JP7312033B2 - Aerosol composition - Google Patents

Description

The present invention relates to aerosol compositions. More particularly, the present invention relates to aerosol compositions capable of readily emulsifying an aqueous concentrate and a highly formulated liquefied gas.

Conventionally, aerosol compositions have been developed in which an aqueous stock solution and a liquefied gas are emulsified. US Pat. No. 5,300,002 discloses a foaming aerosol composition comprising a liquid concentrate containing cellulose nanofibers and a propellant. The aerosol composition of Patent Document 1 is characterized in that it forms dense and uniform bubbles, the formed bubbles have a certain elasticity, and the formed bubbles can be easily spread over an object.

JP 2017-222610 A

However, the foaming aerosol composition described in Patent Document 1 does not emulsify many liquefied gases with the aqueous stock solution.

The present invention has been made in view of such conventional problems, and an object thereof is to provide an aerosol composition that can easily emulsify an aqueous stock solution and a highly-blended liquefied gas.

The present inventors found that by blending cellulose nanofibers at such a low concentration that the thickening effect hardly occurs, it is possible to easily emulsify an aqueous stock solution and a highly blended liquefied gas. In addition, the present inventors have found that even if the aerosol composition separates, it can be re-emulsified very easily by lightly shaking it, and have completed the present invention. That is, the aerosol composition of the present invention that solves the above problems mainly includes the following constitutions.

(1) An aerosol composition in which an aqueous concentrate and a liquefied gas are emulsified, the aqueous concentrate contains cellulose nanofibers and a surfactant, and the blending ratio of the aqueous concentrate and the liquefied gas is 60. /40 to 20/80 (mass ratio), and the content of the cellulose nanofibers is 0.25% by mass or less in the aqueous stock solution.

According to such a configuration, the aerosol composition contains a small amount of cellulose nanofibers in the aqueous concentrate. As a result, even though the aerosol composition contains a large amount of liquefied gas, it is possible to easily emulsify the aqueous undiluted solution and liquefied gas by shaking lightly.

(2) The aerosol composition according to (1), wherein the content of the cellulose nanofibers is 0.001 to 0.20% by mass in the aqueous stock solution.

According to such a configuration, the aqueous undiluted solution is in a low-viscosity state in which the thickening action of the cellulose nanofibers is difficult to develop, and the aerosol composition is light even though it contains a large amount of liquefied gas. By shaking, the aqueous stock solution and the liquefied gas can be emulsified more easily.

(3) Regarding the content of the cellulose nanofibers, M1 is the content of the cellulose nanofibers, M0 is the content when the content is zero, and V1 and V0 are the viscosities of the aqueous stock solution at each content. , the ratio (ΔV/ΔM) of the viscosity increase amount (ΔV=V1−V0) of the aqueous stock solution to the difference in the content of the cellulose nanofibers (ΔM=M1−M0) is −500 to 500. , (1) or (2).

According to such a configuration, the content of cellulose nanofibers satisfies the above ratio, so that the aqueous stock solution is in a state of low viscosity in which the thickening action of cellulose nanofibers is particularly difficult to manifest, and is shaken lightly. By doing so, the aqueous stock solution and the liquefied gas can be easily emulsified.

(4) The aerosol composition according to any one of (1) to (3), further comprising an alcohol, wherein the content of the alcohol is 1 to 50% by mass.

According to such a configuration, it is easy to adjust the viscosity increase of the aqueous concentrate, and the aerosol composition can easily emulsify the aqueous concentrate and the liquefied gas by gently shaking the aerosol composition.

According to the present invention, it is possible to provide an aerosol composition that can easily emulsify an aqueous undiluted solution and a highly-blended liquefied gas.

<Aerosol composition>
The aerosol composition of one embodiment of the present invention is an aerosol composition in which an aqueous stock solution and a liquefied gas are emulsified. The aqueous stock solution contains cellulose nanofibers and a surfactant. The blending ratio of the aqueous stock solution and the liquefied gas is 60/40 to 20/80 (mass ratio), and the content of cellulose nanofibers is 0.25% by mass or less in the aqueous stock solution. Each of these will be described below.

(Aqueous undiluted solution)
The aqueous concentrate contains cellulose nanofibers and a surfactant.

- Cellulose nanofiber Cellulose nanofiber is blended for the purpose of facilitating emulsification of the aqueous stock solution and liquefied gas and stabilizing the emulsion. In addition, cellulose nanofibers are blended in order to retain the liquefied gas in the ejected material for a long time when the aerosol composition is ejected to the outside. As a result, the jetted aerosol composition can easily obtain the effect of the liquefied gas.

In this embodiment, the cellulose nanofibers are fine fibers of unmodified cellulose or chemically modified cellulose. Cellulose nanofibers usually have an average fiber diameter of about 3 to 500 nm. Cellulose nanofibers usually have an average aspect ratio of 10 or more. The upper limit of the aspect ratio is not particularly limited. For example, the upper limit of the aspect ratio is 1000 or less. The average fiber diameter and average fiber length of cellulose nanofibers are measured by, for example, preparing a 0.001% by mass aqueous dispersion of cellulose nanofibers, thinly spreading this diluted dispersion on a mica sample table, and heating at 50°C. A sample for observation is prepared by drying, and the cross-sectional height of the shape image observed with an atomic force microscope (AFM) is measured to calculate the number average fiber diameter or fiber length. Also, the average aspect ratio can be calculated by the following formula:
Average aspect ratio = average fiber length/average fiber diameter

The cellulose nanofibers in the present embodiment can be obtained by defibrating a cellulose raw material, chemically modifying the cellulose raw material and then defibrating it, or chemically modifying the cellulose raw material after defibrating it. Cellulose nanofibers may be cellulose nanofibers produced by a known method, or may be commercially available products.

The content (solid content) of cellulose nanofibers may be 0.25% by mass or less in the aqueous stock solution. The cellulose nanofiber content (solid content) is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, in the aqueous stock solution. In addition, the content (solid content) of cellulose nanofibers is preferably 0.20% by mass or less, more preferably 0.17% by mass or less, in the aqueous stock solution. When the content of the cellulose nanofibers is within the above range, the aerosol composition can easily obtain the effect of promoting emulsification of the aqueous stock solution and the liquefied gas, and the viscosity of the aqueous stock solution does not become too high.

In the aerosol composition of the present embodiment, the content of cellulose nanofibers in the aqueous stock solution should be 0.25% by mass or less, which is a small amount. In addition, as the content of cellulose nanofibers exceeds 0.25% by mass and increases, the thickening effect of cellulose nanofibers is likely to occur, and the viscosity of the aqueous stock solution increases rapidly, making it easy to emulsify with liquefied gas. It tends to be less effective. Also, once the aqueous stock solution and the liquefied gas are separated, they tend to be difficult for the consumer to re-emulsify. Thickening agents, such as other polysaccharides (e.g., hydroxyethylcellulose), are typically added to concentrations that produce a thickening effect, increasing the viscosity of the aqueous stock solution and allowing the liquefied gas to remain in the exudate for a longer period of time. making it easier to obtain On the other hand, as described above, the aerosol composition of the present embodiment has a sufficient emulsification effect without increasing the viscosity of the aqueous stock solution by blending cellulose nanofibers at such a low concentration that the thickening effect is hardly exhibited. can get. In addition, when the aerosol composition contains a large amount of cellulose nanofibers exceeding 0.25% by mass to increase the viscosity of the aqueous stock solution, the emulsification effect tends to decrease. Such a tendency is markedly different from the case of containing other conventional polysaccharides.

-Surfactant Surfactant is blended for the purpose of facilitating emulsification of the aqueous stock solution and liquefied gas, stabilizing the emulsion, and the like.

Surfactants are not particularly limited. By way of example, surfactants include polyoxyethylene polyoxypropylene alkyl ethers such as POE-POP cetyl ether, POE-POP decyltetradecyl ether, POE sorbitan monococoate, POE sorbitan monostearate, POE monooleate. Polyoxyethylene sorbitan fatty acid esters such as sorbitan, polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate, polyoxyethylene hydrogenated castor oils such as POE hydrogenated castor oil, POE cetyl ether, POE stearyl ether, POE oleyl ether, POE Polyoxyethylene alkyl ethers such as lauryl ether, POE behenyl ether, POE octyldodecyl ether, POE isocetyl ether, POE isostearyl ether, polyethylene glycol fatty acid esters such as polyethylene glycol monostearate, hexaglyceryl monolaurate, hexamonomyristate Glyceryl, Pentaglyceryl Monolaurate, Pentaglyceryl Monomyristate, Pentaglyceryl Monooleate, Pentaglyceryl Monostearate, Decaglyceryl Monolaurate, Decaglyceryl Monomyristate, Decaglyceryl Monostearate, Decaglyceryl Monoisostearate, Monooleic Acid Decaglyceryl, polyglycerin fatty acid esters such as decaglyceryl monolinoleate, polyoxyethylene glycerin fatty acid esters such as POE glyceryl monooleate, POE sorbitan coconut oil fatty acid, POE sorbitan monostearate, POE sorbitan monoisostearate, monooleic acid Polyoxyethylene sorbitan fatty acid esters such as POE sorbitan, polyoxyethylene sorbit fatty acid esters such as POE sorbitol monolaurate, POE sorbitol tetrastearate, POE sorbit tetraoleate, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, laurin Nonionic surfactants such as acid diethanolamide, fatty acid alkanolamide such as lauric acid monoisopropanolamide; saponified products of fatty acids such as myristic acid and stearic acid and alkalis such as triethanolamine and potassium, potassium lauryl phosphate, lauryl Alkyl phosphates such as sodium phosphate, polyoxyethylene alkyl ether phosphates such as POE sodium lauryl ether phosphate, alkyls such as ammonium lauryl sulfate, potassium lauryl sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, and sodium cetyl sulfate Sulfates, polyoxyethylene alkyl ether sulfates such as POE sodium lauryl ether sulfate, POE lauryl ether sulfate triethanolamine, POE alkyl ether sulfate sodium, POE alkyl ether sulfate triethanolamine, POE lauryl ether potassium acetate, POE lauryl ether acetic acid sodium, alkyl ether carboxylates such as potassium POE tridecyl ether acetate, sodium POE tridecyl ether acetate, sodium lauryl sulfoacetate, sodium tetradecene sulfonate, dioctyl sodium sulfosuccinate, sodium dialkyl sulfosuccinate, sodium alkyl naphthalene sulfonate, Anionic surfactants such as sodium alkyldiphenyl ether disulfonate, sodium alkanesulfonate, dodecylbenzenesulfonic acid, sulfonates such as sodium dodecylbenzenesulfonate; N-coconut fatty acid acyl-L-glutamic acid triethanolamine, N- Potassium Cocoate Acyl-L-Glutamate, Sodium N-Cocoate Acyl-L-Glutamate, Triethanolamine N-Lauroyl-L-Glutamate, Potassium N-Lauroyl-L-Glutamate, Sodium N-Lauroyl-L-Glutamate , N-acyl glutamates such as potassium N-myristoyl-L-glutamate, sodium N-myristoyl-L-glutamate, sodium N-stearoyl-L-glutamate, potassium N-cocoate acylglycine, N-cocoate acyl N-acylglycine salts such as sodium glycinate, N-acylalanine salts such as N-coconut fatty acid acyl-DL-alanine triethanolamine; amino acid type anionic surfactants such as acylalanine salts such as sodium lauroylmethylalanine; Silicone surfactants such as polyoxyethylene/methylpolysiloxane copolymer, polyoxypropylene/methylpolysiloxane copolymer, poly(oxyethylene/oxypropylene)/methylpolysiloxane copolymer; betaine lauryldimethylaminoacetate (lauryl betaine), stearyl betaine, lauramidopropyl betaine, lauryl hydroxysulfobetaine, stearyldimethylaminoacetate betaine, dodecylaminomethyldimethylsulfopropyl betaine, octadecylaminomethyldimethylsulfopropyl betaine; , cocamidopropyl dimethylamino acetate betaine (cocamidopropyl betaine), fatty acid amidopropyl betaine such as cocamidopropyl hydroxysultaine; 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium Alkyl imidazole type such as betaine; amino acid type such as sodium lauroyl glutamate, potassium lauroyl glutamate, lauroyl methyl-β-alanine; amphoteric surfactant such as amine oxide type such as lauryldimethylamine N-oxide, oleyldimethylamine N-oxide. etc.

The content of the surfactant is not particularly limited. For example, the surfactant content in the aqueous stock solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more. Moreover, the content of the surfactant is preferably 15% by mass or less, more preferably 10% by mass or less, in the aqueous stock solution. When the content of the surfactant is within the above range, the aerosol composition is easy to emulsify the aqueous stock solution and the liquefied gas, and the surfactant is less likely to remain on the adhered surface after being sprayed, resulting in excellent use. you get a feeling.

• Other Ingredients Aqueous concentrates contain water as the main solvent. Water dissolves or disperses the cellulose nanofibers and the surfactant, and emulsifies with the liquefied gas. Water is, for example, purified water, ion-exchanged water, physiological saline, deep sea water, or the like.

The content of water is not particularly limited. For example, the content of water in the aqueous stock solution is preferably 45% by mass or more, more preferably 50% by mass or more. Also, the content of water is preferably 99% by mass or less, more preferably 98% by mass or less, in the aqueous stock solution. When the water content is within the above range, the aerosol composition can easily emulsify the aqueous stock solution and the liquefied gas, and can easily incorporate a surfactant.

The aqueous stock solution may contain active ingredients, alcohols, oils, powders, etc., in addition to the above.

Active ingredients are not particularly limited. For example, active ingredients include cooling agents such as l-menthol and camphor, antiperspirants such as chlorohydroxyaluminum and isopropylmethylphenol, zinc oxide, allantoin hydroxyaluminum, astringents such as citric acid, allantoin, and glycyrrhetinic acid. , anti-inflammatory agents such as dipotassium glycyrrhizinate and azulene, antipruritic agents such as crotamiton and d-camphor, anti-inflammatory analgesics such as methyl salicylate, indomethacin, piroxicam, felbinac and ketoprofen, oxiconazole, clotrimazole, sulconazole, bifonazole, antifungal agents such as miconazole, isoconazole, econazole, tioconazole, butenafine and salts thereof such as hydrochlorides, nitrates and acetates; local anesthetics such as dibucaine hydrochloride, tetracaine hydrochloride, lidocaine, lidocaine hydrochloride; Antihistamines such as chlorpheniramine maleate, bactericidal agents such as paraoxybenzoic acid esters, sodium benzoate, phenoxyethanol, benzalkonium chloride, benzethonium chloride, chlorhexidine chloride, collagen, xylitol, sorbitol, hyaluronic acid, caroninic acid, lactic acid Humectants such as sodium, dl-pyrrolidone carboxylate, keratin, lecithin, and urea; deodorants such as lauric acid methacrylate, methyl benzoate, methyl phenylacetate, geranyl crotolate, acetophenone myristate, benzyl acetate, and benzyl propionate; , N,N-diethyl-m-toluamide (deet), caprylic acid diethylamide, hexyl diethylaminohydroxybenzoylbenzoate, 2-ethylhexyl paramethoxycinnamate, ethylhexyl triazone, oxybenzone, hydroxybenzophenone sulfonic acid, UV absorbers such as sodium dihydroxybenzophenone sulfonate and dihydroxybenzophenone, UV scattering agents such as zinc oxide and titanium oxide, retinol, retinol acetate, retinol palmitate, calcium pantothenate, panthenol, ascorbic acid, sodium ascorbate, dl- Vitamins such as α-tocopherol, tocopherol acetate, tocopherol and mixtures thereof, antioxidants such as ascorbic acid, α-tocopherol, dibutylhydroxytoluene, peony extract, luffa extract, rose extract, lemon extract, aloe extract, calamus root extract , eucalyptus extract, sage extract, tea extract, seaweed extract, placenta extract, extracts such as silk extract, whitening agents such as arbutin and kojic acid, and various fragrances such as natural fragrances and synthetic fragrances.

When an active ingredient is blended, the content of the active ingredient is not particularly limited. For example, the content of the active ingredient in the aqueous stock solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Moreover, the content of the active ingredient is preferably 30% by mass or less, more preferably 25% by mass or less. When the content of the active ingredient is within the above range, the aerosol composition can easily obtain the effect of incorporating the active ingredient.

Alcohols serve as solvents for dissolving active ingredients and surfactants that are difficult to dissolve in water, adjust the cooling performance when sprayed, and adjust the thickening effect of cellulose nanofibers. , and the like.

Alcohols are not particularly limited. For example, alcohols include monohydric alcohols having 2 to 3 carbon atoms such as ethanol and isopropanol; Trivalent polyol and the like.

When alcohols are blended, the content of alcohols is not particularly limited. For example, the alcohol content in the aqueous stock solution is preferably 1% by mass or more, more preferably 2% by mass or more. Also, the alcohol content in the aqueous stock solution is preferably 50% by mass or less, more preferably 45% by mass or less. When the content of the alcohol is within the above range, the aerosol composition is likely to obtain the effect of blending the alcohol, and the emulsification of the aqueous stock solution and the liquefied gas is less likely to be inhibited. Also, the aerosol composition can be easily re-emulsified with the aqueous stock solution and the liquefied gas by lightly shaking.

The oil is preferably added for the purpose of adjusting the emulsified state of the aqueous stock solution and the liquefied gas.

The oil content is not particularly limited. By way of example, the oil may be dimethicone, methylpolysiloxane, cyclopentasiloxane, cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, tetrahydrotetramethylcyclotetrasiloxane. Silicone oils such as siloxane, octamethyltrisiloxane, decamethyltetrasiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane; hydrocarbon oils such as liquid paraffin and isoparaffin; -Neopentyl glycol 2-ethylhexanoate, neopentyl glycol dicaprate, propylene glycol dilaurate, ethylene glycol distearate, diethylene glycol dilaurate, diethylene glycol distearate, diethylene glycol diisostearate, diethylene glycol dioleate, triethylene glycol dilaurate, distearin triethylene glycol diisostearate, triethylene glycol dioleate, propylene glycol monostearate, propylene glycol monooleate, ethylene glycol monostearate, glyceryl tri-2-ethylhexanoate, tri(capryl-capric acid) ) ester oils such as glycerin, isononyl isononanoate, isotridecyl isononanoate, diethoxyethyl succinate, diisostearyl malate, isopropyl myristate, isopropyl palmitate, cetyl isooctanoate, octyl hydroxystearate, ethylhexyl hydroxystearate oils such as olive oil, camellia oil, corn oil, castor oil, safflower oil, jojoba oil and coconut oil; fatty acids such as isostearic acid and oleic acid; higher alcohols such as oleyl alcohol and isostearyl alcohol;

When oil is blended, the content of oil is not particularly limited. For example, the oil content in the aqueous stock solution is preferably 0.5% by mass or more, more preferably 1% by mass or more. In addition, the oil content is preferably 20% by mass or less, more preferably 15% by mass or less, in the aqueous stock solution. When the oil content is within the above range, the aerosol composition can easily obtain the effect of blending the oil, and the emulsification of the aqueous stock solution and the liquefied gas is less likely to be inhibited. Also, the aerosol composition can be easily re-emulsified with the aqueous stock solution and the liquefied gas by lightly shaking.

The powder is preferably blended as an emulsifying aid for facilitating emulsification of the aqueous stock solution and the liquefied gas, or for the purpose of obtaining a smooth feeling.

Powder is not particularly limited. Examples of powders include talc, silica, zeolite, zinc oxide, titanium oxide, kaolin, mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, and the like. In particular, when spherical silica is used, it is easy to emulsify the aqueous undiluted solution and the liquefied gas, and silica having a hollow structure is preferable. Therefore, even if the aerosol composition is not initially emulsified with the aqueous stock solution and the liquefied gas at the time of manufacture and the powder is sedimented, it can be initially emulsified by the action of shaking when used by the consumer.

When powder is blended, the content of powder is not particularly limited. As an example, the powder content in the aqueous stock solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. Also, the content of the powder is preferably 10% by mass or less, more preferably 5% by mass or less, in the aqueous stock solution. When the content of the powder is within the above range, the aerosol composition can easily obtain the effect of blending the powder, and when the aerosol composition is filled in an aerosol container and allowed to stand still, it settles to the bottom of the container. caking is less likely to occur.

Returning to the description of the aqueous stock solution as a whole, the content of the aqueous stock solution is not particularly limited. For example, the content of the aqueous stock solution is preferably 20% by mass or more, more preferably 25% by mass or more, in the aerosol composition. Also, the content of the aqueous stock solution is preferably 60% by mass or less, more preferably 55% by mass or less, in the aerosol composition. When the content of the aqueous stock solution is within the above range, the aerosol composition easily emulsifies the aqueous stock solution and the liquefied gas.

The method for preparing the aqueous stock solution is not particularly limited. The aqueous stock solution can be prepared by a conventionally known method. For example, an aqueous concentrate can be prepared by adding cellulose nanofibers, surfactants, active ingredients, etc. to water and mixing.

The aqueous stock solution of the present embodiment preferably has a viscosity at 20° C. of 100 mPa·s or less, more preferably 50 mPa·s or less. An aqueous stock solution with such a viscosity is easily emulsified with a liquefied gas. The aerosol composition of this embodiment contains cellulose nanofibers as described above. In addition, the aerosol composition has a small amount of cellulose nanofibers (for example, 0.25% by mass or less in the aqueous stock solution), and the thickening effect of the cellulose nanofibers is hardly exhibited, and excellent emulsifiability is obtained. show. Therefore, such cellulose nanofibers do not need to be blended in large amounts to improve emulsifiability, and it is difficult to increase the viscosity of the aqueous stock solution. As a result, the aerosol composition of the present embodiment can exhibit excellent emulsifiability. The viscosity of the aqueous stock solution can be measured at 20° C. with a B-type rotational viscometer.

In the aerosol composition of the present embodiment, regarding the content of the cellulose nanofibers, the content of the cellulose nanofibers is M1, the content is M0 when the content is zero, and the viscosity of the aqueous stock solution at each content is In the case of V1 and V0, the ratio (ΔV/ΔM) of the amount of viscosity increase (ΔV=V1−V0) of the aqueous stock solution to the difference in the content of cellulose nanofibers (ΔM=M1−M0) is −500 or more. The content is preferably -300 or more, and more preferably the content is -300 or more. The content is preferably such that the ratio (ΔV/ΔM) is 500 or less, more preferably 200 or less. When the ratio is within the above range, the aqueous concentrate maintains a low viscosity state, and the aqueous concentrate and liquefied gas can be easily emulsified by lightly shaking.

(liquefied gas)
A liquefied gas is a liquid that has a vapor pressure in the aerosol container and forms an emulsion upon emulsification with the aqueous stock solution.

Liquefied gas is not particularly limited. By way of example, liquefied gases include propane, normal butane, isobutane and mixtures thereof; liquefied petroleum gas; dimethyl ether; hydrofluoroolefins such as trans-1,3,3,3-tetrafluoropropene, and mixtures thereof; etc.

The content of liquefied gas is not particularly limited. For example, the content of the liquefied gas in the aerosol composition is preferably 40% by mass or more, more preferably 45% by mass or more. Also, the content of the liquefied gas is preferably 80% by mass or less, more preferably 75% by mass or less, in the aerosol composition. Thus, the aerosol composition of the present embodiment can contain a large amount of liquefied gas. Even in this case, since the aerosol composition contains cellulose nanofibers, it is easy to emulsify the aqueous undiluted solution and the liquefied gas.

In the aerosol composition of the present embodiment, a compressed gas may be used together as a propellant for the purpose of adjusting the pressure of the aerosol composition to adjust the injection distance. The compressed gas is nitrous oxide gas, carbon dioxide gas, nitrogen gas, compressed air, oxygen gas, or the like.

Returning to the description of the aerosol composition as a whole, the method of preparing the aerosol composition is not particularly limited. For example, the aerosol composition is prepared by filling a pressure-resistant container body with an aqueous stock solution, holding a valve on the opening of the container body, filling the undercup with liquefied gas from the gap between the opening and the valve, and Secure the valve to the body. In addition, after filling the aqueous stock solution, the valve may be fixed and the liquefied gas may be filled from the valve.

A method for emulsifying the aerosol composition of the present embodiment is not particularly limited. The aerosol composition of the present embodiment can emulsify the aqueous stock solution and the liquefied gas by shaking the aerosol container using a shaker. Further, in the aerosol composition of the present embodiment, the aqueous stock solution contains cellulose nanofibers and a surfactant, and the cellulose nanofibers do not exhibit a sufficient thickening effect. Therefore, the aerosol composition is extremely easy to emulsify with the aqueous stock solution and the liquefied gas. For example, the aerosol composition can emulsify the aqueous stock solution and the liquefied gas by a stirring action when the liquefied gas is filled from a valve, vibration during transportation, or the like. In this case, a shaking step using a shaker is not necessary, and the manufacturing method can be simplified. Furthermore, even if the aerosol composition of the present embodiment is left standing for a long period of time at a store or at home, even if the aqueous stock solution and the liquefied gas are separated, the user can shake the composition several times before spraying. It can be easily re-emulsified by simple shaking. Therefore, the aerosol composition is likely to be sprayed with a uniform composition, and a desired spraying state, such as freezing of the sprayed product, is easily obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is by no means limited to these examples.

(Example 1)
An aqueous stock solution A was prepared according to the formulation shown in Table 1 below. A polyethylene terephthalate pressure container was filled with 12 g (30% by mass) of this aqueous stock solution A, and a valve was fixed to the mouth of the pressure container. 28 g (70% by mass) of liquefied petroleum gas was filled through the valve to prepare the aerosol composition (sorbet spray) of Example 1.

(Examples 2-9, Comparative Examples 1-3)
Aqueous stock solutions BL were prepared according to the formulations shown in Table 1. Using the obtained aqueous stock solutions B to L, liquefied petroleum gas was filled in the same manner as in Example 1 to prepare aerosol compositions (sorbet sprays) of Examples 2 to 9 and Comparative Examples 1 to 3, respectively. .

Using the aerosol compositions obtained in Examples 1-9 and Comparative Examples 1-3, viscosity, initial emulsification and re-emulsification were evaluated by the following evaluation methods. Table 2 shows the results.

1. Viscosity of Aqueous Stock Solution The aqueous stock solution was adjusted to 20° C. and measured using a Brookfield viscometer.

2. Initial emulsification After the liquefied gas was filled from the valve, the aerosol container was shaken up and down by 30 cm, and the number of reciprocations until emulsification was counted and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The number of times of shaking required for emulsification was 5 times or less.
○: The number of times of shaking required for emulsification was 6 to 9 times.
Δ: The number of times of shaking required for emulsification was 10 to 15 times.
x: No emulsification even after shaking 16 times or more.

3. Re-emulsification The aerosol container in which the aqueous stock solution and the liquefied gas were separated was shaken up and down by 30 cm, and the number of times until re-emulsification was counted, taking one reciprocation as one.
(Evaluation criteria)
A: The number of times of shaking required for re-emulsification was 1 to 2 times.
○: The number of times of shaking required for re-emulsification was 3 to 5 times.
Δ: The number of times of shaking required for re-emulsification was 6 to 10 times.
x: No re-emulsification occurred even after shaking 11 times or more.

As shown in Table 2, in the aerosol compositions of Examples 1 to 9, cellulose nanofibers were added, and at a viscosity of 100 mPa s or less where the thickening effect was hardly exhibited, the aqueous stock solution and the liquefied gas were mixed. was easy to emulsify initially and easy to re-emulsify.

On the other hand, the aerosol composition of Comparative Example 1, which did not contain cellulose nanofibers, had a low viscosity, but was difficult to undergo initial emulsification and re-emulsification. In addition, the aerosol compositions of Comparative Examples 2 and 3, in which the content of cellulose nanofibers exceeded 0.25% by mass, exhibited a large thickening effect and were less likely to undergo initial emulsification and re-emulsification.

(Example 10)
An aqueous stock solution M was prepared according to the formulation shown below. A pressure container made of polyethylene terephthalate was filled with 12 g (30% by mass) of this aqueous stock solution M, and a valve was fixed to the mouth of the pressure container. 28 g (70% by mass) of liquefied petroleum gas was filled from the valve to prepare the aerosol composition (sorbet spray) of Example 10. The content (solid content) of cellulose nanofibers was 0.1% by mass.

(Aqueous stock solution M)
Cellulose nanofiber (*1) 5.0
POE (20) POP (8) cetyl ether (*2) 1.0
Methylparaben 0.1
Ethanol 5.0
Purified water 87.9
Talc 1.0
Total 100.0 (% by mass)

(Example 11)
An aqueous stock solution N was prepared according to the formulation shown below. A pressure container made of polyethylene terephthalate was filled with 12 g (30% by mass) of this aqueous stock solution N, and a valve was fixed to the mouth of the pressure container. 28 g (70% by mass) of liquefied petroleum gas was filled from the valve to prepare the aerosol composition (cracking foam) of Example 11. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous concentrate N)
Cellulose nanofiber (*1) 2.5
Monococonut oil fatty acid POE (20) sorbitan (*3) 1.0
POE monostearate (20) sorbitan (*4) 0.1
Methylparaben 0.1
Ethanol 5.0
Purified water 90.3
Talc 1.0
Total 100.0 (% by mass)
*3: NIKKOL TL-10 (trade name), manufactured by Nikko Chemicals Co., Ltd. *4: NIKKOL TS-10 (trade name), manufactured by Nikko Chemicals Co., Ltd.

(Example 12)
An aqueous stock solution O was prepared according to the formulation shown below. 14.0 g (35% by mass) of this aqueous stock solution O was filled in a pressure-resistant container made of polyethylene terephthalate, and a valve was fixed to the mouth of the pressure-resistant container. 26.0 g (65% by mass) of liquefied petroleum gas was filled from the valve to prepare the aerosol composition (cracking foam) of Example 12. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous stock solution O)
Cellulose nanofiber (*1) 2.5
POE (20) POP (8) cetyl ether (*2) 1.0
Monococonut oil fatty acid POE (20) sorbitan (*3) 0.5
Hydroxyethyl cellulose 0.1
Ethanol 40.0
Purified water 54.9
Talc 1.0
Total 100.0 (% by mass)

(Example 13)
An aqueous stock solution P was prepared according to the formulation shown below. 12.0 g (30% by mass) of this aqueous stock solution P was filled in a pressure-resistant container made of polyethylene terephthalate, and a valve was fixed to the mouth of the pressure-resistant container. 28.0 g (70% by mass) of liquefied petroleum gas was charged through the bulb to prepare the aerosol composition of Example 13 (astringent cosmetic ice foam). The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous undiluted solution P)
Cellulose nanofiber (*1) 2.5
POE (20) POP (8) cetyl ether (*2) 1.0
Carrageenan 0.5
Menthol 0.2
Methylparaben 0.1
Ethanol 5.0
Purified water 89.7
Talc 1.0
Total 100.0 (% by mass)

(Example 14)
An aqueous stock solution Q was prepared according to the formulation shown below. 12.0 g (30% by mass) of this aqueous stock solution Q was filled in a polyethylene terephthalate pressure-resistant container, and a valve was fixed to the mouth of the pressure-resistant container. 28.0 g (70% by mass) of liquefied petroleum gas was filled through the valve to prepare the aerosol composition (deodorant mist) of Example 14. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous concentrate Q)
Cellulose nanofiber (*1) 2.5
POE (20) POP (8) cetyl ether (*2) 1.0
Monococonut oil fatty acid POE (20) sorbitan (*3) 0.5
Isopropylmethylphenol 1.0
Zinc sulfocarbate 0.3
Menthol 0.2
Dineopentanoate methyl pentanediol 3.0
Methylparaben 0.1
Ethanol 25.0
Purified water 65.4
Talc 1.0
Total 100.0 (% by mass)

(Example 15)
An aqueous stock solution R was prepared according to the formulation shown below. 14.0 g (35% by mass) of this aqueous stock solution R was filled in a polyethylene terephthalate pressure-resistant container, and a valve was fixed to the mouth of the pressure-resistant container. A bulb was filled with 26.0 g (65% by mass) of liquefied petroleum gas to prepare an aerosol composition (UV-blocking cracking foam) of Example 15. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous stock solution R)
Cellulose nanofiber (*1) 2.5
Monococonut oil fatty acid POE (20) sorbitan (*3) 1.5
Mixture of hexyl diethylaminohydroxybenzoylbenzoate and ethylhexyl methoxycinnamate (*5) 10.0
Dineopentanoate methyl pentanediol 5.0
Decamethylcyclopentasiloxane 3.0
Methylparaben 0.1
Ethanol 15.0
Purified water 56.4
Fine particle titanium oxide (*6) 1.0
Fine zinc oxide (*7) 5.0
Talc 0.5
Total 100.0 (% by mass)
*5: Ubinal A Plus B (trade name), manufactured by BASF Japan Ltd. *6: MT-100AQ (trade name), manufactured by Tayca Corporation *7: MZ-500HP (trade name), manufactured by Tayca Corporation

(Example 16)
An aqueous stock solution S was prepared according to the formulation shown below. 16.0 g (40% by mass) of this aqueous stock solution S was filled in a pressure-resistant container made of polyethylene terephthalate, and a valve was fixed to the mouth of the pressure-resistant container. 24.0 g (60% by mass) of liquefied petroleum gas was filled from the valve to prepare an aerosol composition (cracking foam for insect repellent) of Example 16. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous stock solution S)
Cellulose nanofiber (*1) 2.5
POE (21) lauryl ether (*8) 1.0
Polyethylene glycol monostearate (*9) 1.0
N,N-diethyl-m-toluamide 10.0
Menthol 0.2
Methylparaben 0.1
Ethanol 5.0
Purified water 79.2
Talc 1.0
Total 100.0 (% by mass)
*8: NIKKOL BL-21 (trade name), manufactured by Nikko Chemicals Co., Ltd. *9: NIKKOL MYS-4V (trade name), manufactured by Nikko Chemicals Co., Ltd.

(Example 17)
An aqueous stock solution T was prepared according to the formulation shown below. 12.0 g (30% by mass) of this aqueous stock solution T was filled in a pressure-resistant container made of polyethylene terephthalate, and a valve was fixed to the mouth of the pressure-resistant container. 28.0 g (70% by mass) of liquefied petroleum gas was filled through the valve to prepare the aerosol composition (hair-restoring sherbet) of Example 17. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous stock solution T)
Cellulose nanofiber (*1) 2.5
POE (20) POP (8) cetyl ether (*2) 1.0
Monococonut oil fatty acid POE (20) sorbitan (*3) 0.5
d-camphor 0.5
Menthol 0.5
Assembly extract 0.3
Dipotassium glycyrrhizinate 0.1
D-panthenol 0.3
Methylparaben 0.1
Ethanol 5.0
Purified water 88.2
Talc 1.0
Total 100.0 (% by mass)

Using the aerosol compositions obtained in Examples 10 to 17, viscosity, initial emulsification and re-emulsification were evaluated by the same evaluation methods as above. Table 3 shows the results.

As shown in Table 3, in the aerosol compositions of Examples 10 to 17, cellulose nanofibers were added, and at a viscosity of 100 mPa s or less where the thickening effect was hardly exhibited, the aqueous stock solution and the liquefied gas was easy to emulsify initially and easy to re-emulsify.

(Example 18)
An aqueous stock solution U was prepared according to the formulation shown below. A polyethylene terephthalate pressure container was filled with 12 g (30% by mass) of this aqueous stock solution U, and a valve was fixed to the mouth of the pressure container. 28 g (70% by mass) of liquefied petroleum gas was filled from the valve to prepare the aerosol composition (sorbet spray) of Example 18. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous undiluted solution U)
Cellulose nanofiber (*10) 25.0
POE (20) POP (8) cetyl ether (*2) 1.0
Ethanol 2.0
Purified water 71.5
Silica (*11) 0.5
Total 100.0 (% by mass)
*10: Rheocrysta C-2SP was diluted with purified water to adjust the solid content to 0.2%.
*11: SILICA MICRO BEADS BA-1 (trade name), hollow structure silica, manufactured by JGC Catalysts and Chemicals Co., Ltd.

(Example 19)
An aqueous stock solution V was prepared according to the formulation shown below. 12 g (30 mass %) of this aqueous stock solution V was filled in a polyethylene terephthalate pressure-resistant container, and a valve was fixed to the mouth of the pressure-resistant container. 28 g (70% by mass) of liquefied petroleum gas was filled from the valve to prepare the aerosol composition (sorbet spray) of Example 19. The cellulose nanofiber content (solid content) was 0.05% by mass.

(Aqueous stock solution V)
Cellulose nanofiber (*10) 25.0
POE (20) POP (8) cetyl ether (*2) 1.0
Ethanol 2.0
Purified water 71.5
Talc 0.5
Total 100.0 (% by mass)

Using the aerosol compositions obtained in Examples 18 and 19, the viscosity of the aqueous concentrate, initial emulsification, initial emulsification after powder sedimentation, and re-emulsification were evaluated by the following evaluation methods. Table 4 shows the results.

1. Viscosity of Aqueous Stock Solution The aqueous stock solution was adjusted to 20° C. and measured using a Brookfield viscometer.

2. Initial emulsification After the liquefied gas was filled from the valve, the aerosol container was shaken up and down by 30 cm, and the number of reciprocations until emulsification was counted and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The number of times of shaking required for emulsification was 5 times or less.
○: The number of times of shaking required for emulsification was 6 to 9 times.
Δ: The number of times of shaking required for emulsification was 10 to 15 times.
x: No emulsification even after shaking 16 times or more.

3. Initial emulsification after powder sedimentation After filling the liquefied gas from the valve, leave the powder in a constant temperature room at 25°C for 3 days without initial emulsification to settle the powder. The number of times until emulsification was counted as one time was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The number of times of shaking required for emulsification was 5 times or less.
○: The number of times of shaking required for emulsification was 6 to 9 times.
Δ: The number of times of shaking required for emulsification was 10 to 15 times.
x: No emulsification even after shaking 16 times or more.

4. Re-emulsification The aerosol container in which the aqueous stock solution and the liquefied gas were separated was shaken up and down by 30 cm, and the number of times until re-emulsification was counted, taking one reciprocation as one.
(Evaluation criteria)
A: The number of times of shaking required for re-emulsification was 1 to 2 times.
○: The number of times of shaking required for re-emulsification was 3 to 5 times.
Δ: The number of times of shaking required for re-emulsification was 6 to 10 times.
x: No re-emulsification occurred even after shaking 11 times or more.

As shown in Table 4, the aerosol composition of Example 18, which used silica as a powder, was easy to be initially emulsified even when the powder was sedimented, and the initial emulsification immediately after filling and the number of times of shaking did not change. On the other hand, the aerosol composition of Example 19 using talc as the powder was easier to re-emulsify when the initial emulsification was performed immediately after filling than when the initial emulsification was performed while the powder was sedimented.

Claims (4)

An aerosol composition in which an aqueous stock solution and a liquefied gas are emulsified,
The aqueous stock solution contains cellulose nanofibers and a surfactant,
The surfactant comprises a nonionic surfactant,
The content of the surfactant is 0.1 to 15% by mass in the aqueous stock solution,
The blending ratio of the aqueous stock solution and the liquefied gas is 60/40 to 20/80 (mass ratio),
The aerosol composition, wherein the content of the cellulose nanofibers is 0.25% by mass or less in the aqueous stock solution. 2. The aerosol composition according to claim 1, wherein the content of said cellulose nanofibers is 0.001 to 0.20% by mass in said aqueous concentrate. Regarding the content of the cellulose nanofibers, when the content of the cellulose nanofibers is M1, the cellulose nanofiber content is M0 when the content is zero, and the viscosity of the aqueous stock solution at each content is V1 and V0, the cellulose The content is such that the ratio (ΔV/ΔM) of the amount of viscosity increase (ΔV=V1−V0) of the aqueous stock solution to the difference in nanofiber content (ΔM=M1−M0) is −500 to 500. 3. Aerosol composition according to 1 or 2. further including alcohol,
The aerosol composition according to any one of claims 1 to 3, wherein the alcohol content is 1 to 50% by mass.