JP6681628B2 - Effervescent skin external preparation - Google Patents

Description

  The present invention relates to an effervescent skin external preparation.

  Conventionally, effervescent skin external preparations containing a synthetic or natural extract having a blood circulation promoting action on the skin have been used.

  The effects of these extracts are insufficient with a small amount of compounding, and the irritation to the skin is too great with a large amount of compounding. For this reason, carbonic acid gas is added to the effervescent skin external preparation to enhance the blood circulation promoting action. Has been made. Many of these generate carbon dioxide gas by the reaction between an acidic substance and a carbonate, so from the viewpoint of enhancing the stability during storage, the effervescent skin preparation for external use is separated from the acidic substance and the carbonate. A method has been taken in which two storable agents are used, and these are mixed at the time of use to foam. As a form of the above-mentioned two agents, for example, it has been proposed to use an aqueous solution and a solid (Patent Document 1), both using a viscous substance (Patent Document 2), a solid and a viscous substance (Patent Document 3), and the like. The handleability by the user was not always sufficient.

  Further, even when the above-mentioned two-component effervescent skin external preparation is used, an additive (active ingredient, etc.) having reactivity with either the acidic substance or carbonate is present in the same agent. Then, the acidic substance or the carbonate gradually reacts during storage, and the stability during storage may decrease.

  On the other hand, there is also a proposal for a two-component effervescent skin external preparation in which a solid acidic substance and a solid carbonate are allowed to coexist in the same agent (Patent Document 4), but depending on the conditions at the time of production, the solid acidic substance And the solid carbonate may react with each other to generate carbon dioxide gas, or the two may gradually react with each other even during storage to generate carbon dioxide gas. However, no specific solution to this problem is shown.

  In addition, in the two-pack type foamable cosmetic composition disclosed in Patent Document 1, which comprises an aqueous solution and a solid material, the solid material is covered with polyethylene glycol which is solid at room temperature. This coating with polyethylene glycol is intended to obtain a suitable sustained release of carbon dioxide gas when the two agents are mixed at the time of use.

JP-A-63-310807 Japanese Patent Laid-Open No. 05-229933 International Publication No. 99/24043 JP, 2010-275322, A

  The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide an effervescent skin external preparation containing an acidic substance and a carbon dioxide generating substance that generates carbon dioxide by reacting with the acidic substance. Another object of the present invention is to provide an effervescent skin external preparation having excellent stability and durability without causing problems such as unexpected generation of carbon dioxide gas during the production or storage of the effervescent skin external preparation. The second object of the present invention is to provide an effervescent skin external preparation that is easy to handle.

  The present inventors include an acidic substance and a carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance in the same agent so that the acidic substance and the carbon dioxide-generating substance do not come into physical contact with each other. It was found that the above-mentioned problems can be solved by blending into the above, or by not containing water in the same agent containing the acidic substance and the carbon dioxide generating substance, and has completed the present invention. . The present invention specifically provides the following.

(1) A one-pack type or a multi-pack type effervescent skin external preparation, wherein carbon dioxide gas that generates carbon dioxide gas by reacting at least an acidic substance and the acidic substance in the same agent An effervescent skin external preparation containing a generating substance, wherein the acidic substance and the carbon dioxide generating substance coexist so as not to come into contact with each other.
(2) The effervescent skin external preparation according to (1), wherein the acidic substance and / or the carbon dioxide-generating substance has a coat layer.
(3) The effervescent skin external preparation according to (2), wherein the coating layer contains at least one selected from the group consisting of sugars, water-soluble polymers, organic acid salts, fats and oils and hydrocarbon waxes. Is.
(4) The effervescent skin external preparation according to any one of (1) to (3), which further contains a polysaccharide or a metallic soap in the same agent.
(5) The effervescent skin external preparation according to (4), wherein the polysaccharide is dextrin and / or starch and the metal soap is calcium stearate.
(6) The effervescent skin external preparation according to any one of (1) to (5), which is stored in a sealed container.
(7) The effervescent skin external preparation according to (6), which is treated so that the gas in the closed container does not contain water.
(8) The effervescent skin external preparation according to any one of (1) to (7), wherein the carbon dioxide-generating substance is a carbonate.
(9) The effervescent skin external preparation according to any one of (1) to (8), wherein the acidic substance and / or the carbon dioxide-generating substance is solid.

  According to the present invention, even when an acidic substance and a carbon dioxide-generating substance that reacts with the acidic substance to generate carbon dioxide are present in the same agent, during the production or storage of the effervescent skin external preparation. It is possible to provide an effervescent skin external preparation having excellent stability and durability, which does not cause the problem of unexpected generation of carbon dioxide gas. Further, since it becomes possible to make the effervescent skin external preparation as one agent, the packaging etc. can be simplified and the manufacturing cost can be reduced, and the user can easily handle the effervescent skin external preparation. Become. Further, even when the additives such as active ingredients having reactivity with each other are contained in the same agent, it is possible to obtain a foamable skin external preparation having excellent stability and durability.

It is a figure for demonstrating the coat layer formed in an acidic substance and / or a carbon dioxide generating substance.

  Aspects of the present invention are one-part or more effervescent skin external preparations, in which at least an acidic substance and a carbon dioxide-generating substance that reacts with the acidic substance to generate carbon dioxide are in contact with each other. It is characterized in that it is formulated so as not to contain it, or does not contain water in the same agent. The dosage form of the effervescent skin external preparation of the present invention may be a one-pack type, a two-pack type, or a multi-pack type more than that.

  By blending the acidic substance and the carbon dioxide gas-generating substance in the same agent so that they do not come into contact with each other, or by keeping the same agent from containing water, one effervescent skin external preparation is prepared. It can be a mold or a two-pack or more. From the viewpoint of easy handling, the one-pack type is particularly preferable.

  Hereinafter, each component of the effervescent skin external preparation of the present invention and a method for producing the external preparation will be described.

1. Acidic substance The acidic substance used in the present invention may be either an organic acid or an inorganic acid, and one or more of these may be used. Further, these may be solid or gaseous or liquid, and are not particularly limited, but the reaction of carbon dioxide gas is likely to occur quickly, and the generation of carbon dioxide gas is easily controlled by adjusting the amount, It is preferable to adopt a solid one.

  Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid and other straight-chain fatty acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid. Acids, dicarboxylic acids such as terephthalic acid, acidic amino acids such as glutamic acid and aspartic acid, glycolic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, salicylic acid, gallic acid And oxy acids such as tropic acid, ascorbic acid and gluconic acid. Of these, citric acid, ascorbic acid, malic acid, and succinic acid are preferable from the viewpoint of safety and solubility in water.

2. Carbon dioxide generating substance As the carbon dioxide generating substance which reacts with the acid used in the present invention to generate carbon dioxide, various substances can be used without particular limitation. The carbon dioxide generating substance is preferably a carbonate such as sodium carbonate, calcium carbonate, potassium carbonate or magnesium carbonate, ammonium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate or magnesium hydrogen carbonate. , Hydrogen carbonates such as calcium hydrogen carbonate and magnesium carbonate hydroxide, and the like, and one or more of these are used. Among these, sodium hydrogencarbonate is preferably used, and sodium hydrogencarbonate is more preferable because it can realize a proper foaming power. Further, these may be solid or liquid, and are not particularly limited, but the reaction of carbon dioxide gas is likely to occur quickly, and the generation of carbon dioxide gas is easily controlled by adjusting the amount, and thus solid state It is preferable to adopt one.

  The acidic substance and the carbon dioxide generating substance may be a single powder or granular substance, or may be a powder or granules made of a mixture with other components such as an excipient and a granulating agent. , Any powdery material is acceptable.

3. Compounding Substances Other components that can be contained in the powder or granules are, for example, lactose, powdered sugar, starch, xylitol, D-sorbitol, glucose, D-mannitol, fructose, sucrose, sucrose, urea, etc. Alternatively, they may be used alone or in combination of two or more.

  Here, when granules of the acidic substance or the carbon dioxide generating substance are obtained by granulating the mixture of the acidic substance or the carbon dioxide generating substance and other components, other components (however, the acidic substance or the The content of the coating layer for covering the carbon dioxide-generating substance is not included), but the content is preferably less than 80% by mass in the granules. If the other components are present in a content of more than 80% by mass, the foaming property becomes low, which is not preferable.

4. Granulation method The method for producing the above-mentioned powder or granules is not limited to this example, and dry crushing granulation method, wet crushing granulation method, fluidized bed granulation method, high speed stirring granulation method, extrusion granulation method It can be manufactured according to a conventional method such as a method.

  For example, when a low melting point compound is used as a matrix base in a granulating agent, it is sufficient to add the acidic substance or the carbon dioxide gas generating substance to the low melting point granulating agent melted by heating in a container such as a beaker. Stir and mix. If necessary, suitable additives may be added thereto. This is gradually cooled at room temperature with further stirring and allowed to set. When it hardens to some extent, it may be cooled rapidly in a refrigerator or the like.

  Alternatively, for example, the above materials may be put into a fluidized bed granulator, mixed with an air stream for several minutes, and then sprayed with water to granulate.

  When the low melting point compound is not used as the matrix base, the granulating agent is dissolved or dispersed in a suitable solvent such as water or ethanol in a container such as a beaker, and the carbon dioxide generating substance is dissolved or dispersed therein. After sufficiently mixing, the mixture is heated in an oven or the like to remove the solvent and dried. When it is completely solidified, it is crushed, sieved to make the size of the particles uniform, and then made into granules.

  As the shape of the acidic substance or the carbon dioxide generating substance, for example, an irregular shape, a flat shape, a polyhedral shape, a spherical shape, a drop shape, a fibrous shape, a cylindrical shape, a fine powder shape, or the like can be adopted without particular limitation. In addition, a wide range of particle diameters can be used without particular limitation. In particular, from the viewpoint of easy handling and easy mixing with a viscous composition, a particle size distribution of about 1,000 μm or less is more preferable. The particle size distribution in the present invention can be determined by a usual laser diffraction / scattering method.

5. Means for Coexisting Acidic Substance and Carbon Dioxide Generating Substance in Same Agent In the aspect of the present invention, the acidic substance and the carbonic acid gas generating substance are contained in the same agent, and the acidic substance and the carbon dioxide gas are contained in the same agent. It is necessary that the generated substances are mixed so that they do not come into physical contact with each other and coexist, or that the same agent does not contain water, but the coexistence means is not particularly limited and is widely applicable. It is possible.

  When the acidic substance and the carbon dioxide gas-generating substance are blended so as not to physically contact each other, for example, one or both of the acidic substance and the carbon dioxide-generating substance may be provided with a coat layer that wraps the same. Alternatively, either one or both of the acidic substance and the carbon dioxide generating substance may be encapsulated. Further, a layer not containing the acidic substance and the carbon dioxide generating substance may be sandwiched between the acidic substance and the carbon dioxide generating substance so as not to come into direct contact with each other, and compression-molded to obtain a solid state.

  Further, even if the acidic substance and the carbon dioxide generating substance are contained in the same agent, if the water is not contained in the same agent, an unexpected problem of generation of carbon dioxide gas may occur. Can be prevented. For example, powder, oil, a non-aqueous solvent or the like may be used as a component contained in the same agent containing the acidic substance and the carbon dioxide-generating substance, or may be stored in a moisture-impermeable closed container. It is feasible. In addition, it is also preferable to perform processing (for example, vacuum processing or filling with an inert gas) so that the gas in the closed container does not contain water during storage, or to use a desiccant or the like.

  The coexistence means of the acidic substance and the carbon dioxide generating substance in the same agent will be specifically described below, but the means is not limited thereto.

(1) First Coexistence Means within Same Agent First, the first coexistence means within the same agent will be described in detail. That is, it is a method of "mixing and coexisting so that the acidic substance and the carbon dioxide generating substance do not physically contact each other".

(1-1) Formation of Coat Layer The acidic substance and the carbon dioxide gas-generating substance used in the present invention can be used as they are as described above without any particular limitation, but at least one of them has a coat layer. By providing a coat layer, even if the acidic substance, the carbon dioxide generating substance and other components coexist in the same agent, there is no fear of unexpected carbon dioxide generation during production or storage, stability, It is preferable in terms of durability.

  FIG. 1 conceptually shows the formation mode of the coat layer. The coat layer indicated by reference numeral 2 in the drawing is formed so as to cover the entire surface (see A) or part (see B) of the surface of the acidic substance or the carbon dioxide generating substance indicated by reference numeral 1. In the embodiment shown in A, the entire surface of the acidic substance or the carbon dioxide gas generating substance 1 is covered with the coat layer 2, so that the physical contact between the acidic substance and the carbon dioxide gas generating substance can theoretically be completely eliminated.

  As shown in B, the coat layer 2 covers only a part of the surface of the acidic substance or the carbon dioxide generating substance 1 as long as physical contact between the acidic substance and the carbon dioxide generating substance can be suppressed. Good. In this aspect, a portion (exposed portion) not covered with the coat layer 2 exists on the surface of the acidic substance or the carbon dioxide gas generating substance 1. For this reason, when the effervescent skin external preparation is mixed with water, the water comes into contact with the exposed portion of the acidic substance or the carbon dioxide generating substance 1 and quickly dissolves the acidic substance or the carbon dioxide generating substance 1. Sufficient foaming can be obtained in a short time.

  As the coating material preferable for forming the coating layer, any coating material having low reactivity with the acidic substance or the carbon dioxide generating substance can be used without particular limitation. As the coating agent, any one or more selected from the group consisting of sugars, water-soluble polymers, organic acid salts, fatty acids, polymers, fats and oils that dissolve at a certain temperature by heating, and hydrocarbon wax is used. be able to. Among these, sugars, water-soluble polymers, organic acid salts and fats and oils are preferable.

Examples of the sugars include disaccharides such as lactose (lactose), sucrose (sucrose) and maltose (maltose), and trehalose; oligosaccharides or oligosaccharides having three or more sugars; sucrose; sugar alcohols such as mannitol, sorbitol, and xylitol. Can be mentioned.
Examples of the water-soluble polymer include starch, cellulose derivatives such as cellulose gum, xanthan gum, carrageenan, pectin and dextrin. Examples of the cellulose derivative include cellulose gum (carboxymethyl cellulose), methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and carboxymethyl cellulose.
Among these, lactose, sucrose, trehalose and mannitol are preferable as the sugar, and starch, cellulose gum, xanthan gum and dextrin are preferable as the water-soluble polymer.

  Examples of the organic acid salt include citrate, tartrate, succinate, adipate, fumarate, malate, malonic acid and pyrrolidonecarboxylate. Among these, citrate is preferable.

  Examples of the fatty acids include fatty acids having 12 to 22 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.

Examples of the polymer include polymers of N-vinyl-2-pyrrolidone such as polyvinylpyrrolidone and copolymers of vinylpyrrolidone and vinyl acetate. Polymers of ethylene glycol such as polyethylene glycol are not preferable in terms of stability and durability.

  Examples of the oils and fats include rapeseed oil, castor oil, coconut oil, and beef tallow, and hydrogenated hydrogenated oils thereof can also be used. Further, higher alcohols such as behenyl alcohol, cetyl alcohol, myristyl alcohol and stearyl alcohol, and waxes such as beeswax and carnauba wax can also be used.

  Examples of the hydrocarbon wax include petrolatum, paraffin wax, microcrystalline wax, and the like. The solid dosage form is more suitable for coating.

  These coating agents may be used alone or in combination of two or more. In particular, when coating an acidic substance such as citric acid, it is preferable to employ an organic acid salt such as calcium citrate.

  The amount of the coating agent used for the acidic substance and / or the carbon dioxide generating substance is 1 to 100% (w / w) with respect to the acidic substance or the carbon dioxide generating substance (acidic substance or carbon dioxide generating substance: coating agent = 100 : 1 to 100: 100), preferably 1 to 67% (100: 1 to 60:40), more preferably 1 to 43% (100: 1 to 70:30), 1 to 25% (100: 1 to 1). 80:20).

  The coating method of the coat layer may be any method as long as it is usually used for coating particles. For example, it may be coated simultaneously with granulation by spray granulation or tumbling granulation, etc., and powder or granules may be coated with oil and fat, granulation coating, transport layer method, pan coating, tumbling coating, fluidized coating or You may coat using methods, such as dry coating. During coating, if excessive heat or physical force is applied, the acidic substance or the carbon dioxide generating substance is destroyed, and the formed film is broken, and the surface of the acidic substance or the carbon dioxide generating substance is destroyed. Not only it becomes difficult to uniformly coat the lipid powder on the whole, but the acid substance or the carbon dioxide generating substance leaks to the surface and solidifies due to moisture absorption, or it may cause adverse effects on other components during blending. The coating conditions should be such that the coating layer and the coating object are not destroyed.

  In the case of the coat layer of the embodiment shown in FIG. 1A, for example, an acidic substance or a carbon dioxide gas-generating substance is added to a coating agent (oil or fat) dissolved under a certain condition, and the mixture is uniformly mixed and then cooled. As a result, a coat layer that covers the entire surface of the acidic substance or the carbon dioxide generating substance can be formed.

  In the case of the coat layer of the embodiment shown in FIG. 1B, for example, an acidic substance or a carbon dioxide gas-generating substance is moistened, and a coating agent (sugar, water-soluble polymer, organic acid salt, fats and oils) is sprayed and attached. After that, it is dried. As a result, a coat layer that partially covers the surface of the acidic substance or the carbon dioxide generating substance can be formed.

  The coating layer prevents unexpected generation of carbon dioxide gas by physically preventing acid substances and carbon dioxide gas substances from physically contacting each other during manufacturing and storage, while it is used (when mixed with a liquid containing water). Therefore, it is necessary that the acidic substance and the carbon dioxide generating substance react appropriately to generate a desired amount of carbon dioxide. Therefore, in the case of using a coating agent that does not dissolve in water such as fats and oils, the coat layer of the embodiment shown in FIG. 1A is preferable. When a water-soluble coating agent is used, any of the coating layers shown in FIGS. 1A and 1B can be adopted.

(1-2) Encapsulation The method for encapsulating the acidic substance and / or the carbon dioxide-generating substance of the present invention is not particularly limited, and a known method can be adopted.

  As the encapsulation method, a known method can be applied without particular limitation, and as the encapsulation material, gelatin, starch, gum arabic, methyl cellulose, acrylic acid ester, methacrylic acid ester, vinyl acetate, Polyvinyl alcohol, silicone resin, solid wax, polyethylene, fatty acid, higher alcohol, and the like, and those in which multiple layers of surfactants such as liposomes are formed are included, but they can be widely used without limitation. For example, the basic structure of the capsule consists of a homopolymer or copolymer formed from one or more monomers selected from acrylic acid ester, methacrylic acid ester, vinyl acetate, styrene, or the monomer and acrylic acid, methacrylic acid, divinyl. It is also preferable to use a resin capsule made of a copolymer formed of a monomer selected from benzene and ethylene glycol dimethacrylate. In such microcapsules, the contents and the constituent monomers of the polymer that forms the outer shell of the capsule are emulsified in a reaction solvent such as water, and then polymerization of azobisisobutyronitrile or benzoyl peroxide is initiated. Emulsion polymerization may be carried out by adding an agent. As a surface active component used for such emulsification, for example, hexlite sold under the name of "Laponite XLG" can be preferably exemplified. The microcapsules of the present invention can be produced by separating the resulting microcapsules by means such as centrifugation and washing them if desired.

(1-3) Solidification In the present invention, the acidic substance and the carbon dioxide gas are generated so that they do not come into direct contact between the first layer containing the acidic substance and the second layer containing the carbon dioxide generating substance. One of the useful methods is to sandwich a third layer made of a substance other than the substance (for example, an excipient, a thickener, etc.) and compression-mold it to solidify it. The solidified dosage form may be any dosage form such as tablets, spheres, and plates as long as it is solid. Here, the acidic substance and the carbon dioxide gas generating substance to be used may be used as they are, or the acidic substance or the above-mentioned acidic substance provided with a coat layer by the above method on one or more of the first layer and the second layer. A carbon dioxide-generating substance, the encapsulated acidic substance or the carbon dioxide-generating substance may be used. As a solidification method, a known method can be applied without particular limitation.

  The acidic substance and the carbon dioxide-generating substance contained in the first layer and the second layer may be used as they are, or may be mixed with an excipient, a thickener or the like. . As the excipients, thickeners and the like used in the first layer, the second layer and the third layer, those described in the description of the granules can be used without particular limitation.

(1-4) Auxiliary means for coexistence means in the first same agent The effervescent skin external preparation according to the present invention contains a polysaccharide, a metallic soap, etc. in addition to the above-mentioned acidic substance and carbon dioxide gas-generating substance. It is preferable to contain. The effect of preventing the unexpected generation of carbon dioxide can be enhanced by adding a polysaccharide, metal soap or the like to the acidic substance and the carbon dioxide generating substance, at least one of which is coated, encapsulated or solidified. The addition amount of the polysaccharide or the like is, for example, about 1 to 20% (w / w), and preferably 5 to 10% (w / w) with respect to the entire same agent containing the acidic substance and the carbon dioxide gas generating substance. It is considered as a degree. In addition, the polysaccharide or the like added may be in a solid form, and may be in a powder form or a granule form, for example.

  Examples of the polysaccharides and derivatives thereof include, for example, dextrin, maltodextrin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, guar gum, hydroxypropyl guar gum, hydroxyethyl guar gum, carboxymethyl guar gum, Examples include cationized guar gum, locust bean gum, tamarind gum, tragacanth gum, pectin, glucomannan, schizophyllan, carrageenan, alginic acid, agar, agarose, starch, xanthan gum, dextran, curdlan, pullulan, and inulin. Among these, dextrin and starch are preferable.

  Examples of the metallic soaps include calcium salts such as calcium stearate, calcium myristate and calcium palmitate, and magnesium salts such as magnesium stearate, magnesium myristate and magnesium palmitate. Of these, calcium stearate is preferable.

(1-5) Carbon dioxide generating agent for effervescent skin external preparation In the present invention, the acidic substance and the carbon dioxide generating substance are blended, at least one of which has a coat layer, and at least one of which is encapsulated. And a solidified product obtained by forming a third layer between the first layer containing the acidic substance and the second layer containing the carbon dioxide generating substance, and supplying the solidified carbon dioxide generating agent for the external preparation for effervescent skin. May be. The carbon dioxide generating agent for effervescent skin external preparation preferably contains a polysaccharide, a metallic soap and the like.

(2) Second means for coexisting in the same agent Next, the second means for coexisting in the same agent will be described in detail. That is, it is a method of "not containing water in the same agent". It is preferable that the same agent containing the acidic substance and the carbon dioxide generating substance does not contain at least water accelerating the reaction between them.

  In the present invention, the water content in the effervescent skin external preparation includes, in addition to liquid or gas, water released from all the components blended in the effervescent skin external preparation due to changes over time. By not containing these waters in the same agent, even if the acidic substance and the carbon dioxide generating substance come into direct contact with each other, the problem of unexpected generation of carbon dioxide can be prevented.

  Therefore, it is necessary to appropriately select other components contained in the agent containing the acidic substance and the carbon dioxide generating substance so as not to contain water. Further, by preventing the infiltration of water from the environment into the effervescent skin external preparation, or by removing the water released over time from the components contained, the state that the water is not contained in the agent. It is important to maintain.

6. Effervescent skin external preparation The effervescent skin external preparation of the present invention is, in addition to the acidic substance and the carbon dioxide gas generating substance, an active ingredient, a thickener, a pH adjusting agent, a fat and an oil, a fragrance, a coloring agent, an antioxidant, an antioxidant. It is usually used for external skin preparations such as fungicides, alcohols, polyhydric alcohols, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, inorganic salts, lubricants, solvents, etc. By mixing with one or more of the above components, a one-pack effervescent skin external preparation can be obtained. When producing a one-pack type effervescent skin external preparation, the carbon dioxide generating agent for effervescent skin external preparation can also be used.

  In addition, a two-component effervescent skin external preparation comprising a first agent containing at least the acidic substance and the carbon dioxide-generating substance and a second agent containing at least water may be used. It is possible. Also at this time, the carbon dioxide generating agent for effervescent skin external preparation can be used when preparing the first agent.

  In the case of a two-pack effervescent skin external preparation, active ingredients, thickeners, pH adjusters, oils and fats, fragrances, colorants, antioxidants, antibacterial and antifungal agents, alcohols, polyhydric alcohols, nonionic surface active agents One or more components selected from agents, anionic surfactants, cationic surfactants, amphoteric surfactants, inorganic salts, lubricants, solvents and the like may be mixed in the first agent or the second agent. it can.

  As a substance that can be added to the same agent containing the acidic substance and the carbon dioxide gas generating substance, it is preferable to use a non-aqueous solution in a liquid, for example, a liquid oil such as a hydrocarbon oil, a fat and an oil, an ester oil and a silicone oil, Examples include polyhydric alcohols such as propylene glycol, essential oils, fragrances, non-aqueous solvents such as glycol ethers, and nonionic surfactants. On the other hand, examples of the solid include excipients such as lactose, oligosaccharides and starch, and desiccants. Further, examples of the desiccant include chemical desiccants such as calcium chloride, magnesium perchlorate and anhydrous sodium sulfate, and physical desiccants such as silica gel, aluminum oxide, molecular sieves and zeolite.

  The effervescent skin external preparation of the present invention can be made into a multi-agent form of three or more formulations by appropriately changing the mode of the above-mentioned two-component effervescent skin external preparation. On the other hand, it is preferable to make the effervescent skin external preparation of the present invention into a one-pack type in order to simplify the packaging and the like, and thus to reduce the manufacturing cost.

  Hereinafter, representative ones of the components contained in the effervescent skin external preparation of the present invention which can be used in addition to the acidic substance and the carbon dioxide generating substance will be further described.

  The active ingredient used in the present invention is not particularly limited, and drugs or plants usually used in cosmetics, external medicines, quasi drugs and the like can be used according to the purpose. Typical examples include glycyrrhizic acid or a derivative thereof, a whitening agent such as a placenta extract, a moisturizing component such as propylene glycol, polyethylene glycol, sorbitol, sodium lactate, sodium pyrrolidonecarboxylate, and a plant component such as licorice. To be As plant components, whole plants, leaves (leaf blades, petioles, etc.), fruits (mature, immature, etc.), seeds, flowers (petals, ovary, etc.), stems, rhizomes, roots, tuberous roots, etc. can be used as they are. It can be used after cutting, crushing, crushing, squeezing, or after being treated or dried and powdered.

  The thickener used in the present invention is not particularly limited as long as it is a water-soluble component that can be used in the fields of cosmetics, external medicines, quasi drugs, and polyacrylic acid, polyacrylamide, polyalkylacrylamide. / Hydrophilic synthetic polymers such as polyacrylamide copolymer, carboxymethyl cellulose, cationized cellulose, hydrophilic natural polymers such as xanthan gum, succinoglycan, guar gum and locust bean gum, as well as laponite, bentonite, smectite Hydrophilic thickening compounds such as hydrophilic clay minerals are exemplified. Above all, it is preferable to use a hydrophilic thickener having a large interaction with water contained in the external preparation for skin. On the other hand, when an ordinary thickener used in cosmetics or the like is used, the viscosity may be lowered when the acidic substance is contained, which may cause sagging.

  In the case of a one-pack effervescent skin external preparation, foaming is caused by mixing a liquid containing water with a one-pack effervescent skin external preparation, while in the case of a two-pack effervescent skin external preparation, two Foaming can be initiated by mixing. As the liquid containing water used in the present invention, water used in cosmetics, pharmaceuticals, etc., water used in general households, and any liquid containing water can be used without particular limitation as long as it is a liquid containing water. be able to. For example, in addition to tap water, distilled water, membrane filtered water, ion-exchanged water, deep sea water, sake such as sake and wine, soy milk, yogurt drink, acerola juice, sports drinks, beverages such as carbonated water, rice sharpening juice, etc. Is mentioned. These may be used alone or in combination of two or more.

  The amount of the liquid containing water to be used is not particularly limited and can be used in a wide range, but it is preferably added in an amount of 1 to 5 times the weight of the external preparation for skin, and 2 to 4 times. It is more preferable to add an amount. By adding a liquid in an amount exceeding 1 time, the external preparation for skin can be rapidly dissolved, and a sufficient amount of carbon dioxide gas can be generated. On the other hand, by adding the liquid within 5 times the amount, it is possible to prevent the external preparation for skin from dripping due to a decrease in viscosity.

  The temperature of the liquid containing water to be used is not particularly limited and a wide range can be used, but it is particularly preferable to cool the liquid in advance and use it because the action of the active ingredient contained in the one-component external preparation for skin becomes high. preferable. As for the temperature range that can be used, it is preferable to use water or tap water at about room temperature from the viewpoint of the feeling during use and the convenience of the user.

7. Usage form of effervescent skin external preparation In the case of the one-pack effervescent skin external preparation of the present invention, foaming is caused by mixing with a liquid containing water on the palm or in a container during use. In the case of a two-component effervescent skin external preparation, when used, the two agents are mixed on the palm or in a container to cause foaming.

  The method for preserving the effervescent skin external preparation is not particularly limited in the case of the one-pack effervescent skin external preparation and in the case of the two-pack effervescent skin external preparation, as long as it is stored while water is blocked. Therefore, these are preferably stored in a storage container in a sealed state. The shape of the storage container used can be appropriately selected according to the purpose, and examples thereof include a cup shape, a tube shape, a bag shape, a bottle shape, a stick shape, a pump shape, a jar shape, and a canned shape. Further, as the material constituting the storage container, for example, plastic, glass, metal such as aluminum, paper, various polymers and the like can be used alone or in combination of two or more kinds, and can be widely used without being limited thereto.

  Specific examples of the container include an aluminum stick laminated with polyethylene terephthalate on the inner surface, a storage container such as an aluminum bag, a stand pouch with a chuck, and polyethylene terephthalate on the inner surface in terms of hermeticity, storage stability of contents, manufacturing cost, etc. A storage container made of polyethylene terephthalate, the lid of which is heat-sealed with an aluminum film or the like laminated with, is preferable.

  Further, in order to block moisture, it is preferable to evacuate the airtight container to be used or fill it with dry nitrogen or the like.

8. Use of effervescent skin external preparation The effervescent skin external preparation of the present invention promotes an increase in skin blood flow, and is intended for whitening, improving skin quality, improving freckles, rejuvenating the skin, tightening the skin, and partially thinning the skin. It can be suitably used not only for cosmetics such as cosmetics, emulsions, creams, packs and peeling agents, but also for quasi-drugs such as hair, cleaning agents and bath agents, and pharmaceuticals such as drugs. .

1. Stability evaluation test I
<Example 1>
Carbonic acid for effervescent skin external preparation using 0.2 g (2 parts by mass) of citric acid powder having a coat layer as an acidic substance and 0.8 g (8 parts by mass) of sodium hydrogencarbonate powder as a carbon dioxide gas generating substance. A gas generant was prepared. To form a coat layer on the citric acid powder, moisten 0.19 g (95 parts by mass) of citric acid powder, spray 0.01 g (5 parts by mass) of calcium citrate onto it, and then dry it. Went by.

  The citric acid powder on which the coat layer was formed and the sodium hydrogencarbonate powder were housed in an aluminum film bag having an inner surface laminated with polyethylene terephthalate and sealed. It was stored at 40 ° C., 50 ° C. or 60 ° C. for 17 to 27 days, and during the storage period, the presence or absence of carbon dioxide gas was observed with the presence or absence of bag swelling as an index.

<Example 2>
Evaluation was carried out in the same manner as in Example 1 except that 1% w / w dextrin powder was added to the carbon dioxide gas generator for effervescent skin external preparation of Example 1.

<Examples 3 to 6>
Evaluation was carried out in the same manner as in Example 2 except that the amount of dextrin added to the carbon dioxide generating agent for effervescent skin external preparation was 2.5, 5, 7.5, 10% w / w.

<Comparative Example 1>
Citric acid powder 0.19 g (2 parts by mass) and sodium hydrogen carbonate powder 0.8 g (8 parts by mass) were housed in an aluminum film bag without forming a coat layer and sealed. In the same manner as in Example 1, it was observed whether or not carbon dioxide gas was generated.

  The results are shown in "Table 1". In the table, "none" indicates that carbon dioxide was not generated during the storage period (17 to 27 days). In addition, “present” indicates that carbon dioxide gas was generated, and the number in parentheses indicates the number of storage days when foaming was recognized.

  In Comparative Example 1 in which the coat layer was not formed, generation of carbon dioxide gas was confirmed after one day at any of the storage temperatures of 40 ° C, 50 ° C, and 60 ° C. On the other hand, in Example 1 in which the coating layer of calcium citrate was formed on the powder of citric acid, the generation of carbon dioxide gas was not observed during the entire observation period under the storage condition of 40 ° C., and the storage at 50 ° C. and 60 ° C. Even under the conditions, the generation of carbon dioxide was 7 days and 3 days, respectively, which was significantly delayed relative to Comparative Example 1. From this result, it was shown that the formation of the coat layer can prevent the unexpected generation of carbon dioxide gas during storage.

  In Examples 2 to 6 in which dextrin was further added to the carbon dioxide generating agent for effervescent skin external preparation, the generation of carbon dioxide during the storage period could be more effectively prevented. When the added amount of dextrin was 1%, 2.5%, 5%, or 7.5%, the stability of the external preparation for skin was improved in a concentration-dependent manner, and the effect of significantly delaying the generation of carbon dioxide was exhibited. Also, in a test conducted by changing the powder added to the carbon dioxide generating agent for effervescent skin external preparation from dextrin to starch, the effect of preventing the generation of carbon dioxide during the storage period was obtained as with dextrin. It was

<Example 7>
Evaluation was carried out in the same manner as in Example 1 except that 3% w / w calcium stearate powder was added to the carbon dioxide generating agent for effervescent skin external preparation.

<Example 8>
Evaluation was carried out in the same manner as in Example 7 except that the amount of calcium stearate added to the carbon dioxide generating agent for effervescent skin external preparation was 5% w / w.

  The results are shown in "Table 2".

  In Examples 7 and 8 in which calcium stearate was added to the carbon dioxide generating agent for effervescent skin external preparation, Comparative Example 1 in which a coat layer was not formed and Example 1 in which a coat layer was formed using calcium citrate (Table 1 1), the generation of carbon dioxide gas could be significantly delayed. From these results, it was shown that the stability of the skin external preparation can be improved by adding calcium stearate to the carbon dioxide generating agent for effervescent skin external preparation. The mechanism by which calcium stearate and the above dextrin and starch delay the generation of carbon dioxide gas is not clear, but it is considered that they may contribute to the stabilization of the coat layer.

2. Stability evaluation test II
<Example 9>
For effervescent skin external preparation using 0.18 g of citric acid powder (citric acid equivalent, 2 parts by mass) and 0.8 g (8 parts by mass) of sodium hydrogencarbonate powder on which a coating layer of calcium citrate is formed. A carbon dioxide generating agent was prepared. The coating layer was formed on the citric acid powder in the same manner as in Example 1 except that the mass part ratio of the citric acid powder to the calcium citrate was 9: 1.

  The citric acid powder on which the coat layer was formed and the sodium hydrogencarbonate powder were housed in an aluminum film bag having an inner surface laminated with polyethylene terephthalate and sealed. It was stored at 40 ° C., 50 ° C. or 60 ° C. for 20 days, and during the storage period, the presence or absence of carbon dioxide gas was observed by using the presence or absence of bag swelling as an index. As the carbon dioxide gas generating agent for effervescent skin external preparation, which was the standard for evaluation, the above-mentioned example 1 was also tested.

<Example 10>
Evaluation was performed in the same manner as in Example 9 except that 6% of dextrin powder was added to the carbon dioxide gas generator for effervescent skin external preparation of Example 9.

<Example 11>
For effervescent skin external use, using 0.18 g of citric acid powder (citric acid equivalent: 2 parts by mass) and 0.8 g (8 parts by mass) of sodium hydrogencarbonate powder on which a coating layer of oil and fat (rapeseed oil) is formed. A carbon dioxide gas generating agent was prepared. The coating layer was formed on the citric acid powder by moistening 0.16 g (8 parts by mass) of the citric acid powder, spraying 0.04 g (2 parts by mass) of rapeseed oil onto the powder, and then drying it. .

<Example 12>
Evaluation was carried out in the same manner as in Example 11 except that 6% of dextrin powder was added to the carbon dioxide generating agent for effervescent skin external preparation of Example 11.

<Example 13>
Using 0.18 g (2 parts by mass) of citric acid powder and 0.8 g of sodium hydrogencarbonate powder (sodium hydrogencarbonate equivalent, 8 parts by mass) on which a coating layer of fats and oils (hardened rapeseed oil) was formed, foamability A carbon dioxide generating agent for a skin external preparation was prepared. The coating layer was formed on the sodium carbonate powder in the same manner as in Example 11 except that the ratio by mass of the sodium carbonate powder to the fat was 9: 1.

<Example 14>
Evaluation was carried out in the same manner as in Example 13 except that 6% of dextrin powder was added to the carbon dioxide generating agent for effervescent skin external preparation of Example 15.

<Example 15>
0.18 g of citric acid powder with a coating layer of calcium citrate (citric acid equivalent, 2 parts by mass), 0.8 g of sodium hydrogencarbonate powder with a coating layer of fats and oils (hardened rapeseed oil) (hydrogen carbonate) Sodium equivalent, 8 parts by mass) was used to prepare a carbon dioxide gas generating agent for effervescent skin external preparation. The coating layer was formed on the citric acid powder according to the method described in Example 1. The same one as in Example 13 was used as the sodium hydrogencarbonate on which the coat layer of rapeseed hydrogenated oil was formed.

<Example 16>
Evaluation was performed in the same manner as in Example 15 except that 6% of dextrin powder was added to the carbon dioxide gas generator for effervescent skin external preparation of Example 17.

<Comparative example 2>
Foaming was performed using 0.18 g of citric acid powder (citric acid equivalent: 2 parts by mass) and 0.8 g (8 parts by mass) of sodium hydrogencarbonate powder on which a coating layer of polyethylene glycol (molecular weight 4,000) was formed. A carbon dioxide gas generating agent for topical skin external preparation was prepared. The coating layer was formed on the citric acid powder in the same manner as in Example 1 except that 1/10 parts by mass of polyethylene glycol was used with respect to the citric acid powder.

<Comparative example 3>
Using 0.18 g of citric acid powder (2 parts by mass) and 0.8 g of sodium hydrogencarbonate powder having a coating layer of polyethylene glycol (molecular weight 4,000) formed thereon (sodium hydrogencarbonate equivalent, 8 parts by mass), A carbon dioxide generating agent for effervescent skin external preparation was prepared. The coating layer was formed on the sodium carbonate powder in the same manner as in Example 11 except that 1/10 parts by mass of polyethylene glycol was used with respect to the sodium carbonate powder.

<Comparative example 4>
0.18 g of the same coated citric acid powder as in Comparative Example 2 (citric acid equivalent, 2 parts by mass) and 0.8 g of the same coated sodium hydrogen carbonate powder as in Comparative Example 3 (sodium hydrogen carbonate equivalent, 8 parts by mass) Part) was used to prepare a carbon dioxide generating agent for effervescent skin external preparation.

  The results are shown in "Table 4". In the table, “none” indicates that no carbon dioxide was generated during the storage period (20 days). In addition, “present” indicates that carbon dioxide gas was generated, and the number in parentheses indicates the number of storage days when foaming was recognized.

  In Examples 9 to 16, the generation of carbon dioxide was able to be prevented or delayed as compared with Example 1 which was used as the evaluation standard. On the other hand, in Comparative Examples 2 to 4, generation of carbon dioxide gas was confirmed after one day at any of the storage temperatures of 40 ° C, 50 ° C, and 60 ° C.

3. Stability evaluation test III
Powders of citric acid having coat layers formed with various coating agents were used and mixed with sodium hydrogen carbonate to prepare carbon dioxide generating agents for effervescent skin external preparations. The carbon dioxide generating agent for effervescent skin external preparation was housed in an aluminum film bag whose inner surface was laminated with polyethylene terephthalate and sealed. It was stored at 40 ° C. for 1 day, and the presence or absence of carbon dioxide was observed by using the presence or absence of bag swelling as an index.

  As the coating agent, lactose, sucrose, trehalose, mannitol, dextrin, potato starch, cellulose gum, xanthan gum, stearic acid, polyethylene glycol (molecular weight 400, 1,500, 4,000, 20,000) was used.

  0.3 g of purified water was added to 8 g of citric acid powder, and the whole was moistened with thorough mixing. 2 g of the coating agent was added to the moistened citric acid powder, and the mixture was thoroughly sprinkled until uniform, and then dried at 60 ° C. for 2-3 hours. The citric acid powder (2 parts by mass) on which the coat layer was formed was mixed with sodium hydrogen carbonate powder (8 parts by mass).

  As a result, carbon dioxide gas was not observed in the carbon dioxide gas generating agent for effervescent skin external preparation containing citric acid powder having a coat layer formed of lactose, sucrose, trehalose, mannitol, dextrin, potato starch, cellulose gum and xanthan gum. It was On the other hand, carbon dioxide gas was generated in the carbon dioxide gas generating agent for effervescent skin external preparation containing citric acid powder having a coat layer formed of stearic acid and polyethylene glycol or citric acid powder having no coat layer formed.

  Even in an additional test in which the storage temperature was 50 ° C. or 60 ° C., lactose, dextrin, potato starch, cellulose gum, and xanthan gum were confirmed to have good stability without carbon dioxide generation on the 7th day of storage. Further, using lactose as the coating agent, the mass ratio of the citric acid powder and the coating agent (citric acid powder: lactose) was changed from 8: 2 to 7: 3, 6: 4 or 5: 5 and the test was conducted. As a result, good stability was confirmed in each case (60 ° C., 5 days).

4. Efficacy evaluation test I
<Formulation Example 1>
According to the following prescription, a two-pack effervescent skin external preparation comprising a granule and a gel was prepared.
A: Granule (carbon dioxide generating agent for effervescent skin external preparation)
Calcium citrate coated citric acid powder
: 0.2 g (citric acid equivalent)
Sodium hydrogen carbonate powder: 0.8 g B: Gel agent Butylene glycol: 1.95 g
Xanthan gum: 0.13g
Phenoxyethanol: 0.04g
Water: 10.88g

  A clinical test was conducted using the prepared preparation. Four women in their twenties to thirties were used as test subjects. After acclimation for 15 minutes after washing the face, the first measurement of (1) stratum corneum water content, (2) water evaporation amount, and (3) skin elasticity was performed. The effervescent skin preparation was applied to the entire face and left for 15 minutes. The effervescent skin external preparation was removed with a spatula, rinsed off, and acclimated for 15 minutes, and then the second measurement was performed.

(1) The horny layer water content was measured using SKICON-200EX (IBS Co., Ltd.). (2) The water evaporation amount was measured using Tevameter (registered trademark) TM300 (CK). (3) Skin elasticity was measured using a cutometer (registered trademark) MPA580 (CK).

<Formulation Example 2>
The measurement was performed in the same manner as in Formulation Example 1 except that 1% w / w dextrin powder was added to the granules of Formulation Example 1.

<Comparative formulation example 1>
The measurement was performed in the same manner as in Formulation Example 1 except that the citric acid powder coated with calcium citrate in the granules of Formulation Example 1 was changed to uncoated citric acid powder.

<Comparative formulation example 2>
The measurement was performed in the same manner as in Comparative Preparation Example 2 except that 1% w / w dextrin powder was added to the granules of Comparative Preparation Example 2.

  The results are shown in "Table 5" to "Table 7". In each table, the first measurement value, the second measurement value, and the change rate are shown by the average value ± standard deviation of four subjects.

(1) stratum corneum water content

(2) Moisture loss

(3) Skin elasticity

  In Formulation Examples 1 and 2, compared to Comparative Formulation Examples 1 and 2, (1) keratin water content and (3) skin elasticity after use were significantly increased. In addition, in Formulation Examples 1 and 2, compared to Comparative Formulation Examples 1 and 2, (2) the amount of water transpiration after use could be significantly suppressed. From these results, it was confirmed that the effervescent skin external preparation according to the present invention markedly improved the skin condition and exerted an excellent cosmetic effect.

<Prescription example>
A one-pack effervescent skin external preparation was prepared according to the following prescription examples 1 to 4.

Prescription example 1
Sodium hydrogen carbonate: 0.5-40%
Coated citric acid Citric acid: 0.2-30%
Calcium citrate: 0.01-2%
Xanthan gum: 1-20%
Glucose: Remaining amount

Prescription example 2
Sodium hydrogen carbonate: 0.5-40%
Coated citric acid Citric acid: 0.2-30%
Calcium citrate: 0.01-2%
Dextrin: 0.1-30%
Xanthan gum: 1-20%
Glucose: Remaining amount

Prescription example 3
Coated sodium hydrogen carbonate Sodium hydrogen carbonate: 0.5-40%
Rapeseed hydrogenated oil: 0.05-5%
Citric acid: 0.2-30%
Dextrin: 0.1-30%
Xanthan gum: 1-20%
Glucose: Remaining amount

Prescription example 4
Coated sodium hydrogen carbonate Sodium hydrogen carbonate: 0.5-40%
Rapeseed hydrogenated oil: 0.05-5%
Coated citric acid Citric acid: 0.2-30%
Calcium citrate: 0.01-2%
Dextrin: 0.1-30%
Xanthan gum: 1-20%
Glucose: Remaining amount

Prescription example 5
Sodium hydrogen carbonate: 0.5-40%
Coated citric acid Citric acid: 0.2-30%
Lactose: 0.01-2%
Xanthan gum: 1-20%
Glucose: Remaining amount

Prescription example 6
Sodium hydrogen carbonate: 0.5-40%
Coated citric acid Citric acid: 0.2-30%
Cellulose gum: 0.01-2%
Dextrin: 0.1-30%
Xanthan gum: 1-20%
Glucose: Remaining amount

1: acidic substance or carbon dioxide generating substance, 2: coating agent

Claims (2)

A one-pack type or a multi-pack type effervescent skin external preparation, in which at least an acidic substance and a carbon dioxide gas-generating substance which reacts with the acidic substance to generate carbon dioxide in the same agent, And coexist so that the acidic substance and the carbon dioxide generating substance do not contact each other,
The acidic substance has a coat layer containing lactose ,
The acidic substance is at least one selected from malonic acid, succinic acid, glutaric acid, glutamic acid, glycolic acid, malic acid, tartaric acid, citric acid, ascorbic acid, and gluconic acid,
An effervescent skin external preparation characterized in that the amount of lactose is 1 to 43 mass% with respect to the acidic substance .   The effervescent skin external preparation according to claim 1, which is a pack.

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