# US 11,306,231 B2 · Sprayer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,306,231 B2 - Document ID: US11306231B2 - Status: Granted - Kind: B2 - Application number: 16/830,360 - Filed: 2020-03-26 - Published: 2020-07-30 - Granted: 2022-04-19 - Earliest claimed: 2017-09-28 - Assignees: AGC Inc. - Applicants: AGC Inc. - Inventors: Hiroki Hayamizu; Masato Fukushima - Web page: https://patentgrep.com/patent/US11306231B2 ## CPC - C09K 3/30: for aerosols (aerosol containers B65D83/14) - B65D 83/141: specially adapted for specific contents or propellants - C09K 2205/122: Halogenated hydrocarbons - C09K 2205/126: Unsaturated fluorinated hydrocarbons - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - 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 ## Abstract To provide a sprayer with high safety, specifically, a sprayer from which a component to be sprayed is incombustible and which imposes less environmental burden. A sprayer comprising a container, a propellant composition containing 1-chloro-2,3,3,3-tetrafluoropropene contained in the interior of the container, and a spray unit to spray the propellant composition to the outside of the container, wherein the propellant composition to be sprayed satisfies (1) in a predetermined combustion test, the propellant composition to be sprayed is evaluated to “have no combustibility”, and (2) the global warming potential (100 years) in accordance with Intergovernmental Panel on Climate Change (IPCC), Fifth assessment report, is less than 10, throughout the entire period over which the sprayer is used. ## Claims ### Claim 1 A sprayer, comprising: a container, a propellant composition comprising (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, wherein the (Z)-1-chloro-2,3,3,3-tetrafluoropropene is present in an amount of 20 mass % or more and less than 100 mass %, and the (E)-1,3,3,3-tetrafluoropropene is present in an amount of more than 0 mass % and less than 80 mass %, where mass % is based on the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, and wherein the propellant composition is contained under pressure as a liquid and a gas in the interior of the container, and a spray unit to spray the propellant composition out of the container, wherein the propellant composition satisfies the following requirements (1) and (2) throughout an entire period over a first state of the sprayer and a second state of the sprayer: (1) a no combustibility combustion test result in a combustion test on a mixture of the propellant composition and air in a container controlled at 60° C.±3° C. under 101.3 kPa±0.7 kPa as specified in ASTM E-681-09, such that no combustibility corresponds with the combustion test result when the mixture has no combustibility in the entire range of a proportion of the propellant composition to the total volume of the mixture being higher than 0 vol % and up to 100 vol % and when, in a gaseous phase in the vicinity of the center of the container, a fire is made by discharge ignition under 15 kV at 30 mA for 0.4 second, spread of flame is visually confirmed, and when the angle of spread of the flame upward is less than 90 degrees; (2) the global warming potential (100 years) in accordance with Intergovernmental Panel on Climate Change (IPCC), Fifth assessment report, is less than 10; wherein the first state of the sprayer: a first liquid volume of the propellant composition in the container is at most 90 vol % of a volume of the container at a first pressure, and wherein the second state of the sprayer: a second liquid volume of the propellant composition in the container is less than the first liquid volume at a second pressure, wherein the second pressure is atmospheric pressure. ### Claim 2 (depends on 1) The sprayer according to claim 1, wherein the 1-chloro-2,3,3,3-tetrafluoropropene consists essentially of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1-chloro-2,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene to the total amount of 1-chloro-2,3,3,3-tetrafluoropropene is at least 80 mass % and at most 100 mass %. ### Claim 3 (depends on 1) The sprayer according to claim 1, wherein the propellant composition further contains a hydrofluoroolefin. ### Claim 4 (depends on 3) The sprayer according to claim 3, wherein the hydrofluoroolefin contains at least one member selected from 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluoro-2-butene. ### Claim 5 (depends on 1) The sprayer according to claim 1, wherein the propellant composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene is at least 20 mass % and less than 100 mass % to the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene in a gaseous phase portion in the container filled with the propellant composition so that the liquid phase portion is 90 vol %. ### Claim 6 (depends on 1) The sprayer according to claim 1, wherein the propellant composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, and the proportion of (Z)-1-chloro-2,3,3,3-tetrafluoropropene is at least 30 mass % and less than 100 mass % to the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene in a gaseous phase portion in the container filled with the propellant composition so that the liquid phase portion is 90 vol %. ### Claim 7 (depends on 1) The sprayer according to claim 1, wherein the propellant composition is an azeotropic mixture. ### Claim 8 (depends on 1) The sprayer according to claim 1, wherein the propellant composition is a non-azeotropic mixture comprising one or more of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene. ### Claim 9 (depends on 1) The sprayer according to claim 1, wherein the propellant composition consists essentially of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, wherein the (Z)-1-chloro-2,3,3,3-tetrafluoropropene is present in an amount of 30-50 mass % and the (E)-1,3,3,3-tetrafluoropropene is present in an amount of 50-70 mass % based on the total mass of the propellant composition at the first state of the sprayer. ### Claim 10 (depends on 1) The sprayer according to claim 1, wherein the pressure at the first state is up to 241 kPa. ### Claim 11 (depends on 1) The sprayer according to claim 1, wherein the propellant composition contains from 42.0 to 66.6 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 58.0 to 33.4 mass % of (E)-1,3,3,3-tetrafluoropropene in a liquid state, and from 20.0-36.3 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 63.7 to 80.0 mass % of (E)-1-chloro-2,3,3,3-tetrafluoropropene in a gaseous state inside the container. ### Claim 12 (depends on 1) The sprayer according to claim 1, wherein the propellant composition contains from 45.0-58.4 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 41.6 to 55.0 mass % of (E)-1,3,3,3-tetrafluoropropene in a liquid state inside the container, and from 21.7 to 30.0 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 70.0 to 78.3 mass % of (E)-1,3,3,3-tetrafluoropropene in a gaseous state inside the container. ### Claim 13 (depends on 1) The sprayer according to claim 1, wherein at the second state when the pressure is atmospheric pressure, the container contains 11.6-13.3 mass % of the propellant composition based on the total mass of the propellant composition present in the container in an amount of 90 volume % in the liquid phase based on the volume of the container. ### Claim 14 (depends on 1) The sprayer according to claim 1, wherein the propellant composition comprises from 67.0 to 85.9% of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 33.0 to 14.1 mass % of 2,3,3,3-tetrafluoropropene in a liquid state in the container, and from 30.2 to 52.5 mass % of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and from 47.5 to 69.8 mass % of 2,3,3,3-tetrafluoropropene in a gaseous state in the container. ### Claim 15 A sprayer, comprising: a container, a propellant composition comprising (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, wherein the (Z)-1-chloro-2,3,3,3-tetrafluoropropene is present in an amount of 30 mass % or more and less than 100 mass %, and the 2,3,3,3-tetrafluoropropene is present in an amount of more than 0 mass % and less than 70 mass %, where mass % is based on the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, and wherein the propellant composition is contained under pressure as a liquid and a gas in the interior of the container, and a spray unit to spray the propellant composition out of the container, wherein the propellant composition satisfies the following requirements (1) and (2) throughout an entire period over a first state of the sprayer and a second state of the sprayer: (1) a no combustibility combustion test result in a combustion test on a mixture of the propellant composition and air in a container controlled at 60° C.±3° C. under 101.3 kPa±0.7 kPa as specified in ASTM E-681-09, such that no combustibility corresponds with the combustion test result when the mixture has no combustibility in the entire range of a proportion of the propellant composition to the total volume of the mixture being higher than 0 vol % and up to 100 vol % and when, in a gaseous phase in the vicinity of the center of the container, a fire is made by discharge ignition under 15 kV at 30 mA for 0.4 second, spread of flame is visually confirmed, and when the angle of spread of the flame upward is less than 90 degrees; (2) the global warming potential (100 years) in accordance with Intergovernmental Panel on Climate Change (IPCC), Fifth assessment report, is less than 10; wherein the first state of the sprayer: a first liquid volume of the propellant composition in the container is at most 90 vol % of a volume of the container at a first pressure, and wherein the second state of the sprayer: a second liquid volume of the propellant composition in the container is less than the first liquid volume at a second pressure, wherein the second pressure is atmospheric pressure. ### Claim 16 (depends on 1) The sprayer according to claim 1, wherein the propellant composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene, wherein the (Z)-1-chloro-2,3,3,3-tetrafluoropropene is present in an amount of 42 mass % or more and less than 100 mass %, and the (E)-1,3,3,3-tetrafluoropropene is present in an amount of more than 0 mass % and less than 58 mass %, where mass % is based on the total mass of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1,3,3,3-tetrafluoropropene. ### Claim 17 (depends on 1) The sprayer according to claim 1, which is a one-component sprayer containing the propellant composition as the only liquid phase in the sprayer. ### Claim 18 (depends on 1) The sprayer according to claim 1, which is a two-component sprayer containing mainly the propellant composition as the liquid phase in the sprayer.