Water-based dispersions of highly-branched polymers

Abstract

The present invention provides aqueous dispersions of highly-branched polymers for coating applications and methods for making the polymers. The polymers may have high molecular weights and desirably take the form of microgels. The polymers and dispersions may be formulated with functionalities, viscosities, and solids contents that make them well-suited for use in a variety of coatings including, but not limited to, 2-pack coatings, ultraviolet (UV) curable coatings, inks, and air-dry coatings.

What is claimed is: 
     
       1. A method comprising:
 reacting an acid-functional acrylic resin or styrene-acrylic resin dispersed in water with a polyepoxy-functional resin having at least two epoxy groups to produce a first highly-branched polymer; and 
 subsequently reacting the first highly-branched polymer with a monoepoxy-functional resin to yeild an aqueous dispersion of a second highly-branched and further functionalized polymer; 
 wherein:
 the acid-function acid-functional acrylic resin or styrene-acrylic resin has an acid value sufficient to allow for increased branching of the resin. 
 
 
     
     
       2. The method of  claim 1 , wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic, methacrylic, styrene-acrylic, or styrene-methacrylic resin. 
     
     
       3. The method of  claim 1 , wherein the first highly-branched polymer is a microgel. 
     
     
       4. The method of  claim 1 , wherein the second highly-branched polymer is a microgel. 
     
     
       5. The method of  claim 1 , wherein the acid-functional acrylic or styrene-acrylic resin further comprises hydroxyl functionalities. 
     
     
       6. The method of  claim 5 , wherein the acid-functional acrylic or styrene-acrylic resin has a number average molecular weight (M n ) of about 1000 to 10,000, an acid value of about 25 to 300, and a hydroxyl value of about 1 to 250. 
     
     
       7. The method of  claim 1 , wherein the weight percent of the second highly-branched polymer in the aqueous dispersion is at least 40 wt. %. 
     
     
       8. The method of  claim 1 , wherein acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic or methacrylic resin prepared from acrylic acid or methacrylic acid and one or more monomers selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-hydroxypropyl acrylate, 2,3-hydroxypropyl methacrylate, 2,4-hydroxybutyl acrylate, and 2,4-hydroxybutyl methacrylates. 
     
     
       9. The method of  claim 1 , wherein the polyepoxy-functional resin having at least two epoxy groups is a diepoxy resin, a polyepoxy-functional resin, or a mixture thereof. 
     
     
       10. The method of  claim 9 , wherein the polyepoxy-functional resin has an epoxy value of about 100 to 1000. 
     
     
       11. The method of  claim 1 , wherein the polyepoxy-functional resin having at least two epoxy groups is a diglycidyl ether resin, a cyclohexanedimethanol diglycidyl ether resin, a polypropylene oxide diglycidyl ether resin, or a biphenol A diglycidyl ether resin, or a mixture or blend of any two or more thereof. 
     
     
       12. The method of  claim 1 , wherein the monoepoxy-functional resin is mono-functional. 
     
     
       13. The method of  claim 1 , wherein the monoepoxy-functional resin is also hydroxy functional. 
     
     
       14. The method of  claim 1 , wherein the monoepoxy-functional resin is a glycidyl ether resin, a glycidyl ester resin, or a mixture thereof. 
     
     
       15. The method of  claim 1 , wherein the monoepoxy-functional resin is a glycidyl methacrylate, a glycidyl ester of neodecanoic acid, a biphenol A monoglycidyl ether, a2-ethylhexyl glycidyl ether, or a mixture of any two or more thereof. 
     
     
       16. The method of  claim 1 , wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic or methacrylic resin prepared from acrylic acid or methacrylic acid and one or more monomers selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2, 3-hydroxypropyl acrylate, 2, 3-hydroxypropyl methacrylate, 2,4-hydroxybutyl acrylate, 2, 4-hydroxybutyl methacrylates, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, i-amyl methacrylate, s-butyl-methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, or isobornyl methacrylates. 
     
     
       17. The method of  claim 1 , wherein the second highly-branched and further functionalized polymer has a M n  of about 2500 up to the gel point, an acid value of about 15 to 250, and a hydroxyl value of about 10 to 260. 
     
     
       18. The aqueous dispersion of the second highly-branched polymer formed by the method of  claim 1 . 
     
     
       19. The aqueous dispersion of the second highly branched polymer of  claim 18 , wherein the second highly branched polymer is a microgel. 
     
     
       20. A printing ink comprising the aqueous dispersion of the second highly-branched polymer formed by the method of  claim 1 . 
     
     
       21. The printing ink of  claim 20 , wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic, methacrylic, styrene-acrylic. or styrene-methacrylic resin. 
     
     
       22. The printing ink of  claim 20 , wherein the first highly-branched polymer is a microgel. 
     
     
       23. The printing ink of  claim 20 , wherein the second highly-branched polymer is a microgel. 
     
     
       24. A UV curable coating comprising the aqueous dispersion of the second highly-branched polymer formed by the method of  claim 1 . 
     
     
       25. The UV curable coating of  claim 24 , wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic, methacrylic, styrene-acrylic, or styrene-methacrylic resin. 
     
     
       26. The UV curable coating of  claim 24 , wherein the first highly-branched polymer is a microgel. 
     
     
       27. The UV curable coating of  claim 24 , wherein the second highly-branched polymer is a microgel. 
     
     
       28. A 2-pack coating kit comprising:
 a first pack containing the aqueous dispersion of the second highly-branched polymer formed by the method of claim 1; and   a second pack containing an isocyanate.   
     
     
       29. A method comprising:
 reacting an acid-functional acrylic resin or styrene-acrylic resin dispersed in water with a polyepoxy-functional resin to produce a first highly-branched polymer; and   reacting the first highly-branched polymer with a monoepoxy-functional resin to yield an aqueous dispersion of a second highly-branched and further functionalized polymer;   wherein:
 the acid-functional acrylic resin or styrene-acrylic resin has an acid value sufficient to allow for increased branching of the resin. 
   
     
     
       30. A coating composition comprising:
 the aqueous dispersion of the second highly-branched polymer formed by the method of claim 29; and   an isocyanate.   
     
     
       31. The coating of claim 30, wherein the isocyanate is 1,6-hexamethylenediisocyanate, isophorone diisocyanate. 
     
     
       32. The coating of claim 30, wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic, methacrylic, styrene-acrylic, or styrene-methacrylic resin. 
     
     
       33. The coating of claim 30, wherein the first highly-branched polymer is a microgel. 
     
     
       34. The coating of claim 30, wherein the second highly-branched polymer is a microgel. 
     
     
       35. The coating of claim 30, wherein the acid-functional acrylic or styrene-acrylic resin further comprises hydroxyl functionalities. 
     
     
       36. The coating of claim 30, wherein the weight percent of the second highly-branched polymer in the aqueous dispersion is at least 40 wt. %. 
     
     
       37. The coating of claim 30, wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic or methacrylic resin prepared from acrylic acid or methacrylic acid and one or more monomers selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-hydroxypropyl acrylate, 2,3-hydroxypropyl methacrylate, 2,4-hydroxybutyl acrylate, and 2,4-hydroxybutyl methacrylates. 
     
     
       38. The coating of claim 30, wherein the polyepoxy-functional resin is a diepoxy resin, a polyepoxy-functional resin, or a mixture thereof. 
     
     
       39. The coating of claim 30, wherein the polyepoxy-functional resin is a diglycidyl ether resin, a cyclohexanedimethanol diglycidyl ether resin polypropylene oxide diglycidyl ether resin, or a biphenol A diglycidyl ether resin, or a mixture or blend of any two or more thereof. 
     
     
       40. The coating of claim 30, wherein the monoepoxy-functional resin is mono-functional. 
     
     
       41. The coating of claim 30, wherein the monoepoxy-functional resin is also hydroxy functional. 
     
     
       42. The coating of claim 30, wherein the monoepoxy-functional resin is a glycidyl ether resin, a glycidyl ester resin, or a mixture thereof. 
     
     
       43. The coating of claim 30 wherein the monoepoxy-functional resin is a glycidyl methacrylate, a glycidyl ester of neodecanoic acid, a biphenol A monoglycidyl ether, a 2-ethylhexyl glycidyl ether, or a mixture of any two or more thereof. 
     
     
       44. The coating of claim 30, wherein the acid-functional acrylic or styrene-acrylic resin is an acid-functional acrylic or methacrylic resin prepared from acrylic acid or methacrylic acid and one or more monomers selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2,3-hydroxypropyl acrylate, 2,3-hydroxypropyl methacrylate, 2,4-hydroxybutyl acrylate, 2,4-hydroxybutyl methacrylates, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, i-amyl methacrylate, s-butyl-methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, and isobornyl methacrylates. 
     
     
       45. A 2-pack coating kit comprising:
 a first pack containing the aqueous dispersion of the second highly-branched polymer formed by the method of claim 29; and   a second pack containing an isocyanate.