JP2000119160A - Skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent skin bleaching preparation which has never existed conventionally by formulating a specific glycoside and a specified pharmacodynamic component. SOLUTION: This cosmetic comprises (A) at least one kind selected from the group consisting of a 2-18C α-hydroxycarboxylic acid (preferably a 2-8C α-hydroxycarboxylic acid), an essence of Swertia japonica, vitamin E-nicotinate, diisopropylamine dichloroacetate, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid and their salts and (B) a glycoside of the formula (R is a group selected from a monosaccharide and a disaccharide residues) (e.g. raspberry-ketone-D- glucoside). The preferable formulation amount of the component A is 0.01-20 wt.% in the case of the hydroxycarboxylic acid, 0.1-20.0 wt.% in the case of the essence of Swertia japonica and 0.01-5.0 wt.% in the other cases and that of the component B is 0.01-10.0 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to cosmetics and quasi-drugs.

[0002]

2. Description of the Related Art Conventionally, whitening cosmetics for the purpose of preventing or treating skin spots and freckles include L-ascorbic acid and its derivatives, hydroquinone derivatives, pyrones of kojic acid, placenta extract and the like. A placenta extract is included.

[0003] These substances have effects such as suppression of melanin production and light-color bleaching action of the produced melanin, and are widely known as substances having a whitening effect. However, when these substances are used alone, for example, L-ascorbic acid and its derivatives are not sufficiently storage-stable and their effects are not sufficiently exerted, and hydroquinone derivatives are not sufficiently effective, for example, due to safety problems. It was not something.

The glycoside represented by the above general formula 1 is known as a highly safe melanin production inhibitor, and a whitening cosmetic containing the same has been proposed (JP-A-10-17).
462). However, when used alone, it took a long time to obtain a sufficient effect.

[0005]

The present inventors have made intensive studies to solve the above-mentioned drawbacks, and as a result, have found that the number of carbon atoms is two.
Α-hydroxycarboxylic acid, assembly extract, vitamin E-nicotinate, diisopropylamine dichloroacetate, γ-aminobutyric acid, γ-amino-β
-At least one selected from the group consisting of hydroxybutyric acid and salts thereof, or rice bran, which is rice or a purified residue of rice, is extracted with a solvent, and the extract is further treated with an enzyme to obtain a decomposition product and a specific distribution. Skin cosmetics containing saccharides have an excellent whitening effect, such as quickly eliminating melanin present in the epidermis and suppressing the generation of new melanin in the skin, and an even better skin roughness prevention effect The present invention has been found to exhibit an anti-aging effect and a beautiful skin effect.

An object of the present invention is to prevent dark-skinned skin, to quickly lighten dark-skinned skin, and to provide excellent skin roughening prevention, keratin improvement, aging prevention and beautiful skin effects. Another object of the present invention is to provide a skin cosmetic which has a healthy skin.

[0007]

According to the first aspect of the present invention, there is provided an α-hydroxycarboxylic acid having 2 to 18 carbon atoms, an assembly extract, vitamin E-nicotinate, diisopropyl. At least one selected from the group consisting of amine dichloroacetate, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid and salts thereof, and a compound represented by the following general formula:

[0008]

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(Where R is a group selected from the residues of monosaccharides and disaccharides). A skin cosmetic comprising a glycoside represented by the formula:

[0010] Further, the invention of claim 2 of the present invention, which achieves the above object, provides a decomposed product obtained by extracting rice or rice bran, which is a purified residue of rice, with a solvent, and further treating the extract with an enzyme. And a skin cosmetic comprising the glycoside.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention is a skin cosmetic. Hereinafter, the configuration of the present invention will be described in detail. The α-hydroxycarboxylic acid used in the present invention is not particularly limited as long as it has 2 to 18 carbon atoms,
For example, glycolic acid, lactic acid, sodium lactate, citric acid, sodium citrate, malic acid, tartaric acid, α-hydroxyoctanoic acid, α-hydroxypalmitic acid, α
-Hydroxystearic acid and the like, among which those having 2 to 8 carbon atoms are preferable.

The compounding amount is preferably 0.01 to 20% by weight based on the total amount of the cosmetic.

The method for producing the assembly extract used in the present invention is not specified, but the outline is as follows.

Method for Producing Assembly Extract Assembly extract can be obtained from Swertia Jap.
This is an extract obtained by digesting a dried and crushed whole plant of S. onica Makino) in ethanol or water-containing ethanol, and filtering. In Examples, the extract obtained by the following method was used.

[0015] 50 g of the dried and pulverized assembly was added to 250 ml of aqueous ethanol (ethanol 90 wt%) at a temperature of 4 ml.
After being digested by filtration at 0 to 50 ° C., the residue was similarly digested again to obtain 1.5 liter of extract.
100 ml of purified water was added to the residue obtained by concentration under reduced pressure, and after aging for 1 week, the extract obtained by filtering off the insoluble matter was concentrated under reduced pressure, and then ethanol was added. (Wt%) to obtain 100 ml of the assembly extract.

As the γ-amino-β-hydroxybutyrate used in the present invention, γ-amino-β-hydroxybutyric acid is converted to potassium hydroxide, sodium hydroxide or calcium hydroxide,
Potassium salt, sodium salt, calcium salt and magnesium salt of γ-amino-β-hydroxybutyric acid neutralized with magnesium hydroxide, and all of them promote blood circulation to the same extent as γ-amino-β-hydroxybutyric acid. Has an action or cell activating action.

Table 1 shows the preferred amounts of the assembly extract, vitamin E-nicotinate, diisopropylamine dichloroacetate, γ-amino-β-hydroxybutyric acid and salts thereof used in the present invention.

[0018]

[Table 1]

Some of the glycosides used in the present invention are known substances (Pharmaceutical Magazine, Vol. 93, No. 6, pp. 733, 1).
973, and phytochemistry: Vol. 29, 12
No., 3853, 1990).

The glycoside of the present invention can be isolated and purified from natural products. In addition, a method already known as a method for synthesizing arbutin (USP 320)
No. 1385). For example, in an organic solvent such as toluene, 4- (p-hydroxyphenyl) -2-butanone (hereinafter abbreviated as raspberry ketone) and acetylated sugar are condensed using trifluorinated boric acid, phosphorus oxychloride or the like as a catalyst, and then alkali-existing. By removing the acetyl group below, the glycoside of the present invention can be easily obtained as white powdery crystals.

The sugar residue used in the present invention is a reducing monosaccharide or disaccharide, and specifically, monosaccharides such as glucose, galactose, xylose, mannose and N-acetylglucosamine, maltose, cellobiose and gentibiose. And the like. In the glycoside of the present invention, an isomer having an α bond and a β bond can be used either as a mixture or as a mixture thereof.

Specific glycosides used in the present invention include raspberry ketone-D-glucoside (α and β
), Raspberry ketone-D-galactoside (α and β forms), raspberry ketone-D-xyloside (α and β forms), raspberry ketone-D-maltoside (α and β forms), and the like. Among them, raspberry ketone-D-glucoside (β-form) is most preferred because of its existence in the natural world and availability. The glycoside according to the present invention has already been proposed as a "sustained release fragrance composition for human body" (Japanese Patent Application Laid-Open No. Hei 7-179328).

The compounding amount of the specific glycoside of the present invention is 0.01
１10.0% by weight is preferred, but not limited to this.

The extraction solvent for extracting rice or rice bran used in the present invention includes, for example, water such as purified water, monohydric lower alcohols such as ethanol, oleyl alcohol, stearyl alcohol, and octyldodecanol. Higher alcohols, polyols such as ethylene glycol, propylene glycol, glycerin and 1,3-butylene glycol, ketones such as acetone, esters such as ethyl acetate, and hydrocarbon solvents such as hexane, chloroform and benzene. And
These can be used alone or in combination of two or more. Among them, purified water, purified water and ethanol,
A mixed solvent with one or more of glycerin and 1,3-butylene glycol is preferred.

When the mixed solvent is used, for example, in the case of a mixed solvent of purified water and ethanol, the volume ratio of the two is 1: 1 to 25: 1, and the mixed solvent of purified water and glycerin is used. In this case, the capacity ratio between the two is 1: 1 to 15:
1, in the case of a mixed solvent of purified water and 1,3-butylene glycol, the volume ratio of the two is preferably 1: 1 to 15: 1.

In the present invention, the pH of the extraction solvent for rice or rice bran may be about 5 to 9 and the solvent may be used as it is, for example, sodium salts such as sodium hydroxide and sodium carbonate, and potassium hydroxide. Alkaline adjusters such as potassium salts and, for example, citric acid,
An acidic adjuster such as hydrochloric acid, phosphoric acid, sulfuric acid or the like may be added to the solvent to adjust the pH to a desired value. Among these modifiers, low concentration and desired pH
Sodium hydroxide, hydrochloric acid, and phosphoric acid are preferable in that they can be adjusted to be as follows.

The time required for the extraction cannot be determined unequivocally because it depends on the type of the solvent used, the target pH, the extraction temperature and the like.
In the case of 9, usually about 6 hours to 7 days at room temperature is preferable,
More preferably, it is about 12 to 48 hours. Note that the extraction temperature is preferably about 4 to 40 ° C, and more preferably about 10 to 30 ° C.

The extract thus obtained is treated with an enzyme to obtain an enzymatic degradation product. Examples of the enzyme include actinases such as actinase, pepsins such as pepsin, trypsins such as chymotrypsin, papains such as papain and chymopapain, peptidases such as glycylglycine peptidase, carboxypeptidase and aminopeptidase. And a proteolytic enzyme selected from promelain. Among them, a combination of actinase and pepsin, trypsin, papain, peptidase and at least one proteolytic enzyme selected from the group consisting of promelain,
It is preferable from the viewpoint that the storage stability and safety of the skin cosmetic containing the obtained degradation product are excellent, and a combination of actinase with pepsin and trypsin is particularly preferable.

In the present invention, when treating with two or more enzymes, one enzyme is usually used at a time.

The amount of the enzyme used at one time in the enzyme treatment is preferably about 0.0005 to 0.05% by weight, more preferably 0 to 0.05% by weight, based on 100% by weight of the extraction solvent containing rice or rice bran. It is preferably about 0.003 to 0.005% by weight, and the total amount is about 0.003 to 0.015% by weight in view of the effect of the enzyme.

The time required for the enzymatic treatment cannot be unconditionally determined because it varies depending on the type of the enzyme used, the decomposition temperature, and the like, but it is usually preferably about 30 minutes to 24 hours for one type of enzyme, and more preferably. It is about 1 to 4 hours. The decomposition temperature of the above exemplified enzyme is about 3
0-50 ° C.

When performing the enzyme treatment, the pH of the extraction solvent may be adjusted to be the optimum pH of the enzyme to be used. An acid conditioner and an alkalinity conditioner used for the extraction can be used.

The extract thus obtained may be incorporated directly into skin cosmetics, for example, may be concentrated under reduced pressure to adjust the concentration, and then may be incorporated, for example, by freeze-drying or spray-drying. May be compounded. In addition, it is preferable that the solution containing the obtained decomposed product is adjusted to pH 4 to 8 from the viewpoint of safety on the skin.

The compounding amount is preferably 0.00001 to 1% by weight in the total amount of the cosmetic in terms of solids.

The skin cosmetic of the present invention contains, in addition to the above-mentioned raw materials, dyes, fragrances, preservatives, surfactants, pigments, antioxidants, humectants, ultraviolet absorbers, etc. It can be appropriately blended within the range achieved.

The dosage form of the skin cosmetic of the present invention may be any dosage form generally used for cosmetics such as creams, emulsions, lotions, packs and the like.

[0037]

The present invention will be described below in detail based on examples and comparative examples. The percentages shown in the examples are percentages by weight. The skin color lightness recovery test method and sensory test (whitening effect) described in the examples are as follows. The method for preparing enzymatically degraded products and glycosides of the extract obtained by extracting rice or rice bran, which is a purified residue of rice, with a solvent used in the following Examples is as follows. Is not limited to these.

Preparation Example 1 (Production of Enzymatic Hydrolyzate of Rice Neutral Extract) 200 g of rice was added to 800 ml of purified water, and
The pH was adjusted to 6.0 to 8.0 with an aqueous solution of sodium hydroxide, and the mixture was immersed at room temperature for about 24 hours for extraction to obtain about 480 ml of an extract (solid content: about 1.5% by weight). Was.

To the extract thus obtained was added 5 mg of actinase (optimal pH 8.0), and the mixture was added at 30 to 40 ° C. for 1 hour.
Treatment for ~ 2 hours, then pepsin (optimal pH
2.0) 5 mg was added and the treatment was carried out at 30 to 40 ° C. for 1 to 2 hours, and finally trypsin (optimal pH 8.0)
5 mg was added and the treatment was carried out at 30 to 40 ° C. for 1 to 2 hours. In addition, when adding each enzyme, the extract was adjusted so that it might become the optimal pH of each enzyme. This was filtered to obtain about 250 ml of a pale yellow transparent enzyme decomposition product solution (solid content: about 2.0% by weight).

Preparation Example 2 (Production of Enzymatically Degraded Rice Bran Neutral Extract) Extraction solution (solid content: about 1) was prepared in the same manner as in Preparation Example 1 except that rice bran was used instead of rice. About 480 ml).

In the same manner as in Preparation Example 1 except that the extract obtained here was used in place of the extract of Preparation Example 1, a pale yellow transparent enzyme decomposition product solution (solid content: about 2.0 wt. %)
About 250 ml were obtained.

Preparation Example 3 (Production of Enzymatic Hydrolyzate of Rice Bran Neutral Extract) In Preparation Example 2, except that papain (optimum pH 7.0) was used in place of pepsin, a pale yellow color was obtained in the same manner as in Preparation Example 2. About 250 ml of a clear enzyme digest solution (solid content: about 2.0% by weight) was obtained.

Preparation Example 4 (Production of Spray-Dried Product of Enzymatic Hydrolyzate of Rice Bran Neutral Extract) 250 g of the enzymatic hydrolyzate solution obtained in Preparation Example 2 was spray-dried to obtain about 5 g of a dry powder of the hydrolyzate. Was.

(Method for synthesizing raspberry ketone glucoside) 2.76 g (1
6.8 mmol) raspberry ketone, 8 g (20 mm)
ol) of glucose pentaacetate and 2 g of molecular sieves, and the mixture was stirred at room temperature for about 1 hour. Then, 1 ml of a boron trifluoride diethyl ether solution was added, and the mixture was further stirred for 3 hours. After adding 20 ml of water, the molecular sieves were filtered off. The organic layer was separated from the filtrate and washed with 1N sodium hydroxide to remove unreacted raspberry ketone. The organic layer was washed with purified water and dried over sodium sulfate. After removing sodium sulfate, the organic solvent was removed under reduced pressure to obtain raspberry ketone tetraacetylglucoside.

Raspberry ketone tetraacetylglucoside was deacetylated using sodium methoxide according to a conventional method, and then neutralized using an ion exchange resin (Amberlite). After filtering off the ion exchange resin,
The solvent was removed under reduced pressure to obtain 3.4 g of raspberry ketone glucoside (β form). This structure was confirmed by a 13 C-NMR spectrum and an infrared absorption spectrum.

According to this method, raspberry ketone-D
-Glucoside (α and β forms), raspberry ketone-D
-Galactoside (α and β forms), raspberry ketone-
D-xyloside (α and β forms), raspberry ketone
Other glycosides such as D-maltoside (α and β forms) were obtained.

(1) Skin Color Brightness Recovery Test Method The UV light in the UV-B region was irradiated twice as much as the minimum erythema dose to the back skin of 20 subjects, and the sample application site and non-application site were set, and each skin was examined. The reference lightness (V0 value, V0 'value) was measured. Subsequently, the sample was applied twice a day to the application site.
After continuous application for 5 weeks, the lightness (Vn value, Vn) of the skin at the application site and the non-application site after 3, 6, 9, 12, and 15 weeks
n ′ value), and the recovery of skin color was evaluated according to the following criteria. The lightness of the skin (Munsell color system V
Value) was calculated from the X, Y, and Z values obtained by measuring with a high-speed spectral colorimeter. In addition, the evaluation was shown as an average value of the evaluation points after 3 weeks for 20 subjects.

(2) Measurement of keratin turnover speed An ointment containing 5% by weight of a fluorescent dye, dansyl chloride, in white vaseline was prepared and applied to the skin of the subject's forearm.
Apply time occlusion and osmotically bind dansyl chloride to the stratum corneum. Thereafter, the test sample was applied to the same site twice a day (morning and evening), the fluorescence of dansyl chloride was examined every day, and the number of days until the fluorescence disappeared was defined as the skin keratin turnover speed. The turnover speed of the normal skin stratum corneum is 14 to 16 days, but it extends around 18 days in aged skin, and decreases to around 12 days when the anti-aging effect appears.

(3) Method of Measuring the Effect of Improving Rough Skin The effect of continuous application for four weeks was examined on 20 middle-aged and elderly subjects having rough skin on the lower leg. About 1 g of a sample was applied to the left lower leg region of the subject twice a day, and the skin condition before and after the start of the test was determined according to the following criteria. The lower right leg served as a control without the application of the sample. By comparing the judgment results of the test site and the control site before and after the test, if the skin dryness is improved by two or more steps (for example,
−, ++ → ±) are regarded as “valid”, the case where one or more steps are improved is “slightly valid”, and the case where there is no change is “invalid”. The test results are shown by the number of subjects who became “effective” and “slightly effective”.

(4) Sensory Test Twenty test subjects evaluated the characteristics of the sample after continuously using the sample for 10 days. The evaluation was based on the number of respondents who answered "skin became smooth", "felt whitening effect", and "skin became tight" for the questionnaire items for smoothness, whitening effect, and elasticity. .

Examples 1 to 10 and Comparative Examples 1 to 10 Cell activators and specific glycosides were blended in the compositions shown in Tables 2, 3 and 4 and skin creams were prepared according to the usual preparation methods. . The above test was performed for each, and the results are shown in Table 5.

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

The skin creams of Examples 1 to 10 of the present invention show good results in the above tests. On the other hand, the skin creams of Comparative Examples 1 to 10 did not show a sufficient effect, and were inferior to the examples of the present invention.

Example 11 (Skin lotion) The skin lotion of the present invention was prepared according to the usual preparation method according to the composition shown in Table 6.

The skin lotion of Example 11 showed good results in the above tests.

Example 12 (Day Essence) According to the composition shown in Table 7, the day essence of the present invention (daytime serum) was prepared according to a usual preparation method.

[0060]

[Table 7]

The de-essence of Example 12 showed good results in the above tests.

Examples 13 to 18 and Comparative Examples 11 to 15 Cell activators and specific glycosides were blended in the compositions shown in Tables 8 and 9, and skin creams were prepared according to a conventional preparation method. The above test was performed for each, and the results are shown in Table 10.

[0063]

[Table 8]

[0064]

[Table 9]

[0065]

[Table 10]

The skin creams of Examples 13 to 18 of the present invention show good results in the above tests. On the other hand, the skin creams of Comparative Examples 11 to 15 did not show a sufficient effect, and were inferior to the Examples of the present invention.

Example 19 (Skin lotion) A skin lotion of the present invention was prepared according to the composition shown in Table 11 by a conventional method.

[0068]

[Table 11]

The skin lotion of Example 19 showed good results in the above tests.

Example 20 (Day Essence) According to the composition shown in Table 12, the day essence of the present invention (daytime serum) was prepared by a usual production method.

[0071]

[Table 12]

The de-essence of Example 20 showed good results in the above tests.

[0073]

As described above, it is apparent that the present invention provides a skin cosmetic having a whitening effect, a skin roughness preventing effect, an aging preventing effect, and a skin beautiful effect.

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/00 A61K 7/00 F (72) Inventor Kozue Hamada 5-3 Kotobukicho, Odawara City, Kanagawa Prefecture No. 28 Kanebo Co., Ltd. Cosmetics Research Institute F term (reference) 4C083 AA082 AA111 AA112 AB242 AC012 AC022 AC102 AC122 AC212 AC242 AC301 AC302 AC312 AC392 AC402 AC482 AC621 AC622 AC662 AD352 AD391 AD392 AD661 AD662 CC04 CC05 DD27 DD33 EE12 EE13 EE16 FF01

Claims (3)

[Claims] 1. A group consisting of α-hydroxycarboxylic acid having 2 to 18 carbon atoms, assembly extract, vitamin E-nicotinate, diisopropylamine dichloroacetate, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid and salts thereof. And at least one member selected from the group consisting of the following general formula: (Where R is a group selected from the residues of monosaccharides and disaccharides). A skin cosmetic comprising a glycoside represented by the formula: 2. A skin cosmetic comprising: a decomposed product obtained by extracting rice or rice bran, which is a purified residue of rice, with a solvent, and further treating the extract with an enzyme; and a glycoside as described above. . 3. An enzyme obtained by combining (A) an actinase with (B) at least one protease selected from the group consisting of pepsins, trypsins, papains, peptidases and promelain. Certain claim 2
The skin cosmetic according to the above.