# US 11,306,168 B2 · Styrene-free copolymers and coating compositions containing such copolymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,306,168 B2 - Document ID: US11306168B2 - Status: Granted - Kind: B2 - Application number: 17/097,568 - Filed: 2020-11-13 - Published: 2021-04-08 - Granted: 2022-04-19 - Earliest claimed: 2016-04-15 - Assignees: Swimc LLC - Applicants: Swimc LLC - Inventors: Robert M. O'Brien; Mark Stuetelberg - Web page: https://patentgrep.com/patent/US11306168B2 ## CPC - C08F 220/1802: {C2-(meth)acrylate, e.g. ethyl (meth)acrylate} - B65D 25/14: Linings or internal coatings (of containers made by folding or erecting blanks made of paper B65D5/56 {; linings for domestic water storage heaters F24H1/183}) - C08F 2/22: Emulsion polymerisation - C08F 283/06: on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} - C09D 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00 - C09D 133/10: Homopolymers or copolymers of methacrylic acid esters - C09D 133/12: Homopolymers or copolymers of methyl methacrylate - C09D 151/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds - C09D 201/02: characterised by the presence of specified groups {, e.g. terminal or pendant functional groups} - B05D 7/227: {of containers, cans or the like} - B05D 2202/25: based on Al - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate} - C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B65D: CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES - 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) ## Abstract An aqueous coating composition is provided that is preferably substantially free of styrene and structural units derived from styrene. The coating composition includes a resin system that preferably includes a water-dispersible polymer and an emulsion polymerized ethylenically unsaturated monomer component. The resin system is preferably formed using a process that includes emulsion polymerizing the ethylenically unsaturated monomer component in the presence of an aqueous dispersion including the water-dispersible polymer. In certain preferred embodiments, the water-dispersible polymer is a salt of an acid- or anhydride-functional aromatic polyether polymer. ## Claims ### Claim 1 An aqueous food or beverage container coating composition suitable for use in forming a food-contact coating of a metal food or beverage container, the coating composition comprising: an aqueous carrier; and a resin system dispersed in the aqueous carrier, wherein the resin system is substantially free of styrene and comprises: a water-dispersible polymer; and an emulsion polymerized ethylenically unsaturated monomer component comprising: (i) at least 30 wt-% of one or more alkyl (meth)acrylates; and (ii) more than 30 wt-% of one or more ethylenically unsaturated monomers having a cycloaliphatic group. ### Claim 2 (depends on 1) The coating composition of claim 1, wherein the resin system comprises a reaction product of the ethylenically unsaturated monomer component emulsion polymerized in the presence of an aqueous dispersion of the water-dispersible polymer. ### Claim 3 (depends on 2) The coating composition of claim 2, wherein the water-dispersible polymer includes one or more ammonia-neutralized or amine-neutralized carboxylic acid or anhydride groups. ### Claim 4 (depends on 1) The coating composition of claim 1, wherein the total combined weight of the water-dispersible polymer and the emulsion polymerized ethylenically unsaturated monomer component is at least 50 wt-% of the total resin solids present in the coating composition. ### Claim 5 (depends on 1) The coating composition of claim 1, wherein the water-dispersible polymer comprises a polyolefin polymer. ### Claim 6 (depends on 1) The coating composition of claim 1, wherein the water-dispersible polymer has a glass transition temperature of at least 60° C. and a number average molecular weight of at least 2,000. ### Claim 7 (depends on 1) The coating composition of claim 1, wherein the water-dispersible polymer comprises an aromatic polyether polymer, and wherein the aromatic polyether polymer is substantially free of each of bisphenol A, bisphenol F, and bisphenol S, including epoxides thereof. ### Claim 8 (depends on 7) The coating composition of claim 7, wherein the aromatic polyether polymer is formed from reactants including an extender and a diepoxide of an ortho-substituted diphenol. ### Claim 9 (depends on 7) The coating composition of claim 7, wherein the aromatic polyether polymer is formed from reactants including one or both of tetramethyl bisphenol F or a diepoxide of tetramethyl bisphenol F. ### Claim 10 (depends on 1) The coating composition of claim 1, wherein the water-dispersible polymer has an acid number from 40 to 400 mg KOH per gram. ### Claim 11 (depends on 1) The coating composition of claim 1, wherein at least 30 wt-% of the emulsion polymerized ethylenically unsaturated monomer component is selected from one or more methacrylates. ### Claim 12 (depends on 1) The coating composition of claim 1, wherein at least at least 30 wt-% of the emulsion polymerized ethylenically unsaturated monomer component is selected from one or more alkyl methacrylates. ### Claim 13 (depends on 1) The coating composition of claim 1, wherein the ethylenically unsaturated monomer component comprises 80 to 100 wt-% of alkyl or cycloalkyl (meth)acrylates. ### Claim 14 (depends on 1) The coating composition of claim 1, wherein the unsaturated monomer component comprises at least 40 wt-% of one or more ethylenically unsaturated monomers having the cycloaliphatic group or a linear or branched hydrocarbon group including at least 4 carbon atoms. ### Claim 15 (depends on 1) The coating composition of claim 1, wherein the emulsion polymerized ethylenically unsaturated monomer component includes at least 50 wt-% of one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. ### Claim 16 (depends on 1) The coating composition of claim 1, wherein the emulsion polymerized ethylenically unsaturated monomer component includes less than 40 wt-%, if any, of methyl methacrylate and has a glass transition temperature greater than 50° C. ### Claim 17 (depends on 1) The coating composition of claim 1, wherein the one or more ethylenically unsaturated monomer having a cycloaliphatic group is monocyclic. ### Claim 18 (depends on 1) The coating composition of claim 1, wherein the one or more ethylenically unsaturated monomer having a cycloaliphatic group is polycyclic. ### Claim 19 (depends on 1) The coating composition of claim 1, wherein the emulsion polymerized ethylenically unsaturated monomer component comprises one or more of cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate or a mixture thereof. ### Claim 20 (depends on 1) The coating composition of claim 1, wherein the emulsion polymerized ethylenically unsaturated monomer component comprises cyclohexyl methacrylate. ### Claim 21 (depends on 1) The coating composition of claim 1, wherein the coating composition has a viscosity of from 20 to 80 seconds (Ford Cup #2, 25° C.) and is an inside spray coating composition for a food or beverage container. ### Claim 22 (depends on 1) The coating composition of claim 1, wherein the coating composition, when spray applied onto an interior of a standard 12 ounce aluminum drawn & ironed beverage can at a dry film weight of 115 milligrams per can and baked for at least 50 seconds at an oven temperature of at least 188° C. to achieve a dome peak metal temperature of at least 199° C., exhibits a lower sidewall adhesion rating value of 9 or 10 after retort in 2% citric acid under pressure at 121° C. and tested according to ASTM D 3359—Test Method B, using SCOTCH 610 tape, available from 3M Company of Saint Paul, Minn. ### Claim 23 (depends on 1) The coating composition of claim 1, wherein the coating composition is substantially free of bisphenols and any structural units derived from a bisphenol. ### Claim 24 (depends on 1) The coating composition of claim 1, wherein the ethylenically unsaturated monomer component has a glass transition temperature greater than 50° C. ### Claim 25 A food or beverage container, or a portion thereof, having a cured coating formed from an aqueous food or beverage container coating composition suitable for use in forming a food-contact coating of a metal food or beverage container, the cured coating being disposed on at least a portion of a metal substrate and wherein the coating composition comprised: an aqueous carrier; and a resin system dispersed in the aqueous carrier, wherein the resin system is substantially free of styrene and comprises: a water-dispersible polymer; and an emulsion polymerized ethylenically unsaturated monomer component comprising: (iii) at least 30 wt-% of one or more alkyl (meth)acrylates; and (iv) more than 30 wt-% of one or more ethylenically unsaturated monomers having a cycloaliphatic group. ### Claim 26 (depends on 25) The food or beverage container of claim 25, wherein the coating composition is substantially free of bisphenols and any structural units derived from a bisphenol. ### Claim 27 (depends on 26) The food or beverage container of claim 26, wherein the water-dispersible polymer is a polyether polymer formed from ingredients including one or both of tetramethyl bisphenol F or a diepoxide of tetramethyl bisphenol F. ### Claim 28 (depends on 25) The food or beverage container of claim 25, wherein the emulsion polymerized ethylenically unsaturated monomer component comprises one or more of cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate or a mixture thereof. ### Claim 29 (depends on 25) The food or beverage container of claim 25, wherein the emulsion polymerized ethylenically unsaturated monomer component comprises cyclohexyl methacrylate. ### Claim 30 A method of coating a food or beverage container comprising spray applying a coating composition onto an interior surface of a food or beverage container including a sidewall body portion and end portion, wherein the coating composition comprises: an aqueous carrier; and a resin system dispersed in the aqueous carrier, wherein the resin system is substantially free of styrene and comprises: a water-dispersible polymer; and an emulsion polymerized ethylenically unsaturated monomer component comprising: (i) at least 30 wt-% of one or more alkyl (meth)acrylates; and (ii) more than 30 wt-% of one or more ethylenically unsaturated monomers having a cycloaliphatic group. ### Claim 31 (depends on 1) The coating composition of claim 1, wherein the cycloaliphatic groups have 4-membered or larger rings.