Aerosol products and post-foaming aerosol compositions

Abstract

To provide an aerosol product capable of forming a foam that gradually foams after being discharged, shows good foam formation even in extremely low temperature environments, and has excellent volume.SOLUTION: The aerosol product comprises: a container; an inner container provided inside the container and filled with a post-foaming composition; and a discharge mechanism provided in the container and configured to discharge the post-foaming composition. In the container, a space formed between the inner container and a partition wall of the container is filled with a propellant. The post-foaming composition comprises water and a concentrate composition comprising a surfactant, and monochlorotetrafluoropropene. The monochlorotetrafluoropropene is at least one selected from (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)).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to aerosol products and post-foaming aerosol compositions.

Background Art

[0002] Conventionally, liquefied gases such as LPG have been used as blowing agents and foaming agents in aerosol products that form foams. Liquefied gases such as LPG can form foams with good foaming properties and are difficult to drip, but there are concerns about safety because they are flammable gases. Therefore, hydrofluoroolefin (HFO), which is a non-flammable gas with a low global warming potential and ozone depletion potential, has been attracting attention. In Patent Document 1 and Patent Document 2, it has been proposed to use hydrofluoroolefins such as 1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) as the stock solution of the post-foaming composition.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the other hand, a post-foaming aerosol composition that foams after being discharged in a gel form to form a foam is known. When the inventors examined an aerosol product using 1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) as a foaming agent for the post-foaming composition, it was found that the foaming property may be insufficient when used in a low-temperature environment, particularly an extremely low-temperature environment of about 5°C. This disclosure provides an aerosol product that gradually foams after dispensing, exhibits good foam-forming properties even in cryogenic environments, and can form a foam with excellent volume. [Means for solving the problem]

[0005] This disclosure relates to a container, an inner container provided inside the container and filled with a post-foaming composition, and a dispensing mechanism provided in the container for dispensing the post-foaming composition. an aerosol product having, The container is filled with a propellant in the space formed between the inner container and the partition wall of the container. The subsequent foaming composition comprises a stock solution composition containing water and a surfactant, and monochlorotetrafluoropropene. Aerosol product wherein 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)). Regarding. [Effects of the Invention]

[0006] According to this disclosure, it is possible to provide an aerosol product that gradually foams after dispensing, exhibits good foam-forming properties even in cryogenic environments, and forms a foam with excellent volume. [Modes for carrying out the invention]

[0007] Unless otherwise specified, the notation "XX or greater and YY or less" or "XX~YY" which indicates a numerical range should not be used. This refers to a numerical range that includes the lower and upper limits, which are the endpoints. When numerical ranges are given in stages, the upper and lower limits of each range can be combined in any way.

[0008] (Monochlorotetrafluoropropene) The aerosol product 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)). The monochlorotetrafluoropropene can function as a foaming agent.

[0009] Monochlorotetrafluoropropene has a boiling point of 15°C, which is lower than other hydrofluoroolefins (for example, 1-chloro-3,3,3-trifluoropropene (boiling point 19°C)). Therefore, monochlorotetrafluoropropene vaporizes easily when discharged into the environment even at low temperatures, and can exhibit good foam-forming properties.

[0010] Furthermore, the inventors have found that by using monochlorotetrafluoropropene in the aerosol composition, the aerosol product exhibits good foam-forming properties even when used in an extremely low-temperature environment where the boiling point of monochlorotetrafluoropropene is significantly lower. In particular, despite the boiling point difference from that of conventional hydrofluoroolefins being only about 4°C, it was found that when monochlorotetrafluoropropene was used, even when used at extremely low temperatures, after dispensing, it gradually vaporized due to body temperature when applied to the human body, or due to ambient temperature or frictional heat, exhibiting significantly better foam-forming properties compared to when other hydrofluoroolefins were used. Furthermore, despite having a lower boiling point compared to other hydrofluoroolefins, monochlorotetrafluoropropene suppresses foaming immediately after dispensing in cryogenic environments, enabling the dispensing of post-foaming compositions in a gel or cream state. In addition, monochlorotetrafluoropropene allows for the formation of larger volume foams during post-foaming compared to other hydrofluoroolefins, regardless of whether it is used at room temperature or cryogenic environments. The inventors believe that this is because monochlorotetrafluoropropene has a different structure from other hydrofluoroolefins, resulting in better emulsification with the stock solution composition. Furthermore, monochlorotetrafluoropropene is thought to impart viscosity to the stock solution composition by dissolving in it, making it easier to maintain the post-foaming composition stably in a gel or cream state. Therefore, the inventors believe that it can exhibit better foam-forming properties compared to other hydrofluoroolefins.

[0011] The content of monochlorotetrafluoropropene in the post-foaming composition is not particularly limited, but is preferably 1.0% to 35.0% by mass, more preferably 2.0% to 31.0% by mass, even more preferably 6.0% to 31.0% by mass, even more preferably 8.0% to 31.0% by mass, and particularly preferably 8.0% to 22.0% by mass. When the content is within the above range, the emulsification state between monochlorotetrafluoropropene and the stock composition is better, so even in an extremely low temperature environment, more monochlorotetrafluoropropene vaporizes after being discharged, resulting in better foam-forming properties. Furthermore, regardless of whether the usage temperature or storage temperature is room temperature or extremely low temperature, it is easier to form a foam with a larger volume and superior feel such as elasticity compared to when other hydrofluoroolefins are used.

[0012] (Stock composition) The post-foaming composition of an aerosol product contains a stock solution composition. The content of the stock solution composition in the post-foaming composition is not particularly limited, but is preferably 60.0% to 99.0% by mass, more preferably 65.0% to 98.0% by mass, even more preferably 68.0% to 96.0% by mass, and even more preferably 70.0% to 94.0% by mass. When the content is within the above range, good foaming properties are easily obtained during post-foaming, and it is easy to form a foam with a large volume.

[0013] The stock solution composition in the post-foaming composition contains water. The water content in the stock solution composition is not particularly limited. It can be appropriately selected considering the purpose of the aerosol product, etc. The water content in the stock solution composition is preferably 50.00% to 99.00% by mass, more preferably 55.00% to 95.00% by mass, even more preferably 60.00% to 90.00% by mass, and even more preferably 65.00% to 85.00% by mass.

[0014] The stock solution composition in the post-foaming composition contains a surfactant. The surfactant is not particularly limited, and should be present in a type and amount sufficient to enable foaming of the stock solution composition. Surfactants can function as emulsifiers that emulsify monochlorotetrafluoropropene in the stock solution composition. Furthermore, by incorporating surfactants, viscosity is imparted to the stock solution composition through emulsification, suppressing the separation of monochlorotetrafluoropropene within the container and maintaining the stock solution composition stably in a gel or cream state. Additionally, surfactants suppress the vaporization of monochlorotetrafluoropropene when the post-foaming composition is dispensed, thus maintaining the post-foaming composition in a gel or cream state immediately after dispensing. Surfactants slowly vaporize the monochlorotetrafluoropropene emulsified with the stock solution composition, causing the stock solution composition to gradually foam. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant may be used, and one kind or two or more kinds may be used.

[0015] Examples of the anionic surfactant include fatty acid soaps such as potassium coconut oil fatty acid (e.g., potassium cocoil 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 (2) lauryl ether sulfate and triethanolamine polyoxyethylene lauryl ether sulfate; alkyl phosphates such as lauryl phosphate; amino acid-based surfactants such as acylmethyl tauric acid and sodium lauroylmethyl alanine; sulfonates such as sodium lauryl sulfoacetate; and the like.

[0016] Examples of the cationic surfactant include alkyl ammonium salts such as cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride (steartrimonium chloride), behenyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, and stearoxypropyl trimonium chloride; alkyl benzyl ammonium salts; stearyl amine acetate; polyoxyethylene alkyl amines such as polyoxyethylene lauryl amine and polyoxyethylene stearyl amine; stearamidopropyl dimethyl amine; and the like.

[0017] Examples of the nonionic surfactant include Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (6) sorbitan monooleate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) sorbitan monoisostearate; Polyethylene glycol fatty acid esters such as polyoxyethylene (10) monostearate, polyoxyethylene (25) monostearate, polyoxyethylene (40) monostearate, polyoxyethylene (55) monostearate, polyoxyethylene (10) monolaurate, polyoxyethylene (10) monooleate, PEG-20 sorbitan cocoate; Polyoxyethylene alkyl ethers such as polyoxyethylene (4) lauryl ether, polyoxyethylene (9) lauryl ether, polyoxyethylene (21) lauryl ether, polyoxyethylene (150) cetyl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (2) cetyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (25) cetyl ether, polyoxyethylene (30) cetyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (15) oleyl ether, polyoxyethylene (7) oleyl ether, polyoxyethylene (20) oleyl ether, polyoxyethylene (50) oleyl ether, polyoxyethylene (5) behenyl ether, polyoxyethylene (10) behenyl ether, polyoxyethylene (20) behenyl ether, polyoxyethylene (30) behenyl ether, polyoxyethylene (20) stearyl ether; Polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene (20) polyoxypropylene (4) cetyl ether, polyoxyethylene (20) polyoxypropylene (8) cetyl ether, polyoxyethylene (30) polyoxypropylene (6) decyltetradecyl ether; Polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene (60) sorbitol tetrastearate, polyoxyethylene (6) sorbitol tetraoleate, polyoxyethylene (30) sorbitol tetraoleate, polyoxyethylene (60) sorbitol tetraoleate, polyoxyethylene (6) sorbitol monolaurate; Polyoxyethylene glycerin fatty acid esters such as POE(15) glyceryl monostearate, POE(5) glyceryl monostearate, and POE(15) glyceryl monooleate; Polyoxyethylene castor oil / hydrogenated castor oil such as POE(40) castor oil, POE(20) hydrogenated castor oil, POE(40) hydrogenated castor 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, etc. Polyoxyethylene lanolin alcohols such as POE(10) lanolin alcohol, POE(20) lanolin alcohol, and POE(40) lanolin alcohol; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan trioleate; Glycerin fatty acid esters such as glyceryl monooleate, glyceryl monostearate, and glyceryl monomyristate; Diglycerin fatty acid esters such as diglyceryl monostearate, diglyceryl monooleate, and diglyceryl monoisostearate; triglycerin fatty acid esters such as triglyceryl monolaurate, triglyceryl monomyristate, triglyceryl monooleate, and triglyceryl monostearate; tetraglycerin fatty acid esters such as tetraglyceryl monostearate and tetraglyceryl monooleate; pentagglyceryl trimyristate, pentagglyceryl trioleate, pentagglyceryl monolaurate, pentagglyceryl monomyristate, pentagglyceryl monooleate, and pentagglyceryl monostearate; and pentagglycerin lipids. Fatty acid esters, hexaglycerin fatty acid esters such as hexaglyceryl monooleate, hexaglyceryl monostearate, hexaglyceryl tristearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, and polyglycerin fatty acid esters such as decaglyceryl monostearate, decaglyceryl distearate, decaglyceryl diisostearate, decaglyceryl dioleate, decaglyceryl tristearate, decaglyceryl trioleate, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monooleate, decaglyceryl distearate; 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.

[0018] 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.

[0019] The surfactant preferably contains at least one selected from the group consisting of polyoxyethylene alkyl ethers with an average number of moles of ethylene oxide added of 4 to 150 and polyoxyethylene lauryl ether sodium sulfate with an average number of moles of ethylene oxide added of 2 to 4, and more preferably contains at least one selected from the group consisting of POE(5) behenyl ether, POE(20) behenyl ether, POE(15) cetyl ether, POE(30) cetyl ether, POE(4) lauryl ether, POE(20) oleyl ether, and POE(2) lauryl ether sodium sulfate.

[0020] The proportion of surfactant in the stock solution composition is not particularly limited and can be appropriately selected considering the purpose of the aerosol product, etc. The surfactant content in the stock solution composition is preferably 0.50% to 40.00% by mass, more preferably 1.00% to 35.00% by mass, even more preferably 2.00% to 30.00% by mass, and even more preferably 3.00% to 25.00% by mass.

[0021] The stock solution composition may contain a thickening agent. The thickening agent increases the viscosity of the stock solution composition, making it easier to maintain the post-foaming composition in a gel-like state immediately after dispensing, and thus easier to suppress foaming during dispensing. Furthermore, the thickening agent allows for the formation of a foam with superior foam quality and foam retention. The thickening agent is not particularly limited, and known ones can be used. For example, the following can be used: Cellulose-based thickeners such as cellulose gum, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydrophobized hydroxypropylmethylcellulose, sodium cellulose sulfate, and cellulose powder; Polyethylene glycol-based thickeners such as high polymer polyethylene glycol (high polymer PEG), polyethylene glycol distearate, (PEG-240 / decyl tetratredeceth-20 / HDI) copolymer, and glyceryl behenate / polyglyceryl-6 octastearate; Plant-derived thickeners such as gum arabic, locust bean gum, tara gum, guar gum, glucomannan, xanthan gum, and pectin; Starch-based thickeners such as starch, carboxymethyl starch, and methylhydroxypropyl starch; Seaweed-derived thickeners such as sodium alginate, propylene glycol alginate, carrageenan, and agar; Acrylic acid-alkyl methacrylate copolymers, hydroxyethyl acrylate-acryloyldimethyl taurate salt copolymers, sodium acrylate-acryloyldimethyl taurate copolymers, polyvinyl alcohol, (PEG-240 / decyltetradeceth-20 / HDI) copolymers, acrylates / alkyl acrylate crosspolymers, (sodium acrylate / acryloyldimethyl taurate / dimethylacrylamide) crosspolymers, polyacrylic acid or salts thereof, and other acrylic acid-based polymers; Also, vinyl-based thickeners such as polyvinylpyrrolidone, carboxyvinyl polymer, polyvinyl alcohol, and polyvinyl methyl ether; Mucopolysaccharide thickeners such as hyaluronic acid, hyaluronic acid derivatives, and their salts, and chondroitin sulfate sodium; Amino acid-based thickeners such as collagen; Polyurethane, dextrin fatty acid esters, dimethyldistearylammonium hectorite, (acryloyldimethyltaurate ammonium / vinylpyrrolidone) copolymer, ethylene glycol triisostearate, polyoxyethylene (20) methyl glucoside triisostearate, bentonite, macrogol, dibutylethylhexanoyl glutamide, dibutyl lauroyl glutamide, sodium caseinate, and other water-soluble polymers. These may be used one or more types.

[0022] The thickener preferably contains at least one selected from the group consisting of cellulosic thickeners and plant-derived thickeners, and more preferably contains at least one selected from the group consisting of hydroxyethylcellulose and xanthan gum. The proportion of the thickener in the stock solution composition is not particularly limited and can be appropriately selected considering the purpose of the aerosol product, etc. The content of the thickening agent in the stock solution composition is preferably 0.05% to 2.50% by mass, more preferably 0.10% to 1.00% by mass, and even more preferably 0.15% to 0.50% by mass.

[0023] The stock solution composition in the post-foaming composition preferably contains a polyhydric alcohol. The polyhydric alcohol improves emulsification stability and provides a good user experience. The polyhydric alcohol is not particularly limited and can be appropriately selected considering the purpose of the aerosol product. Examples include the following:

[0024] Examples of polyhydric alcohols include sugar alcohols such as glycerin, erythritol, sorbitol, mannitol, and maltitol, as well as propylene glycol, 1,3-butylene glycol, polyethylene glycol, and polyglycerin. The valency of the polyhydric alcohol is preferably 2 to 12, more preferably 3 to 7. One or more of these may be used. The polyhydric alcohol is preferably a sugar alcohol. The sugar alcohol is more preferably sorbitol and / or glycerin. The content of polyhydric alcohols in the stock solution composition is not particularly limited, but is preferably 1.00% to 25.00% by mass, more preferably 1.50% to 20.00% by mass, and even more preferably 2.00% to 15.00% by mass.

[0025] The stock solution composition in the post-foaming composition preferably contains an oily component. The oily component provides good foam quality and a pleasant feel. The stock solution composition may be an oil-in-water (O / W) emulsion (oil-in-water emulsion composition) in which the oil phase is dispersed in the aqueous phase, or a water-in-oil (W / O) emulsion (water-in-oil emulsion composition) in which the aqueous phase is dispersed in the oil phase, but it is preferably an oil-in-water (O / W) emulsion (oil-in-water emulsion composition).

[0026] The oily components are not particularly limited, but include the following: Hydrocarbon oils such as squalane, squalene, mineral oil, liquid paraffin, and petrolatum; Fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid; Vegetable oils such as wheat germ oil, rice germ oil, camellia oil, argan oil, soybean oil, olive oil, castor oil, coconut oil, apricot oil, palm oil, sesame oil, jojoba oil, cottonseed oil, rapeseed oil, linseed oil, and rosehip oil; Silicone oils such as dimethylpolysiloxane, dodecamethylcyclohexasiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane; Esters such as glycerin monostearate, glycerin distearate, isopropyl palmitate, isopropyl stearate, butyl stearate, and isopropyl myristate; Higher alcohols such as behenyl alcohol, cetanol, stearyl alcohol, and isostearyl alcohol; Cetearyl alcohol.

[0027] The fatty acid preferably has 14 to 22 carbon atoms, more preferably 16 to 18 carbon atoms. Furthermore, the fatty acid is preferably a linear or branched saturated or unsaturated fatty acid, more preferably a linear saturated fatty acid. The higher alcohol preferably has 14 to 24 carbon atoms, and more preferably 16 to 22 carbon atoms. Furthermore, the higher alcohol is preferably a linear or branched saturated or unsaturated alcohol, and more preferably a linear saturated alcohol. The oily component preferably contains at least one selected from the group consisting of squalane, liquid paraffin, palmitic acid, stearic acid, isopropyl palmitate, behenyl alcohol, and cetearyl alcohol. The content of oily components in the stock solution composition is not particularly limited, but is preferably 0.50% to 20.00% by mass, more preferably 1.00% to 17.0% by mass, and even more preferably 2.00% to 14.0% by mass.

[0028] The undiluted composition may contain optional ingredients such as active ingredients, fragrances, antioxidants, preservatives, pH adjusters, chelating agents, oils and fats, silicones, cationic polymers, other 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.

[0029] Optional components include, for example, the following: Cooling agents (menthol, camphor, etc.); pH adjusters (e.g., citric acid, sodium citrate, lactic acid, triethanolamine, KOH, NaOH, etc.); rust inhibitors (e.g., ammonia water, ammonium benzoate, sodium nitrite, etc.); preservatives (e.g., parabens, phenoxyethanol, etc.) Diethanol, methyl parahydroxybenzoate; cationic polymers (e.g., polyquaternium-7, polyquaternium-10); urea; minerals such as calcium, iron, and sodium; pigments; dyes; chelating agents such as EDTA-2Na, etc.

[0030] Aerosol products can be provided for various applications depending on the type of their composition. For example, aerosol products can be used in lotions, toners, serums, makeup bases, hair care products, foundations, sunscreens, shaving creams, facial cleansers, facial creams, face masks, shower gels, and more.

[0031] The viscosity of the stock solution composition is not particularly limited and can be adjusted as appropriate depending on the purpose of the aerosol product. The viscosity of the stock solution composition is preferably 10 to 50,000 mPa·s, more preferably 50 to 20,000 mPa·s, even more preferably 200 to 15,000 mPa·s, and particularly preferably 400 to 11,000 mPa·s. For example, the viscosity of the stock solution composition can be increased and adjusted to the above range by including surfactants, thickeners, oily components, etc. Viscosity is measured using a TVB-10 viscometer (Toki Sangyo Co., Ltd.), with the liquid to be measured set to 20°C. The reading after 1 minute from the start of measurement is taken as the measured value.

[0032] The post-foaming composition before post-foaming is preferably in the form of a gel, cream, or gel, and more preferably in the form of a gel or cream. For example, by including a thickener or oily component in the stock composition, or by including monochlorotetrafluoropropene in the post-foaming composition, the viscosity can be increased, making the post-foaming composition gel or cream.

[0033] The aerosol product 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 aerosol product can be stored and / or used at temperatures preferably between -20°C and 15°C, more preferably between -10°C and 10°C, even more preferably between -5°C and 7°C, and even more preferably between 0°C and 7°C. Even when the temperature of the foam immediately after foaming of the post-foaming composition is between -5°C and 10°C (preferably between 0°C and 7°C), excellent foam-forming properties can be obtained, and a large volume of foam can be formed.

[0034] (container) The aerosol product of the present invention comprises a container filled with a post-foaming composition and a propellant, and a dispensing mechanism provided in the container for dispensing the post-foaming composition. While general aerosol containers and double-walled containers can be used as containers, a double-walled container is preferred, which has an inner container for containing the post-foaming composition within a storage compartment (for example, a can-shaped storage compartment), thereby separating and storing the post-foaming composition and the propellant. In other words, the aerosol product is an aerosol product having a container, an inner container provided inside the container and filled with a post-foaming composition, and a dispensing mechanism provided in the container for dispensing the post-foaming composition, wherein a propellant is filled into the space formed between the inner container and the partition wall of the container inside the container. When an aerosol product is packaged in a double-walled container as described above, the post-foaming composition can be contained within the inner container, making it easier to store for extended periods. Furthermore, double-walled aerosol containers are preferable because the propellant does not come into contact with the undiluted composition in the inner container, and the propellant does not affect the foaming properties. This makes it easy to obtain a foam with good foaming properties regardless of the type of propellant used.

[0035] The discharge mechanism and container are not particularly limited and known ones may 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., may be used. This is possible. The discharge mechanism is not particularly limited and known ones can be used. The discharge mechanism includes, for example, a valve device and an actuator. In addition, the structure for mounting the valve device can be appropriately selected depending on the type of pressure vessel. The actuator in the discharge mechanism is not particularly limited and any known actuator may be used. For example, the shape of the spout may be used.

[0036] (propellant) The propellant is not particularly limited and any known propellant that can be used in aerosol products may be used. Liquefied gas or compressed gas may be used, or liquefied gas and compressed gas may be used in combination. The liquefied gas is not particularly limited and includes hydrocarbons such as dimethyl ether (DME), liquefied natural gas (LNG), liquefied petroleum gas (LPG), and isopentane; and hydrofluoroolefins such as HFO-1234ze. The compressed gas is not particularly limited and includes carbon dioxide, nitrogen, nitrous oxide, argon, helium, and compressed air.

[0037] The pressure (gauge pressure) inside the container of an aerosol product is not particularly limited. The post-foaming composition and propellant should be filled into the aerosol container such that the pressure (gauge pressure) inside the inner container is, for example, 1 MPa or less at 25°C.

[0038] The method for manufacturing the post-foaming composition and the aerosol product filled with the post-foaming composition is not particularly limited. For example, the following methods may be used. The stock solution composition for the post-foaming 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 and monochlorotrifluoropropene are filled into an inner container, and a propellant is filled into the space formed between the inner container and the partition wall of the container to obtain an aerosol product filled with a post-foaming composition.

[0039] Furthermore, the present invention relates to a post-foaming aerosol composition, The post-foaming aerosol composition comprises a stock solution composition containing water and a surfactant, a post-foaming composition containing monochlorotetrafluoropropene, and a propellant. 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)), The propellant is selected from the group consisting of nitrogen gas, argon, helium, and compressed air, and is at least One This relates to a post-foaming aerosol composition.

[0040] (Post-foaming composition) The post-foaming composition in the post-foaming aerosol composition has the same formulation as the post-foaming composition in the aerosol product described above.

[0041] (propellant) Post-foaming aerosol compositions contain a propellant. When using a general aerosol container (without an inner container), the propellant comes into contact with the undiluted composition inside the inner container, and the propellant affects the foaming properties; therefore, it is preferable to use compressed gas as the propellant. The compressed gas is at least one selected from the group consisting of nitrogen gas, argon, helium, and compressed air, preferably at least one selected from the group consisting of nitrogen gas and compressed air, and more preferably nitrogen gas. Because these compressed gases have low reactivity, It dissolves in small amounts in the liquid composition, is less likely to foam when dispensed externally, and can gradually foam after dispensing. Furthermore, it is preferable that the propellant does not contain carbon dioxide or nitrous oxide.

[0042] Next, we will describe aerosol products using post-foaming aerosol compositions. The aerosol product comprises a container filled with a post-foaming aerosol composition, and a dispensing mechanism provided in the container for dispensing the post-foaming 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. The discharge mechanism is also not particularly limited and known ones can be used. The discharge mechanism includes, for example, a valve device and an actuator. Furthermore, the structure for mounting the valve device can be appropriately selected depending on the type of pressure vessel. The actuator in the discharge mechanism is not particularly limited and any known actuator may be used. For example, the shape of the spout may be used.

[0043] The pressure (gauge pressure) inside the container of an aerosol product is not particularly limited. The post-foaming aerosol composition and propellant should be filled into the aerosol container such that the pressure (gauge pressure) inside the container when filled is, for example, 1 MPa or less at 25°C.

[0044] The method for manufacturing the post-effervescent aerosol composition and the aerosol product filled with the post-effervescent aerosol composition is not particularly limited. For example, the following methods can be used. The stock solution composition for a post-foaming 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, monochlorotrifluoropropene, and propellant are filled into a pressure vessel to obtain an aerosol product filled with a post-foaming aerosol composition. [Examples]

[0045] The present disclosure will be described in detail below with reference to the following embodiments. However, the present disclosure is not limited to the embodiments described below.

[0046] <Examples 1-7, Comparative Examples 1-6 (Face Pack Agents)> The raw materials were mixed according to the formulations (mass%) shown in Table 1 to prepare the stock solution composition. Furthermore, using a TVB-10 viscometer (Toki Sangyo Co., Ltd.), the viscosity of the obtained stock solution composition was measured under the following conditions: TVB-10M type, rotor: M4, measurement time 1 minute, 12 rpm, and measurement temperature 20°C. The viscosity was found to be 10,000 mPa·s. Furthermore, using the aerosol product formulations (parts by mass) shown in Table 1, a total of 30 g each of the obtained stock solution composition, hydrofluoroolefin, and nitrogen gas was filled into pressure-resistant containers (100 mL glass test bottles for aerosols) to obtain aerosol products, which are face packs filled with the post-foaming aerosol composition. The content ratios of the stock solution composition and other components in the obtained aerosol products are shown in Table 1. In addition, nitrogen gas was filled so that the internal pressure of the product was 0.7 MPa (25°C). The amount of nitrogen gas filled was 0.6 g.

[0047] [Table 1]

[0048] <Examples 8-12, Comparative Examples 7-13 (Shower Gel)> The raw materials were mixed according to the formulations (mass%) shown in Table 2 to prepare the stock solution composition. Furthermore, using a TVB-10 viscometer (Toki Sangyo Co., Ltd.), the viscosity of the obtained stock solution composition was measured under the following conditions: TVB-10M type, rotor: M4, measurement time 1 minute, 60 rpm, and measurement temperature 20°C. The viscosity was found to be 3000 mPa·s. Furthermore, using the aerosol product formulations (parts by mass) shown in Table 2, a total of 30 g each of the obtained stock solution composition, hydrofluoroolefin, and nitrogen gas was filled into pressure-resistant containers (100 mL glass test bottles for aerosols) to obtain aerosol products that were shower gels filled with the post-foaming aerosol composition. The content ratios of the stock solution composition and other components in the obtained aerosol products are shown in Table 2. In addition, nitrogen gas was filled so that the internal pressure of the product was 0.7 MPa (25°C). The amount of nitrogen gas filled was 0.6 g.

[0049] [Table 2]

[0050] <Examples 13-18, Comparative Examples 14-20 (Facial Cleansers)> The raw materials were mixed according to the formulations (mass%) shown in Table 3 to prepare the stock solution composition. Furthermore, using a TVB-10 viscometer (Toki Sangyo Co., Ltd.), the viscosity of the obtained stock solution composition was measured under the following conditions: TVB-10M type, rotor: M4, measurement time 1 minute, 60 rpm, and measurement temperature 20°C. The viscosity was found to be 500 mPa·s. Furthermore, using the aerosol product formulations (parts by mass) shown in Table 3, a total of 30 g each of the obtained stock solution composition, hydrofluoroolefin, and nitrogen gas was filled into pressure-resistant containers (100 mL glass test bottles for aerosols) to obtain aerosol products containing the post-foaming aerosol composition. The content ratios of the stock solution composition and other components in the obtained aerosol products are shown in Table 3. In addition, nitrogen gas was filled so that the internal pressure of the product was 0.7 MPa (25°C). The amount of nitrogen gas filled was 0.6 g.

[0051] [Table 3]

[0052] The materials used are as follows: (Hydrofluoroolefin) H C FO-1224yd:(Z)-1-chloro-2,3,3,3-tetrafluoropropene HFO-1233zd:(E)-1-chloro-3,3,3-trifluoropropene (Oily components) Squalane: NIKKOL Sugar Squalane (Nikko Chemicals Co., Ltd.) Cetearyl alcohol: Calcol 6850 (Kao Corporation) Behenyl alcohol: NIKKOL Behenyl Alcohol 80 (Nikko Chemicals Co., Ltd.) Isopropyl palmitate: Excepearl IPP (Kao Corporation) Palmitic acid: Edenor C16-98MY (Emery Oleochemicals Co., Ltd.) Stearic acid: Edenor C18-98MY (Emery Oleochemicals Co., Ltd.) Liquid paraffin: Carnation (Sonneborn LLC) (Surfactants) Beheneth-20 (POE(20) Behenyl Ether): NIKKOL BB-20 (Nikko Chemicals Co., Ltd.) Beheneth-5 (POE(5) Behenyl Ether): NIKKOL BB-5 (Nikko Chemicals Co., Ltd.) Ceteth-150 (POE(150) cetyl ether): NIKKOL BC-150 (Nikko Chemicals Co., Ltd.) Sodium laureth sulfate (POE(2) lauryl ether sulfate sodium): Emal E-27C (Kao Corporation) Laureth-4 (POE(4) lauryl ether): NIKKOL BL-4.2 (Nikko Chemicals Co., Ltd.) Oleth-20 (POE(20) oleyl ether): NIKKOL BO-20V (Nikko Chemicals Co., Ltd.) Ceteth-30 (POE(30) cetyl ether): NIKKOL BC-30 (Nikko Chemicals Co., Ltd.) (Thickening agent) Xanthan gum: Echo Gum T (DSP Gokyo Food & Chemical Co., Ltd.) Hydroxyethylcellulose: HEC Daicel SE600 (Daicel Mirise Co., Ltd.) (Polyhydric alcohol) Glycerin: Concentrated glycerin for cosmetics (Kao Corporation) Sorbitol: Sorbitol Kao (Kao Corporation) (others) Phenoxyethanol: Phenoxyethanol SP (Yokkaichi Synthetic Co., Ltd.) Polyquaternium-7: MARQUAT 550 Polymer (Lubrizol Corporation) TEA: Triethanolamine 99% (Dow Chemical Co., Ltd.) Dibutylhydroxytoluene:BHT-C (JGC Universal Corporation) Menthol: Menthol JP COS (Takasago International Corporation)

[0053] The following evaluations were performed using the obtained aerosol products. The results are shown in Tables 1-3.

[0054] (1) Appearance immediately after discharge The obtained aerosol product was stored at 5°C for 24 hours. Then, 3 g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the appearance of the composition immediately after dispensing was visually observed and evaluated according to the following criteria. 5: It does not foam at all and is dispensed as a gel or cream. 4. It does not foam and is dispensed as a gel or cream. 3: It is slightly foamy, but dispensed as a gel or cream. 2: It is slightly foamy and dispensed as a foam. 1: It is foamy and dispensed in a foamy form.

[0055] (2) Foam forming property After storing the obtained aerosol product at 5°C for 24 hours, 3g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the foaming ability was observed visually in terms of foaming speed when the composition was stretched using a glass rod at 25°C, 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 relatively low foam-forming properties. 1: Low foam-forming ability.

[0056] (3) Volume of foam (Storage temperature: 5℃) The obtained aerosol product was stored at 5°C for 24 hours. Then, 3g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), spread with a finger, and the volume of foam in the fully foamed state was visually observed and evaluated according to the following criteria. 5: Forms very large bubbles. 4: Forms large, voluminous bubbles. 3: Forms slightly larger bubbles. 2: Forms relatively small bubbles. 1: Forms small bubbles.

[0057] (4) Volume of foam (Storage temperature: 25℃) The obtained aerosol product was stored at 25°C for 24 hours. Then, 3g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), spread with a finger, and the volume of foam in the fully foamed state was visually observed and evaluated according to the following criteria. 5: Forms very large bubbles. 4: Forms large, voluminous bubbles. 3: Forms slightly larger bubbles. 2: Forms relatively small bubbles. 1: Forms small bubbles.

[0058] (5) Feel (storage temperature: 5℃) The obtained aerosol product was stored at 5°C for 24 hours. Then, 3g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the elasticity of the foam, which was spread with a finger and fully foamed, 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 slightly low. 1: It has low elasticity.

[0059] (6) Feel (storage temperature: 25℃) The obtained aerosol product was stored at 25°C for 24 hours. Then, 3g of the post-foaming aerosol composition was dispensed onto a flat plate at room temperature (25°C), and the elasticity of the foam, which was spread with a finger and fully foamed, 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 slightly low. 1: It has low elasticity.

[0060] The results in Tables 1-3 show that the present invention exhibits superior foam-forming properties even in cryogenic environments (5°C) compared to conventional hydrofluoroolefins. Furthermore, it was found that the present invention can form a foam with greater volume and superior tactile properties during post-foaming, regardless of whether it is stored at room temperature or in a cryogenic environment, compared to conventional hydrofluoroolefins. This suggests that the formation of a foam with greater volume and better tactile properties according to the present invention is not due to the influence of storage in a cryogenic environment. Furthermore, inert gases such as nitrogen gas do not affect the stock solution composition. Therefore, the state in which the pressure vessel in each example is pressurized by nitrogen gas simulates the state in which the inner container is pressurized by the propellant filling the space formed between the inner container and the partition wall of the double-walled container when a double-walled container is used. Thus, it is suggested that even when a double-walled container is used as the container for aerosol products, results similar to those shown in Tables 1 to 3 can be obtained.

Claims

1. A container, an inner container provided inside the container and filled with a post-foaming composition, and a dispensing mechanism provided in the container for dispensing the post-foaming composition. an aerosol product having, The container is filled with a propellant in the space formed between the inner container and the partition wall of the container. The subsequent foaming composition comprises a stock solution composition containing water and a surfactant, and 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)), An aerosol product in which the content of monochlorotetrafluoropropene in the post-foaming composition is 1.0% by mass to 20.0% by mass.

2. The aerosol product according to claim 1, wherein the stock solution composition further comprises a polyhydric alcohol and / or a thickening agent.

3. The aerosol product according to claim 1 or 2, wherein the stock solution composition further comprises an oily component.

4. The aerosol product according to claim 3, wherein the stock solution composition is an oil-in-water emulsion composition.

5. The aerosol product according to any one of claims 1 to 4, wherein the content of monochlorotetrafluoropropene in the post-foaming composition is 7.0% by mass to 15.0% by mass.

6. The aerosol product according to any one of claims 1 to 5, wherein the monochlorotetrafluoropropene is (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)).

7. The aerosol product according to any one of claims 1 to 6, wherein the water content in the stock solution composition is 50.00% by mass to 99.00% by mass.

8. The aerosol product according to any one of claims 1 to 7, wherein the content of the surfactant in the stock solution composition is 0.50% by mass to 40.00% by mass.

9. A post-foaming aerosol composition, The post-foaming aerosol composition comprises a stock solution composition containing water and a surfactant, a post-foaming composition containing monochlorotetrafluoropropene, and a propellant. 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)), The content of monochlorotetrafluoropropene in the post-foaming composition is 1.0% by mass to 20.0% by mass. A post-foaming aerosol composition wherein the propellant is at least one selected from the group consisting of nitrogen gas, argon, helium, and compressed air.

10. A container filled with a post-effervescent aerosol composition, and a dispensing mechanism provided in the container for dispensing the post-effervescent aerosol composition. an aerosol product having, An aerosol product wherein the post-foaming aerosol composition is the post-foaming aerosol composition described in claim 9.

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