# US 10,246,604 B2 · Method for producing vinyl polymer-containing aqueous liquid and method for producing water/oil resistant agent > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,604 B2 - Document ID: US10246604B2 - Status: Granted - Kind: B2 - Application number: 15/664,595 - Filed: 2017-07-31 - Published: 2017-11-16 - Granted: 2019-04-02 - Earliest claimed: 2015-02-26 - Assignees: AGC Inc. - Applicants: AGC Inc. - Inventors: Shintaro Fukunaga; Katsuya Ueno; Akio Ogawa; Yutaka Ohyama; Teruhiko Yasuda - Web page: https://patentgrep.com/patent/US10246604B2 ## CPC - C08F 220/24: containing perhaloalkyl radicals - C08F 2/14: Organic medium - C08F 2/16: Aqueous medium - C08F 6/008: {Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes} - C08F 6/10: Removal of volatile materials, e.g. solvents {(C08F6/001, C08F6/003, C08F6/005, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)} - C08F 214/18: Monomers containing fluorine - C08K 3/04: Carbon - 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 133/16: Homopolymers or copolymers of esters containing halogen atoms - D21H 19/20: comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - D21H 21/16: Sizing or water-repelling agents - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - 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) - D21H: PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR ## Abstract To provide a method for producing an aqueous liquid containing a vinyl polymer, of which the production efficiency is high, without lowering the yield of the vinyl polymer. When removing a hydrophilic organic solvent from a mixed liquid comprising a vinyl polymer, the hydrophilic organic solvent and water to produce an aqueous liquid containing the vinyl polymer, a liquid phase and a gas phase are formed in a closed container, a part of the liquid of the liquid phase is formed into small droplets and brought into contact with the gas phase to vaporize the hydrophilic organic solvent, and the vaporized hydrophilic organic solvent is removed from the closed container. Specifically, for example, a closed container 10 having a liquid inlet 22, a gas outlet 30, a liquid outlet 21, a liquid inlet 22 and a liquid outlet 21 which are connected and having an external circulating system provided with means to control the temperature and the pressure of liquid, is filled with a mixed liquid 40 to form a liquid phase 50 and a gas phase 51, the mixed liquid 40 of the liquid phase 50 is circulated from the liquid outlet 21 to the external circulating system 20, and the temperature and the pressure of the mixed liquid 41 in the external circulating system 20 are controlled to conditions such that the hydrophilic organic solvent is easily vaporized in liquid droplets in the gas phase 51, followed by discharging the mixed liquid 41 in the form of the small droplets from the liquid inlet 22 to the gas phase 51 and draining the gas in the gas phase 51 from the gas outlet 30. ## Claims ### Claim 1 A production method of a vinyl polymer aqueous liquid, the production method comprising: filling a closed container having a gas outlet with a mixed liquid containing water and a hydrophilic organic solvent with a boiling point of lower than 10020 C., wherein a vinyl polymer having hydrophobic groups and hydrophilic groups is dissolved or dispersed, to form a liquid phase and a gas phase; forming a part of the liquid of the liquid phase into small droplets; bringing the small droplets into contact with the gas phase to vaporize the hydrophilic organic solvent in the small droplets; and removing the gas of the gas phase containing the vaporized hydrophilic organic solvent from the gas outlet of the closed container, whereby the amount of the hydrophilic organic solvent in the liquid phase is reduced to at most 1 mass % per the total amount of the hydrophilic organic solvent and water. ### Claim 2 (depends on 1) The production method according to claim 1, wherein the closed container has a circulating system to take out a part of the liquid of the liquid phase and control the temperature of the taken out liquid to form it into small droplets and to discharge them in the gas phase. ### Claim 3 (depends on 2) The production method according to claim 2, wherein the closed container has a liquid outlet to discharge the liquid of the liquid phase and a liquid inlet to introduce the liquid to the gas phase, the circulating system is an external circulating system formed between the liquid outlet and the liquid inlet, and the production method further comprises controlling the temperature and the pressure of the liquid flowing in the external circulating system. ### Claim 4 (depends on 1) The production method according to claim 1, wherein the pressure of the gas phase is at most atmospheric pressure, the temperature of the liquid of the liquid phase is lower than the boiling point of water in the gas phase, and the temperature of the liquid to be formed into small droplets and brought into contact with the gas phase is at least the boiling point of the hydrophilic organic solvent and lower than the boiling point of water. ### Claim 5 (depends on 1) The production method according to claim 1, wherein the amount of water in the mixed liquid is at least 50 mass % per the total amount of water and the hydrophilic organic solvent, and in a case where water and the hydrophilic organic solvent have an azeotropic point, the amount of water is water excessive than the azeotropic composition. ### Claim 6 (depends on 1) The production method according to claim 1, wherein the temperature of the liquid of the liquid phase is maintained to be substantially constant, and the removal of the hydrophilic organic solvent is continued, while reducing the pressure of the gas phase in accordance with the change of the composition of water and the hydrophilic organic solvent. ### Claim 7 (depends on 2) The production method according to claim 2, wherein the pressure of the gas phase is maintained to be substantially constant, and the removal of the hydrophilic organic solvent is continued, while increasing the temperature of the liquid in the circulating system in accordance with the change of the composition of water and the hydrophilic organic solvent. ### Claim 8 (depends on 1) The production method according to claim 1, wherein the hydrophilic organic solvent is acetone, methyl ethyl ketone or 2-propanol. ### Claim 9 (depends on 1) The production method according to claim 1, wherein the hydrophobic groups are polyfluoroalkyl groups. ### Claim 10 (depends on 1) The production method according to claim 1, wherein the hydrophilic groups are acidic groups or basic groups. ### Claim 11 (depends on 1) The production method according to claim 1, wherein the hydrophilic groups are neutralized acidic groups or neutralized basic groups. ### Claim 12 (depends on 11) The production method according to claim 11, wherein the mixed liquid is a mixed liquid which comprises an aqueous solution containing a basic substance, and a hydrophilic organic solvent solution containing a vinyl polymer obtained by copolymerizing in a hydrophilic organic soluvent, a vinyl monomer mixture containing a vinyl monomer having a carboxyl group and a vinyl monomer having a polyfluoroalkyl group. ### Claim 13 (depends on 11) The production method according to claim 11, wherein the mixed liquid is a mixed liquid which comprises an aqueous solution containing an acidic substance, and a hydrophilic organic solvent solution containing a vinyl polymer obtained by copolymerizing in a hydrophilic organic solvent, a vinyl monomer mixture containing a vinyl monomer having a dialkyl amino group and a vinyl monomer having a polyfluoroalkyl group. ### Claim 14 (depends on 1) A method for producing a water/oil resistant agent, the method comprising: producing the vinyl polymer aqueous liquid by the production method as defined in claim 1; and preparing a water/oil resistant agent from the aqueous liquid. ### Claim 15 (depends on 14) A method for producing a water/oil resistant substrate, the method comprising: treating a substrate with the water/oil resistant agent obtained by the method as defined in claim 14.