JP2002037742A - Skin care preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin care preparation containing conchiolin which is excellent in early recovering the skin from fatigue, polishing, bleaching pigments, preventing the skin from aging and fine wrinkling, or the like. SOLUTION: The skin care preparation is obtained by formulating at least one kind of substance selected from the group consisting of conchiolin hydrolyzates and substances obtained by treating the conchiolin hydrolyzates with succinic anhydride, an ascorbic acid derivative and a lactobacillus fermentation metabolite. The lactobacillus fermentation metabolite is prepared by crushing the microbial cell body of Lactobacillus acidophilus and the fermentation metabolite of the microbial cell body. In addition, this skin care preparation is obtained by including at least one kind of substance selected from the group consisting of the hydrolyzate of an extract from rice bran, an extract from a plant belonging to the family Gentianaceae, a product obtained by treating the muscus of shellfishes and an acidic polysaccharide obtained from shellfish flesh, and the hydrolyzate of the above extract from rice brain is obtained by treating an alkali extract from rice bran with at least two kinds of proteases.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly safe external preparation for skin which is effective in whitening and rough skin with high whitening action, active oxygen suppressing action, moisturizing property and the like.

[0002]

2. Description of the Related Art Hydrolyzates of conchiolin are disclosed in
JP-A-2-221612 and JP-A-62-223104, which are obtained by hydrolyzing conchiolin produced from shells such as pearl oysters, mussels, mussels, mussels and pearls with mineral acids such as hydrochloric acid and sulfuric acid. , Early recovery of skin fatigue, pigment bleaching, prevention of skin aging,
It is used in cosmetics for the purpose of preventing fine wrinkles and polishing.

[0003] This is because conchiolin or its hydrolyzate is excellent in moisture retention. Also, Japanese Patent Application Laid-Open No. 4-3
No. 6,214, discloses that conchiolin or a hydrolyzate thereof is effective as an antioxidant.

A substance obtained by treating this conchiolin hydrolyzate with succinic anhydride has increased water solubility even if the degree of hydrolysis is small, that is, a large molecular weight, and the moisturizing property is more than that of the conchiolin hydrolyzate. The improvement is disclosed by the present inventors in Japanese Patent Application Laid-Open No. Hei 7-165526.

The mucus of pearl oysters is described in Japanese Patent Publication No. 5-156.
No. 84, which is suitable as a raw material for cosmetics, and JP-A-6-279255 and JP-A-7-10225.
No. 2 and JP-A-7-187948 disclose that the present invention is effective as a hyaluronidase activity inhibitor, an antioxidant, and an emulsification aid.

[0006] The acidic polysaccharide obtained from shellfish meat is
Japanese Patent Application Laid-Open No. 62383/1993 discloses that the composition is effective for use in cosmetics, and Japanese Patent Application Laid-Open No. 6-219954 discloses the effectiveness as a hyaluronidase activity inhibitor.

[0007] Ascorbic acid or ascorbic acid derivatives are widely blended as raw materials for cosmetics for the purpose of whitening and the like. Also, the inventors of the present invention have found that the combination of conchiolin and ascorbic acid or a derivative thereof enhances the effectiveness.
Found in No. 50.

[0008] The hydrolyzate of the rice bran extract is used as a raw material for a skin external preparation for the purpose of whitening and the like.

[0009] The extract of the Gentianaceae plant is used as an external preparation for skin for the purpose of antioxidation and anti-inflammatory.

[0010]

However, external preparations for the skin are required to further add effective effects to the skin such as early recovery of skin fatigue, bleaching of the pigment, prevention of skin aging, prevention of fine wrinkles, and polishing. There is a problem that. For this reason, it is necessary to further effectively use conchiolin, which is a natural substance obtained from the natural world. The present invention has been made to address such problems,
An object of the present invention is to provide a skin external preparation that is more effective in the use of conchiolin and is more effective for early recovery of skin fatigue, pigment bleaching, prevention of skin aging, prevention of fine wrinkles, polishing, and the like.

[0011]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that a substance obtained by treating a hydrolyzate of conchiolin and / or a hydrolyzate of conchiolin with succinic anhydride, an ascorbic acid derivative, By combining with a metabolite, a more excellent skin external preparation has hitherto been obtained.

The present invention further provides at least one selected from the group consisting of a hydrolyzate of a rice bran extract, a plant extract of the Gentianaceae, a treated mucus of shellfish, and an acidic polysaccharide obtained from shellfish meat. It is characterized by containing a substance. Further, the fermented metabolite of lactic acid bacteria is characterized in that cells of Lactobacillus acidophilus and fermented metabolites of the cells are crushed. Further, the hydrolyzate of the rice bran extract is obtained by treating an alkaline extract of rice bran with two or more proteases. The proteolytic enzyme comprises a combination of (a) actinase and (b) at least one enzyme selected from the group consisting of pepsins, trypsins, papains, peptidases and bromelain. . Further, the ascorbic acid derivative is an L-ascorbic acid-2-phosphate ester salt, an L-ascorbic acid-2-sulfate ester salt, or an L-ascorbic acid-2-sulfate ester salt.
It is at least one derivative selected from the group consisting of ascorbic acid-2-glucoside and L-ascorbic acid-5-glucoside.

When a substance obtained by treating a hydrolyzate of conchiolin and / or a hydrolyzate of conchiolin with succinic anhydride, an ascorbic acid derivative, and a metabolite of fermented lactic acid bacteria are combined, the interaction of these substances causes ,
It has excellent effects on whitening, preventing rough skin, improving skin luster and blemishes, and skin scalp.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Conchiolin is a kind of hard protein contained in shells and pearls, and is relatively contained in pearl oysters, mussels, mussels and the like. As the manufacturing method, Japanese Patent Nos. 1587730, 1560610, and 15
87774 and the like.

A method for producing a hydrolyzate of conchiolin is as follows:
The protein may be obtained by decalcification from shells such as pearl oysters, mussels, mussels and the like, which may be subjected to necessary hydrolysis by a usual method. An example is shown below, but the present invention is not limited to this. Crush shells such as pearl oysters, mussels, mussels, etc. and remove calcium with dilute hydrochloric acid, etc., collect insolubles by solid-liquid separation methods such as centrifugation, filtration decantation, etc., add purified water to this, and mix well Then, insoluble materials are collected by centrifugation, filtration, or the like. Repeat as necessary.

Further, a 2 to 10% by weight aqueous hydrochloric acid solution may be added to this conchiolin and hydrolyzed at 50 to 110 ° C. for 5 hours to 5 days to obtain a hydrolyzate of conchiolin. This is sometimes simply called conchiolin.

After hydrolyzing with dilute sulfuric acid instead of dilute hydrochloric acid, neutralizing with barium hydroxide, and further neutralizing with an alkali hydroxide solution to pH 5-6, the precipitate is concentrated. The hydrolyzed liquid removed by centrifugation, filtration, or the like is converted into a concentrated liquid or a dry powder using a known concentration method or drying method. In the hydrolysis, the acid concentration, temperature and time should be controlled so that conchiolin is not completely decomposed into amino acids.

A method for preparing a substance obtained by treating the hydrolyzate of conchiolin with succinic anhydride is to add succinic anhydride while maintaining the pH at 6 to 9 while stirring in an aqueous solution of the hydrolyzate of conchiolin. The amount of succinic anhydride to be added is adjusted depending on the purpose and the like, since it is not necessary to succinylate the rate of hydrolysis of conchiolin or all of it.

Furthermore, a method for producing a hydrolyzate of conchiolin treated with succinic acid is to add a new method of utilization by adding the succinic anhydride to the substance prepared by the above method and maintaining the pH at 6 to 9, followed by stirring. Some cosmetic ingredients are made. Since this method can be carried out irrespective of the method of reducing the molecular weight, conchiolin can be decomposed by various methods such as a method using an ordinary acid.

As the ascorbic acid derivative, various derivatives can be used. Among the derivatives, derivatives that stabilize ascorbic acid are preferable. Suitable derivatives include, for example, ascorbic acid ester salts such as L-ascorbic acid-2-phosphate ester salt and L-ascorbic acid-2-sulfate ester salt (the salt is sodium salt, magnesium salt and the like), L-ascorbic acid -2-glucoside (2-O-α-D-glucopyranosyl-L-ascorbic acid), L-ascorbic acid-5-glucoside (5-O
-Α-D-glucopyranosyl-L-ascorbic acid) and the like. It should be noted that the use of ascorbic acid itself does not cause any problem, but has a problem in stability. Therefore, it is necessary to use some stable method.

There are various fermented metabolites of lactic acid bacteria, but as a result of investigation by the present inventors, the fermented metabolites of lactic acid bacteria obtained by the method described in JP-A-4-356409 were most suitable. This production method is based on Lactobacillus acidophilus (L
Actobacillus acidopbilus) is cultured in a state where other bacteria do not invade. After the culture, the cells are sufficiently pulverized together with the culture solution by using any of ultrasonic waves, a French press, and a microfluidizer or a combination thereof. 0.2 μm
Either filter with the following membrane filter or, depending on the purpose, remove substances having a molecular weight of 1,000 to 100,000 or more with an ultrafilter.

The hydrolyzate of conchiolin and / or a substance obtained by treating the hydrolyzate of conchiolin with succinic anhydride, an ascorbic acid derivative, and a metabolite of a fermented lactic acid bacterium are mixed at least. Reach the purpose Depending on the use as a skin external preparation, the compounding ratio is based on the total amount of the skin external preparation, which is obtained by treating the hydrolyzate of conchiolin and / or the hydrolyzate of conchiolin with succinic anhydride as a solid content. 0.001 to 5% by weight, preferably 0.005 to 2% by weight, the ascorbic acid derivative is 0.1 to 10% by weight, preferably 1 to 5% by weight, and the fermented metabolite of lactic acid bacteria is 0.0001 to 2% by weight, preferably 0.001 to 2% by weight, respectively, is preferably added. Further, the effect of the present invention is enhanced by additionally blending at least one of a hydrolyzate of a rice bran extract, a plant extract of the Gentianaceae, a processed product of mucus of pearl oyster, and an acidic polysaccharide obtained from shellfish meat. These are described. In addition,
It is preferable that the proportion to be additionally blended is 0.01 to 10% by weight, preferably 0.05 to 5% by weight as a solid content.

The hydrolyzate of the rice bran extract used in the present invention is obtained by hydrolyzing an extract obtained by extracting rice bran with a solvent such as water or alcohol with an acid, alkali, enzyme or the like. Solvents used for extraction include water, methanol,
Alcohols such as ethanol, ethylene glycol,
Propylene glycol, 1,3-butylene glycol,
Polyhydric alcohols such as glycerin, esters such as ethyl acetate, butyl acetate and methyl propionate, ketones such as acetone and methyl ethyl ketone, ethers such as ethyl ether and isopropyl ether, and hydrocarbons such as hexane, toluene and chloroform There are solvents and the like, which are used without adjusting the pH or after adjusting the pH with an acid or an alkali. Among them, in the present invention, water or water and alcohols,
Alternatively, it is preferable to use a mixed solution of water and polyhydric alcohols, and particularly to use them with an alkali such as sodium hydroxide, potassium hydroxide, or sodium carbonate at pH 7.5 to 14, particularly
The use of an alkaline aqueous solvent adjusted to a pH in the range of 9 to 12 is most preferable because the extraction from rice bran proceeds efficiently.

The extraction temperature and time vary depending on the solvent used and the like, but are generally about 4 hours to 40 ° C. and about 6 hours to 7 days.
Preferred is 12 to 36 hours at ~ 30 ° C.

The hydrolyzate of the rice bran extract obtained here is treated with an acid, an alkali or an enzyme. Above all, the decomposition treatment with an enzyme provides uniformity of product quality and easy process control. It is preferable from the viewpoint of properties and the like. In the case of hydrolysis by an enzyme, the enzymes used include actinase, pepsin such as pepsin, trypsin such as trypsin, papain such as papain and chymopapain, peptidases such as glycylglycine peptidase, carboxypeptidase and aminopeptidase, and Bromelain and the like, including actinase, are usually used in combination of two or more. When using a combination of enzymes, a combination of actinase and pepsin or trypsin is most preferred.

In the hydrolysis treatment with these enzymes, the enzyme is used in an amount of 0.0005 to 0.05 part by weight, preferably 0.001 to 0.005 part by weight, based on 100 parts by weight of the rice bran extract. The reaction is carried out for 1 to 24 hours under the following conditions.

The obtained rice bran extract hydrolyzate solution is generally adjusted to pH 4 to 8 and then used as it is or after being further adjusted to an appropriate concentration by concentration. Powdered and used according to a conventional method such as a spray drying method and a freeze drying method.

In the case of acid hydrolysis, hydrochloric acid, sulfuric acid or the like is used as the acid, and the pH of the extract is usually adjusted to pH 5 or less.
In particular, the pH may be adjusted to pH 4 or lower, and the mixture may be heated at 60 to 90 ° C for 1 to 6 hours. In the case of alkaline hydrolysis, the pH of the extract is generally adjusted to pH 9 to 13 using sodium hydroxide, potassium hydroxide, sodium carbonate, etc.
Generally, heat treatment is performed at a temperature of up to 90 ° C. for 1 to 6 hours.

Various extracts of plants of the family Gentianaceae are commercially available, and among them, Infran AT (manufactured by Technoble Co., Ltd.) was most effective in the present invention.

The processed product of the mucus of shellfish is a substance obtained by hydrolyzing the mucus of shellfish.
Mussels, mussels and mussels. In particular, pearl oysters are preferred. These shellfish may be used as a mucus source and subjected to a desalting operation such as hydrolysis or dialysis as it is, but when containing seawater or the like, heating or a water-soluble organic solvent such as ethanol, methanol, isopropanol or inorganic salts such as ammonium sulfate , Sodium chloride is added to precipitate the precipitate, and the precipitate is collected by centrifugation, filtration, or the like to reduce the processing amount. With or without precipitation, the mucus component is reduced to a low molecular weight by hydrolysis with an acid, alkali, or enzyme. Hydrolysis may be carried out under substantially the same conditions as for conchiolin, but it is easy to decompose. Therefore, it is better to use slightly mild conditions.

Since the enzyme is easier to use than conchiolin, proteolytic enzymes such as trypsin, papain, pronase, and other animal and plant-derived enzymes can be used. Since the enzyme can be easily used, the required molecular weight and the target peptide can be obtained by utilizing the specificity of the enzyme. In this way, the shellfish mucus is decomposed to a required molecular weight using acids, alkalis, and enzymes and desalted. Although desalination is not always necessary, it may be necessary depending on the use, and desalination is performed using a usual desalination method. For example, dialysis, gel filtration, ultrafiltration, a water-soluble organic solvent, or the like is used.

About acidic polysaccharides obtained from shellfish meat,
A method for preparing an acidic polysaccharide by decomposing shellfish meat with a proteolytic enzyme, removing protein, removing low-molecular substances, and adding a quaternary ammonium salt is described below. As a first step, the shell meat excluding the shell is decomposed by a protease. In order to facilitate this treatment, it is better to heat and denature, and then pulverize using a mixer or the like. When pearl oysters are used, mucus accompanying shellfish is also a raw material, and only mucus may be used. At this time, as in the case of using shell meat, it can be used irrespective of the removal of pearls, etc., so that the raw material can be easily collected and a pulverizing step is not required.

The protease is not particularly limited, but those having no substrate specificity and strong decomposing ability are preferred. For example, it is degraded using one kind of papain, actinase, samoase, denazyme, or a mixture of two or more kinds. In the second step, deproteinization is performed to remove undegraded proteins, nucleic acids and enzymes. The method of protein removal is also not particularly limited, but generally trichloroacetic acid and perchloric acid are used so as to have a concentration of 10% by weight, or the Sevag method is used.
In the third step, low-molecular substances such as deproteinizers, amino acids, peptides, and salts are removed. Examples of the removal method include dialysis, gel filtration, ultrafiltration, and a method of adding an organic solvent in which an acidic polysaccharide precipitates, and dialysis is preferred.

In the fourth step, neutral polysaccharides and glycoproteins present together with acidic polysaccharides are separated. As a removing means, an aqueous solution of a quaternary ammonium salt is added. The acidic polysaccharide binds to the quaternary ammonium salt and precipitates, and is separated by decantation or centrifugation. As a quaternary ammonium salt, one of the alkyl groups has a carbon atom number.
It should be 12 or more. Also, a pyridinium-based compound may be used as long as the alkyl group bonded to nitrogen has 12 or more carbon atoms. For example, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, and cetyl pyridinium chloride can be exemplified. Up to the fourth step, an acidic polysaccharide can be obtained, but since this precipitate contains a quaternary ammonium salt and other salts, it is preferable to further purify the precipitate.

In the purification, an aqueous solution of an inorganic salt is added to the precipitate to dissolve the complex, dissociate and dissolve the complex. Then, alcohol is added to reprecipitate the acidic polysaccharide, and the quaternary ammonium salt is added to the precipitate. Separated and removed. This precipitate is dissolved in purified water, water is added so that the alcohol concentration becomes 80% by weight, the mixture is stirred, allowed to stand, and then centrifuged to obtain a precipitate. This step is preferably repeated two or three times. As the inorganic salt, any inorganic salt capable of dissociating and dissolving a complex of a quaternary ammonium salt of an acidic polysaccharide can be used. For example, sodium chloride, potassium chloride and the like can be exemplified. The salt form used here determines the salt form of the final product. For example, if sodium chloride is used, the final product will be a sodium salt.

The concentration of the inorganic salt is such that the complex is dissociated, and sodium chloride is required to be 1.5 M or more. There is no particular upper limit, but if the concentration is too high, the desalting operation takes time,
It is a waste of reagent, and the limit is about 4M. If it is desired to remove the remaining proteins and dyes, the dyes and proteins are adsorbed and removed by adding a Lloyd reagent or cation to an aqueous solution in which the precipitate is dissolved in water. After removing the adsorbent by centrifugation and filtration, the acidic polysaccharide is freeze-dried. When the acidic polysaccharide thus obtained is added to cosmetics, its effect is as high as water-retention and moisture retention like hyaluronic acid, so that it gives moisture to the skin and hair and prevents drying, It exhibited a unique lubricating effect due to its excellent permeability and tissue affinity. In addition, one of the important effects is to increase the viscosity of the cosmetic itself and to improve the stability and the feeling of use.

These components may contain oily components, surfactants, humectants, thickeners, preservatives and germicides, powder components, ultraviolet absorbers, pigments, fragrances and the like which are usually used in external preparations for skin as required. Be blended.

[0038]

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. First, production examples of the following substances used in Examples will be described. (1) Hydrolyzate of conchiolin (Production Example 1) (2) Substance obtained by treating hydrolyzate of conchiolin with succinic anhydride (Production Example 2) (3) Substance obtained by hydrolyzing mucus of shellfish (Production) Example 3) (4) Acidic polysaccharide obtained from shellfish meat (Production Example 4) (5) Fermented metabolite of lactic acid bacteria (Production Example 5) (6) Hydrolyzate of rice bran extract (Production Examples 6 to 9)

Production Example 1 To 500 g of pearls, 1 kg of hydrochloric acid was gradually added with stirring to demineralize. Further, 300 g of 1 N hydrochloric acid was gradually added with stirring to demineralize, and this was filtered to collect insolubles. 100 ml of sulfuric acid diluted 30 times with water was added to this, sealed in a glass container, and thermally decomposed at 110 ° C for 24 hours. After cooling, barium hydroxide of 90% equivalent of the used sulfuric acid was added little by little with sufficient stirring. In addition, up to pH 5.8 1
A weight percent aqueous sodium hydroxide solution was added. Next 200
After centrifugation at G for 10 minutes, the mixture was further filtered through a 0.45 μm membrane filter to obtain a hydrolyzate of conchiolin. This was lyophilized. The yield was 8.9 g.

Production Example 2 5.0 g of the hydrolyzate of conchiolin obtained in Production Example 1
The samples were collected, dispersed in 100 ml of purified water, and 1 g of succinic anhydride was added 5 times every 15 minutes while stirring with 1N aqueous sodium hydroxide solution at pH 6 to 9 while stirring. This was lyophilized. The yield was 9.9 g.

Production Example 3 10 kg of pearl oysters were unshelled, and 270 g of mucus was obtained by decantation and centrifugation. An equal amount of ethanol was added to 100 g of the mixture, left at 5 ° C, and centrifuged. After adding 20 ml of purified water to the residue and stirring, 20 ml of ethanol was added and stirred, followed by centrifugation. this
Repeated 5 times. After adding 200 ml of purified water and stirring, 0.5 g of actinase E (trade name) was added, and the mixture was stirred and left at 50 ° C. for 6 hours. Then, at 100 ℃, 30
After heating for minutes, the mixture was filtered and freeze-dried.

Production Example 4 a. 100 kg of the pearl oyster shell from which the shell was removed was denatured by heating, and then ground with a mixer. b. 100 g of actinase E was added thereto, and the mixture was allowed to stand at 45 ° C. for 24 hours while stirring. c. 10 kg of trichloroacetic acid was added and stirred, left for 1 hour, and centrifuged to remove the precipitate, thereby removing proteins. Further, cellophane tubes were dialyzed for 48 hours to remove low molecular substances. d. Thereafter, 1 kg of cetylpyridinium chloride was added and stirred, left for 1 hour, and centrifuged to obtain a precipitate of a cetylpyridinium salt of an acidic polysaccharide. e. 2 M sodium chloride was added to the precipitate to dissolve the precipitate. Three times the volume of ethanol was added to this, and the mixture was stirred, left for 1 hour, and centrifuged to obtain a precipitate. f. Dissolve the precipitate by adding a small amount of purified water to the precipitate, add ethanol to a concentration of 80%, and stir.
After standing for a time, the mixture was centrifuged to obtain a precipitate. g. The above operation f was repeated three times. The yield of acidic polysaccharide obtained from the oyster shell meat was 512g.

Production Example 5 Lactobacillus acidophilus
ophilus) (IFO13951) in the medium indicated below.
After incubation at 37 ° C., it was treated twice bacteria and fermented metabolites treatment pressure 700 kg / cm ² at microfluidizer,
The solution was filtered through a 0.1 μm membrane filter. Its nitrogen content was 0.12% by weight (N). Medium composition Polybeptone 5 g Yeast extract 5 g Glucose 5 g Lactose 2 g Polyoxyethylene (20E.O.) monooleate 0.5 g Magnesium sulfate heptahydrate 1 g Add purified water to 1 liter, adjust to pH 6.8-7.0 Was.

Production Example 6 Hydrolyzate 1 of rice bran extract was obtained by the following method. Rice bran 2
00g to 800ml of 0.1N aqueous sodium hydroxide solution
Soaked for 24 hours at room temperature. Next, insoluble matter is removed by filtration,
The filtrate was sequentially treated with actinase, pepsin and trypsin. Enzyme treatment was carried out by using 10 mg of each enzyme and maintaining each at the optimum pH of each enzyme at 40 ° C. for 2 hours. The enzyme-treated solution obtained here was filtered to give a yellow transparent rice bran extract hydrolyzate 1 solution (solid content: about 1.0% by weight, weight average molecular weight: 2500 or less) 30
0 ml was obtained.

Production Example 7 A hydrolyzate 2 of a rice bran extract was obtained by the following method. A rice bran extract hydrolyzate solution (solid content: about 1.0% by weight, weight average molecular weight: 2500 or less) 300 m in the same manner as in Production Example 6 except that papain is used instead of pepsin as the preparation enzyme
got l.

Production Example 8 A hydrolyzate 3 of a rice bran extract was obtained by the following method. Rice bran 1
00g to 400ml of 0.25N aqueous sodium hydroxide solution,
Soaked for 24 hours at room temperature. Next, insoluble matter is removed by filtration,
The filtrate was adjusted to pH 10 with a 2N aqueous sodium hydroxide solution and then kept at 80 ° C for 2 hours. The treated liquid obtained here was filtered to obtain 200 ml of a yellow and transparent rice bran extract hydrolyzate solution (solid content: about 1.0% by weight, weight average molecular weight: 2500 or less).

Production Example 9 A hydrolyzate 4 of a rice bran extract was obtained by the following method. 200 ml of the solution of the hydrolyzate 1 of rice bran extract prepared in the same manner as in Production Example 6 was concentrated and freeze-dried to obtain about 2.0 g of hydrolyzate of rice bran extract.

Example 1 A lotion as an external preparation for skin was prepared by mixing the following components in a conventional manner. In addition, the mixing ratio was shown by weight%. Olive oil 0.5 Polyoxyethylene (20E.O.) sorbitan monostearate 2.0 Polyoxyethylene (60E.O.) hydrogenated castor oil 2.0 Ethanol 10.0 Material obtained in Production Example 1 0.5 Material obtained in Production Example 5 0.5 L -Ascorbic acid-2-glucoside 2.0 1.0% sodium hyaluronate aqueous solution 5.0 Methyl parahydroxybenzoate 0.2 Purified water 77.3

Example 2 Solution A and solution B comprising the following components were each heated to 70 ° C., and solution A was gradually added to solution B while stirring, and then slowly stirred to 30 ° C. Upon cooling, a cream as a skin external preparation was prepared. In addition, the mixing ratio was shown by weight%. Liquid A formulation Squalane 20.0 Olive oil 2.0 Mink oil 1.0 Jojoba oil 5.0 Beeswax 5.0 Cetostearyl alcohol 2.0 Glycerin monostearate 1.0 Sorbitan monostearate 2.0 Solution B formulation Purified water 45.9 Polyoxyethylene (20E.O.) Sorbitan monostearate 2.0 Poly Oxyethylene (60E.O.) hydrogenated castor oil 1.0 Substance obtained in Production Example 2 0.5 Substance obtained in Production Example 5 0.5 L-ascorbic acid-2-glucoside 2.0 Glycerin 5.0 1.0% aqueous solution of sodium hyaluronate 5.0 Paraoxybenzoate Methyl acid 0.1

Example 3 In the composition of Example 1, 0.5% by weight of the substance obtained in Production Example 3, 0.5% by weight of the substance obtained in Production Example 4, and 0.5% by weight of the substance obtained in Production Example 6 % And add purified water
A lotion was prepared in the same manner as in Example 1 except that the content was 75.8% by weight.

Example 4 The substance obtained in Production Example 7 was added in an amount of 0.5% by weight, and a gentian extract (product name: Infran AT manufactured by Technoble Co.) was added in an amount of 0.5% by weight to the liquid B formulation in Example 2. Then, a cream was prepared in the same manner as in Example 2 except that purified water was changed to 44.9% by weight.

Example 5 The procedure of Example 1 was repeated, except that the substance obtained in Production Example 8 was added in an amount of 0.5% by weight to the composition of Example 1 to make purified water 76.8% by weight.
A lotion was prepared in the same manner as described above.

Example 6 A cream was prepared in the same manner as in Example 2 except that 0.5% by weight of the substance obtained in Production Example 9 was added to the solution B in Example 2 to make purified water 54.4% by weight. Prepared.

Comparative Example 1 A lotion was prepared in the same manner as in Example 1, except that the substances obtained in Production Examples 1 and 5 were not blended, and the purified water was changed to 78.3% by weight.

Comparative Example 2 Production Example 2 and Production Example 5 in Example 2 with B liquid blending
56.9% by weight of purified water without blending the substance obtained in
A cream was prepared in the same manner as in Example 2 except that

The lotions and creams obtained in Examples 1 to 6 were evaluated by the following methods. Use test 1 The face of seven women was divided into left and right, one set with the lotion and cream of each example, and the other set with the lotion and cream of the comparative example, and used at least once a day. Three months later, they evaluated skin luster, whitening, improvement of dark spots, skin sticking, and prevention of skin roughness. In addition, 21 people were divided into 3 groups, and tests were performed using each sample according to the evaluation experiment numbers shown in Table 1 below.

[0057]

[Table 1]

The evaluation was made according to the following evaluation criteria, and the results are summarized in Table 2 below. Evaluation criteria Examples are much better 3 Examples are much better 2 Examples are slightly better 1 No difference 0 Comparative examples are slightly better -1 Comparative examples are much better -2 Compare Example is much better -3

[0059]

[Table 2]

As shown in Table 2, the external preparation for skin of the present invention was superior to the comparative example in the improvement of skin luster, whitening, darkening, and prevention of skin sticking and roughening. .

The lotion of Example 1 and the cream of Example 2 containing 0.25% by weight of the substance obtained in Production Example 1 and 0.25% by weight of the substance obtained in Production Example 2 were the same as in Evaluation Experiment No. 1. As a result, similar results were obtained for the improvement of skin luster, whitening and blemishes, and for preventing skin sticking and roughening.

[0062]

The external preparation for skin of the present invention comprises a hydrolyzate of conchiolin and / or a substance obtained by treating a hydrolyzate of conchiolin with succinic anhydride, an ascorbic acid derivative, and a metabolite of fermented lactic acid bacteria. The combination is excellent in early recovery of skin fatigue, pigment bleaching, prevention of skin aging, fine wrinkles, and gloss.

Further, it contains at least one substance selected from the group consisting of a hydrolyzate of a rice bran extract, an extract of a Gentianaceae plant, a processed mucilage of shellfish, and an acidic polysaccharide obtained from shellfish meat. The lactic acid bacteria fermentation metabolite is Lactobacillus acidophilus.
acidophilus) and the fermented metabolite of the cells are crushed, and the hydrolyzate of the rice bran extract is obtained by treating the alkaline extract of rice bran with two or more proteases. The proteolytic enzyme thus obtained comprises a combination of (a) actinase and (b) at least one enzyme selected from the group consisting of pepsins, trypsins, papains, peptidases and bromelain; Since the above ascorbic acid derivative is a stabilized ascorbic acid derivative, it has an unprecedented effect on skin luster, whitening, improvement of dullness, prevention of skin sticking and rough skin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 31/375 A61K 35/56 35/56 35/74 G 35/74 35/78 U 35/78 C A61P 17/00 A61P 17/00 43/00 111 43/00 111 A61K 37/02 F-term (reference) 4C083 AA031 AA071 AA082 AA111 AA112 AA122 AC022 AC072 AC102 AC122 AC422 AC432 AC442 AC482 AD212 AD332 AD392 AD411 AD641 CC04 CC05 EE12 EE16 4C08 A AA03 BA44 CA51 MA02 MA22 MA28 MA63 NA05 ZA892 ZC022 ZC412 4C086 BA18 MA03 MA04 NA05 ZA89 ZC02 ZC41 ZC75 4C087 AA01 AA02 AA04 BB13 BC58 MA02 MA63 NA05 ZA89 ZC02 ZC41 4C088 AB67 AB41 AD22 BA08 CA03

Claims (6)

[Claims] 1. A hydrolyzate of conchiolin and at least one substance selected from the group consisting of a substance obtained by treating the hydrolyzate of conchiolin with succinic anhydride; an ascorbic acid derivative; An external preparation for skin, characterized by being compounded with a substance. 2. At least one substance selected from the group consisting of a hydrolyzate of a rice bran extract, a plant extract of Gentianaceae, a processed mucilage of shellfish, and an acidic polysaccharide obtained from shellfish meat. The external preparation for skin according to claim 1, wherein the external preparation comprises: 3. The method according to claim 1, wherein the fermented metabolite of the lactic acid bacterium is obtained by crushing cells of Lactobacillus acidophilus and fermented metabolites of the cells. External preparation for skin. 4. The hydrolyzate of the rice bran extract obtained by treating an alkaline extract of rice bran with two or more proteases. The topical skin preparation according to the above. 5. The proteolytic enzyme comprising: (a) an actinase; and (b) pepsin, trypsin, papain,
The skin external preparation according to claim 4, comprising a combination with at least one enzyme selected from the group consisting of peptidases and bromelain. 6. The ascorbic acid derivative according to claim 1, wherein the L-ascorbic acid-2-phosphate, L-ascorbic acid-2-sulfate, L-ascorbic acid-2-glucoside, and L-ascorbic acid-5. 6. A derivative according to claim 1, wherein the derivative is at least one selected from the group consisting of -glucoside.
An external preparation for skin as described in the item.