JP7720150B2 - Foaming aerosol composition and aerosol product - Google Patents

Description

The present disclosure relates to foamable aerosol compositions and aerosol products containing monochlorotrifluoropropene.

Conventionally, aerosol products that form foam have used liquefied gases such as LPG and compressed gases such as carbon dioxide and nitrogen as propellants and blowing agents. Liquefied gases such as LPG have good foaming properties and can form foam that is less likely to drip, but they are flammable gases, which raises safety concerns.
On the other hand, for example, Patent Document 1 proposes the use of a non-flammable organic fluorine compound as a propellant for an aerosol product.
Furthermore, Patent Document 2 also proposes the combined use of an organic fluorine compound such as monochlorotrifluoropropene and a compressed gas.

Japanese Patent Application Laid-Open No. 2017-110225 Japanese Patent Application Laid-Open No. 2020-023474

The inventors have conducted research and found that aerosol product foams using compressed gases such as carbon dioxide and nitrogen gas have problems such as lower foaming ability, faster defoaming, and a tendency to drip compared to those using liquefied gases.
Furthermore, even when an organic fluorine compound such as monochlorotrifluoropropene and a compressed gas are used in combination as in Patent Document 2, it has been found that the density and volume of the foam are insufficient, and there are also problems with respect to pleasant defoaming properties.
In view of these problems, the present disclosure provides a foamable aerosol composition that has excellent foam density and volume, and has good defoaming properties that allow the foam to be easily defoamed by rubbing it in with the hands.

The present disclosure provides a foamable aerosol composition comprising:
the foamable aerosol composition comprises a concentrate composition including water and a thickener, and monochlorotrifluoropropene and a compressed gas;
the monochlorotrifluoropropene is at least one selected from the group consisting of transCF ₃ CH═CClH (1233zdE) and cisCF ₃ CH═CClH (1233zdZ);
The foamable aerosol composition is characterized in that, when the foam of the foamable aerosol composition discharged from a pressure-resistant container is measured using a universal testing machine, the maximum load value is 0.95 N or more and 10.00 N or less, and the integrated value is 0.010 or more and 0.050 or less.

The present disclosure makes it possible to provide a foamable aerosol composition that has excellent foam density and volume, as well as good defoaming properties that allow the foam to be easily defoamed by rubbing it in with the hands.

The expressions "XX to YY" and "XX to YY" that represent a numerical range mean a numerical range that includes the endpoints, that is, the lower limit and the upper limit, unless otherwise specified.
When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

The present inventors first conducted studies to obtain dense and voluminous foam from a foamable aerosol composition using an organic fluorine compound. The present inventors investigated the relationship between the rheological evaluation of foam and foam properties and found that the density and volume of foam correlate with the maximum load value and integrated value in the rheological evaluation.
That is, when the foam of the foamable aerosol composition discharged from a pressure-resistant container under the conditions described below is measured using a universal testing machine, the maximum load value must be 0.95 N or more and 10.00 N or less, and the integrated value must be 0.010 or more and 0.050 or less.

As the maximum load value and the integrated value increase, the hardness and tenacity of the foam improve, and dense, voluminous foam tends to be obtained. When the maximum load value and the integrated value are within the above ranges, the foam density and volume are good. When the maximum load value is less than 0.95 N and the integrated value is less than 0.010, the foam density and volume are insufficient.
The maximum load value is preferably 1.00 N or more and 7.00 N or less, more preferably 1.30 N or more and 5.00 N or less. The integrated value is preferably 0.010 or more and 0.040 or less, more preferably 0.012 or more and 0.025 or less.
The maximum load value and the integrated value can be controlled by the content of monochlorotrifluoropropene and the content of thickener. For example, when the content of monochlorotrifluoropropene and the content of thickener are increased, the maximum load value and the integrated value tend to increase. On the other hand, when the content of monochlorotrifluoropropene is too high, the maximum load value and the integrated value tend to decrease.

Each component used in the foamable aerosol composition will now be described.
The foamable aerosol composition comprises a monochlorotrifluoropropene.
The monochlorotrifluoropropene is at least one selected from the group consisting of transCF ₃ CH═CClH (HFO-1233zdE) and cisCF ₃ CH═CClH (HFO-1233zdZ). CF ₃ CH═CClH is also called 1-chloro-3,3,3-trifluoropropene.
It is particularly preferred that the monochlorotrifluoropropene is transCF ₃ CH═CClH (HFO-1233zdE).

The monochlorotrifluoropropene can function as a propellant and a foaming agent. Compared with liquefied gases such as LPG, monochlorotrifluoropropene has a lower vapor pressure, can exhibit moderate foaming and defoaming properties, and can form voluminous foam with a low specific gravity. In addition, the inclusion of monochlorotrifluoropropene can also cause post-foaming, so that foaming occurs when applied to the skin, etc., resulting in a good feeling when used.
Usually, the foam that satisfies the above-mentioned maximum load value and integrated value is hard and tenacious, so it tends to be difficult to defoam.However, by combining monochlorotrifluoropropene with thickener, it can produce dense and voluminous foam, and it continues to foam for a while after being applied to the hand, so that it can obtain a comfortable feeling of use, and it can obtain good defoaming property that it can easily disappear when being massaged by hand.The present inventors believe that such good properties are influenced by the property that monochlorotrifluoropropene is prone to post-foaming.
Furthermore, the monochlorotrifluoropropene is non-flammable and has a very low global warming potential (GWP).

The content of monochlorotrifluoropropene in the aerosol composition is preferably 0.8% by mass to 30% by mass, more preferably 0.8% by mass to 28% by mass, even more preferably 1.5% by mass to 26% by mass, still more preferably 1.8% by mass to 22% by mass, and particularly preferably 4.0% by mass to 17% by mass. By being in the above range, better foaming and defoaming properties are exhibited.

Foamable aerosol compositions contain a compressed gas, which 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. The compressed gas is preferably at least one selected from the group consisting of carbon dioxide gas, nitrogen gas, nitrous oxide, argon, helium, and compressed air, more preferably at least one selected from the group consisting of carbon dioxide gas, nitrogen gas, compressed air, and nitrous oxide, even more preferably at least one selected from the group consisting of carbon dioxide gas and nitrogen gas, and even more preferably carbon dioxide gas. It is believed that carbon dioxide gas dissolves slightly in the concentrate composition, resulting in better foaming properties.

The content of compressed gas in the aerosol composition is not particularly limited as long as the aerosol composition can be ejected. It is preferably 0.5% by mass to 5.0% by mass. Within this range, better foaming properties can be achieved.
The content of compressed gas in the aerosol composition is more preferably 1.0% by mass to 3.0% by mass, and even more preferably 1.5% by mass to 2.5% by mass.

The mass ratio of compressed gas to monochlorotrifluoropropene (compressed gas:monochlorotrifluoropropene) in the aerosol composition is preferably 3:1 to 1:15, more preferably 2:1 to 1:13, and even more preferably 2:3 to 1:11. Being in the above range ensures good foaming and defoaming properties.

The concentrate composition in the foamable aerosol composition contains water.
The water content in the concentrate composition is preferably 50% to 98% by mass, more preferably 70% to 95% by mass, and even more preferably 80% to 92% by mass.

The concentrate composition in the foamable aerosol composition contains a thickener. The thickener can provide good foaming and defoaming properties and suppress dripping. As described above, the combination of monochlorotrifluoropropene and a thickener can produce dense, voluminous foam while still providing good defoaming properties.
The thickener is not particularly limited, and known thickeners can be used. For example, the following can be mentioned.
Cellulose-based thickeners such as cellulose gum, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydrophobized hydroxypropyl methylcellulose, sodium cellulose sulfate, and cellulose powder.
Highly polymerized polyethylene glycol (highly polymerized PEG, preferably with an average degree of polymerization of 2,000 to 150,000).
Plant-based thickeners such as gum arabic, locust bean gum, tara gum, guar gum, glucomannan, xanthan gum, pectin, and agar.
starches such as starch, carboxymethyl starch, and methylhydroxypropyl starch;
Alginic acid polymers such as sodium alginate and propylene glycol alginate;
Also, polymers such as carboxyvinyl polymer, acrylic acid/alkyl methacrylate copolymer, acrylates/alkyl acrylate crosspolymer, sodium polyacrylate, (PEG-240/decyltetradeceth-20/HDI) copolymer, and polyurethane.

Among the above, cellulose-based thickeners and plant-based thickeners are preferred, that is, the thickener preferably includes at least one selected from the group consisting of cellulose-based thickeners and plant-based thickeners.
The content of the thickener (preferably a cellulose-based thickener or a plant-based thickener) in the concentrate composition is not particularly limited as long as it satisfies the above maximum load value and integrated value, and is preferably 0.10% by mass to 2% by mass, more preferably 0.15% by mass to 2.0% by mass, even more preferably 0.15% by mass to 1.2% by mass, still more preferably 0.2% by mass to 0.7% by mass, and particularly preferably 0.2% by mass to 0.4% by mass.

More preferably, the thickener contains hydrophobized hydroxypropyl methylcellulose. Hydrophobized hydroxypropyl methylcellulose is, for example, hydroxypropyl methylcellulose modified with an alkyl group having 14 to 30 carbon atoms (preferably 16 to 22 carbon atoms), and examples thereof include stearoxyhydroxypropyl methylcellulose (Sangelose (Daido Chemical Industry Co., Ltd.)).

The concentrate composition of the foamable aerosol composition may contain a surfactant, which can provide better foaming properties.
The surfactant is not particularly limited, and may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

Preferred examples of the surfactant include the following:
lecithins such as egg yolk lecithin, soybean lecithin, hydroxylated lecithin and hydrogenated lecithin;
Sorbitan fatty acid esters such as sorbitan monostearate;
propylene glycol fatty acid esters such as propylene glycol monostearate;
Examples include polyoxyethylene ethers of sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate (polysorbate 20), polyoxyethylene sorbitan palmitate (polysorbate 40), polyoxyethylene sorbitan monostearate (polysorbate 60), polyoxyethylene sorbitan tristearate (polysorbate 65), and polyoxyethylene sorbitan oleate (polysorbate 80).

Further, the following anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants can also be suitably exemplified.
Examples of anionic surfactants include fatty acid soaps such as potassium coconut oil fatty acid, 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; acyl methyl taurate; and sulfonates such as sodium lauryl sulfoacetate.

Examples of cationic surfactants include alkylammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, and lauryltrimethylammonium chloride; alkylbenzylammonium salts; stearylamine acetate; polyoxyethylene alkylamines such as polyoxyethylene laurylamine and polyoxyethylene stearylamine; and the like.

Amphoteric surfactants include lauryl dimethylaminoacetic acid betaine (lauryl betaine).
betaine-type compounds such as alkyl betaines such as stearyl betaine, lauric acid amidopropyl betaine, lauryl hydroxysulfobetaine, stearyl dimethylaminoacetic acid betaine, dodecylaminomethyl dimethyl sulfopropyl betaine, and octadecylaminomethyl dimethyl sulfopropyl betaine; fatty acid amidopropyl betaines such as coconut acid amidopropyl betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine (cocamidopropyl betaine), and cocamidopropyl hydroxysultaine; alkyl imidazole-type compounds such as 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine; and amine oxide-type compounds such as lauryl dimethylamine N-oxide and oleyl dimethylamine N-oxide.

Examples of nonionic surfactants include polyglycerin fatty acid esters such as pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglyceryl monooleate, pentaglyceryl monostearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl monolaurate, decaglyceryl monomyristate, and decaglyceryl monooleate; polyoxyethylene sorbitan fatty acid esters such as POE (20) sorbitan monolaurate (1, POE (20) sorbitan monopalmitate, POE (20) sorbitan monostearate, POE (20) sorbitan monooleate, and POE (20) sorbitan monoisostearate; polyethylene glycol fatty acid esters such as POE (25) monostearate; POE (9) lauryl ether, POE (15) cetyl ether, POE (20) cetyl ether, and POE (10) oleate. polyoxyethylene alkyl ethers such as POE(15) oleyl ether, POE(20) oleyl ether, POE(20) behenyl ether; polyoxyethylene polyoxypropylene alkyl ethers such as POE(20) POP(4) cetyl ether; polyoxyethylene sorbitan alkyl ethers such as POE(60) sorbitan tetrastearate, POE(60) sorbitan tetraoleate, POE(6) sorbitan monolaurate; Polyoxyethylene glycerin fatty acid esters such as rubit fatty acid esters, POE (15) glyceryl monostearate, POE (15) glyceryl monooleate, etc.; polyoxyethylene castor oils and hydrogenated castor oils such as POE (50) hydrogenated castor oil, POE (60) castor oil, POE (60) hydrogenated castor oil, POE (80) hydrogenated castor oil, POE (100) hydrogenated castor oil; POE (10) lanolin alcohol, POE (20) lanolin alcohol. polyoxyethylene lanolin alcohols such as 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 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, pentaglyceryl ester Polyglycerin fatty acid esters such as pentaglycerin fatty acid esters such as glyceryl myristate and pentaglyceryl trioleate; hexaglycerin fatty acid esters such as hexaglyceryl monooleate, hexaglyceryl monostearate, and hexaglyceryl tristearate; and decaglycerin fatty acid esters such as decaglyceryl monostearate, decaglyceryl distearate, decaglyceryl diisostearate, decaglyceryl dioleate, decaglyceryl tristearate, and decaglyceryl trioleate; polyoxyethylene glycerin fatty acid esters such as POE (5) glyceryl monostearate; polyoxyethylene sorbitan fatty acid esters such as POE (20) sorbitan tristearate, POE (20) sorbitan trioleate, POE (6) sorbitan monostearate, and POE (6) sorbitan monooleate; POE (6)
Polyoxyethylene sorbitol fatty acid esters such as sorbitol tetraoleate and POE (30) sorbitol 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, POE (10) cetyl ether, POE (25) cetyl ether, POE (20) stearyl ether, POE (7) oleyl ether, POE (50) oleyl ether, POE (10) behenyl ether polyoxyethylene alkyl ethers such as POE (30) behenyl ether, polyoxyethylene polyoxypropylene alkyl ethers such as POE (20) POP (8) cetyl ether and POE (30) POP (6) decyltetradecyl ether, polyoxyethylene castor oils/hydrogenated castor oils such as POE (40) castor oil and POE (40) hydrogenated castor oil, alkyl glucosides such as lauryl glucoside, fatty acid alkylol amides such as coconut oil fatty acid diethanolamide, and alkyl dimethyl amine oxide liquids such as lauryl dimethyl amine oxide liquid.

Among the above, lecithin and polyoxyethylene ether of sorbitan fatty acid ester are preferred. That is, the surfactant preferably contains at least one selected from the group consisting of lecithin and polyoxyethylene ether of sorbitan fatty acid ester, more preferably contains lecithin, and even more preferably contains lecithin and polyoxyethylene ether of sorbitan fatty acid ester.
The lecithin is more preferably hydrogenated lecithin.
The polyoxyethylene ether of sorbitan fatty acid ester is more preferably polysorbate 65 or polysorbate 80.
When combined with a cellulose-based thickener, the polyoxyethylene ether of sorbitan fatty acid ester can exhibit better foaming and defoaming properties, and can suitably suppress dripping.

The content of polyoxyethylene ether of sorbitan fatty acid ester in the concentrate composition is preferably 0% to 1.5% by mass, more preferably 0.1% to 1% by mass, and even more preferably 0.3% to 0.7% by mass.

The lecithin content in the concentrate composition is preferably 0.02% to 1% by mass, more preferably 0.1% to 0.7% by mass, and even more preferably 0.15% to 0.4% by mass.

The concentrate composition in the foamable aerosol composition preferably contains an oil. The concentrate composition is preferably an oil-in-water (O/W) emulsion in which an oil phase is dispersed in an aqueous phase. The oil is preferably an oil that is liquid at room temperature (liquid oil). The oil can impart a pleasant feel to the product with reduced stickiness.

The oil agent is not particularly limited, but examples thereof 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.

Among these, hydrocarbon oils are preferred. That is, the oil preferably contains at least one selected from the group consisting of hydrocarbon oils. The oil more preferably contains squalane.
The content of the oil in the concentrate composition is not particularly limited, but is preferably 0.05 to 5% by mass, and more preferably 0.1 to 0.5% by mass.

The concentrate composition in the foamable aerosol composition may contain alcohols.
The alcohol may be an aliphatic alcohol or an aromatic alcohol, and examples thereof include ethanol, propanol, isopropanol, 1,3-butylene glycol, propylene glycol, isopentyl diol, pentylene glycol, 1,3-propanediol, glycerin, and phenoxyethanol.
Among these, diols such as 1,3-butylene glycol, propylene glycol, isopentyl diol, pentylene glycol, and 1,3-propane diol are preferred, and 1,3-butylene glycol is more preferred.
Furthermore, it is preferable that the concentrate composition contains, for example, glycerin as a moisturizing agent. The concentrate composition may contain alcohols such as phenoxyethanol as a preservative.
The type and amount of the alcohol may be appropriately selected taking into consideration the purpose of the foamable aerosol composition, etc. For example, the content of the alcohol in the concentrate composition is preferably about 1% by mass to 30% by mass, and more preferably about 2% by mass to 15% by mass.

Other additives will be explained below. The foamable aerosol composition may contain other known additives to the extent that the effect of the foamable aerosol composition is not impaired.
For example, thickeners other than those mentioned above, surfactants, fragrances, preservatives, colorants, pest repellent components, deodorizing components, odor-preventing components, etc. may also be added. In addition, active ingredients such as cooling components, beauty components, antiperspirant components, anti-inflammatory components, and bactericidal components may also be added.
The foamable aerosol composition can be used, for example, in emulsions, lotions, beauty serums, makeup bases, hair care products, foundations, sunscreens, shaving creams, facial cleansers, and facial cleansing creams.

The pH of the concentrate composition in the foamable aerosol composition is not particularly limited and can be set over a wide range from acidic to alkaline. For example, it is preferably weakly acidic to weakly alkaline, i.e., 4.0 to 9.5, and more preferably 5.0 to 9.0.
The pH can be adjusted using known pH adjusters, such as potassium hydroxide, triethanolamine, citric acid, and sodium citrate.

Next, aerosol products will be described.
Aerosol products are
The device comprises a container filled with a foamable aerosol composition, and a discharge mechanism provided in the container for discharging the foamable aerosol composition.
The discharge mechanism and the container are not particularly limited, and known ones can be used. The container may be made of any material that can withstand the pressure of the propellant, such as a known resin, metal, or glass container.

Monochlorotrifluoropropene and compressed gas are preferably filled into an aerosol container so that the pressure inside the container (gauge pressure) at 25°C is 0.4 MPa to 1 MPa, and more preferably 0.60 MPa to 0.75 MPa.

The method for producing the foamable aerosol composition and the aerosol product is not particularly limited. For example, the following method can be mentioned.
The concentrate composition of the foamable aerosol composition can be obtained by mixing water, a thickener, and, if necessary, other components in any desired ratio.
The aerosol product can be produced as follows: First, water, a thickener, and optionally other ingredients are mixed in any desired ratio to obtain a concentrate composition, which is then filled into a pressure-resistant container with the concentrate composition, monochlorotrifluoropropene, compressed gas, and optionally other propellants to obtain the aerosol product.
As the propellant, in addition to monochlorotrifluoropropene and compressed gas, known propellants may be mixed to the extent that the above effects are not impaired. It is preferable that no flammable propellants are contained.

The viscosity of the concentrate composition is preferably 1.0 mPa·s to 5000 mPa·s, and more preferably 2.0 mPa·s to 1000 mPa·s.
The viscosity of the concentrate composition may be adjusted as appropriate depending on the intended use of the foamable aerosol composition and the form of the discharge mechanism.
The viscosity is measured using a B-type rotational viscometer, with the liquid to be measured set at 20° C., and the reading indicated one minute after the start of measurement is taken as the measured value.

<Measurement of maximum load value and integrated value>
The method for measuring the maximum load value and the integrated value is as follows.
As a sample, an aerosol product is used in which the aerosol composition is filled in a pressure-resistant glass bottle and an aerosol spout for foam formation is used as a discharge mechanism.
The specific evaluation procedure is as follows:
Equipment and test conditions: Testing machine: Tensilon universal material testing machine; Measuring shaft: diameter 6.0 cm
- Petri dish diameter: 9.5 cm, depth: 15 mm
・LOADCELL TYPE: UR-25N-D [Made by ORIENTEC]
Test speed: 100/min
Operating range: 15 mm (the measuring shaft moves up and down within 15 mm, and the pushing load and pulling load are measured) ○ Measurement conditions (1) An aerosol product in which the concentrate and propellant are filled in a pressure-resistant glass bottle is immersed in a constant temperature water bath at 25°C for 30 minutes or more.
(2) The aerosol product, cooled to 25°C, is sprayed into a petri dish using an aerosol spout for foam formation.
(3) After filling the petri dish with foam, scrape off the excess foam so that the top surface is flat.
(4) Set it in the universal testing machine and measure it under the above conditions.
(5) The maximum value of the pressing force obtained from the measurement results is defined as the "maximum load value." In addition, the "integrated value (conceptual value)" is calculated using the following formula.
* Integrated value (conceptual value) = F ₂ (S ₂ - _{S 1} ) + F ₃ (S ₃ - _{S 2} ) + ... + F _n (S _n - _{S n-1} )
F: load value (N), S: movement amount (m), number of samples (n): 890. Note that by performing the measurement under the above conditions, n=890 samples are obtained.

The present disclosure will be specifically described below with reference to examples. However, the present disclosure is not limited to the aspects of the following examples.

<Examples 1 to 11>
The raw materials were mixed according to the formulation (mass %) shown in Table 1 to prepare a milky white emulsion concentrate composition.
Then, a propellant and a foaming agent were added to each of the obtained concentrate compositions according to the formulations shown in Table 1 and filled into a pressure-resistant container (pressure-resistant glass bottle) to prepare an aerosol composition, thereby obtaining each aerosol product. The values in the table indicate mass %. The maximum load value and integrated value of the obtained aerosol products are shown in Table 1.

The materials used are as follows:
Sangelose 60L (thickener): Stearoxyhydroxypropylmethylcellulose (Daido Chemical Industry Co., Ltd.)
Echo Gum T (thickener): Xanthan gum (DSP Gokyo Food & Chemical Co., Ltd.)
HEC SE600 (thickener): Hydroxyethyl cellulose (Daicel Miraize Co., Ltd.)
Nicosome OS (oil, surfactant, moisturizer): a mixture of 5% by mass of squalane, 5% by mass of hydrogenated lecithin, and 90% by mass of glycerin (Nikko Chemicals Co., Ltd.)
Resinol S-10 (surfactant): Hydrogenated lecithin (Nikko Chemicals Co., Ltd.)
NIKKOL TO-10V (surfactant): Polysorbate 80 (Nikko Chemicals Co., Ltd.)
1,3-BG: 1,3-butylene glycol

The resulting aerosol products were evaluated as follows, and the results are shown in Table 1.
(Foam density)
3 g of the liquid content of the aerosol product was sprayed onto the palm of a hand, and the state of the spray was visually observed to evaluate the density of the foam according to the following criteria. Specifically, the evaluation of the density of the foam was based on whether the foam was fine or coarse.
◎ (5 points): The foam is very fine.
○ (4 points): The foam is fine.
△ (3 points): The foam is coarse.
▲ (2 points): The foam is very coarse.
× (1 point): No bubbles are formed.

(foam volume)
3 g of the liquid content of the aerosol product was sprayed onto the palm of the hand, and the state of the sprayed matter was visually observed, and the foam volume was evaluated according to the following criteria.
◎ (5 points): The foam volume is very large.
○ (4 points): Large foam volume.
△ (3 points): The foam volume is small.
▲ (2 points): The foam volume is very small.
× (1 point): No bubbles are formed.

(defoaming)
3 g of the liquid content of the aerosol product was sprayed onto the palm of the hand, and the foam that formed was rubbed into the palm of the hand. The defoaming properties were evaluated according to the following criteria.
◎ (5 points): The bubbles disappear in 3 to 5 seconds.
○ (4 points): The bubbles disappear in 6 to 10 seconds.
△ (3 points): The bubbles disappear in 11 to 30 seconds.
▲ (2 points): The bubbles do not disappear even after 31 seconds.
× (1 point): No bubbles are formed.

(comprehensive evaluation)
The evaluations of density, volume and defoaming property were summed up to give an overall evaluation as follows:
◎: Total 15 points ○: Total 12-14 points △: Total 9-11 points ▲: Total 6-8 points ×: Total 3-5 points

<Comparative Examples 1 to 14>
The raw materials were mixed according to the formulations (mass %) shown in Tables 2 and 3 to prepare concentrate compositions that were milky white emulsions.
Then, a propellant and a foaming agent were added to each of the obtained concentrate compositions according to the formulations shown in Tables 2 and 3 and filled into a pressure-resistant container (pressure-resistant glass bottle), respectively, to prepare an aerosol composition, and each aerosol product was obtained. The values in the tables indicate mass %. The maximum load value and integrated value of the obtained aerosol products, as well as the evaluation results, are shown in Tables 2 and 3.

<Comparative Examples 15 to 20>
The raw materials were mixed according to the formulation (mass %) shown in Table 4 to prepare a concentrate composition.
Aerosol compositions were prepared by filling each of the concentrate compositions obtained with a propellant and a foaming agent into a pressure-resistant container (pressure-resistant glass bottle) according to the formulations shown in Table 4, to obtain each aerosol product. The values in the table indicate mass %. The maximum load value and integrated value of the obtained aerosol products, as well as the evaluation results, are shown in Table 4.

*The internal pressure of the product was adjusted to 0.6 MPa (25°C).

The materials used are as follows:
Mekxance M: Methylparaben (Ueno Pharmaceutical Co., Ltd.)
NIKKOL TL-10: POE coconut oil fatty acid sorbitan (Nikko Chemicals Co., Ltd.)
NIKKOL BS-20: POE (20) stearyl ether (Nikko Chemicals Co., Ltd.)
Amizol CDE: Coconut oil fatty acid diethanolamide (Kawaken Fine Chemicals Co., Ltd.)

Claims (11)

1. A foamable aerosol composition comprising:
the foamable aerosol composition comprises a concentrate composition including water and a thickener, and monochlorotrifluoropropene and a compressed gas;
the monochlorotrifluoropropene is at least one selected from the group consisting of transCF ₃ CH═CClH (1233zdE) and cisCF ₃ CH═CClH (1233zdZ);
The content of the thickener in the concentrate composition is 0.10% by mass to 2% by mass,
the content of the monochlorotrifluoropropene in the foamable aerosol composition is 0.8% by mass to 30% by mass;
A foamable aerosol composition characterized in that, when the foam of the foamable aerosol composition discharged from a pressure-resistant container is measured using a universal testing machine, the maximum load value is 0.95 N or more and 10.00 N or less, and the integrated value is 0.010 or more and 0.050 or less. The foamable aerosol composition according to claim 1, wherein the compressed gas is at least one selected from the group consisting of carbon dioxide gas, nitrogen gas, compressed air, and nitrous oxide. 3. The foamable aerosol composition according to claim 1, wherein the mass ratio of the compressed gas to the monochlorotrifluoropropene (compressed gas:monochlorotrifluoropropene) in the foamable aerosol composition is 3:1 to 1:15. The foamable aerosol composition according to any one of claims 1 to 3, wherein the thickener comprises at least one selected from the group consisting of cellulose-based thickeners and plant-based thickeners. 5. The foamable aerosol composition according to claim 1, wherein the content of the thickener in the concentrate composition is 0.15% by mass to 1.2% by mass. 6. The foamable aerosol composition according to claim 1 , wherein the thickener comprises hydrophobized hydroxypropyl methylcellulose. The concentrate composition contains a surfactant,
7. The foamable aerosol composition according to claim 1, wherein the surfactant comprises lecithin. 8. The foamable aerosol composition according to claim 7 , wherein said surfactant further comprises a polyoxyethylene ether of a sorbitan fatty acid ester. 9. The foamable aerosol composition according to claim 1 , wherein the content of the compressed gas in the foamable aerosol composition is 0.5% by mass to 5% by mass. 10. The foamable aerosol composition according to claim 1 , wherein the content of the monochlorotrifluoropropene in the foamable aerosol composition is 0.8% by mass to 28 % by mass. An aerosol product comprising a container filled with a foamable aerosol composition, and a discharge mechanism provided in the container for discharging the foamable aerosol composition,
An aerosol product, wherein the foamable aerosol composition is the foamable aerosol composition according to any one of claims 1 to 10 .