Resin-support emulsion polymerization of hydrophobic monomers
US-2017166706-A1 · Jun 15, 2017 · US
US10759959B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10759959-B2 |
| Application number | US-201715597192-A |
| Country | US |
| Kind code | B2 |
| Filing date | May 17, 2017 |
| Priority date | May 18, 2016 |
| Publication date | Sep 1, 2020 |
| Grant date | Sep 1, 2020 |
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The present invention provides waterborne curable film-forming compositions comprising: a) an aqueous dispersion of polymeric acrylic particles, wherein the particles have a Z average particle size less than 80 nm and have reactive functional groups; wherein the particles are prepared from a monomer mixture comprising ethylenically unsaturated monomers that are polymerized in the presence of a branched polymer having an acid value of 40-200, wherein the branched polymer is prepared from ethylenically unsaturated monomers; b) a crosslinking agent having functional groups reactive with functional groups on the polymeric acrylic particles; and c) an aqueous dispersion of at least one additional polymer having hydroxyl and/or acid functional groups and having a Z average particle size greater than 100 nm. Further provided are multilayer coated substrates comprising the curable film-forming compositions and methods for forming a composite coating on a substrate using the curable film-forming compositions.
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Therefore, we claim: 1. A waterborne curable film-forming composition comprising: a) an aqueous dispersion of polymeric acrylic particles, wherein the particles have a Z average particle size less than 80 nm and have reactive functional groups; wherein the particles are prepared from a monomer mixture comprising ethylenically unsaturated monomers that are polymerized in the presence of a branched polymer having an acid value of 40-200, wherein the branched polymer is prepared from ethylenically unsaturated monomers; b) a crosslinking agent having functional groups reactive with functional groups on the polymeric acrylic particles; and c) an aqueous dispersion of at least one additional polymer having hydroxyl and/or acid functional groups and having a Z average particle size greater than 100 nm. 2. The waterborne curable film-forming composition according to claim 1 , wherein the polymeric acrylic particles have free acid and/or hydroxyl functional groups. 3. The waterborne curable film-forming composition according to claim 1 , wherein the branched polymer contains free ethylenically unsaturated functional groups that may react with monomers in the monomer mixture. 4. The waterborne curable film-forming composition according to claim 1 , wherein the composition comprises less than 20 percent by weight of any polymeric component having a number average molecular weight less than 2000, excluding the crosslinking agent (b). 5. The waterborne curable film-forming composition according to claim 1 , wherein the polymeric acrylic particles are present in the film-forming composition in an amount ranging from 2 weight percent to 25 weight percent, based on the total weight of the resin solids of the components which form the curable film-forming composition. 6. The waterborne curable film-forming composition according to claim 1 , wherein the crosslinking agent comprises an at least partially alkylated aminoplast resin and/or a polyisocyanate. 7. The waterborne curable film-forming composition according to claim 6 , wherein the crosslinking agent comprises an at least partially alkylated aminoplast resin and optionally an imino functional aminoplast comprising at least 15 mol percent imino functional groups, wherein the mass ratio of at least partially alkylated aminoplast resin to imino functional aminoplast is 100:0 to 10:90. 8. The waterborne curable film-forming composition according to claim 1 , wherein the additional polymer c) comprises a polyurethane, polyester, polyether, polycarbonate, polyurea, polyolefin and/or acrylic polymer, and is present in the composition in an amount of 50 to 70 percent by weight, based on the total weight of resin solids in the curable film-forming composition. 9. The waterborne curable film-forming composition according to claim 1 , wherein after application of the composition to a substrate and after dehydration to form a dehydrated coating, the dehydrated coating demonstrates a concentration of the polymeric acrylic particles within a surface region of the coating that is greater than a concentration of the polymeric acrylic particles within a bulk region of the coating. 10. A multilayer coated substrate comprising: A) a substrate; B) a primary composition applied directly to a surface of the substrate, forming a first coating; C) a first topcoat applied on top of the first coating; and D) a second topcoat that is different from the first topcoat applied on top of the first topcoat; wherein the primary composition B) comprises a waterborne curable film-forming composition, the waterborne curable film-forming composition comprising: a) an aqueous dispersion of polymeric acrylic particles, wherein the particles have a Z average particle size less than 80 nm and have reactive functional groups; wherein the particles are prepared from a monomer mixture comprising ethylenically unsaturated monomers that are polymerized in the presence of a branched polymer having an acid value of 60-100, wherein the branched polymer is prepared from ethylenically unsaturated monomers; b) a crosslinking agent having functional groups reactive with functional groups on the polymeric acrylic particles; and c) an aqueous dispersion of at least one additional polymer having hydroxyl and/or acid functional groups and having a Z average particle size greater than 100 nm. 11. The multilayer coated substrate according to claim 10 , wherein the polymeric acrylic particles have free acid and/or hydroxyl functional groups. 12. The multilayer coated substrate according to claim 10 , wherein the branched polymer contains free ethylenically unsaturated functional groups that may react with monomers in the monomer mixture. 13. The multilayer coated substrate according to claim 10 , wherein the composition comprises less than 20 percent by weight of any polymeric component having a number average molecular weight less than 2000, excluding the crosslinking agent (b). 14. The multilayer coated substrate according to claim 10 , wherein the polymeric acrylic particles are present in the film-forming composition in an amount ranging from 2 weight percent to 25 weight percent, based on the total weight of the resin solids of the components which form the curable film-forming composition. 15. The multilayer coated substrate according to claim 10 , wherein the crosslinking agent comprises an at least partially alkylated aminoplast resin and optionally an imino functional aminoplast comprising at least 15 mol percent imino functional groups, wherein the mass ratio of at least partially alkylated aminoplast resin to imino functional aminoplast is 100:0 to 10:90. 16. The multilayer coated substrate according to claim 10 , wherein the additional polymer c) comprises a polyurethane, polyester, polyether, polycarbonate, polyurea, polyolefin and/or acrylic polymer, and is present in the primary composition is an amount of 50 to 70 percent by weight, based on the total weight of resin solids in the curable film-forming composition. 17. The multilayer coated substrate according to claim 10 , wherein upon application to a vertically oriented substrate having an initial R a value of 0.3 to 0.4 and upon curing of the primary composition, the first topcoat, and the second topcoat in a vertical orientation, the multilayer coated substrate demonstrates a longwave value of no more than 10. 18. A method for forming a composite coating on a substrate comprising: (A) applying a primary composition in the form of a waterborne curable film-forming composition to at least a portion of a surface of the substrate to form a substantially uncured primary coating thereon, the waterborne curable film-forming composition comprising: a) an aqueous dispersion of polymeric acrylic particles, wherein the particles have a Z average particle size less than 80 nm and have reactive functional groups; wherein the particles are prepared from a monomer mixture comprising ethylenically unsaturated monomers that are polymerized in the presence of a branched polymer having an acid value of 60-100, wherein the branched polymer is prepared from ethylenically unsaturated monomers; b) a crosslinking agent having functional groups reactive with functional groups on the polymeric acrylic particles; and c) an aqueous dispersion of at least one additional polymer having hydroxyl and/or acid functional groups and having a Z average particle size greater than 100 nm; (B) applying a first topcoat to at least a portion of the primary coating formed in step (A) prior to substantially curing the primary coating, to form a
Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title
to metal, e.g. car bodies (involving a chemical reaction between the metal and the coating C23) · CPC title
used for films · CPC title
all layers being cured or baked together · CPC title
Polyureas · CPC title
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