Foaming aerosol compositions and aerosol products

Abstract

To provide a foamable aerosol composition capable of forming a foam with good foamability, foam quality and foam retention even in a low-temperature environment.SOLUTION: Provided is a foamable aerosol composition comprising: a stock solution composition comprising water and a surfactant; and monochlorotetrafluoropropene and compressed gas, the monochlorotetrafluoropropene being at least one selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224 yd(Z)) and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224 yd(E)), a content ratio of the monochlorotetrafluoropropene in the foamable aerosol composition is 0.5 mass% to 25.0 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a foaming aerosol composition and an aerosol product.

Background Art

[0002] Conventionally, liquefied gases such as LPG have been used as an aerosol product for forming a foam and as a blowing agent. Liquefied gases such as LPG can form a foam with good foaming properties and are difficult to drip, but since they are flammable gases, there are concerns about safety. In recent years, efforts have been made worldwide to realize a sustainable society, and the use of non-flammable gases is desired as an environmentally friendly product. Hydrofluoroolefin (HFO) is a non-flammable gas with a low global warming potential and ozone depletion potential, and has attracted attention as a more environmentally friendly alternative to conventional hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, etc. In Patent Document 1, it has been proposed to use a hydrofluoroolefin such as 1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) as a stock solution of a foaming composition.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, through the studies by the present inventors, it has been found that a foaming composition using a hydrofluoroolefin as described in the above literature may have insufficient foaming properties when used in a low-temperature environment, particularly in an extremely low-temperature environment such as around 0°C. This disclosure provides an effervescent aerosol composition that can form a foam with good foaming, foam quality, and foam retention even in extremely low temperature environments. [Means for solving the problem]

[0005] This disclosure relates to a foaming aerosol composition, The effervescent aerosol composition comprises a stock solution composition containing water and a surfactant, as well as monochlorotetrafluoropropene and compressed gas. The monochlorotetrafluoropropene is at least one selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), This invention relates to an effervescent aerosol composition in which the content of monochlorotetrafluoropropene is 0.5% to 25.0% by mass. [Effects of the Invention]

[0006] According to this disclosure, it is possible to provide an aerosol composition that can form a foam with good foaming, foam quality, and foam retention even in an extremely low temperature environment. [Modes for carrying out the invention]

[0007] The notation "XX or greater and YY or less" or "XX~YY" indicating a numerical range means a numerical range that includes the lower and upper limits, unless otherwise specified. In this case, the upper and lower limits of each numerical range can be combined in any way.

[0008] (Monochlorotetrafluoropropene) The foaming aerosol composition contains monochlorotetrafluoropropene. The monochlorotetrafluoropropene is at least one selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)). 1-chloro-2,3,3,3-tetrafluoropropene is also represented as CF3CF=CHCl. ​​The monochlorotetrafluoropropene is particularly preferably (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)).

[0009] The above-mentioned monochlorotetrafluoropropene can function as a propellant and foaming agent. Monochlorotetrafluoropropene has a boiling point of 15°C, which is lower than other hydrofluoroolefins (e.g., 1-chloro-3,3,3-trifluoropropene (boiling point 19°C)). Therefore, even in low-temperature environments, monochlorotetrafluoropropene vaporizes easily when discharged, forming a foam with good foaming, foam quality, and foam retention. Furthermore, the inventors have found that the foaming aerosol composition of this disclosure can form a foam with good foaming, foam quality, and foam retention even when used in an extremely low temperature environment that is significantly below the boiling point of monochlorotetrafluoropropene. In particular, monochlorotetrafluoropropene exhibits very good foaming properties even at extremely low temperatures, despite the difference in boiling point from conventional hydrofluoroolefins being only about 4°C. The inventors believe that this is because, although the reason is not clear, monochlorotetrafluoropropene has a different structure from other hydrofluoroolefins, allowing more compressed gas to dissolve within it.

[0010] The monochlorotetrafluoropropene content in the effervescent aerosol composition is 0.5% to 25.0% by mass, preferably 1.0% to 22.0% by mass. When the content is within the above range, a sufficient and appropriate amount of monochlorotetrafluoropropene is included for the compressed gas to dissolve, so even in low-temperature environments, the compressed gas and monochlorotetrafluoropropene vaporize easily when discharged to the outside, forming a foam with good foaming, foam quality, and foam retention. The amount of monochlorotetrafluoropropene in the effervescent aerosol composition can be appropriately selected considering the purpose of the effervescent aerosol composition. For example, if the effervescent aerosol composition is a shampoo, it is preferably 1.0% to 22.0% by mass, and more preferably 2.0% to 18.0% by mass. For example, if it is a hair styling agent, it is preferably 4.0% to 13.0% by mass, and more preferably 6.0% to 12.0% by mass. For example, if it is a facial cleanser, it is preferably 1.0% to 22.0% by mass, and more preferably 2.0% to 20.0% by mass. For example, if it is a hair treatment, it is preferably 0.5% to 22.0% by mass, and more preferably 1.0% to 20.0% by mass. For example, if it is a pack or cleansing agent, it is 0.5% to 22.0% by mass, and more preferably 1.0% to 10.0% by mass.

[0011] (Compressed gas) The foaming aerosol composition contains compressed gas. The compressed gas can function as both a propellant and a foaming agent. The compressed gas is not particularly limited and any known gas that can be used in aerosol products can be used. Preferably the compressed gas is carbon dioxide, nitrogen gas, nitrous oxide, argon, helium and It is at least one selected from the group consisting of carbon dioxide, nitrogen gas, compressed air, and nitrous oxide, more preferably at least one selected from the group consisting of carbon dioxide and nitrogen gas, and even more preferably carbon dioxide. It is presumed that carbon dioxide dissolves slightly in the stock solution composition and affects the effervescence.

[0012] The compressed gas content in the effervescent aerosol composition is not particularly limited, as long as it allows the aerosol composition to be dispensed. Preferably, it is 0.5% to 5.0% by mass. Within this range, better effervescence is obtained. The carbon dioxide content in the aerosol composition is more preferably 1.0% to 3.0% by mass, and even more preferably 1.5% to 2.5% by mass.

[0013] In the foaming aerosol composition, the mass ratio of the monochlorotetrafluoropropene content to the compressed gas content (monochlorotetrafluoropropene / compressed gas) is preferably 0.1 to 13.0, more preferably 0.2 to 12.0, and even more preferably 0.3 to 11.0. The inventors have found that by using a specific amount of monochlorotetrafluoropropene and compressed gas, it is possible to form a foam with better foaming, foam quality, and foam retention, even when used in extremely low temperature environments. Furthermore, the ratio can be appropriately selected considering the purpose of the foaming aerosol composition. For example, if the foaming aerosol composition is a shampoo, facial cleanser, hair treatment, etc., the ratio is preferably 0.1 to 10.0, and more preferably 1.0 to 8.0. If it is a hair styling agent or pack, the ratio is preferably 1.0 to 8.0, and more preferably 2.0 to 6.5. If it is a cleansing agent, the ratio is preferably 0.5 to 6.0, and more preferably 1.0 to 4.0.

[0014] (Stock composition) The stock solution composition in the effervescent aerosol composition contains water. The proportion of water in the stock solution composition is not particularly limited. It can be appropriately selected considering the purpose of the effervescent aerosol composition. The water content in the stock solution composition is preferably 20.00% to 99.00% by mass, and more preferably 30.00% to 95.00% by mass. For example, if the foaming aerosol composition is a shampoo or hair treatment, the preferred mass is 60.00% to 99.00%, more preferably 70.00% to 95.00%, and even more preferably 80.00% to 90.00%. For example, if it is a hair styling product, the preferred mass is 30.00% to 85.00%, more preferably 40.00% to 75.00%, and even more preferably 50.00% to 65.00%. For example, if it is a facial cleanser or face mask, the preferred mass is 40.00% to 99.00%, more preferably 50.00% to 90.00%, and even more preferably 60.00% to 80.00%. For example, in the case of a cleansing agent, the amount is preferably 20.00% to 65.00% by mass, more preferably 25.00% to 50.00% by mass, and even more preferably 30.00% to 40.00% by mass.

[0015] The stock solution composition in the effervescent aerosol composition contains a surfactant. The surfactant can also function as an emulsifier that emulsifies monochlorotetrafluoropropene in the stock solution. Furthermore, the surfactant is included for purposes such as causing the compressed gas dissolved in the stock solution to disperse as fine bubbles when discharged to the outside, and promoting the vaporization of the monochlorotetrafluoropropene emulsified in the stock solution by foaming the stock solution and forming a foam. It will be done. The surfactant may be anionic, cationic, nonionic, or amphoteric, and one or more types may be used.

[0016] Examples of anionic surfactants include fatty acid soaps such as potassium coconut oil fatty acid (e.g., potassium coco-glutamate), potassium myristate, and potassium laurate; alkyl sulfates such as potassium lauryl sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, and sodium myristyl sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene lauryl ether sulfate; alkyl phosphates such as lauryl phosphate; polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether phosphate; amino acid-based surfactants such as acylmethyltauric acid and sodium lauroylmethylalanine; sulfonates such as sodium lauryl sulfoacetate; and the like.

[0017] Examples of cationic surfactants include alkylammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride (steartrimonium chloride), behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, and stearoxypropyltrimonium chloride; alkylbenzylammonium salts; stearylamine acetate; polyoxyethylene alkylamines such as polyoxyethylene laurylamine and polyoxyethylene stearylamine; stearamidopropyldimethylamine; polyquaternium-10; and the like.

[0018] Nonionic surfactants include polyglycerin fatty acid esters such as pentagglyceryl monolaurate, pentagglyceryl monomyristate, pentagglyceryl monooleate, pentagglyceryl monostearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monooleate, and decaglyceryl distearate, as well as POE(20) sorbitan monolaurate, POE(20) sorbitan monopalmitate, and POE(20) sorbitan monosulfate. Polyoxyethylene sorbitan fatty acid esters such as thearate, POE(20) sorbitan monooleate, POE(20) sorbitan monoisostearate, polyethylene glycol fatty acid esters such as POE(25) monostearate, PEG-20 sorbitan cocoate, polyoxyethylene ethers such as POE(9) lauryl ether, POE(15) cetyl ether, POE(20) cetyl ether, POE(10) oleyl ether, POE(15) oleyl ether, POE(20) oleyl ether, POE(20) behenyl ether, etc. Polyoxyethylene polyoxypropylene alkyl ethers such as lucyl ether and POE(20)POP(4) cetyl ether, polyoxyethylene sorbitol fatty acid esters such as POE(60) sorbitol tetrastearate, POE(60) sorbitol tetraoleate, and POE(6) sorbitol monolaurate, polyoxyethylene glycerin fatty acid esters such as POE(15) glyceryl monostearate and POE(15) glyceryl monooleate, POE(40) castor oil, POE(20) hydrogenated castor oil, and POE(40) hydrogenated castor oil. Oil, POE(50) hydrogenated castor oil, POE(60) castor oil, POE(60) hydrogenated castor oil, POE(80) hydrogenated castor oil, POE(100) hydrogenated castor oil, and other polyoxyethylene castor oils / hydrogenated castor oils, POE(10) lanolin alcohol, POE(20) lanolin alcohol, POE(40) lanolin alcohol, and other polyoxyethylene lanolin alcohols, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan monooleate, sorbitan sesquioleate,Sorbitan fatty acid esters such as sorbitan trioleate, glycerin fatty acid esters such as glyceryl monostearate and glyceryl monomyristate, diglycerin such as diglyceryl monostearate, diglyceryl monooleate, and diglyceryl monoisostearate, Triglycerin fatty acid esters such as triglyceryl monolaurate, triglyceryl monomyristate, triglyceryl monooleate, triglyceryl monostearate, tetraglycerin fatty acid esters such as tetraglyceryl monostearate, tetraglyceryl monooleate, pentagricerin fatty acid esters such as pentagriceryl trimyristate, pentagriceryl trioleate, hexaglyceryl monooleate, hexaglyceryl monostearate, hexaglyceryl tristearate, etc. Xaglycerin fatty acid esters, and polyglycerin fatty acid esters such as decaglyceryl monostearate, decaglyceryl distearate, decaglyceryl diisostearate, decaglyceryl dioleate, decaglyceryl tristearate, decaglyceryl trioleate, etc., polyoxyethylene glycerin fatty acid esters such as POE(5) glyceryl monostearate, POE(20) sorbitan tristearate, POE(20) sorbitan trioleate, POE(6) sorbitan mo Polyoxyethylene sorbitan fatty acid esters such as nostearate and POE(6) sorbitan monooleate, polyoxyethylene sorbitan fatty acid esters such as POE(6) sorbitan tetraoleate and POE(30) sorbitan tetraoleate, polyethylene glycol fatty acid esters such as POE(10) monolaurate, POE(10) monostearate, POE(40) monostearate, POE(55) monostearate, and POE(10) monooleate, POE(21) ​​lauryl ether, and POE(10) cetyl ether. , polyoxyethylene alkyl ethers such as POE(25) cetyl ether, POE(20) stearyl ether, POE(7) oleyl ether, POE(50) oleyl ether, POE(10) behenyl ether, POE(30) behenyl ether, polyoxyethylene polyoxypropylene alkyl ethers such as POE(20)POP(8) cetyl ether, POE(30)POP(6) decyltetradecyl ether, alkyl glucosides such as lauryl glucoside, fatty acid alkylolamides such as coconut oil fatty acid diethanolamide,Examples include alkyldimethylamine oxide solutions such as lauryldimethylamine oxide solution.

[0019] Examples of amphoteric surfactants include alkyl betaines such as lauryldimethylaminoacetic acid betaine (lauryl betaine), stearyl betaine, lauric acid amidopropyl betaine, lauryl hydroxysulfobetaine, stearyldimethylaminoacetic acid betaine, dodecylaminomethyldimethylsulfopropyl betaine, and octadecylaminomethyldimethylsulfopropyl betaine; betaine types such as cocamidopropyl betaine, cocamidopropyl fatty acid amidopropyl betaine, and cocamidopropyl hydroxysultaine; alkylimidazole types such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; and amine oxide types such as lauryldimethylamine N-oxide, oleyldimethylamine N-oxide, and lauramine oxide.

[0020] The proportion of surfactant is not particularly limited and can be appropriately selected considering the purpose of the foaming aerosol composition. For example, the surfactant content in the stock solution composition is preferably 0.10% to 40.00% by mass, and more preferably 0.20% to 30.00% by mass. For example, if the foaming aerosol composition is a hair styling agent or hair treatment agent, the preferred amount is 0.10% to 10.00% by mass, more preferably 0.20% to 1.50% by mass. For example, if it is a shampoo or facial cleanser, the preferred amount is 3.00% to 30.00% by mass, more preferably 5.00% to 20.00% by mass, and even more preferably 8.00% to 15.00% by mass. For example, if it is a pack agent, the preferred amount is 0.10% to 10.00% by mass, more preferably 1.00% to 5.00% by mass. For example, if it is a cleansing agent, the preferred amount is 10.00% to 30.00% by mass, more preferably 15.00% to 25.00% by mass. It is 0% by mass.

[0021] The undiluted composition may contain optional ingredients such as active ingredients, fragrances, antioxidants, preservatives, pH adjusters, chelating agents, oils and fats, silicones, thickeners, humectants, disinfectants, skin protectants (amino acids), vitamins, various extracts, deodorizers / odor inhibitors, cooling agents, UV absorbers, UV scatterers, insect repellents, insecticides, and others, to an extent that does not impair the above-mentioned effects. The proportion of optional ingredients will be determined appropriately based on the intended use of the composition.

[0022] Optional components include, for example, the following: Oily components (e.g., ester compounds, hydrocarbon compounds, silicone compounds, oils and fats); lower alcohols (e.g., aliphatic monohydric alcohols with 1-3 carbon atoms such as ethanol and isopropanol); higher alcohols (e.g., cetyl alcohol, stearyl alcohol, hexyldecanol, isostearyl alcohol, octyldodecanol, decyltetradecanol, etc.); polyhydric alcohols of trihydric or higher hydricity (e.g., glycerin, etc.); pH adjusters (e.g., citric acid, lactic acid, triethanolamine, KOH, NaOH, etc.); rust inhibitors (e.g., aqueous ammonia, ammonium benzoate, sodium nitrite, etc.); preservatives (e.g., parabens, phenoxyethanol, methyl parahydroxybenzoate); urea; minerals such as calcium, iron, and sodium; pigments; dyes; silicone oils such as dimethicone; chelating agents such as EDTA-2Na, etc.

[0023] The effervescent aerosol composition of the present invention can be provided as an aerosol product for various uses depending on the type of its constituent components. Furthermore, the effervescent aerosol composition of the present invention may be used for human use. Examples of effervescent aerosol compositions for human use include shampoos, hair styling agents, facial cleansers, hair treatments, face masks, cleansing agents, body lotions, skincare agents, hair growth agents, massagers, conditioners, repellents, UV absorbers, and UV scattering agents. The effervescent aerosol composition of the present invention is not limited to use on the human body, but can be commercialized as an insecticide, cleaner, coating agent, or for other purposes. Preferably, the effervescent aerosol composition can be used as a shampoo, hair styling agent, facial cleanser, hair treatment, face mask, or cleansing agent. In particular, the foaming aerosol composition of the present invention exhibits excellent foaming properties even in extremely low temperature environments, making it suitable for use in such environments. For example, the foaming aerosol composition of the present invention can be stored and / or used at a temperature preferably between -30°C and 15°C, more preferably between -20°C and 10°C, and even more preferably between -15°C and 7°C. Even when the temperature of the foam immediately after foaming is between -5.0°C and 5.0°C, it can form foam with good foaming, foam quality, and foam retention. Furthermore, even when the temperature of the foam two minutes after foaming is between -3.0°C and 6.0°C, it can form foam with good foaming, foam quality, and foam retention.

[0024] Next, we will discuss aerosol products. Aerosol products are A container filled with a foaming aerosol composition, and The container is equipped with a dispensing mechanism for dispensing the effervescent aerosol composition. The discharge mechanism and container are not particularly limited and known ones can be used. The container only needs to be able to withstand the pressure of the propellant, and known containers made of resin, metal, glass, etc., can be used.

[0025] There are no particular restrictions on the pressure (gauge pressure) inside the container of an aerosol product. Monochlorotetrafluoropropene and carbon dioxide should be filled into the aerosol container such that the pressure (gauge pressure) inside the container is, for example, 1 MPa or less at 25°C.

[0026] The method for manufacturing effervescent aerosol compositions and aerosol products is not particularly limited. For example, the following method can be used. The stock solution composition in the effervescent aerosol composition can be obtained by mixing water, a surfactant, and other components as needed in any proportion. Aerosol products can be manufactured as follows: First, water, a surfactant, and other components as needed are mixed in any proportion to obtain a stock solution composition. The obtained stock solution composition, monochlorotetrafluoropropene, and compressed gas are then filled into a pressure vessel to obtain an aerosol product. [Examples]

[0027] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the embodiments described below.

[0028] <Examples 1-5, Comparative Examples 1-7 (Shampoos)> The raw materials were mixed according to the formulations (mass %) shown in Table 1 to prepare the stock solution composition. The pH of the obtained stock solution composition was measured by a conventional method. Then, for each of the obtained stock solutions, hydrofluoroolefin and carbon dioxide were added according to the formulations in Table 1, and each was filled into a pressure-resistant container (100 mL glass test bottle for aerosols) to prepare an aerosol composition for the shampoo, thereby obtaining each aerosol product.

[0029] [Table 1]

[0030] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene HFO-1233zd:(Z)-1-chloro-3,3,3-trifluoropropene Polyquaternium-10: Catinal HC-200 (Toho Chemical Industry Co., Ltd.) Potassium Cocoyl Glutamate: Amisoft CK-22 (Ajinomoto Co., Inc.) Lauryl glucoside: Mydol 12 (Kao Corporation) Lauramine oxide: Amhitol 20N (Kao Corporation)

[0031] The following evaluations were performed on the obtained aerosol products. The results are shown in Table 1.

[0032] (1) Foam forming property The foam quality of the effervescent aerosol composition was evaluated from the viewpoint of foam formation during dispensing. Specifically, the aerosol products of Examples 1-5 and Comparative Examples 1-7 were left to stand in a freezer (-14°C) for 90 minutes. Then, 3 g of the foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the foam formation immediately after dispensing was visually observed and evaluated according to the following criteria. 5: It has excellent foam-forming properties. 4. It has good foam-forming properties. 3: It has slightly good foam-forming properties. 2: It has somewhat poor foam-forming properties. 1: Poor foam-forming ability.

[0033] (2) Foaming The foaming action of effervescent aerosol compositions during dispensing was evaluated. Specifically, the aerosol products of Examples 1-5 and Comparative Examples 1-7 were left to stand in a freezer (-14°C) for 90 minutes. Then, 3 g of the foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the foaming immediately after dispensing was visually observed and evaluated according to the following criteria. 5: It forms very voluminous foam. 4: It forms a voluminous foam. 3: Forms a slightly voluminous foam. 2: Forms relatively small bubbles. 1: Forms small bubbles.

[0034] (3) The feel of the foam The foam quality of the effervescent aerosol composition was evaluated from the perspective of foam texture (elasticity). Specifically, the aerosol products of Examples 1-5 and Comparative Examples 1-7 were left to stand in a freezer (-14°C) for 90 minutes. Then, 3 g of the foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the elasticity of the foam when it was pressed and stretched with a finger immediately after dispensing was evaluated according to the following criteria. 5: The elasticity is excellent. 4: It has good elasticity. 3: The elasticity is slightly good. 2: The elasticity is somewhat poor. 1: It has poor elasticity.

[0035] Furthermore, the aerosol product of Example 3 was left to stand in a freezer (-14°C) for 90 minutes, and then 3g of the aerosol product of Example 3 was dispensed onto a flat plate at room temperature (25°C). The temperature of the pressure-resistant container was measured immediately after dispensing and 2 minutes after dispensing. As a result, the temperature of the pressure-resistant container was 0.6°C immediately after dispensing and 1.7°C 2 minutes after dispensing.

[0036] (4) Foam retention The foam retention of effervescent aerosol compositions was evaluated from the perspectives of foam formation and foam texture (elasticity) 2 minutes after dispensing the effervescent aerosol composition. Regarding foam formation after 2 minutes from dispensing, specifically, the evaluation of foam formation described in (1) above. The aerosol products of Examples 1-5 and Comparative Examples 1-7, which were dispensed at the specified value, were left to stand for 2 minutes at room temperature (25°C). After this, the foam-forming properties were visually observed and evaluated according to the following criteria. 5: The degree to which the foam shape is maintained immediately after dispensing is very high. 4: The foam maintains its shape well immediately after dispensing. 3: The degree to which the foam shape is maintained immediately after dispensing is slightly higher. 2: The degree to which the foam shape is maintained immediately after dispensing is somewhat low. 1: The degree to which the foam shape is maintained immediately after dispensing is low. Regarding the feel two minutes after dispensing, specifically, the aerosol products of Examples 1-5 and Comparative Examples 1-7, which were dispensed in the evaluation of foam feel described in (3) above, were left to stand at room temperature (25°C) for two minutes, and the elasticity of the foam when pressed and stretched with a finger was evaluated according to the following criteria. 5: The elasticity is excellent. 4: It has good elasticity. 3: The elasticity is slightly good. 2: The elasticity is somewhat poor. 1: It has poor elasticity.

[0037] <Examples 6-7, Comparative Examples 8-11 (Hair Styling Agents)> The raw materials were mixed according to the formulations (mass%) shown in Table 2 to prepare the stock solution composition. Then, hydrofluoroolefin and carbon dioxide were added to each of the obtained stock compositions according to the formulations in Table 2, and each was filled into a pressure-resistant container (100 mL glass test bottle for aerosols) to prepare an aerosol composition for hair styling, thereby obtaining each aerosol product.

[0038] [Table 2]

[0039] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene HFO-1233zd:(Z)-1-chloro-3,3,3-trifluoropropene PEG-20 Sorbitan Cocoate: NIKKOL TL-10 (Nikko Chemicals Co., Ltd.) PEG-60 Hydrogenated Castor Oil: NIKKOL HCO-60 (Nikko Chemicals Co., Ltd.) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) 1,3-Butylene glycol: 1,3-Butylene glycol-P (KH Neochem Co., Ltd.) (Methacryloyloxyethyl Carboxybetaine / Alkyl Methacrylate) Copolymer : Yukaformer SM (Osaka Organic Chemical Industry Co., Ltd.) Dimethicone: SH200C-3000cs (Dow-Toray Industries, Inc.)

[0040] The obtained aerosol products were evaluated immediately after dispensing for foam formation, foaming, and foam texture using the same method as in Examples 1-5 and Comparative Examples 1-7, except that they were left to stand at 3°C ​​for 30 minutes. The results are shown in Table 3. Furthermore, for Examples 6 and 7, the temperature of the pressure vessel immediately after discharge was measured in the same manner as in Example 3, except that it was left to stand at 3°C ​​for 30 minutes. As a result, in both Examples 6 and 7, the temperature of the pressure vessel immediately after discharge was 4.6°C.

[0041] <Examples 8-13, Comparative Examples 12-19 (Facial Cleansers)> The raw materials were mixed according to the formulations (mass%) shown in Table 3 to prepare the stock solution composition. Then, hydrofluoroolefin and carbon dioxide were added to each of the obtained stock compositions according to the formulations in Table 3, and each was filled into a pressure-resistant container (100 mL glass test bottle for aerosols) to prepare an aerosol composition for facial cleansing, thereby obtaining each aerosol product.

[0042] [Table 3]

[0043] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene HFO-1233zd:(Z)-1-chloro-3,3,3-trifluoropropene PEG-20 Hydrogenated Castor Oil: NIKKOL HCO-20 (Nikko Chemicals Co., Ltd.) Potassium Cocoyl Glutamate: Amisoft CK-22 (Ajinomoto Co., Inc.) Lauryl glucoside: Mydol 12 (Kao Corporation) Xanthan gum: Echo Gum T (DSP Gokyo Food & Chemical Co., Ltd.) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) 1,3-Butylene glycol: 1,3-Butylene glycol-P (KH Neochem Co., Ltd.)

[0044] The obtained aerosol products were evaluated using the same method as in Examples 1-5 and Comparative Examples 1-7, except that they were left to stand in a freezer (-14°C) for 60 minutes instead of 90 minutes. This evaluation included foam formation immediately after dispensing and 2 minutes after dispensing, foaming immediately after dispensing, and the feel of the foam immediately after dispensing and 2 minutes after dispensing. The results are shown in Table 3. Furthermore, for Examples 8 to 13, the temperature of the pressure vessel was measured immediately after dispensing and 2 minutes after dispensing, using the same method as in Example 3, except that it was left to stand in a freezer (-14°C) for 60 minutes. As a result, in all of Examples 8 to 13, the temperature of the pressure vessel immediately after dispensing was -5.0°C, and the temperature of the pressure vessel 2 minutes after dispensing was -2.6°C.

[0045] <Examples 14-19, Comparative Examples 20-27 (Hair Treatment Agents)> The raw materials were mixed according to the formulations (mass%) shown in Table 4 to prepare the stock solution composition. Then, hydrofluoroolefin and carbon dioxide were added to each of the obtained stock compositions according to the formulations in Table 4, and each was filled into a pressure-resistant container (100 mL glass test bottle for aerosols) to prepare an aerosol composition for hair treatment, thereby obtaining each aerosol product.

[0046] [Table 4]

[0047] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene HFO-1233zd:(Z)-1-chloro-3,3,3-trifluoropropene Stearamidopropyldimethylamine: Palner SDPA-4B (Miyoshi Oil & Fat Co., Ltd.) Stearoxypropyltrimonium chloride:Cotamin E-80K (Kao Corporation) Steartrimonium chloride: NIKKOL CA-2450 (Nikko Chemicals Co., Ltd.) Cetanol: Calcol 6870 (Kao Corporation) Cetyl ethylhexanoate: NIKKOL CIO (Nikko Chemicals Co., Ltd.) Dimer dilinoleate (phytosteryl / isostearyl / cetyl / stearyl / behenyl): Plandool-H (Nippon Seika Co., Ltd.) Squalane: NIKKOL Sugar Squalane (Nikko Chemicals Co., Ltd.) Dimethicone: SH200C-3000cs (Dow-Toray Industries, Inc.) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) Lactic acid: Musashino Lactic Acid F-90 (Musashino Chemical Research Institute Co., Ltd.) EDTA-2Na: Kirest 2B-SD (Kirest Co., Ltd.) Phenoxyethanol: Phenoxyethanol SP (Yokkaichi Synthetic Co., Ltd.) Methyl parahydroxybenzoate: Mekkins M (Ueno Pharmaceutical Co., Ltd.)

[0048] The obtained aerosol products were evaluated using the same method as in Examples 1-5 and Comparative Examples 1-7, except that they were left to stand in a freezer (-14°C) for 30 minutes instead of 90 minutes. This evaluation included foam formation immediately after dispensing and 2 minutes after dispensing, foaming immediately after dispensing, and the tactile feel of the foam immediately after dispensing and 2 minutes after dispensing. The results are shown in Table 4. Furthermore, for Examples 14 to 19, the temperature of the pressure vessel was measured immediately after dispensing and 2 minutes after dispensing, using the same method as in Example 3, except that it was left to stand in a freezer (-14°C) for 30 minutes. As a result, in all of Examples 14 to 19, the temperature of the pressure vessel immediately after dispensing was 3.8°C, and the temperature of the pressure vessel 2 minutes after dispensing was 5.6°C.

[0049] <Example 20 (Pack Agent)> The raw materials were mixed according to the formulations (mass%) shown in Table 5 to prepare the stock solution composition. Then, hydrofluoroolefin and carbon dioxide were added to the obtained stock solution composition according to the formulation in Table 5, and the aerosol composition, which is the packing agent, was prepared by filling a pressure-resistant container (100 mL glass test bottle for aerosols) with the mixture shown in Table 5, thereby obtaining the aerosol product.

[0050] [Table 5]

[0051] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene Polyglyceryl-1 distearate: NIKKOL Decaglyn 2-SV (Nikko Chemicals Co., Ltd.) Polysorbate 80: NIKKOL TO-10V (Nikko Chemicals Co., Ltd.) PEG-20 Sorbitan Cocoate: NIKKOL TL-10 (Nikko Chemicals Co., Ltd.) Squalane: NIKKOL Sugar Squalane (Nikko Chemicals Co., Ltd.) Cetearyl alcohol: Calcol 6850 (Kao Corporation) Behenyl alcohol: Calcol 220-80 (Kao Corporation) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) PEG-150:PEG-6000 (NOF Co., Ltd.) Xanthan gum: Echo Gum T (DSP Gokyo Food & Chemical Co., Ltd.) 1,3-Butylene glycol: 1,3-Butylene glycol-P (KH Neochem Co., Ltd.) Phenoxyethanol: Phenoxyethanol SP (Yokkaichi Synthetic Co., Ltd.)

[0052] <Example 21 (Cleansing Agent)> The raw materials were mixed according to the formulations (mass%) shown in Table 6 to prepare the stock solution composition. Then, hydrofluoroolefin and carbon dioxide were added to the obtained stock solution composition according to the formulation in Table 6, and an aerosol composition, which is a cleansing agent, was prepared by filling a pressure-resistant container (100 mL glass test bottle for aerosols) with the same formulation as shown in Table 6, thereby obtaining an aerosol product.

[0053] [Table 6]

[0054] The materials used are as follows: HFO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene Polyglyceryl-6 Laurate: NIKKOL Hexaglyn 1-L (Nikko Chemicals Co., Ltd.) Lauramine oxide: Amhitol 20N (Kao Corporation) Sodium Lauroyl Methylalanine: Alanone ALE (Kawaken Fine Chemicals Co., Ltd.) Hydrogenated polyisobutene: Chloratum LES (Croda Japan Co., Ltd.) PG isostearate: cisrol PGMIS (Croda Japan Co., Ltd.) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) 1,3-Butylene glycol: 1,3-Butylene glycol-P (KH Neochem Co., Ltd.) Phenoxyethanol: Phenoxyethanol SP (Yokkaichi Synthetic Co., Ltd.)

Claims

1. A foaming aerosol composition, The effervescent aerosol composition comprises a stock solution composition containing water and a surfactant, as well as monochlorotetrafluoropropene and compressed gas. The monochlorotetrafluoropropene is at least one selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), An effervescent aerosol composition in which the content of monochlorotetrafluoropropene is 0.5% by mass to 13.0% by mass.

2. The foaming aerosol composition according to claim 1, wherein the mass ratio of the content of monochlorotetrafluoropropene to the content of the compressed gas in the foaming aerosol composition is 0.1 to 13.

0.

3. The effervescent aerosol composition according to claim 1 or 2, wherein the monochlorotetrafluoropropene is (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)).

4. The foaming aerosol composition according to any one of claims 1 to 3, wherein the compressed gas is at least one selected from the group consisting of carbon dioxide, nitrogen gas, compressed air, and nitrous oxide.

5. The effervescent aerosol composition according to any one of claims 1 to 4, wherein the water content in the stock solution composition is 20.00% by mass to 99.00% by mass.

6. The foaming aerosol composition according to any one of claims 1 to 5, wherein the content of the surfactant in the stock solution composition is 0.10% by mass to 40.00% by mass.

7. A foaming aerosol composition for human use, according to any one of claims 1 to 6.

8. Shampoo, hair styling products, facial cleansers, hair treatments, and makeup removers. The foaming aerosol composition according to any one of claims 1 to 7, which is either a pack agent or a foaming aerosol composition according to any one of claims 1 to 7.

9. A container filled with a foaming aerosol composition, and A dispensing mechanism provided in the container for dispensing the foaming aerosol composition. an aerosol product having, An aerosol product wherein the effervescent aerosol composition is the effervescent aerosol composition according to any one of claims 1 to 8.

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