JP6694118B2 - Cream and its manufacturing method - Google Patents

Description

  The present invention relates to a cream and a method for producing the cream.

  In recent years, hydrogen gas is expected to have various functions such as a function of removing active oxygen and a function of enhancing biological activity. Therefore, cosmetics, foods, beverages, etc. containing hydrogen gas are drawing attention.

As the cream containing hydrogen gas or the cream capable of generating hydrogen gas, for example, the followings have been proposed.
(1) An aqueous phase in which a moisturizing component, an alkaline agent, etc. are mixed with hydrogen water having a dissolved hydrogen amount of 0.5 to 1.5 ppm, and a surfactant, a drug, a preservative, an antioxidant, a fragrance, etc. are added to the oil component. A cream obtained by mixing and emulsifying the blended oil phase (Patent Document 1).
(2) A cream containing fine particles of a hydrogen storage alloy such as magnesium hydride (Patent Document 2).

JP, 2007-308467, A International Publication No. 2012/111834

The cream of (1) has maximum hydrogen water, and contains 1.5 ppm (1.8 vol% [v / w]) of hydrogen gas as dissolved hydrogen, which is close to the saturated solubility of hydrogen gas in water. However, since the cream of (1) is manufactured through a heating process and a degassing process, the final product does not contain hydrogen gas in a bubble state other than dissolved hydrogen in hydrogen water.
In order to sufficiently express various functions of hydrogen gas, it is desired to further increase the content rate of hydrogen gas contained in the whole cream.

  The cream of (2) generates hydrogen gas by the chemical reaction between the hydrogen storage alloy and the water content of the skin, and there is a concern that it may have an adverse effect on the skin.

  The present invention provides a cream having a high hydrogen gas content and having less adverse effects on the skin, and a method for producing the cream.

The present invention has the following aspects.
<1> A cream containing a hydrogen gas in a bubble state in a composition containing a fatty acid salt having a carbon number of 10 or more, a fatty acid having a carbon number of 10 or more, and a liquid medium, wherein the hydrogen gas in the bubble state is contained in the cream. A cream having a rate of 0.1 to 100% by volume [v / w].
<2> The cream according to <1>, wherein the composition further contains a higher alcohol.
<3> The cream according to <1> or <2>, wherein the composition further contains a surfactant.
<4> The cream according to any one of the above <1> to <3>, wherein the composition further contains one or both of oil and fat and wax.
<5> The cream according to any one of <1> to <4>, wherein the hydrogen gas in the bubble state has an average bubble diameter of 1 μm to 1 mm.
<6> The method for producing a cream according to any one of <1> to <5>, wherein a composition containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms, and a liquid medium is prepared, and the composition is A method for producing a cream, comprising the step of incorporating hydrogen gas in the form of bubbles into the composition to thicken the composition containing the hydrogen gas in the form of bubbles.
<7> The method for producing a cream according to <6>, wherein the solution A containing an alkaline agent and a liquid medium and the solution B containing a fatty acid having 10 or more carbon atoms are mixed to prepare the composition.

The cream of the present invention has a high hydrogen gas content and has little adverse effect on the skin.
According to the method for producing a cream of the present invention, it is possible to produce a cream having a high hydrogen gas content and a small adverse effect on the skin.

It is an external appearance photograph of the cream of Example 1 with which a headspace vial was filled. 3 is a photograph of the cream of Example 1 observed with a microscope. It is a graph which shows the time change of the content rate of hydrogen gas in the cream of Example 1 stored in the glass sample bottle.

The following definitions of terms apply throughout the specification and claims.
“Higher alcohol” means an alcohol having 6 or more carbon atoms.
"The content rate of hydrogen gas in a bubble state in the cream (volume% [v / w])" means a ratio of the volume (cm ³ ) of hydrogen gas contained in a bubble state in a predetermined amount (100 g) of the cream. ..
The “saturated solubility of hydrogen gas in water” refers to the saturated solubility of hydrogen gas in water under atmospheric pressure. The "gas dissolution" that defines the saturation solubility is a state in which Henry's law is satisfied and the gas is dissolved in a molecular state according to the pressure.

The content rate of bubbled hydrogen gas in the cream is obtained as follows. A small amount of cream is precisely weighed and sealed in a headspace vial used for GC analysis under the conditions of atmospheric pressure and room temperature. Heat the headspace vial to 70 ° C and continue heating at 70 ° C until air bubbles disappear from the cream. After the bubbles disappeared, the gas in the headspace vial was sampled, and the hydrogen gas was quantified by gas chromatograph (GC) analysis (TCD detector). % [V / w]) is calculated. The saturated solubility of hydrogen gas in water is 1.6 ppm (2% by volume [v / w]) at 20 ° C and 1.5 ppm (1.8% by volume [v / w]) at 70 ° C, which is almost unchanged. That is, since the amount of dissolved hydrogen gas in the composition (almost water) hardly changes before and after the measurement, the content rate of hydrogen gas obtained by the above method can be regarded as the content rate of hydrogen gas in a bubble state.
The average bubble diameter of hydrogen gas in the bubble state is obtained by measuring the bubble diameters of 10 randomly selected bubbles by observing with a microscope and calculating the average value thereof. If the observed bubble is an ellipse or the like that is not a true sphere, the average value of its maximum and minimum diameters is taken as the bubble diameter.
In the present specification and claims, “to” indicating a numerical range means that numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

<< Cream >>
The cream of the present invention contains hydrogen gas in an aerated state in a composition containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms, and a liquid medium.

<Hydrogen gas in bubble state>
The average bubble diameter of hydrogen gas in a bubble state is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 30 μm or more. When the average bubble diameter of the hydrogen gas in the bubble state is equal to or more than the lower limit value of the above range, it is easy to increase the content rate of the hydrogen gas in the bubble state in the cream.
The average bubble diameter of hydrogen gas in a bubble state is preferably 1 mm or less, more preferably 500 μm or less, further preferably 300 μm or less, and particularly preferably 100 μm or less. When the average bubble diameter of the hydrogen gas in the bubble state is equal to or less than the upper limit value of the above range, it is easy to retain the hydrogen gas in the bubble state in the cream for a long time. Further, the hydrogen gas in a bubble state is uniformly dispersed in the cream, and the cream becomes a good cream having a milky white appearance due to fine bubbles.

  The average bubble diameter of hydrogen gas in a bubble state is preferably 1 μm to 1 mm, more preferably 10 μm to 500 μm, further preferably 30 μm to 300 μm, and particularly preferably 30 μm to 100 μm.

  The content of hydrogen gas in a bubble state in the cream is 0.1 to 100% by volume [v / w], preferably 10 to 100% by volume [v / w], and 20 to 95% by volume [v / w]. ] Is more preferable, and 40-90 volume% [v / w] is still more preferable. If the content of hydrogen gas in the foam state in the cream is equal to or higher than the lower limit value of the above range, the content of total hydrogen gas in the cream summed with the amount of dissolved hydrogen gas in the composition is higher than that of the conventional cream. As the number of hydrogen gas increases, various functions of hydrogen gas can be sufficiently exhibited. When the content rate of hydrogen gas in a bubble state in the cream is up to the upper limit value of the above range, hydrogen gas bubbles can be dispersed and a good appearance is exhibited. If the bubbles are dispersed over this range, it becomes difficult to form a stable bubble liquid film, and stable bubbles cannot be formed.

  The bubble diameter of the hydrogen gas in the bubble state and the content rate of the hydrogen gas in the bubble state in the cream are the amount and composition of fatty acids having 10 or more carbon atoms, higher alcohols, surfactants, fats and oils, wax, etc. in the production method described later. It can be adjusted by changing the supply amount of hydrogen gas when the hydrogen gas in the form of bubbles is included in the substance and the stirring conditions (rotation speed, time, etc.) of the composition.

<Composition>
The composition is a cream obtained by thickening an emulsion obtained by emulsifying an oil component and an aqueous component. The emulsion may be a W / O type or an O / W type.

Typical creams include a base that serves as a base for the cream; a drug that imparts various functions to the cream; a raw material for imparting a sensory characteristic that imparts a feeling of satisfaction that acts on the visual sense, the sense of smell, and the like; retains the quality of the cream. Including quality retention raw materials.
The composition of the present invention serves as a base for containing hydrogen gas in an air bubble state in the cream of the present invention, and is a fatty acid having 10 or more carbon atoms classified as an oily component of a base and a salt thereof, and a group. A liquid medium classified as an aqueous component of the agent is contained as an essential component. The composition in the present invention preferably further contains a higher alcohol classified as an oil component of the base. The composition in the present invention preferably further contains a surfactant classified as a base. The composition of the present invention preferably further contains either or both of a fat and a wax classified as an oil component of the base. The composition in the present invention comprises, if necessary, a fatty acid having 10 or more carbon atoms, a liquid medium, a higher alcohol, a surfactant, a base other than fats and oils and waxes, a drug, a sensory characteristic imparting raw material, and a quality keeping raw material. Etc. may be included.

(Fatty acids having 10 or more carbon atoms and salts thereof)
A fatty acid having 10 or more carbon atoms serves as a raw material for a fatty acid salt having 10 or more carbon atoms. The unneutralized fatty acid that has not been converted to a fatty acid salt also acts as a thickening agent to make the composition creamy. The thickened creamy composition can retain a large amount of hydrogen gas in a bubble state for a long time.
Examples of the fatty acid having 10 or more carbon atoms include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, isostearic acid and hydroxystearic acid. The fatty acids may be used alone or in combination of two or more.
As the fatty acid, a fatty acid having 10 to 18 carbon atoms is preferable from the viewpoint of easily forming a good fatty acid salt (soap) as an emulsifier, and capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (carbon C14), palmitic acid (C16) and stearic acid (C18) are more preferable, and myristic acid (C14), palmitic acid (C16) and stearic acid (C18) are more preferable.

The fatty acid salt having 10 or more carbon atoms is produced by reacting a fatty acid having 10 or more carbon atoms with an alkaline agent in the production method described later. The fatty acid salt having 10 or more carbon atoms acts as an emulsifier that emulsifies the aqueous component and the oil component of the base.
Examples of the fatty acid salt include sodium salt, potassium salt and triethanolamine salt of fatty acid.
As the fatty acid salt, salts of fatty acids having 10 to 18 carbon atoms are preferable, and capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), stearin A salt of an acid (having 18 carbon atoms) is more preferable, and a salt of myristic acid (having 14 carbon atoms), palmitic acid (having 16 carbon atoms) and stearic acid (having 18 carbon atoms) is further preferable.

(Liquid medium)
The liquid medium serves as a medium for dissolving or dispersing other components.
As the liquid medium, an aqueous medium containing water is preferable because it easily emulsifies with an oily component to form an emulsion. The aqueous medium may further contain a lower alcohol or glycol.
Examples of water include purified water. Examples of the lower alcohol include ethyl alcohol and isopropyl alcohol. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, and 1,4-butanediol.
The proportion of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass, of the aqueous medium (100% by mass).

(Higher alcohol)
Higher alcohol improves the feeling of use of the cream of the present invention. The higher alcohol also acts as a thickener to adjust the viscosity of the composition.
Examples of the higher alcohols include caproyl alcohol, caprylyl alcohol, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, hexyldecanol, isostearyl alcohol, and octyldodecanol. .. The higher alcohols may be used alone or in combination of two or more.
As the higher alcohol, an alcohol having 12 to 22 carbon atoms is preferable from the viewpoint that the composition is easily creamed, and at least cetyl alcohol is contained from the viewpoint that the content of hydrogen gas in a foam state in the cream can be sufficiently increased. Is particularly preferable.

(Surfactant)
A surfactant is a solubilizing action that dissolves an oily component in water, an emulsifying action that disperses an oily component in water, a dispersing action that disperses a powder component in oil or water, a cleaning action that removes dirt, and a foaming that improves foaming. It is an ingredient that is added to creams to impart functions such as action.
In the cream of the present invention, the surfactant has a function of uniformly and finely dispersing the hydrogen gas in the foam state in the composition, and at the same time, having a function of keeping the hydrogen gas in the foam state in the cream for a long time.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. As the surfactant, a nonionic surfactant is preferable because it works as an emulsifier even at a relatively low temperature.

  As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyalkylene derivative, reactive surfactant, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, glycerin fatty acid Examples thereof include esters, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkylalkanolamides, and fatty acid sucrose. As the nonionic surfactant, fatty acid sucrose is preferable from the viewpoint of mildness.

Examples of the anionic surfactant include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylbenzene sulfonates, other sulfonates, reactive surfactants, fatty acid salts, and naphthalene sulfonic acid formalin condensates. Is mentioned.
Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
Examples of the amphoteric surfactant include alkyl betaine and alkyl amine oxide. As the amphoteric surfactant, alkyl betaine is preferable.
As the surfactant, one type may be used alone, or two or more types may be used in combination.

(Oil and fat)
Oils and fats are components (emollients: emollients) added for the purpose of smoothing the skin.
Examples of fats and oils include natural fats and oils (castor oil, camellia oil, olive oil, apricot oil, shea oil, avocado oil, almond oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, persic oil, palm oil). , Sunflower oil, grape seed oil, macadamia nut oil, meadowfoam oil, cottonseed oil, coconut oil, peanut oil, beef tallow, horse oil, mink oil, etc., hydrocarbons (isodecane, dodecane, tetradecane, squalane, α-olefin oligomer, fluid) Paraffin, petrolatum, isoparaffin, microcrystalline wax, ceresin, etc.) and the like. The fats and oils may be used alone or in combination of two or more.
Examples of fats and oils are castor oil, camellia oil, olive oil, apricot oil, shea oil, avocado oil, almond oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, persic oil, palm oil, sunflower oil. , Grape seed oil, macadamia nut oil, meadowfoam oil, cottonseed oil, coconut oil, peanut oil, beef tallow, horse oil, mink oil, isodecane, dodecane, tetradecane, squalane, α-olefin oligomer, liquid paraffin, petrolatum, isoparaffin, microcrystalline Wax and ceresin are preferred.

(Row)
Wax is an ingredient added to improve the feel of the cream.
Examples of the wax include beeswax, carnauba wax, candelilla wax, rice bran wax, lanolin, jojoba oil, orange laffy oil and the like. The wax may be used alone or in combination of two or more.
As the wax, beeswax, carnauba wax, candelilla wax, rice bran wax, lanolin, jojoba oil, and orange laffy oil are preferable.

(Other bases)
Other bases include purified water, other aqueous components other than lower alcohols, fatty acids having 10 or more carbon atoms, higher alcohols, oils and fats other than waxes and waxes, powder components and the like.

Other aqueous components include thickeners.
The thickener is a component added for adjusting the viscosity of the cream, stabilizing it, and adjusting the feeling of use.
Examples of the thickener include water-soluble polymers. Examples of the water-soluble polymer include organic water-soluble polymers and inorganic water-soluble polymers.
Examples of organic water-soluble polymers include natural polymers (xanthan gum, mannan, pectin, etc.), cellulosic semi-synthetic polymers (carboxymethyl cellulose sodium, etc.), vinyl synthetic polymers (carboxyvinyl polymers and their derivatives, polyvinyl alcohol, Polyvinylpyrrolidone and derivatives thereof, etc.) and the like.
Examples of the inorganic water-soluble polymer include pentonite, which is a type of clay mineral.

Other oily components include esters (fatty acid esters such as monoglyceride, diglyceride, triglyceride) and silicone oils (dimethylpolysiloxane, dimethylcyclopentasiloxane, amino-modified silicone, alkyl-modified silicone, etc.).
Examples of powder components include colored pigments (alumina etc.), white pigments (titanium oxide, zinc oxide etc.), pearl agents (iron oxide, mica-based synthetic pearls etc.), extender pigments (talc, kaolin, mica etc.) and the like. ..

(Drug)
Examples of the drug include a moisturizing component, an astringent (antiperspirant), a refreshing agent, an anti-UV agent, and other agents.
Examples of the moisturizing component include hydrolyzed collagen, glycerin, steariztrimethylammonium chloride, propylene glycol, 1,3-butylene glycol, betaine, hyaluronic acid, lavender oil, ethylhexylglycerin and the like.
Examples of the astringent agents include citric acid, lactic acid, aluminum sulfate, lemon water, hamamelis and the like.
Examples of the cooling agent include menthol, ethyl alcohol, camphor, eucalyptus oil and the like.
Examples of the anti-UV agent include titanium oxide, zinc oxide, octyltriazone and the like.
Other agents include whitening agents (vitamin C or its derivatives), hair restorers, acne agents, dandruff / itch agents, armpit odor inhibitors, anti-inflammatory agents (dipotassium glycyrrhizinate, etc.), bactericides, nutritional agents, and activating agents. Agents, biophysiological function improving agents and the like.

(Raw material for imparting sensual characteristics)
Examples of the raw material for imparting sensory characteristics include fragrances and pigments.
Examples of the fragrance include natural fragrances derived from plants or animals, synthetic fragrances synthesized organically, and the like.
Examples of the pigment include tar pigments (organic synthetic pigments, etc.) that can be used in cosmetics specified by the Ministry of Health, Labor and Welfare, natural pigments extracted from animals and plants or microorganisms, inorganic pigments and the like.

(Quality-maintaining raw material)
Examples of the quality maintaining raw material include preservatives, antioxidants, sequestering agents (metal ion element sealing agents), anti-fading agents, buffers and the like.
Examples of the preservatives include paraoxybenzoic acid ester (paraben), sorbic acid, sodium dehydroacetate, quaternary ammonium salts (benzalkonium chloride, benzethonium chloride, etc.), chloroxidine, pentylene glycol, phenoxyethanol, ethylhexylglycerin and the like. ..
Examples of the antioxidant include tocopherol (vitamin E), ascorbic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and the like.
Examples of the sequestering agent include chelating agents (sodium edetate, ethylenediaminetetraacetic acid salt (EDTA), citric acid, etc.) and the like.

(Ratio of each component)
The ratio of the liquid medium in the composition is the balance excluding the ratio of components other than the liquid medium.
The proportion of the liquid medium in the composition (100% by mass) is preferably 80 to 99.99% by mass, more preferably 85 to 99.9% by mass, and further preferably 92 to 99% by mass. When the ratio of the liquid medium is not more than the upper limit value of the above range, the thickening effect is sufficiently exhibited, and a large amount of hydrogen gas in a bubble state in the composition can be easily retained for a long time. When the ratio of the liquid medium is at least the lower limit value of the above range, the viscosity of the composition does not become too high, and the cream of the present invention has a good feeling in use.

  The total proportion of fatty acids having 10 or more carbon atoms and salts thereof is preferably 0.01 to 20% by mass, and more preferably 1 to 8% by mass in the composition (100% by mass). When the total ratio of the fatty acids having 10 or more carbon atoms and salts thereof is at least the lower limit value of the above range, the thickening effect is sufficiently exerted, and a large amount of hydrogen gas in a bubble state is contained in the composition for a long time. Easy to hold. When the total ratio of the fatty acids having 10 or more carbon atoms and salts thereof is at most the upper limit value of the above range, the viscosity of the composition does not become too high, and the cream of the present invention has a good feeling in use.

The proportion of fatty acid salts in the total of fatty acids having 10 or more carbon atoms and salts thereof is preferably 0.1 to 40 mol%, more preferably 0.5 to 25 mol%, and further preferably 1 to 10 mol%. When the proportion of the fatty acid salt is within the above range, the aqueous component and the oily component are sufficiently emulsified.
The proportion of fatty acids in the total of fatty acids having 10 or more carbon atoms and salts thereof is preferably 60 to 99.9 mol%, more preferably 75 to 99.5 mol%, and further preferably 90 to 99 mol%. When the proportion of fatty acid is within the above range, the aqueous component and the oily component are sufficiently emulsified.

  When the composition contains a higher alcohol, the proportion of the higher alcohol in the composition (100% by mass) is preferably 0.01 to 20% by mass, and more preferably 1 to 10% by mass. When the proportion of the higher alcohol is at least the lower limit value of the above range, the thickening effect is sufficiently exerted, and a large amount of hydrogen gas in a foam state in the composition can be easily retained for a long time. When the proportion of the higher alcohol is at most the upper limit value of the above range, the viscosity of the composition does not become too high and the cream of the present invention has a good feeling in use.

  When the composition contains a surfactant, the proportion of the surfactant is preferably 0.01 to 5% by mass and more preferably 0.1 to 3% by mass in the composition (100% by mass). When the ratio of the surfactant is at least the lower limit value of the above range, it is easy to uniformly disperse the hydrogen gas in the composition in the composition and to retain the hydrogen gas in the composition in the composition for a long time. It is useless to add an amount of the surfactant exceeding the upper limit of the above range, and a problem due to an excessive amount of the surfactant may occur.

  When the composition contains one or both of fats and oils and wax, the total proportion of the fats and oils and wax is preferably 0.01 to 90% by mass, and 0.1 to 50% by mass of the composition (100% by mass). Mass% is more preferable. 1 to 20 mass% is more preferable, and 2 to 10 mass% is further preferable. When the total ratio of the fats and oils and the wax is at least the lower limit value of the above range, the unpleasant feeling of use such as bulkiness when the cream is applied to the skin can be suppressed. When the total proportion of fats and oils and wax is not more than the upper limit value of the above range, adverse effects on usability such as stickiness can be suppressed.

  The proportions of the other bases, the medicines, the organoleptic characteristic imparting raw materials, and the quality maintaining raw materials may be appropriately selected within the range of known blending proportions depending on the characteristics and functions required of the cream.

<Use>
As the use of the cream of the present invention, lip cream, eye cream, nail cream, massage cold cream, moisture cream, other skin cream, cleansing cream, hair cream, sunscreen cream, sunscreen cream, shaving cream, etc. Is mentioned.

<Mechanism of action>
In the cream of the present invention described above, the composition containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms, and a liquid medium contains hydrogen gas in an aerated state, and therefore the composition A large amount of hydrogen gas in a bubble state can be retained for a long time. The cream of the present invention contains hydrogen gas dissolved in the composition, and 0.1 to 100% by volume [v / w] hydrogen gas in a bubble state contained in the composition. Since the cream of the present invention contains gas in the form of bubbles, it means that hydrogen gas is dissolved in the composition in an amount equal to the saturated solubility of hydrogen gas in water. That is, the total amount of the hydrogen gas dissolved in the composition and the hydrogen gas in a bubble state exceeds the saturated solubility of hydrogen gas in water (the amount of hydrogen gas contained in the conventional hydrogen gas-dissolved cream). Thus, a cream containing a large amount of hydrogen gas can sufficiently exhibit various functions of hydrogen gas (a function of removing active oxygen, a function of increasing biological activity, etc.).

<< Method of manufacturing cream >>
According to the method for producing a cream of the present invention, a composition containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms, and a liquid medium is prepared. A method of thickening a composition containing gas to obtain a cream.
Specifically, it has the following steps (I) to (III).
Step (I): A step of preparing a composition (emulsion) containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms, and a liquid medium.
Step (II): A step of incorporating hydrogen gas in a bubble state into the emulsion after the step (I).
Step (III): A step of thickening the emulsion containing hydrogen gas in a bubble state into a cream after the step (II).

<Process (I)>
As a method of preparing the composition (emulsion), a method of mixing the liquid A containing the alkaline agent and the liquid medium and the liquid B containing the fatty acid having 10 or more carbon atoms is preferable from the viewpoint of obtaining a good emulsion.
When the higher alcohol is used, it is preferable that the higher alcohol is contained in the liquid B.
When a surfactant is used, it is preferable to include the surfactant in the liquid A.
When fats and oils are used, it is preferable to include the fats and oils in the liquid B.
When a wax is used, it is preferable that the wax is contained in the liquid B.
When using other components (other bases, drugs, raw materials for imparting organoleptic characteristics, and quality maintaining raw materials), it is preferable that the water-soluble components are contained in the liquid A and the oil-soluble components are contained in the liquid B. Preferably.

  Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, ammonia, amines (triethanolamine, triethylamine, diisopropanolamine, di (2-ethylhexyl) amine, etc.) and the like. As the alkaline agent, sodium hydroxide, potassium hydroxide and triethanolamine are preferable.

The solutions A and B before mixing are preferably heated so as to be in a solution state. It is more preferable that solution B before mixing is heated to a temperature equal to or higher than the melting point of a fatty acid having 10 or more carbon atoms.
When the liquid A and the liquid B are mixed, the liquid A may be added thereto while stirring the liquid B, or the liquid B may be added thereto while stirring the liquid A. For example, when the liquid A is added to the liquid B while stirring the liquid B, a fine and uniform emulsion is obtained.
By mixing the liquid A and the liquid B, a part of the fatty acid having 10 or more carbon atoms is neutralized by the alkaline agent to form a fatty acid salt (emulsifier) having 10 or more carbon atoms.
The mixed liquid of the liquid A and the liquid B is emulsified using a known emulsifying device such as a homomixer to obtain an emulsion.
The amount of the alkaline agent used in the step (I) depends on the proportion of the fatty acid salt in the total of the fatty acids having 10 or more carbon atoms and their salts in the composition, and in the total of the fatty acids having 10 or more carbon atoms and their salts. It can be determined according to the ratio of the fatty acid.

<Step (II)>
By supplying hydrogen gas to the composition (emulsion), a composition containing hydrogen gas in a bubble state is obtained.

The viscosity of the composition at the time of supplying hydrogen gas is preferably 1 to 30,000 mPa · s, more preferably 10 to 25,000 mPa · s, further preferably 300 to 20,000 mPa · s, and particularly preferably 500 to 15,000 mPa · s. When the viscosity of the composition is equal to or higher than the lower limit value of the above range, it is easy to prevent the hydrogen gas from floating and to easily retain the hydrogen gas in the composition. When the viscosity of the composition is equal to or lower than the upper limit value of the above range, hydrogen gas is easily dispersed as bubbles in the composition, and uniform distribution of hydrogen gas is facilitated.
The temperature of the composition at the time of supplying hydrogen gas may be any temperature as long as the viscosity range of the composition described above can be achieved, and may be appropriately set.

  The amount of hydrogen gas supplied is such that the total amount of hydrogen gas dissolved in the composition and hydrogen gas in a bubble state exceeds the saturated solubility of hydrogen gas in water. The content of hydrogen gas in the bubble state is 0.1 to 100% by volume [v / w].

  The amount of the fatty acid having 10 or more carbon atoms, the alkaline agent, the liquid medium, and the like, and the supply amount of the hydrogen gas may be appropriately set according to the content rate of the hydrogen gas in the bubble state in the desired composition and the bubble diameter. Also, the temperature and viscosity of the composition may be appropriately set according to the type of fatty acid having 10 or more carbon atoms, the alkaline agent, the liquid medium, the content of hydrogen gas in a bubble state in the desired composition, and the bubble diameter. Good.

  As a device used in the step (II), a device and equipment used in a known gas-liquid dispersion operation can be used as long as the device can uniformly disperse hydrogen gas in the composition as desired bubbles. The material of the device is, in a range that does not impair the effects of the present invention, in consideration of corrosion resistance to fatty acids having 10 or more carbon atoms, liquid medium, alkaline agent, hydrogen gas, etc .; heat resistance at use temperature; elution into composition, etc. Can be selected.

In the step (II), supplying hydrogen gas to the composition while stirring the composition; or supplying hydrogen gas to the composition without stirring the composition and then shaking the composition. preferable.
Examples of the stirring method include a method using a stirrer, a method using a homomixer, and a method using a line mixer.
Examples of the shaking method include a method using a shaker.

<Step (III)>
By thickening the composition (emulsion) containing gas in the bubble state to form a cream, a cream containing hydrogen gas in the bubble state in the composition is obtained.
The thickening of the composition can be carried out, for example, by cooling the composition.
In order to reduce as much as possible the volatilization loss of hydrogen gas contained in the composition in the form of bubbles, it is preferable to thicken the composition as quickly as possible.

<Filling into container>
Fill the container with cream as needed and seal.
In order to suppress the loss of vaporized hydrogen gas in the gas phase, it is preferable to perform filling and sealing as quickly as possible.

  The container is preferably made of a material that does not easily permeate hydrogen gas in order to suppress hydrogen gas permeation loss. Examples of the container include a pouch having an aluminum layer, a bag made of a film having low hydrogen gas permeability, a metal container, and a composite container in which these are combined.

As a filling method, from the viewpoint of suppressing volatilization loss of hydrogen gas in a bubble state into the gas phase, a method is preferable in which the container is filled with cream so that there is as little gas phase space as possible and the container can be quickly sealed.
The sealing method depends on the type of the container, but examples thereof include known sealing methods such as heat sealing and sealing with a lid having an inner lid.

The viscosity of the cream during storage is preferably 1000 mPa · s or more, more preferably 5000 mPa · s or more, still more preferably 10000 mPa · s or more. If the viscosity of the cream during storage is not less than the lower limit of the above range, bubble hydrogen gas can be stably retained in the cream during storage.
The temperature of the cream during storage may be any temperature as long as the above-mentioned cream viscosity range can be achieved, and may be appropriately set.

<Mechanism of action>
In the method for producing a cream of the present invention described above, a composition containing a fatty acid salt having 10 or more carbon atoms, a fatty acid having 10 or more carbon atoms and a liquid medium is prepared, and the composition contains hydrogen gas in a bubble state. This is a method of increasing the viscosity of a composition containing hydrogen gas in a bubble state, and thus a cream having a high hydrogen gas content can be produced, as described below.
Generally, the lower the viscosity of the composition, the easier the hydrogen gas moves in the composition and the more easily it is dispersed as bubbles. However, the fact that hydrogen gas easily moves in the composition means that it is difficult for the hydrogen gas to remain in the composition, and there is a high possibility that it will be vaporized into the gas phase. On the contrary, when the composition has a high viscosity, hydrogen gas is difficult to disperse, which is not preferable for forming bubbles. Of course, after the composition has thickened and turned into a cream, it becomes virtually impossible to disperse hydrogen gas.
According to the method for producing a cream of the present invention, hydrogen gas is uniformly dispersed as bubbles in the composition before thickening to a high concentration, and then the composition is rapidly thickened to form a cream composition. Hydrogen gas in the form of bubbles can be contained therein at a high concentration.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<Measurement>
The methods for measuring each physical property in the examples are shown below.
(viscosity)
The viscosity was measured using an E-type viscometer (manufactured by Brookfield, RV DV1M).

(Observation of dispersed state of bubbles of hydrogen gas in cream)
By observing the side surface of the bottle from above with a microscope (Digital Microscope VHX-900F manufactured by Keyence Corp.) in a state where the headspace vial filled with cream is laid down sideways, the dispersed state of hydrogen gas in a bubble state can be confirmed. I observed.

(Average bubble diameter of hydrogen gas in bubble state)
The average bubble diameter of hydrogen gas in the bubble state was determined by measuring the bubble diameters of 10 randomly selected bubbles by microscope observation (magnification: 175 times) and calculating the average value thereof. When the observed bubble is an ellipse or the like that is not a true sphere, the average value of the maximum diameter and the minimum diameter is taken as the bubble diameter.

(Content of bubbled hydrogen gas in cream)
0.5 to 1 g of the cream was put into a headspace vial (capacity: 20 mL) used for GC analysis precisely at 25 ° C under atmospheric pressure, the headspace vial was heated to 70 ° C, and bubbles were generated from the cream. Heating was continued at 70 ° C. until it disappeared. After the bubbles disappeared, the gas phase gas in the headspace vial was sampled, and the hydrogen gas was quantified by GC analysis (TCD detector), and the hydrogen gas content in the foam state in the cream (volume% [v / w]) was calculated.

<Evaluation>
(Dispersion of bubbles)
The dispersion state of air bubbles in the cream 24 hours after the production of the cream was evaluated according to the following criteria.
A: Air bubbles in the cream are uniformly dispersed.
B: Bubbles in the cream floated and a transparent layer was slightly formed on the lower side.
C: Bubbles in the cream floated up and were completely separated into an upper gas phase and a lower transparent layer.

(Usage)
The feeling of use of the cream was evaluated by the 4 persons on the following items in 3 grades (good: 3, normal: 2, poor: 1), and the average thereof was evaluated according to the following criteria.
Evaluation item:
1) Familiarity and spread on the skin 2) Smoothness 3) Smoothness 4) Stickiness 5) Softness 6) Preference evaluation criteria:
A: 2 or more B: 1.5 or more and less than 2 C: less than 1.5

<Raw material>
(Liquid A)
Preservative 1: Ethylhexylglycerin (manufactured by Schalke & Meyer (obtained from Seiwa Kasei), SENSIVA (registered trademark) SC50JP).
Preservative 2: Phenoxyethanol (Phenoxyethanol-S manufactured by Yokkaichi Gosei Co., Ltd.).
Moisturizing component 1: concentrated glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., concentrated glycerin for cosmetics).
Moisturizing component 2: Propylene glycol (manufactured by Asahi Glass Co., Ltd., dipropylene glycol / DPG-FC).
Surfactant 1: Nonionic surfactant (Surf Hope (registered trademark) SE COSME C-1811 manufactured by Mitsubishi Chemical Foods).
Hydrogen water: (Evolution water (registered trademark) hydrogen water (bottle) manufactured by ITO EN).
Alkaline agent 1: 10% by mass potassium hydroxide aqueous solution (Kako hydroxide, manufactured by Wako Pure Chemical Industries, Ltd.).

(B liquid)
Row 1: Jojoba oil (NIKKOL (registered trademark) Jojoba oil S manufactured by Nikko Chemical Co., Ltd.).
Fat 1: Olive oil (containing a small amount of antioxidant tocopherol) (CRODA JAPAN, CROPURE (registered trademark) MEADOWFOAM-LQ- (JP)).
Fat 2: Shea oil (containing a trace amount of antioxidant tocopherol) (CRODA JAPAN, CROPURE (registered trademark) SHEA BUTTER-SO- (JP)).
Fat 3: Mineral oil (liquid paraffin) (Kaydol (registered trademark), manufactured by Shima Trading Co., Ltd.).
Higher alcohol 1: Behenyl alcohol (Calcor (registered trademark) 220-80 manufactured by Kao Corporation).
Higher alcohol 2: Stearyl alcohol (Kalcoal (registered trademark) 8688 manufactured by Kao Corporation).
Higher alcohol 3: Cetyl alcohol (Calcol (registered trademark) 6098 manufactured by Kao Corporation).
Fatty acid 1: Stearic acid (Lunack (registered trademark) S-70V, manufactured by Kao Corporation).
Ester 1: Butyl stearate (Exepearl (registered trademark) BS, manufactured by Kao Corporation).
Surfactant 2: Nonionic surfactant (manufactured by Kao, Leodol (registered trademark) MS-165V).
Preservative 3: Methylparaben (Wako Pure Chemical Industries, Ltd., methyl p-hydroxybenzoate).

<Examples 1 to 5>
(Process (I))
Each component of the liquid A shown in Table 1 was placed in a glass beaker at the ratio shown in Table 1, and heated to 70 ° C. in a water bath to make a solution.
Each component of the liquid B shown in Table 1 was put in another glass beaker in the ratio shown in Table 1, and heated to 70 ° C. in a water bath to be in a solution state.
The liquid A was added to the liquid B while stirring the liquid B to obtain a mixed liquid. The mixture was cooled to 55 ° C. with stirring using a homomixer (Labulution, manufactured by Primix) at a rotation speed of 1,400 to 3,000 rpm to obtain a composition (emulsion) having a viscosity shown in Table 1. It was

(Process (II))
While bubbling hydrogen gas from the bottom of the glass beaker containing the emulsion at a flow rate of 50 mL / min, the homomixer was used to stir the emulsion for 4 minutes at a rotation speed of 3,000 to 6,000 rpm to form a bubble state in the emulsion. Hydrogen gas was dispersed.

(Process (III))
The emulsion in which bubbled hydrogen gas was dispersed was allowed to cool to room temperature, and the emulsion having the viscosity shown in Table 1 was thickened to obtain a cream.
The cream was filled in a headspace vial (volume: 10 mL). A photograph of the appearance of the cream of Example 1 is shown in FIG. A photograph of the cream of Example 1 observed with a microscope is shown in FIG.
Table 1 shows the viscosities of the creams of Examples 1 to 5 at 25 ° C., the average bubble diameter of hydrogen gas in a bubble state, the content rate of hydrogen gas in a bubble state in the cream, the dispersibility of bubbles, and the feeling of use.

<Comparative Example 1>
Each component of the liquid A shown in Table 1 was placed in a glass beaker at the ratio shown in Table 1, and heated to 70 ° C. in a water bath to make a solution.
Each component of the liquid B shown in Table 1 was put in another glass beaker in the ratio shown in Table 1, and heated to 70 ° C. in a water bath to be in a solution state.
The liquid B was added to the liquid A while stirring the liquid A to obtain a mixed liquid. The mixture was stirred for 3 minutes at a rotation speed of 3,000 rpm using a homomixer (Labulution (registered trademark) manufactured by PRIMIX Corporation), and then deaerated to obtain a cream.

(Hydrogen gas retention)
The cream of Example 1 was filled in a glass sample bottle, sealed, and stored in an incubator set at 25 ° C. After 2 weeks, it was opened and the content of hydrogen gas in the form of bubbles in the cream was evaluated. Results are shown in FIG.
The content of bubbled hydrogen gas in the cream did not change after two weeks.

  INDUSTRIAL APPLICABILITY The cream of the present invention is useful as a creamy cosmetic capable of sufficiently exhibiting various functions of hydrogen gas.

Claims (5)

Fatty acid salts having a carbon number of 10 to 18, the number 10 to 18 of the fatty acid carbon include higher alcohols liquid medium and having 12 to 22 carbon atoms, creamy composition emulsion thickens in which the oil component and an aqueous component emulsified Is a cream containing hydrogen gas in the form of bubbles,
The content of the hydrogen gas in the bubble state in the cream is 10 to 100% by volume [v / w],
The viscosity at 25 ° C. is 10,000 mPa · s or more,
The fatty acid salt having 10 to 18 carbon atoms is at least one selected from sodium salt, potassium salt and triethanolamine salt of fatty acid having 10 to 18 carbon atoms,
Wherein one composition (100 mass%), the total content of the carbon number from 10 to 18 fatty acid salt and the carbon number from 10 to 18 fatty acid, 1 to 8 wt%,
The fraction of total carbon number 10 to 18 of the fatty acid salt and the carbon number from 10 to 18 fatty acids (100 mol%), the content of the number 10 to 18 of the fatty acid salt carbon, 1 to 10 mol%,
In the composition (100% by mass), the content ratio of the higher alcohol having 12 to 22 carbon atoms is 1 to 10% by mass,
The composition further comprises one or both of fats and oils,
A cream in which the total content of the oil and fat and the wax is 2 to 10% by mass in the composition (100% by mass). The composition further comprises a surfactant,
The cream according to claim 1, wherein a content ratio of the surfactant is 0.01 to 5% by mass in the composition (100% by mass). The cream according to claim 1 or 2 , wherein the average bubble diameter of the hydrogen gas in the bubble state is 1 µm to 1 mm. A method for manufacturing cream according to any one of claims 1 to 3
Fatty acid salts having a carbon number of 10 to 18, the number 10 to 18 of the fatty acid carbon include higher alcohols liquid medium and having 12 to 22 carbon atoms, creamy composition emulsion thickens in which the oil component and an aqueous component emulsified And prepare
Including hydrogen gas in a bubble state in the composition,
Hydrogen gas in a bubble state such that the content rate of the hydrogen gas in the bubble state in the cream is 10 to 100% by volume [v / w] and the viscosity of the cream at 25 ° C. is 10,000 mPa · s or more. A method for producing a cream, comprising thickening the composition comprising:
The fatty acid salt having 10 to 18 carbon atoms is at least one selected from sodium salt, potassium salt and triethanolamine salt of fatty acid having 10 to 18 carbon atoms,
Wherein one composition (100 mass%), the total content of the carbon number from 10 to 18 fatty acid salt and the carbon number from 10 to 18 fatty acid, 1 to 8 wt%,
The fraction of total carbon number 10 to 18 of the fatty acid salt and the carbon number from 10 to 18 fatty acids (100 mol%), the content of the number 10 to 18 of the fatty acid salt carbon, 1 to 10 mol%,
In the composition (100% by mass), the content ratio of the higher alcohol having 12 to 22 carbon atoms is 1 to 10% by mass,
The composition further comprises one or both of fats and oils,
The method for producing a cream, wherein the total content of the oil and fat and the wax is 2 to 10% by mass in the composition (100% by mass). To prepare the composition, a solution A containing an alkali agent and a liquid medium, mixing the solution B containing higher alcohol having 12 to 22 carbon fatty acids and carbon having 10 or more carbon atoms, according to claim 4 Cream manufacturing method.