JP6424356B2 - Effervescent skin external preparation - Google Patents

Description

  The present invention relates to a skin external preparation.

  Conventionally, a skin external preparation containing a synthetic or natural extract or the like having blood circulation promoting action on the skin has been used.

These extracts do not work well in a small amount of formulation, and in large amounts of formulation a skin external preparation containing carbon dioxide to enhance the blood circulation promoting action is proposed because the skin irritation is too large. Is being done. Most of these generate carbon dioxide gas by the reaction of an acidic substance and a carbon dioxide gas generating substance. As a dosage form of these external skin preparations, an acidic substance and a carbon dioxide gas generating substance are used as separate agents from the viewpoint of maintaining the carbonic acid generating ability of the external skin preparations for a long time, and these are mixed and foamed at the time of use It is known (patent documents 1 and 2).
On the other hand, a skin external preparation which contains an acidic substance and a carbon dioxide gas-generating substance and is mixed with a viscous composition containing water and a thickener at the time of use is also known (Patent Document 3).

JP-A-63-310807 Unexamined-Japanese-Patent No. 05-229933 gazette WO 99/24043

An effervescent skin external preparation of a type containing an acidic substance and a carbon dioxide gas-generating substance and mixed with a water-containing substance at the time of use has advantages such as easy handling when it is made into a one-part type.
However, conventionally, this type of external skin preparation improves the feeling of use such as easiness of mixing and easiness of mixing when used with a water-containing substance, and improves the moist feeling, elasticity, brightness, etc. of the skin. It was insufficient from the viewpoint of achieving both the state improvement effect.

  The present invention is a skin external preparation comprising at least a solid acidic substance and a solid carbon dioxide gas-generating substance that reacts with the acidic substance to generate carbon dioxide gas, and further, a polysaccharide or a derivative thereof It is an object of the present invention to provide a skin external preparation which contains at least one kind and is mixed with a water-containing substance when the skin external preparation is used.

  According to the present invention, it is possible to provide a skin external preparation which has a good feeling of use and is effective for improving the condition of the skin.

FIG. 1 is a graph showing the rate of change of L * value (whiteness) in Examples and Comparative Examples. FIG. 2: is a graph which shows the change rate of the amount of keratin water in an Example and a comparative example. FIG. 3 is a graph showing the rate of change in elasticity in the example and the comparative example. FIG. 4 is a graph showing the amount of foam (volume increase rate of the mixture of the external skin preparation and the water-containing material) in Examples and Comparative Examples. FIG. 5 is a graph showing the amount of generated carbon dioxide gas in the example and the comparative example. FIG. 6 is a graph showing the rate of change of the amount of water evaporation in the example. FIG. 7 is a graph showing the rate of change of stratum corneum water content in another example.

  The skin external preparation of the present invention contains at least a solid acidic substance, and a solid carbon dioxide gas-generating substance that reacts with the acidic substance to generate carbon dioxide gas.

  The external preparation for skin of the present invention is used by the user to mix the external preparation for skin and the water-containing substance at the time of use by causing foaming due to carbon dioxide gas generation and applying it to the skin. Hereinafter, each component contained in a skin external preparation and its manufacturing method are demonstrated.

<Solid acidic substance>
The solid acidic substance used in the present invention may be any of an inorganic acid and an organic acid, and one or more of these may be used. In addition, any dosage form may be used as long as it is solid, but powders such as granular and powder are preferable, and powder is particularly preferable.

  As inorganic acids, phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite, potassium pyrosulfite, sodium acid hexametaphosphate, potassium acid hexametaphosphate, sodium acid pyrophosphate, acid Potassium pyrophosphate, sulfamic acid and the like can be mentioned.

  As organic acids, linear fatty acids such as formic acid, acetic acid, propionic acid, butyric acid and valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, phthalic acid and 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, talthronic acid, salicylic acid, gallic acid And oxalic acid such as tropic acid, ascorbic acid and gluconic acid.

  Among these, citric acid, ascorbic acid, malic acid and succinic acid are preferable from the viewpoint of safety and solubility in water.

  The content of the solid acidic substance in the external preparation for skin of the present invention is preferably 1% by mass or more and 20% by mass or less, and further preferably 2% by mass or more and 18% by mass or less in the external preparation for skin. preferable.

<Solid carbon dioxide gas-generating substance>
Various solid carbon dioxide gas generating substances which react with the acidic substance to generate carbon dioxide used in the present invention can be used without particular limitation. In addition, any dosage form may be used as long as it is solid, but powders such as granular and powder are preferable, and powder is particularly preferable.

  As the carbon dioxide gas generating material, carbonates such as sodium carbonate, calcium carbonate, potassium carbonate, magnesium carbonate, sodium sesquicarbonate, ammonium hydrogencarbonate, potassium hydrogencarbonate, sodium hydrogencarbonate, lithium hydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate, magnesium hydrogencarbonate And hydrogen carbonates such as calcium hydrogen carbonate, and the like, and one or more of these may be used. Among these, sodium hydrogencarbonate is more preferable in that a hydrogen carbonate can be preferably used and a moderate foaming power can be realized.

  The content of the carbon dioxide gas generating substance in the external preparation for skin of the present invention is preferably 1% by mass to 30% by mass, and further preferably 2% to 25% by mass in the external preparation for skin. preferable.

<Polysaccharides or derivatives thereof>
Examples of polysaccharides or derivatives thereof used in the present invention include various substances that can be used in the cosmetic and pharmaceutical fields. Specific examples of polysaccharides include xanthan gum, succinoglycan, carrageenan, guar gum, locust bean gum, galactan, gum arabic, tragant gum, tamarind gum, agar, agarose, mannan, hyaluronic acid or salts thereof, chondroitin sulfate or its Hydrophilic natural polymers such as salts, curdlan, pectin, alginic acid or salts thereof, starches, dextrins, celluloses; starch derivatives such as carboxymethyl starch; hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl methyl cellulose phthalate Sulfonated cellulose derivatives, carboxymethyl cellulose and its salts, carboxymethyl ethyl cellulose and its salts, acetic acid phthalate Loin, hydrophilic synthetic polymers, and the like, such as cellulose derivatives such as cationized cellulose. These can be used 1 type or in combination of 2 or more types.

  In addition, it is possible to use polysaccharides or derivatives thereof used in the present invention which are highly soluble and / or dispersible in water without causing lumps when mixing the external preparation for skin of the present invention with a water-containing substance. It is preferable because it can be dissolved or dispersed in water, and it can alleviate the feeling of rough skin caused by the undissolved matter. Here, the solubility in water or the dispersibility is that the external preparation for skin is uniformly dissolved or dispersed in a short time when adding water at about room temperature and stirred, or no lumps are generated at the time of dissolution, etc. It can be judged from

  Preferred examples of polysaccharides or derivatives thereof from the viewpoint of water solubility and dispersibility include xanthan gum, succinoglycan, carrageenan, guar gum, locust bean gum, galactan, gum arabic, tragacanth gum, and the like. There may be mentioned tamarind gum, agar, agarose, mannan, hyaluronic acid and salts thereof, curdlan, alginic acid and salts thereof, starch and derivatives thereof, dextrin, cellulose and cellulose derivatives.

Among the polysaccharides or derivatives thereof used in the present invention, only one type may be used, but it is preferable to use two or more types in combination. This is due to the following reasons.
Many polysaccharides or derivatives thereof are dissolved or dispersed in water to exert a thickening effect. In addition, the addition of polysaccharides or derivatives thereof to the external preparation for skin improves the stability of the external preparation for skin before use and during storage, and prevents the reaction between an acid and a carbon dioxide gas-generating substance to prevent carbon dioxide It also has the advantage of preventing the occurrence. Among polysaccharides or derivatives thereof, those which contribute more to the thickening effect than the stability during storage (hereinafter also referred to as polysaccharides of type A or derivatives thereof) are also more stable during storage than the thickening effect There are also many types of polysaccharides (hereinafter referred to as B type polysaccharides or their derivatives), and by combining both types of polysaccharides or their derivatives, the thickening effect and the stability during storage can be obtained. Both can be improved. Polysaccharides of type A or derivatives thereof include xanthan gum, carrageenan, hyaluronic acid and cellulose and salts or derivatives thereof. Type B polysaccharides or derivatives thereof include starch or derivatives thereof and dextrin. It is mentioned as saccharides. By using B-type polysaccharides or derivatives thereof, it is possible to suppress the generation of carbon dioxide gas during storage of the external preparation for skin. In particular, use of starch or a derivative thereof is preferable because generation of carbon dioxide gas is effectively suppressed and storage stability for a long period is further improved. When starch or a derivative thereof is used in the present invention, the preferred amount used is 3% by mass or more, particularly 5% by mass or more, particularly 10% by mass or more in the skin external preparation.
In the present invention, it is also preferable to combine many types of polysaccharides or derivatives thereof, for example, three or more.

  Furthermore, as apparent from the comparison of the examples described later, for example, Examples 1 and 2, the present inventors used only one kind of polysaccharide or its derivative when used in combination. The ability to retain carbon dioxide of skin external preparations (mixtures) when mixed with water-containing substances is high, and the mixture applied to the skin is less likely to drip, and skin condition improvement effects such as redness improvement and elasticity improvement are obtained. We found that the ease of use, including ease of application and ease of removal, improved. Furthermore, as apparent from Examples 6 to 10, it was found that these effects are higher in the presence of the water soluble protein and / or the natural surfactant, in particular, the extract containing saponin.

  In the present invention, the content of the polysaccharide or derivative thereof in the external preparation for skin is preferably 8% by mass to 50% by mass, and more preferably 11% by mass to 45% by mass. The content of the polysaccharide or derivative thereof of 8% by mass to 50% by mass is preferable from the viewpoint of handling at the time of use, in particular, from the viewpoint of easy mixing when mixing with a water-containing substance and sagging at the time of use. If it is less than 8% by mass, it tends to sag at the time of use, and if it is more than 50% by mass, mixing becomes difficult at the time of mixing, and thickening immediately after mixing with a water-containing substance makes application to the use site difficult. Unfavorable.

When a polysaccharide of A type or a derivative thereof and a polysaccharide of B type or a derivative thereof are used in combination as a polysaccharide or a derivative thereof, the mass ratio of the two is 100 mass of the polysaccharide of A or a derivative thereof It is preferable that they are 10 mass parts or more and 1000 mass parts or less of the polysaccharide of B or its derivative with respect to part, and it is more preferable that they are 20 mass parts or more and 800 mass parts or less.

  It is further preferable that the skin external preparation of the present invention contains a water-soluble protein. Here, the water-soluble protein refers to a protein obtained by concentrating, separating and purifying animal or vegetable protein, and having the property of being easily dispersed or dissolved in water or various liquids, specifically, When 5 mass% or more is added to water at 25 ° C. under 1 atmospheric pressure, it means one that can be uniformly dispersed or dissolved without generating lumps. Water soluble proteins include protein hydrolysates. As this hydrolyzate, those obtained by hydrolyzing proteins derived from various organisms such as animals and fish by alkali treatment or enzyme treatment are preferable. As a specific water-soluble protein, casein, collagen, hydrolyzed collagen such as gelatin, albumin, elastin, keratin, sericin and the like can be used. These can be used 1 type or in combination of 2 or more types. Among them, the skin external preparation of the present invention preferably contains albumin, collagen and hydrolyzed collagen as the water-soluble protein. The water-soluble protein also has a role as a foaming aid, and in particular, it strengthens the bubbles and has the function of keeping the foam stable for a long time. For this reason, the addition of the water-soluble protein contributes to the ease of adjusting the viscosity of the external preparation for skin and the improvement of the solubility in water, and an increase in the amount of carbonic acid generation, so that the skin condition improving effect is easily improved. The present inventors have found that the effect of the water-soluble protein is excellent by containing a polysaccharide or a derivative thereof, particularly two or more polysaccharides or a derivative thereof.

  Moreover, although the skin external preparation of this invention may contain only 1 type of water-soluble protein, it is also preferable to contain 2 or more types of water-soluble protein. This is shown, for example, in the comparison of Examples 13 and 14 described later with Example 17. As is clear from these examples, compared with the case where only albumin is contained as a water-soluble protein, when collagen or hydrolyzed collagen is contained together with albumin, skin quality improving effects such as moist feeling and smoothness of the skin after use, The feeling of use of the mixture obtained by mixing the external preparation for skin with the water-containing substance is likely to be improved. In particular, as apparent from Example 14 to be described later, the effervescent skin external preparation of the present invention, when containing hydrolyzed collagen, is easy to improve the ease of application and the comfort upon application and the appearance. As apparent from the comparison of Examples 18 and 19 described later, even when hydrolyzed collagen is used alone, retention of carbon dioxide in the mixture of the external preparation for skin and the water-containing substance, and the skin condition after use of the external preparation for skin The effect is as high as or higher than albumin.

  When the skin external preparation of the present invention contains a water-soluble protein, the water-soluble protein in the skin external preparation is preferably 0.01% by mass or more and 10% by mass or less, and 0.05% by mass or more and 8% by mass or less It is more preferable that When the content is 0.01% by mass or more and 10% by mass or less, the strength of the bubbles containing the water-soluble protein is increased, and the effect of keeping the foam stable for a long time is easily obtained, which is preferable.

  When the external preparation for skin contains a water-soluble protein, the content of the water-soluble protein is a polysaccharide or a derivative thereof from the viewpoint of further enhancing the retention of carbon dioxide gas when the external preparation for skin of the present invention is dissolved in water. It is preferable that it is 0.1 mass part or more with respect to 100 mass parts, and it is more preferable that it is 1 mass part or more and 50 mass parts or less.

  The external preparation for skin of the present invention can contain various components other than the solid acidic substance, the solid carbon dioxide gas-generating substance, polysaccharide or derivative thereof, and water-soluble protein according to the use and purpose. . Such components are further described below.

  The skin external preparation of the present invention is preferable from the viewpoint of retention of the generated foam, such as nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant and the like. At this time, the surfactant used is preferably a solution, solid, flake, granule, fine particle or powder that does not contain water from the viewpoint of storage stability, solid, flake It is preferable to use granular, fine granular or powdery ones. As said surfactant, a natural surfactant is preferable. Natural surfactants refer to surfactants derived from animals and plants. For example, phospholipids such as lecithin, lanolin, cholesterol, saponin, sphingolipids, pectin, dipotassium glycyrrhizinate, plant extract amino acid surfactant etc. It can be mentioned. The skin external preparation of the present invention preferably contains a natural surfactant in an amount of 0.001% to 10% by mass, and more preferably 0.005% to 8% by mass.

  Among the above mentioned natural surfactants used in the present invention, phospholipids, saponins, pectins, glycyrrhizinic acid or salts thereof are preferable, and an extract containing saponin and / or glycyrrhizinic acid or a salt thereof is preferably contained. Is particularly preferred. Saponin is a glucoside widely distributed in plants, and is a generic name of a group of compounds having a steroid or triterpenoid as a non-sugar part, and depending on the type of aglycone (non-sugar part of glycoside), triterpenoid saponin It can be roughly divided into steroidal saponins. A common property of saponins is that the aqueous solution has high foamability.

  As described above, saponin is known to have foamability, and the present inventors have found that water soluble protein can be obtained by adding an extract containing this saponin instead of the water soluble protein. It has been found that the long-term stability of the foam, the improvement of the feeling of use such as sagging of the mixture and the ease of mixing, and the improvement effect of the skin condition such as moist feeling and elasticity can be obtained. The external preparation for skin containing a water-soluble protein may be difficult to use, for example, for users of allergic substances, but an extract containing saponin can be effectively used as a water-soluble protein substitute. It is. Furthermore, the addition of the extract containing saponin has an effect of increasing the amount of carbon dioxide gas generated, and thus can contribute to effectively promoting skin blood circulation. The present inventors improve the effect by adding an extract containing saponin, particularly the improvement of feeling in use and the improvement of skin condition, by containing polysaccharides or their derivatives, in particular, two or more kinds of polysaccharides or their derivatives. It has been found that the effects such as are excellent.

As an extract containing saponin used for the external preparation for skin of the present invention, it is preferable to use a plant-derived extract. Examples of the plants referred to here include, as plants containing triterpenoid saponins, soybean, hetima, adzuki bean, green beans, spinach, sugar beet, grapes, Chinese radish, licorice, licorice, Senega, quillaja, mulberry, saponos, ginseng, tea seeds, As a plant containing a steroidal saponin, mention may be made of a liliaceous plant, a boletus family, a chimo (chimo), a bakumondo (mochimon winter) and the like.
Among these plants, the agent of the present invention is preferably an extract of any one or more of the above-mentioned various plants containing triterpenoid saponin, among them, mucrodi, soybean, licorice, hematma It is preferable to contain the extract of 1 or more types of plants chosen from, and it is preferable to contain the extract of a mucrodi especially. Here, mukuroji is a plant belonging to the genus Sapindaceae (Sapindaceae) and belonging to the genus Sapindus. mukurossi and S. This applies to delavayi etc.

  The plant parts that are the raw materials of the extract include whole grass, leaves (leaf, petiole, etc.), fruits (mature, immature, etc.), seeds, flowers (petal, ovary, etc.), stem, rhizome, root And tuberous root. In the present invention, when an extract of mukurodi is used as an extract containing saponin, it is preferably an extract of mukuroji fruit and / or peel, particularly preferably an extract of peel.

  The extract can be used as it is or whole plants or the above-mentioned parts as they are, or after cutting, crushing, crushing, squeezing, or drying or processing these treated ones. These treatments can be used alone or in combination of two or more.

  As a solvent used for extraction, for example, water; methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, glycerin, methyl acetate, ethyl acetate, Organic solvents such as isopropyl acetate, ethyl ether, acetone and the like can be mentioned. These can be used singly or in combination of two or more. From the viewpoint of safety etc., it is preferable to use water, ethanol or a mixed solvent thereof harmless to the human body as the extraction solvent. The extraction may be performed at a temperature equal to or lower than the boiling point of the extraction solvent, and the extraction time can be appropriately changed depending on the extraction temperature. The extract may contain water as an extraction solvent, but when the external preparation for skin of the present invention is a one-part external preparation for skin, the acidic substance reacts with the carbon dioxide gas generating substance during storage to generate carbon dioxide gas. It is also possible to use a water-containing extraction solvent, as it will not be substantially water-free unless it contains the amount of water necessary to do so.

  The extract is contained in the external preparation for skin of the present invention in the form of a solid such as powder after removal of contaminants by filtration. As a method of setting it as a solid, for example, a method of making an extract obtained by extraction with the above-mentioned solvent into powder by freeze drying, spray drying or the like can be mentioned. Before solidifying the above-mentioned extract, a purification operation may be added to the extent that the physiological action of saponin is not impaired.

  From the viewpoint of further enhancing the above effects, when the external preparation for skin of the present invention contains an extract containing saponin, the content thereof is 0.001% by mass or more and 10% by mass or less in the external preparation for skin Preferably, it is more preferably 0.005% by mass to 8% by mass. It is preferable that the content of the extract is 0.001% by mass or more and 10% by mass or less from the viewpoint of achieving both the long-term stability of the foam and the improvement effect of the skin condition.

  In addition, examples of glycyrrhizinic acid and salts thereof as natural surfactants in the present invention include dipotassium glycyrrhizinate (GK2) and the like. As described later, glycyrrhizinic acid and its salts also function as anti-inflammatory agents and whitening agents. In the present invention, when glycyrrhizinic acid and salts thereof are used as natural surfactants (or anti-inflammatory agents, whitening agents), it is apparent from the comparison of Examples 4 and 5 described later that the external skin preparation and the water-containing substance In the mixture, carbon dioxide gas can be easily retained for a long time, and carbon dioxide gas generation can be increased, and also, the moisture content of the skin is increased, and the skin condition improving effect such as redness enhancement is enhanced. It is possible to improve the feeling of use of the external preparation. The preferable content of glycyrrhizinic acid and its salt in the external preparation for skin of the present invention is the same as the preferable content of the anti-inflammatory agent described later.

  Furthermore, the skin external preparation of the present invention preferably contains at least one selected from a germicide, an anti-inflammatory agent and a skin lightening agent.

  The bactericidal agent is a substance that has bactericidal, bacteriostatic or antibacterial activity and does not cause problems with the skin when it is added to external skin preparations, and examples thereof include salicylic acid and its salt or salicylic acid derivative; erythromycin, clinda Antibiotics such as mycin, gentamicin, penicillin, chloramphenicol, tetracycline, benzoyl peroxide, nadifloxacin, ethanol, benzalkonium chloride, sulfur, parahydroxybenzoate esters, hinokitiol, triclosan, homosulfamine, chloramine T, catechin and the like Derivatives thereof; chitin and chitosan derivatives and the like can be mentioned. Furthermore, an extract having an antibacterial action may be used as an antibacterial agent, and examples of such an extract include fennel, oobac, tea, rosehip, chamomile, orange, pomegranate purpurea, turmeric, gardenia, clove, sage, yukinoshita And extracts of clove, eucalyptus, cypress, cedar and the like. These can be used 1 type or in combination of 2 or more types.

It is preferable to use especially salicylic acid and its salt or a salicylic acid derivative among these microbicides, and it is preferable to use especially a salicylic acid. As apparent from the examples described later, it is possible to improve the keratin water content and elasticity of the skin after use in the skin external preparation of the present invention by using a bactericidal agent such as salicylic acid.
From the viewpoint of further enhancing this effect, when the external preparation for skin of the present invention contains a bactericide, the content thereof is preferably 0.001% by mass or more and 20% by mass or less in the external preparation for skin, 0 It is more preferable that it is .005 mass% or more and 10 mass% or less.

  The anti-inflammatory agent is a substance having an action of suppressing inflammation, and examples thereof include glycyrrhizinic acid and its salt described above as a natural surfactant and derivatives thereof. Glycyrrhetinic acid and salts thereof, mefenamic acid and salts thereof, phenylbutazone, indomethacin, ibuprofen acid and salts thereof, ketoprofen, allantoin, guaiazulene and derivatives thereof, ε-aminocaproic acid Zinc oxide, diclofenac sodium, proanthocyanidin and the like can be mentioned. Furthermore, an extract having an anti-inflammatory activity may be used as an anti-inflammatory agent, and examples of such an extract include Yukinoshita extract, licorice extract, aloe extract, sikon extract, salvia extract, and Arnica extract. Extracts of animals and plants such as chamomile extract, birch extract, hypericillium extract, eucalyptus extract, peach leaf extract, pine bark extract, grape seed extract, and cowberry extract. These can be used 1 type or in combination of 2 or more types.

Among these anti-inflammatory agents, glycyrrhizinic acid and salts thereof, glycyrrhetinic acid and salts thereof, and derivatives thereof are preferably used, and glycyrrhizinic acid and salts thereof are particularly preferably used for the reasons described above, and glycyrrhizinic acid is particularly preferred. It is preferred to use dipotassium (GK2). In the skin external preparation of the present invention, the use of an anti-inflammatory agent can suppress the inflammation of the skin and obtain the effect of preventing acne and rough skin.
From the viewpoint of further enhancing such effects, when the skin external preparation of the present invention contains an anti-inflammatory agent, its content is preferably 0.001% by mass or more and 20% by mass or less in the skin external preparation, It is more preferable that it is 0.005 mass% or more and 10 mass% or less.
When GK 2 is used as the external preparation for skin of the present invention, as is apparent from Example 7 described later, not only a high skin whiteness improvement effect can be obtained, but also high skin condition improvement such as improvement of stratum corneum water content and elasticity An effect is obtained. Furthermore, the skin external preparation using GK2 is excellent also in usability, such as easiness of mixing and dripping resistance, as is clear also from the description of Example 6 and 7 mentioned later.

  As the skin lightening agent, one having tyrosinase activity or one having an activity to decolorize the melanin pigment is mainly used. Examples thereof include L-cysteine and its derivatives, ascorbic acid and its derivatives, tranexamic acid derivatives, glabridin, liquiritin, isoliquiritin, hydroquinone, arbutin, kojic acid, placenta and the like. In addition, the above-mentioned glycyrrhizin acid or salt, glycyrrhetinic acid and salts thereof and derivatives thereof can also be used as a skin-whitening agent. Furthermore, an extract having a whitening effect as a whitening agent may be used, and such an extract may be Sohakuhi extract, toukiki extract, Ibukitoranoo extract, Keiketsou extract, Clara extract, hawthorn extract, White lily extract, hop extract, Neubara extract and the like can be mentioned. These can be used 1 type or in combination of 2 or more types.

  It is preferable to use 1 or more types chosen from arbutin, a placenta, glycyrrhizinic acid or its salt, ascorbic acid, and its derivative (s) among these whitening agents.

The arbutin used in the present invention is a compound whose system name is also called 4- (β-D-glucopyranosyloxy) phenol.
When arbutin is used as the external preparation for skin of the present invention, not only a high skin whiteness improvement effect can be obtained, but also a high skin condition improvement effect such as moistness and elasticity of the skin, as apparent from Example 10 described later. can get. Furthermore, the external preparation for skin using arbutin is also excellent in usability such as ease of application, comfort upon application, ease of removal, and ease of removal, as is apparent from the description of Examples 10 and 16 described later. ing.

  Placents are extracts of growth factors and other nutrients that promote cell division from animals, particularly preferably pigs, horses, cattle, sheep, human placenta, extracts of nutrients from fish's ovarian membranes, plant embryos It is a generic term of what extracted the nutrient component from The external preparation for skin of the present invention containing a placenta has an effect that the amount of water evaporation tends to be reduced after application and the smoothness and the feeling of smoothness are easily increased, as is apparent from the description of Example 15 described later. In the present invention, any placenta can be used, but an animal-derived placenta and a fish-derived placenta can be preferably used.

  From the viewpoint of further enhancing the above effects, when the skin external preparation of the present invention contains a whitening agent, its content is preferably 0.001% by mass or more and 30% by mass or less in the skin external preparation, More preferably, it is 0.005% by mass or more and 20% by mass or less.

  In the skin external preparation of the present invention, other active ingredients can be used in place of or in addition to the above-mentioned extract containing saponin, a bactericidal agent, an anti-inflammatory agent and a skin lightening agent. Such active ingredients include gold leaf and pearl powder (pearl), mud, charcoal, gypsum, enzymes, herbs, seaweed, yoghurt, whey, fermented products such as sake, sake, honey, propylene glycol, polyethylene glycol, sorbitol Examples thereof include moisturizing ingredients such as sodium lactate and sodium pylori pyrrolidone carboxylate, plant ingredients such as licorice, and vitamins. Among them, gold foil and pearl powder are particularly preferable. As apparent from the description of Example 11 to be described later, use of gold foil improves the feeling of use such as comfort upon application and good appearance, and also provides a skin condition improving effect. Further, as is clear from the description of Example 12 described later, when pearl powder is used, the effect of improving the skin condition such as the brightness of the skin is obtained, and the feeling in use is also improved.

  Pearl powder refers to cultured or natural pearls which are spherical or amorphous metabolic products formed in the body of freshwater clams such as pearl oysters, black clasps, white clams, mabes, abalone and other freshwater clams. It is the powder which sifted what was ground by the publicly known method, such as a ball mill, a jet mill, and a turbo mill. When the pearl powder is contained, its content is preferably 0.0001% by mass or more and 10% by mass or less in the skin external preparation. When it contains gold foil, it is preferable that the content is 0.0001 mass% or more and 10 mass% or less in a skin external preparation.

  In addition to polysaccharides and derivatives thereof and thickeners other than water-soluble proteins, effervescent skin external preparations of the present invention, excipients, granulating agents, pH adjusters, oils and fats, perfumes, coloring agents, antioxidants Alcohol, polyhydric alcohol, inorganic salt, lubricant, solvent, extract of animals and plants, etc., can contain one or more components usually used for external skin preparations.

  As polysaccharides and derivatives thereof and thickeners other than water-soluble proteins, polyvinyl alcohol, acrylate / alkyl acrylate crosspolymer, polyacrylic acid, polyacrylamide, polyalkylacrylamide / polyacrylamide copolymer, poloxamer (Pluronic (registered trademark)) And hydrophilic hydrophilic compounds such as hydrophilic clay minerals such as laponite, bentonite and smectite.

  As an excipient or a granulating agent, for example, powders such as lactose, powdered sugar, xylitol, D-sorbitol, glucose (glucose), D-mannitol, fructose, sucrose, sucrose, urea and the like are not particularly limited and may be used alone. Or in combination of two or more. When such an excipient and / or granulating agent is contained, the content is preferably 10% by mass or more, and 20% by mass or more and 88% by mass or less in the external preparation for skin of the present invention. Is more preferred.

  In the skin external preparation of the present invention, the acid substance, the carbon dioxide gas generating substance, the polysaccharide or derivative thereof, the water-soluble protein, the natural surfactant, the bactericidal agent, the anti-inflammatory agent, the whitening agent, The total content of the components other than the excipient or the granulating agent is preferably 40% by mass or less, more preferably 30% by mass or less.

  The dosage form of the external preparation for skin of the present invention is usually solid, and may be powder, granules, fine granules, pellets or a combination of two or more of them. Powdered form is preferable from the viewpoint of cost reduction at the time of production and ease of dissolution at the time of use.

  For example, when the external preparation for skin of the present invention is in the form of granules, the entire agent may be in the form of granules, or a part may be in the form of granules. When a part is granulated, the acidic substance and / or the carbon dioxide gas generating substance may be granulated. In this case, the granules may contain other components (excipients, granulating agents, polysaccharides or derivatives thereof, water-soluble proteins, etc., one or more of the various components described above). In addition, components other than the acidic substance and the carbon dioxide gas generating substance may be in the form of granules.

  For example, in the case of obtaining the solid acidic substance and / or the granules of the solid carbon dioxide-generating substance by granulating the mixture of the acidic substance and / or the carbon dioxide-generating substance and other components, Although there is no restriction | limiting in particular as content of another component, It is preferable to set it as less than 80 mass% in the said granule. When the other components are present in a content of more than 80% by mass, the foamability is unfavorably lowered.

  The method for producing the granules is not limited to the present example, and conventional methods such as dry crushing granulation method, wet crushing granulation method, fluidized bed granulation method, high speed stirring granulation method, extrusion granulation method, etc. It can be manufactured according to

  For example, when a low melting point compound is used as a matrix base as a matrix base, the low melting point granulation agent melted by heating in a container such as a beaker or the like, the acidic substance and / or the carbon dioxide gas generating substance, and necessary Add other ingredients depending on the condition and mix well. If necessary, suitable additives may be added thereto. The mixture is further stirred while being gradually cooled at room temperature, and left to solidify. If it solidifies to some extent, it may be cooled rapidly by a refrigerator or the like.

  Alternatively, for example, the material may be charged into a fluid bed granulator, mixed for several minutes by air flow, and granulated by spraying water thereon.

  When a 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 or the like to generate the acid substance and / or the carbon dioxide gas. After dissolving or dispersing the substance and other components as required and mixing well, the solvent is removed by heating in an oven or the like, and dried. When it is completely solidified, it is crushed and sieved to adjust the particle size, and then made into granules.

  The shape of the solidified acidic substance or solid carbon dioxide gas generating substance is, for example, irregular shape, planar shape, polyhedral shape, spherical shape, drop shape, fibrous shape, cylindrical shape, fine powder shape, etc. There is no particular limitation. Moreover, as the particle size, the thing of a wide range can be especially used without a restriction | limiting. In particular, those having a particle size distribution of about 1,000 μm are more preferable in terms of ease of handling and ease of mixing with a water-containing substance. The above particle size distribution in the present invention can be determined by a conventional laser diffraction / scattering method.

  In the present invention, the acidic substance and the carbon dioxide gas generating substance are contained in the same agent, and the acidic substance and the carbon dioxide gas generating substance are mixed and coexist in the same agent so as not to be in physical contact with each other. Is preferred. The coexistence means is not particularly limited and can be widely applied.

  When the acid substance and the carbon dioxide gas generating substance are blended so as not to be in physical contact with each other, for example, a coating layer which wraps the acid substance and the carbon dioxide gas generating substance may be provided Alternatively, one or both of the acidic substance and the carbon dioxide gas generating substance may be encapsulated. Further, compression molding may be performed by sandwiching a layer not containing the acid substance and the carbon dioxide gas generating substance between the acid substance and the carbon dioxide gas generating substance so that they are not in direct contact with each other.

  Hereinafter, means for coexistence of the acid substance and the carbon dioxide gas generating substance in the same agent will be specifically described, but the present invention is not limited thereto.

[Coat layer formation]
As a method for forming a coat layer, for example, a method of forming a coat layer on at least one of an acidic substance or a carbon dioxide gas generating substance may be used. By providing a coating layer, even if the acid substance, the carbon dioxide gas generating substance and other components coexist in the same agent, there is no risk of carbon dioxide gas being unexpectedly generated during production or storage, so that the stability, It is preferable from the point of durability.

  As a preferable coating agent for constituting the above-mentioned coat layer, it can be used without particular limitation as long as it has low reactivity with the acidic substance or the carbon dioxide gas generating substance. For example, fats and oils, fatty acids, fatty acid salts, acetylcellulose, hydroxyethylcellulose, carboxymethylcellulose sodium, polyvinylpyrrolidone, polyvinyl alcohol, sodium polyacrylate, hydroxypropyl methylcellulose, methyl methacrylate-methacrylic acid copolymer, ethyl acrylate-methacrylic acid Copolymers, gum arabic, sodium alginate, soluble starch, hydroxypropyl cellulose, wheat starch, sucrose, lactose etc., citrate etc. may be mentioned. In particular, when an acidic substance such as citric acid is coated, it is preferable to use a citrate such as calcium citrate. Alternatively, the coating layer may be formed using a solid hydrocarbon wax, a solid fat and the like, and the like, which are melted at a predetermined temperature or more by heating.

    The amount of coating agent used for the acidic substance and / or carbon dioxide gas generating substance is preferably 1 to 20% (w / w), more preferably 1 to 10% (w / w) based on the acidic substance or carbon dioxide gas generating substance w) about.

  The coating method of the coating layer may be carried out by any method as long as it is commonly used to coat particles. For example, it may be coated simultaneously with granulation by spray granulation, rolling granulation, etc., oil coating, granulation coating, transport layer method, pan coating, rolling coating, fluidized coating or powder or granules It may be coated using a method such as dry coating. During coating, if excessive heat or physical force is applied, the acid substance or the carbon dioxide gas generating substance is destroyed and the formed film is broken, and the surface of the acid substance or the carbon dioxide gas generating substance Not only is it difficult to uniformly coat the whole lipid powder, but also the acid substance or the carbon dioxide gas-generating substance leaks to the surface, causing solidification due to moisture absorption, or causing adverse effects on other components during compounding. The coating conditions should be such that the coating layer and the object to be coated can not be destroyed.

[Encapsulation]
In the case of encapsulating the acidic substance and / or the carbon dioxide gas generating substance, a known method may be employed without particular limitation.

  As a method of encapsulation, known methods can be applied without particular limitation, and as a material of encapsulation, gelatin, starch, gum arabic, methyl cellulose, acrylic ester, methacrylic ester, vinyl acetate, Although polyvinyl alcohol, silicone resin, solid wax, polyethylene, fatty acid, higher alcohol, etc., and those in which multiple layers of surfactant such as liposome are formed are included, 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 ester, methacrylic ester, vinyl acetate, styrene, or acrylic acid, methacrylic acid, divinyl with said monomer It is also preferable to use a resin capsule made of a copolymer formed from a monomer selected from benzene and ethylene glycol dimethacrylate. Such microcapsules are prepared by emulsifying the content and the constituent monomers of the polymer constituting the shell of the capsule in a reaction solvent such as water, and initiating polymerization of azobisisobutyronitrile, benzoyl peroxide, etc. An agent may be added to carry out emulsion polymerization. As a surfactant component used for this emulsification, for example, Hexlight sold under the name of "Laponite XLG" can be suitably exemplified. The microcapsules of the present invention can be produced by separating the resulting microcapsules by means such as centrifugation and optionally washing.

[Compression molding]
As a method of compression molding, substances other than the acidic substance and the carbon dioxide gas generating substance (so that they are not in direct contact between the first layer containing the acidic substance and the second layer containing the carbon dioxide gas generating substance) For example, a method may be employed in which a third layer comprising an excipient, a thickener, etc.) is sandwiched and compression-molded. The compression-molded dosage form may be any solid dosage form such as tablet, sphere, plate and the like. 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 acidic substance in which the coating layer is provided by any of the above methods on one or more of the first layer and the second layer. A carbon dioxide gas generating substance, or the encapsulated acidic substance or carbon dioxide gas generating substance may be used. The method of compression molding can apply a well-known method, without being limited in particular.

The skin external preparation of the present invention may exclude the following skin external preparations.
“A single-part skin external preparation containing at least a solid acidic substance, a solid carbon dioxide gas-generating substance that reacts with the acidic substance to generate carbon dioxide gas, and a thickener, and does not contain water, The thickener is contained in an amount of 12 to 45% by mass in the total external preparation for skin, and the thickener is used in combination with albumin and other thickeners and mixed with a liquid containing water when the external preparation for skin is used "One-part type skin external preparation". Here, examples of the thickener include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sulfonated cellulose derivative, acrylate / alkyl acrylate crosspolymer, polyacrylic acid, polyacrylamide, polyalkylacrylamide / polyacrylamide copolymer, carboxy Other than hydrophilic synthetic polymers such as methylcellulose, cationized cellulose and pluronics, and hydrophilic natural polymers such as starch, xanthan gum, sodium alginate, succinoglycan, carrageenan, guar gum, locust bean gum, celluloses, etc. , Chondroitin sulfate, casein, collagen, gelatin, hydrophilic protein compounds such as albumin, laponite, bentonite, smek Hydrophilic thickening compound such as a hydrophilic clay minerals such sites are mentioned.

<Use form of external skin preparation>
The skin external preparation of the present invention causes foaming by mixing with the water-containing substance on the palm or in the container when used.
The external preparation for skin of the present invention may be used as a one-part external preparation for skin, or may be used as a two-part type comprising a water-containing substance and a kit. When the external preparation for skin of the present invention is a one-part type, as described above, the external preparation for skin is usually a solid composition, and more preferably in a solid, granular, fine granular or powder form. It is particularly preferable that it is in the form of granular, fine granular, or powdery form because it is easy to mix with the water-containing substance and to cause foaming easily. In addition, the external preparation for skin of the present invention generally does not contain water substantially in the case of one-part type. Here, the term "substantially free of water" means that the acidic substance reacts with the carbon dioxide gas-generating substance during storage of the external preparation for skin and does not contain an amount of water necessary to generate carbon dioxide gas. . Specifically, the amount of water contained in the external preparation for skin of the present invention is 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less. When the external preparation for skin of the present invention is a two-component type comprising a water-containing substance and a kit, an agent containing an acidic substance, a carbon dioxide gas-generating substance and at least one polysaccharide is usually a solid composition It is more preferable that it is in the form of solid, granular, fine granular or powder, and it is in the form of granular, fine granular or powder because it is easy to mix with the water-containing substance and foam easily occurs. Particularly preferred. In addition, when the external preparation for skin of the present invention of the present invention is a two-part type, the composition in solid form usually contains substantially no water. Here, the term "substantially free of water" means that the acidic substance reacts with the carbon dioxide gas-generating substance during storage of the external preparation for skin and does not contain an amount of water necessary to generate carbon dioxide gas. . Specifically, the amount of water contained in the external preparation for skin of the present invention is 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less. When the external preparation for skin of the present invention is a one-part type, the user usually prepares a water-containing substance for mixing with the external preparation for skin, and in the case of a two-part type, as described above, the external preparation for skin of the present invention And the water-containing substance constitute a kit. When the external skin preparation is a one-part type, a liquid containing water is often used as the water-containing substance. In the case of a two-part type, examples of the water-containing substance can include a liquid containing water, a gel, and the like. As the water-containing substance, a liquid is preferable, a liquid having a low viscosity is more preferable, and a liquid having no viscosity is particularly preferable. It is preferable that the water-containing substance does not substantially contain the above-mentioned thickener. Specifically, the content of the thickener in the water-containing material is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and 0.01% by mass or less Is particularly preferred. In particular, when the skin external preparation is a two-part type, the effect of the present invention is more effective when mixing the skin external preparation with a liquid, particularly a liquid having a relatively low viscosity, as compared with mixing with a gel. It is preferable because it is played. When the skin external preparation of the present invention is mixed with a gel or a relatively high viscosity liquid, it is difficult to mix the two agents, and it tends to take a long time to foam, which is not preferable. Specifically, the water-containing material has a viscosity at 25 ° C. of preferably 50000 mPa · s or less, more preferably 30000 mPa · s or less, particularly preferably 10000 mPa · s or less, still more preferably 5000 mPa · s or less . This viscosity can be measured by the viscometer used in the following examples. The water content in the water-containing substance may be 10% by mass or more, preferably 30% by mass or more. More preferably, it is 40% by mass or more, further preferably 50% by mass, and particularly preferably 70% by mass or more, and particularly preferably 80% by mass or more. When the water content is less than 10% by mass, carbon dioxide gas is less likely to be generated when mixing the external preparation for skin and the water-containing substance, and an effect such as blood flow promotion at the time of use can not be obtained. Here, a high lower limit value such as 70% by mass or more and 80% by mass or more can be adopted in both one-component type and two-component type, but is particularly preferable in the case of one-component type.

  When the external preparation for skin of the present invention is a one-part type, it is characterized in that it is easy to be handled by the user at low cost and easier to handle than the two-part type by being made one-part. In the case of the one-part type, as the water-containing substance used in the present invention, a liquid containing water generally used for cosmetics, pharmaceuticals and the like and used in general homes can be mentioned. The liquid containing water may be water itself. Specifically, tap water, distilled water, membrane filtered water, ion-exchanged water, deep ocean water, sake, liquor such as wine, soy milk, soy milk, drinking yogurt, acerola juice, sports drink, beverage such as carbonated water, rice Noji soup and the like. These may be used alone or in combination of two or more.

  When the external preparation for skin of the present invention and the water-containing material are combined to form a two-component type, as the water-containing material, as described above, a liquid or gel containing water may be mentioned. In addition to the liquid containing, the thing which added the arbitrary components to these is mentioned. As this component, a known one contained in a liquid preparation for a two-part type external preparation for skin, such as a moisturizer, surfactant, pH adjuster, volatile alcohol, oils and fats, perfume, extracts of animals and plants, etc. Can. For example, as a humectant, polyglycerin such as glycerin, diglycerin, triglycerin, tetraglycerin, ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1 Polyhydric alcohol such as 3-propanediol, sorbitol, polyglycerin derivative, polyoxyalkylene alkyl glucoside, sodium lactate, sodium pyrrolidonecarboxylate, almond, avocado, altea, aloe, usvenia oasis, nononis, oats, licorice, quince seed, Clara (Kujin), Gardenia, Grapefruit, Watercress, Gentiana, Genno Shoko, Burdock, Wheat, Saishin, Cactus, Soapwort, Hawthorn, Geow Shimoku, ginger, zinnia koji, mulberry, sageum sage, caterpillar herbaceous, dokdami, peppermint, stalk, hamamelis, rose, cypress, rhubarb, dandelion, grape, prune, lice, bodice, hop, pine, quince, marronier, melissa, cornflower, lilies, lime And plant extracts such as lavender, apple, rice and rice bran, blackcurrant, ibuquitoranoo, neubara, eleostoke, seaweed etc., and one or more of them can be used.

  The amount of the water-containing substance to be used is not particularly limited and can be used in a wide range, but for example, it is preferably added in an amount of 1 to 10 times by mass to the external preparation for skin, 2 to 5 times It is more preferred to add the amount. By adding more than one volume of liquid, the skin external preparation can be rapidly dissolved, and a sufficient amount of carbon dioxide gas can be generated. On the other hand, dripping of the external skin preparation due to viscosity reduction can be prevented by adding the liquid within 10 times the amount.

  The temperature of the water-containing substance to be used is not particularly limited, and a wide range can be used. However, pre-cooling before use is particularly preferable because the function of the active ingredient of the external skin preparation becomes high. As for the temperature range which can be used, it is preferable to use water or tap water at about room temperature from the viewpoint of the feeling of use at the time of application and the convenience of the user.

  The method for storing the skin external preparation is not particularly limited as long as it is stored in a state where the water is blocked and not in contact. The shape of the storage container to be used can be suitably selected according to the purpose, and cup shape, tube shape, bag shape, bottle shape, stick shape, pump shape, jar shape, canned shape etc. are mentioned. Moreover, although the material which comprises a storage container can select and use plastic, glass, aluminum, paper, various polymers etc. individually or 2 types or more, for example, it is not limited to these.

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

  According to the external preparation for skin of the present invention, as is clear from the description of the examples described later, the feeling in use is good, and an excellent skin condition improving effect can be obtained. Examples of the feeling of use include the ease of mixing the mixture of the external skin preparation and the water-containing substance on the skin, the ease of application, the sagging resistance and the ease of removal. Further, as the skin condition improving effect, improvement in moist feeling, elasticity, brightness, redness, whiteness degree, increase in keratinous water content and the like can be mentioned. As apparent from Example 24 described later, according to the external preparation for skin of the present invention, it may be possible to obtain an effect of making wrinkles inconspicuous.

<Application of skin external preparation>
The skin external preparation of the present invention promotes skin blood flow, and makes use of the above effects to whiten skin, improve skin quality, improve freckles, rejuvenate skin, tighten skin, partially thin skin and cleanse skin. Improve skin condition, keep skin firm, keep skin healthy, prevent skin roughening, squeeze skin, moisturize skin, keep skin moisture and oil, keep skin flexible, skin Protect the skin, prevent dryness on the skin, soften the skin, give skin aggravation, give gloss on the skin, smooth the skin, prevent stains and drippings due to sunburn, make the small wrinkles due to dryness inconspicuous Not only cosmetic products intended to do, but also the skin, that kind of thing, that kind of heat, the heat, the heat, the crack, the crack, the aggravation, the acne prevention, the oiled skin, the prevention of the razor burn, the prevention of the stain and freckles by the sun, the sun, In the snow To prevent irritating, squeeze the skin, cleanse the skin, condition the skin, keep the skin healthy, moisturize the skin, protect the skin, prevent the skin from drying out, etc. It can be suitably used in any of pharmaceutical products such as goods and drugs. The skin external preparation of the present invention is preferably used as cosmetics and quasi-drugs, and is preferably used as cosmetics and cosmeceutical products such as emulsions, creams, packs and peeling agents. Among them, when used as a pack agent, it is preferable because it has a good feeling in use and a high skin condition improving effect is easily obtained.

  EXAMPLES The present invention will be more specifically described below with reference to examples, but the scope of the present invention is not limited to these examples. In the following examples and comparative examples, the raw materials used were commercial products unless otherwise specified.

<Examples 1 to 10, Comparative Examples 1 to 3>
The components described in Table 1 were mixed and mixed according to the compositions shown in the same Table, and the powdery external skin preparations of Examples 1 to 10 and the powdery external skin preparations of Comparative Examples 1 to 3 were manufactured. . The numerical values in Table 1 below are the mass ratio (mass%) in the external preparation for skin.

  The characteristics of the external preparation for skin of the above examples and comparative examples were evaluated according to the following [Evaluation of Examples 1 to 10, Comparative Examples 1 to 3].

[Evaluation of Examples 1 to 10, Comparative Examples 1 to 3]
(1) Sensory evaluation Three healthy women in their twenties and thirties were randomly selected as subjects. The inside of the subject's forearm was washed with a face wash and rested in the measuring room for 15 minutes. Subsequently, a powdery skin external preparation sample and water were mixed at a ratio of 1: 3 (mass ratio) in a container to obtain a mixture as a foamy pack cosmetic. This mixture was applied to the 4 cm × 4 cm portion inside the above forearm. Ten minutes after application, the mixture was removed from the forearm and the forearm was washed with water. After that, as evaluation of feeling in use, 4 items of “easiness of mixing”, “easiness of applying”, “hard to drip” and “easiness of removal”, and “feeling moist” as the condition of the skin after use Questionnaire was conducted on 4 items of “skin elasticity”, “skin brightness” and “skin redness”. About each item, the score was attached to seven steps shown in Table 2, and after totaling, the average value of three persons was calculated. The results are shown in Table 3. In addition, after application | coating about "slipperiness", it was highly evaluated that the mixture was hard to drip from skin. As for the "water content", the higher the water content of the skin, the higher the point, and the "redness of the skin", the higher the redness of the skin, the higher the point.

  From the results in Table 3 above, in the skin external preparation of each example containing a polysaccharide or a derivative thereof, the feeling of use such as ease of mixing, ease of application, sagging, ease of removal, and moist feeling It can be seen that it is superior to Comparative Examples 1 to 3 in terms of both elasticity, brightness, and skin condition improvement effects such as redness. Furthermore, it turns out that Example 2, 6-10 which contains 2 or more types of polysaccharides or its derivative (s) has a still higher effect of both the improvement of this feeling in use, and the improvement of a skin condition. Also, as in Examples 3, 6, 8 and 10, when a water-soluble protein is contained, the effects of improving the feeling in use and the condition of the skin are further enhanced, as in Examples 4, 5, 7 and 9. Also in the case where an extract containing saponin, which is a natural surfactant, is contained instead of the water-soluble protein, it is understood that these effects become higher than or equal to the water-soluble protein. In addition, it can also be seen that high effects are obtained in Examples 3 and 5 containing GK2, salicylic acid or arbutin. For example, as is apparent from the comparison of Examples 4 and 5, the inclusion of GK2 which is a natural surfactant (and an anti-inflammatory agent and a skin lightening agent) not only enhances the condition improving effect such as redness of the skin but also the skin It also improves the feeling of using external preparations. From the above results, when two polysaccharides or derivatives thereof are used as in Examples 2 to 5 as compared to Example 1 in which one polysaccharide or derivative thereof is used, a water-soluble protein or a natural surfactant is used. It is understood that, by using in combination, a higher feeling of use and a skin condition improving effect can be obtained. In addition, it is understood that the combination of the polysaccharide or two or more derivatives thereof and the water-soluble protein or the natural surfactant as in Examples 6 to 10 further improves both the feeling in use and the skin condition improving effect. .

(2) Measurement of skin condition For sensory evaluation of the above (1), the L * value, the amount of keratinous water and the elasticity at the planned portion of the mixture application on the inner side of the forearm before the mixture application were measured by the following measuring devices. After the mixture was removed and washed with water, the L * value, the amount of keratinous water, and the elasticity were also measured in the same manner as in the place where the mixture was applied on the inner side of the forearm. From the measured values obtained, the average value of 3 subjects was determined. The average value after use of the external skin preparation was divided by the average value before use, and the obtained value was defined as the rate of change. The rate of change in L * value (whiteness) is shown in FIG. 1, the rate of change in the amount of stratum corneum water is shown in FIG. 2, and the rate of change in elasticity is shown in FIG. In these figures, the higher the rate of change, the higher the evaluation.

L * value: Measured with a color difference meter (CR-400 manufactured by Konica Minolta).
-Keratinous water content: It measured by skin surface keratin water content measuring device SKICON-200EX (made by an eye BIS company). The skin surface stratum corneum water content measuring device is an evaluation of the skin conductance (electrical conductivity, unit: μS) as the water content of the stratum corneum.
Elasticity: Measured with a skin viscosity measuring apparatus Cutometer MPA 580 (manufactured by Courage + Khazaka).
These measurements were performed in a standard manner as described in the instructions supplied with the instrument.

  From the results in FIG. 1 to FIG. 3, in each example, a change rate equal to or higher than that of each comparative example is obtained with respect to the L * value, the moisture content and the elasticity of the skin after using the external preparation for skin. Can be seen. In particular, containing two or more of polysaccharides or derivatives thereof, containing water soluble protein, containing an extract containing saponin which is a natural surfactant, glycyrrhizinate which is a natural surfactant (inflammatory agent and whitening agent) It can be seen that the rate of change in L * value, stratum corneum water content, and elasticity is increased by one or more factors selected from the inclusion of the other skin lightening agents or bactericidal agents. For example, it can be seen from the comparison of Examples 1 and 2 that when two or more of polysaccharides or their derivatives are contained, the L * value, the amount of keratinous water and the elasticity are improved. Further, it is understood from the comparison of Examples 1 and 3 that the inclusion of the water-soluble protein and glycyrrhizinate improves the L * value, the amount of keratinous water, and the elasticity. Further, it can be seen from the comparison of Examples 1 and 4 that the inclusion of the extract containing saponin improves the L * value, the amount of keratinous water, and the elasticity. Further, it can be seen from the comparison of Examples 4 and 5 that the inclusion of glycyrrhizinate improves the stratum corneum water content. Also, from the comparison of Examples 6 and 8 and the comparison of Examples 7 and 9, it can be seen that the inclusion of a bactericidal agent improves the moisture content and elasticity of the stratum corneum. Further, it is understood from Example 10 that the L * value is improved by containing arbutin as a whitening agent.

(3) Evaluation of external skin preparation 27 mL of water is placed in a bottle (225 mL) having a diameter of about 4.8 cm and a height of about 10.5 cm, 9 g of a powdery external skin preparation sample is added thereto, and 20 times in 10 seconds. It stirred. The following <foaming amount> and <carbon dioxide gas generation amount> were evaluated about the obtained mixture.

<Foaming amount>
The volume of the mixture after 1 minute, 10 minutes and 20 minutes after stirring was measured, and the rate of increase (%) in volume relative to the volume before stirring was determined. The results are shown in FIG.

<CO2 emissions>
Carbon dioxide gas generated from the mixture after stirring was collected by replacement over water. The accumulated amount (mL) of carbon dioxide gas collected at each time 3, 5, 7, 10, 15, 20 and 30 minutes after stirring was measured. The results are shown in FIG.

From the results shown in FIG. 4, it can be seen that the skin external preparation of each example hardly reduces the volume of the mixture even after a lapse of time after stirring, and a certain amount of carbon dioxide gas is retained in the mixture. This effect is selected from the inclusion of two or more of polysaccharides or their derivatives, the inclusion of water-soluble proteins, the inclusion of saponin, the inclusion of glycyrrhizinate, and the inclusion of other skin lightening agents or bactericidal agents. It is enhanced by the inclusion of one or more factors, in particular extracts containing water soluble proteins or saponins, and the inclusion of glycyrrhizinate. For example, it can be seen from the comparison of Examples 1 and 2 that when two or more of polysaccharides or their derivatives are contained, carbon dioxide gas retention in the obtained mixture is improved. Further, it is understood from the comparison of Examples 1 and 3 that the inclusion of the water-soluble protein and glycyrrhizinate improves the carbon dioxide gas retention in the obtained mixture. Further, it is understood from the comparison of Examples 1 and 4 that the inclusion of the extract containing saponin improves the carbon dioxide gas retention in the obtained mixture. In addition, it is understood from the comparison of Examples 4 and 5 that when the glycyrrhizinate is contained, the carbon dioxide gas retention in the obtained mixture is improved.
On the other hand, in each comparative example, bubbles of the mixture are hard to be held, and the volume of the mixture after stirring tends to decrease, that is, it can be seen that the amount of carbon dioxide gas that can be held in the mixture is small.

According to the results in FIG. 5, in each example, carbon dioxide gas is generated relatively gradually in the period from stirring to 5 minutes, and thereafter, although there is a gradual gradient, carbon dioxide gas generation from the mixture is stopped. It is understood that it is continuing without. In particular, in Examples 2 to 10, which contain two or more polysaccharides or derivatives thereof, a water-soluble protein or an extract containing saponin, glycyrrhizinate, or other skin-whitening agents, and a bactericidal agent, the generation of carbon dioxide gas It can be seen that there is a tendency to continue for a long time. For example, it can be seen from the comparison of Examples 1 and 3 that when the water-soluble protein and glycyrrhizinate are contained, the generation amount of carbon dioxide gas is improved. Further, it is understood from the comparison of Examples 1 and 4 that when the extract containing saponin is contained, the generation amount of carbon dioxide gas is improved. Further, it can be seen from the comparison of Examples 4 and 5 that when glycyrrhizinate is contained, the amount of carbon dioxide gas generation is improved.
On the other hand, in each of Comparative Examples 1 to 3, it can be seen that although the carbon dioxide gas generation rate up to 3 minutes after stirring is high, the subsequent generation is stopped or the generated carbon dioxide gas amount itself is low. .

Examples 11 to 17
Each component was compounded and mixed in the compounding ratio of following Table 4, and the powdery external preparation for skin was manufactured. The numerical values in Table 4 are the mass ratio (mass%) in the skin external preparation.

[Evaluation of Examples 11 to 17]
<Sensory evaluation>
As healthy subjects other than the test subject who evaluated said Examples 1-10 and Comparative Examples 1-3, three healthy women of 20-30 generations were chosen at random. Other than that, after using the powdered external preparation for skin according to the same method as “(1) Sensory evaluation” in the above [Examples 1 to 10, Comparative Examples 1 to 3 evaluation] A questionnaire was conducted on the evaluation items of For each item, using Example 17 as a standard (4.0 points), a score was added to the seven levels shown in Table 2 above, and after counting, the average value of three persons was determined. The results are shown in Table 5 below. The following "irritating feeling" was rated as high as possible. In addition, "stickiness of the skin" was rated high enough to be less sticky.
Evaluation items: Ease of application "Ease of application", "Comfort at application", "Good appearance of the applied mixture", "It is difficult to drip", "Stimulation (presence or absence of irritability)", " 8 items of "smoothness of mixture", "poor stickiness of mixture", "easiness of removal of mixture", skin condition after use, "moisture of skin", "smoothness of skin", There are a total of 15 items of 7 items: "Smoothness of the skin", "Tackiness of the skin", "Sense of skin firmness", "Skinning of the skin" and "Brightness of the skin".

  From the results in Table 5 above, each active ingredient (a second type water soluble protein is also included in the composition of Example 17 containing an acidic substance, a carbon dioxide gas generating substance, a polysaccharide or derivative thereof, and one type of water soluble protein In Examples 11 to 16 in which B) was added, it is understood that the effects of both the feeling in use and the improvement of the skin condition are improved. In particular, it can be seen that when the external preparation for skin of Example 11 to which gold foil is added is used, the feeling of use such as comfort upon application and good appearance etc. is improved. In addition, it is understood that when the external preparation for skin of Example 12 to which pearl powder is added is used, the brightness etc. of the skin is improved. Also, it can be seen that the use of the skin external preparation of Example 13 to which collagen is added improves especially the moist feeling and smoothness. Moreover, when the skin external preparation of Example 14 to which hydrolyzed collagen is added is used, easiness of application at the time of use, comfort, goodness of appearance etc. improve, and the moistness and smoothness etc. of the skin after use. It turns out that it improves. In addition, it can be seen that the use of the external preparation for skin of Example 15 to which a placenta is added improves the smoothness, the feeling of slipping, etc. after use. It can be seen that the use of Example 16 with the addition of arbutin improves ease of application, comfort and spread during use, and improves the smoothness, brightness, etc. of the skin after use.

[Evaluation of Examples 14 to 17]
<Measurement of skin condition>
In <Sensory evaluation> of the above-mentioned [Evaluation of Examples 11 to 17], the amount of water evaporation (g / m ² / hr) at the planned application site on the inner side of the forearm before applying the mixture was measured by the following measuring device. After that, the mixture was removed, and after washing with water, the amount of water evaporation (g / m ² / hr) at the location where the mixture was applied on the inner side of the forearm was similarly measured.

Moisture loss (g / m ² / hr): Measured with Tewameter TM 300 (Courage + Khazaka). The measurements were carried out in the standard manner described in the instructions supplied with the instrument.
From the measured values obtained, the average value of 3 subjects was determined. The mean value before use was divided from the mean value after use of the external skin preparation to determine the rate of change. The rate of change of the amount of water evaporation obtained is shown in FIG. The lower the rate of change, the higher the evaluation.

  From the results of FIG. 6 above, when using each external preparation for skin of Example 14 where hydrolyzed collagen was added, Example 15 where a placenta was added, and Example 16 where arbutin was added to the composition of Example 17, It can be seen that the amount of water loss in the In particular, it is understood that the suppressing effect of the embodiment 15 in which the placenta is added is high.

Examples 18 to 20
Each component described in Table 6 was blended and mixed according to the composition shown in the same Table, and a powdery external preparation for skin of Examples 18 to 20 was manufactured. The numerical values in Table 6 are the mass percentage (mass%) in the skin external preparation.

[Evaluation of Examples 18 to 20]
<Sensory evaluation>
Five healthy women in their twenties and thirties were randomly selected as subjects. Other than that, the same sensory evaluation as (1) sensory evaluation in [Evaluation of Examples 1 to 10, Comparative Examples 1 to 3] was performed. However, the evaluation items were four items of "skin smoothness", "moisture of skin", "moisture of skin", and "softness of skin" as the condition of the skin after use. In addition, the test subject was given the 7-point evaluation point shown in Table 2 with Example 20 as a reference (4.0 points). After tabulation, the average value of the score of 5 persons was obtained. The results are shown in Table 7.

[Evaluation of Examples 18 and 19]
<Measurement of skin condition>
In <Sensory evaluation> of the above-mentioned [Evaluation of Examples 18 to 20], the amount of stratum corneum water at the mixture application planned place on the inner side of the forearm before the mixture application was measured by the above-mentioned measuring apparatus. Then, the mixture was removed, and after washing with water, the stratum corneum water content at the site where the mixture was applied on the inner side of the forearm was similarly measured. From the obtained measurement values, the average value of five subjects was determined. The average value after use of the external skin preparation was divided by the average value before use, and the obtained value was defined as the rate of change. The results are shown in FIG.

<Evaluation of skin external preparation>
The amount of water used was 30 mL, and the amount of the powdery external skin preparation sample used was 10 g, except for [foaming amount] in (3) of [Examples 1 to 10, evaluation of comparative examples 1 to 3]. Similarly, the increase rate (%) of the volume of the mixture after stirring was determined. The results are shown in Table 8 below.

Example 21
Each component described in Table 9 was blended and mixed according to the composition shown in the same Table, and a powdery external preparation for skin of Example 21 was manufactured. The numerical values in Table 9 are mass percentages (mass%) in the external preparation for skin.

Comparative Example 4
Each component described in Table 10 was blended and mixed according to the composition shown in the same Table, to prepare a powder containing carbonate and a solution containing an acid. The numerical values in Table 10 are parts by mass. It was 16.9 mPa * s, as a result of measuring the viscosity in 25 degreeC using the viscometer (Brookfield company make RVT type | mold) about the obtained liquid containing an acid.

Comparative Example 5
The respective components described in Table 11 were blended and mixed according to the compositions shown in the same Table, to produce a powder containing an acid and a viscous composition containing a carbonate. The numerical values in Table 11 are parts by mass. The viscosity of the obtained viscous composition was measured at 25 ° C. using the above-mentioned viscometer, and as a result, it was 549,600 mPa · s.

[Evaluation of Example 21 and Comparative Examples 4 and 5]
(1) Sensory evaluation Four healthy women in their twenties and thirties were randomly extracted and used as subjects. Other than that, the same sensory evaluation as (1) sensory evaluation in [Evaluation of Examples 1 to 10, Comparative Examples 1 to 3] was performed. However, in Example 21, it was obtained by mixing a powdered external preparation for skin and water at a mass ratio of 1: 2.7. In Comparative Example 4, a powder containing a carbonate and a liquid containing an acid were mixed in a mass ratio of 1: 3 to obtain a mixture. In Comparative Example 5, the powder containing the acid and the viscous composition containing a carbonate were mixed in a mass ratio of 1: 3.68 to obtain a mixture. In addition, the evaluation items are two items of "skin elasticity" and "redness of skin" as the condition of the skin after using the external preparation for skin, and the score of 7 steps shown in Table 2 is based on Comparative Example 4 (4. An evaluation score was given as 0). After tabulation, the average value of the evaluation points of 4 persons was obtained. The results are shown in Table 12. In addition, when the viscosity of 25 degreeC of water used in Example 21 was measured with the said viscometer, the numerical value below the lower limit (10 mPa * s) of the viscometer was shown.

(2) Measurement of Skin Condition In the sensory evaluation of the above (1), L * value at the planned application site of the mixture on the inner side of the forearm was measured by the above-mentioned measuring apparatus before the mixture application. Then the application, the mixture was removed and washed with water. The L * value of the portion to which the mixture was applied on the inner side of the forearm was measured with the above-mentioned measuring device at each time point of 15, 60 and 120 minutes after the end of the removal. From the obtained measurement values, the average value of four subjects was determined. The value obtained by subtracting the average value before use from the average value after use of the external skin preparation was taken as the change value. The change value of the obtained L * value (whiteness) is shown in Table 13. In the table, the higher the change value, the higher the evaluation.

  As apparent from the description of Table 12 and Table 13, Example 21 in which the skin external preparation containing an acidic substance, a carbon dioxide gas generating substance and a polysaccharide or a derivative thereof was mixed with a water-containing substance was a powder containing a carbonate. It is understood that the condition improving effect on the skin after use is higher than that of Comparative Example 4 mixed with the liquid containing the powder and Comparative Example 5 where the powder containing the acid is mixed with the viscous composition containing the carbonate.

Examples 22 to 23
Each component was compounded and mixed in the compounding ratio of following Table 14, and the powdery external preparation for skin was manufactured. The numerical values in Table 14 represent the mass ratio (mass%) in the skin external preparation.

[Evaluation of Examples 22 to 23]
<Evaluation of storage stability>
The powdery skin external preparation obtained in Examples 22 to 23 was sealed by 9 g each in an aluminum film bag laminated with polyethylene terephthalate on the inner surface. It was stored at 50 ° C. or 60 ° C. for 2 months, and during the storage period, the presence or absence of generation of carbon dioxide gas was observed by using the presence or absence of expansion of the bag as an index. The results are shown in Table 15. In the table, "none" indicates that no generation of carbon dioxide gas was observed during the storage period (2 months).

  As is clear from Table 15, in Examples 22 and 23 in which 10% by mass or more of potato starch was blended, no generation of carbon dioxide gas was observed even after storage at 60 ° C. for 2 months, confirming good storage stability. did it.

[Evaluation of Example 24]
Each component was compounded and mixed in the compounding ratio of following Table 16, and the powdery external preparation for skin was manufactured. The numerical values in Table 16 are the mass ratio (mass%) in the skin external preparation.

  The characteristics of the external preparation for skin of the above-mentioned Examples and Comparative Examples were evaluated according to the following [Example 24].

[Evaluation of Example 24]
<Anti-wrinkle function evaluation>
The subjects were 16 adult females with wrinkles at the end of their eyes. A mixture of powdery external skin preparation sample and water in a container at a ratio of 1: 3 (mass ratio) and being a foamy pack cosmetic is applied to a designated half face centered on either the left or right side of the eye It applied. Ten minutes after application, the mixture was removed and rinsed with water or lukewarm water. The subject performed this once a day for 4 weeks. The evaluation of wrinkles took the replica of the wrinkles part (with and without application of the mixture) of the test subject's right and left eyes and carried out the image analysis by a replica. Collection of replicas The replica agent (SILFLO) was used to collect replicas in the range of 4 cm × 4 cm outward from the external eye angle of the subject. The obtained replica was analyzed in a range of 10 mm × 10 mm based on a point about 5 mm away from the outer eye angle on the outer side of the face. The analysis was performed using a reflection replica analysis system (ASA-03 RXD) and 3D skin analysis software. Table 17 shows the result of the maximum wrinkle maximum depth which is the evaluation result of the wrinkles. A positive change indicates that the wrinkles are deeper than before use, and a negative change indicates that the wrinkles are shallower than before use.

  From Table 17, it can be confirmed that by using the external preparation for skin of the present invention, the maximum wrinkle maximum depth at the corners of the eyes is shallower than when not used. From the above results, it can be seen that the use of the foamable skin external preparation of the present invention has the effect of making wrinkles less noticeable.

[Formulation example of one-part type external skin preparation]
Below, the specific formulation example of the one-part type external skin preparation of this invention is shown.

Example 25
Each component was mix | blended by the compounding ratio of Table 18, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water was added to the powder 1 in a mass ratio of 3 with respect to the powder 1 and stirred to obtain a foamy pack cosmetic.

Example 26
Each component was compounded by the compounding ratio of Table 19, and it was set as the powdery one-part type skin external preparation. The single-component type skin external preparation powder was placed in a container, and water with a mass ratio of 5 to powder 1 was added and stirred, whereby a foamy pack cosmetic was obtained.

Example 27
Each component was compounded in the compounding ratio of Table 20, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water was added at a weight ratio of 10 to powder 1 with stirring to obtain a foamy pack cosmetic.

Example 28
Each component was compounded in the compounding ratio of Table 21, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water was added to the powder 1 in a mass ratio of 3 with respect to the powder 1 and stirred to obtain a foamy pack cosmetic.

Example 29
Each component was compounded in the compounding ratio of Table 22, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water with a mass ratio of 4 to powder 1 was added and stirred to obtain a foamy pack cosmetic.

Example 30
Each component was mix | blended by the compounding ratio of Table 23, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water was added at a weight ratio of 10 to powder 1 with stirring to obtain a foamy pack cosmetic.

Example 31
Each component was compounded in the compounding ratio of Table 24, and it was set as the powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water with a mass ratio of 4 to powder 1 was added and stirred to obtain a foamy pack cosmetic.

Example 32
Each component was blended at a blending ratio described in Table 25 to make a powdery one-part type skin external preparation. The single-part type external skin preparation powder was placed in a container, and water with a mass ratio of 4 to powder 1 was added and stirred to obtain a foamy pack cosmetic.

Claims (1)

One-component type used to improve the amount of keratinous water and / or elasticity of skin having at least a solid acid substance and a solid carbon dioxide gas generating substance that reacts with the acid substance to generate carbon dioxide gas an effervescent skin external preparation,
Furthermore, at least one selected from starch or a derivative thereof,
Cellulose and at least one selected from salts and derivatives thereof,
Containing dipotassium glycyrrhizinate,
An effervescent skin external preparation to be mixed with water when the skin external preparation is used.

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