WO1992017283A1 - Non-isocyanate ambient temperature curable coating compositions - Google Patents
Non-isocyanate ambient temperature curable coating compositions Download PDFInfo
- Publication number
- WO1992017283A1 WO1992017283A1 PCT/US1992/001943 US9201943W WO9217283A1 WO 1992017283 A1 WO1992017283 A1 WO 1992017283A1 US 9201943 W US9201943 W US 9201943W WO 9217283 A1 WO9217283 A1 WO 9217283A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- polymer
- compositions according
- urethane
- epoxy
- Prior art date
Links
- 239000008199 coating composition Substances 0.000 title claims description 27
- 239000012948 isocyanate Substances 0.000 title description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 45
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004069 aziridinyl group Chemical group 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 40
- 239000004593 Epoxy Substances 0.000 claims description 27
- -1 or higher Chemical group 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 19
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 description 16
- 229920001451 polypropylene glycol Polymers 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010960 cold rolled steel Substances 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000002987 primer (paints) Substances 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- VYONOYYDEFODAJ-UHFFFAOYSA-N 2-(1-Aziridinyl)ethanol Chemical compound OCCN1CC1 VYONOYYDEFODAJ-UHFFFAOYSA-N 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001541 aziridines Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- DIXBSCZRIZDQGC-UHFFFAOYSA-N diaziridine Chemical compound C1NN1 DIXBSCZRIZDQGC-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
- C08G59/5066—Aziridines or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/06—Triglycidylisocyanurates
Definitions
- the present invention relates to isocyanate-free coating compositions containing (1) at least one polymer and/or oligomer selected from the group consisting of acrylic, urethane and urea polymers and oligomers and combinations thereof having a molecular weight of at least about 100 and bearing at least two specific aziridine groups and (2) at least one polymer and/or oligomer selected from the group consisting of acrylic, urethane and urea polymers and oligomers and combinations thereof having a molecular weight of at least about 100 and bearing at least two specific epoxy groups capable of forming a durable coating under ambient conditions.
- compositions which cure at low temperatures, for example, at ambient conditions, for use as highly durable automotive topcoats are usually based on two-package systems. These include, for example, hydroxy functional components cured with either isocyanate or anhydride functional components.
- isocyanate functional components requires that specific precautions be taken based on toxicity considerations. Such necessary precautions can be relatively burdensome in areas where said materials are used but controlled conditions do not exist or are difficult to obtain.
- One such example of a generally non-controlled environment is an automobile body repair shop.
- the application of isocyanate-containing materials is relatively hazardous to exposed workers without proper protection.
- isocyanate/polyol cured compositions deliver the quality and durability demanded by the user. If the crosslinking composition is an anhydride/polyol system, the general overall appearance of the cured coating, i.e., gloss and D.O.I. (depth of image), is inferior to isocyanate-cured coatings. Accordingly, there is an urgent need for high quality, durable coating compositions which cure under ambient conditions, are relatively non-toxic and have the aesthetic appearance of an isocyanate-cured composition.
- the present invention addresses these issues.
- the coating compositions disclosed and claimed herein are not isocyanate curing, are relatively non-toxic compared to isocyanate, are curable at ambient temperature and are equal, or even better, in performance and appearance to both isocyanate/polyol or anhydride/polyol cured compositions.
- British Patent No. 1,190,979 to Strother discloses a coating composition comprising a diepoxide, a diphenol and a diaziridine.
- the diaziridine compounds used are those in which the aziridinyl groups are tertiary amine groups, preferably defined by the following formula
- R is a divalent hydrocarbon radical having 1 to 10 carbon atoms.
- Diepoxides that are used include diglycidyl ether, the diglycidyl ethers of bisphenols, diglycidyl ether adduct of adipic acid, vinyl cyclohexene dioxide and the diglycidyl ethers of
- Diphenols a necessary component of the system, include bisphenol A, bisphenol F, hydroquinone and resorcinol.
- the present invention does not require diphenols to obtain curing. Curing of the above mixture requires elevated
- Martin et al relate to coating compositions containing an epoxy-bisphenol adduct, an adduct of an aziridine compound with a polyepoxide and, optionally, a
- Strother et al in U.S. Patent No. 3,346,533 disclose the use of a diphenol for curing a diaziridine compound with cycloaliphatic 1,2-diepoxide.
- This patent is similar to British Patent No. 1,190,979 to Strother, supra, and for the same reason neither discloses nor teaches the compositions and processes claimed herein.
- the present invention is directed to isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, containing the following components:
- X represents O, S, NH, NR, wherein R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl,
- R 1 represents (CH 2 )m 1 , m 1 being an integer ranging from 1 to 3 and
- Ro represents H, CH 3 or combinations thereof
- R 3 represents (CH 2 )m 2 , m 2 being an integer ranging from 1 to 2.
- the present invention is directed to isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, particularly suitable as coating compositions for coating substrates, especially automotive bodies and parts, and which are relatively non-toxic, containing the following components:
- X represents O, S, NH or NR
- R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl, preferably 0,
- R 1 represents (CH 2 )m 1 , m 1 being an integer ranging from 1 to 3, preferably 2, and
- R 2 represents H, CH 3 or combinations thereof, preferably H and
- Component A can be prepared, for example, from the reaction of isocyanate functional acrylic, urethane or urea polymers and/or oligomers with, for example, hydroxy, amino or mercapto functional alkyl aziridines. Examples of procedures suitable for the preparation of acrylic polymers that can be used herein are disclosed in U.S.
- Component B(1) can be obtained, for example, from the reaction of isocyanate functional acrylic, urethane or urea polymers and/or oligomers with glycidol.
- Component B(2) is commercially available from MONSANTO
- Component B(3) can be obtained, for example, from the free radical polymerization of ethylenically-unsaturated monomers, of which one will be selected from glycidyl functional acrylate or
- methacrylates such as glycidyl acrylate or glycidyl methacrylate.
- the coating composition herein is usually a two-package composition, that is, the aziridine component and the epoxy component are usually mixed, at ambient temperature, just prior to their application to a substrate.
- the two components can be used such that the range of aziridine (equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3, preferably about 1:1.
- a “pot life" which is defined as the useful time interval between mixing of the
- the coating composition defined and claimed herein can be applied to the substrate by any conventional technique, such as spraying, brushing, dipping, rolling, etc., with the preferred method before spraying. Additionally, the components can be devolatalized and converted into sprayable powder form.
- the coating composition can be applied onto many substrates, such as metals, for example, steel and aluminum, wood, glass, plastics, concrete, etc. Additionally, the substrate can be primed or electrocoated prior to applying thereto the coating composition of this invention.
- the topcoat composition can be pigmented one-coat system or, more preferably, a clear coat over a pigmented base coat.
- the coating compositions herein can also contain ingredients, such as inorganic or organic pigments or metal flakes typically used in automobile refinishing operations, plasticizers, inert filters, adhesion promoters, flow additives, thixotropes and additives for sag control and metallic flake orientation (sometimes referred to as microgel) and described in U.S. Patent Nos. 4,025,474, 4,055,607, 4,075,141, 4,115,472, 4,147,688, 4,180,489, 4,242,384, 4,268,547 and 4,290,932, the disclosures of which are hereby incorporated by reference, and other such formulating additives.
- ingredients such as inorganic or organic pigments or metal flakes typically used in automobile refinishing operations, plasticizers, inert filters, adhesion promoters, flow additives, thixotropes and additives for sag control and metallic flake orientation (sometimes referred to as microgel) and described in U.S. Patent Nos. 4,025,474,
- the coating compositions herein containing the defined aziridines and epoxies are usually solutions in organic solvents, although other forms can also be used, such as aqueous dispersions, non-aqueous dispersions and powder forms.
- organic solvents that can be used include esters, such as butyl acetate;
- ketones such as methyl isobutyl ketone
- aromatic hydrocarbons such as xylene
- glycol ethers such as propylene glycol methyl ether acetate.
- the solvents or carriers can be used in a range of about 20 to about 70 weight percent, based on the final coating composition.
- the coating compositions herein are most useful for refinishing automobiles.
- the curing of the components can,
- a coating composition was prepared by mixing the following materials:
- 1,3-dimethy1-2-imidazolidinone were added to 400 grams of isocyanurate of isophorone diisocyanate (T-1890L) over a period of one hour at temperatures ranging from 23o to 50oC.
- T-1890L isocyanurate of isophorone diisocyanate
- 1.2 grams of butanol and 0.4 grams of butyl tin dilaurate were added and the temperature was raised to 70oC.
- the reaction was held at this temperature until the NCO disappeared by IR (about one hour).
- 121 grams of butanol and 10 grams of 1,3-dimethy1-2-imidazolidinone were then added to the reaction mixture.
- the product showed no NCO in the IR, had a non-volatile content of 61.7 weight percent (110oC./one hour), a Gardner viscosity of X-Y and a theoretical aziridine
- a solution of epoxy functional urethane polymer was then prepared as follows. 4180 grams of dibasic ester (obtainable from Dupont
- Desmodur N 3390 a trimer of hexamethylene diisocyanate available from MOBAY
- 103.1 grams of the hydroxy functional polymer obtained above 0.06 grams of dibutyl tin dilaurate and 347.1 grams of methyl isobutyl ketone.
- the resulting mixture was heated to 80oC, while watching for an exotherm at 50oC, and then held at 80oC, until the isocyanate equivalent weight reached about 600.
- the reaction mixture was then cooled to 50°C, after which 210.9 grams of glycidol and 30 grams of methyl isobutyl ketone were added thereto.
- the reaction mixture was held at 50oC. until the NCO peak disappeared from IR (about three hours) and there were then added 14.5 grams of absolute ethanol and cooled to room temperature.
- the product obtained was a glycidyl based urethane having no NCO peak in the IR, a non-volatile content of 49.0 weight percent, and a GPC peak molecular weight of 7530.
- a coating composition was prepared by mixing the following materials:
- Epoxy Resin (Glycidyl based
- the product obtained was a glycidyl methacrylate functional acrylic resin having a non-volatile content of 75.2 weight percent (150oC./two hours), a Gardner Viscosity of Z , a GPC number average molecular weight of 2559, and an epoxy equivalent weight of 375 (solution).
- a coating composition was prepared by mixing the following materials:
- the above clearcoat package was then spray applied to 24 gauge cold rolled steel panels (treated with BONDERITE 40, primed with DP 40/401 and basecoated with DELTRON ® Universal Basecoat).
- the clearcoat film was allowed to cure at ambient conditions.
- the resulting coating was found to have the following properties after a one-week cure time:
- the product showed no isocyanate peak in the IR, had a non-volatile content of 63.2 percent (110o/hour), a Gardner viscosity of Z 4 and a theoretical aziridine equivalent weight of 348.5 (solid) and a GPC peal molecular weight of 2524.
- a coating composition was prepared by mixing the following materials : Component Parts by Weight. Grams
- the above clearcoat package was then spray applied to 24 gauge cold-rolled steel panels (treated with BONDERITE 40, primed with DP-40/401, a two-component epoxy primer from PPG INDUSTRIES, INC., PPG FINISHES, and basecoated with DELTRON ® Universal Basecoat from PPG INDUSTRIES, INC., PPG FINISHES).
- the clearcoat film was allowed to cure at ambient conditions.
- the resulting coating was found to have the following properties after a one-week cure time. 20 Degree Gloss : 92
- the clearcoat film was allowed to cure at ambient conditions.
- the resulting coating was found to have the following properties after a one-week cure time:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
An ambient temperature-curable coating for automotive bodies and parts which is non-toxic and aesthetic in appearance is provided by an isocyanate-free composition comprising an aziridinyl groups-containing acrylic, urethane or urea polymer and an epoxyamide or epoxyester groups-containing acrylic, urethane or urea polymer.
Description
NON-ISOCYANATE AMBIENT TEMPERATURE
CURABLE COATING COMPOSITIONS
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to isocyanate-free coating compositions containing (1) at least one polymer and/or oligomer selected from the group consisting of acrylic, urethane and urea polymers and oligomers and combinations thereof having a molecular weight of at least about 100 and bearing at least two specific aziridine groups and (2) at least one polymer and/or oligomer selected from the group consisting of acrylic, urethane and urea polymers and oligomers and combinations thereof having a molecular weight of at least about 100 and bearing at least two specific epoxy groups capable of forming a durable coating under ambient conditions.
BRIEF_DESCRIPTION OF PRIOR ART
Known compositions which cure at low temperatures, for example, at ambient conditions, for use as highly durable automotive topcoats are usually based on two-package systems. These include, for example, hydroxy functional components cured with either isocyanate or anhydride functional components.
The use of isocyanate functional components requires that specific precautions be taken based on toxicity considerations. Such necessary precautions can be relatively burdensome in areas where said materials are used but controlled conditions do not exist or are difficult to obtain. One such example of a generally non-controlled environment is an automobile body repair shop. The application of isocyanate-containing materials is relatively hazardous to exposed workers without proper protection. However, isocyanate/polyol cured compositions deliver the quality and durability demanded by the user. If the crosslinking composition is an anhydride/polyol system, the general overall appearance of the cured coating, i.e., gloss and D.O.I. (depth of image), is inferior to isocyanate-cured coatings.
Accordingly, there is an urgent need for high quality, durable coating compositions which cure under ambient conditions, are relatively non-toxic and have the aesthetic appearance of an isocyanate-cured composition.
The present invention addresses these issues. The coating compositions disclosed and claimed herein are not isocyanate curing, are relatively non-toxic compared to isocyanate, are curable at ambient temperature and are equal, or even better, in performance and appearance to both isocyanate/polyol or anhydride/polyol cured compositions.
In the prior art, there is disclosed the curing of diepoxides with a combination of diaziridines and diphenols. The epoxies used are aromatic based or glycidyl functional bisphenol A materials. Such epoxies are not suitable for application to a substrate where high durability is required, such as in refinishing of automobile surfaces.
British Patent No. 1,190,979 to Strother discloses a coating composition comprising a diepoxide, a diphenol and a diaziridine. The diaziridine compounds used are those in which the aziridinyl groups are tertiary amine groups, preferably defined by the following formula
wherein R is a divalent hydrocarbon radical having 1 to 10 carbon atoms. Diepoxides that are used include diglycidyl ether, the diglycidyl ethers of bisphenols, diglycidyl ether adduct of adipic acid, vinyl cyclohexene dioxide and the diglycidyl ethers of
polyhydric aliphatic alcohols. Diphenols, a necessary component of the system, include bisphenol A, bisphenol F, hydroquinone and resorcinol. The present invention does not require diphenols to obtain curing. Curing of the above mixture requires elevated
temperatures in the range of 100° to 200°C. for a period of 10 minutes to one hour. The epoxides and diphenols used by Strother contribute
to poor durability and therefore are not useful for automotive topcoat compositions. In addition, curing at elevated temperatures further render such compositions unattractive for use in the automotive refinishing industry.
In U.S. Patent No. 3,763,100, Martin et al relate to coating compositions containing an epoxy-bisphenol adduct, an adduct of an aziridine compound with a polyepoxide and, optionally, a
mono-functional secondary amine that can be air dried or baked at temperatures of from about 25º to about 400ºC. for about five minutes to about 24 hours. Martin et al thus use an aromatic diphenol and, as with Strother, produce a composition not useful for durable automotive refinish topcoats. In fact, Martin et al's coating is used as a metal primer coating to improve adhesion between said primer and a
subsequent topcoat.
Strother et al in U.S. Patent No. 3,346,533 disclose the use of a diphenol for curing a diaziridine compound with cycloaliphatic 1,2-diepoxide. This patent is similar to British Patent No. 1,190,979 to Strother, supra, and for the same reason neither discloses nor teaches the compositions and processes claimed herein.
SUMMARY OF THE INVENTION
The present invention is directed to isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, containing the following components:
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea, polymers and oligomers having a molecular weight of at least about 100 and bearing at least two aziridinyl groups defined by the following structural formula:
wherein
X represents O, S, NH, NR, wherein R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl,
R1 represents (CH2)m1, m1 being an integer ranging from 1 to 3 and
Ro represents H, CH3 or combinations thereof and
(B) at least one polymer, oligomer or combinations thereof selected from the groups consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two groups selected from epoxy groups defined by one of the following structural formulas:
;
wherein R represents alkyl having from one to 20 carbon atoms and n = 0-20; and
wherein R3 represents (CH2)m2, m2 being an integer ranging from 1 to 2.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, particularly suitable as coating compositions for coating substrates, especially automotive bodies and parts, and which are relatively non-toxic, containing the following components:
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100, preferably from about 100 to about 20,000, and bearing at least two, preferably from two to about 75, aziridinyl groups defined by the following structural formula:
wherein
X represents O, S, NH or NR,
wherein R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl, preferably 0,
R1 represents (CH2)m1, m1 being an integer ranging from 1 to 3, preferably 2, and
R2 represents H, CH3 or combinations thereof, preferably H and
(B) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100, preferably from about 100 to about 20,000, and bearing at least two, preferably from two to 75, epoxy groups selected from the epoxy groups defined by one of the following structural formulas:
J
wherein R3 represents (CH2)m2, m2 being an integer ranging from 1 to 2, preferably 1. Component A can be prepared, for example, from the reaction of isocyanate functional acrylic, urethane or urea polymers and/or oligomers with, for example, hydroxy, amino or mercapto functional alkyl aziridines. Examples of procedures suitable for the preparation of acrylic polymers that can be used herein are disclosed in U.S.
Patent Application No. 07/643,253 of Charles M. Kania, filed on
January 22, 1991, for Aziridine Compounds, Acrylic Polymers Containing Same and Coating Compositions Containing Said Polymers, assigned to the same assignee as the present patent application.
Component B(1) can be obtained, for example, from the reaction of isocyanate functional acrylic, urethane or urea polymers and/or oligomers with glycidol.
Component B(2) is commercially available from MONSANTO
Corporation under the Trade Name LSE-120 Light Stable Epoxy.
Component B(3) can be obtained, for example, from the free radical polymerization of ethylenically-unsaturated monomers, of which one will be selected from glycidyl functional acrylate or
methacrylates, such as glycidyl acrylate or glycidyl methacrylate.
The invention herein is also directed to processes for coating a substrate using such compositions.
The coating composition herein is usually a two-package composition, that is, the aziridine component and the epoxy component are usually mixed, at ambient temperature, just prior to their application to a substrate. The two components can be used such that the range of aziridine (equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3, preferably about 1:1. There is generally associated with two-package component compositions a "pot life", which is defined as the useful time interval between mixing of the
components and the application thereof to the substrate. Generally, such time is about eight hours.
The coating composition defined and claimed herein can be applied to the substrate by any conventional technique, such as spraying, brushing, dipping, rolling, etc., with the preferred method before spraying. Additionally, the components can be devolatalized and converted into sprayable powder form. The coating composition can be applied onto many substrates, such as metals, for example, steel and aluminum, wood, glass, plastics, concrete, etc. Additionally, the substrate can be primed or electrocoated prior to applying thereto the coating composition of this invention. The topcoat composition can be pigmented one-coat system or, more preferably, a clear coat over a pigmented base coat.
The coating compositions herein can also contain ingredients, such as inorganic or organic pigments or metal flakes typically used in automobile refinishing operations, plasticizers, inert filters, adhesion promoters, flow additives, thixotropes and additives for sag control and metallic flake orientation (sometimes referred to as microgel) and described in U.S. Patent Nos. 4,025,474, 4,055,607, 4,075,141, 4,115,472, 4,147,688, 4,180,489, 4,242,384, 4,268,547 and 4,290,932, the disclosures of which are hereby incorporated by reference, and other such formulating additives.
The coating compositions herein containing the defined aziridines and epoxies are usually solutions in organic solvents, although other forms can also be used, such as aqueous dispersions, non-aqueous dispersions and powder forms. Common examples of organic solvents that can be used include esters, such as butyl acetate;
ketones, such as methyl isobutyl ketone; aromatic hydrocarbons, such as xylene; and glycol ethers, such as propylene glycol methyl ether acetate. The solvents or carriers can be used in a range of about 20 to about 70 weight percent, based on the final coating composition.
The coating compositions herein are most useful for refinishing automobiles. The curing of the components can,
preferably, be achieved at ambient conditions; or the cure can be promoted at elevated temperatures if desired.
DESCRIPTION OF PREFERRED EMBODIMENTS
EXAMPLE 1
50.72 grams of hydroxy ethyl ethyleneimine were added to 200.0 grams of T-1890L, the isocyanurate of isophorone diisocyanate
(obtainable from HULS) over a period of one hour at temperatures ranging from 25° to 47ºC. and then maintained at such temperature for 30 minutes. 42.7 grams of hexyl acetate were then added to the mixture along with 0.2 grams of dibutyl tin dilaurate, and the reaction temperature was raised to 85° to 91°C. and maintained within the latter temperature range for an additional 30 minutes. The resulting product showed no NCO peak in the IR, had a non-volatile content of 66.3 percent (110ºC./one hour), a Gardner viscosity of Z8 and a theoretical aziridine equivalent weight of 327 (solid).
A coating composition was prepared by mixing the following materials:
Component Parts by Weight, Grams Aziridine Resin obtained above 81 .2
Polysiloxane solution1 (flow control) 1 .0
U.V. Absorber2 3 .0
Toluene (solvent) 15 .9
Propylene Glycol Methyl Ether Acetate
(solvent) 26 .4
Butyl Acetate (solvent) 35. 1
Ethyl-3-Ethoxy Propionate (solvent) 10.5
Epoxy Resin3 86. 2 1 Available from DOW Corning Corporation as DC 200, 135 csk dissolved in xylene to give a 0.5 weight percent polysiloxane content.
2 Available from Ciba-Geigy Corp. as TINUVIN 328.
3 A melamme-based epoxy oligomer available from MONSANTO Chemical Co. as LSE-120.
The above clearcoat package was then spray applied to 24 gauge cold rolled steel panels (treated with BONDERITE 40, primed with
DP-40/401, a two-component epoxy primer from PPG INDUSTRIES, INC., and basecoated with DELTRON® Universal Basecoat from PPG INDUSTRIES, INC.). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time:
20 Degree Gloss : 95
D.O.I. : 70
Pencil Hardness : B
Solvent Resistance : Excellent EXAMPLE 2
96.4 grams of hydroxy ethyl ethyleneimine and 20 grams of
1,3-dimethy1-2-imidazolidinone were added to 400 grams of isocyanurate of isophorone diisocyanate (T-1890L) over a period of one hour at temperatures ranging from 23º to 50ºC. Upon completion of the feed 1.2 grams of butanol and 0.4 grams of butyl tin dilaurate were added and the temperature was raised to 70ºC. The reaction was held at this temperature until the NCO disappeared by IR (about one hour). 121 grams of butanol and 10 grams of 1,3-dimethy1-2-imidazolidinone were then added to the reaction mixture. The product showed no NCO in the IR, had a non-volatile content of 61.7 weight percent (110ºC./one hour), a Gardner viscosity of X-Y and a theoretical aziridine
equivalent weight of 327 (solid).
A solution of epoxy functional urethane polymer was then prepared as follows. 4180 grams of dibasic ester (obtainable from Dupont
Corporation), 2950 grams of 1,6-hexanediol, 1800 grams of cyclohexane dimethanol, 3.6 grams of 50 weight percent aqueous hypophosphorous acid solution, 7.1 grams of butane sulfonic acid and 7.1 grams of t-butyl titanate were added to a 12-liter round bottom flask equipped with a stirrer thermometer, nitrogen inlet and distillation receiver and was heated to a maximum temperature of 210ºC. to remove methyl alcohol therefrom, using a nitrogen sparge to facilitate such removal.
Over a nine-hour period 1487 grams of methyl alcohol was removed from the reaction mixture, the remainder was cooled to 115ºC. and then 1246.4 grams of methyl isobutyl ketone were added thereto, resulting in a hydroxy functional polymer.
To a three-liter round bottom flask equipped with a nitrogen inlet, stirrer, thermometer and condenser, there was added 390.6 grams of Desmodur N 3390 (a trimer of hexamethylene diisocyanate available from MOBAY), 103.1 grams of the hydroxy functional polymer obtained above, 0.06 grams of dibutyl tin dilaurate and 347.1 grams of methyl isobutyl ketone. The resulting mixture was heated to 80ºC, while watching for an exotherm at 50ºC, and then held at 80ºC, until the isocyanate equivalent weight reached about 600. The reaction mixture was then cooled to 50°C, after which 210.9 grams of glycidol and 30 grams of methyl isobutyl ketone were added thereto. The reaction mixture was held at 50ºC. until the NCO peak disappeared from IR (about three hours) and there were then added 14.5 grams of absolute ethanol and cooled to room temperature. The product obtained was a glycidyl based urethane having no NCO peak in the IR, a non-volatile content of 49.0 weight percent, and a GPC peak molecular weight of 7530.
A coating composition was prepared by mixing the following materials:
Component Parts by Weight, Grams
Aziridine Resin obtained above 76 .5
Polysiloxane solutions1 1 .0
Additive2 1 .0
U.V. Absorber3 3 .0
Toluene 13 .3
Propylene Glycol Methyl Ether Acetate 22 .2
Ethylene Glycol Butyl Ether Acetate 22. 2
Butyl Acetate 29. 4
Ethyl-3-Ethoxy Propionate 8. 9
Epoxy Resin (Glycidyl based
Urethane obtained above) 100.2 1 Same as used in Example No. 1.
2 Slip and mar additive available from BYK-MALLINCKRODT as BYK-300.3 Same as used in Example No. 1.
The above clearcoat package was then spray applied to 24 gauge cold rolled steel panels (treated with BONDERITE 40, primed with DP-40/401 and basecoated with DELTRON® Universal Basecoat). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time:
20 Degree Gloss : 86
D.O.I. : 65
Pencil Hardness : 4B
Solvent Resistance : Excellent
EXAMPLE 3
To 2400 grams of refluxing xylene was added a mixture of 750 grams of styrene, 750 grams of methyl methacrylate, 2250 grams of isobornyl methacrylate, 3750 grams of glycidyl methacrylate and an initiator solution containing 250 grams of Lupersol 555 (t-amyl peracetate from Atochem) and 746 grams of xylene. The monomer solution was added over a period of three hours and the initiator solution over a period of 3.5 hours. Upon completion of such additions, 300 grams of xylene were added to the mixture. One hour after the latter addition, there were added 37.5 grams of di-t-butyl peroxide and the reaction mixture was held for an additional two hours. Reflux conditions were maintained throughout the reaction. The product obtained was a glycidyl methacrylate functional acrylic resin having a non-volatile content of 75.2 weight percent (150ºC./two hours), a Gardner Viscosity of Z , a GPC number average molecular weight of 2559, and an epoxy equivalent weight of 375 (solution).
A coating composition was prepared by mixing the following materials:
Component Parts by Weight. Grains
Aziridine Resin used in Example 1 80.3
Polysiloxane solution1 1.0
Additive 1.0
U.V. Absorber3 3.0
Toluene 19.0
Propylene Glycol Methyl Ether Acetate 31.6
Ethylene Glycol Butyl Ether Acetate 31.6
Butyl Acetate 41.9
Ethyl-3-Ethoxy Propionate 12.6
Epoxy Resin (Glycidyl methacrylate
resin obtained above) 63.7 1 Same as used in Examples Nos. 1 and 2.
2 Same as used in Example No. 2.
3 Same as used in Examples Nos. 1 and 2.
The above clearcoat package was then spray applied to 24 gauge cold rolled steel panels (treated with BONDERITE 40, primed with DP 40/401 and basecoated with DELTRON® Universal Basecoat). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time:
20 Degree Gloss : 92
D.O.I. : 80
Pencil Hardness : 4B
Solvent Resistance: Excellent
EXAMPLE 4
80.17 grams of hydroxy ethyl ethyleneimine and 45.1 grams of butyl acetate were added to 70 percent isocyanate prepolymer solution in butyl acetate based on three moles of m-TMXDI (a diisocyanate available from American Cyanamid) and one mole of trimethylolpropane over a period of one hour at a temperature of 25° to 61ºC. Upon completion of the addition, 3.6 grams of butyl alcohol and 0.34 grams of dibutyl tin dilaurate were added and the temperature raised to 85ºC. The reaction was held for two hours at this temperature until the NCO disappeared by IR. 38.1 grams of butyl acetate were then added. The product showed no isocyanate peak in the IR, had a non-volatile content of 63.2 percent (110º/hour), a Gardner viscosity of Z4 and a theoretical aziridine equivalent weight of 348.5 (solid) and a GPC peal molecular weight of 2524.
A coating composition was prepared by mixing the following materials :
Component Parts by Weight. Grams
Aziridine Resin obtained above 100 .0
Polysiloxane solution 1 .0
Additive2 1 .0
U.V. Absorber3 3 .0
Toluene 19 .0
Propylene Glycol Methyl Ether Acetate 31 .6
Ethylene Glycol Butyl Ether Acetate 31 .6
Butyl Acetate 41 .9
Ethyl-3-Ethpxy Propionate 12 .6
Epoxy Resin 44 .0 1 Same as used in Example 1.
2 Same as used in Example 2.
3 Same as used in Example 1.
4A melamine-based epoxy oligomer available from MONSANTO Chemical Co. as LSE-20.
The above clearcoat package was then spray applied to 24 gauge cold-rolled steel panels (treated with BONDERITE 40, primed with DP-40/401, a two-component epoxy primer from PPG INDUSTRIES, INC., PPG FINISHES, and basecoated with DELTRON® Universal Basecoat from PPG INDUSTRIES, INC., PPG FINISHES). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time. 20 Degree Gloss : 92
D.O.I. : 80
Pencil Hardness : 4B
Solvent Resistance : Excellent
EXAMPLE 5
In this Example 5, which was used as an isocyanate/polyol control, it can be seen that isocyanate/polyol cured systems, which are toxic, do not result in a coating having all of the desirable properties obtained using the novel compositions defined and claimed herein.
Thus, a clearcoat paint commercially available from PPG INDUSTRIES, INC., PPG FINISHES under the trade name DELTRON® DAU-82, containing an isocyanate and a polyol as component, was spray applied to 24 gauge
cold rolled steel panels (treated with BONDERITE 40, primed with DP 40/401, a two-component epoxy primer from PPG INDUSTRIES, INC., PPG FINISHES, and basecoated with DELTRON® Universal Basecoat from PPG INDUSTRIES, INC., PPG FINISHES). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time:
20 Degree Gloss : 91
D.O.I. : 65
Pencil Hardness : 5B
Solvent Resistance : Fair
EXAMPLE 6
It can be seen in this Example 6 that when compositions are used containing a bisphenol A type epoxy for curing, the coatings obtained are nondurable and much inferior to the coatings resulting from the use of the novel compositions defined and claimed herein. Thus, a clearcoat composition containing the following materials was prepared:
Component Parts by Weight. Grams
Aziridine Resin obtained in Example 4 100 .0
Polysiloxane solution 1 .0
Additive2 1 .0
U.V. Absorber3 3 .0
Toluene 20 .8
Propylene Glycol Methyl Ether Acetate 33 .4
Ethylene Glycol Butyl Ether Acetate 33 .4
Butyl Acetate 43. 7
Ethyl-3-Ethpxy Propionate 14.4
Epoxy Resin 35 .0 1 Same as used in Example 1.
2 Same as used in Example 2.
3 Same as used in Example 3.
4 A bisphenol A type epoxy available from SHELL Chemical Co. as EPON 1001F.
The clearcoat package was spray applied to 24 gauge cold rolled steel panels (treated with BONDERITE 40, primed with DP 40/401, a two-component epoxy primer from PPG INDUSTRIES, INC., PPG FINISHES, and basecoated with DELTRON® Universal Basecoat from PPG INDUSTRIES, INC., PPG FINISHES). The clearcoat film was allowed to cure at ambient conditions. The resulting coating was found to have the following properties after a one-week cure time.
20 Degree Gloss : 96
D.O.I. : 80
Pencil Hardness : 6B
Solvent Resistance : Excellent The data obtained above are summarized below in Table I.
TABLE I
Pencil Solvent3 Q.U.V.4 Blushing5
Example Epoxy Gloss1 D.O.I.2 Hardness Resistance Percent Gloss Retention Tendency
1 LSE-120 95 70 B Excellent 93 None 2 Glycidyl 86 65 4B Excellent 100 None
Functional
Urethane
3 Glycidyl 92 80 4B Excellent 100 None
Methacrylate
Acrylic
4 LSE-120 92 80 4B Excellent 100 None 5 (Control) 91 65 5B Fair 100 None
Isocyanate
Cured
6 EPON 1001 L 96 80 6B Excellent 14 Severe
1 20 Degree Gloss
2 Depth-of-Image
3 Gasoline Spot Resistance
4 300 Hours Accelerated Weathering
5 Tendency to Blush and Whiten During Q.U.V. Exposure
According to the provisions of the patent statutes, there are described above the invention and what are now considered to be its best embodiments. However, within the scope of the appended claims, it is to be understood that the invention may be practiced otherwise than as specifically described hereinabove.
Claims
1. Isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, comprising
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two aziridinyl groups defined by the following structural formula:
,
wherein
X represents O, S, NH, NR, wherein R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl,
R1 represents (CH2)m1, m1 being an integer ranging from 1 to 3 and
R2 represents H, CH3 or combinations thereof and
(B) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two groups selected from epoxy groups defined by one of the following structural formulas:
;
wherein R3 represents (CH2)m2, m2 being an integer ranging from 1 to 2.
2. Compositions according to claim 1 wherein Component (A) is an acrylic polymer.
3. Compositions according to claim 1 wherein Component (B) is an acrylic polymer.
4. Compositions according to claim 1 wherein each of Components (A) and (B) is an acrylic polymer.
5. Compositions according to claim 1 wherein Component (A) is a urethane polymer.
6. Compositions according to claim 1 wherein Component (B) is a urethane polymer.
7. Compositions according to claim 1 wherein each of Components (A) and (B) are urethane polymers.
8. Compositions according to claim 1 wherein Component (A) is a urea polymer.
9. Compositions according to claim 1 wherein Component (B) is a urea polymer.
10. Compositions according to claim 1 wherein each of Components (A) and (B) are urea polymers.
11. Compositions according to claim 1 wherein the molecular weight of Component (A) is from about 100 to about 20,000.
12. Compositions according to claim 1 wherein the molecular weight of Component (B) is from about 100 to about 20,000.
13. Compositions according to claim 1 wherein the number of aziridinyl groups in Component (A) are from two to about 75.
14. Compositions according to claim 1 wherein the number of epoxy groups in Component (B) are from two to about 75.
15. Compositions according to claim 1 wherein the number of aziridinyl groups in Component (A) are from two to about 75 and the number of epoxy groups in Component (B) are from two to about 75.
16. Compositions according to claim 1 wherein X=0, m1 is the integer 2, R2 represents H and m2 is the integer 1.
17. Compositions according to claim 1 wherein the range of aziridine (equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3.
18. Compositions according to claim 1 wherein the range of aziridine (equivalents) to epoxy (equivalents) is about 1:1.
19. A process for coating a substrate which comprises applying thereto an isocyanate-free coating composition, capable of forming a durable coating under ambient conditions comprising
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two aziridinyl groups defined by the following structural formula:
wherein
X represents O, S, NH, NR, wherein R represents an alkyl having from one to 12 carbon atoms, or higher, or phenyl,
R1 represents (CH2)m1, m1 being an integer ranging from 1 to 3 and
R2 represents H, CH3 or combinations thereof, and
(B) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane or urea polymers and oligomers having a molecular weight of at least 100 and bearing at least two groups selected from epoxy groups defined by one of the following structural formulas:
integer ranging from 1 to 2.
20. The process of claim 19 wherein Component (A) is an acrylic polymer.
21. The process of claim 19 wherein Component (B) is an acrylic polymer.
22. The process of claim 19 wherein each of Components (A) and (B) is an acrylic polymer.
23. The process of claim 19 wherein Component (A) is a urethane polymer.
24. The process of claim 19 wherein Component (B) is a urethane polymer.
25. The process of claim 19 wherein each of Components (A) and (B) are urethane polymers.
26. The process of claim 19 wherein Component (A) is a urea polymer.
27. The process of claim 19 wherein Component (B) is a urea polymer.
28. The process of claim 19 wherein each of Components (A) and (B) are urea polymers.
29. The process of claim 19 wherein the molecular weight of Component (A) is from about 100 to about 20,000.
30. The process of claim 19 wherein the molecular weight of Component (B) is from about 100 to about 20,000.
31. The process of claim 19 wherein the number of aziridinyl groups in Component (A) are from two to about 75.
32. The process of claim 19 wherein the number of epoxy groups in Component (B) are from two to about 75.
33. The process of claim 19 wherein the number of aziridinyl groups in Component (A) are from two to about 75 and the number of epoxy groups in Component (B) are from two to about 75.
34. The process of claim 19 wherein X=0, m1 is the integer 2, R2 represents H and m2 is the integer 1. 35. The process of claim 19 wherein the range of aziridine
(equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3.
36. The process of claim 19 wherein the range of aziridine
(equivalents) to epoxy (equivalents) is about 1:1.
AMENDED CLAIMS
[received by the International Bureau on 18 September 1992 (18.09.92); original claims 1 and 19 amended; other claims unchanged ( 7 pages )]
1. Isocyanate-free coating compositions, capable of forming a durable coating under ambient conditions, comprising
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two aziridinyl groups defined by the following structural formula:
,
wherein
X represents O, S, NH, NR, wherein R represents alkyl having from one to 12 carbon atoms, or higher, or phenyl,
R1 represents (CH2)m1, m1 being an integer ranging from 1 to 3 and
R2 represents H, CH3 or combinations thereof; and a member selected from the group consisting of (B) and (C) wherein
(B) is at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two groups selected from epoxy groups defined by one of the following structural formulas:
; and
wherein R3 represents (CH2)m2, m2 being an integer ranging from 1 to 2; and
(C) is a polymer or oligomer represented by the following structural formula:
14. Compositions according to claim 1 wherein the number of epoxy groups in Component (B) are from two to about 75.
15. Compositions according to claim 1 wherein the number of aziridinyl groups in Component (A) are from two to about 75 and the number of epoxy groups in Component (B) are from two to about 75.
16. Compositions according to claim 1 wherein X=0, m1 is the integer 2, R2 represents H and m2 is the integer 1.
17. Compositions according to claim 1 wherein the range of aziridine (equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3. 18. Compositions according to claim 1 wherein the range of aziridine (equivalents) to epoxy (equivalents) is about 1:1.
19. A process for coating a substrate which comprises applying thereto an isocyanate-free coating composition, capable of forming a durable coating under ambient conditions comprising
(A) at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane and urea polymers and oligomers having a molecular weight of at least about 100 and bearing at least two aziridinyl groups defined by the following structural formula:
wherein
X represents O, S, NH, NR. wherein R represents an alkyl having from one to 12 carbon atoms, or higher, or phenyl,
R^ represents (CH2)m1, m1 being an integer ranging from 1 to 3 and
R2 represents H, CH3 or combinations thereof; and a member selected from the group consisting of (B) and (C) wherein (B) is at least one polymer, oligomer or combinations thereof selected from the group consisting of acrylic, urethane or urea polymers and oligomers having a molecular weight of at least 100 and bearing at least two groups selected from epoxy groups defined by one of the following structural formulas:
: and
1 to 2; and (C) is a polymer or oligomer represented by the following structural formula:
20. The process of claim 19 wherein Component (A) is an acrylic polymer.
21. The process of claim 19 wherein Component (B) is an acrylic polymer.
22. The process of claim 19 wherein each of Components (A) and (B) is an acrylic polymer.
23. The process of claim 19 wherein Component (A) is a urethane polymer.
24. The process of claim 19 wherein Component (B) is a urethane polymer. 25. The process of claim 19 wherein each of Components (A) and (B) are urethane polymers.
26. The process of claim 19 wherein Component (A) is a urea polymer.
27. The process of claim 19 wherein Component (B) is a urea polymer.
28. The process of claim 19 wherein each of Components (A) and (B) are urea polymers.
29. The process of claim 19 wherein the molecular weight of Component (A) is from about 100 to about 20,000. 30. The process of claim 19 wherein the molecular weight of Component (B) is from about 100 to about 20,000.
31. The process of claim 19 wherein the number of aziridinyl groups in Component (A) are from two to about 75.
32. The process of claim 19 wherein the number of epoxy groups in Component (B) are from two to about 75.
33. The process of claim 19 wherein the number of aziridinyl groups in Component (A) are from two to about 75 and the number of epoxy groups in Component (B) are from two to about 75. 34. The process of claim 19 wherein X=0, m1 is the integer 2, R2 represents H and m2 is the integer 1.
35. The process of claim 19 wherein the range of aziridine (equivalents) to epoxy (equivalents) is from about 3:1 to about 1:3.
36. The process of claim 19 wherein the range of aziridine (equivalents) to epoxy (equivalents) is about 1:1.
STATEMENT UNDER ARTICLE 19
Claims 1 and 19 have been amended to correct language and
typographical errors in the way the claims are written and in the structural formula, respectively. The amended claim specifies that the material that was originally referred to as B(2), now referred to as (C), is itself a polymer or oligomer represented by the given structural formula rather than a group. This is not new matter but is supported by the specification on page.8, lines 22-23 as well as Examples 1 and 4. The structural formula read within the context of the disclosure and Examples makes clear that the melamine based epoxy oligomer is itself an oligomer and not a group pendant to another polymer. Also, the bonds in the
structural formula for the melamine based epoxy oligomer have been corrected. The methylene group of the upper diglycidyl melamine radical is now bonded to the nitrogen of the lower diglycidyl melamine radical rather than to the alkoxymethylene group which is already tetravalent. This amendment simply corrects a
typographical error and does not constitute new matter. Also, a missing bond between the nitrogen and one of the groups has been added. The amendment to the Summary of the Invention and Abstract are simply to make them consistent with the amended claims.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67601491A | 1991-03-27 | 1991-03-27 | |
US676,014 | 1991-03-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992017283A1 true WO1992017283A1 (en) | 1992-10-15 |
Family
ID=24712862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/001943 WO1992017283A1 (en) | 1991-03-27 | 1992-03-09 | Non-isocyanate ambient temperature curable coating compositions |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU1880192A (en) |
MX (1) | MX9201253A (en) |
WO (1) | WO1992017283A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4070354A (en) * | 1970-07-23 | 1978-01-24 | The Dow Chemical Company | Polymers from N-(2-hydroxyethyl)aziridines |
USRE29586E (en) * | 1970-04-29 | 1978-03-21 | The Dow Chemical Company | Low temperature curing process and coating compositions suitable therefor |
US4656217A (en) * | 1983-05-31 | 1987-04-07 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Reactive polymer, method for manufacturing thereof and use thereof |
-
1992
- 1992-03-09 WO PCT/US1992/001943 patent/WO1992017283A1/en active Application Filing
- 1992-03-09 AU AU18801/92A patent/AU1880192A/en not_active Abandoned
- 1992-03-20 MX MX9201253A patent/MX9201253A/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE29586E (en) * | 1970-04-29 | 1978-03-21 | The Dow Chemical Company | Low temperature curing process and coating compositions suitable therefor |
US4070354A (en) * | 1970-07-23 | 1978-01-24 | The Dow Chemical Company | Polymers from N-(2-hydroxyethyl)aziridines |
US4656217A (en) * | 1983-05-31 | 1987-04-07 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Reactive polymer, method for manufacturing thereof and use thereof |
Also Published As
Publication number | Publication date |
---|---|
MX9201253A (en) | 1992-10-01 |
AU1880192A (en) | 1992-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4732790A (en) | Color plus clear application of thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides | |
EP1280842B1 (en) | Aqueous two-component cross-linkable composition | |
US5359005A (en) | Stable, one-package, non-gelled coating composition curable under ambient conditions | |
US6962730B2 (en) | Coating composition containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms | |
US4699814A (en) | Color plus clear application of high solids thermosetting coating compositions containing epoxy-functional polyurethanes | |
US6239212B1 (en) | Clearcoat composition and method for intercoat adhesion | |
EP0553701A2 (en) | Epoxy-functional polyurethane and curable coating composition | |
KR920002990B1 (en) | Coating composition based on polyepoxieds and polyacid curing agents | |
US5241001A (en) | Coating composition of aziridinyl polymer and epoxy polymer(s) | |
US5891960A (en) | Coating compositions with citric acid containing polymers for enhanced adhesion to substrates | |
US4755582A (en) | Thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides | |
JPS6384674A (en) | Thermosetting coating composition | |
KR920002989B1 (en) | Coating composition based on polyepoxides and urethane-containing polyacid curing agents | |
KR910003506B1 (en) | Thermosetting coating composition | |
EP1088040B1 (en) | Use of a crosslinking component comprising a polyamine, a polyketimine or combination thereof | |
WO1992017283A1 (en) | Non-isocyanate ambient temperature curable coating compositions | |
AU714522B2 (en) | Curable coating composition | |
JPH05230167A (en) | Binder composition, its production, coating agent containing same, and use of coating agent | |
AU751351B2 (en) | Method for improving the adhesion of a repair coating to a previously coated substrate | |
EP0263429A2 (en) | Epoxy-functional polyurethanes and high solids thermosetting coating compositions thereof and color plus clear mode of applying the same | |
AU741972B2 (en) | Oligomeric epoxy/isocyanate systems | |
JPH0121191B2 (en) | ||
US6426148B1 (en) | Oligomeric epoxy/isocyanate systems | |
US20040006185A1 (en) | Carbamate-functional polymer, curable coating composition thereof, and method of preparing the polymer | |
WO1997000281A1 (en) | Two-package sprayable coating composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA JP KR NO |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1992921697 Country of ref document: EP |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWW | Wipo information: withdrawn in national office |
Ref document number: 1992921697 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: CA |
|
122 | Ep: pct application non-entry in european phase |