# US 9,434,846 B2 · Anti-settling and thickening compositions and methods for using same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,434,846 B2 - Document ID: US9434846B2 - Status: Granted - Kind: B2 - Application number: 14/132,893 - Filed: 2013-12-18 - Published: 2014-06-26 - Granted: 2016-09-06 - Earliest claimed: 2012-12-21 - Assignees: Rhodia Operations - Applicants: Rhodia Operations - Inventors: Nemesio Martinez-Castro; Jose P. Ruiz - Web page: https://patentgrep.com/patent/US9434846B2 ## CPC - A61K 8/8152: {Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers} - A61K 8/86: Polyethers - A61Q 19/00: Preparations for care of the skin - C09D 5/024: {characterised by the additives} - C09D 7/43: Thickening agents - C09D 7/45: Anti-settling agents - C09D 133/08: Homopolymers or copolymers of acrylic acid esters - C09K 8/035: Organic additives - C09K 8/584: characterised by the use of specific surfactants - C09K 8/588: characterised by the use of specific polymers {(polymeric surfactants C09K8/584)} - C09K 8/68: containing organic compounds - C09K 8/685: {containing cross-linking agents} - C09K 8/725: {Compositions containing polymers} - C11D 3/3707: {Polyethers, e.g. polyalkyleneoxides} - C11D 3/3757: {(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions} - A61K 2800/10: General cosmetic use - A61K 2800/548: Associative polymers - C08F 220/1802: {C2-(meth)acrylate, e.g. ethyl (meth)acrylate} - A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D) - A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS - 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) - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract An anti-settling additive, composition containing the anti-settling additive, and methods for use in coating compositions or formulations. A HASE thickener with improved resistance to surfactants and anti-sag properties, compositions containing the thickener and methods for use of the thickener in coating compositions or formulations and the like. The anti-settling additive and the thickener being a polymer synthesized using a specialized associative monomer that contains C1-C4 alkyl, propylene oxide, ethylene oxide and a polymerizable group. ## Claims ### Claim 1 A polymer which is an anti-settling additive, the polymer comprising (a) about 25 to about 70 weight percent based on total monomers of at least one carboxylic acid monomer selected from the group consisting of methacrylic acid, acrylic acid, and a combination thereof; (b) about 30 to about 70 weight percent based on total monomers of at least one copolymerizable non-ionic C2-C12 alpha beta-ethylenically unsaturated monomer of the structure (III): CH2═CYZ (III) wherein Y is H; Z is —COOR′, wherein R′ is alkyl such that the at least one copolymerizable non-ionic C2-C12 alpha beta-ethylenically unsaturated monomer comprises ethyl acrylate; (c) about 0.05 to about 20 weight percent based on total monomer weight of at least one specialized associative monomer wherein the specialized associative monomer is an alkyl alkoxylate according to structure (VI): wherein R3 is CH3, R4 is CH3, R5 is CH3, N is from 8 to 10, and M is from 18 to 22. ### Claim 2 (depends on 1) The polymer of claim 1, wherein the polymer is an anti-settling additive having a weight average molecular weight of 1,000 to 1,200,000 g/mol. ### Claim 3 (depends on 1) The polymer of claim 1, wherein the polymer is a hydrophobically modified alkali swellable emulsion thickener pH responsive polymer having a molecular weight of 750,000 to 5,000,000 g/mol. ### Claim 4 (depends on 1) A coating composition comprising the polymer of claim 1, wherein the coating composition has a viscosity of less than about 200 KU. ### Claim 5 (depends on 1) A coating composition comprising the polymer of claim 1, wherein the polymer has a weight average molecular weight of less than about 250,000 g/mole and the coating composition has a viscosity of less than about 100 KU. ### Claim 6 (depends on 1) The polymer of claim 1, wherein the polymer is a pH responsive copolymer, comprising based on total weight of monomers: A. about 25-40 weight percent of said at least one carboxylic acid monomer; B. about 30-50 weight percent of said at least one non-ionic, copolymerizable C2-C12 alpha, beta-ethylenically unsaturated monomer; and C. about 5 to 20 weight percent of said at least one specialized nonionic ethylenically unsaturated specialized hydrophobic associative monomer. ### Claim 7 (depends on 1) The polymer of claim 1, wherein the at least one carboxylic acid monomer (a) is present from about 25 weight percent to about 40 weight percent based on total monomer weight. ### Claim 8 (depends on 1) An aqueous composition comprising water and the polymer of claim 1, wherein the polymer is a pH responsive polymer. ### Claim 9 (depends on 8) The aqueous composition of claim 8, further comprising an emulsifier, wherein the aqueous composition is a pH responsive composition. ### Claim 10 (depends on 8) The aqueous composition of claim 8, containing particles having an average particle size of about 500 to about 3000 angstroms and wherein the aqueous composition has a Brookfield viscosity of about 100 to about 500,000 cps as a 1 percent solution in ammonium salt at pH 9.0 and 25 degrees C. ### Claim 11 (depends on 8) The aqueous composition of claim 8, wherein the composition is an emulsion comprising an effective amount of the pH responsive polymer, and further comprises an emulsifier and a film forming polymer latex. ### Claim 12 (depends on 11) The aqueous composition of claim 11, wherein the emulsion is selected from the group consisting of a latex paint, a latex coating, a cosmetic, a detergent/cleanser, and an oilfield drilling fluid, and wherein the pH responsive polymer is present in an amount effective for modifying the rheological properties of the emulsion. ### Claim 13 (depends on 11) The aqueous composition of claim 11, wherein the emulsion is a latex paint and further comprising at least one additive selected from the group consisting of dispersants, surfactants, rheology modifiers, defoamers, thickeners, biocides, mildewcides, colorants, waxes. ### Claim 14 (depends on 8) The aqueous composition of claim 8, wherein the composition is a personal care composition and further comprises one or more surfactants. ### Claim 15 (depends on 14) The aqueous composition of claim 14, wherein the one or more surfactants comprise at least one anionic surfactant and the composition further comprises a structuring agent for the anionic surfactant. ### Claim 16 (depends on 14) The aqueous composition of claim 14, further comprising a personal care benefit agent. ### Claim 17 (depends on 8) The aqueous composition of claim 8, wherein the composition is a particle dispersion and further comprises particles dispersed in the composition. ### Claim 18 (depends on 8) The aqueous composition of claim 8, wherein the composition is a hydraulic fracturing composition and further comprises a proppant. ### Claim 19 (depends on 1) A method for inhibiting settling of particles in an aqueous composition, the method comprising adding the polymer of claim 1 to an aqueous composition. ### Claim 20 (depends on 1) A method for inhibiting settling of particles in an aqueous composition, the method comprising forming the aqueous composition by combining the polymer of claim 1, water and the particles. ### Claim 21 (depends on 20) The method of claim 20, wherein the aqueous composition is a coating composition having a viscosity of less than about 200 KU. ### Claim 22 (depends on 20) The method of claim 20, wherein the aqueous composition is a coating composition having a viscosity of less than about 100 KU and wherein the polymer has a weight average molecular weight of less than about 250,000 g/mol. ### Claim 23 (depends on 20) The method of claim 20, wherein the aqueous composition is an aqueous paint composition comprising a resin binder, particles selected from the group consisting of pigments, fillers and reflecting agents, and water or a water-miscible solvent. ### Claim 24 (depends on 18) A method comprising directing a stream of the composition of claim 18 into a subterranean formation. ### Claim 25 (depends on 18) A method for fracturing a geologic formation, comprising directing a stream of the composition of claim 18 at a surface of the formation at a pressure and flow rate at least sufficient to initiate, extend, or initiate and extend one or more fractures in the formation. ### Claim 26 (depends on 1) A method for thickening an aqueous emulsion comprising forming a blend by blending the aqueous emulsion with the polymer of claim 1 in an amount effective to thicken the aqueous emulsion when pH of the blend is adjusted to a pH in the range of about 6.5 to about 11, wherein the polymer is a pH responsive polymer. ### Claim 27 (depends on 1) A method for promoting personal care comprising applying the polymer of claim 1 to skin or hair of a user. ### Claim 28 (depends on 1) A home care or industrial cleaning composition for cleaning fabrics or hard surfaces comprising the polymer of claim 1, a surfactant, and one of a home care agent or an industrial benefit agent. ### Claim 29 (depends on 1) A method for cleaning a substrate selected from the group consisting of a hard surface and a fabric, comprising applying the polymer of claim 1 to the substrate. ### Claim 30 (depends on 1) The polymer of claim 1, wherein the at least one carboxylic acid monomer comprises methacrylic acid, and the at least one copolymerizable non-ionic C2-C12 alpha beta-ethylenically unsaturated monomer comprises ethyl acrylate.