JP7349802B2 - Cosmetics containing CO2 ultra fine bubbles - Google Patents

Description

The present invention relates to cosmetics (cosmetics with high UFB content) containing 20 million or more ultra fine bubbles (UFB)/mL.

(Cosmetics containing carbon dioxide gas)
In recent years, in the beauty field, the blood flow promoting effect, thermal effect, and cleansing effect of carbon dioxide gas have attracted attention, and cosmetics containing carbon dioxide gas (serums, facial cleansers, packs, mask materials, etc.) have actually become commercially available. ing.

For example, Patent Documents 1, 2, and 3 disclose foam-like cosmetics (ie, aerosol cosmetics) containing carbon dioxide gas. However, aerosol cosmetics require a pressure-resistant container and a carbon dioxide propellant, and while consumers can easily handle them, there are problems with high product prices, and the amount of filling is limited due to the pressure resistance and safety of cans. There were problems such as being exposed.

Furthermore, for example, Patent Document 4 discloses that at least two independent compositions, a composition containing a carbonate such as soda ash or sodium bicarbonate, and a composition containing an acidic component such as citric acid, are described. Cosmetics have been disclosed, and in the actual market, cosmetics (packs, etc.) that generate carbon dioxide gas by a combination of carbonate and acid are sold. However, cosmetics that use carbonates and acids have problems such as the generation of salts that puts a strain on the skin and the need to use large amounts of carbonates to obtain a sufficient amount of carbon dioxide. there were.

In addition, there are also known methods of incorporating carbon dioxide gas into cosmetics using a foaming pump container, manual stirring, or bubbling using a gas cylinder. Among these methods, foaming using a foaming pump container has the advantage that foaming pump containers are relatively easy to obtain and that foam can be added to cosmetics relatively easily, but the resulting foam is coarse. There was a problem that the carbon dioxide concentration in the bubbles was extremely low. Furthermore, although manual stirring has the advantage of being low in monetary cost, there are problems in that the labor required for foaming is large and that the carbon dioxide concentration in the foam is extremely low. Furthermore, although bubbling using a gas cylinder has the advantage of not requiring manual labor for foaming, there are problems in that a gas cylinder is required and that the resulting foam is coarse and does not last.

As mentioned above, conventional cosmetics containing carbonated foam each have their own problems, and a new type of cosmetic containing carbonated foam has been desired.

(Ultra fine bubble)
On the other hand, fine bubbles with a diameter of 1000 nm or less in a solvent such as water under normal pressure are also referred to as "ultra fine bubbles." Compared to normal bubbles having a diameter of 1 mm or more, such ultra-fine bubbles have (1) a significantly larger bubble interfacial surface area, (2) a greater internal pressure, and (3) a higher gas dissolution efficiency. Because of its excellent properties such as (4) slow bubble rise rate, it is thought to be useful in, for example, semiconductor cleaning processing, water purification processing, sterilization processing, oyster and shellfish farming, etc. . Various methods for generating such ultra-fine bubbles have been proposed and implemented so far (Patent Documents 5, 6, and 7). However, since these generation methods require an ultra-fine bubble generator, the environment in which the ultra-fine bubbles can be used is restricted and consumers cannot easily handle them.

( _CO2 hydrate)
By the way, a substance called CO ₂ hydrate (carbon dioxide hydrate) is known as a type of ice with a high CO ₂ content. CO ₂ hydrate refers to an inclusion compound in which carbon dioxide molecules are trapped in the void space of a water molecule crystal. The water molecules that form the crystal are called "host molecules," and the molecules trapped in the void space of the water molecule crystal are called "guest molecules" or "guest substances." CO ₂ hydrate decomposes into CO ₂ (carbon dioxide) and water when melted, and thus generates CO ₂ when melted. CO ₂ hydrate can be produced by subjecting CO ₂ and water to low temperature and high partial pressure of CO ₂ .For example, CO ₂ hydrate can be produced at a certain temperature and at It can be produced under conditions including a CO ₂ partial pressure higher than the equilibrium pressure of the rate (hereinafter also referred to as "CO ₂ hydrate production conditions"). Although the CO ₂ content of CO ₂ hydrate depends on the manufacturing method of CO ₂ hydrate, it can be about 3 to 28% by weight, and the CO ₂ content of carbonated water (about 0.5% by weight) ) is significantly higher than that of

As a use of CO ₂ hydrate, it is known to add and mix CO ₂ hydrate to beverages. For example, Patent Document 8 discloses that a carbonated beverage is produced by mixing CO ₂ hydrate with a beverage to add carbonation to the beverage, and Patent Document 9 discloses that CO ₂ hydrate is mixed with ice to produce a carbonated beverage. It is disclosed to cool a lukewarm beverage and to replenish carbon dioxide to a deflated beverage by adding a carbonation replenishment medium formed by the process to the beverage.

However, it is not known to add ice (preferably CO ₂ hydrate) with a CO ₂ content of 3% by weight or more to cosmetics to obtain cosmetics containing a high concentration of CO ₂ ultra-fine bubbles. Ta.

Special Publication No. 2005-506325 JP2011-93877A JP 2017-114915 Publication Japanese Patent Application Publication No. 2017-178884 Japanese Patent Application Publication No. 2008-149209 Japanese Patent Application Publication No. 2004-330050 Japanese Patent Application Publication No. 2007-275893 Japanese Patent Application Publication No. 2005-224146 Patent No. 4969683

An object of the present invention is to provide a cosmetic containing ultrafine bubbles at a high concentration.

The present inventors, while conducting intensive studies to solve the above problems, attempted to generate high-concentration ultra-fine bubbles in cosmetics such as lotion using a commercially available ultra-fine bubble generator. . However, the present inventors have found that it is not possible to generate ultra-fine bubbles at high concentrations in cosmetics such as lotions, which have a higher viscosity than water and contain various ingredients. I found it.

While conducting further studies to solve the above problems, the present inventors discovered that CO ₂ Ultra by incorporating ice (preferably CO ₂ hydrate) with a CO 2 content _of 3% by weight or more into cosmetics. The present inventors have discovered that cosmetics containing fine bubbles at a high concentration can be produced easily and at low cost, and have completed the present invention.

That is, the present invention
(1) Cosmetics containing 20 million or more ultra-fine bubbles/mL;
(2) The cosmetic according to (1) above, containing 20 million or more ultra-fine bubbles/mL as measured by the following measurement method D1;
(Measurement method D1)
Measuring the concentration of ultrafine bubbles (pieces/mL) in the cosmetic by laser diffraction/scattering method or nanotracking method;
(3) The cosmetic according to (1) or (2) above, which has a viscosity of 3 to 6500 mPa·s at 25°C;
(4) The cosmetic according to any one of (1) to (3) above, wherein the cosmetic is selected from the group consisting of skin cosmetics, hair cosmetics, cleaning products, shaving foam, mouth cosmetics, and hand disinfectants. cosmetics;
(5) Measuring the concentration of ultra-fine bubbles (pieces/mL) using a laser diffraction/scattering method is to measure the concentration of ultra-fine bubbles (pieces/mL) using the SALD-7500 Ultra-Fine Bubble Measurement System manufactured by Shimadzu Corporation. To measure the concentration of ultra-fine bubbles (pieces/mL) using the nanotracking method is to measure the concentration of ultra-fine bubbles (pieces/mL) using Malvern's NanoSight NS300. Cosmetics according to any one of 1) to (4); or
(6) The cosmetic according to any one of (1) to (5) above, which is housed in a container;
(7) The cosmetic according to (6) above, wherein the gauge pressure of the container is higher than 0 MPa and lower than 1 MPa;
Regarding.

According to the present invention, cosmetics containing ultra-fine bubbles at a high concentration can be provided easily and at low cost.

Upper panel of FIG. 1: This is a diagram showing the results of measuring ultrafine bubbles in a very moist diluted solution containing CO ₂ hydrate using the SALD-7500 ultrafine bubble measurement system manufactured by Shimadzu Corporation. The horizontal axis represents the bubble particle diameter (μm), and the vertical axis represents the bubble concentration (bubbles/mL). Figure 1 lower panel: Shows the results of measuring ultra-fine bubbles in a super _- wet diluted solution containing the same weight of water instead of CO2 hydrate using the SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation. It is a diagram. The horizontal axis represents the bubble particle diameter (μm), and the vertical axis represents the bubble concentration (bubbles/mL). FIG. 2 is a diagram showing the ultra-fine bubble concentration (100 million bubbles/mL) in the diluted solution of "Hada Labo Gokujun Hyaluronic Solution". The rightmost bar graph represents the ultrafine bubble concentration in the diluted solution obtained by adding CO ₂ hydrate to the above diluted solution. The second bar graph from the right corresponds to the measurement control (background) of the rightmost bar graph, and was obtained by adding the same weight of water to the diluted solution instead of _CO2 hydrate. represents the ultrafine bubble concentration in the diluted solution. The second bar graph from the left represents the ultra-fine bubble concentration in the diluted solution obtained by operating the ultra-fine bubble generator on the diluted solution. The leftmost bar graph corresponds to the measurement control (background) of the second bar graph from the left, and instead of activating the ultrafine bubble generator on the diluted solution described above, it simply generates the ultrafine bubble generator. It represents the ultra-fine bubble concentration in the diluted liquid circulated within the bubble generator. FIG. 3 is a diagram showing the amount of ultra-fine bubbles (100 million bubbles/mL) generated in the diluted solution of "Hada Labo Gokujun Hyaluronic Solution". The bar graph on the right represents the amount of ultra-fine bubbles (100 million bubbles/mL) generated by adding CO ₂ hydrate, and the second bar graph from the right represents the measured value of the rightmost bar graph in Figure 2. represents the value obtained by subtracting the measured value of The bar graph on the left represents the amount of ultra-fine bubbles (100 million bubbles/mL) generated by operating the ultra-fine bubble generator. Represents the value obtained by subtracting the measured value of the bar graph. FIG. 4 is a diagram showing a comparison of ultra-fine bubble concentrations when CO ₂ hydrate is added to two types of cosmetics. The bar graph on the far right represents the ultra-fine bubble concentration in the solution obtained by adding CO ₂ hydrate to the stock solution of "Chifure Lotion Very Moist Type." The second bar graph from the right corresponds to the measurement control (background) of the rightmost bar graph, and was obtained by adding the same weight of water to the Chifure stock solution instead of _CO2 hydrate. represents the ultrafine bubble concentration in the solution. The second bar graph from the left and the rightmost bar graph represent the ultra-fine bubble concentration in the diluted solution obtained by adding CO ₂ hydrate to the diluted solution of "Hada Labo Gokujun Hyaluronic Solution". The leftmost bar graph corresponds to the measurement control (background) of the second bar graph from the left, and was obtained by adding the same weight of water to the diluted solution instead of _CO2 hydrate. represents the ultrafine bubble concentration in the diluted solution. FIG. 5 is a diagram showing a comparison of the amount of ultra-fine bubbles generated (100 million bubbles/mL) when CO ₂ hydrate is added to two types of cosmetics or water. The bar graph on the right represents the amount of ultra-fine bubbles (100 million bubbles/mL) generated by adding CO ₂ hydrate to the diluted solution of "Hada Labo Gokujun Hyaluronic Solution". The bar graph in the center represents the amount of ultra-fine bubbles (100 million bubbles/mL) generated by adding CO ₂ hydrate to the stock solution of "Chifure Lotion Very Moist Type". The bar graph on the left represents the amount of ultra-fine bubbles (100 million bubbles/mL) generated by adding CO ₂ hydrate to water. FIG. 6 is a diagram showing the results of an ultra-fine bubble stability confirmation test. Such a stability confirmation test involves adding CO ₂ hydrate to two types of cosmetics or water, freezing those solutions, then thawing them, and comparing ultra-fine bubbles in the solution before freezing. The percentage of ultra-fine bubbles remaining ("residual rate after freezing and thawing (%)") was measured. The bar graph on the right represents the residual rate (%) of ultrafine bubbles after freezing and thawing when water is used as the solution. The bar graph in the center represents the residual rate (%) of ultra fine bubbles after freezing and thawing when the stock solution of "Chifure Lotion Very Moist Type" is used as the solution. The bar graph on the right represents the residual rate (%) of ultra fine bubbles after freezing and thawing when a diluted solution of "Hada Labo Gokujun Hyaluronic Solution" is used as the solution.

<Cosmetics of the present invention>
The cosmetic of the present invention is not particularly limited as long as it contains 20 million or more ultrafine bubbles/mL.

In the present invention, the value of the concentration of ultra-fine bubbles (pieces/mL) in cosmetics may be a value measured by any measurement method that can measure the concentration of ultra-fine bubbles; Preferably, it is a value measured by method D1.
(Measurement method D1)
The concentration of ultrafine bubbles (pieces/mL) in the cosmetic is measured by a laser diffraction/scattering method (preferably a quantitative laser diffraction/scattering method) or a nanotracking method.

The cosmetic used in the above measurement method D1 is preferably a cosmetic with a liquid temperature of 20 to 30°C.

In this specification, as for measuring the concentration of ultra-fine bubbles by a laser diffraction/scattering method, it is preferable to measure the concentration of ultra-fine bubbles using a SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation. The SALD-7500 Ultra Fine Bubble Measurement System is a measurement device that uses quantitative laser diffraction/scattering method. Furthermore, in this specification, as the method of measuring the concentration of ultra-fine bubbles by the nanotracking method, it is preferable to measure the concentration of ultra-fine bubbles using Nanosite NS300 manufactured by Malvern.

(Ultra fine bubble in the present invention)
The term "ultra fine bubbles (UFB)" in the present invention refers to microbubbles with a diameter of 1000 nm or less in cosmetics under normal pressure. The ultra-fine bubbles of the present invention include ice with a CO ₂ content of 3% by weight or more (hereinafter also referred to as "high CO ₂ content ice") (preferably CO ₂ hydrate, more preferably consolidated CO ₂ Preferable examples include CO ₂ ultrafine bubbles that are produced by incorporating CO 2 hydrate into cosmetics.

(UFB concentration in cosmetics of the present invention)
The UFB concentration (UFB cells/mL) in the cosmetic of the present invention is not particularly limited as long as it is 20 million cells/mL or more, but preferably 40 million cells/mL or more, more preferably 80 million cells/mL. Above, the number is more preferably 100 million pieces/mL or more, more preferably 300 million pieces/mL or more, and still more preferably 500 million pieces/mL or more. The upper limit of the UFB concentration in the cosmetic of the present invention is not particularly limited, but examples include 5 billion cells/mL or less, 4 billion cells/mL or less, and 3 billion cells/mL or less. More specifically, the UFB concentrations in the cosmetics of the present invention include 20 million to 5 billion pieces/mL, 40 million to 5 billion pieces/mL, 80 million to 5 billion pieces/mL, and 100 million to 5 billion pieces/mL. cells/mL, 300 million to 5 billion cells/mL, 500 million to 5 billion cells/mL, 20 million to 4 billion cells/mL, 40 million to 4 billion cells/mL, 80 million to 4 billion cells/mL mL, 100 million to 4 billion pieces/mL, 300 million to 4 billion pieces/mL, 500 million to 4 billion pieces/mL, 20 million to 3 billion pieces/mL, 40 million to 3 billion pieces/mL, 8 Examples include 10 million to 3 billion cells/mL, 100 million to 3 billion cells/mL, 300 million to 3 billion cells/mL, and 500 million to 3 billion cells/mL.

(Viscosity of the cosmetic of the present invention)
The cosmetic of the present invention is not particularly limited as long as it is liquid at 25°C, but it is preferably a cosmetic with a specific viscosity. Examples of such "cosmetics with a specific viscosity" include cosmetics with a viscosity of 3 to 6,500 mPa·s at 25°C, and among them, cosmetics with a viscosity of 3 to 6,500 mPa·s at 25°C. Preferably.
4-6500mPa・s, 6-6500mPa・s, 8-6500mPa・s, 3-5000mPa・s, 4-5000mPa・s, 6-5000mPa・s, 8-5000mPa・s, 3-4000mPa・s, 4- 4000mPa・s, 6~4000mPa・s, 8~4000mPa・s, 3~3000mPa・s, 4~3000mPa・s, 6~3000mPa・s, 8~3000mPa・s, 3~2000mPa・s, 4~2000mPa・s, 6-2000mPa・s, 8-2000mPa・s, 3-1000mPa・s, 4-1000mPa・s, 6-1000mPa・s, 8-1000mPa・s, 3-500mPa・s, 4-500mPa・s, 6-500mPa・s, 8-500mPa・s, 3-250mPa・s, 4-250mPa・s, 6-250mPa・s, 8-250mPa・s, 3-100mPa・s, 4-100mPa・s, 6- 100mPa・s, 8-100mPa・s;

The viscosity of cosmetics can be measured using a commercially available viscometer, and a suitable measurement method is to use the "Precision Rotational Viscometer RST-CC Double Cylindrical Model" manufactured by Hideko Seiki Co., Ltd. with spindle No. 25. , a method of measuring using a 16.8 mL solution of cosmetics can be mentioned.

(Types of cosmetics of the present invention)
The type of cosmetic in the present invention is not particularly limited as long as it is liquid under 25°C conditions, and includes skin cosmetics, hair cosmetics, cleaning products, shaving foam, hand sanitizer, mouth cosmetics, etc. . The skin cosmetics include cosmetics, lotions, emulsions, serums, creams, face packs, foundations, depilators, etc. The hair cosmetics include hair rinses, conditioners, treatments, hair colors, hair removal products, etc. Color treatments, hair restorers, hair styling products, hair lotions, etc. are mentioned, the above-mentioned cleaning products include face washes, cleansing products, hair detergents, body cleansing products, etc., and the mouth cosmetics include toothpastes, Examples include gargles, mouthwashes, etc.

(Ingredients of the cosmetic of the present invention)
The components of the cosmetic in the present invention are not particularly limited as long as they are liquid at 25° C., and include components commonly used in cosmetics. Such components include oils, powders (pigments, pigments, resins), surfactants, adhesives, resins, preservatives, fragrances, and ultraviolet absorbers (including organic and inorganic types. Either UV-A or UV-B). ), solvents (ethanol, polyhydric alcohol, etc.), natural plant extracts, seaweed extracts, herbal medicine ingredients, amino acids, moisturizers, whitening agents, blood circulation promoters, anti-inflammatory agents , bactericidal agents, cooling agents, antiperspirants, salts, antioxidants, skin activators, pigments, vitamins, neutralizing agents, pH adjusters, insect repellents, and the like. In addition, these agents are not limited to their use as individual agents, but can be used for other purposes depending on the purpose, such as using vitamins as antioxidants, or combining them with other purposes, such as It can also be used as a moisturizer and preservative.

Examples of the oil agent include volatile and nonvolatile oil agents, solvents, and resins commonly used in cosmetics, and may be in the form of liquid, paste, or solid at room temperature. Examples of oil agents include higher alcohols such as cetanol; branched higher alcohols such as isostearyl alcohol and octyldodecanol; fatty acids such as isostearic acid, undecylenic acid, oleic acid, lauric acid, palmitic acid, and stearic acid; isononanoic acid. Isononyl, isotridecyl isononanoate, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyldecyl dimethyloctoate, glyceryl monostearate, glyceryl distearate, glyceryl trioctanoate, glyceryl tri-2-heptylundecanoate, Esters such as diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, diisostearyl malate, alkyl benzoate, neopentyl glycol dicaprate; hydrocarbons such as liquid paraffin, paraffin, vaseline, squalane, squalene; Waxes such as lanolin, reduced lanolin, liquid lanolin, carnauba wax, candelilla wax, ceresin, ozokerite, microcrystalline wax; mink oil, cacao butter, coconut oil, palm kernel oil, camellia oil, jojoba oil, sesame oil, castor oil, olive oil , macadamia nut oil, avocado oil, and other fats and oils; polyethylene wax, ethylene/α-olefin cooligomer, ethylene propylene polymer, and the like.

Examples of powders include pigments such as Red No. 104, Red No. 102, Red No. 226, Red No. 201, Red No. 202, Yellow No. 4, and Black No. 401, Blue No. 1 Aluminum Lake, Yellow No. 4 Aluminum Lake, Lake pigments such as yellow No. 5 aluminum lake and yellow No. 203 barium lake; nylon powder, silk powder, urethane powder, Teflon (registered trademark) powder, silicone powder, polymethyl methacrylate powder, cellulose powder, silicone elastomer spherical powder, Polymers such as polyethylene powder; Colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine, and navy blue; White pigments such as zinc oxide, titanium oxide, and cerium oxide; talc, mica, and sericite Extender pigments such as , kaolin, and platy barium sulfate; Pearl pigments such as titanium mica; Metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, and magnesium silicate; Inorganic powders such as silica and alumina; Bentonite and smectite , boron nitride, fine-particle titanium oxide, fine-particle zinc oxide, etc., and these can be treated with conventionally known surface treatments such as N-acylated lysine treatment, amino acid treatment, hydrophilic polymer treatment, oil treatment, silicone treatment, metal treatment, etc. It is also possible to use those subjected to soap treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc. There is no particular restriction on the shape of these powders (spherical, rod-like, needle-like, plate-like, irregularly shaped, scaly, spindle-like, etc.). The size of the powder is preferably in the range of 5 nm to 100 μm, more preferably 10 nm to 25 μm. These powders may be treated alone, or a mixture may be formed and the mixture may be treated together. It is also possible to process a mixture whose color has been adjusted to a skin color or the like. Furthermore, by using ultraviolet scattering components such as finely divided titanium oxide and finely divided zinc oxide, it is also possible to obtain a treated powder having an ultraviolet protection function.

As the surfactant, for example, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. More specifically, fatty acid soap, α-acyl sulfonate, N-acyl amino acid salt, alkyl sulfonate, alkylaryl sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl ether phosphate. , alkyl ether, alkyl amide sulfate, alkyl phosphate, alkyl phosphoric acid, alkyl amide phosphate, alkyl alkyl taurate, sulfosuccinate, dialkyl sulfosuccinate, dialkyl sulfosuccinic acid, perfluoroalkyl phosphate, Anionic surfactants such as alkyl sulfate, alkyl ether sulfate, laurate, palmitate, stearate, acylsarcosine, acylsarcosine salt; alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyltrimethyl bromide Cationic surfactants such as ammonium, cetostearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, behenyltrimethylammonium bromide; sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester , polyethylene glycol fatty acid ester, sucrose fatty acid ester, lauric acid alkanolamide, POE fatty acid ester, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE fatty acid ester, POE alkyl ether, POE sorbitol fatty acid ester, POE propylene glycol fatty acid ester, POE Nonions such as castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil fatty acid ester, POE cholestanol ether, POE phytostanol ether, POE phytosterose ether, POE cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyether-modified silicone, etc. amphoteric surfactants such as carboxybetaine type, amidobetaine type, sulfobetaine type, hydroxysulfobetaine type, amidosulfobetaine type, phosphobetaine type, aminocarboxylate type, imidazoline derivative type, amidoamine type; can be mentioned. Furthermore, natural surfactants such as saponin and sugar-based surfactants can also be used.

Examples of adhesives and resins include polyacrylic acid, sodium polyacrylate, polymethacrylic acid, carboxyvinyl polymer, acrylic acid/alkyl acrylate copolymer, cellulose ether, calcium alginate, ethylene/acrylic acid copolymer, and vinylpyrrolidone. cationic polymers such as vinyl alcohol/vinylpyrrolidone copolymers, nitrogen-substituted acrylamide polymers, cationized guar gum, dimethylacrylammonium polymers, POE/POP copolymers, polyvinyl alcohol, pullulan, deoxyribonucleic acid and its salts , acidic mucopolysaccharides and their salts such as chondroitin sulfate, tamarind seed polysaccharides, agar, xanthan gum, carrageenan, high methoxyl pectin, low methoxyl pectin, guar gum, gum arabic, crystalline cellulose, arabinogalactan, karaya gum, tragacanth gum, alginic acid, Hyaluronic acid and its salts, albumin, casein, curdlan, gellan gum, dextran, cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyethyleneimine, highly polymerized polyethylene glycol, synthetic latex, curdlan, carboxymethyl chitin, chitosan, etc. can be mentioned. The above-mentioned nano-sized materials are also included.

Examples of preservatives include benzoic acid, sodium benzoate, undecylenic acid, salicylic acid, sorbic acid or its salts, dehydroacetic acid or its salts, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, isopropyl paraoxybenzoate, Organic acids and their derivatives such as butyl paraoxybenzoate, isobutyl paraoxybenzoate, benzyl paraoxybenzoate, isopropylmethylphenol, chlorhexidine gluconate, cresol, thymol, parachlorophenol, phenylethyl alcohol, phenylphenol, sodium phenylphenol, phenoxyethanol , phenoxydiglycol, phenol, phenols such as benzyl alcohol, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, lauryltrimethylammonium chloride, alkylisoquino bromide Examples include quaternary ammonium salts such as domiphenone and domiphenone bromide, plant extracts such as tea extract, hinokitiol, and apple extract, as well as chloramine T, chlorhexidine, zinc pyrithione, and the like.

Examples of organic UV absorbers include 2-ethylhexyl para-methoxycinnamate, 2-ethylhexyl para-dimethylaminobenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydrocinnamic acid diethanolamine salt, para-aminobenzoic acid (hereinafter abbreviated as PABA), homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano -3,3-diphenylacrylate, octyldimethyl PABA, octyl salicylate, 2-phenyl-benzimidazole-5-sulfuric acid, triethanolamine salicylate, 3-(4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenylene, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxy Dibenzoylmethane, 2-ethylhexyl 4-(3,4-dimethoxyphenylmethylene)-2,5-dioxo-1-imidazolidinepropionate, and the like.

Examples of the solvent include purified water, cyclic silicone, ethanol, light liquid isoparaffin, lower alcohols, ethers, LPG, fluorocarbons, N-methylpyrrolidone, fluoroalcohol, next-generation fluorocarbons, and the like.

Examples of natural plant extracts, seaweed extracts, and herbal medicine ingredients include Ashitaba extract, avocado extract, amacha extract, althea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo biloba extract, fennel extract, and turmeric. Extract, oolong tea extract, staghorn extract, scutellariae leaf extract, scutellariae extract, scutellariae extract, scutellariae extract, barley extract, hypericum extract, deadlock root extract, mustard extract, orange extract, dried seawater, seaweed extract, hydrolyzed elastin, hydrolyzed Wheat powder, hydrolyzed silk, chamomilla extract, carrot extract, mugwort extract, karkade extract, katyoku extract, kiwi extract, cinchona extract, cucumber extract, guanosine, gardenia extract, kumazasa extract, clara extract, walnut extract, grapefruit extract, clematis extract, Chlorella extract, mulberry extract, gentian extract, black tea extract, yeast extract, burdock extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, lingonberry extract, saicin extract, saiko extract, rhinoceros extract, salvia extract, soapwort extract , Sasa extract, Hawthorn extract, Japanese cabbage extract, Shiitake extract, Rhododendron extract, Citrus extract, Perilla extract, Linden extract, Meadowsweet extract, Peony extract, Calamus root extract, Birch extract, Horsetail extract, Ivy extract, Hawthorn extract, Sambucus extract, Yarrow extract, peppermint extract, sage extract, mallow extract, nebula extract, Japanese japonica extract, soybean extract, Japanese turmeric extract, thyme extract, tea extract, clove extract, chigaya extract, chimpi extract, Japanese acanthus extract, calendula extract, Japanese apricot extract, spruce extract, Heutyami extract, tomato extract, natto extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, bacterium extract, lotus extract, parsley extract, honey, hamamelis extract, parietalia extract, hikiokoshi extract, bisabolol, loquat extract, coltsfoot extract, coltsfoot extract Extract, bud extract, butcher bloom extract, grape extract, propolis, loofah extract, safflower extract, peppermint extract, bodega extract, button extract, hop extract, pine extract, horse chestnut extract, skunk cabbage extract, Japanese starch extract, melissa extract, peach extract, cornflower extract , eucalyptus extract, saxifrage extract, yuzu extract, yokuinin extract, mugwort extract, lychee extract, lavender extract, apple extract, lettuce extract, lemon extract, astragalus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, etc. I can do it.

Examples of amino acids include glycine, alanine, valine, glutamic acid, and the like.

(Container for cosmetics of the present invention)
The cosmetic of the present invention does not need to be housed in a container, but is preferably housed in a container. The shape and material of the container are not particularly limited, but the shape of the container includes a substantially rectangular parallelepiped shape, a substantially cubic shape, a substantially cylindrical shape, a bag shape, etc. The material of the container includes polyolefin resin such as polyethylene and polypropylene; Preferred examples include polyester resins such as polyethylene terephthalate; glass; and metals such as aluminum. Further, although the container does not need to be a pressure-resistant container, it is preferably a pressure-resistant container when internal pressure is applied to the container. Examples of such pressure-resistant containers include aerosol containers and the like.

(Internal pressure of the cosmetic container of the present invention)
When the cosmetic of the present invention is housed in a container, the internal pressure of the container may be 0 MPa (that is, the pressure inside the container is the same as the atmospheric pressure outside the container), but it may be higher than 0 MPa, For example, it may be 0.2 MPa or more or 0.4 MPa or more. As for the internal pressure of the container, for example, the gauge pressure (difference between the pressure inside the container and the atmospheric pressure outside the container) at 35°C is higher than 0 MPa and lower than 1 MPa, higher than 0 MPa and lower than 0.8 MPa, 0.2 to 1 MPa, 0 Examples include .2 to 0.8 MPa, 0.4 to 1 MPa, and 0.4 to 0.8 MPa. Note that when the inside of the container is pressurized (gauge pressure is positive), the efficiency of ultra-fine bubble generation when adding CO2 _- rich ice to cosmetics improves (i.e., the ultra-fine bubbles (occurs at higher concentrations).

(How to use the cosmetic of the present invention)
The method of using the cosmetic of the present invention is not particularly limited, and any usual method of use depending on the type of cosmetic can be adopted. Preferred methods for using the cosmetic of the present invention include methods that include bringing the cosmetic into contact with the skin.

(Method for producing cosmetics of the present invention)
The method for producing the cosmetic of the present invention includes the step of incorporating CO ₂ -rich ice (preferably CO ₂ hydrate, more preferably compacted CO ₂ hydrate) into the cosmetic. Usual methods of production may be mentioned. In this specification, "incorporating high CO ₂ -containing ice into cosmetics" includes not only adding (i.e. adding) high CO ₂ -containing ice to cosmetics, but also including adding high CO ₂ -containing ice to cosmetics. As long as the cosmetic is brought into contact with the ice, it may be convenient to put the cosmetic into ice containing a high _CO2 content, but from the perspective of obtaining a cosmetic containing a higher concentration of ultra-fine bubbles, _the ice containing a high CO2 It is preferably included in cosmetics. In addition, as a method for manufacturing the cosmetic of the present invention housed in a container, a preferable example is a method in which the cosmetic of the present invention is placed in a container and ice with a high CO ₂ content is added to the container. Furthermore, as a method for producing the cosmetic of the present invention in a container having a positive gauge pressure, for example, the cosmetic of the present invention is placed in a container (preferably a pressure-resistant container), and CO ₂ is added to the container. A preferred method is to seal the container after adding high ice content.

When producing the cosmetics of the present invention, commercially available cosmetics may be used as cosmetics containing high CO ₂ content ice, or cosmetics produced by oneself using known production methods may be used. . Further, the viscosity of the cosmetic containing high CO ₂ ice may be adjusted at 25° C., if necessary. Examples of methods for adjusting the viscosity of cosmetics include adding a thickener to the cosmetic to increase the viscosity, and diluting the cosmetic with water to lower the viscosity.

The liquid temperature of the cosmetic when containing high CO ₂ ice is not particularly limited, and may be within the range of 0 to 50°C, for example.

The amount of CO2 _- rich ice contained in the cosmetic is not particularly limited as long as the cosmetic of the present invention can be prepared by imparting ultra-fine bubbles to the cosmetic. By referring to the specification, it is possible to determine the content of CO ₂ -rich ice (preferably CO ₂ hydrate), the CO ₂ content of the CO ₂ -rich ice (preferably CO ₂ hydrate), and how much The amount of _CO2- rich ice to be used can be adjusted depending on whether the concentration of ultra-fine bubbles is desired, etc.

A specific example of the amount of CO2 _- rich ice to be included in the cosmetic is, for example, within the range of 0.05 to 10 g/mL, preferably 0.1 to 10 g/mL, more preferably 0.1 to 3.0 g/mL. mL, more preferably 0.1 to 2.0 g/mL, more preferably 0.1 to 1.0 g/mL, even more preferably 0.1 to 0.8 g/mL, more preferably 0.1 -0.5 g/mL. These numerical ranges for the amount of CO ₂ high content ice to be included in cosmetics are based on CO ₂ high content ice being CO ₂ hydrate, and the CO ₂ content of the CO ₂ hydrate being 3 to 28. % by weight, preferably 5-28% by weight, more preferably 7-28% by weight, even more preferably 10-28% by weight, more preferably 13-28% by weight, even more preferably 16-28% by weight, more preferably It can be particularly preferably used when the amount is 19 to 28% by weight, more preferably 22 to 28% by weight.

(CO ₂ high content ice in the present invention)
The high CO ₂ -containing ice in the present invention is not particularly limited as long as it has a CO ₂ content of 3% by weight or more. Such high CO ₂ -content ice may be ice with a high CO ₂ content that is not a CO ₂ hydrate, but from the viewpoint of obtaining a cosmetic containing ultra fine bubbles at a higher concentration, it must be a CO ₂ hydrate. is preferred, and consolidated CO ₂ hydrate is more preferred. Further, as the high CO ₂ content ice in the present invention, two or three types selected from the group consisting of high CO _{2 content ice that is not CO 2 hydrate} , CO ₂ hydrate, and compacted CO ₂ hydrate. May be used together.

CO ₂ hydrate is a solid clathrate compound that traps carbon dioxide molecules in the void spaces of water molecule crystals. CO ₂ hydrate is usually an ice-like crystalline substance, and when it is placed under, for example, standard atmospheric pressure conditions and temperature conditions where ice melts, it releases CO ₂ as it melts.

The CO2 _- rich ice in the present invention has a concentration of ultra-fine bubbles (units/mL) measured by the following measurement method D2, preferably 5 million units/mL or more, more preferably 10 million units/mL. /mL or more, more preferably 20 million pieces/mL or more, more preferably 25 million pieces/mL or more, even more preferably 30 million pieces/mL or more, more preferably 35 million pieces/mL. Above, more preferably 50 million cells/mL or more, more preferably 75 million cells/mL or more, still more preferably 100 million cells/mL or more, even more preferably 150 million cells/mL or more, and Preferably, CO2 _- rich ice that can generate ultra-fine bubbles in water, preferably 200 million bubbles/mL or more, more preferably 250 million bubbles/mL or more, can be mentioned. The upper limit of the concentration of ultra-fine bubbles that can be generated in water by the CO2 _- rich ice in the present invention is not particularly limited, but the concentration of ultra-fine bubbles when measured by the above-mentioned measurement method D2 is , for example, 10 billion cells/mL or less, 1 billion cells/mL or less.
(Measurement method D2)
Add 333 mg/mL of ice having a temperature of -80 to 0 °C and a CO ₂ content of 3% by weight or more to water at 20 to 30 °C, and leave it for 1 hour at 25 °C. The concentration of ultrafine bubbles (pieces/mL) is measured by a laser diffraction/scattering method or a nanotracking method.

More specifically, the CO2 _- rich ice in the present invention is defined as the concentration of ultra-fine bubbles (units/mL) of 5 million to 10 billion units/mL, 1,000 units/mL when measured by the above-mentioned measurement method D2. 10,000 to 10 billion cells/mL, 20 million to 10 billion cells/mL, 25 million to 10 billion cells/mL, 30 million to 10 billion cells/mL, 35 million to 10 billion cells/mL , 50 million to 10 billion cells/mL, 75 million to 10 billion cells/mL, 100 million to 10 billion cells/mL, 150 million to 10 billion cells/mL, 200 million to 10 billion cells/mL /mL, 250 million cells/mL to 10 billion cells/mL, 5 million to 1 billion cells/mL, 10 million to 1 billion cells/mL, 20 million to 1 billion cells/mL, 2,000 cells/mL 500 million to 1 billion cells/mL, 30 million to 1 billion cells/mL, 35 million to 1 billion cells/mL, 50 million to 1 billion cells/mL, 75 million to 1 billion cells /mL, 100 million to 1 billion pieces/mL, 150 million to 1 billion pieces/mL, 200 million to 1 billion pieces/mL, or 250 million pieces/mL to 1 billion pieces/mL, etc. are preferred.

The CO ₂ content of the CO 2 -rich ice ( _preferably CO ₂ hydrate, more preferably consolidated CO ₂ hydrate) in the present invention is not particularly limited as long as it is 3% by weight or more; From the viewpoint of obtaining a cosmetic containing a higher concentration, preferably 5% by weight or more, more preferably 7% by weight or more, still more preferably 10% by weight or more, more preferably 13% by weight or more, even more preferably 16% by weight. As mentioned above, it is more preferably 19% by weight or more, and even more preferably 22% by weight or more, and the upper limit of the CO ₂ content is, for example, 28% by weight or less and 26% by weight or less. More specifically, the _CO2 content of the CO2 _- rich ice in the present invention is 3 to 28% by weight, 5 to 28% by weight, 7 to 28% by weight, 10 to 28% by weight, and 13 to 28% by weight. , 16-28% by weight, 19-28% by weight, 22-28% by weight, 3-26% by weight, 5-26% by weight, 7-26% by weight, 10-26% by weight, 13-26% by weight, 16 Preferred examples include ~26% by weight, 19~26% by weight, and 22~26% by weight.

The CO ₂ content _of the CO 2 -rich ice in the present invention can be adjusted by adjusting the CO ₂ partial pressure when producing _the CO ₂ -rich ice in the present invention. If the value is increased, the CO ₂ content of the CO ₂ -rich ice can be increased. In addition, when the CO ₂ -rich ice in the present invention is CO ₂ hydrate, "high/low CO ₂ partial pressure", "degree of dehydration treatment", "compression treatment" when producing CO ₂ hydrate, etc. It can be adjusted by "whether or not", "the level of compression pressure when performing compression processing", etc. For example, when producing CO ₂ hydrate, "increase the partial pressure of CO ₂ ,""increase the degree of dehydration treatment,""perform compression treatment," and "increase the compression pressure when performing compression treatment." With this, the CO ₂ content of the CO ₂ hydrate can be increased. Note that when CO ₂ -rich ice such as CO ₂ hydrate melts, the CO ₂ contained in the CO ₂ -rich ice is released, and the weight of the released CO ₂ decreases. Therefore, the CO ₂ content of the CO 2 -rich ice can be calculated using the following formula, for example, from _the weight change when the CO ₂ -rich ice is melted at room temperature.
( _CO2 content) = (sample weight before melting - sample weight after melting) / sample weight before melting

The shape of the CO2 _- rich ice (preferably _CO2 hydrate) in the present invention can be set as appropriate, and includes, for example, approximately spherical; approximately ellipsoidal; approximately polyhedral such as rectangular parallelepiped; For example, a shape that is further provided with unevenness. In addition, the CO ₂ -rich ice (preferably CO ₂ hydrate) in the present invention can be obtained by appropriately crushing chunks of CO ₂ -rich ice (preferably CO ₂ hydrate) and have various shapes (clumps). ).

The size of the CO2 _- rich ice (preferably _CO2 hydrate) in the present invention can be set as appropriate, but the lower limit of the maximum length is preferably 3 mm or more, more preferably 5 mm or more, and even more preferably 10 mm or more, and the upper limit of the maximum length is 150 mm or less, 100 mm or less, 80 mm or less, and 60 mm or less, and more specifically, 3 mm or more and 150 mm or less, 3 mm or more and 100 mm or less, 3 mm or more and 80 mm or less, and 3 mm or more and 60 mm or less. Examples include 5 mm to 150 mm, 5 mm to 100 mm, 5 mm to 80 mm, 5 mm to 60 mm, 10 mm to 150 mm, 10 mm to 100 mm, 10 mm to 80 mm, and 10 mm to 60 mm. If the maximum length of the CO ₂ -rich ice (preferably CO ₂ hydrate) is less than 3 mm, foamy parts (foam parts) will occur when such CO ₂ -rich ice is included in cosmetics. Ice with a high CO ₂ content may be incorporated into the cosmetics, resulting in rough foaming, and it may not be possible to obtain cosmetics with a desirable aesthetic appearance.

In this specification, "maximum length of CO ₂ -rich ice" refers to the longest line segment among the line segments that connect two points on the surface of the block of CO ₂ -rich ice and pass through the center of gravity of the block. means the length of In addition, when the CO ₂ high content ice is, for example, approximately ellipsoidal, the maximum length represents the major axis (longest diameter); when it is approximately spherical, the maximum length represents the diameter; If there is, it represents the length of the longest diagonal among the diagonals. In addition, in this specification, the "minimum length of CO ₂ -rich ice" refers to the distance between two points on the surface of the block of CO ₂ -rich ice (preferably CO ₂ hydrate) and the center of gravity of the block. It means the length of the shortest line segment among the line segments that pass through it. The maximum length and minimum length can be measured using a commercially available image analysis type particle size distribution measuring device, or can be measured by applying a ruler to a block of high _CO2 content ice (preferably _CO2 hydrate). You can also do that.

As a preferred embodiment of the CO ₂ -rich ice (preferably CO ₂ hydrate) in the present invention, the aspect ratio (maximum length/minimum length) is preferably within the range of 1 to 5, more preferably within the range of 1 to 4. , more preferably ice with a high CO ₂ content in the range of 1 to 3 (preferably CO ₂ hydrate).

In the present invention, when using CO ₂ -rich ice (preferably CO 2 hydrate) of a specific size (for example, maximum length of 3 mm or more), the _{CO 2 -rich} ice (preferably CO ₂ hydrate) used is It is preferable that all of the ice have a specific size, but within the range where the effects of the present invention can be obtained, CO2 _- rich ice (preferably CO ₂ hydrate) may also be contained. Among the CO ₂ high content ice (preferably CO ₂ hydrate) in the present invention, the proportion (wt%) of CO ₂ high content ice (preferably CO ₂ hydrate) having a maximum length of less than 3 mm or less than 5 mm. is preferably 10% by weight or less, more preferably 5% by weight or less, even more preferably 3% by weight or less, even more preferably 1% by weight or less.

In the present invention, when using _CO2- rich ice (preferably _CO2 hydrate) of a specific size (for example, maximum length of 3 mm or more), the size can be adjusted by the following method. For example, the maximum length of CO ₂ -rich ice that is not CO ₂ hydrate can be adjusted by adjusting the maximum length of a mold when producing such CO ₂ -rich ice, or when crushing CO ₂ -rich ice after production. This can be adjusted by adjusting the degree of crushing. In addition, the maximum length of CO ₂ hydrate can be adjusted by adjusting the maximum length of the mold used when compression molding CO ₂ hydrate, or by adjusting the degree of crushing when crushing CO ₂ hydrate after compression molding. It can be adjusted by Further, the minimum length can be adjusted by adjusting the minimum length of the mold or by adjusting the degree of crushing of the produced CO2 _- rich ice.

(Method for producing ice with high CO ₂ content in the present invention)
The method for producing ice with a high CO ₂ content in the present invention is not particularly limited as long as it can produce ice with a CO ₂ content of 3% by weight or more. An example of a method for producing high CO ₂ -content ice that is not CO ₂ hydrate is a method of freezing raw water while blowing CO ₂ into the raw water under conditions that do not satisfy the CO ₂ hydrate production conditions. In addition, methods for producing CO ₂ hydrate include a gas _- liquid stirring method in which raw water is stirred while blowing CO ₂ into the raw material water under conditions that satisfy the CO 2 hydrate production conditions, and a method that satisfies the CO ₂ hydrate production conditions. Conventional methods such as a water spray method in which raw water is sprayed into CO ₂ under conditions can be used. CO ₂ hydrate produced by these methods is usually in the form of a slurry in which fine particles of CO ₂ hydrate are mixed with unreacted water, so in order to increase the concentration of CO ₂ hydrate, dehydration is required. Preferably, the treatment is carried out. CO ₂ hydrate whose water content has become relatively low through dehydration treatment (i.e. CO ₂ hydrate with a relatively high CO ₂ content) is compression molded into a certain shape (e.g. spherical or rectangular parallelepiped shape) using a pellet molding machine. It is preferable to do so. The compression-molded CO ₂ hydrate may be used in the present invention as it is, or may be further crushed if necessary. As a method for producing CO ₂ hydrate, as mentioned above, a method using raw water is relatively widely used, but fine ice (raw material ice) is used instead of water (raw material water) to produce CO _{2 hydrate} . It is also possible to use a method in which CO ₂ hydrate is produced by reacting the CO 2 hydrate under conditions of low temperature and low CO ₂ partial pressure.

As mentioned above, the above-mentioned "CO ₂ hydrate generation conditions" are a certain temperature and a condition where the CO ₂ partial pressure (CO ₂ pressure) is higher than the equilibrium pressure of CO ₂ hydrate at that temperature. be. The above "conditions including the CO ₂ partial pressure being higher than the equilibrium pressure of CO ₂ hydrate" are shown in Figure 2 of J. Chem. Eng. Data (1991) 36, 68-71, and in J. Chem. In the equilibrium pressure curve of CO ₂ hydrate (for example, the vertical axis represents CO ₂ pressure and the horizontal axis represents temperature) disclosed in Figure 7. and Figure 15. of Eng. Data (2008), 53, 2182-2188. , combinations of CO 2 pressure and temperature within the region on the high pressure side of such a curve (for example, in _a CO ₂ hydrate equilibrium pressure curve, when the vertical axis represents CO ₂ pressure and the horizontal axis represents temperature, above the curve). expressed as the condition of Specific examples of CO ₂ hydrate generation conditions include a combination of "within the range of -20 to 4°C" and "within the range of carbon dioxide pressure of 1.8 to 4 MPa," and a combination of "within the range of -20 to -4°C" Examples of conditions include a combination of "within the range of carbon dioxide pressure" and "within the range of carbon dioxide pressure of 1.3 to 1.8 MPa."

In the present invention, "consolidated CO ₂ hydrate" means CO ₂ hydrate having a CO ₂ hydrate ratio of 40 to 90% (preferably 50 to 90%, more preferably 60 to 90%). The CO ₂ hydrate ratio means the ratio (%) of the weight of CO ₂ hydrate to the weight of the lump of CO ₂ hydrate. This CO ₂ hydrate rate can be calculated using the following equation (2).
CO ₂ hydrate rate (%) = {(Sample weight before melting - Sample weight after melting) + (Sample weight before melting - Sample weight after melting) ÷ 44 x 5.75 x 18} x 100 ÷ Melting Previous sample weight Equation (2)
Equation (2) will be explained below. (Sample weight before melting−Sample weight after melting) is the weight of CO ₂ gas to be encapsulated. The amount of water required to include CO ₂ gas as a hydrate is calculated using the theoretical hydration number 5.75, the molecular weight of CO ₂ 44, and the molecular weight of water 18. Other water constitutes the hydrate. It is considered as attached water.

The preferable compacted CO ₂ hydrate in the present invention has an ultrafine bubble density of 50 million to 10 billion bubbles/mL and 75 million to 10 billion bubbles/mL when measured by the above-mentioned measurement method D2. mL, 100 million to 10 billion pieces/mL, 150 million to 10 billion pieces/mL, 200 million to 10 billion pieces/mL, 250 million pieces/mL to 10 billion pieces/mL, 50 million pieces/mL ~1 billion cells/mL, 75 million to 1 billion cells/mL, 100 million to 1 billion cells/mL, 150 million to 1 billion cells/mL, 200 million to 1 billion cells/mL, or , CO ₂ hydrate, which can generate ultra-fine bubbles of 250 million bubbles/mL to 1 billion bubbles/mL in water.

In addition, the CO ₂ content of the compacted CO ₂ hydrate suitable for the present invention is preferably 7% by weight or more, more preferably 10% by weight or more, and even more preferably is 13% by weight or more, more preferably 16% by weight or more, still more preferably 19% by weight or more, even more preferably 22% by weight _or more. Further, the upper limit is not particularly limited, but examples thereof include 28% by weight and 26% by weight. More specifically, the CO ₂ content of the compacted CO ₂ hydrate suitable for the present invention is 7-28% by weight, 10-28% by weight, 13-28% by weight, 16-28% by weight, 19-28% by weight. CO that is 28% by weight, 22-28% by weight, 7-26% by weight, 10-26% by weight, 13-26% by weight, 16-26% by weight, 19-26% by weight, or 22-26% by weight ₂ hydrate. In addition, particularly suitable compacted CO ₂ hydrate in the present invention has an ultra-fine bubble concentration within one of the numerical ranges listed in the paragraph immediately preceding this paragraph, and has a CO ₂ content Includes CO ₂ hydrate in any of the numerical ranges listed in this paragraph.

Although the method for producing the compacted CO ₂ hydrate in the present invention is not particularly limited, for example, the following production method can be preferably mentioned.
There is a gas _- liquid stirring method in which raw water is stirred while blowing CO ₂ into the raw water under conditions that meet the CO ₂ hydrate production conditions, and raw water is sprayed into CO ₂ under conditions that meet the CO 2 hydrate production conditions. A conventional method such as a water spray method can be used. The CO ₂ hydrate produced by these methods is usually in the form of a slurry in which fine particles of CO ₂ hydrate are mixed with unreacted water. Consolidated CO ₂ hydrate can be produced by subjecting such slurry to dehydration treatment and compression treatment. The dehydration treatment and compression treatment of a slurry containing CO ₂ hydrate particles and water can be carried out separately and sequentially, for example by dehydrating the slurry and then compressing the CO ₂ hydrate particles. Alternatively, dehydration and compression may be performed simultaneously, such as by compressing the slurry under conditions where the water in the slurry can be discharged, but it is possible to obtain a higher concentration of ultra-fine bubbles. From this point of view, it is preferable to perform the dehydration treatment and the compression treatment at the same time, and especially, it is more preferable to perform the dehydration treatment and the compression treatment at the same time under CO ₂ hydrate generation conditions. The compression treatment of the CO ₂ hydrate particles and the compression treatment of the slurry can be performed using a commercially available compression molding machine or the like. Examples of the pressure during the compression treatment include 1 to 100 Mpa, 1 to 50 Mpa, 1 to 30 Mpa, 1 to 15 Mpa, 1 to 10 Mpa, 1 to 9 MPa, 1.5 to 8 Mpa, 1.5 to 6 Mpa, etc. can. In addition, if the slurry described above is sufficiently dehydrated, the CO ₂ hydrate ratio will normally be about 40%, and if the CO ₂ hydrate particles are compressed at 2.5 MPa after sufficient dehydration treatment, the CO ₂ hydrate The rate rate is usually about 60%, and if the CO ₂ hydrate particles are compressed at 9 MPa after dehydration, the CO ₂ hydrate rate is usually about 90%.

(Improving the stability of ultra-fine bubbles in the cosmetic of the present invention)
It is preferable that the ultra-fine bubbles in the cosmetic of the present invention have improved stability compared to the ultra-fine bubbles in water. In the present invention, high "stability of ultra-fine bubbles" means that when a cosmetic containing ultra-fine bubbles is frozen and thawed, the concentration of ultra-fine bubbles in the cosmetic before freezing is higher than that of the cosmetic after thawing. When water containing ultra-fine bubbles is frozen and thawed, the ratio (%) of the ultra-fine bubble concentration in the water after thawing is the ratio of the ultra-fine bubble concentration in the water before freezing to the ultra-fine bubble concentration in the water before freezing. (%) is preferably included. As a method for calculating such a ratio, the method described in Test 8 of Examples below is preferably mentioned.

(Effects expected from the cosmetics of the present invention containing ultra-fine bubbles)
It is known that carbonated springs in which carbon dioxide gas (CO ₂ ) is dissolved have the effect of dilating blood vessels in the skin and promoting blood circulation in the skin when it comes into contact with the skin. In addition, cosmetics containing carbonated foam have the effect of normalizing skin turnover, adjusting skin texture, softening skin keratin, improving skin complexion, whitening effect, reducing age spots, and reducing dullness. It is said to have the effect of reducing the skin's moisture retention, improving the skin's ability to retain moisture, improving fine lines, improving the adhesion of makeup, and improving the elasticity of the skin. It is also known that fine bubbles, such as ultra-fine bubbles, can penetrate deeper into pores than larger bubbles. From these facts, the cosmetics of the present invention containing fine CO ₂ ultra-fine bubbles at a high concentration (20 million bubbles/mL or more) improve the above-mentioned effects known for existing cosmetics containing carbonated bubbles. It is expected that you will do so.

EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples.

Test 1. [Selection of lotion]
In a later test, after the lotion contains CO ₂ hydrate, the ultra-fine bubble concentration in the lotion is measured. Therefore, we selected a lotion suitable for such measurements. A lotion that is suitable for measuring the concentration of ultra-fine bubbles derived from CO ₂ hydrate is a lotion that is transparent, and a lotion that contains a certain amount of μm-order particles in the initial ingredients of the lotion. . As a lotion that satisfies these conditions and also has a certain degree of viscosity, select "Hada Labo Gokujun Hyaluronic Liquid" (manufactured by Rohto Pharmaceutical Co., Ltd.) or "Chifure Lotion Very Moist Type" (manufactured by Chifure Cosmetics Co., Ltd.). It was decided to use it for later tests.

The ingredients of the above-mentioned "Hada Labo Gokujun Hyaluronic Liquid" are as follows.
Water, BG (1,3-butylene glycol), glycerin, hydrolyzed hyaluronic acid, sodium acetyl hyaluronate, sodium hyaluronate, PPG-10 methylglucose, disodium succinate, hydroxyethylcellulose, succinic acid, methylparaben

In addition, the ingredients of the above-mentioned "Chifure Lotion Very Moist Type" are as follows.
Glycerin, BG, DPG (dipropylene glycol), methylgluceth-10, erythritol, PEG (polyethylene glycol)/PPG (polypropylene glycol)/polybutylene glycol-8/5/3 glycerin, PEG-75, trehalose, hyaluronate Na, Sodium citrate, citric acid, methylparaben, phenoxyethanol

Test 2. [Preparation of CO ₂ hydrate]
CO ₂ gas was blown into 4 L of water at a pressure of 3 MPa, and the CO ₂ hydrate production reaction was allowed to proceed at 1° C. with stirring.
"CO ₂ hydrate slurry" in which CO ₂ hydrate particles are suspended in water is poured into a cylinder-type consolidation machine, and dehydrated by the differential pressure (within 1 MPa) between the inside of the consolidation machine and the dehydration drain to produce CO ₂ hydrate. The crystals of rate particles were concentrated. Then, the CO ₂ hydrate particle crystals were compressed for 3 minutes at a compression pressure of 2 MPa. Thereafter, it was cooled to −20° C., and the cylindrical lump of CO ₂ hydrate was recovered from the compaction molding machine, and then the cylindrical lump was crushed. Polyhedral-shaped CO ₂ hydrate with a maximum length of 3 mm or more and 60 mm or less was selected and recovered and used in subsequent experiments. Note that this CO ₂ hydrate was a compacted CO ₂ hydrate, the CO ₂ content was 24%, and the CO ₂ hydrate rate was about 60%. In addition, in all subsequent tests, this CO ₂ hydrate was used as the CO ₂ hydrate.

Test 3. [Confirmation of ultra-fine bubble generation by incorporating CO ₂ hydrate into lotion Part 1]
The following experiment was conducted to confirm whether ultra-fine bubbles are generated by incorporating CO ₂ hydrate into a lotion, and if so, at what concentration. As a control, we checked whether ultra-fine bubbles were generated in the lotion using an ultra-fine bubble generator.

(1) Generation of ultra-fine bubbles using CO ₂ hydrate A solution obtained by diluting “Hada Labo Gokujun Hyaluronic Solution” by 2 times (hereinafter also referred to as “Gokujun diluted solution”) (viscosity 11.8 mPa・s). Prepared. In addition, in this test (Test 3) and subsequent tests, the viscosity of the lotion was measured using a "Precision rotational viscometer RST-CC double cylinder model" manufactured by Hideko Seiki Co., Ltd. with spindle No. 25, cosmetics The measurement was performed using a 16.8 mL solution.

10 mL of extremely wet diluted solution was added to a glass vial. After adding 3 g of the CO ₂ hydrate prepared in Test 2 above to 10 mL of the extremely moist diluted solution, it was left for a while until the CO ₂ hydrate was completely melted, and then the vial was sealed. It was left standing at 4°C overnight. The ultra-fine bubble concentration in this extremely moist diluted solution (25° C.) was measured using a SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation (upper row of FIG. 1). As a measurement control (corresponding to the background), we used a Gokujun diluted solution (25°C) in which 3 g of water was added instead of hydrate to 10 mL of the aforementioned Gokujun diluted solution. The ultrafine bubble concentration was also measured using the measurement system described above (lower row of Figure 1). The ultrafine bubble concentration of the ultra-wet diluted solution to which CO ₂ hydrate was added is shown in the rightmost bar graph of FIG. Further, the ultra-fine bubble concentration of the measurement control described above is shown in the second bar graph from the right in FIG. In addition, the measured value obtained by subtracting the measured value of the ultra-fine bubble concentration of the measurement control described above from the measured value _of the ultra-fine bubble concentration when CO ₂ hydrate is added, as shown in FIG. The rate is shown in the bar graph on the right side of FIG. 3 as the ultra-fine bubble concentration generated.

(2) Generation of ultra-fine bubbles using an ultra-fine bubble generator 10 L of a 10-fold diluted solution (viscosity 4.4 mPa·s) of "Hada Labo Gokujun Hyaluronic Solution" was prepared. The diluted solution was operated with a swirl flow type ultra-fine bubble generator for 10 minutes to generate bubbles, and then placed in a glass vial and allowed to stand overnight at 4°C. The ultra-fine bubble concentration in this diluted solution (25° C.) was measured using a SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation. As a measurement control, instead of operating the ultra-fine bubble generator described above for the diluted liquid described above, the diluted liquid (25°C) that was simply circulated within the ultra-fine bubble generator was also used as described above. The ultra-fine bubble concentration was measured using a measurement system. The ultra-fine bubble concentration of the diluted solution in which the ultra-fine bubble generator was operated is shown in the second bar graph from the left in FIG. Furthermore, the ultrafine bubble concentration of the measurement control (corresponding to the background) is shown in the leftmost bar graph of FIG. In addition, the measurement value obtained by subtracting the measurement value of the ultra-fine bubble concentration of the measurement control described above from the measurement value of the ultra-fine bubble concentration when the ultra-fine bubble generator is operated as shown in FIG. The ultra-fine bubble concentration generated by the fine bubble generator is shown in the bar graph on the left side of FIG.

(3) Results As can be seen from the results in Figures 1 to 3 (especially Figure 3), when using the ultra-fine bubble generator, it was possible to generate only about 10 million ultra-fine bubbles/mL. On the other hand, when CO ₂ hydrate was used, it was shown that ultrafine bubbles could be generated at a very high concentration of approximately 2.55 billion bubbles/mL.

Test 4. [Confirmation of ultra-fine bubble generation by including CO ₂ hydrate in lotion Part 2]
In order to confirm whether it is possible to generate ultra-fine bubbles at a high concentration by adding CO ₂ hydrate even if the lotion has different ingredients from the lotion used in Test 3 above, the following experiment was conducted. went.

(1) Generation of ultra-fine bubbles by _CO2 hydrate In Test 3 above, a diluted solution of "Hada Labo Gokujun Hyaluronic Solution" was used, but in this test, the undiluted solution (viscosity 8.7 mPa·s) was used. The same test as the test related to FIG. 2 above was conducted in the same manner as described in Test 3 (1) above, except that Chifure undiluted solution was used instead of the Gokujun diluted solution. The ultra-fine bubble concentration when CO ₂ hydrate is added to Chifure stock solution is shown in the rightmost bar graph in Figure 4, and the ultra-fine bubble concentration in the measurement control (background) is shown in the second bar graph from the right in Figure 4. Shown below. In addition, in order to compare the results between Gokujun and Chifure lotion, the results of the two bar graphs on the right side of FIG. 2 (results for Gokujun) are shown in the two bar graphs on the left side of FIG. 4.

(2) Results As can be seen from the results in Figure 4, it was shown that ultra-fine bubbles could be generated at a high concentration by adding CO ₂ hydrate in either of the two types of lotions. . However, the concentration of ultra-fine bubbles generated was approximately 2.55 billion bubbles/mL in the Gokujun diluted solution, while it was approximately 440 million bubbles/mL in the Chifure stock solution (subtracting the measurement control value). value). From this, it was also shown that the concentration of ultra-fine bubbles produced by the addition of CO ₂ hydrate varies depending on the type of lotion.

Test 5. [Confirmation of ultra-fine bubble generation by incorporating CO ₂ hydrate into lotions of various viscosities]
In order to confirm whether it is possible to generate ultra-fine bubbles at a high concentration by adding CO ₂ hydrate even in a lotion with a viscosity different from that used in Tests 3 and 4 above, the following experiment was conducted. I did it.

(1) Generation of ultra-fine bubbles using CO ₂ hydrate Glycerin, sodium hyaluronate, etc. are known as ingredients often used in lotions. Therefore, we mixed deionized water ("Milli-Q Water"), glycerin, and sodium hyaluronate (manufactured by Natural Cosmetics Research Institute) in the proportions shown in Table 1 below to create a total of 5 types of lotions with various viscosities. Created. A CO ₂ hydrate-containing lotion was applied in the same manner as described in Test 3 (1) above, except that one of the five types of lotion was used instead of the Gokujun diluted solution. The ultra-fine bubble concentration in each lotion was measured after it was prepared and allowed to stand overnight at 4°C. The results of these ultra fine bubble concentrations (adjusted with the measured values of the measurement control) are shown in Table 1.

(2) Results As can be seen from the results in Table 1, CO ₂ hydrate can be added not only to lotions with a viscosity of about 8.5 mPa/s, but also to lotions with a high viscosity of about 100 mPa/s. It was shown that ultra-fine bubbles can be generated at high concentration using this method.

Test 6. [Confirmation of ultra-fine bubble generation under pressurized conditions]
In Tests 3 to 5 above, the CO 2 hydrate prepared in Test 2 above was added to the lotion in a _{glass vial, left for a while until the CO 2 hydrate} finished melting, and then the After the vial was sealed and allowed to stand overnight at 4°C, the ultrafine bubble concentration was measured. Therefore, in order to confirm whether ultra-fine bubbles are generated even under pressurized conditions by immediately sealing the container after adding CO ₂ hydrate into a container containing lotion, we conducted the following steps. An experiment was conducted.

(1) Generation of ultra-fine bubbles using CO ₂ hydrate Pour "Gokujun Diluted Solution" (a solution obtained by diluting "Hada Labo Gokujun Hyaluronic Solution" twice (viscosity 11.8 mPa・s)) into a pressure-resistant plastic bottle. I put it in. After adding 30% by weight of CO ₂ hydrate to the ultra-wet diluted liquid into this pressure-resistant PET bottle, immediately seal the pressure-resistant PET bottle tightly to generate ultra-fine bubbles inside the pressure-resistant PET bottle. I let it happen. Inside this closed pressure-resistant PET bottle, a pressurized condition of about 0.4 MPa (gauge pressure) or higher was quickly established due to carbon dioxide generated from the CO ₂ hydrate. After this closed pressure-resistant PET bottle was allowed to stand at 4° C. overnight, the ultrafine bubble concentration in the extremely moist diluted solution was measured (“Pressure+”). As a measurement control (corresponding to the background), ultra-humidity in a pressure-resistant PET bottle (open system) was measured using the same method except that the pressure-resistant PET bottle was not capped even after adding _CO2 hydrate. The concentration of ultrafine bubbles (100 million bubbles/mL) and the median particle diameter (nm) of the bubbles in the diluted solution were measured ("Pressure -").

In addition, the concentration of ultra-fine bubbles (100 million bubbles/mL) and the median particle diameter (nm) of bubbles in water in a pressure-resistant PET bottle were measured using the same method except that water was used instead of the ultra-wet diluted liquid. ("Pressure +", "Pressure -").

These results are shown in Table 2.

(2) Results As can be seen from the results in Table 2, it was shown that ultra-fine bubbles can be generated at a high concentration by adding CO ₂ hydrate to lotion even under pressurized conditions. In addition, the ultra-fine diluted solution under pressurized conditions (sample no. 9) has a concentration about three times that of the ultra-fine diluted solution under atmospheric pressure conditions (open system) (sample no. 8). It has been shown that bubbles can be generated. This indicates that the generation efficiency of ultra-fine bubbles increases when ultra-fine bubbles are generated in a pressure-resistant container under conditions where the pressure is higher than atmospheric pressure. Furthermore, these results indicate that the ultra-fine bubble-containing cosmetic composition of the present invention can also be provided in containers such as aerosol cans, which are frequently used in general carbonated foam cosmetic products.
In addition, water under pressurized conditions (sample No. 7) generates ultra-fine bubbles at a concentration approximately 1.5 times that of water under atmospheric pressure conditions (open system) (sample No. 6). It was shown that it is possible to

Test 7. [Confirmation of ultra-fine bubble generation by incorporating CO ₂ hydrate in water]
In order to confirm whether there is a difference in the concentration of ultra-fine bubbles generated when CO ₂ hydrate is added to lotion and when it is added to water, the following experiment was conducted.

(1) Generation of ultra-fine bubbles using _CO2 hydrate Ultra-fine bubbles were generated using the same method as described in Test 3 (1) above, except that water was used instead of the Gokujun diluted solution. A test was conducted to measure the concentration. The concentration of ultrafine bubbles generated by adding CO ₂ hydrate to water (the value after subtracting the measurement control value) is shown in the leftmost bar graph of FIG. In addition, as a result of the concentration of ultra-fine bubbles generated by adding CO ₂ hydrate to the lotion, the bar graph in the center of Figure 5 shows the concentration of ultra-fine bubbles in the Chifure stock solution obtained in Test 4 above ( The bar graph on the right side of Figure 5 shows the concentration of ultra-fine bubbles in the extremely wet diluted solution obtained in Test 3 above (value minus the measurement control value). show.

(2) Results As can be seen from the results in Figure 5, when CO ₂ hydrate is added to lotion, ultra-fine bubbles are generated at a higher concentration than when CO ₂ hydrate is added to water. Shown. Specifically, when CO ₂ hydrate was added to water, the number of ultra-fine bubbles was about 300 million/mL, whereas in the Chifure stock solution, the number was about 440 million/mL, and the number of ultra-fine bubbles was about 440 million/mL. In the diluted solution, it was 2.55 billion pieces/mL.

Test 8. [Confirmation of stability of ultra-fine bubble]
In order to confirm whether there is a difference in the stability of ultra-fine bubbles generated when CO ₂ hydrate is added to water and when it is added to lotion, the following experiment was conducted.

(1) Ultra-fine bubble stability confirmation test It is known that when a solution containing micro-bubbles is frozen and then thawed, some of the micro-bubbles are destroyed. Therefore, in order to confirm the stability of ultra-fine bubbles, a solution containing ultra-fine bubbles was frozen and then thawed. I decided to check to see if it remained.

In the same manner as described in Test 3 (1) above, CO ₂ hydrate was added to the ultra-wet diluted solution to prepare a ultra-wet diluted solution containing ultra-fine bubbles. Further, in the same manner as described in Test 4 (1) above, CO ₂ hydrate was added to the Chifure stock solution to prepare a Chifure stock solution containing ultra-fine bubbles. Further, in the same manner as described in Test 7 (1) above, CO ₂ hydrate was added to water to prepare water containing ultra-fine bubbles. The concentration of ultra-fine bubbles contained in these three types of solutions prepared was measured using a SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation.

These three types of solutions were put into glass vials, and then the vials were placed in a -20°C freezer and frozen overnight. The vials were taken out of the freezer and placed at room temperature (25° C.) for 24 hours to thaw the frozen solution. The concentration of ultra-fine bubbles contained in these three types of melted solutions was measured using a SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation.

For each of the three solutions, the ratio (%) of the ultrafine bubble concentration after thawing to the ultrafine bubble concentration before freezing ("post-freeze-thaw survival rate") was calculated. The results are shown in FIG.

(2) Results As can be seen from Figure 6, in the case of water, the survival rate of ultrafine bubbles after freezing and thawing was about 40%, while for Gokujun it was about 64%, and for Chifure stock solution it was about 98%. It was 5%. This indicates that the stability of ultra-fine bubbles is improved in lotion than in water.

According to the present invention, cosmetics containing ultra-fine bubbles at a high concentration can be provided easily and at low cost.

Claims (6)

A cosmetic containing 20 million or more ultra-fine bubbles/mL as measured by the following measurement method D1, wherein the ultra-fine bubbles are CO ₂ hydrate with a CO ₂ content of 3% by weight or more. Ultra-fine bubbles created by incorporating into cosmetics,
The cosmetic.
(Measurement method D1)
The concentration of ultrafine bubbles (pieces/mL) in the cosmetic is measured by a laser diffraction/scattering method or a nanotracking method. The cosmetic according to claim 1, which has a viscosity of 3 to 6,500 mPa·s at 25°C. 3. The cosmetic according to claim 1, wherein the cosmetic is selected from the group consisting of a skin cosmetic, a hair cosmetic, a cleaning agent, a shaving foam, a mouth cosmetic, and a hand disinfectant. The concentration of ultra-fine bubbles (pieces/mL) can be measured using the laser diffraction/scattering method, and the concentration of ultra-fine bubbles (pieces/mL) can be measured using the SALD-7500 ultra-fine bubble measurement system manufactured by Shimadzu Corporation. Claims 1 to 3 : Yes, and measuring the concentration of ultra-fine bubbles (pieces/mL) by the nanotracking method means measuring the concentration of ultra-fine bubbles (pieces/mL) using NanoSight NS300 manufactured by Malvern. Cosmetics described in any of the above. The cosmetic according to any one of claims 1 to 4 , which is housed in a container. The cosmetic according to claim 5 , wherein the gauge pressure of the container is higher than 0 MPa and lower than 1 MPa.