Aerosol components and aerosol products.

Abstract

Invention details;

Description

Aerosol compositions and aerosol products

[0001] The present disclosure relates to aerosol compositions that are substantially free of surfactants, and to ejection compositions that are substantially free of surfactants.

[0002] Emulsions are widely used in foods, cosmetics, pharmaceuticals, etc., and it is widely known that surfactants are used as emulsifiers to stabilize emulsion dispersion. However, in recent years, with the growing trend toward natural products, there has been an increasing demand for emulsifier (surfactant)-free products in order to reduce the burden on the human body, such as irritation caused by surfactants, and to conserve resources.

[0003] For example, Patent Document 1 proposes a technique of adding an interfacially inactive substance as a water-soluble additive for stabilizing dispersion in a water-in-oil (W / O) emulsion in which the dispersoid is water and the dispersion medium is oil. Furthermore, Patent Documents 2 and 3 disclose emulsions that contain an oil phase and an aqueous phase but do not contain an emulsifier.

[0004] JP 2016-165716 A JP 2019-064971 A JP 2021-028317 A

[0005] Meanwhile, due to diversifying customer needs in the cosmetics market and the like, there is an increasing demand for O / W emulsions containing a large amount of oily components. However, it is difficult to increase the amount of oily components in the emulsions of Patent Documents 2 and 3. Also, although there is a method of using a water-soluble polymer instead of a surfactant to stabilize the dispersion of an O / W emulsion, this increases the viscosity of the emulsion, resulting in insufficient droplet stability and foam stability in an aerosol composition. Furthermore, when made into an aerosol product, the spray pattern becomes narrow, making it difficult to spray fine droplets.

[0006] In view of these problems, the present disclosure provides an aerosol composition and an aerosol product that are substantially free of surfactants and have good emulsion stability even when a large amount of oily components is contained.

[0007] The present disclosure relates to an aerosol composition containing water, an oily component, and a water-soluble polymer, wherein the water-soluble polymer comprises at least one selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone, the content of the water-soluble polymer in the aerosol composition is 0.01% by mass to 2.5% by mass, the aerosol composition forms an emulsion, the average particle size of droplets of the emulsion is 0.5 μm to 7.0 μm, and the aerosol composition is substantially free of a surfactant.

[0008] A preferred form of the composition is a foam-forming aerosol composition, and another preferred form is a spray composition. The composition is also applicable to products having a discharge mechanism that can discharge the contents without using a propellant, and another form is a discharge composition.

[0009] According to the present disclosure, it is possible to provide an aerosol composition and an aerosol product that are substantially free of surfactants and that exhibit good emulsion stability even when containing a large amount of oily components. Furthermore, because the emulsion stability is good even when the content of water-soluble polymer is low, a low-viscosity composition can be obtained. Therefore, it is possible to provide an aerosol composition for foam formation that exhibits good foaming properties and foam stability, or an aerosol composition for spraying that enables the spraying of fine droplets with a wide spray pattern even at low internal pressure and reduces spray noise. Furthermore, the composition can be applied to products with a discharge mechanism that can discharge contents without using a propellant, and it is possible to provide a substantially surfactant-free discharge composition that exhibits good emulsion stability even when containing a large amount of oily components.

[0010] Unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a range of values ​​mean a range of values ​​including the lower and upper limits, which are the endpoints. When a range of values ​​is described in stages, the upper and lower limits of each range can be combined in any way.

[0011] The aerosol composition included in the present disclosure is an aerosol composition containing water, an oily component, and a water-soluble polymer, wherein the water-soluble polymer comprises at least one selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone, the content of the water-soluble polymer in the aerosol composition is 0.01% by mass to 2.5% by mass, the aerosol composition forms an emulsion, the average particle size of the emulsion droplets is 0.5 μm to 7.0 μm, and the aerosol composition is substantially free of a surfactant.

[0012] In the present disclosure, a surfactant refers to an amphipathic substance having within its molecule a hydrophilic portion that is compatible with water and a hydrophobic portion that is compatible with hydrophobic substances (i.e., a distinct hydrophilic head group and a hydrophobic tail group), and is adsorbed to the water-hydrophobic substance interface by the hydrophilic portion interacting with water and the hydrophobic portion interacting with the hydrophobic substance, thereby significantly reducing the interfacial tension at the water-hydrophobic substance interface and improving the dispersion stability of emulsions and suspensions.

[0013] Examples include sodium lauryl sulfate, stearyl trimethylammonium chloride, glyceryl stearate, polyglyceryl-10 diisostearate, polyoxyethylene coconut oil fatty acid glyceryl, sorbitan laurate, polysorbate 80, polyoxyethylene hydrogenated castor oil, polyoxyethylene lauryl ether, PEG 45 stearate, coconut oil fatty acid sodium methyl taurate, and lauryl dimethylaminoacetate betaine.

[0014] Other surfactants include the following: anionic surfactants, such as fatty acid salts, alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl ether carboxylates, alkyl sulfosuccinates, N-acylamino acid salts, N-acylmethylamino acid salts, acyl lactates, α-olefin sulfonates, α-sulfofatty acid methyl ester salts, alkyl sulfosuccinates, alkanesulfonates, alkenesulfonates, acyl isethionates, alkyl sulfate ester salts, alkylbenzenesulfonates, fatty acid alkanolamide sulfate esters, monoacylglycerol sulfate esters, alkyl phosphate ester salts, and polyoxyethylene alkylphenyl ether phosphate salts. Examples of cationic surfactants include fatty acid amidoamine salts, ester-containing tertiary amine salts, Arcobel-type tertiary amine salts, monoalkyl quaternary ammonium salts, dialkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, alkylamine salts, monoalkyl ether-type quaternary ammonium salts, alkylpyridinium salts, alkylisoquinolium salts, benzethonium chloride, and benzalkonium-type quaternary ammonium salts.

[0015] Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oil, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, monoglycerin fatty acid esters, diglycerin fatty acid esters, sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkyl polyglucosides, polyoxyalkylene sterol ethers, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl glyceryl ethers, and Pluronic surfactants.

[0016] Examples of amphoteric surfactants include glycine-type amphoteric surfactants, aminopropionic acid-type amphoteric surfactants, acetate betaine-type amphoteric surfactants, imidazoline-type amphoteric surfactants, alkyl betaines, amido betaines, sulfobetaines, alkylamine oxides, alkyldimethylamine oxides, amino acetate betaines, alkyldimethylamino acetate betaines, alkylcarboxymethylhydroxyethyl imidazolium betaines, alkylamidopropyl betaines, alkylhydroxysulfobetaines, alkyl sulfobetaines, amido sulfobetaines, and fatty acid amidopropyl betaines. Other examples include silicone surfactants such as polyether-modified silicones, amino-modified silicones, and polyglycerin-modified silicones; fluorine-based surfactants; and natural surfactants such as lecithin, saponin, bile acid, surfactin, spiculisporic acid, agaritic acid, long-chain dicarboxylic acids, rhamnolipids, trehalose lipids, succinoyl trehalose lipids, oligosaccharide fatty acid esters, and glycosyl lipids.

[0017] The aerosol composition is substantially free of surfactants. In the present disclosure, "substantially free of surfactants" means that no surfactants are intentionally added to the aerosol composition, and may contain trace amounts of surfactants that are inevitably mixed in during the production of the aerosol composition. For example, the aerosol composition may contain surfactants that are incidental to the formulated components and are present in the aerosol composition in amounts less than the amount at which the surfactant exerts its effect (so-called carryover components). For example, the content of surfactants in the aerosol composition is less than 0.10% by mass, preferably 0.05% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.001% by mass or less, and particularly preferably 0% by mass.

[0018] Each component used in the aerosol composition is described below. The aerosol composition contains an oily component. The aerosol composition also forms an emulsion. The aerosol composition is preferably an oil-in-water (O / W) emulsion in which an oil phase containing an oily component is dispersed in an aqueous phase containing water. The content of the oily component in the aerosol composition is preferably greater than 1.0% by mass and not greater than 35.0% by mass, more preferably greater than 1.0% by mass and not greater than 30.0% by mass, even more preferably greater than 1.0% by mass and not greater than 20.0% by mass, still more preferably 2.0 to 15.0% by mass, even more preferably 5.0 to 12.0% by mass, and particularly preferably 8.0 to 12.0% by mass. Within the above ranges, the dispersion stability of the droplets is improved.

[0019] The oil component is not particularly limited, and a wide variety of known water-insoluble (phase-separated from water) oil components can be used. "Water-insoluble" means, for example, that the solubility in 100 g of water at 25°C is 1.0 g or less. Specific examples include the following: Vegetable fats and oils such as apricot kernel oil, camellia oil, argan oil, soybean oil, olive oil, castor oil, coconut oil, palm oil, palm kernel oil, sesame oil, jojoba oil, cottonseed oil, rapeseed oil, linseed oil, rosehip oil, sunflower oil, essential oils, avocado oil, almond oil, rice bran oil, safflower oil, corn oil, grapeseed oil, palm oil, Argania spinosa kernel oil, wheat germ oil, rice germ oil, kukui nut oil, crambe abyssinica seed oil, hemp seed oil, peanut oil, camellia oil, evening primrose oil, pistachio oil, macadamia nut oil, meadowhoo oil, cocoa butter, shea butter, and Japan wax; animal fats and oils such as emu oil, horse oil, beef tallow, lard, mutton tallow, mink oil, egg yolk oil, carp fat, tuna fat, and menhaden fat; Hydrocarbon oils such as light isoparaffin, squalane, liquid paraffin, petrolatum, dodecane, tetradecane, ozokerite, microcrystalline wax, isoparaffin, ceresin, α-olefin oligomer, polybutene, hydrogenated polyisoparaffin, limonene, and turpentine; fatty acids (preferably having 6 to 40 carbon atoms, more preferably 12 to 30 carbon atoms) such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, isostearic acid, behenic acid, oxystearic acid, palmitoleic acid, linoleic acid, linolenic acid, ricinoleic acid, and undecylenic acid; higher alcohols such as caproyl alcohol, caprylyl alcohol, capryl alcohol, lauryl alcohol, isostearyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol, oleyl alcohol, hexyldecanol, octyldodecanol, decyltetradecanol, cholesterol, and phytosterol;Esters of straight-chain fatty acids and lower alcohols such as isopropyl myristate, isopropyl palmitate, and ethyl oleate; esters of straight-chain fatty acids and higher straight-chain alcohols such as hexyl laurate, myristyl myristate, decyl oleate, and stearyl stearate; esters of straight-chain fatty acids and branched alcohols such as octyldodecyl myristate, isostearyl palmitate, and ethylhexyl stearate; esters of branched fatty acids and lower alcohols such as ethyl isostearate and isopropyl isostearate; cetyl ethylhexanoate, isostearyl ester oils such as esters of branched fatty acids such as hexyl allyl acetate and straight-chain higher alcohols, esters of fatty acids such as PG dicaprylate, triethylhexanoin and tri(caprylic / capric acid)glyceryl and polyhydric alcohols, esters of branched fatty acids such as 2-octyldodecyl neopentanoate and isostearyl isostearate and branched alcohols, esters of hydroxycarboxylic acids such as lauryl lactate, trioctyldodecyl citrate and diisostearyl malate and alcohols, and esters of dibasic acids such as diisopropyl adipate and diethyl sebacate; Wax esters such as jojoba oil, jojoba butter, carnauba wax, candelilla wax, rice bran wax, shellac, lanolin, beeswax, montan wax, spermaceti, orange roughy oil, sugarcane wax, palm wax, insect wax, and wool fat; other oily ingredients include ethers of polyhydric alcohols and monohydric alcohols such as chimyl alcohol, batyl alcohol, and selachyl alcohol; batyl isostearate, batyl stearate; silicones such as alkyl-modified polysiloxane (dimethylpolysiloxane (dimethicone)), methylphenylpolysiloxane, and fluorine-modified polysiloxane; oily active ingredients such as ultraviolet absorbers (diethylaminohydroxybenzoylhexylbenzoate, ethylhexyl methoxycinnamate, polysilicone-15), DEET, icaridin, and fragrances;

[0020] From the viewpoints of emulsion stability and handling during preparation, the oily component is preferably liquid at 20° C. The oily component preferably contains at least one selected from the group consisting of hydrocarbon oils, fatty acids, higher alcohols, ester oils, wax esters, silicones, vegetable oils and animal oils and oily active ingredients, more preferably contains at least one selected from the group consisting of hydrocarbon oils, fatty acids, ester oils, silicones, vegetable oils and oily active ingredients, even more preferably contains at least one selected from the group consisting of fatty acids, ester oils, vegetable oils and oily active ingredients, even more preferably contains at least one selected from the group consisting of vegetable oils and oily active ingredients, and particularly preferably contains at least one selected from the group consisting of vegetable oils and oily active ingredients. Furthermore, the oily component preferably contains at least one selected from the group consisting of olive oil, jojoba oil, rosehip oil, sunflower oil, avocado oil, almond oil, grapeseed oil, macadamia nut oil, apricot kernel oil, and soybean oil, more preferably at least one selected from the group consisting of apricot kernel oil and soybean oil, and even more preferably apricot kernel oil. Another preferred embodiment is that the oily component contains at least one selected from the group consisting of vegetable oils and fats, and an oily active ingredient such as DEET or icaridin. Since it is possible to incorporate a large amount of oily component into the aerosol composition, it becomes easier to utilize the active ingredient.

[0021] In an aerosol composition, the average particle size of the emulsion droplets must be 0.5 μm to 7.0 μm. By keeping the size within this range, emulsion stability is improved, a good foam that is less likely to drip can be formed, and spray characteristics upon spraying are improved. If the average particle size of the droplets is less than 0.5 μm, the total surface area of ​​the droplets will be too large, resulting in reduced emulsion stability. Furthermore, an excessive amount of water-soluble polymer will be required to disperse the droplets. On the other hand, if the average particle size of the droplets exceeds 7.0 μm, emulsion stability will be reduced.

[0022] The average particle size of the emulsion droplets is preferably 0.6 μm to 5.0 μm, more preferably 0.7 μm to 4.0 μm, even more preferably 0.9 μm to 3.0 μm, and even more preferably 1.0 μm to 2.0 μm. When the aerosol composition is an oil-in-water emulsion, the average particle size of the droplets is the average particle size of the oil droplets due to the oil phase. The average particle size of the droplets can be controlled by the dispersion strength during emulsion production, the content of the water-soluble polymer, and the like.

[0023] The average particle size of emulsion droplets is measured using a laser diffraction / scattering particle size distribution analyzer (LA-960V2: Horiba, Ltd.) using a flow cell and purified water as the dispersion medium at 20°C.

[0024] The aerosol composition contains a water-soluble polymer. The water-soluble polymer comprises at least one selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. As represented by Stokes' equation, adding a water-soluble polymer to a sufficient degree to thicken the emulsion can increase the viscosity of the water and suppress the floating of oil droplets (creaming). However, thickening the emulsion reduces the spray characteristics when made into an aerosol product, as described above. Furthermore, it has been found that the addition of liquefied gas to many water-soluble polymers, such as hydroxypropyl methylcellulose, significantly reduces emulsion stability. In addition, it has been found that when a relatively large amount of oily components is added, the foaming properties and foam stability are insufficient, resulting in foam that tends to drip.

[0025] The inventors have conducted studies and found that adding a water-soluble polymer selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone to an emulsion containing an oily component and water but not containing a significant amount of surfactant can stably disperse the oily component. The inventors believe the mechanism behind this is as follows: Unlike conventional surfactants, these water-soluble polymers possess the property of being able to orient toward the oily component while remaining water-soluble. Therefore, the particle size of the oily component dispersion can be reduced, enabling stable dispersion even when a large amount of oily component is present in the aerosol composition. These water-soluble polymers are not considered to be conventional surfactants. Furthermore, it has been found that adding polyvinyl alcohol as a water-soluble polymer to an emulsion containing an oily component and water but not containing a surfactant can stably disperse the oily component even when a liquefied gas is added. Furthermore, it has been found that foams with good foaming properties and foam stability can be formed even when a large amount of oily component is present. The addition of a specific water-soluble polymer can form foams that are resistant to bubble breakage and dripping even when applied to a glass surface or the like, even without the addition of a surfactant.

[0026] Furthermore, with conventional surfactants, when the internal pressure decreases during use, the spray particle size tends to increase and the spray pattern tends to become smaller, but by using the above-mentioned water-soluble polymer, it has been found that the small particle size and wide spray pattern can be maintained well, which makes the sprayed mist softer and less irritating, and also reduces the spray noise of the aerosol product.

[0027] The water-soluble polymer includes at least one selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. Other known water-soluble polymers, such as those listed below, may be used in combination to the extent that the effects of the present disclosure are not impaired. These other water-soluble polymers are not considered to be conventional surfactants. Examples of such polymers include synthetic polymers such as carboxyvinyl polymer, polyacrylic acid amide, sodium polyacrylate, polyethyleneimine, and highly polymerized polyethylene glycol; natural polymers such as alginic acid, carrageenan, agar, guar gum, dextrin, locust bean gum, pectin, chitosan, xanthan gum, and cyclodextrin; and natural polymer derivatives such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, stearoxyhydroxypropyl methylcellulose, carboxymethyl cellulose, and cationized cellulose. When other water-soluble polymers are used in combination, the content of the other water-soluble polymers in the aerosol composition is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, and even more preferably 0.01% by mass or less.

[0028] The water-soluble polymer more preferably includes polyvinyl alcohol. Even more preferably, the water-soluble polymer is polyvinyl alcohol. It has been found that polyvinyl alcohol can exhibit dispersion stability of oily components regardless of molecular weight or degree of saponification.

[0029] The number average molecular weight Mn of the water-soluble polymer is preferably 400 or more, more preferably 500 or more, even more preferably 1000 or more, and still more preferably 2000 or more. On the other hand, the upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0030] When the water-soluble polymer contains polyvinyl alcohol, the degree of saponification of the polyvinyl alcohol, i.e., the ratio of hydroxyl groups to the total of hydroxyl groups and acetoxy groups in the polyvinyl alcohol [hydroxyl groups / (hydroxyl groups+acetoxy groups)×100] (mol %) is preferably 70 to 100 mol %, more preferably 80 to 98 mol %, even more preferably 82 to 97 mol %, and still more preferably 85 to 96 mol %.

[0031] The content of the water-soluble polymer in the aerosol composition is 0.01% by mass to 2.5% by mass. The content of the water-soluble polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more. On the other hand, the upper limit is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.2% by mass or less, even more preferably 1.0% by mass or less, and especially preferably 0.7% by mass or less. With this content, the oily component can be well dispersed in water with almost no thickening effect, and good spray characteristics of the aerosol product can be exhibited. Furthermore, a water-soluble polymer content of 2.5% by mass or less results in a better feel when used.

[0032] The content ratio (mass ratio) of the oily component to the water-soluble polymer in the air sole composition (oily component / water-soluble polymer) is preferably 5 / 1 to 120 / 1, more preferably 10 / 1 to 30 / 1, and even more preferably 15 / 1 to 25 / 1. By being in the above range, the dispersibility of the oily component becomes better.

[0033] The aerosol composition contains water. The content of water in the aerosol composition is preferably 50.0% by mass to 97.0% by mass, more preferably 75.0% by mass to 95.0% by mass, even more preferably 80.0% by mass to 92.0% by mass, and still more preferably 85.0% by mass to 91.0% by mass.

[0034] The viscosity of the aerosol composition at 25°C is preferably 0.5 mPa·s to 5.0 mPa·s, more preferably 0.7 mPa·s to 3.5 mPa·s, even more preferably 0.8 mPa·s to 2.8 mPa·s, and even more preferably 1.2 mPa·s to 2.5 mPa·s. The viscosity here is a value measured using a tuning fork vibration viscometer (RV-10000A: A&D Co., Ltd.) at an amplitude of 0.4 mm and at 25°C.

[0035] The aerosol composition may contain additives such as water-miscible active ingredients (which do not phase separate), fragrances, antioxidants, and preservatives, to the extent that the above-mentioned effects are not impaired. For example, alcohol may be contained. Specific examples include the following: lower alcohols (e.g., aliphatic monohydric alcohols having 1 to 3 carbon atoms such as ethanol); polyhydric alcohols (e.g., glycerin, propylene glycol (PG), dipropylene glycol (DPG), 1,3-butanediol, and other butanediols); pH adjusters (e.g., citric acid, lactic acid, triethanolamine, KOH, NaOH); rust inhibitors (e.g., ammonia water, ammonium benzoate, sodium nitrite); preservatives (e.g., parabens, phenoxyethanol); urea; minerals such as calcium, iron, and sodium; pigments; colorants; anti-inflammatory agents (e.g., dipotassium glycyrrhizinate); and ultraviolet absorbers (e.g., terephthalylidene dicamphorsulfonic acid).

[0036] Next, the aerosol product will be described. The present disclosure provides an aerosol product filled with the above-described aerosol composition and a propellant. Various known pressure-resistant containers can be used as the aerosol container for the aerosol product. Furthermore, the structure for attaching the valve device can be appropriately selected depending on the type of pressure-resistant container.

[0037] Aerosol products are produced by filling an aerosol composition into an aerosol container, i.e., a pressure-resistant container equipped with an aerosol valve (spray valve). For example, an aerosol composition is prepared, and the resulting aerosol composition and a propellant are filled into an aerosol container to produce the aerosol product. A so-called double container may be used, in which an inner container is provided inside the pressure-resistant container to separate the propellant from the aerosol composition.

[0038] When the aerosol composition is an aerosol composition for spraying, the mixing ratio of the aerosol composition to the propellant is preferably 90 / 10 to 10 / 90 by mass (aerosol composition / propellant) for the liquefied gas, and more preferably about 70 / 30 to 35 / 65. When the compressed gas is filled into the aerosol container, the pressure inside the container (gauge pressure) is preferably 0.3 MPa to 1.0 MPa at 25°C, and more preferably 0.6 MPa to 0.8 MPa. When the aerosol composition is an aerosol composition for foaming, the ratio of the aerosol composition to the liquefied gas is preferably 1 to 30 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the aerosol composition.

[0039] The discharge form of the aerosol product is not particularly limited, but when the aerosol composition is an aerosol composition for spraying, it is preferably in the form of a spray or mist. That is, the aerosol composition is preferably a spray composition that is sprayed in the form of a spray or mist. The discharge mechanism of the aerosol product is also not particularly limited, and a known actuator that can spray in the form of a spray or mist can be used. For example, an actuator that generates a swirling flow of the aerosol composition by passing the aerosol composition through a flow path inside the actuator, thereby discharging the aerosol composition in the form of a spray or mist. Furthermore, when the aerosol composition is an aerosol composition for foaming, it is preferable that the aerosol product be discharged in the form of a foam. To discharge the aerosol composition in the form of a foam, a known spout for forming foam or the like can be used for the aerosol product.

[0040] The propellant is not particularly limited, and liquefied gas or compressed gas may be used, or a combination of liquefied gas and compressed gas may be used. When the aerosol composition is an aerosol composition for spraying, the aerosol product preferably contains compressed gas. When the aerosol composition is an aerosol composition for foaming, the aerosol product preferably contains liquefied gas.

[0041] 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 gas, argon, helium, and compressed air, and more preferably at least one selected from the group consisting of carbon dioxide gas and nitrogen gas. The liquefied gas is not particularly limited, and any known gas that can be used in aerosol products can be used. Examples include hydrocarbons such as dimethyl ether (DME), liquefied petroleum gas (LPG), liquefied natural gas (LNG), and isopentane, and hydrofluoroolefins such as HFO-1233zd. LPG is preferred.

[0042] When the aerosol composition is an oil-in-water (O / W) emulsion, the method for producing the emulsion is not particularly limited, and known methods can be used, such as a method in which an aqueous phase and an oil phase are mixed together and then emulsified using a rotary homogenizer, a high-pressure homogenizer, an ultrasonic emulsifier, or the like.

[0043] The aerosol composition described above can also be applied to products having a discharge mechanism capable of discharging the contents without using a propellant, and the emulsion stability is good even when a large amount of oily components is contained. Therefore, a discharge composition that is substantially free of surfactants is also included in the present disclosure. The discharge composition can be applied to pump products. The pump container that stores the discharge composition is a container having a discharge mechanism that can discharge the contents without using a propellant, and is not particularly limited. The contents discharged from the pump product may form a foam, or may be in the form of a spray or mist.

[0044] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0045] Example A: Aerosol Compositions for Spraying <Examples A1 to A3 and Comparative Examples A1 to A3> Aerosol compositions of Examples A1 to A3 and Comparative Examples A1 to A3 were prepared by placing each raw material in a glass beaker according to the formulation (mass %) shown in Table 1. The numbers for the method of preparing the stock solution of each aerosol composition shown in Table 1 indicate that the procedure shown in Table 2 was followed. Table 1 shows the evaluation results of the viscosity of the aerosol compositions, the average particle size of the emulsion droplets, and the emulsion stability described below.

[0046]

[0047]

[0048] Examples A4 and A5 Aerosol compositions of Examples A4 and A5 were obtained using the formulations (mass %) and concentrate preparation methods shown in Tables 2 and 3. The viscosity of the aerosol compositions and the average particle size of the emulsion droplets are shown in Table 3. 5.00 parts by mass of the propellant (LPG or HFO-1233zd) shown in Table 3 was filled into a pressure-resistant container equipped with an injection valve device relative to 100.00 parts by mass of each obtained aerosol composition, and nitrogen gas was further added to adjust the internal pressure of the product to 0.75 MPa or 0.30 MPa. A button for compressed gas (inner diameter φ0.3 mm) was attached, and the aerosol products of Examples 4 and 5 were obtained. The obtained aerosol compositions and aerosol products were evaluated as described below. The results are shown in Table 3.

[0049] *After filling with liquefied gas, the internal pressure of the sample was adjusted to 0.75 MPa or 0.30 MPa with nitrogen.

[0050] Examples A6 to A27 and Comparative Examples A4 to A18 Aerosol compositions of Examples A6 to A27 and Comparative Examples A4 to A18 were prepared using the formulations (mass %) and concentrate preparation methods shown in Tables 2, 4 to 8.

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] The raw materials used in the table are as follows: (Oil-based ingredients) NIKKOL Apricot Kernel Oil: Apricot Kernel Oil (Nikko Chemicals Co., Ltd.) Soybean Oil: Soybean Oil (Fujifilm Wako Pure Chemical Industries, Ltd.) NIKKOL Olive Oil: Olive Fruit Oil (Nikko Chemicals Co., Ltd.) NIKKOL Jojoba Oil S: Jojoba Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Grapeseed Oil: Grape Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Sweet Almond Oil: Almond Oil (Nikko Chemicals Co., Ltd.) NIKKOL Macadamia Nut Oil: Macadamia Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Sunflower Oil: Sunflower Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Refined Avocado Oil: Avocado Oil (Nikko Chemicals Co., Ltd.) NIKKOL Rosehip oil: Rosa canina fruit oil (Nikko Chemicals Co., Ltd.) NIKKOL Sugar Squalane: Squalane (Nikko Chemicals Co., Ltd.) EXCEPARL IPM: Isopropyl myristate (Kao Corporation) DEET: DEET (Nippon Fine Chemicals Co., Ltd.) NIKKOL CIO: Cetyl ethylhexanoate (Nikko Chemicals Co., Ltd.) KF-96-100cs: Dimethicone (Shin-Etsu Chemical Co., Ltd.)

[0057] (Water-soluble polymers) EG-05C: Polyvinyl alcohol (Mn approx. 10200, saponification degree 86.5 to 89.0 mol%, Mitsubishi Chemical Corporation) JT-05: Polyvinyl alcohol (Mn approx. 23800, saponification degree 93.5 to 95.0 mol%, Japan Vinyl Acetate & Poval Co., Ltd.) PVP: Polyvinylpyrrolidone (Mn 29000, Fujifilm Wako Pure Chemical Industries, Ltd.) Sangelose 60L: Hydroxypropyl methylcellulose stearoxy ether (Daido Chemical Industry Co., Ltd.) Metrose 60SH-06: Hydroxypropyl methylcellulose (Shin-Etsu Chemical Co., Ltd.) SE600: Hydroxyethyl cellulose (Daicel Corporation) Lipidure-PMB: Polyquaternium-51, water (NOF Corporation) Lipidure-NA: Polyquaternium-61, glycerin, BG, cocoyl arginine ethyl PCA, water (NOF Corporation) Carbopol 980: Carboxyvinyl polymer (Lubrizol Corporation)

[0058] (Surfactants) EMAL 10PT: Sodium lauryl sulfate (Kao Corporation) QUARTAMIN 86W: Stearyl trimethyl ammonium chloride, water (Kao Corporation) NIKKOL TO-10V: Polysorbate 80 (Nikko Chemicals Co., Ltd.) (Additives) Triethanolamine: Triethanolamine (Ando Parachemie Co., Ltd.) 1,3-Butylene glycol-P: 1,3 butylene glycol (KH Neochem Co., Ltd.)

[0059] The resulting aerosol compositions of Examples A6 to A27 and Comparative Examples A4 to A18 and a propellant (nitrogen gas) were filled into pressure-resistant containers equipped with a spray valve device, and the internal pressure of the product was adjusted to 0.75 MPa or 0.30 MPa. A button for compressed gas (inner diameter φ0.3 mm) was attached, and the aerosol products of Examples A6 to A27 and Comparative Examples A4 to A18 were obtained. The resulting aerosol compositions and aerosol products were evaluated as follows. The results are shown in Tables 4 to 8. The viscosities of the aerosol compositions are also shown in Tables 4 to 8.

[0060] (1) Average particle size of oil droplets The average particle size of oil droplets in each aerosol composition was measured by the method described above and evaluated according to the following criteria: (Evaluation criteria) A: Average particle size is 1.0 μm or more and less than 2.0 μm B+: Average particle size is 0.7 μm or more and less than 1.0 μm, or 2.0 μm or more and less than 4.0 μm B: Average particle size is 0.5 μm or more and less than 0.7 μm, or 4.0 μm or more and less than 7.0 μm C+: Average particle size is 0.2 μm or more and less than 0.5 μm, or more than 7.0 μm and less than 10.0 μm C: Average particle size is less than 0.2 μm, or 10.0 μm or more

[0061] (2) Emulsification Stability The aerosol composition was collected in a 50 ml vial and stored in a thermostatic chamber at 40°C for 40 days as an accelerated test, and the state of the aerosol composition after storage was evaluated according to the following criteria: (Evaluation criteria) A: No demulsification B: Separation occurred but re-emulsification was achieved by shaking C: Separation occurred and re-emulsification was not achieved even after shaking

[0062] (3) Spray particle size Using each aerosol product with the internal pressure adjusted to 0.75 MPa, the spray particle size (cumulative 50% particle size on a volume basis (DV(50))) was measured using a laser diffraction particle size distribution analyzer (Spraytec: Malvarn). The spray distance was 15 cm and the spray time was 3 seconds. (Evaluation criteria) A: DV(50) value is 50.0 μm or more and less than 70.0 μm B+: DV(50) value is 70.0 μm or more and less than 75.0 μm B: DV(50) value is 75.0 μm or more and less than 80.0 μm C+: DV(50) value is 80.0 μm or more and less than 100.0 μm C: DV(50) value is less than 50.0 μm or 100.0 μm or more

[0063] In addition, similar evaluations were performed using each aerosol product with the internal pressure of the product adjusted to 0.30 MPa. (Evaluation criteria) A: DV(50) value is 50.0 μm or more and less than 85.0 μm B+: DV(50) value is 85.0 μm or more and less than 90.0 μm B: DV(50) value is 90.0 μm or more and less than 95.0 μm C+: DV(50) value is 95.0 μm or more and less than 100.0 μm C: DV(50) value is less than 50.0 μm or 100.0 μm or more

[0064] (4) Spray Pattern Each aerosol product with an internal pressure of 0.75 MPa and 0.30 MPa was sprayed onto a glass surface from a distance of 15 cm for 1 second, and the diameter of the spray pattern was measured and evaluated according to the following criteria. The spray was positioned horizontally to the glass surface, and the spray was performed perpendicular to the glass surface. The average value of three tests was used. (Evaluation criteria) A: 250 mm or more and less than 300 mm B+: 200 mm or more and less than 250 mm B: 150 mm or more and less than 200 mm C+: 100 mm or more and less than 150 mm C: Less than 100 mm, or 300 mm or more

[0065] (5) Spray noise Using a standard sound level meter (NL-42A: Rion Co., Ltd.), the contents of each aerosol product with an internal pressure of 0.75 MPa were sprayed for 5 seconds, and the equivalent noise level measured by a sound detector placed 4 cm away from the aerosol product was evaluated. The average value of three tests was used. (Evaluation criteria) A: Less than 60.0 dB B+: 60.0 dB or more and less than 65.0 dB B: 65.0 dB or more and less than 70.0 dB C+: 70.0 dB or more and less than 75.0 dB C: 75.0 dB or more

[0066] Example A28 An aerosol spray emulsion was prepared according to the following procedure. The aerosol composition of Example A28 was obtained using the formulation (mass%) and concentrate preparation method shown in Tables 2 and 9. The obtained aerosol composition and propellant (nitrogen gas) were filled into a pressure-resistant container equipped with an injection valve device, and the internal pressure of the product was adjusted to 0.75 MPa or 0.30 MPa. A button for compressed gas (inner diameter φ0.3 mm) was attached, and the aerosol product of Example A28 was obtained. The obtained aerosol composition and aerosol product were subjected to the above-described evaluations. The results are shown in Table 9.

[0067]

[0068] Example A29 An aerosol spray of sunscreen was prepared according to the following procedure. The aerosol composition of Example A29 was obtained using the formulation (mass%) and concentrate preparation method shown in Tables 2 and 10. The obtained aerosol composition and propellant (nitrogen gas) were filled into a pressure-resistant container equipped with an injection valve device, and the internal pressure of the product was adjusted to 0.75 MPa or 0.30 MPa. A button for compressed gas (inner diameter φ0.3 mm) was attached, and the aerosol product of Example A29 was obtained. The obtained aerosol composition and aerosol product were subjected to the above-described evaluations. The results are shown in Table 10.

[0069]

[0070] In addition to the above, the materials used were manufactured by the following manufacturers: TDSA aqueous solution (Shinsung Materials), Uvinul A plus B (BASF Japan Ltd.), Parsol SLX (DSM Co., Ltd.).

[0071] Example B: Foam Aerosol Compositions <Examples B1 to B25 and Comparative Examples B1 to B14> Each raw material was collected in a glass beaker according to the formulation (mass%) shown in Tables 11 to 15 and uniformly dispersed using either of the following stock solution preparation methods 1 or 2 to prepare the aerosol compositions of Examples B1 to B25 and Comparative Examples B1 to B14. The stock solution preparation methods employed in each Example and Comparative Example are shown in Tables 11 to 15. The average particle diameters of the emulsion droplets and the evaluation results described below are also shown in Tables 11 to 15.

[0072] (Method for preparing stock solution) 1: An emulsion was prepared by stirring at 10,000 rpm for 15 minutes using a rotary homogenizer (Homomixer MARK II 2.5 type) manufactured by Primix Corporation. 2: An emulsion was prepared by irradiating with ultrasonic waves at 28.5 kHz for 5 minutes using an ultrasonic welding machine (SONOPET JII430SA) manufactured by Seidensha Kogyo Co., Ltd.

[0073] Furthermore, a pressure-resistant container equipped with an injection valve device was filled with the propellant (LPG, a mixture of dimethyl ether (DME) and LPG, or HFO-1234ze) shown in Tables 12 to 15 in an amount of parts by mass per 100 parts by mass of each of the obtained aerosol compositions, to obtain aerosol products of Examples B4 to B25 and aerosol products of Comparative Examples B4 to B14. A foam spout (02-1211-50, Japan Precision Valve Co., Ltd.) was used as the discharge mechanism. The obtained aerosol compositions and aerosol products were used to perform the evaluations described below. The results are shown in Tables 11 to 15.

[0074]

[0075] *After filling with liquefied gas, the internal pressure of the sample was adjusted to 0.6 MPa with carbon dioxide gas.

[0076]

[0077]

[0078]

[0079] The raw materials used in the table are as follows: (Oil-based ingredients) NIKKOL Apricot Kernel Oil: Apricot Kernel Oil (Nikko Chemicals Co., Ltd.) NIKKOL Olive Oil: Olive Fruit Oil (Nikko Chemicals Co., Ltd.) NIKKOL Jojoba Oil S: Jojoba Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Grapeseed Oil: Grape Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Sweet Almond Oil: Almond Oil (Nikko Chemicals Co., Ltd.) NIKKOL Macadamia Nut Oil: Macadamia Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Sunflower Oil: Sunflower Seed Oil (Nikko Chemicals Co., Ltd.) NIKKOL Refined Avocado Oil: Avocado Oil (Nikko Chemicals Co., Ltd.) NIKKOL Rosehip Oil: Rosa Canina Fruit Oil (Nikko Chemicals Co., Ltd.) NIKKOL Sugar Squalane: Squalane (Nikko Chemicals Co., Ltd.) EXCEPARL IPM: Isopropyl myristate (Kao Corporation) NIKKOL CIO: Cetyl ethylhexanoate (Nikko Chemicals Co., Ltd.) NIKKOL TOC: Tri-2-ethylhexyl citrate (Nikko Chemicals Co., Ltd.) KF-96-50cs: Dimethicone (Shin-Etsu Chemical Co., Ltd.)

[0080] (Water-soluble polymers) EG-40C: Polyvinyl alcohol (Mn approx. 39,700, saponification degree 86.5 to 89.0 mol%, Mitsubishi Chemical Corporation) EG-05C: Polyvinyl alcohol (Mn approx. 10,200, saponification degree 86.5 to 89.0 mol%, Mitsubishi Chemical Corporation) Sangelose 60L: Hydroxypropyl methylcellulose stearoxy ether (Daido Chemical Industry Co., Ltd.) Metrose 60SH-06: Hydroxypropyl methylcellulose (Shin-Etsu Chemical Co., Ltd.) Pemulen TR-2: (Acrylates / Alkyl acrylate (C10-30)) Crosspolymer (Lubrizol Corporation) Inutec SL1: Concentrated glycerin, inulin lauryl carbamate (Nippon SiberHegner Co., Ltd.) SE600: Hydroxyethyl cellulose HEC Daicel SE600 (Daicel Miraize Co., Ltd.)

[0081] (Surfactants) NIKKOL TO-10V: Polysorbate 80 (Nikko Chemicals Co., Ltd.) NIKKOL Decaglyn 1-L: Polyglyceryl-10 laurate (Nikko Chemicals Co., Ltd.) NIKKOL BB-20: Beheneth-20 (Nikko Chemicals Co., Ltd.) Triethanolamine: Triethanolamine (Ando Parachemie Co., Ltd.)

[0082] (1) Average particle size of oil droplets The average particle size of oil droplets was measured using a laser diffraction / scattering particle size distribution measuring device (LA-960V2: Horiba, Ltd.) using the method described above, and evaluated according to the following criteria. (Evaluation criteria) A: Average particle size is 1.0 μm or more and less than 2.0 μm B+: Average particle size is 0.7 μm or more and less than 1.0 μm, and 2.0 μm or more and less than 4.0 μm B: Average particle size is 0.5 μm or more and less than 0.7 μm, and 4.0 μm or more and less than 7.0 μm C+: Average particle size is 0.2 μm or more and less than 0.5 μm, and 7.0 μm or more and less than 10.0 μm C: Average particle size is less than 0.2 μm, and 10.0 μm or more

[0083] (2) Oil droplet stability Each aerosol product was stored at 45°C for 2 weeks, and the particle size of the emulsion droplets was measured before and after storage. ａｖｇ１ is the initial average oil droplet diameter, D ａｖｇ２ The average oil droplet diameter of the sample after storage for 2 weeks was calculated using the following formula and evaluated according to the following criteria. (Evaluation criteria) A: Oil droplet stability is less than 0.075 B+: Oil droplet stability is 0.075 or more and less than 0.125 B: Oil droplet stability is 0.125 or more and less than 0.250 C+: Oil droplet stability is 0.250 or more and less than 0.500 C: Oil droplet stability is 0.500 or more

[0084] (3) Stability of the ejected liquid Each aerosol product was stored at 45°C for two weeks, and after two weeks of storage, a sample of the content liquid was ejected, the foam was left to stand for a certain period of time, and the content after the foam had disappeared was observed and visually evaluated according to the following criteria. (Evaluation criteria) A: No oil floating B: Almost no oil floating C: Oil floating is clearly observed

[0085] (4) Appearance of Foam 0.5 g of foam was discharged onto a glass substrate, and the appearance of the foam was observed and visually evaluated according to the following criteria: (Evaluation criteria) A: Fine foam B: Slightly fine foam C: Coarse foam

[0086] (5) Foam Stability 0.5 g of foam was dispensed onto a glass substrate and stirred 10 times with a finger. The appearance of the foam was observed and visually evaluated according to the following criteria: (Evaluation criteria) A: The foam was stable and not crushed. B: The foam was slightly crushed, but remained foamy. C: The foam was crushed and most of the foam disappeared.

[0087] (6) Ease of Dripping of Foam 0.5 g of foam was dispensed onto the edge of a 10 cm x 10 cm glass substrate. The glass substrate was held upright, and the time the foam was retained on the glass substrate was evaluated according to the following criteria: (Evaluation criteria) A: 3 minutes or more B+: 1 minute or more but less than 3 minutes B: 30 seconds or more but less than 1 minute C+: 15 seconds or more but less than 30 seconds C: Less than 15 seconds

[0088] Reference Examples B1 to B3 Aerosol compositions of Reference Examples were prepared in the same manner as in Example B1, using the formulations (mass %) shown in Tables 16 to 18. Furthermore, 5 parts by mass of propellant (LPG) per 100 parts by mass of each obtained aerosol composition was filled into a pressure-resistant container equipped with an injection valve device to obtain aerosol products of Reference Example B1 (refreshing emulsion formulation), Reference Example B2 (moist emulsion formulation), and Reference Example B3 (sunscreen agent). A foam spout (02-1211-50, Japan Precision Valve Co., Ltd.) was used as the discharge mechanism. The above-described evaluations were performed using the obtained aerosol compositions and aerosol products. The results are shown in Tables 16 to 18.

[0089]

[0090]

[0091]

[0092] Example C: Composition for Discharge <Example C1 and Comparative Example C1> The compositions of Example C1 and Comparative Example C1 were prepared by collecting the raw materials in a glass beaker according to the formulation (mass%) shown in Table 19. The numbers for the method of preparing the concentrate of the composition described in Example C1 in Table 19 indicate that the procedure described in Table 2 for Example A was followed. The evaluation results for the viscosity of the composition, the average particle size of the emulsion droplets, and the emulsion stability are shown in Table 19. The emulsion stability was evaluated in the same manner as in Example A. The compositions prepared in Example C1 and Comparative Example C1 were filled into a commercially available pump mist container (trigger-type spray head, capacity 200 mL), and the spray pattern was evaluated. Specifically, the compositions were sprayed onto a glass surface from a distance of 15 cm, and the diameter of the spray pattern was measured. The measurement results are shown in Table 19.

[0093]

[0094] The raw materials used in the table are as follows: (Oil-based components) NIKKOL olive oil: olive fruit oil (Nikko Chemicals Co., Ltd.) Icaridin: 1-(1-methylpropoxycarbonyl)-2-(2-hydroxyethyl)piperidine (Saltigo) (Water-soluble polymer) EG-05C: polyvinyl alcohol (Mn approximately 10200, saponification degree 86.5 to 89.0 mol%, Mitsubishi Chemical Corporation) From Example C1 and Comparative Example C1, it can be seen that the composition according to this embodiment provides a stable emulsion even when discharged by a pump, and exhibits a good spray pattern.

[0095] Although the present invention will be described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Claims

DEPCT6808 / 11 / 25671. Aerosol composition consisting of water, oil components, and water-soluble polymers, of which at least one selected water-soluble polymer is included from the group of polyvinyl alcohol and polyvinylpyrrolidone. The amount of water-soluble polymer in the aerosol composition is 0.01% by mass to 2.5% by mass. The aerosol composition forms an emulsion; the average diameter of the emulsion droplets is 0.5 µm to 7.0 µm.

1. Not containing a significant surfactant.

2. Aerosol composition under claim 1 where a water-soluble polymer is incorporated with polyvinyl alcohol, and the aerosol composition is used for foam formation.

3. Aerosol composition under claim 1 where the aerosol composition is the composition for spraying.

4. Aerosol composition under any one of claims 1 through 3 where the emulsion is an oil-in-water emulsion in which the oil phase, containing oil components, is dispersed in an aqueous phase, containing water. 5.Aerosol composition under any of Claims 1 through 4 where the oil component is liquid at 20°C and the oil component contains at least one of the following selected types from the group of hydrocarbon oils, fatty acids, high molecular weight alcohols, ester oils, ester waxes, silicones, vegetable oils and fats, animal oils and fats, and oil-based active ingredients.

6. Aerosol composition under Claim 5 where the oil component contains at least one of the following selected types from the group of hydrocarbon oils. Carbon, fatty acids, oil esters, silicones, vegetable oils and fats, and oil-based active ingredients.

7. Aerosol compositions under any of the claims 1 through 6 where the amount of oil components in the aerosol composition is greater than 1.0% by mass and 35.0% by mass or less.

8. Aerosol compositions under claim 3 where the viscosity of the aerosol composition at 25°C is 0.5 millipascals•s to 5.0 millipascals•s.

9. Aerosol compositions under claim 4 where the amount of water-soluble polymers in the aerosol composition is 0.0.05% by mass to 1.2% by mass.

10. Aerosol products in which the aerosol product is packed with aerosol components and propellants and the aerosol components are aerosol components according to one of the claims 1 to 9.

11. Release components which consist of water, oil components, and water-soluble polymers in which the water-soluble polymers consist of at least one type selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone; the amount of water-soluble polymer in the aerosol components is 0.01% by mass to 2.5% by mass; the aerosol components form an emulsion, the average particle diameter of the small droplets of the emulsion is 0.5 µm to 7.0 µm, and the aerosol components do not consist of a significant surfactant;