JPS6389520A - Polyurethane resin composition - Google Patents
Polyurethane resin compositionInfo
- Publication number
- JPS6389520A JPS6389520A JP61233680A JP23368086A JPS6389520A JP S6389520 A JPS6389520 A JP S6389520A JP 61233680 A JP61233680 A JP 61233680A JP 23368086 A JP23368086 A JP 23368086A JP S6389520 A JPS6389520 A JP S6389520A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyurethane resin
- polyol
- acid
- alcohol
- 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
- 229920005749 polyurethane resin Polymers 0.000 title claims description 32
- 239000011342 resin composition Substances 0.000 title claims description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 23
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 abstract description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract description 8
- 235000019260 propionic acid Nutrition 0.000 abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract description 4
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- -1 ether polyol Chemical class 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 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 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- FNJSWIPFHMKRAT-UHFFFAOYSA-N Monomethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(O)=O FNJSWIPFHMKRAT-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 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 2
- 238000003786 synthesis reaction Methods 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 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
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-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
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- WMZNGTSLFSJHMZ-UHFFFAOYSA-N 3-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=CC(C(O)=O)=C1 WMZNGTSLFSJHMZ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000270299 Boa Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- COYJIMCVCRLOIW-UHFFFAOYSA-L [Mn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Mn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O COYJIMCVCRLOIW-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 1
- 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 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- 150000003955 ε-lactams Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリウレタン樹脂組成物に関し、特に絶縁電線
用塗料に供する焼付作業性の良好な低公害性のポリウレ
タン樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyurethane resin composition, and particularly to a low-pollution polyurethane resin composition with good baking workability and used as a coating for insulated wires.
（従来の技術）
絶縁電線用ポリウレタン塗料は高速焼付は塗工ができる
こと、皮膜を剥離することなく半田付けが可能であるこ
となどに特長があり、弱電機器用絶縁電線等に広く用い
られている。(Conventional technology) Polyurethane paint for insulated wires has the characteristics of being able to be coated at high speed and being able to be soldered without peeling off the coating, and is widely used for insulated wires for light electrical equipment. .
しかし、一般的に絶縁電線用ポリウレタン塗料は人体に
有害なフェノール系溶媒を用いており、作業時の環境衛
生上に問題がある。そこで、フェノール系溶媒を有害性
の少ないアルコール系溶媒に換えて無公害化する提案が
行われている（例えば、特開昭５８−９６６６３号公報
、特開昭５７−１２５２７０号公報）。However, polyurethane paints for insulated wires generally use phenolic solvents that are harmful to the human body, which poses problems in terms of environmental hygiene during work. Therefore, proposals have been made to replace the phenolic solvent with a less harmful alcoholic solvent to make it non-polluting (for example, Japanese Patent Laid-Open No. 58-96663 and Japanese Patent Laid-Open No. 57-125270).
（発明が解決しようとする問題点）
これらの無公害性ポリウレタン塗料は銅線等の基材への
焼付塗工時に皮膜表面が肌荒れするなど、焼付作業性（
以下、外観という）に問題があった。(Problems to be Solved by the Invention) These non-polluting polyurethane paints have poor baking workability (such as roughening of the film surface when baking coated on base materials such as copper wires).
There was a problem with the appearance (hereinafter referred to as appearance).
外観が不十分であると、電線に要求される性能の信頼性
が著しく損なわれるため、焼付炉や焼付条件が違っても
、つねに良好な外観を有する低公害性ポリウレタン塗料
が望まれている。If the appearance is insufficient, the reliability of the performance required for electric wires will be significantly impaired, so there is a desire for a low-pollution polyurethane paint that always has a good appearance even if the baking oven or baking conditions are different.
焼付塗工時における外観を良好に保つ要因は、ポリウレ
タン塗料の構成材料であるポリウレタン樹脂の硬化反応
速度と、溶媒および／またはブロック剤の揮散速度をバ
ランスさせることにある。The key to maintaining a good appearance during baking coating is to balance the curing reaction rate of the polyurethane resin, which is a constituent material of the polyurethane paint, and the volatilization rate of the solvent and/or blocking agent.
特に、アルコール系溶媒を用いる場合は、焼付時にアル
コール系溶媒が遊離のイソシアネート基と付加反応する
か、またはウレタン結合と交換反応して熱解離温度の高
いウレタン結合を生じ、硬化反応の遅延を生ずる。した
がってアルコール系溶媒による硬化反応の遅延効果を適
度に制御することは、外観の良好な低公害性ポリウレタ
ン塗料を得る上で重要である。In particular, when an alcohol-based solvent is used, during baking, the alcohol-based solvent undergoes an addition reaction with free isocyanate groups or an exchange reaction with urethane bonds, producing urethane bonds with a high thermal dissociation temperature, resulting in a delay in the curing reaction. . Therefore, it is important to appropriately control the effect of retarding the curing reaction by alcohol solvents in order to obtain a low-pollution polyurethane coating with good appearance.
本発明の目的は、前記従来技術の欠点を除去し、低公害
性で、かつ銅線等の基材への焼付塗工時に良好な外観を
与えるポリウレタン樹脂組成物を提供することにある。It is an object of the present invention to provide a polyurethane resin composition that eliminates the drawbacks of the prior art, has low pollution properties, and provides a good appearance when baked onto a substrate such as a copper wire.
（問題点を解決するための手段）
本発明は、ポリオール（Ｉ）、ブロックボリイソシアネ
ー） （Ｉりおよび有機金属化合物（Ｉ）を、アルコー
ルの少なくとも１種を５〜１００重量％含む溶媒（ＩＶ
）に溶解してなるポリウレタン樹脂組成物において、（
Ｉ）および（Ｖ）の混合物の酸価が４〜２０になるよう
に有機酸（Ｖ）を配合してなるポリウレタン樹脂組成物
に関する。(Means for Solving the Problems) The present invention provides polyol (I), blocked polyisocyanate (I) and organometallic compound (I) in a solvent containing 5 to 100% by weight of at least one alcohol ( IV
) in a polyurethane resin composition dissolved in (
The present invention relates to a polyurethane resin composition in which an organic acid (V) is blended so that the mixture of I) and (V) has an acid value of 4 to 20.
本発明におけるポリオール（Ｉ）は、ポリエステルポリ
オール、ポリエーテルポリオール、ポリエステルエーテ
ルポリオールなどの通常のポリウレタン樹脂の製造に用
いられるポリオールであれば特に制限されるものではな
いが、耐熱性の面からポリエステルポリオールが好まし
い、このポリエステルポリオールとしては、例えば、−
級、二級または三級のヒドロキシル基をもつ脂肪族、脂
環族、複素環族または芳香族多価アルコールと脂肪族、
脂環族、複素環族または芳香族多価カルボン酸またはこ
れらのエステルとの重縮合反応によって得られるものが
用いられる。市販されている材料としては、例えばデス
モーフエン６００、デスモーフエン８００ （以上、バ
イエル社製商品名）などのポリエステルポリオールが用
いられる。Polyol (I) in the present invention is not particularly limited as long as it is a polyol used in the production of ordinary polyurethane resins such as polyester polyol, polyether polyol, polyester ether polyol, etc., but from the viewpoint of heat resistance, polyester polyol The preferred polyester polyol is, for example, -
aliphatic, alicyclic, heterocyclic or aromatic polyhydric alcohols and aliphatic alcohols having primary, secondary or tertiary hydroxyl groups;
Those obtained by polycondensation reaction with alicyclic, heterocyclic, or aromatic polycarboxylic acids or esters thereof are used. Commercially available materials include polyester polyols such as Desmorphen 600 and Desmorphen 800 (trade names manufactured by Bayer AG).
好ましくは、多価アルコールとしてグリセリン、トリメ
チロールプロパン、または炭素数が２〜８の脂肪族アル
コール、多価カルボン酸としてテレフタル酸、イソフタ
ル酸、無水フタル酸、炭素数が２〜６の脂肪族ジカルボ
ン酸またはこれらのエステルとの重縮合反応によって得
られるものであり、特に、硬化反応性、耐熱性などから
多価アルコール中５０〜９０当量％のグリセリンを含む
分岐型ポリエステルポリオールが好ましい。Preferably, the polyhydric alcohol is glycerin, trimethylolpropane, or an aliphatic alcohol having 2 to 8 carbon atoms, and the polyhydric carboxylic acid is terephthalic acid, isophthalic acid, phthalic anhydride, or an aliphatic dicarboxylic acid having 2 to 6 carbon atoms. It is obtained by a polycondensation reaction with an acid or an ester thereof, and a branched polyester polyol containing 50 to 90 equivalent % of glycerin in a polyhydric alcohol is particularly preferred from the viewpoint of curing reactivity and heat resistance.
ポリエーテルポリオールとしては、例えば、−級、二級
または三級のヒドロキシル基をもつ脂肪族、脂環族、複
素環族または芳香族のポリエーテルポリオールが用いら
れる。具体的には、例えばヒドロキシエチル化ビスフェ
ノールＡ１ヒドロキシプロピル化ビスフエノールＡ、ヒ
ドロキシエチル化ノボラック型フェノール樹脂等のポリ
フェノール化合物のポリヒドロキシエチル化またはポリ
ヒドロキシプロピル化物、分子量約１００〜２０００の
ポリエチレングリコールまたはポリプロピレングリコー
ル、エチレングリコール、プロピレングリコール、１，
４−ブタンジオール、トリメチロールプロパン、グリセ
リン、ペンタエリスリトール等のポリオールのポリヒド
ロキシエチル化またはポリヒドロキシプロピル化物、エ
チレンジアミン、プロピレンジアミン、ヘキサメチレン
ジアミン、アニリン、４．４’ −ジアミノジフェニ
ルメタン等のポリアミンのポリヒドロキシエチル化また
はポリヒドロキシプロピル化物などが用いられる。As the polyether polyol, for example, an aliphatic, alicyclic, heterocyclic or aromatic polyether polyol having a -class, secondary or tertiary hydroxyl group is used. Specifically, for example, hydroxyethylated bisphenol A, hydroxypropylated bisphenol A, polyhydroxyethylated or polyhydroxypropylated polyphenol compounds such as hydroxyethylated novolac type phenolic resin, polyethylene glycol or polypropylene with a molecular weight of about 100 to 2000. Glycol, ethylene glycol, propylene glycol, 1,
Polyhydroxyethylated or polyhydroxypropylated polyols such as 4-butanediol, trimethylolpropane, glycerin, and pentaerythritol; polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, aniline, and 4,4'-diaminodiphenylmethane; Hydroxyethylated or polyhydroxypropylated products are used.
ポリエステルポリオールとしては、例えば上記のポリエ
ステルポリオールの多価アルコールとして、上記のポリ
エーテルポリオールを併用して製造されるポリエステル
ポリオールなどが用いられる。As the polyester polyol, for example, a polyester polyol produced by using the above-mentioned polyether polyol in combination with the polyhydric alcohol of the above-mentioned polyester polyol is used.
なお多価カルボン酸を用いる場合は、最終的に得られる
ポリオール中にカルボン酸が残存する場合があり、この
カルボン酸は本発明において配合される有機酸（ＩＶ）
の代用とすることができる。In addition, when using a polyhydric carboxylic acid, the carboxylic acid may remain in the polyol finally obtained, and this carboxylic acid is used as the organic acid (IV) blended in the present invention.
It can be used as a substitute.
ポリオール（Ｉ）は単独でまたは二種以上が用いられる
。Polyol (I) may be used alone or in combination of two or more.
本発明におけるブロックポリイソシアネート（ＩＩ）は
ポリイソシアネートをブロック剤で封鎖した通常のポリ
ウレタン樹脂の製造において用いられるブロックポリイ
ソシアネートであればよく特に制限はない。このブロッ
クポリイソシアネートのポリイソシアネート成分として
は、例えばトリレンジイソシアネート、キシリレンジイ
ソシアネ−）、４．４’−ジフェニルエーテルジイソシ
アネート、ナフタレン−１，５−ジイソシアネート、４
．４′−ジフェニルメタンジイソシアネート等の芳香族
ジイソシアネート、エチレンジイソシアネート、１．４
−テトラメチレンジイソシアネート、１，６−へキサメ
チレンジイソシアネート、１．１２−ドデカンジイソシ
アネート等の脂肪族ジイソシアネート、シクロブテン１
，３−ジイソシアネート、シクロヘキサン１．３−およ
び１゜４−ジイソシアネート、イソフォロンジイソシア
ネート等の脂環式ジイソシアネート、トリフェニルメタ
ン−４，４’４”−）ジイソシアネート、ポリフェニル
メチルポリイソシアネート、例えばアニリンとフォルム
アルデヒドとの縮合物をフォスゲン化したもの等のポリ
イソシアネート、これらのポリイソシアネートの三量化
反応によって得られるイソシアヌレート環含有ポリイソ
シアネート、またはこれらのポリイソシアネートと前述
したポリオール（ＩＮ）のアルコール成分を反応させた
ポリウレタンポリイソシアネートなどがあげられる。ま
た、ブロック剤としては、１分子中に１個の活性水素を
含有する化合物、例えば、炭素数が１〜１２であってエ
ーテル結合を主鎖または側鎖に含んでいてもよい脂肪族
１価アルコール、ベンジルアルコール、シクロヘキサノ
ール等のアルコール類、フェノール、クレゾール、キシ
レノール等のフェノール類、２−ブタノンオキシム、シ
クロへキサノンオキシム等のオキシム類、ε−カプロラ
クタム等のラクタム類などが用いられる。The blocked polyisocyanate (II) in the present invention is not particularly limited as long as it is a blocked polyisocyanate used in the production of ordinary polyurethane resins in which polyisocyanate is blocked with a blocking agent. Examples of the polyisocyanate component of this block polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate,
．． Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, ethylene diisocyanate, 1.4
-Aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1
, 3-diisocyanate, cyclohexane 1,3- and 1°4-diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, triphenylmethane-4,4'4''-) diisocyanate, polyphenylmethyl polyisocyanate, e.g. Polyisocyanates such as phosgenated condensates with formaldehyde, isocyanurate ring-containing polyisocyanates obtained by trimerization reaction of these polyisocyanates, or alcohol components of these polyisocyanates and the above-mentioned polyols (IN). Examples include reacted polyurethane polyisocyanate.Also, as a blocking agent, a compound containing one active hydrogen per molecule, for example, a compound having 1 to 12 carbon atoms and having an ether bond in the main chain or on the side. Aliphatic monohydric alcohols that may be included in the chain, alcohols such as benzyl alcohol and cyclohexanol, phenols such as phenol, cresol and xylenol, oximes such as 2-butanone oxime and cyclohexanone oxime, ε- Lactams such as caprolactam are used.
これらのうち、イソシアネート成分が４，４°−ジフェ
ニルメタンジイソシアネート、トリレンジイソシアネー
トまたはこれらのジイソシアネート３モルとトリメチロ
ールプロパン１モルとを付加させたポリウレタンポリイ
ソシアネート、ブロック剤がフェノール類、オキシム類
、またはラクタム類である組み合わせが好ましい。市販
されているフ゛ロックポリイソシアネートとしては、日
本ポリウレタン社製の商品名ミリオネートＭＳ−５０、
コロネート２５０３、コロネートＡＰステーブル、バイ
エル社製の商品名デスモジュールＡＰステーブル等があ
げられる。これらのブロックポリイソシアネートは単独
でまたは二種以上が用いられる。Among these, the isocyanate component is 4,4°-diphenylmethane diisocyanate, tolylene diisocyanate, or a polyurethane polyisocyanate prepared by adding 3 moles of these diisocyanates and 1 mole of trimethylolpropane, and the blocking agent is phenols, oximes, or lactams. Combinations of the same type are preferred. Commercially available block polyisocyanates include Millionate MS-50 manufactured by Nippon Polyurethane Co., Ltd.;
Examples include Coronate 2503, Coronate AP Stable, and Desmodule AP Stable manufactured by Bayer. These block polyisocyanates may be used alone or in combination of two or more.
本発明における有機金属化合物（Ｉｆｆ）としては、Ｐ
ｂ、Ｚｎ、Ｍｎ、、Ｃｏ、Ｓｎ等の全屈のカルボン酸塩
、アミン塩、キレート化物などが用いられる。例えばナ
フテン酸鉛、オクテン酸鉛、ナフテン酸亜鉛、オクテン
酸亜鉛、安息香酸亜鉛、ジメチルジチオカルバミン酸亜
鉛、ジブチルジチオカルバミン酸亜鉛、亜鉛アセチルア
セトネート、ナフテン酸マンガン、オクテン酸マンガン
、ナフテン酸コバルト、オクテン酸コバルト、ジブチル
錫ジラウレート、ジブチル錫ジアセテート等があげられ
る。これらのうち、外観、硬化反応性等から有機亜鉛化
合物が好ましく、これらは単独でまたは二種以上が用い
られる。As the organometallic compound (Iff) in the present invention, P
Fully diagonal carboxylates, amine salts, chelates, etc. of Zn, Mn, Co, Sn, etc. are used. For example, lead naphthenate, lead octenoate, zinc naphthenate, zinc octenoate, zinc benzoate, zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc acetylacetonate, manganese naphthenate, manganese octenoate, cobalt naphthenate, octenoic acid. Examples include cobalt, dibutyltin dilaurate, and dibutyltin diacetate. Among these, organic zinc compounds are preferred from the viewpoint of appearance, curing reactivity, etc., and these may be used alone or in combination of two or more.
本発明における溶媒（ＩＶ）としてはアルコールの少な
くとも１種を５〜１００重量％含むものが用いられる。As the solvent (IV) in the present invention, a solvent containing 5 to 100% by weight of at least one alcohol is used.
アルコールとしては１価および多価アルコールが用いら
れるが、１価アルコールとしては、例えば前述したブロ
ックボリイソシアネーては、例えば前述したブロックポ
リイソシアネート（ＩＩ）のブロック剤に使用された１
価のアルコール類などが用いられ、多価アルコールとし
ては、例えば前述したポリオール（Ｉ）に用いたアルコ
ール成分などが用いられる。外観、ポリウレタン樹脂の
溶解性、コスト面等からｎ−オクチルアルコール、ジプ
ロピレングリコール、３−メトキシ−３−メチルブタノ
ールおよびメチルカルビトールの少なくとも１種を用い
ることが好ましい。アルコールは単独でまたは二種以上
が用いられる。As the alcohol, monohydric and polyhydric alcohols are used, and examples of the monohydric alcohol include, for example, the above-mentioned block polyisocyanate, such as 1, which is used as a blocking agent for the above-mentioned block polyisocyanate (II).
Polyhydric alcohols are used, and as the polyhydric alcohol, for example, the alcohol component used in the polyol (I) described above is used. From the viewpoint of appearance, solubility of the polyurethane resin, cost, etc., it is preferable to use at least one of n-octyl alcohol, dipropylene glycol, 3-methoxy-3-methylbutanol, and methyl carbitol. Alcohols may be used alone or in combination of two or more.
アルコール以外の溶媒としては、フェノール、クレゾー
ル、キシレノール等のフェノール類、トルエン、キシレ
ン、Ｎｌ５ＳＥＫＩ ＨＩＳＯＬ−１００、Ｎｌ５Ｓ
ＥＫＩ ＨＩＳＯＬ−１５０（以上、日本石油化学社
製、商品名、沸点範囲が８０〜３００℃程度の石油系芳
香族炭化水素）等の芳香族炭化水素類などが用いられ、
これらは単独でまたは二種以上で用いられる。また溶媒
の沸点は１００〜３００℃の範囲であることが好ましい
。Solvents other than alcohol include phenols such as phenol, cresol, and xylenol, toluene, xylene, Nl5SEKI HISOL-100, and Nl5S.
Aromatic hydrocarbons such as EKI HISOL-150 (manufactured by Nippon Petrochemical Co., Ltd., trade name, petroleum-based aromatic hydrocarbon with a boiling point range of about 80 to 300°C) are used,
These may be used alone or in combination of two or more. Moreover, it is preferable that the boiling point of the solvent is in the range of 100 to 300°C.
ポリオールｔ、■）および有機酸（Ｖ）の混合物の酸価
とは、ポリオール（Ｉ）および有機酸（■）の総量１ｇ
に含まれるカルボキシル基の数に５６１００（ＫＯＨＯ
ｍｇ数）を乗じた値である。The acid value of a mixture of polyol t, ■) and organic acid (V) is the total amount of polyol (I) and organic acid (■) per gram.
The number of carboxyl groups contained in is 56,100 (KOHO
It is the value multiplied by the number of mg).
この値は、実測によりあるいはポリオール（Ｉ）および
有機酸（Ｖ）の配合量から計算される。This value is calculated from actual measurements or from the amounts of polyol (I) and organic acid (V).
本発明におけるポリオール（Ｉ）とブロックポリイソシ
アネート（ｎ）は、主に外観の上から当量比で
の割合で用いることが好ましい。The polyol (I) and the blocked polyisocyanate (n) in the present invention are preferably used in an equivalent ratio based on the appearance.
また本発明における（Ｉ）と（ＩＩ）は、重量比で
となる割合で用いることが好ましい。この割合が低すぎ
ると、樹脂成分が低（なり、コスト高になり、一方、高
すぎると組成物の溶液粘度が高くなり、塗装作業性、外
観に影響を与える。Moreover, it is preferable that (I) and (II) in the present invention are used in a weight ratio. If this ratio is too low, the resin component will be low (and the cost will be high), while if it is too high, the solution viscosity of the composition will be high, which will affect the coating workability and appearance.
有機金属化合物（ＩＩＩ）は触媒としての作用、耐熱性
、外観性の点から（Ｉ）と（ｎ）の総量に対して金属分
で０．０１〜１重量％となる割合で用いることが好まし
い。The organometallic compound (III) is preferably used in a proportion of 0.01 to 1% by weight of metal based on the total amount of (I) and (n) from the viewpoint of catalytic action, heat resistance, and appearance. .
本発明における有機酸（Ｖ）はポリオール（Ｉ）および
有機酸（Ｖ）の混合物の酸価が４〜２０になるように配
合される。酸価が４未満であると焼付皮膜に著しい発泡
を生じて外観が劣り、２０を越えると焼付皮膜に肌荒れ
等が生じ、やはり外観が劣る。とくに好ましい酸価は５
〜１５である。The organic acid (V) in the present invention is blended so that the mixture of polyol (I) and organic acid (V) has an acid value of 4 to 20. If the acid value is less than 4, significant foaming occurs in the baked film and the appearance is poor; if it exceeds 20, the baked film becomes rough and the appearance is also poor. A particularly preferable acid value is 5
~15.
この有機酸（Ｖ）としては、例えば酢酸、プロピオン酸
、ステアリン酸、パルミチン酸等の炭素数１〜２０の脂
肪族モノカルボン酸、安息香酸、を−ブチル安息香酸、
テレフタル酸モノメチルエステル、イソフタル酸モノメ
チルエステル、フタル酸モノメチルエステル、アビエチ
ン酸等の芳香族モノカルボン酸、前述したポリオール（
Ｉ）に用いた多価カルボン酸、ｐ−トルエンスルホン酸
、前述したカルボン酸を含有するポリオール（Ｉ）など
が用いられる。Examples of the organic acid (V) include aliphatic monocarboxylic acids having 1 to 20 carbon atoms such as acetic acid, propionic acid, stearic acid, palmitic acid, benzoic acid, -butylbenzoic acid,
Aromatic monocarboxylic acids such as terephthalic acid monomethyl ester, isophthalic acid monomethyl ester, phthalic acid monomethyl ester, abietic acid, the above-mentioned polyols (
The polyhydric carboxylic acid used in I), p-toluenesulfonic acid, the polyol (I) containing the above-mentioned carboxylic acid, and the like are used.
本発明における（Ｉ）〜（Ｖ）は均一に熔解してポリウ
レタン樹脂組成物とするが、熔解する温度は室温〜１０
０℃の範囲、特に室温〜５０℃の範囲が好ましい。In the present invention, (I) to (V) are uniformly melted to form a polyurethane resin composition, and the melting temperature is room temperature to 10%
A range of 0°C, particularly a range of room temperature to 50°C is preferred.
本発明におけるポリウレタン樹脂組成物は必要に応じて
、少量のアミン系触媒および改質剤を用いることができ
る。アミン系触媒としては、例えばトリエチルアミン、
トリエチレンジアミン、ジメチルアミノエタノール、ト
リエタノールアミンジメチルベンジルアミン、ジメチル
アニリン、Ｎ−メチルモルホリン、Ｎ−ヒドロキシエチ
ルモルホリン、１．２−ジメチルイミダゾール、１−シ
アノエチル−２−フェニルイミタソール、１，８−ジア
ザ−ビシクロ（５，４，０）ウンデセン−７等の三級ア
ミン類、ジェタノールアミン、ジブチルアミン、イミダ
ゾール、モルホリン等の二級アミン類またはこれらの有
機酸塩などが用いられる。アミン系触媒は（Ｉ）と（ｎ
）の総量に対して０．０１〜５重量％の範囲で用いるこ
とが好ましい。The polyurethane resin composition of the present invention may contain a small amount of an amine catalyst and a modifier, if necessary. Examples of amine catalysts include triethylamine,
Triethylenediamine, dimethylaminoethanol, triethanolaminedimethylbenzylamine, dimethylaniline, N-methylmorpholine, N-hydroxyethylmorpholine, 1,2-dimethylimidazole, 1-cyanoethyl-2-phenylimitasol, 1,8- Tertiary amines such as diaza-bicyclo(5,4,0)undecene-7, secondary amines such as jetanolamine, dibutylamine, imidazole, and morpholine, or organic acid salts thereof are used. Amine catalysts are (I) and (n
) is preferably used in a range of 0.01 to 5% by weight based on the total amount.
改質剤としては、例えばシェル化学社製の商品名エピコ
ート８２８、エピコー）１００１、エピコート１００４
、エビコー）１００７等のビスフェノール型エポキシ樹
脂、ダウケミカル社製の商品名ＤＥＮ−４３８等のフェ
ノールノボラック型エポキシ樹脂、ＵＣＣ社製の商品名
ＣＨ２２１等の脂環式エポキシ樹脂、トリスグリシジル
イソシアヌレート等の複素環含有エポキシ樹脂などのエ
ポキシ樹脂、６−ナイロン、６．６−ナイロン、１２−
ナイロン等の脂肪族系ポリアミド樹脂、ポリビニルブチ
ラール樹脂、ポリビニルホルマール樹脂などが用いられ
る。改質剤は（Ｉ）と（ｎ）の総量１００Ｍ量部に対し
て０．１〜１０重量の範囲で用いることが好ましい。Examples of the modifier include, for example, Epikot 828, Epicor 1001, and Epicort 1004 manufactured by Shell Chemical Co., Ltd.
, Ebicor) 1007, phenol novolak epoxy resins such as DEN-438 manufactured by Dow Chemical Co., alicyclic epoxy resins such as CH221 manufactured by UCC, trisglycidyl isocyanurate, etc. Epoxy resins such as heterocycle-containing epoxy resins, 6-nylon, 6.6-nylon, 12-
Aliphatic polyamide resins such as nylon, polyvinyl butyral resins, polyvinyl formal resins, etc. are used. The modifier is preferably used in an amount of 0.1 to 10 parts by weight per 100 M parts of the total amount of (I) and (n).
（実施例）
以下、本発明を実施例により説明するが、本発明はこれ
らに制限されるものではない。(Examples) The present invention will be explained below using Examples, but the present invention is not limited thereto.
比較例１
（Ｉ）ポリエステルポリオールの合成
攪拌機、温度計、熱電対、水捕集器を付した分留管およ
び窒素ガス送入管を装備した２１四ツロフラスコにグリ
セリン４９８．７ｇ（Ｉ６，２当量）、プロピレングリ
コール３３２．９ ｇ （８，７６当量）、無水フタル
酸５８４．２ ｇ （７，８ｇ当量）、アジピン酸３８
４．２ ｇ （５，２６当量）を仕込み、１５０ｍ１１
分の窒素ガスを通しながら約１５０℃に昇温しで溶解し
た。その後、徐々に昇温しで５時間で２１０℃とした。Comparative Example 1 (I) Synthesis of polyester polyol 498.7 g of glycerin (I6,2 equivalent ), propylene glycol 332.9 g (8,76 eq.), phthalic anhydride 584.2 g (7,8 g eq.), adipic acid 38
Charge 4.2 g (5.26 equivalents), 150 m11
The temperature was raised to about 150° C. while nitrogen gas was passed through the solution for a few minutes to melt it. Thereafter, the temperature was gradually raised to 210° C. over 5 hours.
途中、生成した縮合水を留去しながら２１０℃で１時間
反応を進めた０次に１１０℃に冷却して減圧ラインを連
結し、水流ポンプでの減圧下、２１０℃で反応を進め、
酸価が０゜５に達したところを終点としてポリエステル
ポリオールを得た。The reaction was allowed to proceed for 1 hour at 210°C while distilling off the condensed water produced during the process. Next, the mixture was cooled to 110°C, a vacuum line was connected, and the reaction was allowed to proceed at 210°C under reduced pressure with a water jet pump.
A polyester polyol was obtained with the end point being when the acid value reached 0°5.
（２）ポリウレタン樹脂組成物の調整
次に、上記（Ｉ）で得たポリエステルポリオール１４６
ｇ（Ｉ，０当Ｎ）、ミリオネートＭＳ−５０，１４８，
５ｇ （０，６当量）、コロネート２５０３．１６０ｇ
（０，４当量）、６．６−ナイロン１７ｇ、ナフテン
酸亜鉛（金属分６重量％）５．５１ｇ１メチル力ルピト
ール１４０ｇ、クレゾール１６４ｇ１キシレン３０４ｇ
を混合し、約５０℃で攪拌して完全に溶解させた。この
溶液を３０℃での粘度（ＢＬ型粘度針）が０．７ポアズ
になるように上記と同様の溶媒組成の希釈溶媒で希釈調
整してポリウレタン樹脂組成物を得た。(2) Preparation of polyurethane resin composition Next, the polyester polyol 146 obtained in the above (I)
g (I, 0 equivalent N), Millionate MS-50,148,
5g (0,6 equivalent), Coronate 2503.160g
(0.4 equivalent), 6.6-nylon 17g, zinc naphthenate (metal content 6% by weight) 5.51g 1 methyllupitol 140g, cresol 164g 1 xylene 304g
were mixed and stirred at about 50°C to completely dissolve. This solution was diluted with a diluting solvent having the same solvent composition as above so that the viscosity at 30° C. (BL type viscosity needle) was 0.7 poise to obtain a polyurethane resin composition.
比較例２
ポリエステルポリオールとして市販のデスモーフエン８
００（商品名、バイエル社製）１９３ｇ 。Comparative Example 2 Desmorphene 8 commercially available as polyester polyol
00 (trade name, manufactured by Bayer) 193g.
（Ｉ，０当量）を用いた以外は比較例１ （２）のポリ
ウレタン樹脂組成物の調整と同様にしてポリウレタン樹
脂組成物を調整し、このポリウレタン樹脂組成物５５１
ｇにフタル酸モノメチルエステル９、２９ ｇを添加し
、完全に熔解させて、デスモーフエン８００およびフタ
ル酸モノメチルエステルの混合物の酸価が３０であるポ
リウレタン樹脂組成物を得た。A polyurethane resin composition was prepared in the same manner as the preparation of the polyurethane resin composition in Comparative Example 1 (2) except that (I, 0 equivalent) was used, and this polyurethane resin composition 551
9.29 g of phthalic acid monomethyl ester were added to the mixture and completely melted to obtain a polyurethane resin composition in which the mixture of Desmorphene 800 and phthalic acid monomethyl ester had an acid value of 30.
実施例１
比較例１ （Ｉ）のポリエステルポリオールの合成と同
様の配合、装置、操作で反応を行ない、酸価が８に達し
たところを終点とし、得られたポリエステルポリオール
１３３ｇ（Ｉ，０当量）を比較例１ （２）のポリウレ
タン樹脂組成物の調整と全く同様にして行ない、３０℃
の粘度（ＢＬ型粘度針）が０．７ボアズのポリウレタン
樹脂組成物を得た。Example 1 Comparative Example 1 The reaction was carried out using the same formulation, equipment, and operation as in the synthesis of polyester polyol in (I), and the end point was when the acid value reached 8, and 133 g of the obtained polyester polyol (I, 0 equivalent ) was carried out in exactly the same manner as the preparation of the polyurethane resin composition in Comparative Example 1 (2), and
A polyurethane resin composition having a viscosity (BL type viscosity needle) of 0.7 boas was obtained.
実施例２
比較例１で得たポリウレタン樹脂組成物５２７ｇに安息
香酸１．２７ｇを添加し、完全に溶解させて、ポリエス
テルポリオールおよび安息香酸の混合物の酸価が８であ
るポリウレタン樹脂組成物を得た。Example 2 1.27 g of benzoic acid was added to 527 g of the polyurethane resin composition obtained in Comparative Example 1 and completely dissolved to obtain a polyurethane resin composition in which the mixture of polyester polyol and benzoic acid had an acid value of 8. Ta.
実施例３
比較例１で得たポリウレタン樹脂組成物５２７ｇにプロ
ピオン酸１．４４ ｇを添加し、完全に溶解させて、ポ
リエステルポリオールおよびプロピオン酸の混合物の酸
価が１５であるポリウレタン樹脂組成物を得た。Example 3 1.44 g of propionic acid was added to 527 g of the polyurethane resin composition obtained in Comparative Example 1 and completely dissolved to obtain a polyurethane resin composition in which the mixture of polyester polyol and propionic acid had an acid value of 15. Obtained.
比較例１．２および実施例１〜３で得たポリウレタン樹
脂組成物を下記の焼付条件によりｏ、２６鰭ψの銅線に
塗布焼付し、皮膜厚さ０．０１８ ＩＩＩの電線を得た
。その特性結果を第１表に示した。The polyurethane resin compositions obtained in Comparative Example 1.2 and Examples 1 to 3 were coated and baked on a copper wire with a diameter of 26 fins under the following baking conditions to obtain an electric wire with a coating thickness of 0.018 III. The characteristic results are shown in Table 1.
焼付条件
炉温：入ロ／出ロ＝３６０℃／３７０℃塗布回数：６回
塗装方法：フェルト絞り
焼付線速：６０ｍ／分
表よりポリエステルポリオールおよび有機酸の混合物の
酸価を特定量に調整したポリウレタン樹脂組成１ｔｊＡ
（実施例１〜３）では、発泡、肌荒れなどのない優れた
外観と電線特性を有していることが知られる。Baking conditions Furnace temperature: Input/output = 360°C/370°C Number of applications: 6 times Coating method: Felt drawing Baking line speed: 60 m/min Adjust the acid value of the mixture of polyester polyol and organic acid to a specific amount from the table Polyurethane resin composition 1tjA
(Examples 1 to 3) are known to have excellent appearance and wire characteristics without foaming, rough skin, etc.
以下余白
第１表
（発明の効果）
本発明のポリウレタン樹脂組成物は、低公害性で、かつ
銅線等の基材への焼付塗工時に皮膜表面の発泡や肌荒れ
のない良好な焼付作業性（外観）を有する。Table 1 (Effects of the Invention) The polyurethane resin composition of the present invention is low-pollution and has good baking workability without foaming or roughening on the surface of the film during baking coating on base materials such as copper wires. (appearance).
Claims (1)
（II）および有機金属化合物（III）を、アルコールの
少なくとも１種を５〜１００重量％含む溶媒（IV）に溶
解してなるポリウレタン樹脂組成物において、（ I ）
および（Ｖ）の混合物の酸価が４〜２０になるように有
機酸（Ｖ）を配合してなるポリウレタン樹脂組成物。 ２、ブロックポリイソシアネート（II）を （II）／（ I ）＝０．８〜１．５（当量比）、ポリオ
ール（ I ）とブロックポリイソシアネート（II）を ［（ I ）＋（II）］／［（ I ）＋（II）＋（IV）］＝
０．３〜０．６（重量比）、有機金属化合物（III）を
（ I ）と（II）の総量に対して金属分で０．０１〜１
重量％となる割合で用いてなる特許請求の範囲第１項の
ポリウレタン樹脂組成物。 ３、有機金属化合物（III）が有機亜鉛化合物である特
許請求の範囲第１項のポリウレタン樹脂組成物。 ４、溶媒（IV）のアルコールがｎ−オクチルアルコール
、ジプロピレングリコール、３−メトキシ−３−メチル
ブタノールおよびメチルカルビトールの少なくとも１種
である特許請求の範囲第１項のポリウレタン樹脂組成物
。[Claims] 1. A polyurethane obtained by dissolving a polyol (I), a blocked polyisocyanate (II), and an organometallic compound (III) in a solvent (IV) containing 5 to 100% by weight of at least one alcohol. In the resin composition, (I)
A polyurethane resin composition containing an organic acid (V) such that the mixture of (V) and (V) has an acid value of 4 to 20. 2. Block polyisocyanate (II) (II) / (I) = 0.8 to 1.5 (equivalent ratio), polyol (I) and block polyisocyanate (II) [(I) + (II)] /[(I)+(II)+(IV)]=
0.3 to 0.6 (weight ratio), and the metal content of organometallic compound (III) to the total amount of (I) and (II) is 0.01 to 1.
The polyurethane resin composition according to claim 1, wherein the polyurethane resin composition is used in a proportion of % by weight. 3. The polyurethane resin composition according to claim 1, wherein the organometallic compound (III) is an organozinc compound. 4. The polyurethane resin composition according to claim 1, wherein the alcohol in the solvent (IV) is at least one of n-octyl alcohol, dipropylene glycol, 3-methoxy-3-methylbutanol, and methyl carbitol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61233680A JPS6389520A (en) | 1986-10-01 | 1986-10-01 | Polyurethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61233680A JPS6389520A (en) | 1986-10-01 | 1986-10-01 | Polyurethane resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6389520A true JPS6389520A (en) | 1988-04-20 |
Family
ID=16958854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61233680A Pending JPS6389520A (en) | 1986-10-01 | 1986-10-01 | Polyurethane resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6389520A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0343473A (en) * | 1989-07-12 | 1991-02-25 | Nitto Denko Corp | Polyurethane-based insulating coating compound |
| JPH05105843A (en) * | 1991-10-15 | 1993-04-27 | Aisin Chem Co Ltd | Coating composition for forming thick film |
-
1986
- 1986-10-01 JP JP61233680A patent/JPS6389520A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0343473A (en) * | 1989-07-12 | 1991-02-25 | Nitto Denko Corp | Polyurethane-based insulating coating compound |
| JPH05105843A (en) * | 1991-10-15 | 1993-04-27 | Aisin Chem Co Ltd | Coating composition for forming thick film |
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