反応
だけがスムーズに進行し、脱水反応を伴う通常のエステ
ル化反応が進行しないので、オリゴマーの一端に定量的
に二重結合を付与することが簡単に行なえる。また、反
応温度を約１８０〜２００℃に上げ、反応時間を長くす
ることにより、分子鎖の末端に付加したマレイン酸（シ
ス型）をフマル酸（トランス型）へ転移させることがで
き（ＮＭＲ等で確認できる）、これにより、重合性単量
体（例；スチレン）との共重合が更に迅速となり、より
良好な硬化性を示す樹脂が得られる。無水マレイン酸を
開環付加させた後に、重合禁止剤（例；ハイドロキノン
）を添加し、重合性単量体に溶解し、分子鎖の残存末端
ヒドロキシ基と等当量比以下好適には０．８０〜０．９
５比のジイソシアナートとをウレタン化触媒の存在下で
ウレタン化を５０〜１００℃で行ない、実質上イソシア
ナート基の残存しないウレタン変性ポリエステル樹脂組
成物を特殊なアクリル単量体を使用せずに、より簡単に
得ることができる。A preferred embodiment will be described to aid understanding of the present invention. Divalent alcohol (e.g. ethylene glycol) and divalent carboxylic acid (e.g. adipic acid) are esterified with excess dihydric alcohol until the acid value is close to zero, and the end of the molecular chain is a hydroxy group. A dihydroxy oligomer is obtained. A calculated amount of maleic anhydride is then added to the dihydroxy oligomer and the reaction is carried out at a temperature of about 140 DEG to 180 DEG C., which is lower than the reaction temperature of conventional polyester resins. In this reaction, only the reaction in which maleic anhydride opens the ring and adds it to the hydroxyl group at the end of the oligomer proceeds smoothly, and the normal esterification reaction that accompanies the dehydration reaction does not proceed. It is easy to add a double bond. In addition, by raising the reaction temperature to about 180-200°C and lengthening the reaction time, maleic acid (cis type) added to the end of the molecular chain can be transferred to fumaric acid (trans type) (NMR etc. ), thereby copolymerizing with the polymerizable monomer (e.g. styrene) becomes more rapid, resulting in a resin exhibiting better curability. After ring-opening and addition of maleic anhydride, a polymerization inhibitor (e.g., hydroquinone) is added and dissolved in the polymerizable monomer to give an equivalent ratio of less than or equal to the remaining terminal hydroxyl group of the molecular chain, preferably 0.80. ~0.9
5 ratio of diisocyanate in the presence of a urethanization catalyst at 50 to 100°C to produce a urethane-modified polyester resin composition with virtually no remaining isocyanate groups without using special acrylic monomers. can be obtained more easily.
以下に、２価アルコールとしてエチレングリコール、２
価カルボン酸としてアジピン酸、無水マレイン酸及びジ
イソシアナートとして４．４′−ジフェニルメタンジイ
ソシアナートを用いてウレタン変性ポリエステル樹脂を
合成するための反応式を示す。Below, the dihydric alcohols are ethylene glycol, 2
A reaction formula for synthesizing a urethane-modified polyester resin using adipic acid, maleic anhydride as the carboxylic acid, and 4,4'-diphenylmethane diisocyanate as the diisocyanate is shown below.
（以下余白）
本発明において、使用可能なジヒドロキシオリゴマーと
しては、通常のポリエステル樹脂の製造に使用されてい
る２価アルコールと２価カルボン酸とのエステル化によ
って合成される数平均分子量５００〜３０００程度のジ
ヒドロキシポリエステルオリゴマーが最適であるが、そ
れだけに限られず、分子両端にヒドロキシ基を有するオ
リゴマーであれば使用可能であり、例えば分子内にエー
テル基を有するジヒドロキシポリエーテルオリゴマーポ
リカプロラクトンオリゴマー、シリコンジオールも良好
な原料となる。(Left below) In the present invention, usable dihydroxy oligomers have a number average molecular weight of about 500 to 3000 and are synthesized by esterification of a dihydric alcohol and a dihydric carboxylic acid, which are used in the production of ordinary polyester resins. dihydroxy polyester oligomer is most suitable, but it is not limited thereto, and any oligomer that has hydroxy groups at both ends of the molecule can be used; for example, dihydroxy polyether oligomer, polycaprolactone oligomer, and silicone diol that have an ether group in the molecule are also suitable. It becomes a raw material.
前記２価カルボン酸としては、芳香族飽和二塩基酸また
はその酸無水物として、フタル酸、無水フタル酸、イソ
フタル酸、テレフタル酸、ニトロフタル酸、テトラヒド
ロ無水フタル酸、エンドメチレンテトラヒドロ無水フタ
ル酸、ハロゲン化無水フタル酸およびこれらのエステル
等があり、脂肪族あるいは脂環族飽和二塩基酸として、
シュウ酸、マロン酸、コハク酸、アジピン酸、セパシン
酸−アゼライン酸、グルタル酸、ヘキサヒドロ無水フタ
ル酸およびこれらのエステル等があり、それぞれ単独あ
るいは併用して使用される。The divalent carboxylic acids include aromatic saturated dibasic acids or their acid anhydrides such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and halogen phthalic anhydride and their esters, and as aliphatic or alicyclic saturated dibasic acids,
Examples include oxalic acid, malonic acid, succinic acid, adipic acid, sepacic acid-azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination.
また、２価アルコールとしては、エチレングリコール、
プロピレングリコール、ジエチレングリコール、ジプロ
ピレングリコール、■、３〜ブタンジオール、１．４−
ブタンジオール、２−メチルプロパン−１，３−ジオー
ル、ネオペンチルグリコール、トリエチレングリコール
、テトラエチレングリコール、１．５−ベンタンジオー
ル、１．６−ヘキサンジオール、ビスフェノールＡ、水
素化ビスフェノールＡ１エチレングリコールカーボネー
ト、２．２−ジ＋４−ヒドロキシプロポキシジフェニル
Ｙプロパン等が挙げられ、単独あるいは併用で使用され
るが、その他にエチレンオキサイド、プロピレンオキサ
イド等の酸化物も同様に使用できる。またグリコール類
と酸成分の一部としてポリエチレンテレフタレート等の
重縮合物も使用できる。In addition, dihydric alcohols include ethylene glycol,
Propylene glycol, diethylene glycol, dipropylene glycol, ■, 3-butanediol, 1.4-
Butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-bentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A1 ethylene glycol carbonate , 2,2-di+4-hydroxypropoxydiphenyl Y propane, etc., which can be used alone or in combination, but other oxides such as ethylene oxide and propylene oxide can also be used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycol and acid components.
本発明で使用するジイソシアナートとしては、例えば、
トリレンジイソシアナート（ＴＤＩ）いフェニレンジイ
ソシアナート（ＰＰＩ）、キシレンジイソシアナート（
ＸＤ Ｉ ） 、１．６へキサメチレンジイソシアナー
ト（ＨＭＤＩ）、４．４′−ジフェニルメタンジイソシ
アナート（ＭＤＩ）、イソホロンジイソシアナート（Ｉ
ＰＤＩ）、テトラメチルキシリレンジイソシアナート（
ＴＭＩＤＩ）等市販されている２価のイソシアナートは
ほとんど使用できる。Examples of the diisocyanate used in the present invention include:
Tolylene diisocyanate (TDI), phenylene diisocyanate (PPI), xylene diisocyanate (
XD I ), 1.6 hexamethylene diisocyanate (HMDI), 4.4′-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (I
PDI), tetramethylxylylene diisocyanate (
Most commercially available divalent isocyanates such as TMIDI) can be used.
ウレタン化触媒としては、トリエチルアミン、トリエチ
レンジアミン、Ｎ−メチルモルホリン、ナフテン酸亜鉛
、ナフテン酸コバルト、オクトエ酸銅、ジブチル錫ジラ
ウレートなどが用いられる。As the urethanation catalyst, triethylamine, triethylenediamine, N-methylmorpholine, zinc naphthenate, cobalt naphthenate, copper octoate, dibutyltin dilaurate, etc. are used.
かくして得られるウレタン変性ポリエステル樹脂は、数
平均分子量が１０００〜８０００程度のものであり、こ
の範囲のものが、作業性にすぐれ且つ物性も良好である
。The urethane-modified polyester resin thus obtained has a number average molecular weight of about 1,000 to 8,000, and those within this range have excellent workability and good physical properties.
本発明で使用されるラジカル重合性モノマーとしては、
スチレン、ビニルトルエン、α−メチルスチレン、クロ
ルスチレン、ジクロルスチレン、ビニルナフタレン、エ
チルビニルエーテル、メチルビニルケトン、メチルアク
リレート、エチルアクリレート、メチルメタアクリレー
ト、アクリロニトリノ呟メタクリロニトリル等のビニル
化合物およびジアリルフタレート、ジアリルフマレート
、ジアリルサクシネート、トリアリルシアヌレート等の
アリル化合物などのウレタン変性ポリエステル樹脂と架
橋可能なビニルモノマーあるいはビニルオリゴマー等が
挙げられ、単独あるいは併用で使用されるが、一般的に
はスチレンが使用される。The radically polymerizable monomer used in the present invention includes:
Vinyl compounds and diallyl such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, etc. Examples include vinyl monomers or vinyl oligomers that can be crosslinked with urethane-modified polyester resins such as allyl compounds such as phthalate, diallyl fumarate, diallyl succinate, and triallyl cyanurate, and are used alone or in combination, but generally Styrene is used.
本発明におけるウレタン変性ポリエステル樹脂は、通常
の不飽和ポリエステル樹脂の硬化に使用されている硬化
触媒及び硬化促進剤を添加することによって容易に硬化
することができ、また増感剤の存在下で光硬化させるこ
とも可能である。得られる硬化物はゴム弾性に富み、耐
衝撃性に大変優れており、また不飽和ポリエステル樹脂
及びビニルエステル樹脂などのラジカル硬化性樹脂に混
合することによって樹脂の伸び及び耐衝撃性を容易に向
上させることができる。The urethane-modified polyester resin of the present invention can be easily cured by adding a curing catalyst and a curing accelerator that are used for curing ordinary unsaturated polyester resins, and can be easily cured by adding a curing catalyst and a curing accelerator that are used for curing ordinary unsaturated polyester resins. It is also possible to harden it. The resulting cured product is rich in rubber elasticity and has excellent impact resistance, and the elongation and impact resistance of the resin can be easily improved by mixing it with radical curable resins such as unsaturated polyester resins and vinyl ester resins. can be done.
次に本発明をより詳細に説明するために実施例を示すが
、これらをもって本発明の範囲を限定するものではない
。なお、特に断らない限り、例中の部は重量部である。EXAMPLES Next, Examples are shown to explain the present invention in more detail, but the scope of the present invention is not limited thereto. In addition, unless otherwise specified, parts in the examples are parts by weight.
実施例 １
エチレングリコール２２４部とアジピン＠ ４５３部を
窒素気流中において、２２０℃で酸価が１，６、水酸化
が６４までエステル反応を行ない、数平均分子ｆｆ１１
７００のヒドロキシポリエステルオリゴマーを得た。引
き続き、無水マレイン酸４３部を１２０℃で添加して、
１５０℃で２時間開環付加反応を行ない末端マレイン酸
型ポリエステル化合物を得た（核磁気共鳴スペクトルに
よって確認した）。次にハイドロキノン０．２部を添加
し、スチレン２７３部に溶解した後に、４．４’ ジフ
ェニルメタンジイソシアナート２８．５部を添加し、５
０℃で１時間反応後、ウレタン化触媒としてジブチル錫
ジラウレートを０．５部ずつ３０分間隔に３回添加し、
最後の触媒を添加後１時間反応を続け、赤外吸収スペク
トルによってインシアナート基の２２７０〜２２８０ｃ
＋ｎ−１の吸収ピークが消失したことを確認し、反応を
終了し、活性なイソシアナート基の残存しない透明で淡
黄色の樹脂（Ａ）を得た（第１図参照）。得られた樹脂
（Ａ）の粘度は８，０ポアズ（２５℃）であった。樹脂
（Ａ）１００部に対して６％のナフテン酸コバルトを１
．５部と、５５％のアセチルアセトンパーオキサイドを
２．０部を添加して、常温にて硬化させ、厚さ３Ｉｕの
シート状硬化物を作成した。硬化後４０℃のオーブン中
で１６時間養生後、ダンベル状に打ち抜き、引張り強さ
、引裂き強さ、伸びを調べた。さらに、樹脂（Ａ）１０
０部に対してスチレン４０部を添加して、樹脂組成物（
Ｂ）を作り、同様にして、シート状硬化物を作成して試
験を行なった。Example 1 In a nitrogen stream, 224 parts of ethylene glycol and 453 parts of adipine were subjected to an ester reaction at 220°C until the acid value was 1.6 and the hydroxylation was 64, resulting in a number average molecule ff11.
A hydroxy polyester oligomer of 700 was obtained. Subsequently, 43 parts of maleic anhydride was added at 120°C,
A ring-opening addition reaction was carried out at 150° C. for 2 hours to obtain a terminal maleic acid type polyester compound (confirmed by nuclear magnetic resonance spectrum). Next, 0.2 parts of hydroquinone was added and dissolved in 273 parts of styrene, and then 28.5 parts of 4.4' diphenylmethane diisocyanate was added.
After reacting at 0°C for 1 hour, 0.5 parts of dibutyltin dilaurate was added as a urethanization catalyst three times at 30 minute intervals.
After adding the last catalyst, the reaction was continued for 1 hour, and infrared absorption spectroscopy showed that the incyanato group was 2270-2280c.
After confirming that the +n-1 absorption peak had disappeared, the reaction was terminated to obtain a transparent, pale yellow resin (A) in which no active isocyanate groups remained (see Figure 1). The resulting resin (A) had a viscosity of 8.0 poise (25°C). 6% cobalt naphthenate per 100 parts of resin (A)
．． 5 parts of acetylacetone peroxide and 2.0 parts of 55% acetylacetone peroxide were added and cured at room temperature to create a sheet-like cured product with a thickness of 3 Iu. After curing and curing in an oven at 40° C. for 16 hours, dumbbell shapes were punched out and tensile strength, tear strength, and elongation were examined. Furthermore, resin (A) 10
By adding 40 parts of styrene to 0 parts, the resin composition (
B) was prepared, and a sheet-like cured product was prepared and tested in the same manner.
実施例 ２
実施例１と同様にして、数平均分子ｆｆ１１７００のヒ
ドロキシポリエステルオリゴマーを得た。次に無水マレ
イン酸４３部を１２０℃で添加して、１９０℃で４時間
反応して、無水マレイン酸を開環付加し、更にマレイン
酸を一部分フマル酸転移させた反応物を得た（核磁気共
鳴スペクトルによって確認した）。その他実施例１と同
様にして、樹脂（Ｃ）とスチレン４０部を追加した樹脂
組成物（Ｄ）を作成して、実施例１と同様にしてシート
状硬化物を作成して物性試験を行なった。Example 2 In the same manner as in Example 1, a hydroxy polyester oligomer with a number average molecular weight ff of 11,700 was obtained. Next, 43 parts of maleic anhydride was added at 120°C, and the reaction was carried out at 190°C for 4 hours to obtain a reaction product in which maleic anhydride was subjected to ring-opening addition and a portion of maleic acid was transferred to fumaric acid (nuclear confirmed by magnetic resonance spectroscopy). In addition, a resin composition (D) was prepared by adding resin (C) and 40 parts of styrene in the same manner as in Example 1, a sheet-like cured product was prepared in the same manner as in Example 1, and a physical property test was conducted. Ta.
実施例 ３
市販のポリカプロラクトン（ヒドロキシポリエステルオ
リゴマー、数平均分子量２００Ｇ） ５１０部に無水マ
レイン酸２５部を添加して、１５０℃で２時間開環付加
反応を行ない末端マレイン酸型ポリエステル化合物を得
た。次に実施例１と同様にしてハイドロキノン０．１６
部とスチレン２４０部を添加し溶解後、イソホロンジイ
ソシアナート２７部を添加し、ジブチル錫ジラウレート
１．５部を用いて９０℃で実施例１と同様に反応を行な
い、樹脂（Ｅ）とスチレン４０部を追加した樹脂組成物
（Ｐ）を作成し、実施例１と同様にしてシート状硬化物
を作成し物性試験を行なった。Example 3 25 parts of maleic anhydride was added to 510 parts of commercially available polycaprolactone (hydroxy polyester oligomer, number average molecular weight 200 G), and a ring-opening addition reaction was performed at 150°C for 2 hours to obtain a terminal maleic acid type polyester compound. . Next, in the same manner as in Example 1, hydroquinone 0.16
After adding and dissolving 240 parts of styrene, 27 parts of isophorone diisocyanate was added, and the reaction was carried out in the same manner as in Example 1 at 90°C using 1.5 parts of dibutyltin dilaurate to dissolve the resin (E) and styrene. A resin composition (P) with 40 parts added was prepared, and a sheet-like cured product was prepared in the same manner as in Example 1, and a physical property test was conducted.
実施例 ４
エチレングリコール７５部と１，６ヘキサンジオ一ルｔ
ｔＳ部とアジピン酸１４６部とジメチルテレフタレート
１９４部を実施例１と同様にしてエステル化して、数平
均分子ｊｌ１８００のヒドロキシポリエステルオリゴマ
ーを作り、実施例１と同様にして無水マレイン酸２７部
を開環付加し、ハイドロキノン０．１４部、スチレン２
０４１部に溶解後、テトラメチルキシリレンジイソシア
ナート２４．５部を添加し、ジブチル錫ジラウレー１．
５部を用いて９５℃で反応し、その他実施例１と同様に
して樹脂（Ｇ）とスチレン４０部を追加した樹脂組成物
（）ｌ）とそれぞれのシート状硬化物を作成し物性試験
を行なった。Example 4 75 parts of ethylene glycol and 1,6 hexanediol
The tS part, 146 parts of adipic acid, and 194 parts of dimethyl terephthalate were esterified in the same manner as in Example 1 to produce a hydroxy polyester oligomer with a number average molecular weight of 1800, and 27 parts of maleic anhydride was ring-opened in the same manner as in Example 1. Added, 0.14 parts of hydroquinone, 2 parts of styrene
After dissolving in 0.41 parts of dibutyltin dilaure, 24.5 parts of tetramethylxylylene diisocyanate was added.
A resin composition ()l) in which resin (G) and 40 parts of styrene were added was reacted at 95° C. using 5 parts of resin (G) and 40 parts of styrene, and each sheet-shaped cured product was prepared and the physical properties were tested. I did it.
実施例において作成した樹脂組成物の粘度及びシート状
硬化物の物性試験の測定値を表１に示す。Table 1 shows the viscosity of the resin composition prepared in the examples and the measured values of the physical property test of the sheet-like cured product.
（以下余白）
〔発明の効果〕
本発明によれば、特殊なアクリル単量体を使用しなくて
も、より一般的な原料である無水マレイン酸を使用して
、開環付加反応をうまくさせることによって、高性能な
ウレタン変性ポリエステル樹脂を極めて容易に製造でき
、また得られるウレタン変性樹脂の硬化物は極めて良好
なゴム弾性を示し、またジヒドロキシオリゴマーの種類
を変えることにより、多種多様のものが製造可能であり
、更に本発明によるウレタン変性樹脂は、不飽和ポリエ
ステル樹脂及びビニルエズテル樹脂に添加するだけで大
変良好な改質材となり、柔軟性及び耐衝撃性を簡単に向
上させることができ、ウレタン変性樹脂組成物単独並び
に改質材として、塗料、注型物、ライニング材、積層材
、成形材料などの広範囲の用途に大変有用である。(Left below) [Effects of the Invention] According to the present invention, the ring-opening addition reaction can be successfully carried out using maleic anhydride, which is a more general raw material, without using a special acrylic monomer. This makes it possible to produce high-performance urethane-modified polyester resins extremely easily, and the resulting cured urethane-modified resins exhibit extremely good rubber elasticity, and by changing the type of dihydroxy oligomer, a wide variety of products can be produced. Furthermore, the urethane modified resin according to the present invention becomes a very good modifier just by adding it to unsaturated polyester resin and vinyl ester resin, and can easily improve flexibility and impact resistance. The modified resin composition alone or as a modifier is very useful for a wide range of applications such as paints, cast materials, lining materials, laminated materials, and molding materials.
第１図は、実施例１により得られたウレタン変性ポリエ
ステル樹脂（Ａ）の赤外線吸収スペクトルである。FIG. 1 is an infrared absorption spectrum of the urethane-modified polyester resin (A) obtained in Example 1.
Claims (5)
イソシアナートを反応させて得られる、硬化可能なウレ
タン変性ポリエステル樹脂。(1) A curable urethane-modified polyester resin obtained by reacting a dihydroxy oligomer, maleic anhydride, and diisocyanate.
無水マレイン酸を開環付加させて得られる反応生成物の
残のヒドロキシ基を、ジイソシアナートの両イソシアナ
ート基に付加させて得られる、分子末端にマレロイル基
又はフマロイル基を有することを特徴とする、硬化可能
なウレタン変性ポリエステル樹脂。(2) A molecular terminal obtained by adding the remaining hydroxy group of the reaction product obtained by ring-opening addition of one hydroxy group of a dihydroxy oligomer with maleic anhydride to both isocyanate groups of a diisocyanate. A curable urethane-modified polyester resin, characterized in that it has a maleloyl group or a fumaroyl group.
を除いた残基、Ｒはジイソシアナートからイソシアナー
ト基を除いた残基を表わす〕 で表わされる硬化可能なウレタン変性ポリエステル樹脂
。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, X represents the residue obtained by removing the hydroxyl group from the dihydroxy oligomer, and R represents the residue obtained by removing the isocyanate group from the diisocyanate] Curable urethane-modified polyester resin.
ルボン酸との反応で得られる両末端にヒドロキシ基を有
するポリエステルオリゴマーを用いることを特徴とする
第１項、第２項又は第３項記載の硬化可能なウレタン変
性ポリエステル樹脂。(4) The curable urethane according to item 1, item 2, or item 3, characterized in that the dihydroxy oligomer is a polyester oligomer having hydroxyl groups at both ends obtained by a reaction between a diol and a dicarboxylic acid. Modified polyester resin.
第３項記載の硬化可能なウレタン変性ポリエステル樹脂
に配合してなる、硬化可能なウレタン変性ポリエステル
樹脂組成物。(5) A curable urethane-modified polyester resin composition comprising a radically polymerizable monomer blended with the curable urethane-modified polyester resin described in item 1, 2, or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1085602A JPH02263817A (en) | 1989-04-04 | 1989-04-04 | Curable urethane modified polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1085602A JPH02263817A (en) | 1989-04-04 | 1989-04-04 | Curable urethane modified polyester resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02263817A true JPH02263817A (en) | 1990-10-26 |
Family
ID=13863374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1085602A Pending JPH02263817A (en) | 1989-04-04 | 1989-04-04 | Curable urethane modified polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02263817A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8940818B2 (en) | 2007-07-28 | 2015-01-27 | Chemische Fabrik Budenheim Kg | Halogen-free flame-proofing agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4935464A (en) * | 1972-08-08 | 1974-04-02 | ||
| JPS5262393A (en) * | 1975-11-18 | 1977-05-23 | Showa Highpolymer Co Ltd | Unsaturated polyester resin compositions |
| JPS52140541A (en) * | 1976-05-18 | 1977-11-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame-retardant polyurethane coating compositions |
| JPS5556115A (en) * | 1978-10-23 | 1980-04-24 | Dainippon Ink & Chem Inc | Preparation of sheet molding compound |
| JPS60229918A (en) * | 1984-04-28 | 1985-11-15 | Chisso Corp | Polyurethane resin and polyester polyol therefor |
-
1989
- 1989-04-04 JP JP1085602A patent/JPH02263817A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4935464A (en) * | 1972-08-08 | 1974-04-02 | ||
| JPS5262393A (en) * | 1975-11-18 | 1977-05-23 | Showa Highpolymer Co Ltd | Unsaturated polyester resin compositions |
| JPS52140541A (en) * | 1976-05-18 | 1977-11-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame-retardant polyurethane coating compositions |
| JPS5556115A (en) * | 1978-10-23 | 1980-04-24 | Dainippon Ink & Chem Inc | Preparation of sheet molding compound |
| JPS60229918A (en) * | 1984-04-28 | 1985-11-15 | Chisso Corp | Polyurethane resin and polyester polyol therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8940818B2 (en) | 2007-07-28 | 2015-01-27 | Chemische Fabrik Budenheim Kg | Halogen-free flame-proofing agent |
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