# US 11,441,092 B2 · Coating solutions, coatings formed therefrom, and coated medical devices > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,441,092 B2 - Document ID: US11441092B2 - Status: Granted - Kind: B2 - Application number: 15/777,983 - Filed: 2016-11-24 - Published: 2018-09-13 - Granted: 2022-09-13 - Earliest claimed: 2015-11-24 - Assignees: BioInteractions Ltd. - Applicants: BioInteractions Ltd. - Inventors: Alan Rhodes; Bethany Sheila Huddart - Web page: https://patentgrep.com/patent/US11441092B2 ## CPC - C10M 107/42: Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - A61L 29/085: {Macromolecular materials} - A61L 29/14: Materials characterised by their function or physical properties {, e.g. lubricating compositions} - C08F 226/10: N-Vinyl-pyrrolidone - C09D 5/00: 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 - C09D 139/06: Homopolymers or copolymers of N-vinyl-pyrrolidones - C10M 149/18: Polyamides - C10M 169/041: {the additives being macromolecular compounds only} - C10M 169/044: {the additives being a mixture of non-macromolecular and macromolecular compounds} - C10M 173/00: Lubricating compositions containing more than 10% water - A61L 2400/10: Materials for lubricating medical devices - A61L 2420/02: Methods for coating medical devices - A61L 2420/06: Coatings containing a mixture of two or more compounds - B05D 1/18: performed by dipping - B05D 3/06: by exposure to radiation (B05D3/02 takes precedence {; plasma treatment B05D3/141}) - C10M 2201/02: Water - C10M 2207/0215: used as base material - C10M 2209/04: containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical - C10M 2209/084: Acrylate; Methacrylate - C10M 2209/0845: used as base material - C10M 2209/104: of alkylene oxides containing two carbon atoms only - C10M 2209/12: Polysaccharides, e.g. cellulose, biopolymers - C10M 2215/086: Imides [having hydrocarbon substituents containing less than thirty carbon atoms] - C10M 2215/10: Amides of carbonic or haloformic acids - C10M 2215/22: Heterocyclic nitrogen compounds - C10M 2217/024: containing monomers having an unsaturated radical bound to an amido or imido group - C10M 2217/028: containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring - C10M 2217/0285: used as base material - C10M 2217/044: Polyamides - C10M 2217/045: Polyureas; Polyurethanes - C10N 2040/50: {Medical uses} - C10N 2050/02: dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating - C10N 2050/08: Solids - C10N 2070/00: Specific manufacturing methods for lubricant compositions - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - 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) - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract A method of making a coating solution includes the steps of polymerising an initial monomer feed comprising an N-vinyl pyrrolidone and an acrylate, preferably methacrylate, salt in water to synthesise a copolymer thereof, acidifying the resulting copolymer-water mixture to give free carboxylic acid groups along the copolymer backbone, diluting the aqueous solution down with alcohol, and adding a cross-linking agent which is capable of reacting with the carboxylic acid groups and curing the copolymer at a later stage after the coating solution has been applied to a substrate and the copolymer coated thereon. Also disclosed are a coating solution in storage, a method of coating a substrate which is on, or is part of, a medical device or other article, a substrate, article or medical device having a coating so applied, and a coated medical device packaged in a hydration solution. The aqueous-alcoholic coating solution may be stored for an extended period, suitably for at least one month and desirably for substantially longer, without deteriorating. ## Claims ### Claim 1 A coating solution which is an acidified aqueous-alcoholic solution, comprising: (a) a poly(N-vinyl pyrrolidone-co-(meth)acrylic acid) copolymer in an amount between about 0.57% to about 6% by weight, wherein the N-vinyl pyrrolidone component of the copolymer is derived from an unsubstituted N-vinyl pyrrolidone and the (meth)acrylic component of the copolymer is derived from a substituted or unsubstituted (meth)acrylate salt, and wherein the (meth)acrylic acid component comprises from about 3% to about 35% by weight of the copolymer, calculated as weight of the corresponding (meth)acrylate sodium salt; the said copolymer having free carboxylic acid groups along the copolymer backbone, together with (b) a cross-linking agent which is capable of reacting with the carboxylic acid groups on the copolymer backbone such as to cure the copolymer, which cross-linking agent is present in the solution in an amount between about 5% and about 50% by weight relative to the copolymer; wherein the pH of the coating solution is about 4.5 or lower. ### Claim 2 (depends on 1) The coating solution according to claim 1 wherein the (meth)acrylic component is derived from one or more of acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, and mono-2-(methacryloyloxy)ethyl maleate. ### Claim 3 (depends on 1) The coating solution according to claim 1 wherein the (meth)acrylic component comprises from about 5 to about 25% by weight of the copolymerised species, calculated as weight of corresponding (meth)acrylate sodium salt. ### Claim 4 (depends on 1) The coating solution according to claim 1 wherein the copolymer includes one or more additional monomer species selected from vinyl acetate, acrylamide, glycerol methacrylate, 2-hydroxethyl methacrylate, methoxy polyethylene glycol methacrylate, polyethylene glycol methacrylate, 2-methacryloyloxyethyl phosphorylcholine [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 2-((2-(methacryloyloxy)ethyl)dimethylammonio)ethyl 2-methoxyethyl phosphate, and 2-((2-(methacryloyloxy)propyl)dimethylammonio)ethyl 2-methoxyethyl phosphate. ### Claim 5 (depends on 4) The coating solution according to claim 4 wherein the additional monomer species amount to not more than 40% by weight of the total copolymer. ### Claim 6 (depends on 1) The coating solution according to claim 1 wherein the alcohol diluent comprises isopropyl alcohol. ### Claim 7 (depends on 1) The coating solution according to claim 1 comprising 1 part copolymer-water mixture to 1-6 parts of alcohol, by weight. ### Claim 8 (depends on 1) The coating solution according to claim 1 wherein the cross-linking agent comprises a multifunctional carbodiimide or polycarbodiimide or aziridine or polyaziridine. ### Claim 9 (depends on 1) The coating solution according to claim 1 including one or more further hydrophilic polymers. ### Claim 10 (depends on 9) The coating solution according to claim 9 wherein the one or more further hydrophilic polymers include a hydrophilic polyurethane polymer in a weight proportion of about 1 part polyurethane to between 1.5 and 3 parts copolymer. ### Claim 11 (depends on 10) The coating solution according to claim 10 wherein the hydrophilic polyurethane polymer is present at from an equal weight to four times the weight of the cross-linking agent. ### Claim 12 (depends on 9) The coating solution according to claim 9 wherein the one or more further hydrophilic polymers include a hydrophilic polymer selected from poly(vinyl pyrrolidone), poly(ethylene glycol), poly(acrylamide), poly(vinyl alcohol), hyaluronic acid, poly(methyl vinyl ether), poly(methyl vinyl ether-alt-maleic acid), poly(methyl vinyl ether-alt-maleic anhydride), poly(acrylic acid), poly(N-vinyl pyrrolidone-co-4-benzoylphenyl methacrylate-co-methoxy polyethylene glycol methacrylate-co-butyl methacrylate), and mixtures thereof. ### Claim 13 (depends on 1) The coating solution according to claim 1 having the following composition by weight: Poly(N-vinyl pyrrolidone-co- 15-30% methacrylic acid) in water: Hydrophilic polyurethane: 0.4-1.4% Isopropyl alcohol (IPA): 60-80% Water: 3-10% Hydrophilic polymer: 0.2-5.0% and Polycarbodiimide cross-linker: 0.15-0.5%. ### Claim 14 (depends on 1) The coating solution according to claim 1 contained in a closed storage vessel. ### Claim 15 (depends on 1) The coating solution according to claim 1 contained in a storage vessel for at least 30 days. ### Claim 16 (depends on 1) The coating solution according to claim 1, wherein the pH of the coating solution is in the range of 3 to 4.5. ### Claim 17 (depends on 1) The coating solution according to claim 1 having the property of remaining usable for applying coatings, without further adjustment, after storage in a closed vessel for at least 30 days at a temperature not exceeding 40° C. ### Claim 18 (depends on 1) A method of coating a substrate comprising applying a coating solution according to claim 1 to a substrate, evaporating the solution to leave an uncured polymer coating thereon, and curing the coating on to the substrate. ### Claim 19 (depends on 18) A method according to claim 18, wherein the coating solution has previously been stored in a closed storage vessel for at least 30 days. ### Claim 20 (depends on 18) A method according to claim 18 wherein the coating is cured by heating in an oven or by microwave radiation. ### Claim 21 (depends on 18) A method according to claim 18, wherein the substrate is a surface of a medical device.