JPS6249116B2 - - Google Patents
Info
- Publication number
- JPS6249116B2 JPS6249116B2 JP54167037A JP16703779A JPS6249116B2 JP S6249116 B2 JPS6249116 B2 JP S6249116B2 JP 54167037 A JP54167037 A JP 54167037A JP 16703779 A JP16703779 A JP 16703779A JP S6249116 B2 JPS6249116 B2 JP S6249116B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- isocyanatomethyl
- cyclohexane
- acid
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005862 polyol Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002981 blocking agent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000003951 lactams Chemical class 0.000 claims description 4
- 150000002923 oximes Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 229920001228 polyisocyanate Polymers 0.000 description 14
- 239000005056 polyisocyanate Substances 0.000 description 14
- -1 acrylic polyols Chemical class 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- 229920005906 polyester polyol Polymers 0.000 description 10
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 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 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- GHXPTDPKJYFMOE-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCCC1CN=C=O GHXPTDPKJYFMOE-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical group CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000223760 Cinnamomum zeylanicum Species 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical compound O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical compound NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- FZBIESPTFIVNEJ-UHFFFAOYSA-N oxiran-2-ylmethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC1CO1 FZBIESPTFIVNEJ-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran 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
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical class NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
本発明はプレコートメタルに関する。
一般にプレコートメタルは金属板に塗料を塗布
し、加熱硬化することによつて製造されている。
従来、プレコート用塗料としては、アミノアルキ
ツド樹脂、メラミン硬化アクリルポリオールもし
くはエポキシ樹脂が用いられていた。ところが、
これらの樹脂では塗膜の加工性(折り曲げ性)が
悪く、90゜以上の角度に折り曲げた場合には塗膜
に亀裂を生じることがわかつた。
このような事情に鑑み、本発明者らは鋭意研究
した結果、公知の有機ポリイソシアネートのなか
で特に特定のブロツク剤によりブロツク化された
ビス(イソシアナートメチル)シクロヘキサン系
組成物が加工性(折り曲げ性)が良好で、しかも
硬度、耐汚染性、耐薬品性ともにすぐれた塗膜を
有するプレコートメタルを与えることを知見し、
この知見にもとづき、本発明を完成するに至つ
た。
すなわち、本発明はオキシム系ブロツク剤また
はラクタム系ブロツク剤でブロツク化されたビス
(イソシアナートメチル)シクロヘキサンまたは
その付加体(A)とポリオール樹脂(B)とを含有してな
る組成物を金属板に塗布し、加熱硬化せしめたこ
とを特徴とするプレコートメタルに関する。
本発明において用いられるビス(イソシアナー
トメチル)シクロヘキサンとしては、たとえば
1・2−ビス(イソシアナートメチル)シクロヘ
キサン、1・3−ビス(イソシアナートメチル)
シクロヘキサン、1・4−ビス(イソシアナート
メチル)シクロヘキサンおよびこれらの混合物な
どがあげられる。
ビス(イソシアナートメチル)シクロヘキサン
の付加体としては、たとえば上記イソシアネート
の過剰とたとえばエチレングリコール、プロピレ
ングリコール、1・3−ブチレングリコール、
1・4−ブチレングリコール、ネオペンチルグリ
コール、2・2・4−トリメチル−1・3−ペン
タンジオール、ヘキサメチレングリコール、シク
ロヘキサンジメタノール、シクロヘキサンジオー
ル、トリメチロールエタン、トリメチロールプロ
パン、グリセリン、ヘキサントリオール、水添ビ
スフエノールA、ソルビトール、ソルビツト、シ
ユークローズ、ペンタエリスリトール、クワドロ
ールなどの低分子ポリオールあるいはたとえばポ
リエステルポリオール、ポリエーテルポリオー
ル、エポキシ樹脂などの分子量500〜3000の高分
子ポリオールとを反応させて得られるウレタン化
物、たとえば水、エチレンジアミンなどの低級ア
ミンと過剰のビス(イソシアナートメチル)シク
ロヘキサンを反応させて得られるビユレツト化
物、あるいは上記低分子ポリオールや高分子ポリ
オールと過剰のビス(イソシアナートメチル)シ
クロヘキサンとを反応させて得られるアロフアネ
ート化物などがあげられる。
上記ウレタン化物、ビユレツト化物あるいはア
ロフアネート化物中にビス(イソシアナートメチ
ル)シクロヘキサンモノマーが多量に含有されて
いるような場合でも本発明ではこれを除去するこ
となく用いることができる。
本発明において用いられるブロツク剤として
は、オキシム系あるいはラクタム系のものがあげ
られる。ブロツク剤の具体例としては、次のもの
があげられる。
ラクタム系ブロツク剤:
ε−カプロラクタム、δ−バレロラクタム、γ
−ブチロラクタム、β−プロピオラクタムなど。
オキシム系ブロツク剤:
ホルムアミドキシム、アセトアルドキシム、ア
セトキシム、メチルエチルケトキシム、ジアセチ
ルモノオキシム、ベンゾフエノンオキシム、シク
ロヘキサノンオキシムなど。
本発明において用いられるブロツク化物(A)はビ
ス(イソシアナートメチル)シクロヘキサンまた
はその付加体と上記のブロツク剤とをNCO/ブ
ロツク剤=約0.9〜1.0、好ましくは約0.95〜1.0の
当量比で反応させる手段、ビス(イソシアナート
メチル)シクロヘキサンとブロツク剤とを
NCO/ブロツク剤=約1.1〜3.0、好ましくは約
1.2〜2.0の当量比で反応させた後、これに前述の
低分子ポリオール、高分子ポリオール、水あるい
は低級アミンとを反応させる手段、ビス(イソシ
アナートメチル)シクロヘキサンと低分子ポリオ
ール、高分子ポリオール、水あるいは低級アミン
をNCO/活性水素=約1.5〜10.0、好ましくは約
2.0〜7.0の当量比で反応させた後、これにブロツ
ク剤を反応させる手段などによつて得られる。
上記の各反応は活性水素基を持たない溶媒中
(例;酢酸エチル、酢酸ブチルなどのエステル
系、たとえばアセトン、メチルエチルケトン、メ
チルイソブチルケトンなどのケトン系、たとえば
テトラヒドロフランなどのエーテル系など)ある
いはこのような溶媒の不存在下に公知の方法でお
こなわれる。反応に際しては、たとえば3級アミ
ン、有機金属などの公知の触媒を使用してもよ
い。
本発明において用いられるポリオール樹脂(B)と
しては、たとえばポリエステル樹脂、アクリルポ
リオール樹脂あるいはこれらの混合物などがあげ
られる。ポリエステル樹脂としては、たとえばフ
タル酸、イソフタル酸、テレフタル酸、マレイン
酸、フマル酸、コハク酸、アジピン酸、セバチン
酸、アゼライン酸、トリメツト酸などの多塩基酸
とたとえばエチレングリコール、ジエチレングリ
コール、プロピレングリコール、ジプロピレング
リコール、1・3−ブタンジオール、1・4−ブ
タンジオール、1・5−ペンタンジオール、ネオ
ペンチルグリコール、ヘキサメチレングリコー
ル、デカメチレングリコール、ハイドロキノンビ
ス(ヒドロキシエチルエーテル)、2・2・4−
トリメチル−1・3−ペンタンジオール、水添ビ
スフエノールA、トロメチロールエタン、トリメ
チロールプロパン、ヘキサントリオール、グリセ
リン、ペンタエリスリトール、トリス(ヒドロキ
シエチル)イソシアヌレート、シクロヘキサンジ
オール、シクロヘキサンジメタノール、キシリレ
ングリコール、クワドロールなどのポリオールを
常法により水酸基過剰の条件下に縮合させること
により得られる。この場合酸あるいはポリオール
はそれぞれ2種又はそれ以上を併用することも可
能である。またヒマシ油、高級脂肪酸などを併用
していわゆる油変性ポリエステルポリオールとし
てもよい。
上記原料の組み合わせで得られるポリエステル
樹脂としては分子量約500〜20000、好ましくは約
2000〜10000、水酸基価約10〜300、好ましくは約
20〜200、酸価約1〜50、好ましくは約2〜20の
ものが好んで用いられる。
アクリルポリオール樹脂としては、たとえば(1)
アクリル酸2−ヒドロキシエチル、アクリル酸2
−ヒドロキシプロピル、メタクリル酸2−ヒドロ
キシエチル、メタクリル酸2−ヒドロキシプロピ
ル、アリルアルコール、ケイヒアルコール、クロ
トニルアルコールあるいはたとえばアクリル酸、
メタクリル酸、マレイン酸、フマル酸、クロトン
酸、イタコン酸等の不飽和カルボン酸とたとえば
エチレングリコール、エチレンオキサイド、プロ
ピレングリコール、プロピレンオキサイド、ブチ
レングリコール、1・4−シクロヘキシルジメタ
ノール、フエニルグリシジルエーテル、グリシジ
ルデカノエートなどとの反応生成物である水酸基
含有単量体と(2)たとえばアクリル酸メチル、アク
リル酸エチル、アクリル酸n−プロピル、アクリ
ル酸イソプロピル、アクリル酸n−ブチル、アク
リル酸tert−ブチル、アクリル酸2−エチルヘキ
シルなどのアクリル酸エステル類、たとえばメタ
クリル酸メチル、メタクリル酸エチル、メタクリ
ル酸n−プロピル、メタクリル酸イソプロピル、
メタクリル酸n−ブチル、メタクリル酸tert−ブ
チル、メタクリル酸2−エチルヘキシルなどのメ
タクリル酸エステル類、たとえばスチレン、ビニ
ルトルエン、α−メチルスチレンなどのスチレン
系単量体;その他アクリル酸、メタクリル酸、酢
酸ビニル、プロピオン酸ビニル、アクリロニトリ
ル、ステアリン酸ビニル、アリルアセテート、ア
ジピン酸ジアリル、イタコン酸ジメチル、マレイ
ン酸ジエチル、塩化ビニル、塩化ビニリデン、エ
チレン、メタクリル酸グリシジル、N−メチロ−
ルアクリルアミド、N−ブトキシメチルアクリル
アミド、アクリルアミド、ダイアセトンアクリル
アミドなどの共重合可能なα・β−エチレン性不
飽和単量体の1種あるいは2種以上とを共重合さ
せて得られるものがあげられる。
上記原料の組み合わせで得られるアクリルポリ
オール樹脂としては、分子量約5000〜100000、好
ましくは約10000〜50000、水酸基価約10〜300、
好ましくは約20〜200のものが好んで用いられ
る。
本発明においてはまず、このポリオール樹脂(B)
とブロツク化物(A)とを含有してなる組成物を金属
板に塗布する。ポリオール樹脂(B)とブロツク化物
(A)との配合割合はブロツク化物(A)の再生イソシア
ネート基とポリオール樹脂(B)の水酸基との当量比
が約0.5〜2.0、好ましくは約0.5〜1.5になるよう
に調節する。
この組成物はブロツク化物(A)およびポリオール
樹脂(B)以外に、たとえば酢酸エチル、酢酸ブチ
ル、アセト酢酸メチル、2−エトキシエチル ア
セテートなどのエステル系、キシレン、トルエン
などの芳香族系、メチルエチルケトン、メチルイ
ソブチルケトン、シクロヘキサノンなどのケトン
系、ジエチレングリコールジメチルエーテルなど
のエーテル系などの有機溶媒、たとえばビス(イ
ソシアナートメチル)シクロヘキサンなどの末端
にイソシアネート基を有するものなど、たとえ
ば、顔料、レベリング剤、消泡剤、解離触媒、安
定剤などを含有していてもよい。有機溶媒の量は
ブロツク化物(A)とポリオール樹脂(B)の固形分に対
して約0〜90重量%程度である。また、ビス(イ
ソシアナートメチル)シクロヘキサンなどの末端
にイソシアネート基を有するものを含有する場
合、その量はブロツク化物(A)とポリオール樹脂(B)
の固形分に対して約0.1〜5重量%程度である。
本発明において用いられる金属板は、通常、プ
レコートメタル用金属として用いられるものであ
れば如何なるものでもよいが、たとえばアルミニ
ウム、チンフリースチール、亜鉛びき鉄板、鉄板
などがあげられ、たとえばリン酸塩処理などの化
学表面処理を施したものが好ましい。
金属板の形状としては、たとえば平板状、筒状
など、いずれでもよい。塗布量は乾燥重量で約10
g/m2〜30g/m2程度が好ましい。
塗布する手段としては、たとえばスプレーガ
ン、ロールコーター、フローコーターなどがあげ
られる。
つぎに本発明では、ブロツク化物(A)とポリオー
ル樹脂(B)とを含有してなる組成物を塗布した金属
板を加熱硬化する。
加熱温度はブロツク剤の種類などによつて異な
るが、約150〜350℃で、その時間は約20秒〜120
秒程度が好ましい。この加熱操作によつてブロツ
ク化物(A)中のブロツク化イソシアネートとポリオ
ール樹脂(B)中の水酸基との反応によつて架橋がお
こり、強靭な塗膜が得られる。この塗膜には加熱
操作によるヤケや熱劣化は全くみられず、しかも
硬度が高く、加工性(折り曲げ性)、耐汚染性、
耐薬品性がともに良好であるので、本発明により
得られるプレコートメタルは、たとえばカラート
タンなどの建材用、たとえば冷蔵庫、自動販売機
などの羽電機器用などに有利に用いられる。
以下実施例によつて本発明をより具体的に説明
する。実施例中、部あるいは%はそれぞれ重量部
もしくは重量%を示す。
実施例 1
イソフタル酸581.5部、セバシン酸707.9部、ネ
オペンチルグリコール624.9部、エチレングリコ
ール124.1部を220℃に加熱しチツソガスを吹き込
み、生成する水を留去しながら反応させ酸価
2.4、水酸基価55のポリエステルポリオール樹脂
を得た。この樹脂をキシレンとシクロヘキサノン
の等量混合溶剤に溶解し固形分40%の溶液とし
た。一方1・3−ビス(イソシアナートメチル)
シクロヘキサン582.6部を酢酸エチル326部、エト
キシエチルアセテート326部に混合し75〜80℃に
加熱する。この温度を保つように熔融したトリメ
チロールプロパン134.1部を加え、75〜80℃で5
時間反応させる。次にメチルエチルケトキシム
261.3部を1時間にわたつて滴下し、滴下終了後
さらに1時間75〜80℃に加熱する。かくして再生
イソシアネート基含量7.7%、固形分60%のブロ
ツクポリイソシアネート溶液を得た。
上記ポリエステルポリオール樹脂2550部、酸化
チタン(タイベークR−930:石原産業)898部を
混練しさらに1・1・3・3−テトラ−ブチル−
1・3−ジアセトキシジスタノキサン2部及び上
記ブロツクポリイソシアネート溶液545部を混合
し0.3mm厚の表面処理亜鉛びき鉄板に乾燥膜厚20
μになるようにスプレー塗装し、280℃の雰囲気
で60秒焼付けると、光沢のある白色塗膜が得られ
た。塗膜性能を第1表に示した。
比較例 1
ヘキサメチレンジイソシアネート504.6部を酢
酸エチル300部及びエトキシエチルアセテート300
部に溶解し75〜80℃に加熱する。この温度を保つ
ように熔融したトリメチロールプロパン134.1部
をゆつくり滴下する。滴下終了後さらに5時間75
〜80℃に加熱する。次にメチルエチルケトキシム
261.3部を1時間にわたつて滴下し、滴下終了後
さらに1時間75〜80℃に加熱する。かくして再生
イソシアネート基含量8.4%、固形分60%のブロ
ツクイソシアネート溶液を得た。ポリエステルポ
リオール樹脂(実施例1と同じ)2550部、酸化チ
タン(実施例1と同じ)880部混練し、さらに
1・1・3・3−テトラn−ブチル−1・3−ジ
アセトキシジスタノキサン1.5部及び上記ブロツ
クポリイソシアネート溶液500部を混合し、0.3mm
厚の表面処理亜鉛びき鉄板に乾燥膜厚が20μにな
るように塗装し280℃の雰囲気で60秒焼付ける
と、光沢のある白色塗膜が得られた。塗膜性能を
第1表に示した。
比較例 2
3−イソシアナートメチル−3・5・5−トリ
メチルシクロヘキシルイソシアネート666.9部を
酢酸エチル354.1部、エトキシエチルアセテート
354.1部に溶解し、75〜80℃に加熱する。1・
1・3・3−テトラn−ブチル−1・3−ジアセ
トキシジスタノキサン0.2部を添加後、熔融した
トリメチロールプロパン134.1部を1時間にわた
つて滴下する。滴下終了後さらに5時間75〜80℃
に加熱する。次にメチルエチルケトキシム261.3
部を1時間にわたつて滴下する。滴下終了後さら
に1時間75〜80℃に加熱する。かくして再生イソ
シアネート基含量7.1%、固形分60%のブロツク
ポリイソシアネート溶液を得た。ポリエステルポ
リオール樹脂(実施例1と同じ)2550部と酸化チ
タン(実施例1と同じ)916部を混練し、さらに
1・1・3・3−テトラn−ブチル−1・3−ジ
アセトキシジスタノキサン2部及び上記ブロツク
ポリイソシアネート溶液590部を混合し、0.3mm厚
の表面処理亜鉛びき鉄板に乾燥膜厚が20μになる
ように塗装し、280℃の雰囲気で60秒焼付ける
と、光沢のある白色塗膜が得られた。塗膜性能を
第1表に示した。
実施例 2
1・4−ビス(イソシアナートメチル)シクロ
ヘキサン233部をエトキシエチルアセテート375部
に溶解し、この溶液にメチルエチルケトキシム
174.2部を徐々に滴下する。滴下終了後75〜80℃
に1時間加熱する。次に分子量620のポリテトラ
メチレンエーテルグリコール155.2部とジブチル
錫ジラウレート0.7部を添加し75〜80℃で5時間
反応させる。かくして再生イソシアネート基含量
8.5%、固形分60%のブロツクポリイソシアネー
ト溶液を得た。ポリエステルポリオール樹脂(実
施例1と同じ)2550部と酸化チタン(実施例1と
同じ)878部を混練し、さらに1・1・3・3−
テトラn−ブチル−1・3−ジアセトキシジスタ
ノキサン1.5部と上記ブロツクポリイソシアネー
ト溶液494部を混合し、0.3mm厚の表面処理亜鉛び
き鉄板に乾燥膜厚が20μになるようにスプレー塗
装し、280℃の雰囲気で60秒焼付けると、光沢の
ある白色塗膜が得られた。塗膜性能を第1表に示
した。
実施例 3
メチルメタクリレート700部、n−ブチルアク
リレート207部、2−ヒドロキシエチルメタクリ
レート93部をキシレン250部、酢酸ブチル250部中
で常法により共重合させて、分子量約15000、固
形分50%、水酸基価20のアクリルポリオール樹脂
を得た。一方、1・3−ビス(イソシアナートメ
チル)シクロヘキサン116.5部をエトキシエチル
アセテート156.1部に溶解しメチルエチルケトキ
シム87.1部を1時間にわたつて滴下する。滴下終
了後さらに1時間75〜80℃に加熱する。次にジブ
チル錫ジラウレート0.38部と油変性ポリエステル
ポリオール(無水フタル酸444部、ヤシ油脂肪酸
200部、プロピレングリコール152部、トリメチロ
ールプロパン268部を常法により縮合して得られ
る樹脂を酢酸ブチルの70%溶液とする。酸価
4.0、水酸基価115)溶液122部を添加し、75〜80
℃で4時間反応させる。かくして再生イソシアネ
ート基含量8.3%、固形分60%のブロツクポリイ
ソシアネート溶液を得た。
上記アクリルポリオール樹脂2800部と酸化チタ
ン(実施例1と同じ)1137部を混練し1・1・
3・3−テトラブチル−1・3−ジアセトキシジ
スタノキサン1.5部及び上記ブロツクポリイソシ
アネート溶液508部を混合し、0.3mm厚の表面処理
亜鉛びき鉄板に乾燥膜厚が20μになるようにスプ
レー塗装し280℃の雰囲気で60秒焼付けると、光
沢のある白色塗膜が得られた。塗膜性能を第1表
に示した。
比較例 3
4・4′−メチレンビス(シクロヘキシルイソシ
アネート)157.4部をエトキシエチルアセテート
183.3部に溶解し、メチルエチルケトキシム87.1
部を1時間で滴下する。滴下終了後さらに1時間
75〜80℃に加熱する。次にジブチル錫ジラウレー
ト0.44部と油変性ポリエステル樹脂溶液(実施例
3と同じ)122部を加え75〜80℃で6時間反応さ
せる。かくして再生イソシアネート基含量7.3
%、固形分60%のブロツクポリイソシアネート溶
液を得た。アクリルポリオール樹脂(実施例3と
同じ)2800部と酸化チタン(実施例1と同じ)
1165部を混練し、1・1・3・3−テトラn−ブ
チル−1・3−ジアセトキシジスタノキサン1.7
部及び上記ブロツクポリイソシアネート溶液579
部を混合し、0.3mm厚の表面処理亜鉛びき鉄板に
乾燥膜厚が20μになるように塗装し280℃の雰囲
気で60秒焼付けると、光沢のある白色塗膜が得ら
れた。塗膜性能を第1表に示した。
実施例 4
1・3−ビス(イソシアナートメチル)シクロ
ヘキサン361.2部をエトキシエチルアセテート
474.9部に溶解し、ジブチル錫ジラウレート1.26
部を加えた後、熔融したε−カプロラクタムを反
応混合液の温度が70〜75℃になるようにゆつくり
滴下する。滴下終了後さらに2時間75〜80℃に加
熱する。次にポリエステルポリオール樹脂(アジ
ピン酸876.6部、エチレングリコール186.3部、ト
リメチロールプロパン201.2部、ジプロピレング
リコール402.3部を常法により縮合させて得られ
る、酸価3.5、水酸基価172、固形分100%)239部
を加え75〜80℃に5時間加熱する。かくして再生
イソシアネート基含量7.8%、固形分60%のブロ
ツクポリイソシアネート溶液を得た。ポリエステ
ルポリオール樹脂(実施例1と同じ)2550部と酸
化チタン(実施例1と同じ)895部を混練し、
1・1・3・3−テトラn−ブチル−1・3−ジ
アセトキシジスタノキサン1.6部と上記ブロツク
ポリイソシアネート溶液538部を混合し、0.3mm厚
の表面処理亜鉛びき鉄板に乾燥膜厚が20μになる
ようにスプレー塗装し280℃の雰囲気で60秒焼付
けると、光沢のある白色塗膜が得られた。塗膜性
能を第1表に示した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to precoated metals. Generally, precoated metal is manufactured by applying paint to a metal plate and curing it by heating.
Conventionally, aminoalkyd resins, melamine-cured acrylic polyols, or epoxy resins have been used as precoating paints. However,
It was found that these resins have poor processability (bending properties) of the coating film, and cracks occur in the coating film when bent at an angle of 90° or more. In view of these circumstances, the present inventors conducted extensive research and found that, among known organic polyisocyanates, bis(isocyanatomethyl)cyclohexane compositions blocked with a specific blocking agent have improved processability (bending and bending). found that it is possible to provide a pre-coated metal that has a coating film with good hardness, stain resistance, and chemical resistance.
Based on this knowledge, we have completed the present invention. That is, the present invention provides a metal plate containing a composition containing bis(isocyanatomethyl)cyclohexane or its adduct (A) blocked with an oxime-based blocking agent or a lactam-based blocking agent and a polyol resin (B). The present invention relates to a pre-coated metal, characterized in that it is coated on a metal and cured by heating. Bis(isocyanatomethyl)cyclohexane used in the present invention includes, for example, 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane,
Examples include cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and mixtures thereof. Examples of adducts of bis(isocyanatomethyl)cyclohexane include excess of the above-mentioned isocyanate and, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol,
1,4-butylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, cyclohexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, It is obtained by reacting with low molecular weight polyols such as hydrogenated bisphenol A, sorbitol, sorbitol, sucrose, pentaerythritol, and quadrol, or with high molecular weight polyols with a molecular weight of 500 to 3000 such as polyester polyols, polyether polyols, and epoxy resins. For example, a urethanized product obtained by reacting water, a lower amine such as ethylenediamine, and an excess of bis(isocyanatomethyl)cyclohexane, or a urethanized product obtained by reacting water, a lower amine such as ethylenediamine, and an excess of bis(isocyanatomethyl)cyclohexane, or the above-mentioned low-molecular-weight polyol or high-molecular-weight polyol and an excess of bis(isocyanatomethyl)cyclohexane. Examples include allophanate compounds obtained by reacting with. Even when the above-mentioned urethane compound, binder compound or allophanate compound contains a large amount of bis(isocyanatomethyl)cyclohexane monomer, it can be used in the present invention without removing it. The blocking agents used in the present invention include oxime-based and lactam-based ones. Specific examples of blocking agents include the following. Lactam blocking agents: ε-caprolactam, δ-valerolactam, γ
-butyrolactam, β-propiolactam, etc. Oxime blocking agents: formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, etc. The blocked product (A) used in the present invention is obtained by reacting bis(isocyanatomethyl)cyclohexane or its adduct with the above blocking agent at an equivalent ratio of NCO/blocking agent = about 0.9 to 1.0, preferably about 0.95 to 1.0. The means for
NCO/blocking agent = about 1.1-3.0, preferably about
After reacting at an equivalent ratio of 1.2 to 2.0, a means for reacting the above-mentioned low molecular polyol, high molecular polyol, water or lower amine, bis(isocyanatomethyl)cyclohexane and low molecular polyol, high molecular polyol, Water or lower amine with NCO/active hydrogen = about 1.5 to 10.0, preferably about
It can be obtained by reacting at an equivalent ratio of 2.0 to 7.0 and then reacting with a blocking agent. Each of the above reactions can be carried out in a solvent that does not have an active hydrogen group (e.g. ester type such as ethyl acetate, butyl acetate, ketone type such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ether type such as tetrahydrofuran) or This is carried out by a known method in the absence of a suitable solvent. In the reaction, known catalysts such as tertiary amines and organic metals may be used. Examples of the polyol resin (B) used in the present invention include polyester resins, acrylic polyol resins, and mixtures thereof. Examples of the polyester resin include polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and trimethic acid, and polybasic acids such as ethylene glycol, diethylene glycol, propylene glycol, Dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, hydroquinone bis(hydroxyethyl ether), 2,2,4 −
Trimethyl-1,3-pentanediol, hydrogenated bisphenol A, tromethylolethane, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, tris(hydroxyethyl)isocyanurate, cyclohexanediol, cyclohexanedimethanol, xylylene glycol, It can be obtained by condensing polyols such as quadrol by a conventional method under conditions with an excess of hydroxyl groups. In this case, it is also possible to use two or more types of acids or polyols in combination. Also, castor oil, higher fatty acids, etc. may be used in combination to form a so-called oil-modified polyester polyol. The polyester resin obtained by combining the above raw materials has a molecular weight of about 500 to 20,000, preferably about
2000-10000, hydroxyl value about 10-300, preferably about
20 to 200, acid value of about 1 to 50, preferably about 2 to 20. Examples of acrylic polyol resins include (1)
2-hydroxyethyl acrylate, acrylic acid 2
-hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, cinnamon alcohol, crotonyl alcohol or e.g. acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid, such as ethylene glycol, ethylene oxide, propylene glycol, propylene oxide, butylene glycol, 1,4-cyclohexyl dimethanol, phenyl glycidyl ether, A hydroxyl group-containing monomer which is a reaction product with glycidyl decanoate etc. (2) such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-acrylate Acrylic esters such as butyl, 2-ethylhexyl acrylate, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
Methacrylic acid esters such as n-butyl methacrylate, tert-butyl methacrylate, and 2-ethylhexyl methacrylate; styrenic monomers such as styrene, vinyltoluene, and α-methylstyrene; other acrylic acid, methacrylic acid, and acetic acid Vinyl, vinyl propionate, acrylonitrile, vinyl stearate, allyl acetate, diallyl adipate, dimethyl itaconate, diethyl maleate, vinyl chloride, vinylidene chloride, ethylene, glycidyl methacrylate, N-methyl-
Examples include those obtained by copolymerizing one or more types of copolymerizable α/β-ethylenically unsaturated monomers such as polyacrylamide, N-butoxymethylacrylamide, acrylamide, and diacetone acrylamide. . The acrylic polyol resin obtained by combining the above raw materials has a molecular weight of about 5,000 to 100,000, preferably about 10,000 to 50,000, a hydroxyl value of about 10 to 300,
Preferably, about 20 to 200 is used. In the present invention, first, this polyol resin (B)
A composition containing the block compound (A) and the block compound (A) is applied to a metal plate. Polyol resin (B) and blocked products
The blending ratio with (A) is adjusted so that the equivalent ratio of the recycled isocyanate groups of the blocked product (A) to the hydroxyl groups of the polyol resin (B) is about 0.5 to 2.0, preferably about 0.5 to 1.5. In addition to the blocked product (A) and the polyol resin (B), this composition also contains ester types such as ethyl acetate, butyl acetate, methyl acetoacetate, 2-ethoxyethyl acetate, aromatic types such as xylene and toluene, methyl ethyl ketone, Organic solvents such as ketones such as methyl isobutyl ketone and cyclohexanone, and ethers such as diethylene glycol dimethyl ether, those having an isocyanate group at the end such as bis(isocyanatomethyl)cyclohexane, etc., such as pigments, leveling agents, antifoaming agents , a dissociation catalyst, a stabilizer, and the like. The amount of the organic solvent is about 0 to 90% by weight based on the solid content of the blocked product (A) and the polyol resin (B). In addition, if it contains a substance having an isocyanate group at the terminal such as bis(isocyanatomethyl)cyclohexane, the amount is the same as that of the blocked product (A) and the polyol resin (B).
The amount is about 0.1 to 5% by weight based on the solid content. The metal plate used in the present invention may be any metal as long as it is normally used as a metal for pre-coated metal, such as aluminum, chin-free steel, galvanized iron plate, iron plate, etc. For example, phosphate-treated metal plate may be used. It is preferable to use chemical surface treatments such as The shape of the metal plate may be, for example, flat or cylindrical. The amount applied is approximately 10% by dry weight.
About g/m 2 to 30 g/m 2 is preferable. Examples of the coating means include a spray gun, a roll coater, a flow coater, and the like. Next, in the present invention, a metal plate coated with a composition containing a blocked product (A) and a polyol resin (B) is heated and cured. The heating temperature varies depending on the type of blocking agent, but it is approximately 150 to 350 degrees Celsius, and the heating time is approximately 20 seconds to 120 degrees Celsius.
About seconds is preferable. By this heating operation, crosslinking occurs due to the reaction between the blocked isocyanate in the blocked product (A) and the hydroxyl group in the polyol resin (B), resulting in a tough coating film. This coating shows no signs of fading or thermal deterioration due to heating operations, and has high hardness, workability (bending ability), stain resistance, and
Since both have good chemical resistance, the precoated metal obtained by the present invention can be advantageously used for building materials such as colored galvanized iron, for example, and for electrical appliances such as refrigerators and vending machines. The present invention will be explained in more detail below using Examples. In the examples, parts and % indicate parts by weight and % by weight, respectively. Example 1 581.5 parts of isophthalic acid, 707.9 parts of sebacic acid, 624.9 parts of neopentyl glycol, and 124.1 parts of ethylene glycol were heated to 220°C, nitrous gas was blown in, and the resulting water was distilled off while reacting to determine the acid value.
2.4, a polyester polyol resin having a hydroxyl value of 55 was obtained. This resin was dissolved in a mixed solvent of equal amounts of xylene and cyclohexanone to form a solution with a solid content of 40%. On the other hand, 1,3-bis(isocyanatomethyl)
Mix 582.6 parts of cyclohexane with 326 parts of ethyl acetate and 326 parts of ethoxyethyl acetate and heat to 75-80°C. Add 134.1 parts of melted trimethylolpropane while maintaining this temperature, and heat to 75-80℃ for 5 minutes.
Allow time to react. Then methyl ethyl ketoxime
261.3 parts were added dropwise over 1 hour, and after the addition was completed, the mixture was further heated to 75-80°C for 1 hour. In this way, a blocked polyisocyanate solution with a regenerated isocyanate group content of 7.7% and a solid content of 60% was obtained. 2550 parts of the above polyester polyol resin and 898 parts of titanium oxide (Thaibake R-930: Ishihara Sangyo) were kneaded and further 1,1,3,3-tetra-butyl-
2 parts of 1,3-diacetoxydistanoxane and 545 parts of the above blocked polyisocyanate solution were mixed and a dry film thickness of 20 mm was coated on a surface-treated galvanized iron plate with a thickness of 0.3 mm.
A glossy white paint film was obtained by spray painting it to a μm and baking it for 60 seconds in an atmosphere of 280°C. The coating film performance is shown in Table 1. Comparative Example 1 504.6 parts of hexamethylene diisocyanate was mixed with 300 parts of ethyl acetate and 300 parts of ethoxyethyl acetate.
Dissolve in 1 part and heat to 75-80℃. 134.1 parts of molten trimethylolpropane is slowly added dropwise while maintaining this temperature. Another 5 hours after the completion of dripping75
Heat to ~80°C. Then methyl ethyl ketoxime
261.3 parts were added dropwise over 1 hour, and after the addition was completed, the mixture was further heated to 75-80°C for 1 hour. In this way, a blocked isocyanate solution with a regenerated isocyanate group content of 8.4% and a solid content of 60% was obtained. 2550 parts of polyester polyol resin (same as Example 1) and 880 parts of titanium oxide (same as Example 1) were kneaded, and further 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistanoxane Mix 1.5 parts and 500 parts of the above block polyisocyanate solution to form a 0.3 mm
A glossy white coating was obtained by coating a thick surface-treated galvanized iron plate to a dry film thickness of 20 μm and baking it for 60 seconds in an atmosphere of 280°C. The coating film performance is shown in Table 1. Comparative Example 2 666.9 parts of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate was mixed with 354.1 parts of ethyl acetate and ethoxyethyl acetate.
Dissolve in 354.1 parts and heat to 75-80℃. 1・
After adding 0.2 parts of 1,3,3-tetra-n-butyl-1,3-diacetoxydistanoxane, 134.1 parts of molten trimethylolpropane was added dropwise over 1 hour. 75-80℃ for another 5 hours after completion of dripping
Heat to. Then methyl ethyl ketoxime 261.3
portion was added dropwise over 1 hour. After the addition is complete, the mixture is further heated to 75-80°C for 1 hour. In this way, a blocked polyisocyanate solution with a regenerated isocyanate group content of 7.1% and a solid content of 60% was obtained. 2,550 parts of polyester polyol resin (same as Example 1) and 916 parts of titanium oxide (same as Example 1) were kneaded, and 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistano Mix 2 parts of xane and 590 parts of the above blocked polyisocyanate solution, apply the mixture to a surface-treated galvanized iron plate with a thickness of 0.3 mm to a dry film thickness of 20 μm, and bake it in an atmosphere of 280°C for 60 seconds to create a glossy finish. A white coating was obtained. The coating film performance is shown in Table 1. Example 2 233 parts of 1,4-bis(isocyanatomethyl)cyclohexane was dissolved in 375 parts of ethoxyethyl acetate, and methyl ethyl ketoxime was added to this solution.
Gradually drip 174.2 parts. 75-80℃ after completion of dripping
Heat for 1 hour. Next, 155.2 parts of polytetramethylene ether glycol having a molecular weight of 620 and 0.7 parts of dibutyltin dilaurate are added and reacted at 75 to 80°C for 5 hours. Thus, the recycled isocyanate group content
A blocked polyisocyanate solution having a solid content of 8.5% and a solid content of 60% was obtained. 2550 parts of polyester polyol resin (same as in Example 1) and 878 parts of titanium oxide (same as in Example 1) were kneaded, and further 1.1.3.3-
1.5 parts of tetra-n-butyl-1,3-diacetoxydistanoxane and 494 parts of the above block polyisocyanate solution were mixed and spray-painted on a surface-treated galvanized iron plate with a thickness of 0.3 mm to a dry film thickness of 20μ. When baked in an atmosphere of 280℃ for 60 seconds, a glossy white coating was obtained. The coating film performance is shown in Table 1. Example 3 700 parts of methyl methacrylate, 207 parts of n-butyl acrylate, and 93 parts of 2-hydroxyethyl methacrylate were copolymerized in 250 parts of xylene and 250 parts of butyl acetate by a conventional method to obtain a product with a molecular weight of about 15,000 and a solid content of 50%. An acrylic polyol resin with a hydroxyl value of 20 was obtained. Separately, 116.5 parts of 1,3-bis(isocyanatomethyl)cyclohexane was dissolved in 156.1 parts of ethoxyethyl acetate, and 87.1 parts of methyl ethyl ketoxime was added dropwise over 1 hour. After the addition is complete, the mixture is further heated to 75-80°C for 1 hour. Next, 0.38 parts of dibutyltin dilaurate and oil-modified polyester polyol (444 parts of phthalic anhydride, coconut oil fatty acid)
200 parts of propylene glycol, 152 parts of propylene glycol, and 268 parts of trimethylolpropane are condensed using a conventional method, and the resulting resin is made into a 70% solution of butyl acetate. acid value
4.0, hydroxyl value 115) add 122 parts of solution, 75-80
React at ℃ for 4 hours. In this way, a blocked polyisocyanate solution with a regenerated isocyanate group content of 8.3% and a solid content of 60% was obtained. 2,800 parts of the above acrylic polyol resin and 1,137 parts of titanium oxide (same as in Example 1) were kneaded and 1.1.
Mix 1.5 parts of 3,3-tetrabutyl-1,3-diacetoxydistanoxane and 508 parts of the above block polyisocyanate solution, and spray paint on a 0.3 mm thick surface-treated galvanized iron plate to a dry film thickness of 20μ. When baked for 60 seconds at 280°C, a glossy white coating was obtained. The coating film performance is shown in Table 1. Comparative Example 3 157.4 parts of 4,4'-methylenebis(cyclohexyl isocyanate) was converted into ethoxyethyl acetate.
Dissolved in 183.3 parts methyl ethyl ketoxime 87.1 parts
1 hour. Another 1 hour after completion of dripping
Heat to 75-80°C. Next, 0.44 parts of dibutyltin dilaurate and 122 parts of an oil-modified polyester resin solution (same as in Example 3) are added and reacted at 75-80°C for 6 hours. Thus the regenerated isocyanate group content is 7.3
%, a blocked polyisocyanate solution with a solid content of 60% was obtained. 2800 parts of acrylic polyol resin (same as Example 3) and titanium oxide (same as Example 1)
1,165 parts of 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistanoxane were mixed and 1.7
Part and the above blocked polyisocyanate solution 579
A glossy white paint film was obtained by mixing the two parts and coating it on a 0.3 mm thick surface-treated galvanized iron plate to a dry film thickness of 20 μm and baking it in an atmosphere of 280°C for 60 seconds. The coating film performance is shown in Table 1. Example 4 361.2 parts of 1,3-bis(isocyanatomethyl)cyclohexane was converted into ethoxyethyl acetate.
Dissolved in 474.9 parts dibutyltin dilaurate 1.26
After adding 50% of the reaction mixture, molten ε-caprolactam is slowly added dropwise so that the temperature of the reaction mixture becomes 70 to 75°C. After the addition is complete, the mixture is further heated to 75-80°C for 2 hours. Next, polyester polyol resin (obtained by condensing 876.6 parts of adipic acid, 186.3 parts of ethylene glycol, 201.2 parts of trimethylolpropane, and 402.3 parts of dipropylene glycol, acid value 3.5, hydroxyl value 172, solid content 100%) Add 239 parts and heat to 75-80°C for 5 hours. In this way, a blocked polyisocyanate solution with a regenerated isocyanate group content of 7.8% and a solid content of 60% was obtained. 2550 parts of polyester polyol resin (same as Example 1) and 895 parts of titanium oxide (same as Example 1) were kneaded,
1.6 parts of 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistanoxane and 538 parts of the above block polyisocyanate solution were mixed, and a dry film thickness of 0.3 mm thick surface-treated galvanized iron plate was obtained. When spray-painted to a thickness of 20μ and baked for 60 seconds at 280℃, a glossy white coating was obtained. The coating film performance is shown in Table 1. 【table】
Claims (1)
ツク剤でブロツク化されたビス(イソシアナート
メチル)シクロヘキサンまたはその付加体(A)とポ
リオール樹脂(B)とを含有してなる組成物を金属板
に塗布し、加熱硬化せしめたことを特徴とするプ
レコートメタル。 2 成分(A)と成分(B)とを含有してなる組成物が更
にビス(イソシアナートメチル)シクロヘキサン
を含有したものである特許請求の範囲第1項記載
のプレコートメタル。[Claims] 1. A composition comprising bis(isocyanatomethyl)cyclohexane or its adduct (A) blocked with an oxime-based blocking agent or a lactam-based blocking agent and a polyol resin (B). Pre-coated metal is characterized by being coated onto a metal plate and hardened by heating. 2. The precoated metal according to claim 1, wherein the composition containing component (A) and component (B) further contains bis(isocyanatomethyl)cyclohexane.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16703779A JPS5689548A (en) | 1979-12-21 | 1979-12-21 | Manufacture of precoating metal |
GB8036694A GB2066275B (en) | 1979-12-21 | 1980-11-14 | Precoated metal and its production |
DE19803047687 DE3047687A1 (en) | 1979-12-21 | 1980-12-18 | PRE-PAINTED METAL AND METHOD FOR THE PRODUCTION THEREOF |
CA000367169A CA1154639A (en) | 1979-12-21 | 1980-12-19 | Precoat metal and its production |
FR8027100A FR2473053A1 (en) | 1979-12-21 | 1980-12-19 | METAL COMPRISING A COATING AND METHOD FOR MANUFACTURING THE SAME |
US06/550,991 US4562714A (en) | 1979-12-21 | 1983-11-14 | Precoat metal and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16703779A JPS5689548A (en) | 1979-12-21 | 1979-12-21 | Manufacture of precoating metal |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5689548A JPS5689548A (en) | 1981-07-20 |
JPS6249116B2 true JPS6249116B2 (en) | 1987-10-16 |
Family
ID=15842207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16703779A Granted JPS5689548A (en) | 1979-12-21 | 1979-12-21 | Manufacture of precoating metal |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5689548A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51139830A (en) * | 1975-05-28 | 1976-12-02 | Takeda Chem Ind Ltd | Powdered coating composition |
-
1979
- 1979-12-21 JP JP16703779A patent/JPS5689548A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51139830A (en) * | 1975-05-28 | 1976-12-02 | Takeda Chem Ind Ltd | Powdered coating composition |
Also Published As
Publication number | Publication date |
---|---|
JPS5689548A (en) | 1981-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4482721A (en) | 1,2,4-Triazole-blocked polyisocyanates as cross-linkers for lacquer binders | |
JP2688288B2 (en) | Method for producing a two-layer lacquer coating and a non-aqueous lacquer suitable for this method | |
US5688598A (en) | Non-blistering thick film coating compositions and method for providing non-blistering thick film coatings on metal surfaces | |
KR960011005B1 (en) | One-can resin composite | |
JPS62236817A (en) | One-component thermosetting resin composition | |
JP2001089683A (en) | Elastic coating system containing ultraviolet-curable urethane (meth)acrylate bearing isocyanate group and its use | |
JP5542301B2 (en) | Coating composition | |
KR100356885B1 (en) | Composition and Their Use for Coating Heat Resistant Substrates | |
US4235766A (en) | Coating composition having an improved pot life | |
US4562714A (en) | Precoat metal and its production | |
JPS63301215A (en) | One-pack thermosetting resin composition and precoated metal | |
EP1268597A1 (en) | Novel bonding agent combination for water-proof coatings that are produced by coil coating | |
JPS63301217A (en) | One-pack thermosetting resin composition and precoated metal | |
JP2628046B2 (en) | One-part thermosetting resin composition | |
JPH05271616A (en) | Powdery coating composition and use of the composition for coating heat resistant substrate | |
JPS6249116B2 (en) | ||
EP0778326A2 (en) | Coating compositions for precoated metal sheets | |
JPS633668B2 (en) | ||
JPH02276878A (en) | One pack type polyurethane thermosetting coating composition | |
JPS6386715A (en) | Resin composition and cured resin therefrom | |
US5532313A (en) | Heat curable coating compositions and their use as top coats | |
JP3352472B2 (en) | Block polyisocyanate composition and one-pack type thermosetting coating composition | |
JPS5840591B2 (en) | powder coating composition | |
JPH01167376A (en) | Production pur-baking paint | |
EP1320565B1 (en) | Clearcoat composition with improved scratch and mar resistance |