JP2020050669A - Foamable skin external preparation - Google Patents

Abstract

To provide a foamable skin external preparation which has good use feeling and is effective for improving skin conditions.SOLUTION: There is provided a foamable skin external preparation having at least a solid acid substance and a solid carbon dioxide generating substance which generates carbon dioxide by reacting with the acid substance, which further contains at least one selected from a cellulose derivative and a starch derivative as a polysaccharide or a derivative thereof and at least one selected from a hydrophilic natural polymer which is alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum (provided that alginic acid or a salt thereof is excluded when sodium carboxymethyl cellulose is contained as a cellulose derivative), in which the skin external preparation is mixed with a water-containing substance when used.SELECTED DRAWING: None

Description

  The present invention relates to an external preparation for skin.

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

Proposal of an external preparation for skin that contains carbon dioxide to enhance blood circulation promoting action, because these extracts are insufficiently effective when used in small amounts and cause excessive irritation to the skin in large amounts. Has been made. Many of these generate carbon dioxide gas by the reaction between an acidic substance and a carbon dioxide gas generating substance. Examples of the dosage form of these external preparations for skin include those in which an acidic substance and a carbon dioxide generating substance are separately prepared from the viewpoint of maintaining the carbon dioxide generating ability of the external preparation for a long period of 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 containing an acidic substance and a carbon dioxide-generating substance and mixing with a viscous composition containing water and a thickener at the time of use is also known (Patent Document 3).

JP-A-63-310807 JP 05-229933 A WO99 / 24043

An effervescent skin preparation of the type containing an acidic substance and a carbon dioxide-generating substance and being mixed with a water-containing substance at the time of use has advantages such as being easy to handle when used in a single-part form.
However, conventionally, this type of skin external preparation improves the feeling of use such as ease of mixing and application when mixed with a water-containing substance and the moist feeling, elasticity, and brightness of the skin. The state improvement effect was insufficient from the viewpoint of achieving both.

The present invention is at least an effervescent skin external preparation having a solid acidic substance and a solid carbon dioxide generating substance that reacts with the acidic substance to generate carbon dioxide gas,
As the polysaccharide or a derivative thereof, at least one selected from a cellulose derivative and a starch derivative,
Alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or at least one selected from hydrophilic natural polymers that are tamarind gum (however, when the cellulose derivative contains sodium carboxymethylcellulose, the alginic acid or a salt thereof is used. Excluding) and
An object of the present invention is to provide an effervescent skin preparation that is mixed with a water-containing substance when the skin preparation is used.

Further, the present invention is at least a solid acidic substance, an effervescent skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
As the polysaccharide or a derivative thereof, it contains alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or two or more kinds selected from hydrophilic natural polymers that are tamarind gum,
An object of the present invention is to provide an effervescent skin preparation that is mixed with a water-containing substance when the skin preparation is used.

Further, the present invention is at least a solid acidic substance, an effervescent skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
As a polysaccharide or a derivative thereof, containing two or more kinds selected from a cellulose derivative and a starch derivative,
An object of the present invention is to provide an effervescent skin preparation that is mixed with a water-containing substance when the skin preparation is used.

Further, the present invention is at least a solid acidic substance, an effervescent skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
At least one polysaccharide or a derivative thereof;
Inorganic hydrophilic thickening compound, or contains at least one hydrophilic synthetic polymer that is an organic thickener,
An object of the present invention is to provide an effervescent skin preparation that is mixed with a water-containing substance when the skin preparation is used.

  According to the present invention, it is possible to provide an external preparation for skin that has a good feeling in use and is effective for improving skin conditions.

FIG. 1 is a graph showing the rate of change of the L * value (whiteness) in Examples and Comparative Examples. FIG. 2 is a graph showing the rate of change in the amount of keratin water in Examples and Comparative Examples. FIG. 3 is a graph showing the rate of change of elasticity in Examples and Comparative Examples. FIG. 4 is a graph showing the foaming amount (volume increase rate of a mixture of a skin external preparation and a water-containing substance) in Examples and Comparative Examples. FIG. 5 is a graph showing the amount of carbon dioxide gas generated in Examples and Comparative Examples. 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 in the amount of keratin water in another example. FIG. 8 is a graph showing the rate of change of the L * value in another example. FIG. 9 is a graph showing the rate of change in the amount of keratin water in another example. FIG. 10 is a graph showing the rate of change of elasticity in another example. FIG. 11 is a graph showing the rate of change of the amount of water evaporation in another example.

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

  The external preparation for skin of the present invention is used by a user, when used, by mixing the external preparation for skin and a water-containing substance to generate foaming due to the generation of carbon dioxide gas, and applying it to the skin. Hereinafter, each component contained in the external preparation for skin and its manufacturing method will be described.

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

  Inorganic acids include phosphoric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite, potassium pyrosulfite, sodium acid hexametaphosphate, potassium acid hexametaphosphate, sodium acid pyrophosphate, acidity Examples include potassium pyrophosphate and sulfamic acid.

  Examples of organic acids include 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, tartronic acid, salicylic acid, and gallic acid And oxyacids such as tropic acid, ascorbic acid and gluconic acid.

  Among them, citric acid, ascorbic acid, malic acid and succinic acid are preferred from the viewpoints 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 more preferably 2% by mass or more and 18% by mass or less in the external preparation for skin. preferable.

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

  Examples of the carbon dioxide generating substance include carbonates such as sodium carbonate, calcium carbonate, potassium carbonate, magnesium carbonate, and sodium sesquicarbonate, ammonium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, and magnesium hydrogen carbonate. , Calcium bicarbonate and the like, and one or more of these are used. Among these, sodium bicarbonate is more preferable because bicarbonate can be preferably used and moderate foaming power can be realized.

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

<Polysaccharide or derivative thereof>
Examples of the polysaccharide or a derivative thereof used in the present invention include various types that can be used in the cosmetic and pharmaceutical fields. Examples of specific polysaccharides include xanthan gum, succinoglycan, carrageenan, guar gum, locust bean gum, galactan, gum arabic, tragacanth gum, tamarind gum, agar, agarose, mannan, hyaluronic acid and its salts, chondroitin sulfate and its Salts, curdlan, pectin, alginic acid and salts thereof, starch, dextrin, hydrophilic natural polymers such as celluloses; carboxymethyl starch and salts thereof, starch derivatives such as acrylic acid-grafted starch and salts thereof, and hydroxypropyl cellulose and Derivatives thereof, hydroxyethylcellulose and its derivatives, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate and hydroxy having a hydrocarbon group such as stearyl group Derivatives of hydroxypropylmethylcellulose such as propylmethylcellulose, sulfonated cellulose derivatives, carboxymethylcellulose and its derivatives and salts thereof, carboxymethylethylcellulose and its salts, cellulose acetate phthalate, O- [2-hydroxy-3- (trimethylammonium chloride) E) propyl] hydroxyethylcellulose (also referred to as "polyquaternium-10"); and hydrophilic synthetic polymers such as cellulose derivatives such as ethylcellulose, chlorocarmellose and salts thereof. These can be used alone or in combination of two or more. As exemplified above, dextrin is not included in the starch derivative herein. Examples of the above salts include a sodium salt, a potassium salt, and a calcium salt. Derivatives of hydroxypropylcellulose include hydroxypropylcellulose acetate, hydroxypropylcellulose propionate and the like, and derivatives of hydroxyethylcellulose include hydroxyethylcellulose acetate, hydroxyethylcellulose propionate and polyquaternium-67. Derivatives of methylcellulose include carboxymethylcellulose acetate, carboxymethylcellulose propionate, methylamide cellulose gum and the like.

  In addition, the polysaccharide or derivative thereof used in the present invention should have high solubility and / or dispersibility in water, so that when the external preparation for skin of the present invention is mixed with a water-containing substance, uniformity can be prevented. And / or can be dissolved and / or dispersed, and the roughness of the skin due to undissolved components can be reduced. Here, whether the solubility or dispersibility in water is good or not is that, when water at about room temperature is added and stirred, the external preparation for skin is uniformly dissolved or dispersed in a short time, and no lumps are generated at the time of dissolution. Can be determined from

  From the viewpoint of solubility and dispersibility in water described above, preferred among the polysaccharides or derivatives thereof include, for example, xanthan gum, succinoglycan, carrageenan, guar gum, locust bean gum, galactan, gum arabic, tragacanth gum, Examples include tamarind gum, agar, agarose, mannan, hyaluronic acid and its salts, curdlan, alginic acid and its salts, starch and its derivatives, dextrin, cellulose and cellulose derivatives.

Of 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 for the following reason.
Many of the polysaccharides or derivatives thereof are dissolved or dispersed in water to exhibit a thickening effect. In addition, the addition of a polysaccharide or a derivative thereof to the external preparation for skin increases the stability of the external preparation for skin before use and during storage, and prevents the reaction between the acid and the carbon dioxide-generating substance to prevent the reaction of carbon dioxide. It also has the advantage of preventing occurrence. Among the polysaccharides or derivatives thereof, those that contribute more to the thickening effect than the stability during storage (hereinafter also referred to as type A polysaccharides or derivatives thereof) are more stable during storage than the thickening effect. There are also polysaccharides (hereinafter referred to as type B polysaccharides or derivatives thereof) that greatly contribute to the property, and therefore, by combining both types of polysaccharides or derivatives thereof, the thickening effect and the stability during storage can be obtained. Both can be improved. Examples of the type A polysaccharides or derivatives thereof include xanthan gum, carrageenan, hyaluronic acid and cellulose and salts or derivatives thereof, and examples of the type B polysaccharides or starches include starch or derivatives thereof and dextrin. Examples include sugars. By using the B-type polysaccharide or a derivative thereof, it is possible to suppress the generation of carbon dioxide gas during storage of the external preparation for skin. In particular, the use of starch or a derivative thereof is preferable because the generation of carbon dioxide is effectively suppressed and the long-term storage stability is further improved. In the case of using starch or a derivative thereof in the present invention, the preferred amount of use can be 3% by mass or more, particularly 5% by mass or more, especially 10% by mass or more in the external preparation for skin.
In the present invention, it is also preferable that there are many types of polysaccharides or derivatives thereof, for example, a combination of three or more types.

  Furthermore, the present inventors have found that, as will be apparent from a comparison of Examples described later, for example, Examples 1 and 2, when two or more kinds of polysaccharides or derivatives thereof are used in combination, only one kind is used. Compared with water-containing substances, the external preparation for skin (mixture) has a higher ability to retain carbon dioxide gas when mixed with a water-containing substance, so that the mixture applied to the skin is less likely to sag, and it has the effect of improving skin conditions such as improving redness and elasticity. It has been found that it is easy to use, and that the usability including ease of application and removal is improved. Furthermore, as is evident from Examples 6 to 10, it has been found that these effects are higher in the presence of extracts containing water-soluble proteins and / or natural surfactants, especially saponins.

  In the present invention, the content of the polysaccharide or a derivative thereof in the external preparation for skin is preferably from 8% by mass to 50% by mass, and more preferably from 11% by mass to 45% by mass. It is preferable that the content of the polysaccharide or a derivative thereof is 8% by mass or more and 50% by mass or less, from the viewpoint of handling at the time of use, in particular, since it is easy to mix at the time of mixing with a water-containing substance and does not drip at the time of use. If it is less than 8% by mass, it easily drips when used, and if it is more than 50% by mass, it is difficult to mix at the time of mixing, and it becomes thick immediately after mixing with the water-containing substance, making it difficult to apply to the use site. Therefore, it is not preferable.

  When the polysaccharide or its derivative is used in combination with the type A polysaccharide or its derivative and the type B polysaccharide or its derivative, the mass ratio of both is 100 mass of the polysaccharide of A or its derivative. The polysaccharide of B or a derivative thereof is preferably 10 parts by mass or more and 1000 parts by mass or less, more preferably 20 parts by mass or more and 800 parts by mass or less.

The present inventors further provide that, when the external preparation for skin of the present invention contains one or more of the following polysaccharides or derivatives thereof in any of the following (1) to (3), "the feeling of use is good, In addition, the effect of the present invention of "improving skin condition" was found to be remarkable.
(1) At least one selected from cellulose derivatives and starch derivatives, and at least one selected from hydrophilic natural polymers such as alginic acid or salts thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum (provided that the cellulose derivative is , When sodium carboxymethylcellulose is contained, excluding alginic acid and its salts).
(2) When the polysaccharide or its derivative contains two or more kinds selected from hydrophilic natural polymers such as alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum (3) polysaccharide or A case where the derivative contains two or more selected from a cellulose derivative and a starch derivative.

  Hereinafter, the hydrophilic natural polymer that is alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum may be simply referred to as “specific hydrophilic natural polymer”.

First, the case (1) will be described.
In the case of (1), as an embodiment containing two or more kinds of polysaccharides or derivatives thereof, the following embodiment (a) or (b) is described in the book "The feeling of use is good and the skin condition is improved". It is preferable from the viewpoint of more reliably enhancing the effects of the invention.
(A) As cellulose derivatives, hydroxyethyl cellulose and its derivatives, carboxymethyl cellulose and its derivatives and salts thereof, hydroxypropylmethyl cellulose and its derivatives, sulfonated cellulose derivatives, carboxymethyl ethyl cellulose and its salts, cellulose acetate phthalate, and cationized cellulose Containing at least one selected from ethyl cellulose and croscarmellose and salts thereof, and / or
Contains starch derivatives.

(B) The cellulose derivative contains at least one selected from hydroxypropylcellulose and its derivatives, and the hydrophilic natural polymer contains at least one selected from alginic acid and its salts, carrageenan, guar gum, xanthan gum and tamarind gum.

In the case of (1), particularly preferable embodiments containing two or more kinds of polysaccharides or derivatives thereof include any of the following cases (A) to (C).
(A) The cellulose derivative contains at least one selected from hydroxypropylmethylcellulose and derivatives thereof and cationized cellulose, and / or as starch derivatives, carboxymethyl starch and salts thereof, and acrylic acid-grafted starch and salts thereof. At least one selected from the group consisting of:
(A) The cellulose derivative contains at least one selected from hydroxyethyl cellulose and its derivatives, and the hydrophilic natural polymer contains at least one selected from alginic acid and its salts, carrageenan, guar gum, locust bean gum, and tamarind gum. .
(C) It contains at least one selected from carboxymethylcellulose and derivatives thereof and salts thereof as the cellulose derivative, and at least one selected from carrageenan, guar gum, locust bean gum and tamarind gum as the hydrophilic natural polymer.

In the case of (1), a particularly preferred embodiment containing two or more kinds of polysaccharides or derivatives thereof includes a case where the polysaccharides or derivatives thereof contain any of the following combinations.
A combination of at least one selected from hydroxypropylmethylcellulose and derivatives thereof and at least one selected from alginic acid and salts thereof and xanthan gum;
A combination of cationized cellulose and tamarind gum;
Combination of a starch derivative with tamarind gum;
A combination of at least one selected from hydroxyethylcellulose and derivatives thereof and at least one selected from alginic acid and salts thereof and carrageenan;
A combination of at least one selected from carboxymethylcellulose and its derivatives and salts thereof with at least one selected from carrageenan and guar gum.

  When the cellulose derivative or the starch derivative is combined with the specific hydrophilic natural polymer as in the case (1) above, the amount of the specific hydrophilic natural polymer with respect to 100 parts by mass of the cellulose derivative or the starch derivative Is preferably 1 part by mass or more and 10,000 parts by mass or less from the viewpoint of more reliably obtaining the effects of the present invention. From this viewpoint, the amount of the specific hydrophilic natural polymer based on 100 parts by mass of the cellulose derivative or the starch derivative is preferably from 1 part by mass to 10,000 parts by mass, and more preferably from 5 parts by mass to 5,000 parts by mass. More preferably, it is particularly preferably from 10 parts by mass to 1000 parts by mass. Here, the amount of the cellulose derivative or the starch derivative is the total amount when the external preparation for skin contains the cellulose derivative and the starch derivative. The amounts of the cellulose derivative, starch derivative, and hydrophilic natural polymer as used herein refer to the amount of the skin external preparation of the present invention when the skin external preparation contains a specific type of cellulose derivative, starch derivative, or hydrophilic natural polymer. The amount of seed cellulose derivative, starch derivative, hydrophilic natural polymer can be. Similarly, the amount of each of the cellulose derivative, starch derivative, and hydrophilic natural polymer described below also includes the skin external preparation of the present invention containing a specific type of cellulose derivative, starch derivative, or hydrophilic natural polymer. In this case, the amount of the specific type of cellulose derivative, starch derivative, or hydrophilic natural polymer can be used.

  In both cases (1) and (2) to (4) below, the proportion occupied by the total amount of the cellulose derivative, the starch derivative and the specific hydrophilic natural polymer in the external preparation for skin is 5% by mass or more. In order to enhance the effect of the present invention, it is preferable that the content is 50% by mass or less, and the amount of the acidic substance and the carbon dioxide-generating substance is secured to reduce the foaming property of the external preparation for skin of the present invention. This is preferable from the viewpoint of preventing the occurrence of the odor and improving the functionality such as a feeling of use and an effect of improving the skin condition. In this respect, the ratio of the total amount of the cellulose derivative, the starch derivative, and the specific hydrophilic natural polymer in the external preparation for skin is more preferably from 10% by mass to 45% by mass, and more preferably from 12% by mass to 45% by mass. % Is particularly preferable.

  Subsequently, the case (2) will be described. In the case of the above (2), the external preparation for skin contains, as a polysaccharide or a derivative thereof, at least two kinds selected from hydrophilic natural polymers which are alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum. contains. In this case, from the viewpoint of making the effect of the present invention that "the feeling of use is good and the skin condition is improved" more remarkable, the combination of two or more kinds of the specific hydrophilic natural polymers is as follows. (A) to (C) are particularly preferable.

(A) A combination of alginic acid or a salt thereof and at least one selected from carrageenan, guar gum, locust bean gum and tamarind gum.
(B) A combination of carrageenan and at least one selected from alginic acid and salts thereof, guar gum, xanthan gum and tamarind gum.
(C) Combination with two or more selected from guar gum, locust bean gum, xanthan gum and tamarind gum.

Particularly preferred combinations when two or more specific hydrophilic natural polymers are contained include any of the following (A) ′ to (C) ′.
(A) 'a combination of alginic acid or a salt thereof and at least one selected from carrageenan and tamarind gum;
(B) a combination of carrageenan and at least one selected from xanthan gum and tamarind gum;
(C) ′ A combination of tamarind gum and at least one selected from guar gum and xanthan gum.

  As in (2), when the polysaccharide or a derivative thereof contains two or more kinds selected from hydrophilic natural polymers which are alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or tamarind gum, Among them, the content of any one type with respect to 100 parts by mass of one type is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 5 parts by mass or more and 5000 parts by mass or less, and 10 parts by mass. It is particularly preferable that the amount is not less than 1000 parts by mass.

In the case of (A), the content of at least one selected from carrageenan, guar gum, locust bean gum, and tamarind gum is 1 part by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of alginic acid or a salt thereof. Is more preferably 5 parts by mass or more and 5000 parts by mass or less, and particularly preferably 10 parts by mass or more and 1000 parts by mass or less.
In the case of (B), the content of at least one selected from alginic acid and its salts, guar gum, xanthan gum and tamarind gum is preferably 1 part by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of carrageenan. It is more preferably from 5 parts by mass to 5,000 parts by mass, and particularly preferably from 10 parts by mass to 1,000 parts by mass.
In addition, "at least one kind of content" here is the total amount of two or more kinds.
In the case of (C), the total amount of the other three is preferably 1 part by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of one selected from guar gum, locust bean gum, xanthan gum, and tamarind gum. The content is more preferably from 5 parts by mass to 5,000 parts by mass, and particularly preferably from 10 parts by mass to 1,000 parts by mass.

  In the case of (2), the proportion occupied by the total amount of the specific hydrophilic natural polymer in the external preparation for skin is preferably 5% by mass or more in order to enhance the effect of the present invention. By mass% or less, the amounts of the acidic substance and the carbon dioxide-generating substance are secured to prevent the foaming property of the external preparation for skin of the present invention from decreasing, and the feeling of use of the external preparation for skin and the skin It is preferable from the viewpoint that functionality such as a state improvement effect can be secured. From this viewpoint, the proportion occupied by the total amount of the specific hydrophilic natural polymer in the external preparation for skin is more preferably from 10% by mass to 45% by mass, and more preferably from 12% by mass to 45% by mass. Particularly preferred.

  Subsequently, (3) a case where two or more kinds selected from a cellulose derivative and a starch derivative are contained as a polysaccharide or a derivative thereof will be described.

  In the case of (3), from the viewpoint of making the effect of the present invention even more remarkable, (a) a combination of at least one selected from cellulose derivatives and at least one selected from starch derivatives is contained. Or (b) two or more specific cellulose derivatives are preferably used in combination.

In the case of (a), for example, as a cellulose derivative, hydroxyethylcellulose and its derivative, hydroxypropylmethylcellulose and its derivative, sulfonated cellulose derivative, carboxymethylcellulose and its derivative and salts thereof, carboxymethylethylcellulose and its salt, acetic acid Cellulose phthalate, cationized cellulose, ethylcellulose, at least one selected from croscarmellose and salts thereof, and at least one selected from carboxymethyl starch and salts thereof and grafted starch acrylic acid and salts thereof as starch derivatives It is particularly preferable to contain a combination of
In the case of (a), it is particularly preferable to use, as the cellulose derivative, at least one selected from carboxymethylcellulose and its derivatives and salts thereof.

As the case (b), the following cases (X) and (Y) are preferred.
(X) The cellulose derivative contains at least one selected from hydroxypropylmethylcellulose and its derivatives, and at least one selected from hydroxyethylcellulose and its derivatives and cationized cellulose.
(Y) as a cellulose derivative, at least one selected from carboxymethylcellulose and its derivatives and salts thereof, and hydroxyethylcellulose and its derivatives, hydroxypropylcellulose and its derivatives, sulfonated cellulose derivatives, carboxymethylethylcellulose and its salts, Contains cellulose acetate phthalate, cationized cellulose, ethylcellulose, and at least one selected from croscarmellose and salts thereof.

When the external preparation for skin contains two or more selected from a cellulose derivative and a starch derivative as a polysaccharide or a derivative thereof as in (3), the content of any one of them is 100 parts by mass of one of them. The amount is preferably from 1 part by mass to 10,000 parts by mass, more preferably from 5 parts by mass to 5,000 parts by mass, and particularly preferably from 10 parts by mass to 1,000 parts by mass.
In addition, when the external preparation for skin contains a combination of at least one selected from cellulose derivatives and at least one selected from starch derivatives as in (a), the effect of the present invention is more remarkable. In light of the above, the starch derivative is preferably contained in an amount of 1 part by mass or more and 10,000 parts by mass or less, more preferably 5 parts by mass or more and 5000 parts by mass or less, and more preferably 10 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the cellulose derivative. It is particularly preferred that the amount is not more than mass part.

  Further, as shown in (X) in (b), the external preparation for skin includes at least one kind (former) selected from hydroxypropylmethylcellulose and its derivatives, and at least one kind selected from hydroxyethylcellulose and its derivatives and cationized cellulose. When a seed (the latter) is contained, the total amount of the latter is preferably 1 to 10,000 parts by mass, preferably 5 to 5,000 parts by mass, based on 100 parts by mass of the former. It is more preferable that the amount is 10 parts by mass or more and 1000 parts by mass or less.

  Further, as in (B), the external preparation for skin comprises at least one (former) selected from carboxymethylcellulose and its derivatives and salts thereof as a cellulose derivative, hydroxyethylcellulose and its derivatives, When containing at least one selected from the group consisting of propylcellulose and its derivatives, sulfonated cellulose derivatives, carboxymethylethylcellulose and its salts, cellulose acetate phthalate, cationized cellulose, ethylcellulose and croscarmellose and its salts (the latter) The total amount of the former is preferably 1 to 10,000 parts by mass, more preferably 5 to 5,000 parts by mass, more preferably 10 parts by mass or more, based on 100 parts by mass of the former. 100 And particularly preferably less parts by mass.

  In the case of (3), the proportion occupied by the total amount of the cellulose derivative and the starch derivative in the external preparation for skin is preferably 5% by mass or more in order to enhance the effect of the present invention, and 50% by mass or less. Is preferred from the viewpoint of ensuring the functionality such as the feeling of use and the effect of improving the skin condition of the external preparation for skin of the present invention. In this respect, the ratio of the total amount of the cellulose derivative and the starch derivative in the skin external preparation is more preferably 10% by mass or more and 45% by mass or less, and particularly preferably 12% by mass or more and 45% by mass or less. .

The external preparation for skin of the present invention employing any one of the following constitutions (1) to (3) is used after the external preparation for skin is used as compared with the case where a combination of a conventional polysaccharide or a derivative thereof is employed. The amount of water transpiration from the skin is suppressed as compared with before. Alternatively and / or after use of the external preparation for skin, whiteness, skin water content and / or elasticity are increased as compared to before use. As a result, skin conditions such as skin moistness, elasticity, brightness, redness, smoothness, and / or smoothness are improved.
Moreover, when the external preparation for skin of the present invention adopts any one of the following constitutions (1) to (3), it is characterized by an effect of improving skin condition in addition to the above-mentioned effect of improving skin condition. Is greatly improved. The external preparation for skin of the present invention, when adopting the following constitutions (1) to (3), is easier to mix, dissolve and apply than the conventional combination of polysaccharides or derivatives thereof. It also has properties required for a skin external preparation that is foamed by mixing with a water-containing substance, such as ease, sagging, and / or ease of removal.
Furthermore, in addition, when the composition for external use of the skin of the present invention adopts the following constitutions (1) to (3), smoothness of foam, fineness of foam, lack of roughness, elasticity of foam, and foam retention , A high carbonation sensation, and / or a high carbonation sensation. Therefore, the skin external preparation of the present invention greatly improves the feeling in use as compared with the case where a combination of a conventional polysaccharide or a derivative thereof is employed.
In addition, the skin external preparation of the present invention, which has a high carbonation sensation, has a high skin tightening sensation.
By obtaining these effects, the external preparation for skin of the present invention adopts any one of the following constitutions (1) to (3), so that “the feeling of use is good and the skin condition is improved”. The effect is remarkable.
The effect of the present invention is obtained by the fact that the agent of the present invention contains a specific combination of the polysaccharides (1) to (3) or a derivative thereof together with a solid acidic substance and a solid carbon dioxide generating substance. The effect is. Therefore, for example, one or both of the combinations of (1) to (3) are contained together with water to form a viscous composition, and this viscous composition is used at the time of use as a solid acidic substance and / or a solid carbon dioxide gas generating substance. It cannot be obtained depending on the agent to be mixed.

  The external preparation for skin of the present invention further preferably contains a water-soluble protein. Here, the water-soluble protein is a protein obtained by concentrating, separating, and purifying an animal or vegetable protein, and refers to a protein having a property of being easily dispersed or dissolved in water or various liquids. When added at 5% by mass or more to water at 25 ° C. under 1 atm, it can be uniformly dispersed or dissolved without producing lumps. The water-soluble protein includes a protein hydrolyzate. As the hydrolyzate, those obtained by hydrolyzing proteins derived from various organisms such as animals and fishes by alkali treatment or enzyme treatment are preferable. Specific examples of the water-soluble protein include hydrolyzed collagen such as casein, collagen, and gelatin, albumin, elastin, keratin, and sericin. These can be used alone or in combination of two or more. In particular, the skin external preparation of the present invention preferably contains albumin, collagen, and hydrolyzed collagen as water-soluble proteins. The water-soluble protein also has a role as a foaming aid, and particularly has a function of increasing the strength of bubbles and keeping the foam stable for a long time. For this reason, the addition of a water-soluble protein contributes to easy adjustment of the viscosity of the external preparation for skin, improvement in solubility in water, and increase in the amount of carbon dioxide generated, and it is easy to improve the skin condition improving effect. The present inventors have found that by containing a polysaccharide or a derivative thereof, particularly two or more polysaccharides or a derivative thereof, the effect of this water-soluble protein is improved.

The external preparation for skin of the present invention may contain only one kind of water-soluble protein, but it is also preferable to contain two or more kinds of water-soluble proteins. This is shown in, for example, a comparison between Examples 13 and 14 and Example 17 described later. As is clear from these examples, compared to the case where albumin alone was contained as a water-soluble protein, the skin quality improving effect such as moist feeling and smoothness of the skin after use when containing collagen or hydrolyzed collagen together with albumin, The feeling of use of a mixture obtained by mixing a skin external preparation with a water-containing substance is easily improved.
In particular, when the foamable skin external preparation of the present invention contains a hydrolyzed collagen, as is clear from Example 14 described later, the ease of application, the comfort when applied, and the appearance are easily improved. In addition, as is clear from the comparison of Examples 18 and 19 described later, even when hydrolyzed collagen is used alone, the retention of carbon dioxide in a mixture of a skin external preparation and a water-containing substance, and the skin condition after use of the skin external preparation It has the same or higher effect as albumin on the improvement.

  When the external preparation for skin of the present invention contains a water-soluble protein, the content of the water-soluble protein in the external preparation for skin 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. Is more preferable. 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 foams stable for a long period of time is easily obtained.

  In addition, when the external preparation for skin contains a water-soluble protein, the content of the water-soluble protein is preferably a polysaccharide or a derivative thereof from the viewpoint of further increasing the holding power of carbon dioxide when the external preparation for skin of the present invention is dissolved in water. It is preferably at least 0.1 part by mass, more preferably at least 1 part by mass and up to 50 parts by mass, per 100 parts by mass.

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

  The external preparation for skin of the present invention is preferably used from the viewpoint of retaining generated foams by using a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. At this time, the surfactant to be used is preferably a water-free solution, solid, flake, granule, fine granule, or powder from the viewpoint of storage stability. It is preferable to use granules, fine granules or powder. As the above-mentioned surfactant, a natural surfactant is preferable. Natural surfactants refer to surfactants derived from animals and plants, for example, phospholipids such as lecithin, lanolin, cholesterol, saponins, sphingolipids, pectin, dipotassium glycyrrhizinate, plant-extracted amino acid-based surfactants, and the like. No. The external preparation for skin of the present invention preferably contains a natural surfactant in an amount of 0.001% by mass or more and 10% by mass or less, and more preferably 0.005% by mass or more and 8% by mass or less.

  As the natural surfactant used in the present invention, among those mentioned above, phospholipids, saponins, pectins, glycyrrhizic acid or salts thereof are preferable, and extracts containing saponin and / or glycyrrhizic acid or salts thereof are contained. Is particularly preferred. Saponin is a glycoside that is widely distributed in plants and is a general term for a group of compounds that use steroids and triterpenoids as non-sugar parts. Depending on the type of aglycone (non-sugar part of glycosides), triterpenoid saponins are They can be roughly divided into steroidal saponins. A common property of saponins is that their aqueous solutions have high foaming properties.

  As described above, saponin is known to have a foaming property, but the present inventors have added a saponin-containing extract in place of a water-soluble protein to thereby obtain a water-soluble protein. It has been found that the same or better foam stability for a long period of time can be obtained, thereby improving the usability such as difficulty in dripping and mixing of the mixture, and improving skin conditions such as moist feeling and elasticity. Skin external preparations containing a water-soluble protein may be difficult to use, for example, for allergic users, but an extract containing saponin can be effectively used as a water-soluble protein substitute It is. Furthermore, since the addition of the extract containing saponin has an effect of increasing the amount of carbon dioxide gas generated, it can contribute to effectively promoting blood circulation of the skin. The present inventors have found that by containing a polysaccharide or a derivative thereof, in particular, two or more polysaccharides or a derivative thereof, the effect of adding an extract containing saponin, in particular, improving the feeling of use and improving the skin condition It is found that such effects as the above become excellent.

As the extract containing saponin used in the skin external preparation of the present invention, it is preferable to use a plant-derived extract. Examples of plants referred to herein include plants containing triterpenoid saponins, soybean, loofah, adzuki bean, bean, spinach, sugar beet, grape, sycamore, liquorice, senega, kirya, mukuroji, sabonso, panax ginseng, tea seed, Plants containing steroidal saponins include lily plants, yam plants, timo (chimbo), bakmondou (wheaten winter), and the like.
The agent of the present invention, as an extract containing saponin, of these plants, it is preferable to use an extract of any one or more of the above-mentioned various plants containing a triterpenoid saponin, mukuro, soybean, licorice, loofah It is preferable to contain an extract of at least one plant selected from the group consisting of: Here, the muk roe is a plant belonging to the family Sapindaceae and the genus Sapindus. mukurossi and S.M. delavayi, etc. correspond to this.

  The plant parts that are the raw materials of the extract include whole plants, leaves (leaves, petiole, etc.), fruits (mature, immature, etc.), seeds, flowers (petals, ovary, etc.), stems, rhizomes, roots And tuberous roots. In the present invention, when using an extract of mud moji as an extract containing saponin, it is preferably an extract of fruit and / or pericarp of the mud mushroom, and particularly preferably an extract of pericarp.

  The extract can be used as it is, or by cutting, crushing, pulverizing, and squeezing the whole plant or the above-mentioned site, or by drying or pulverizing the treated product. These treatments can be used alone or in combination of two or more.

  As the solvent used for the 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 and acetone can be mentioned. These can be used alone or in combination of two or more. From the viewpoint of safety and the like, 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 any temperature below 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 single-part external preparation, the acidic substance and the carbon dioxide-generating substance react during storage to generate carbon dioxide. If the water does not contain the necessary amount of water, the water does not substantially contain water, so that a water-containing extraction solvent can be used.

  After removing contaminants by filtration, the extract is contained in the external preparation for skin of the present invention as a solid such as a powder. Examples of the method for solidification include a method in which the extract obtained by extraction with the above-described solvent is powdered by freeze drying, spray drying, or the like. Before the extract is solidified, a further purification operation may be added as long as the physiological action of saponin is not impaired.

  From the viewpoint of further enhancing the above effects, when the skin external preparation of the present invention contains an extract containing saponin, the content is preferably 0.001% by mass or more and 10% by mass or less in the skin external preparation. More preferably, it is 0.005% by mass or more and 8% by mass or less. 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 effect of improving the skin condition.

  In addition, examples of glycyrrhizic acid and salts thereof as a natural surfactant in the present invention include dipotassium glycyrrhizinate (GK2). As described below, glycyrrhizic acid and its salts also function as anti-inflammatory agents and whitening agents. In the present invention, when glycyrrhizic acid and a salt thereof are used as a natural surfactant (or an anti-inflammatory agent or a whitening agent), as is apparent from a comparison between Examples 4 and 5 described below, a skin external preparation and a hydrated substance are used. In a mixture of the above, carbon dioxide gas is easily retained for a long time, the amount of generated carbon dioxide gas can be increased, the keratin moisture content of the skin increases, the effect of improving the condition of the skin such as enhancement of redness increases, and It is possible to improve the feeling of use of the external preparation. The preferred contents of glycyrrhizic acid and salts thereof in the skin external preparation of the present invention are the same as the preferred contents of the anti-inflammatory agent described later.

  Further, the external preparation for skin of the present invention preferably contains at least one selected from a bactericide, an anti-inflammatory agent and a whitening agent.

  A bactericide is a substance that has a bactericidal, bacteriostatic or antibacterial action and does not cause a problem for the skin when incorporated into an external preparation for the skin. Examples thereof include salicylic acid and its salts or salicylic acid derivatives; erythromycin, clinda Benzoyl peroxide; nadifloxacin; ethanol; benzalkonium chloride; sulfur; parahydroxybenzoate esters; hinokitiol; triclosan; homosulfamine; chloramine T; Derivatives thereof; chitin / chitosan derivatives and the like. Further, an extract having an antibacterial action and the like as an antibacterial agent may also be used, and such extracts include fennel, oak, tea, rose hips, chamomile, orange, achillea millefolium, turmeric, gardenia, clove, sage, yukinoshita , Clove, eucalyptus, hinoki, cedar and the like. These can be used alone or in combination of two or more.

Among these fungicides, it is particularly preferable to use salicylic acid and its salts or salicylic acid derivatives, and it is particularly preferable to use salicylic acid. As is clear from the examples described below, the use of a bactericide such as salicylic acid in the skin external preparation of the present invention can improve the keratin moisture content and elasticity of the used skin.
From the viewpoint of further enhancing this effect, when the external preparation for skin of the present invention contains a bactericide, the content is preferably 0.001% by mass or more and 20% by mass or less in the external preparation for skin. More preferably, the content is 0.005% by mass or more and 10% by mass or less.

  The anti-inflammatory agent is a substance having an action of suppressing inflammation, and examples thereof include glycyrrhizic acid and salts thereof described above as natural surfactants, and derivatives thereof. Examples of other anti-inflammatory agents, glycyrrhetinic acid and its salts, mefenamic acid and its salts, phenylbutazone, indomethacin, ibuprofenic acid and its salts, ketoprofen, allantoin, guaiazulene, and derivatives thereof, ε-aminocaproic acid, Zinc oxide, diclofenac sodium, proanthocyanidin and the like can be mentioned. Further, an extract having an anti-inflammatory effect and the like as an anti-inflammatory agent may also be used, and such extracts include Saxifrage extract, Licorice extract, Aloe extract, Sicon extract, Salvia extract, Arnica extract And animal and plant extracts such as chamomile extract, birch extract, hypericum extract, eucalyptus extract, peach leaf extract, pine bark extract, grape seed extract and lingonberry extract. These can be used alone or in combination of two or more.

Among these anti-inflammatory agents, it is particularly preferable to use glycyrrhizic acid and its salts, glycyrrhetic acid and its salts, and derivatives thereof, and it is particularly preferable to use glycyrrhizic acid and its salts for the reasons described above, It is preferable to use dipotassium (GK2). When an anti-inflammatory agent is used in the external preparation for skin of the present invention, the effect of suppressing skin irritation and preventing acne and rough skin can be obtained.
From the viewpoint of further enhancing such effects, when the skin external preparation of the present invention contains an anti-inflammatory agent, the content thereof is preferably 0.001% by mass or more and 20% by mass or less in the skin external preparation, More preferably, the content is 0.005% by mass or more and 10% by mass or less.
When GK2 is used as the external preparation for skin of the present invention, not only high skin whiteness improvement effect is obtained but also high skin condition improvement such as improvement of horny layer moisture content and elasticity, as is apparent from Example 7 described later. The effect is obtained. Further, the external preparation for skin using GK2 is excellent in usability such as ease of mixing and resistance to dripping, as is clear from the description of 16 and 7 described later.

  As the whitening agent, those having tyrosinase activity or those having the activity of decolorizing melanin pigment are mainly used. Examples include L-cysteine and its derivatives, ascorbic acid and its derivatives, tranexamic acid derivatives, glabridine, liquiritin, isoliquiritin, hydroquinone, arbutin, kojic acid, placenta, and the like. Further, the above-mentioned glycyrrhizic acid or salt, glycyrrhetinic acid and its salt, and derivatives thereof can also be used as a whitening agent. Further, an extract having a whitening effect and the like as a whitening agent may also be used, and such extracts include soybean sprouts extract, squid extract, Ibukitorano extract, cinnamon extract, Clara extract, hawthorn extract, Shirai lily extract, hop extract, radix extract and the like. These can be used alone or in combination of two or more.

  Among these whitening agents, it is preferable to use one or more selected from arbutin, placenta, glycyrrhizic acid or a salt thereof, ascorbic acid and a derivative thereof.

Arbutin used in the present invention is a compound whose system name is also referred to as 4- (β-D-glucopyranosyloxy) phenol.
When arbutin is used in the external preparation for skin of the present invention, not only a high skin whiteness improving effect is obtained but also a high skin condition improving effect such as a moist feeling and elasticity of the skin, as is apparent from Example 10 described later. can get. Further, the external preparation for skin using arbutin is also excellent in usability such as ease of application and comfort at the time of application, spreadability, and ease of removal, as is clear from the description of Examples 10 and 16 described later. ing.

  Placenta is an extract of growth factors and other nutrients that promote cell division from the placenta of animals, particularly preferably pigs, horses, cows, sheep, and humans, an extract of nutrients from the ovarian membrane of fish, and embryos of plants. It is a generic term for nutrients extracted from. The skin external preparation of the present invention containing placenta has an effect that the amount of water transpiration tends to decrease after application and the smoothness and smoothness easily increase after application, 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 or 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, the content is preferably 0.001% by mass or more and 30% by mass or less in the skin external preparation, More preferably, the content is 0.005% by mass or more and 20% by mass or less.

  In the external preparation for skin of the present invention, other active ingredients can be used in place of or in addition to the above-mentioned extract containing saponin, a bactericide, an anti-inflammatory agent, and a whitening agent. Such active ingredients include gold leaf, pearl powder (pearl), mud, charcoal, gypsum, enzymes, herbs, seaweed, yogurt, fermented products such as whey, sake, koji, honey, propylene glycol, polyethylene glycol, sorbitol , Sodium lactate, moisturizing components such as sodium pyrrolpyrrolidone carboxylate, plant components such as licorice, vitamins and the like. Among them, gold foil and pearl powder are particularly preferred. As is clear from the description of Example 11 to be described later, the use of gold foil improves the feeling of use during application, such as pleasantness and appearance, and also improves skin condition. Further, as is apparent from the description of Example 12 described later, the use of pearl powder provides an effect of improving the skin condition such as the brightness of the skin, and also improves the usability.

  Pearl powder is a pearl oyster, black mussel, white mussel, mabe, abalone and other marine shellfish, and aquaculture or natural pearls, which are spherical or amorphous metabolites formed in the body of freshwater shellfish such as pokeweed, It is a powder that has been pulverized by a known method such as a ball mill, a jet mill, and a turbo mill and sieved. When pearl powder is contained, the content is preferably 0.0001% by mass or more and 10% by mass or less in the external preparation for skin. When a gold foil is contained, the content is preferably 0.0001% by mass or more and 10% by mass or less in the external preparation for skin.

  The effervescent skin external preparation of the present invention further includes a thickener other than polysaccharides and derivatives thereof and water-soluble proteins; excipients, granulating agents; pH adjusters; oils and fats; fragrances; Antibacterial and fungicidal agents; alcohols, polyhydric alcohols; inorganic salts; lubricants; solvents; and one or more components usually used in skin external preparations such as extracts of animals and plants.

  Examples of the thickener other than polysaccharides and derivatives thereof and water-soluble proteins include polyvinyl alcohol, acrylates / alkyl acrylate crosspolymer, polyacrylic acid, polyacrylamide, polyalkylacrylamide / polyacrylamide copolymer, Examples include hydrophilic synthetic polymers such as poloxamer (Pluronic (registered trademark)), polyvinylpyrrolidone, and acrylic acid / alkyl methacrylate copolymer, and inorganic ones such as laponite, bentonite, and smectite Examples include clay minerals and the like, and hydrophilic thickening compounds such as silica and talc. Note that the acrylic acid / alkyl methacrylate copolymer is a compounding component that functions as a polymer emulsifier, and for example, an (acrylates / alkyl acrylate (C10-30)) crosspolymer can be used.

  Examples of the excipient or granulating agent include powders such as lactose, powdered sugar, xylitol, D-sorbitol, glucose (glucose), D-mannitol, fructose, sucrose, sucrose, urea, etc., without particular limitation. Or two or more of them can be used in combination. When such an excipient and / or granulating agent is contained, the content is preferably 10% by mass or more, and more preferably 20% by mass or more and 88% by mass or less in the external preparation for skin of the present invention. Is more preferable.

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

The external preparation for skin of the present invention comprises (4) the above-mentioned inorganic hydrophilic thickening compound and organic thickener as a thickener other than the above-mentioned polysaccharides and derivatives thereof and water-soluble proteins, in addition to the polysaccharides and derivatives thereof. In the case of containing at least one selected from the above-mentioned hydrophilic synthetic polymers as agents, the "feeling of use" is the same as in the case of (1) to (3) in which two or more of the above-mentioned polysaccharides or derivatives thereof are combined. The effect is improved, and the condition of the skin is improved.
The effect of the present invention is that the agent of the present invention contains a polysaccharide or a derivative thereof, the hydrophilic thickening compound or the hydrophilic synthetic polymer, together with a solid acidic substance and a solid carbon dioxide gas generating substance. This is an effect obtained by performing Therefore, the effect of the present invention is, for example, a viscosity containing water or one or both of the combination of the polysaccharide of (4) or a derivative thereof and the hydrophilic thickening compound or the hydrophilic synthetic polymer. When this viscous composition is used as a composition, it cannot be obtained by an agent mixed with a solid acidic substance and / or a solid carbon dioxide generating substance.

  In the present invention, when (4) a hydrophilic synthetic polymer which is an inorganic hydrophilic thickening compound or an organic thickener is contained, a preferable example of the polysaccharide or a derivative thereof contained in the external preparation for skin is hydrophilic. Examples include natural polymers, cellulose derivatives or starch derivatives. Examples of the hydrophilic natural polymer include alginic acid and salts thereof, carrageenan, locust bean gum, tamarind gum, and guar gum.

  In particular, polysaccharides or derivatives thereof of (4) include alginic acid and salts thereof, carrageenan, locust bean gum, tamarind gum, guar gum, ethylcellulose, carboxymethylcellulose and derivatives thereof, and salts thereof, hydroxyethylcellulose and derivatives thereof, and hydroxypropylmethylcellulose. And derivatives thereof, sulfonated cellulose derivatives, carboxymethylethylcellulose and salts thereof, cellulose acetate phthalate, cationized cellulose and croscarmellose and at least one selected from salts thereof, alginic acid and salts thereof, carrageenan, Carboxymethylcellulose and its derivatives and salts thereof, guar gum, hydroxyethylcellulose and its derivatives and cations And particularly preferably at least one selected from cellulose.

  Further, in the present invention, (4) when the above-mentioned inorganic hydrophilic thickening compound or a hydrophilic synthetic polymer which is an organic thickener is contained, it is also preferable to use xanthan gum as a polysaccharide or a derivative thereof. In this case, it is particularly preferable to combine xanthan gum and talc.

  In the case of (4), when the external preparation for skin of the present invention contains a specific hydrophilic natural polymer, a cellulose derivative or a starch derivative as a polysaccharide or a derivative thereof, the hydrophilic natural polymer, cellulose The amount of the hydrophilic synthetic polymer which is an inorganic hydrophilic thickening compound or an organic thickener is preferably from 1 part by mass to 10,000 parts by mass, and more preferably 5 parts by mass with respect to 100 parts by mass of the derivative or starch derivative. It is more preferably at least 10 parts by mass and at most 1000 parts by mass. Here, the amount of the specific hydrophilic natural polymer, cellulose derivative or starch derivative is the total amount of two or more of them if they are contained. The amount of the hydrophilic thickening compound or the hydrophilic synthetic polymer is the total amount of the two or more of them if they are contained. When a specific kind of hydrophilic natural polymer, cellulose derivative, starch derivative, hydrophilic thickening compound, or hydrophilic synthetic polymer is contained, the above-mentioned hydrophilic natural polymer, cellulose derivative, starch, The amount of the derivative, hydrophilic thickening compound, and hydrophilic synthetic polymer may be the amount of the specific kind of hydrophilic natural polymer, cellulose derivative, starch derivative, hydrophilic thickening compound, and hydrophilic synthetic polymer. (The same applies hereinafter).

  In the skin external preparation of the present invention, the total content of the specific hydrophilic natural polymer, cellulose derivative, starch derivative, hydrophilic thickening compound and hydrophilic synthetic polymer is 5% by mass or more and 50% by mass or more. The content is preferably at most 10% by mass and at most 45% by mass, more preferably at least 12% by mass and at most 45% by mass.

  The dosage form of the external preparation for skin of the present invention is usually in a solid form, and may be in the form of powder, granules, fine granules, pellets or a combination of two or more of these. Powder is preferred from the viewpoint of cost reduction during production and ease of dissolution during use.

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

  For example, when granulating a mixture of the acidic substance and / or the carbon dioxide-generating substance and other components to obtain granules of the solid acidic substance and / or the solid carbon dioxide-generating substance, The content of other components is not particularly limited, but is preferably less than 80% by mass in the granules. If the other components are present in a content of more than 80% by mass, the foaming property is undesirably reduced.

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

  For example, when a low melting point compound is used as a granulating agent as a matrix base, the acidic substance and / or the carbon dioxide-generating substance and the low melting point granulating agent melted by heating in a container such as a beaker are used. Other components are added according to the above, and sufficiently stirred and mixed. If necessary, a suitable additive may be added thereto. This is further stirred while gradually cooling it at room temperature, and allowed to stand until it hardens. When it has hardened to some extent, it may be cooled rapidly in a refrigerator or the like.

  Alternatively, for example, the above-described materials may be charged into a fluidized bed granulator, mixed for several minutes by an air stream, and granulated by spraying water.

  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, and the acidic substance and / or the carbon dioxide gas is generated. After the substance and other components are dissolved or dispersed as required and thoroughly mixed, the mixture is heated in an oven or the like to remove the solvent and dried. After it is completely hardened, it is pulverized and sieved to adjust the size of the granules to obtain granules.

  Examples of the shape of the solidified acidic substance or solid carbon dioxide gas generating substance as described above include, for example, an irregular shape, a planar shape, a polyhedral shape, a spherical shape, a spherical shape, a droplet shape, a fiber shape, a cylindrical shape, and a fine powder shape. Can be adopted without particular limitation. Further, as the particle size, those having a wide range can be used without particular limitation. Particularly, those having a particle size distribution of about 1,000 μm are more preferable from the viewpoint of easy handling and mixing with a water-containing substance. The particle size distribution in the present invention can be determined by a usual laser diffraction / scattering method.

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

  When the acidic substance and the carbon dioxide-generating substance are blended so as not to physically contact each other, for example, a coating layer wrapping the acidic substance and the carbon dioxide-generating substance is provided on one or both of the acidic substance and the carbon dioxide-generating substance. Alternatively, one or both of the acidic substance and the carbon dioxide generating substance may be encapsulated. Also, a layer not containing the acidic substance and the carbon dioxide-generating substance may be sandwiched between the acidic substance and the carbon dioxide-generating substance so that they do not come into direct contact with each other, and compression-molded.

  Hereinafter, means for coexisting the acidic 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 of forming a coat layer, for example, a method of forming a coat layer using at least one of an acidic substance and a carbon dioxide gas generating substance may be used. By providing the coating layer, even if the acidic substance, the carbon dioxide-generating substance and other components coexist in the same agent, there is no fear of unexpected carbon dioxide generation at the time of production or storage, so that stability, It is preferable from the viewpoint of durability.

  As a preferable coating agent for forming the coat layer, any one having low reactivity with the acidic substance or the carbon dioxide generating substance can be used without particular limitation. For example, fats and oils, fatty acids, fatty acid salts, acetylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyvinylalcohol, sodium polyacrylate, hydroxypropylmethylcellulose, methyl methacrylate-methacrylic acid copolymer, ethyl acrylate-methacrylic acid Copolymers, gum arabic, sodium alginate, soluble starch, hydroxypropylcellulose, wheat starch, sucrose, lactose, etc., citrate and the like can be mentioned. In particular, when coating with an acidic substance such as citric acid, it is preferable to employ a citrate such as calcium citrate. Further, the coat layer may be formed using a solid hydrocarbon wax, a solid fat or the like, which is dissolved at a certain temperature or more by heating.

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

  The coating method of the coat layer may be performed by any method that is usually used for coating particles. For example, by spray granulation or tumbling granulation, etc., it may be coated simultaneously with granulation, and powder or granules may be coated with oils and fats, granulation coating, transport layer method, pan coating, tumbling coating, fluid coating or You may coat | cover using methods, such as dry coating. At the time of coating, when excessive heat or physical force is applied, the acidic substance or the carbon dioxide generating substance is destroyed, and the generated film is broken, and the surface of the acidic substance or the carbon dioxide generating substance is broken. Not only is it difficult to uniformly coat the lipid powder on the whole, but the acidic substance or the carbon dioxide gas generating substance leaks to the surface and solidifies due to moisture absorption, or causes a bad influence on other components at the time of blending. The coating conditions must be such that the coating layer and the object to be coated are not destroyed.

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

As a method of encapsulation, a known method can be applied without particular limitation, and as a material for encapsulation, gelatin, starch, gum arabic, methylcellulose, acrylate, methacrylate, vinyl acetate, Examples include polyvinyl alcohol, silicone resin, solid wax, polyethylene, fatty acids, higher alcohols, and the like, and those in which multiple layers of surfactants such as liposomes are formed, but can be widely used without limitation. For example, the basic structure of the capsule is a homopolymer or a copolymer formed from one or more monomers selected from acrylates, methacrylates, vinyl acetate, and styrene, or the monomers and acrylic acid, methacrylic acid, divinyl 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 contents and a monomer constituting the polymer constituting the outer shell of the capsule in a reaction solvent such as water, and then starting polymerization of azobisisobutyronitrile and benzoyl peroxide. An emulsion polymerization may be performed by adding an agent. As a surfactant component used for such emulsification, for example, hexlite sold under the name of “Laponite XLG” can be preferably exemplified.
The microcapsules of the present invention can be produced by separating the resulting microcapsules by means such as centrifugation and washing if necessary.

[Compression molding]
As a method of compression molding, a substance other than the acidic substance and the carbon dioxide-generating substance (a substance other than the acidic substance and the carbon dioxide-generating substance such that they do not come into direct contact between the first layer containing the acidic substance and the second layer containing the carbon dioxide-generating substance) For example, a method of sandwiching a third layer composed of an excipient, a thickener, etc.) and compression molding may be adopted. The compression-molded dosage form may be any dosage form as long as it is in a solid form such as a tablet, a sphere, and a plate. Here, the acidic substance and the carbon dioxide generating substance to be used may be used as they are, or the first layer or the second layer or more, the acidic substance or the acidic substance provided with a coat layer by the above method. A carbon dioxide-generating substance, the encapsulated acidic substance or the carbon dioxide-generating substance may be used. The compression molding method is not particularly limited, and a known method can be applied.

The external preparation for skin of the present invention may exclude the following external preparation for skin.
`` At least a solid acidic substance, containing a solid carbon dioxide-generating substance and a thickener that generate carbon dioxide by reacting with the acidic substance, and is a one-part type skin external preparation containing no water, In the total skin external preparation, the thickener is contained in an amount of 12 to 45% by mass, and the thickener is used in combination with albumin and other thickeners, and is mixed with a liquid containing water when the skin external preparation is used. One-part type external preparation for skin. " Here, examples of the thickener include polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylmethylcellulose, sulfonated cellulose derivatives, acrylates / alkyl acrylate crosspolymer, polyacrylic acid, polyacrylamide, polyalkylacrylamide / polyacrylamide copolymer, carboxy Hydrophilic synthetic polymers such as methylcellulose, cationized cellulose, pluronic, and hydrophilic natural polymers such as starch, xanthan gum, sodium alginate, succinoglycan, carrageenan, guar gum, locust bean gum, and celluloses , Chondroitin sulfate, casein, collagen, gelatin, hydrophilic protein compounds such as albumin, laponite, bentonite, smectic Hydrophilic thickening compound such as a hydrophilic clay minerals such sites are mentioned.

<Use form of external preparation for skin>
When used, the external preparation for skin of the present invention causes foaming by mixing with a water-containing substance on the palm or in a container.
The external preparation for skin of the present invention may be used as a one-part type 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 single-part preparation, the external preparation for skin is usually a solid composition as described above, and is more preferably in the form of solid, granule, fine granule, or powder. It is particularly preferable that the particles are in the form of granules, fine granules, or powder, because they are easily mixed with a water-containing substance and foaming easily occurs. When the external preparation for skin of the present invention is in the form of a single preparation, it usually does not substantially contain water. Here, "substantially free of water" means that the acidic substance and the carbon dioxide gas generating substance react during storage of the external preparation for skin, and do not contain an amount of water necessary for generating 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 of a two-part composition comprising a water-containing substance and a kit, the agent containing an acidic substance, a carbon dioxide-generating substance and at least one kind of polysaccharide is usually a solid composition, Solid, granular, fine-grained, more preferably in the form of a powder, since it is easily mixed with hydrated substances and easily foamed, it may be in the form of granules, fine-grained, powdery Particularly preferred. When the external preparation for skin of the present invention is a two-part composition, the solid composition generally does not substantially contain water. Here, "substantially free of water" means that the acidic substance and the carbon dioxide gas generating substance react during storage of the external preparation for skin, and do not contain an amount of water necessary for generating 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 single-part preparation, the user usually prepares a hydrated substance for mixing with the external preparation for skin, and when the two-part external preparation is used, as described above, the external preparation for skin of the present invention And the water-containing substance constitute a kit. When the external preparation for skin is a single-part preparation, a liquid containing water is often used as a water-containing substance. In the case of the two-pack type, examples of the water-containing substance include a liquid containing water and a gel. 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 substance 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 external preparation for skin is a two-part formulation, mixing the external preparation for skin with a liquid, particularly a liquid having a relatively low viscosity, is more effective than the case of mixing with a gel, whereby the effect of the present invention is more effective. It is preferable because it is played. When the external preparation for skin of the present invention is mixed with a gel or a liquid having a relatively high viscosity, it is not preferable because the two agents are hardly mixed and it takes time to foam. Specifically, the viscosity of the water-containing substance at 25 ° C. is preferably 50,000 mPa · s or less, more preferably 30,000 mPa · s or less, particularly preferably 10,000 mPa · s or less, and still more preferably 5000 mPa · s or less. . This viscosity can be measured by the viscometer used in the following examples. The amount of water in the water-containing substance may be 10% by mass or more, and preferably 30% by mass or more. It is more preferably 40% by mass or more, further preferably 50% by mass, particularly preferably 70% by mass or more, particularly preferably 80% by mass or more. If the water content is less than 10% by mass, it becomes difficult to generate carbon dioxide gas when mixing the external preparation for skin and the water-containing substance, and it becomes impossible to obtain effects such as promoting blood flow during use.
Here, a high lower limit of 70% by mass or more or 80% by mass or more can be employed in both the one-pack type and the two-pack type, but is particularly preferable in the case of the one-pack type.

  When the external preparation for skin of the present invention is of one-part type, it is characterized in that it is made into one part, and it is easier to handle at low cost than a two-part type. In the case of a one-pack type, examples of the water-containing substance used in the present invention include liquids containing water which are usually used in cosmetics, pharmaceuticals, and the like, or used in ordinary households. The liquid containing water may be water itself. Specifically, in addition to tap water, distilled water, membrane filtered water, ion-exchanged water, deep sea water, alcoholic beverages such as sake and wine, soy milk, drinking yogurt, acerola juice, sports beverages, carbonated water and other beverages, rice Noto juice and the like. These may be used alone or in combination of two or more.

  When the external preparation for skin and the hydrated substance of the present invention are combined into a two-part form, the hydrated substance includes, as described above, a liquid or gel containing water, and the water or water mentioned above. In addition to the liquid containing, a liquid obtained by adding an arbitrary component to these liquids may be used. As this component, a known component contained in a liquid preparation in a two-part type external preparation for skin, for example, a humectant, a surfactant, a pH adjuster, a volatile alcohol, a fat or oil, a fragrance, an animal or plant extract, or the like may be added. Can be. For example, examples of the humectant include polyglycerin such as glycerin, diglycerin, triglycerin, and tetraglycerin, ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, and the like. , 3-propanediol, sorbitol, polyhydric alcohols such as polyglycerin derivatives, polyoxyalkylene alkyl glucosides, sodium lactate, sodium pyrrolidone carboxylate, almonds, avocados, altea, aloe, usbenioi, ononis, oats, licorice, quince seed, Clara (Kudin), Gardenia, Grapefruit, Watercress, Gentian, Gennoshoko, Burdock, Wheat, Psychic, Cactus, Soapwort, Hawthorn, Jio Spiraea, ginger, mallow, mulberry, caterpillar, cordyceps, pterodactyl, peppermint, adlay, hammerellis, rose, hinoki, coltsfoot, grape, prunes, loofah, bodaiju, hops, pine, quince, marronnier, melissa, cornflower, lily, lily And plant extracts such as lavender, apple, rice and rice bran, black currant, Ibukitorano, neubara, eleuthero, seaweed and the like, and one or more of these can be used.

  The amount of the hydrated substance to be used can be used in a wide range without any particular limitation. For example, it is preferable to add the hydrated substance in an amount of 1 to 10 times by mass with respect to the external preparation for skin, and 2 to 5 times. More preferably, the amount is added. By adding more than one volume of the liquid, the external preparation for skin can be rapidly dissolved, and a sufficient amount of carbon dioxide can be generated. On the other hand, by adding the liquid within 10 times the amount, dripping due to a decrease in the viscosity of the external preparation for skin can be prevented.

  The temperature of the hydrated substance to be used is not particularly limited and can be used in a wide range. However, it is particularly preferable to use the hydrated substance after cooling in advance because the function of the active ingredient of the external preparation for skin is enhanced. As for the temperature range that can be used, it is preferable to use water at about room temperature or tap water from the viewpoint of the feeling of use during application and the convenience of the user.

  The method for storing the external preparation for skin is not particularly limited as long as it is stored in a state where it blocks moisture and does not come into contact with it. The shape of the storage container used can be appropriately selected according to the purpose, and examples thereof include a cup shape, a tube shape, a bag shape, a bottle shape, a stick shape, a pump shape, a jar shape, a canned shape and the like. In addition, as a material constituting the storage container, for example, plastic, glass, aluminum, paper, various polymers, and the like can be used alone or in combination of two or more, but are not limited thereto.

  Specific examples of the container include a storage container such as an aluminum stick or an aluminum bag whose inner surface is laminated with polyethylene terephthalate, a stand pouch with a zipper, and a polyethylene terephthalate inner surface in terms of hermeticity, storage stability of contents, production cost, and the like. A storage container or the like made of polyethylene terephthalate, whose lid is heat-sealed with an aluminum film or the like laminated with 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 of use is good and an excellent effect of improving skin condition is obtained. Examples of feeling of use include, for example, the ease of mixing a mixture of a skin external preparation and a water-containing substance to the skin, the ease of application, the ease of dripping, the ease of removal, the smoothness of foam, the fineness of foam, The uniformity of the foam (the absence of roughness of the powder), the elasticity of the foam, the durability of the foam, the feeling of carbonation (stimulation), the sustainability of the feeling of carbonation, and the like can be given. Examples of the skin condition improving effect include moist feeling, elasticity, brightness, redness, smoothness, firmness, improvement in whiteness, increase in keratin water content, suppression of water evaporation, and the like. As is clear from Example 24 to be described later, according to the external preparation for skin of the present invention, an effect of making wrinkles less noticeable may be obtained.

<Uses of external preparation for skin>
The external preparation for skin of the present invention promotes an increase in the blood flow rate in the skin, and makes use of the above-mentioned effects to improve skin whitening, skin quality, freckle improvement, skin rejuvenation, skin tightening, partial thinning, and skin cleansing. To make the skin smooth, prepare the skin texture, keep the skin healthy, prevent the rough skin, tighten the skin, give the skin moisture, keep the skin moisture and oil, keep the skin soft, Protects, prevents skin from drying, softens skin, gives skin a shine, gives skin a luster, smoothes skin, prevents sunburn spots and freckles, makes dry wrinkles less noticeable Not only cosmetics for the purpose of doing, but also skin roughness, irritability, prevention of rash, morbidity, cracks, irritations, acne, prevention of oily skin, razor break, prevention of spots and freckles due to sunburn, sunburn, After the snow Non-pharmaceuticals for the purpose of preventing skin irritation, tightening the skin, purifying the skin, conditioning the skin, keeping the skin healthy, giving the skin moisture, protecting the skin, preventing the skin from drying out, etc. It can be suitably used for any of products and pharmaceuticals such as medicines. The external preparation for skin of the present invention is preferably used as cosmetics and quasi-drugs, and is preferably used as cosmetics such as emulsions, creams, packs, and peeling agents, and cosmeceuticals. In particular, it is preferable to use it as a pack agent because it has a good feeling in use and a high skin condition improving effect is easily obtained.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. In each of the following Examples and Comparative Examples, commercial materials were used as raw materials to be used unless otherwise specified.

<Examples 1 to 10, Comparative Examples 1 to 3>
The components shown in Table 1 were blended and mixed according to the compositions shown in the same table to produce powdered skin external preparations of Examples 1 to 10 and powdered skin external preparations of Comparative Examples 1 to 3. . The numerical values in Table 1 below are mass ratios (% by mass) in the external preparation for skin.

  The characteristics of the skin external preparations of the above Examples and Comparative Examples were evaluated according to the following [Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3].

[Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3]
(1) Sensory evaluation Three healthy women in their 20s to 30s were randomly selected as subjects. The inside of the subject's forearm was washed with a face wash, and the subject spent a rest in the measurement room for 15 minutes. Subsequently, the powdery skin external preparation sample and water were mixed in a container at a ratio of 1: 3 (mass ratio) to obtain a mixture as a foamed pack cosmetic. This mixture was applied to a 4 cm × 4 cm area inside the forearm. Ten minutes after application, the mixture was removed from the forearm and the forearm was washed with water. After that, the evaluation of the feeling of use was evaluated as the four items of “easiness of mixing”, “easiness of application”, “easiness of sagging” and “easiness of removal”, and as the condition of the skin after use, “moist feeling” , "Skin elasticity", "skin brightness", and "skin redness" were surveyed. For each item, a score was assigned to each of the seven levels shown in Table 2, and after aggregation, an average value of three persons was obtained. Table 3 shows the results. In addition, about "resistance to dripping", the higher the evaluation, the more difficult the mixture dripped from the skin after application. The higher the moisture content of the skin, the higher the score. The higher the skin redness, the higher the score.

  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, resistance to sagging, and ease of removal, and moist feeling It can be seen that both of the effects of improving skin condition such as elasticity, brightness and redness are superior to Comparative Examples 1 to 3. Furthermore, it can be seen that Examples 2, 6 to 10 containing two or more polysaccharides or derivatives thereof are more effective in both improving the feeling of use and the condition of the skin. In addition, when the water-soluble protein is contained as in Examples 3, 6, 8, and 10, the effect of improving the feeling of use and the condition of the skin is further enhanced, but as in Examples 4, 5, 7, and 9, It can also be seen that when an extract containing saponin, which is a natural surfactant, is contained in place of the water-soluble protein, these effects are higher than those of the water-soluble protein. Also, it can be seen that in Examples 3, 5 to 10 containing GK2, salicylic acid or arbutin, high effects were obtained. For example, as is clear from the comparison of Examples 4 and 5, the inclusion of GK2 which is a natural surfactant (and an anti-inflammatory agent and a whitening agent) not only enhances the effect of improving the condition such as redness of the skin, but also enhances the skin. The feeling of use of external preparations is also improved. From the above results, when using two kinds of polysaccharides or derivatives thereof as in Examples 2 to 5 as compared to Example 1 using one kind of polysaccharides or derivatives thereof, or using a water-soluble protein or a natural surfactant, It can be seen that by using them together, a higher feeling of use and a skin condition improving effect can be obtained. In addition, it can be seen that by using two or more kinds of polysaccharides or derivatives thereof and a water-soluble protein or a natural surfactant in combination as in Examples 6 to 10, both the feeling of use and the effect of improving skin condition are further improved. .

(2) Measurement of skin condition Regarding the sensory evaluation of the above (1), the L * value, keratin water content, and elasticity at the portion where the mixture is to be applied inside the forearm before application of the mixture were measured using the following measuring devices. After the mixture was removed and washed with water, the L * value, keratin moisture content, and elasticity of the portion where the mixture was applied inside the forearm were measured in the same manner. From the obtained measurement values, the average value of three subjects was determined. The average value after use of the external preparation for skin was divided by the average value before use, and the obtained value was defined as the rate of change. FIG. 1 shows the rate of change of the L * value (whiteness), FIG. 2 shows the rate of change of keratin water content, and FIG. 3 shows the rate of change of elasticity. In these figures, the higher the rate of change, the higher the evaluation.

L * value: Measured with a colorimeter (CR-400 manufactured by Konica Minolta).
-Horny water content: It was measured by a skin surface horny water content measuring device SKICON-200EX (manufactured by IBS). This skin surface keratin water content measuring device evaluates skin conductance (electric conductivity, unit: μS) as keratin water content.
Elasticity: It was measured with a skin viscoelasticity measuring device Cutometer MPA580 (Courage + Khazaka).
These measurements were performed in a standard manner as described in the instructions provided with the instrument.

  From the results of FIGS. 1 to 3, the L * value, the keratin moisture content, and the elasticity of the skin after use of the external preparation for the skin show that, in each example, a change rate equal to or higher than that of each comparative example is obtained. I understand. In particular, containing two or more kinds of polysaccharides or derivatives thereof, containing a water-soluble protein, containing an extract containing saponin which is a natural surfactant, and glycyrrhizinate which is a natural surfactant (inflammatory agent and whitening agent) It can be seen that the rate of change of the L * value, keratin moisture content, and elasticity is increased by one or more factors selected from the content of, and other whitening agents or fungicides. For example, a comparison of Examples 1 and 2 shows that the inclusion of two or more polysaccharides or derivatives thereof improves the L * value, keratin moisture content, and elasticity. In addition, a comparison between Examples 1 and 3 reveals that the inclusion of a water-soluble protein and glycyrrhizinate improves L * value, keratin water content, and elasticity. In addition, a comparison between Examples 1 and 4 shows that the inclusion of an extract containing saponin improves the L * value, keratin moisture content, and elasticity. Also, a comparison between Examples 4 and 5 shows that the content of keratin water is improved when glycyrrhizinate is contained. Also, from the comparison between Examples 6 and 8, and the comparison between Examples 7 and 9, it can be seen that the keratin moisture content and elasticity are improved when a bactericide is contained. In addition, it can be seen from Example 10 that the addition of arbutin as a whitening agent improves the L * value.

(3) Evaluation of external preparation for skin In a bottle (225 mL) having a diameter of about 4.8 cm and a height of about 10.5 cm, 27 mL of water was added, and 9 g of a powdery external preparation for skin was added thereto. Stirred. The resulting mixture was evaluated for the following <foaming amount> and <carbon dioxide generation amount>.

<Foaming amount>
One minute, 10 minutes, and 20 minutes after stirring, the volume of the mixture was measured, and the rate of increase (%) of the volume with respect to the volume before stirring was determined. FIG. 4 shows the results.

<Amount of carbon dioxide generated>
Carbon dioxide gas generated from the mixture after stirring was collected by displacement on water. The accumulated amount (mL) of the collected carbon dioxide gas was measured at each time point 3, 5, 7, 10, 15, 20, and 30 minutes after the stirring. The result is shown in FIG.

From the results in FIG. 4, it can be seen that the volume of the mixture hardly decreases even after a lapse of time after stirring, and that a certain amount of carbon dioxide is retained in the mixture. This effect is selected from two or more kinds of polysaccharides or derivatives thereof, a water-soluble protein, an extract containing saponin, a glycyrrhizinate, and other whitening agents or fungicides. It is increased by the inclusion of an extract containing one or more factors, especially water-soluble proteins or saponins, and the inclusion of glycyrrhizinate. For example, a comparison between Examples 1 and 2 shows that when two or more polysaccharides or derivatives thereof are contained, the carbon dioxide retention in the resulting mixture is improved. From the comparison between Examples 1 and 3, it can be seen that when the water-soluble protein and glycyrrhizinate are contained, the carbon dioxide retention in the resulting mixture is improved. From the comparison between Examples 1 and 4, it can be seen that when an extract containing saponin is contained, the carbon dioxide retention power in the obtained mixture is improved. Also, a comparison of Examples 4 and 5 shows that the presence of glycyrrhizinate improves the carbon dioxide retention in the resulting mixture.
On the other hand, in each of the comparative examples, it is found that bubbles of the mixture are not easily retained, and the volume of the mixture after stirring is easily reduced, that is, the amount of carbon dioxide gas that can be retained in the mixture is small.

From the results shown in FIG. 5, in each example, carbon dioxide gas was generated relatively slowly during the period from stirring to 5 minutes, and thereafter, although the gradient was gentle, the generation of carbon dioxide gas from the mixture was stopped. It can be seen that it is continuing without. In particular, in Examples 2 to 10 containing two or more polysaccharides or derivatives thereof, an extract containing water-soluble protein or saponin, glycyrrhizinate, or other whitening agents and fungicides, the generation of carbon dioxide gas It tends to last for a long time. For example, a comparison of Examples 1 and 3 shows that the inclusion of water-soluble protein and glycyrrhizinate increases the amount of carbon dioxide gas generated. In addition, a comparison between Examples 1 and 4 shows that when an extract containing saponin is contained, the amount of generated carbon dioxide gas is improved. Also, a comparison of Examples 4 and 5 shows that the presence of glycyrrhizinate increases the amount of carbon dioxide gas generated.
On the other hand, in each of Comparative Examples 1 to 3, although the carbon dioxide gas generation rate was high up to 3 minutes after stirring, the subsequent generation was stopped or the amount of generated carbon dioxide gas itself was low. .

<Examples 11 to 17>
Each component was blended and mixed at the blending ratio shown in Table 4 below to produce a powdery external preparation for skin. The numerical values in Table 4 are mass ratios (% by mass) in the external preparation for skin.

[Evaluation of Examples 11 to 17]
<Sensory evaluation>
Three healthy women in their 20s and 30s were randomly selected as subjects different from the subjects evaluated in Examples 1 to 10 and Comparative Examples 1 to 3 described above. Otherwise, after using a powdered skin external preparation sample in the same manner as in “(1) Sensory evaluation” in the above [Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3,] A questionnaire survey was conducted for the evaluation items. For each item, based on Example 17 (4.0 points), scores were assigned to the seven levels shown in Table 2 above, and after tallying, the average value of three persons was obtained. The results are shown in Table 5 below. In addition, the following "stimulus feeling" was evaluated as higher as there was a sharp feeling. In addition, "skin stickiness" was evaluated as high as it was difficult to stick.
Evaluation items: “Ease of application”, “Pleasantness of application”, “Good appearance of applied mixture”, “Drip resistance”, “Stimulation (presence or absence of tingling)”, “ 8 items of "easiness of mixture mixture", "easiness of mixture stickiness", "easiness of mixture removal", skin condition after use, "moist skin feeling", "smooth skin", A total of 15 items: 7 "Skin smoothness", "Skin stickiness", "Skin firmness", "Skin tightness" and "Skin brightness".

  From the results shown in Table 5 above, the composition of Example 17 containing an acidic substance, a carbon dioxide-generating substance, a polysaccharide or a derivative thereof, and one water-soluble protein was further added to each active ingredient (including the second water-soluble protein). In Examples 11 to 16 to which (1) was added, it was found that both effects of improving the usability and skin condition were improved. In particular, when the skin external preparation of Example 11 to which gold foil was added was used, it was found that the feeling of use at the time of application, the appearance, and the like, were improved. It is also found that the use of the external preparation for skin of Example 12 to which pearl powder is added improves the skin brightness and the like. In addition, it can be seen that the use of the skin external preparation of Example 13 to which collagen was added particularly improved the moist feeling and smoothness. In addition, when the external preparation for skin of Example 14 to which hydrolyzed collagen was added was used, the ease of application at the time of use, the pleasantness, the appearance were improved, and the moist feeling and smoothness of the skin after use were improved. It turns out that it improves. In addition, it is found that the use of the external preparation for skin of Example 15 to which the placenta is added improves smoothness, smoothness, and the like after use. It can be seen that when Example 16 to which arbutin was added was used, the ease of application at the time of use, the comfort, and the spread were improved, and the smoothness and brightness of the skin after use were improved.

[Evaluation of Examples 14 to 17]
<Measurement of skin condition>
In the <Sensory evaluation> of the above [Evaluation of Examples 11 to 17], the amount of water transpiration (g / m ² / hr) at the scheduled application location inside the forearm before application of the mixture was measured by the following measurement device. Thereafter, 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 inside the forearm was measured in the same manner.

-Water loss (g / m ² / hr): Measured with Tewameter TM300 (Courage + Khazaka). This measurement was performed by standard methods described in the instructions attached to the instrument.
From the obtained measurement values, the average value of three subjects was determined. The rate of change was determined by dividing the average value before use from the average value after use of the external preparation for skin. FIG. 6 shows the change rate of the obtained water evaporation. The lower the value, the higher the evaluation.

  From the results shown in FIG. 6, the skin external preparations of Example 14 to which the hydrolyzed collagen was added, Example 15 to which placenta was added, and Example 16 to which arbutin was added were further used. It can be seen that the amount of water transpiration is further suppressed. In particular, it can be seen that the suppression effect of Example 15 with the addition of the placenta is high.

<Examples 18 to 20>
The components shown in Table 6 were blended and mixed with the compositions shown in the same table to produce powdered skin external preparations of Examples 18 to 20. The numerical values in Table 6 are mass ratios (% by mass) in the external preparation for skin.

[Evaluation of Examples 18 to 20]
<Sensory evaluation>
Five healthy women in their 20s to 30s were randomly selected as subjects. Otherwise, the same sensory evaluation as (1) sensory evaluation in [Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3] was performed. However, four evaluation items were used as the skin condition after use: "skin smoothness", "skin moist feeling", "skin moisture feeling", and "skin softness". In addition, the subject was given an evaluation score of seven grades shown in Table 2 based on Example 20 (4.0 points). After the aggregation, the average value of the five evaluation points was obtained. Table 7 shows the results.

[Evaluation of Examples 18 and 19]
<Measurement of skin condition>
In the <Sensory evaluation> of the above [Evaluation of Examples 18 to 20], the keratin moisture content at the portion where the mixture was to be applied inside the forearm before the mixture was applied was measured by the above-described measuring device. Then, after removing the mixture and washing with water, the amount of keratin water at the location where the mixture was applied inside the forearm was measured in the same manner. From the obtained measurement values, the average value of five subjects was determined. The average value after use of the external preparation for skin was divided by the average value before use, and the obtained value was defined as the rate of change. The result is shown in FIG.

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

<Example 21>
The components shown in Table 9 were blended and mixed with the compositions shown in the same table to produce the powdery external preparation for skin of Example 21. The numerical values in Table 9 are mass ratios (% by mass) in the external preparation for skin.

<Comparative Example 4>
The components shown in Table 10 were blended and mixed according to the compositions shown in the same table to produce a carbonate-containing powder and an acid-containing liquid. The numerical values in Table 10 are parts by mass. The viscosity of the obtained acid-containing liquid at 25 ° C. using a viscometer (RVT type manufactured by Brookfield) was 16.9 mPa · s.

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

[Evaluation of Example 21 and Comparative Examples 4 and 5]
(1) Sensory evaluation Four healthy women in their 20s and 30s were randomly extracted and used as subjects. Otherwise, the same sensory evaluation as (1) sensory evaluation in [Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3] was performed. However, in Example 21, a powdery external preparation for skin and water were mixed 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 at a mass ratio of 1: 3 to obtain a mixture. In Comparative Example 5, a powder containing an acid and a viscous composition containing a carbonate were mixed at a mass ratio of 1: 3.68 to obtain a mixture. In addition, the evaluation items were two items of “skin elasticity” and “skin redness” as the skin condition after use of the external preparation for skin, and the seven-point score shown in Table 2 was based on Comparative Example 4 (4. An evaluation score was given as (0 point). After the aggregation, the average value of the four evaluation points was obtained. Table 12 shows the results. The viscosity at 25 ° C. of the water used in Example 21 was measured with the above-mentioned viscometer, and the value was lower than the lower limit (10 mPa · s) of the viscometer.

(2) Measurement of skin condition In the sensory evaluation of the above (1), before application of the mixture, the L * value at the portion where the mixture was to be applied inside the forearm was measured by the above-mentioned measuring device. Then, the coating and the mixture were removed, and the mixture was washed with water.
At 15 minutes, 60 minutes, and 120 minutes after the end of removal, the L * value of the portion of the inner forearm to which the mixture was applied was measured by the above-described measuring device. From the obtained measured 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 preparation for skin was used as the change value. Table 13 shows the obtained L * value (whiteness) change values. In the table, the higher the change value, the higher the evaluation.

  As is clear from the descriptions in Tables 12 and 13, Example 21 in which an external preparation for skin containing an acidic substance, a carbon dioxide-generating substance and a polysaccharide or a derivative thereof was mixed with a water-containing substance, powder containing carbonate was converted to an acid. It can be seen that the effect of improving the condition of the skin after use is higher than that of Comparative Example 4 mixed with a liquid containing the compound and Comparative Example 5 mixed with a powder containing an acid with a viscous composition containing a carbonate.

<Examples 22 to 23>
Each component was blended and mixed at the blending ratio shown in Table 14 below to produce a powdery external preparation for skin.
The numerical values in Table 14 are mass ratios (% by mass) in the external preparation for skin.

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

  As is clear from Table 15, in Examples 22 and 23 in which potato starch was blended at 10% by mass or more, generation of carbon dioxide was not observed even after storage at 60 ° C. for 2 months, confirming good storage stability. did it.

<Example 24>
Each component was blended and mixed at the blending ratio shown in Table 16 below to produce a powdery external preparation for skin.
The numerical values in Table 16 are mass ratios (% by mass) in the external preparation for skin.

  In accordance with the following procedure of [Example 24], the properties of the skin external preparations of the above Examples and Comparative Examples were evaluated.

[Evaluation of Example 24]
<Anti-wrinkle function evaluation>
Sixteen adult women with wrinkles in the outer corners of the eyes were selected as subjects. A powdered skin external preparation sample and water are mixed at a ratio of 1: 3 (mass ratio) in a container, and the mixture, which is a foamed pack cosmetic, is applied to the designated half face centering on the right or left eye corner. Applied. Ten minutes after application, the mixture was removed and rinsed with water or lukewarm water. Subjects performed this once a day for four weeks. For the evaluation of wrinkles, replicas of the wrinkles at the right and left corners of the eyes (with and without application of the mixture) were collected, and image analysis was performed using the replicas. The replica was collected using a replica agent (SILFLO) in a range of 4 cm × 4 cm outward from the external canthus of the subject. The obtained replica was analyzed in a range of 10 mm × 10 mm with a point about 5 mm outside the face from the external canthus as a base point. The analysis was performed using a replica analysis system for reflection (ASA-03RXD) and three-dimensional skin analysis software. Table 17 shows the result of the maximum wrinkle maximum depth, which is the evaluation result of wrinkles. A positive change indicates that the wrinkles have become deeper than before use, and a negative change indicates that the wrinkles have become shallower than before use.

  From Table 17, it was confirmed that the use of the external preparation for skin of the present invention reduced the maximum wrinkle maximum depth of the outer corner of the eye compared to the case where it was not used. The above results show that the use of the foamable skin external preparation of the present invention has an effect of making wrinkles less noticeable.

[Prescription example of one-part type external preparation for skin]
Hereinafter, further specific examples of the one-pack type external preparation for skin of the present invention are shown.

<Example 25>
Each component was blended at the blending ratio shown in Table 18 to obtain a powdery one-part skin external preparation. This one-part type skin external preparation powder was placed in a container, water was added to the powder 1 at a mass ratio of 3 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 26>
Each component was blended in the blending ratio shown in Table 19 to obtain a powdery one-part skin external preparation. This one-part type skin external preparation powder was placed in a container, water was added to the powder 1 at a mass ratio of 5 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 27>
Each component was blended in the blending ratio shown in Table 20 to obtain a powdery one-part external preparation for skin. This one-part type external skin powder was placed in a container, water was added to the powder 1 at a mass ratio of 10 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 28>
Each component was blended at the blending ratio shown in Table 21 to obtain a powdery one-part external preparation for skin. This one-part type skin external preparation powder was placed in a container, water was added to the powder 1 at a mass ratio of 3 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 29>
Each component was blended at the blending ratio shown in Table 22 to obtain a powdery one-part skin external preparation. This one-part type external skin powder was placed in a container, water was added to the powder 1 at a mass ratio of 4 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 30>
Each component was blended in the blending ratio shown in Table 23 to obtain a powdery one-part external preparation for skin. This one-part type external skin powder was placed in a container, water was added to the powder 1 at a mass ratio of 10 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 31>
Each component was blended at the blending ratio shown in Table 24 to obtain a powdery one-part external preparation for skin. This one-part type external skin powder was placed in a container, water was added to the powder 1 at a mass ratio of 4 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Example 32>
Each component was blended at the blending ratio shown in Table 25 to obtain a powdery one-part external preparation for skin. This one-part type external skin powder was placed in a container, water was added to the powder 1 at a mass ratio of 4 and the mixture was stirred, whereby a foamed pack cosmetic was obtained.

<Examples 2-1 to 2-28, Comparative Examples 2-1 and 2-2>
The components shown in Table A below were blended and mixed with the compositions shown in the same table, and the powdery skin external preparations of Examples 2-1 to 2-28, and of Comparative Examples 2-1 and 2-2. A powdery skin external preparation was produced. The numerical values in Table A below are mass ratios (% by mass) in the external preparation for skin. Note that, as carboxymethyl cellulose described in Table A below, sodium carboxymethyl cellulose was used. As the acrylic acid / alkyl methacrylate copolymer shown in Table A below, (Acrylates / alkyl acrylate (C10-30)) crosspolymer was used. The “pattern” in Table A refers to the above (1) to (3) related to a combination of two or more polysaccharides or derivatives thereof, or a combination of a polysaccharide or a derivative thereof and an inorganic or organic thickening compound. It indicates which of the above (4) pertains. This classification is also shown in Table C below.

  The characteristics of the external preparation for skin of <Examples 2-1 to 2-28, Comparative Examples 2-1 and 2-2> in the composition of Table A above were described above [Examples 1 to 10 and Comparative Examples 1 to 3]. Evaluation] was evaluated in the same manner as in the sensory evaluation of (1). However, the questionnaire items were as shown in Table C (1) to (19) below. The results are shown in Table C below. The evaluation criteria were seven-step absolute evaluations shown in Table B below. In Table C, "(4) Fineness of foam" was evaluated higher as the foam was finer. "(10) Carbonation feeling (pitch feeling)" was evaluated higher as the feeling of pich feeling was higher. “(11) Persistence of carbonic acid sensation” was evaluated to be higher as the carbonic acid sensation continued. “(12) Skin tightening feeling” was evaluated higher as the tightening feeling was higher.

  CMC in Table C is an abbreviation for sodium carboxymethylcellulose, tamarind is an abbreviation for tamarind gum, HPMC is an abbreviation for hydroxypropylmethylcellulose, HEC is an abbreviation for hydroxyethylcellulose, and graft starch is a sodium acrylate graft. Abbreviation of starch, acrylic acid is an abbreviation of acrylic acid / alkyl methacrylate copolymer, and PVP is an abbreviation of polyvinylpyrrolidone.

  As is clear from the results in Table C, the skin external preparations of Examples 2-1 to 2-28 corresponding to any of (1) to (4) employed a combination of a conventional polysaccharide or a derivative thereof. Compared with the skin external preparations of Comparative Examples 2-1 and 2-2, the evaluations of ease of mixing, dissolving, ease of removal, and skin brightness were equal to or higher than the above, and the fineness and uniformity of the foam Ease of application, foam elasticity, foam retention, carbonated feeling, persistence of carbonated feeling, skin moistness, skin elasticity, skin redness, skin smoothness, skin smoothness, skin smoothness Was also excellent. Therefore, it is clear that the skin external preparation of the present invention, which corresponds to any one of (1) to (4), has a remarkable effect of "good feeling of use and improvement of skin condition".

L * value, keratin water content (μS), elasticity before and after use of the external preparation for skin of <Examples 2-1 to 2-28, Comparative Examples 2-1 and 2-2> of the formulation in Table A above Was measured by the same method as described in "(2) Measurement of skin condition" in [Evaluation of Examples 1 to 10 and Comparative Examples 1 to 3] described above. With respect to the obtained L * value, keratin water content, and elasticity, the ratio of the measured value after use to the measured value before use of the external preparation for skin was determined and defined as a rate of change. The results are shown in FIGS. In addition, the amount of water transpiration (g / m ² / hr) before and after use of the external preparation for skin of <Examples 2-1 to 2-28 and Comparative Examples 2-1 and 2-2> in the composition of Table A above. ) Was measured by the same method as described in “<Skin condition measurement>” in [Evaluation of Examples 14 to 17] described above. With respect to the obtained water loss, the ratio of the measured value after use to the measured value before use of the external preparation for skin was determined and defined as a change rate. The result is shown in FIG.

  As is clear from the results of FIGS. 8 to 10, the change rates of the elasticity of the external preparations for skin of Examples 2-1 to 2-28 corresponding to any of (1) to (4) are shown in Comparative Example 2-2. Was equal to or higher than that of the external preparation for skin of Example 1, and was higher than that of Comparative Example 2-1. In addition, the change rates of the L * value and the keratin water content of the skin external preparations of Examples 2-1 to 2-28 were superior to both Comparative Examples 2-1 and 2-2. Therefore, it is clear that the effect of "improving the skin condition" of the skin external preparation of the present invention corresponding to any of (1) to (4) is remarkable.

Claims (11)

At least a solid acidic substance, a foamable skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
As the polysaccharide or a derivative thereof, at least one selected from a cellulose derivative and a starch derivative,
Alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or at least one selected from hydrophilic natural polymers that are tamarind gum (however, when containing sodium carboxymethylcellulose as a cellulose derivative, alginic acid and its salts are used. Excluding) and
An effervescent skin preparation for external use, which is mixed with a water-containing substance at the time of use of the skin external preparation. The effervescent external preparation for skin according to claim 1, which is (a) or (b) below.
(A) As cellulose derivatives, hydroxyethyl cellulose and its derivatives, carboxymethyl cellulose and its derivatives and salts thereof, hydroxypropylmethyl cellulose and its derivatives, sulfonated cellulose derivatives, carboxymethyl ethyl cellulose and its salts, cellulose acetate phthalate, and cationized cellulose Containing at least one selected from ethyl cellulose and croscarmellose and salts thereof, and / or
The starch derivative contains at least one selected from carboxymethyl starch and salts thereof and acrylic acid-grafted starch and salts thereof.
(B) It contains hydroxypropylcellulose and its derivatives as cellulose derivatives, and at least one selected from alginic acid and its salts, carrageenan, guar gum, xanthan gum and tamarind gum as hydrophilic natural polymers. At least a solid acidic substance, a foamable skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
As the polysaccharide or a derivative thereof, it contains alginic acid or a salt thereof, carrageenan, guar gum, locust bean gum, xanthan gum or two or more kinds selected from hydrophilic natural polymers that are tamarind gum,
An effervescent skin preparation for external use, which is mixed with a water-containing substance at the time of use of the skin external preparation. The effervescent skin external preparation according to claim 3, which is any one of the following (A) to (C).
(A) Alginic acid and salts thereof, and at least one selected from carrageenan, guar gum, locust bean gum, and tamarind gum.
(B) Carrageenan and at least one selected from guar gum, xanthan gum and tamarind gum.
(C) It contains two or more kinds selected from guar gum, locust bean gum, xanthan gum and tamarind gum. At least a solid acidic substance, a foamable skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
As a polysaccharide or a derivative thereof, containing two or more kinds selected from a cellulose derivative and a starch derivative,
An effervescent skin preparation for external use, which is mixed with a water-containing substance at the time of use of the skin external preparation. As cellulose derivatives, hydroxyethyl cellulose and its derivatives, hydroxypropylmethyl cellulose and its derivatives, sulfonated cellulose derivatives, carboxymethyl cellulose and its derivatives and salts thereof, carboxymethylethyl cellulose and its salts, cellulose acetate phthalate, cationized cellulose, ethyl cellulose and At least one selected from croscarmellose and salts thereof,
The effervescent external preparation for skin according to claim 5, comprising, as the starch derivative, carboxymethyl starch and salts thereof and at least one selected from acrylic acid-grafted starch and salts thereof. The effervescent skin preparation for external use according to claim 5, which is (X) or (Y) below.
(X) The cellulose derivative contains at least one selected from hydroxypropylmethylcellulose and its derivatives, and at least one selected from hydroxyethylcellulose and its derivatives and cationized cellulose.
(Y) as a cellulose derivative, at least one selected from carboxymethylcellulose and its derivatives and salts thereof, and hydroxyethylcellulose and its derivatives, hydroxypropylcellulose and its derivatives, sulfonated cellulose derivatives, carboxymethylethylcellulose and its salts, Contains cellulose acetate phthalate, cationized cellulose, ethylcellulose, and at least one selected from croscarmellose and salts thereof. At least a solid acidic substance, a foamable skin external preparation having a solid carbon dioxide-generating substance that generates carbon dioxide by reacting with the acidic substance, further comprising:
At least one polysaccharide or a derivative thereof;
Containing an inorganic hydrophilic thickening compound, and at least one selected from hydrophilic synthetic polymers that are organic thickeners,
An effervescent skin preparation for external use, which is mixed with a water-containing substance at the time of use of the skin external preparation.   As polysaccharides or derivatives thereof, alginic acid and its salts, carrageenan, locust bean gum, tamarind gum, guar gum, carboxymethylcellulose and its derivatives and salts thereof, hydroxyethylcellulose and its derivatives, hydroxypropylmethylcellulose and its derivatives, sulfonated cellulose derivatives The foamable external preparation for skin according to claim 8, comprising at least one selected from carboxymethylethylcellulose and salts thereof, cellulose acetate phthalate, cationized cellulose, ethylcellulose, and croscarmellose and salts thereof.   The inorganic hydrophilic thickening compound is talc or silica, and the hydrophilic synthetic polymer that is an organic thickener is polyvinylpyrrolidone or an acrylic acid / alkyl methacrylate copolymer. Foaming skin external preparation.   The foamable external preparation for skin according to any one of claims 8 to 10, wherein the polysaccharide or a derivative thereof contains xanthan gum, and talc is contained as an inorganic hydrophilic thickening compound.

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