# US 11,299,640 B2 · Polyurethane-silica composite-based coating composition, polyurethane-silica composite film, and method of preparing the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,640 B2 - Document ID: US11299640B2 - Status: Granted - Kind: B2 - Application number: 16/419,388 - Filed: 2019-05-22 - Published: 2020-05-07 - Granted: 2022-04-12 - Earliest claimed: 2018-11-07 - Assignees: Hyundai Motor Company; Kia Motors Corporation; Unist (Ulsan National Institute of Science and Technology) - Applicants: Hyundai Motor Company; Kia Motors Corporation; UNIST (Ulsan National Institute of Science and Technology) - Inventors: Ho-Tak Jeon; Choon-Soo Lee; Minsoo Kim; Hyunhyub Ko - Web page: https://patentgrep.com/patent/US11299640B2 ## CPC - C09D 7/62: modified by treatment with other compounds - B05D 1/00: Processes for applying liquids or other fluent materials (B05D5/00, B05D7/00 take precedence) - C08F 2/04: Polymerisation in solution (C08F2/32 takes precedence) - C08F 4/04: Azo-compounds - C08F 12/08: Styrene - C08J 3/20: Compounding polymers with additives, e.g. colouring - C08J 5/18: Manufacture of films or sheets - C09C 1/3063: {Treatment with low-molecular organic compounds} - C09C 1/3072: {Treatment with macro-molecular organic compounds} - C09C 1/3081: {Treatment with organo-silicon compounds} - 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 5/16: Antifouling paints; Underwater paints - C09D 5/1681: {Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect} - C09D 5/1687: {Use of special additives} - C09D 7/67: {Particle size smaller than 100 nm} - C09D 175/04: Polyurethanes - C01P 2004/03: obtained by SEM - C01P 2004/04: obtained by TEM, STEM, STM or AFM - C01P 2004/32: Spheres - C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer - C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer - C08K 3/36: Silica - C08K 9/04: Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} - C08K 2201/011: Nanostructured additives - 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) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS} - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Disclosed is a coating composition which includes: polyurethane; and amphiphilic silica nanoparticles having an amine functional group and a fluorine functional group in their structure. Further provided are a polyurethane-silica composite film including the coating composition and a method of preparing the same. ## Claims ### Claim 1 A method for preparing a polyurethane-silica composite film, comprising the steps of: (a) preparing polystyrene particles; (b) preparing silica-polystyrene particles by admixing the polystyrene particles with silica nanoparticles; (c) preparing amphiphilic silica nanoparticles by subjecting the silica-polystyrene particles to a first surface treatment, removing the polystyrene particles, and then subjecting the remaining silica nanoparticles to a second surface treatment, (d) preparing a coating composition by admixing the amphiphilic silica nanoparticles with polyurethane; and (e) applying the coating composition to a surface of a substrate to form a coating layer, and curing the coating layer. ### Claim 2 (depends on 1) The method of claim 1, further comprising, in step (a): preparing a styrene fluid admixture by placing a styrene monomer and a solvent in a reactor, and stirring under a nitrogen atmosphere for a predetermined time; and heating the styrene fluid admixture to a predetermined temperature, and adding an initiator to the reactor and reacting the styrene fluid admixture with the initiator. ### Claim 3 (depends on 2) The method of claim 2, wherein the solvent comprises one or more selected from the group consisting of water, ethanol, methanol, ethyl acetate, chloroform, and hexane. ### Claim 4 (depends on 2) The method of claim 2, wherein the styrene fluid admixture is heated to a temperature of 60° C. to 70° C. ### Claim 5 (depends on 2) The method of claim 2, further comprising adding a surfactant or a stabilizer to the styrene fluid admixture. ### Claim 6 (depends on 2) The method of claim 2, wherein the initiator comprises 2,2′-azobis(2-methylpropionamidine)dihydrochloride. ### Claim 7 (depends on 1) The method of claim 1, further comprising in the step (b), preparing the silica-polystyrene particles by admixing and stirring a polystyrene solution comprising the polystyrene particles and a first silica solution comprising silica nanoparticles at a volume ratio of 1:1 for a predetermined time. ### Claim 8 (depends on 7) The method of claim 7, further comprising, in the step (b), adding sodium chloride solution having a concentration of 0.1 mM to 10.0 mM to the admixture of the polystyrene solution and the first silica solution. ### Claim 9 (depends on 1) The method of claim 1, further comprising, in the step (c): subjecting the silica-polystyrene particles to a first surface treatment by adding the silica-polystyrene particles either to i) a first compound having a carboxyl group and an amine group or ii) a second compound having a carboxyl group and a fluorine functional group, and stirring; adding the silica-polystyrene particles, after the first surface treatment, to tetrahydrofuran, and removing the polystyrene particles; and subjecting the silica particles, which remain after removing of the polystyrene particles after the first surface treatment, to a second surface treatment by adding the silica particles to a compound, wherein the compound comprises the first compound or the second compound, which is not used in the first surface treatment, and stirring the silica particles and the compound. ### Claim 10 (depends on 9) The method of claim 9, wherein the first compound comprises N-(tert-butoxycarbonyl)-β-alanine. ### Claim 11 (depends on 9) The method of claim 9, wherein the second compound comprises perfluorooctanoic acid. ### Claim 12 (depends on 1) The method of claim 1, further comprising, in the step (d): preparing a second silica solution by dispersing the amphiphilic silica nanoparticles in tetrahydrofuran; preparing a polyurethane solution comprising polyurethane and a curing agent; and preparing the coating composition by admixing the polyurethane solution with the second silica solution. ### Claim 13 (depends on 1) The method of claim 1, wherein the coating composition comprises the silica nanoparticles in an amount of 0.3 wt % to 10.7 wt % based on the total weight of the coating composition. ### Claim 14 (depends on 1) The method of claim 1, wherein, in the step (e), the coating layer is cured at a temperature of 60° C. to 90° C.