Michael adducts of polymeric materials useful in coating applications

Abstract

Resinous compositions which are the Michael adducts of primary and/or secondary amines and polymers containing alpha, beta-ethylenically unsaturated moieties in conjugation with carbonyl moieties are disclosed. The compositions are depositable on substrates to form films. The films are amenable to oxidative and aminoplast cures and cure with light color. The compositions are desirable for use in cationic electrodeposition.

We claim: 
     
       1. A heat-curable resinous coating composition dispersible in aqueous medium with the aid of cationic salt groups comprising as a resinous binder: (A) .[.a.]. .Iadd.an active hydrogen-containing .Iaddend.polymeric material containing alpha, beta-ethylenically unsaturated moieties in conjugation with carbonyl moieties selected from the class consisting of ##STR4## and being substantially free of epoxy functionality reacted under conditions sufficient to form a Michael adduct with   (b) a primary and/or secondary amine which has a boiling point below .[.200.]. .Iadd.100.Iaddend.° C.; said reaction product of (A) and (B) being at least partially neutralized with an acid to provide said cationic salt groups .Iadd.and being in combination with a curing agent which is reactive with the active hydrogens at elevated temperatures to form a crosslinked product; .Iaddend.said coating composition being electrodepositable on a substrate to form a film thereon.   
     
     
       2. The coating composition of claim 1 in which the cationic salt groups are amine salt groups. 
     
     
       3. The resinous composition of claim 1 in which the polymeric material (A) is formed from reacting an epoxy resin with acrylic acid or methacrylic acid. 
     
     
       4. The resinous composition of claim 1 in which the polymeric material (A) is formed from reacting a polymeric polyol with an N-alkoxymethyl-containing acrylamide or methacrylamide. 
     
     
       5. The resinous composition of claim 4 in which the polymeric polyol is derived from an epoxy resin. 
     
     
       6. The resinous composition of claim 1 in which the polymeric material (A) contains active hydrogens selected from the class consisting of hydroxyl, thiol, primary amino and secondary amino.  .[.7. The resinous composition of claim 6 which includes a curing agent reactive with the active 
     
     
        hydrogens..]. 8. The resinous composition of claim .[.7.]. .Iadd.6 .Iaddend.in which the curing agent is selected from the class consisting of .[.amionoplasts.]. .Iadd.aminoplasts .Iaddend.and capped isocyanates. 
     
     
           An aqueous dispersion of a .Iadd.heat-curable .Iaddend.resinous coating composition which comprises as the resinous binder: (A) .[.a.]. .Iadd.an active hydrogen-containing .Iaddend.polymeric material containing alpha, beta-ethylenically unsaturated moieties in conjugation with carbonyl moieties selected from the class consisting of ##STR5## and being substantially free of epoxy functionality reacted under conditions sufficient to form a Michael adduct with   (B) a primary and/or secondary amine which has a boiling point below .[.200.]. .Iadd.100.Iaddend.° C.; said reaction product of (A) and (B) being at least partially neutralized with acid to provide cationic salt groups and .Iadd.being in combination with a curing agent which is reactive with the active hydrogens at elevated temperatures to form a crosslinked product; .Iaddend.said coating composition being   
     
     
        electrodepositable on a substrate to form a film thereon. 10. The aqueous dispersion of claim 9 .Iadd.in .Iaddend.which the cationic groups are 
     
     
        amine salt groups. 11. The aqueous dispersion of claim 9 in which the polymeric material (A) is formed from reacting a polymeric polyol with an 
     
     
        N-alkoxymethyl-containing acrylamide or methacrylamide. 12. The aqueous dispersion of claim 11 in which the polymeric polyol is derived from an 
     
     
        epoxy resin. 13. The aqueous dispersion of claim 9 in which the polymeric material (A) contains active hydrogens selected from the class consisting of hydroxyl, thiol, primary amino and secondary amino.  .[.14. The aqueous dispersion of claim 13 which includes a curing agent reactive with the 
     
     
        active hydrogens..]. 15. The aqueous dispersion of claim .[.14.]. .Iadd.13 .Iaddend.in which the curing agent is selected from the class consisting 
     
     
        of aminoplast and capped ioscyanates. 16. A .Iadd.heat-curable .Iaddend.resinous coating composition dispersible in aqueous medium with the aid of cationic salt groups comprising as a resinous binder: (A) .[.a.]. .Iadd.an active hydrogen-containing .Iaddend.polymeric material containing alpha, beta-ethylenically unsaturated moieties in conjugation with ##STR6## moieties reacted under conditions sufficient to form a Michael adduct with (B) a primary and/or secondary amine which has a boiling point below .[.200.]. .Iadd.100.Iaddend.° C.; said reaction product of (A) and (B) being at least partially neutralized with an acid to provide said cationic salt groups.[.,.]. .Iadd.and being in combination with a curing agent which is reactive with the active hydrogens at elevated temperatures to form a crosslinked product; .Iaddend.   said coating composition being electrodepositable on a substrate to form a   
     
     
        film thereon. 17. The coating composition of claim 16 in which the 
     
     
        cationic salts are amine salt groups. 18. The resinous composition of claim 16 in which the polymeric material (A) is formed from reacting a polymeric polyol with an N-alkoxymethyl- containing acrylamide or 
     
     
        methacrylamide. 19. The resinous composition of claim 18 in which the 
     
     
        polymeric polyol is derived from an epoxy resin. 20. The resinous composition of claim 16 in which the polymeric material (A) contains active hydrogens selected from the class consisting of hydroxl, thiol, primary amine and secondary amino.  .[.21. The resinous composition of claim 20 which includes a curing agent reactive with the active 
     
     
        hydrogens..]. 22. The resinous composition of claim .[.21.]. .Iadd.20 .Iaddend.in which the curing agent is selected from the class consisting 
     
     
        of aminoplast and capped isocyanates. 23. An aqueous dispersion of a .Iadd.heat-curable .Iaddend.resinous coating composition which comprises as the resinous binder: (A) .[.a.]. .Iadd.an active hydrogen-containing .Iaddend.polymeric material containing alpha, beta-ethylenically unsaturated moieties in conjugation with ##STR7## moieties reacted under conditions sufficient to form a Michael adduct with (B) a primary and/or secondary amine which has a boiling point below .[.200.]. .Iadd.100.Iaddend.° C.; said reaction product of (A) and (B) being at least partially neutralized with acid to provide cationic salt groups and .Iadd.being in combination with a curing agent which is reactive with the active hydrogens at elevated temperatures to form a crosslinked product; .Iaddend.said composition being electrodepositable on   
     
     
        a substrate to form a film thereon. 24. The aqueous dispersion of claim 23 
     
     
        in which the cationic groups are amine salt groups. 25. The aqueous dispersion of claim 23 in which the polymeric material (A) is formed from reacting a polymeric polyol with an N-alkoxymethyl-containing acrylamide 
     
     
        or methacrylamide. 26. The aqueous dispersion of claim 25 in which the 
     
     
        polymeric polyol is derived from an epoxy resin. 27. The aqueous dispersion of claim 23 in which the polymeric material (A) contains active hydrogens selected from the class consisting of hydroxyl, thiol, primary amino and secondary amino.  .[.28. The aqueous dispersion of claim 27 
     
     
        which includes a curing agent reactive with the active hydrogens..]. 29. The aqueous dispersion of claim .[.43.]. .Iadd.27 .Iaddend.in which the curing agent is selected from the class consisting of aminoplast and capped isocyanates.