JP2013075849A - Gallotannin-containing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent coloring of a plant extract containing gallotannin without impairing its whitening ability.SOLUTION: The plant extract containing gallotannin is combined with ethylenediamine disuccinate to obtain a gallotannin-containing composition that has whitening ability and is free from the problem of coloring.

Description

  The present invention relates to a composition comprising (A) a plant extract containing gallotannin and (B) ethylenediamine disuccinic acid or a salt thereof. Moreover, this invention relates to the coloring prevention method of the plant extract containing gallotannin.

  Gallotannin refers to a group of compounds having a structure in which a galloyl group is bonded to glucose. Gallotannin is known to have a whitening effect (Patent Document 1: Japanese Patent Application Laid-Open No. 2008-214272) and is used in cosmetics and the like. Although gallotannins can be chemically synthesized, plant-derived ones are generally preferred by consumers as cosmetic raw materials. However, in general, plant-derived raw materials are a mixture of many compounds, and when blended in cosmetics, problems of coloring and precipitation often occur over time. In order to solve this problem, for example, a method of adding a porphyrin metal complex and an organic reducing agent (Japanese Patent Laid-Open No. 63-145213), a method of adding an antioxidant such as ascorbic acid (Japanese Patent Laid-Open No. 6-239716) Etc. are known. However, in the method using a porphyrin metal complex, since the porphyrin metal complex itself is colored, the blending amount is limited and it cannot be said that it is sufficient in actual implementation. Antioxidants such as ascorbic acid have still not been sufficiently effective.

JP 2008-214272 A JP 63-145213 A JP-A-6-239716

  An object of the present invention is to prevent coloring without impairing the whitening effect of a plant extract containing gallotannin.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have found that ethylenediamine disuccinic acid significantly prevents coloring of a plant extract containing gallotannin and completed the invention.

That is, the present invention includes the following aspects.
[1]
(A) A plant extract containing gallotannin, and (B) a composition containing ethylenediamine disuccinic acid or a salt thereof.
[2]
2. The composition according to 1 above, wherein gallotannin is a compound in which 4 to 12 gallic acids are bonded to the hydroxyl group of glucose.
[3]
3. The composition according to 1 or 2 above, wherein the plant is one or more selected from the group consisting of pentaploid, gallic, glaze and large yellow.
[4]
4. The composition according to 1 to 3 above, wherein 50% to 90% by weight of all gallotannins contained in the composition is pentagalloylglucose.
[5]
5. The composition according to 1 to 4 above, containing from 0.01 to 100 parts by weight of ethylenediamine disuccinic acid or a salt thereof with respect to 100 parts by weight of gallotannin.
[6]
Cosmetics containing the composition of said 1-5.
[7]
A method for preventing coloration of a plant extract containing gallotannin, which comprises adding ethylenediamine disuccinic acid or a salt thereof to a plant extract containing gallotannin.
[8]
8. The method according to 7 above, further comprising removing the added ethylenediamine disuccinic acid or a salt thereof.

  According to the present invention, it is possible to provide a gallotannin-containing composition having a whitening effect and having no coloring problem.

FIG. 1 is a diagram showing a whitening effect of a plant extract (an extract of A-1 and an extract of A-5) containing gallotannin.

  Hereinafter, the present invention will be described in detail.

  The composition of the present invention contains (A) a plant extract containing gallotannin and (B) ethylenediamine disuccinic acid or a salt thereof.

[(A) Plant extract containing gallotannin]
In the present invention, gallotannin refers to a group of compounds in which the carboxyl group of gallic acid is ester-bonded to the hydroxyl group of glucose. Specific examples include compounds in which one or more gallic acids are bonded to the hydroxyl group of glucose, such as monogalloyl glucose, digalloyl glucose, trigalloyl glucose, tetragalloyl glucose, pentagalloyl glucose, hexagalloyl glucose, Examples include heptagalloyl glucose octagalloyl glucose, nonagaroyl glucose, decagalloyl glucose, undecagalloyl glucose, and dodecagalloyl glucose. From the viewpoint of whitening, a compound in which 4 to 12 gallic acids are bonded to the hydroxyl group of glucose is preferable, a compound in which 4 to 7 gallic acids are bonded to the hydroxyl group of glucose is more preferable, and 4 to 6 compounds are bonded to the hydroxyl group of glucose. More preferred is a compound in which five gallic acids are bonded to the hydroxyl group of glucose, that is, pentagalloylglucose.

  In the present invention, pentagalloylglucose means 1,2,3,4,6-penta-O-galloyl-β-D-glucose and has the following structure.

  The extract of the present invention can be obtained from plants such as pentaploids, gallic varieties, glazes, Daihuang, strawberry plum skin, cinnamon bark, radish peel, bilberry leaves, peony skin, rhododendron, ground peony and peony skin. These may use only 1 type and may use 2 or more types. Ploidy, gallic, glaze and Daihuang are more preferred, quintup and gallic are more preferred, and quintuplet is even more preferred.

  Extraction can be performed using water, an alcohol such as methanol or ethanol, a hydrophilic organic solvent such as acetone, and a mixture thereof as an extraction solvent. Of these, water and / or alcohol are preferably used, and ethanol is more preferably used as the alcohol. In particular, it is more preferable to use hydrous ethanol. The ethanol concentration in the water-containing ethanol can be 40 to 90% by volume, preferably 60 to 80% by volume, when the total volume of the water-containing ethanol is 100% by volume. After extraction, the extraction solvent can be removed and the extract can be obtained as a solid.

  The extract of the present invention contains several types of gallotannins, but the desired gallotannins can be increased by separating and purifying using methanolysis, recrystallization, re-extraction, and / or liquid chromatography as appropriate. It can be included. The desired gallotannin is preferably gallotannin in which 4 to 12 gallic acids are bonded to the hydroxyl group of glucose, more preferably a compound in which 4 to 7 gallic acid is bonded to the hydroxyl group of glucose, from the viewpoint of preventing coloring. A compound in which 4 to 6 gallic acids are bonded to the hydroxyl group is more preferable, and pentagalloylglucose is still more preferable. Of the total gallotannins contained in the composition of the present invention, 50% by weight to 100% by weight is preferably the desired gallotannin, more preferably 75% by weight to 99.7% by weight, and even more preferably 80% by weight to 96 wt%, even more preferably 90 wt% to 95 wt%. It is particularly preferable that 50% to 90% by weight of all gallotannins contained in the composition is pentagalloylglucose.

[(B) Ethylenediamine disuccinic acid or its salt]
Examples of ethylenediamine disuccinic acid include ethylenediamine disuccinic acid, 1,3-propanediamine disuccinic acid, (S, S) -ethylenediamine diglutaric acid, 1,3-propanediamine diglutaric acid, and 2-hydroxy-1,3. -Propanediamine disuccinic acid and 2-hydroxy-1,3-propanediamine diglutaric acid. These may be hydrates. Examples of the salt include alkali metal salts such as potassium salt and sodium salt, ammonium salt, and amine salt. Ethylenediamine disuccinic acid alkali metal salt is preferable, and ethylenediamine disuccinic acid trisodium salt is more preferable.

  In the composition of the present invention, ethylenediamine disuccinic acid or a salt thereof is added by 0.01 parts by weight or more with respect to 100 parts by weight of gallotannin. 0.1 parts by weight or more is preferable, 0.2 parts by weight or more is more preferable, 0.5 parts by weight or more is further preferable, and 1 part by weight or more is even more preferable. The upper limit is not particularly limited, but is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

  As long as ethylenediamine disuccinic acid or a salt thereof is mixed evenly with a plant extract containing (A) gallotannin, the anti-coloring effect of the present invention is exhibited. , The anti-coloring effect can be maintained.

  The composition of the present invention has a whitening action and can be used for cosmetics (including quasi drugs) and pharmaceuticals. Cosmetics include cleansing cream, facial cleanser, facial cleanser, body shampoo, various soaps, hair remover, face pack, face mask, emulsion, lotion, lotion, beauty essence, cream, hand cream, makeup products, sunscreen Skin care products such as products, wet tissues, after-shave lotions and shaving foams, shampoos, hair rinses, hair conditioners, split hair coats, hair creams, first and second agents for permanent waves, set lotions, hair dyes, dyes Hair cosmetics such as hair, liquid hair conditioner, hair nourishing and hair restorer are listed.

  For cosmetics, the composition of the present invention is 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, still more preferably 0.05% by weight or more, and even more preferably. Contains 0.1% by weight or more. Although there is no restriction | limiting in particular in an upper limit, 10 weight% or less is preferable and 5 weight% or less is more preferable.

  Before blending the composition of the present invention in a cosmetic, (B) ethylenediamine disuccinic acid or a salt thereof can be separated by a usual separation means such as extraction.

  Various other components can be used for the cosmetics of this invention as needed. For example, nonionic, anionic or cationic surfactants, colorants, viscosity modifiers, antioxidants, pH adjusters, fragrances, antibacterial / antifungal agents, preservatives, physiologically active substances and the like can be mentioned.

[Coloring prevention method]
As one aspect of the present invention, there is provided a method for preventing coloration of a plant extract containing gallotannin, which comprises adding ethylenediamine disuccinic acid or a salt thereof to the plant extract containing gallotannin.

  The plant extract containing gallotannin is dissolved as it is, or the plant extract containing gallotannin is dissolved in a solvent, and ethylenediamine disuccinic acid or a salt thereof is added. Examples of the solvent include lower alcohols such as water, methanol, ethanol, propanol, butanol, isopropanol, and t-butanol, and polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycol.

  Ethylenediamine disuccinic acid or a salt thereof is added in an amount of 0.01 parts by weight or more with respect to 100 parts by weight of gallotannin. 0.1 parts by weight or more is preferable, 0.2 parts by weight or more is more preferable, 0.5 parts by weight or more is further preferable, and 1 part by weight or more is even more preferable. The upper limit is not particularly limited, but is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.

  As long as ethylenediamine disuccinic acid or a salt thereof is mixed evenly with a plant extract containing (A) gallotannin, the anti-coloring effect of the present invention is exhibited. , The anti-coloring effect can be maintained.

  The present invention will be described in more detail with reference to examples. However, the present invention is not limited only to the following embodiments.

Plant extracts containing gallotannins In the examples, plant extracts from A-1 to A-6 were used. The content of each gallotannin was measured using liquid chromatography (LC-10 manufactured by Shimadzu Corporation). Ultraviolet absorption 220 nm was used for detection.

[Extract of A-1]
“BREWTAN” manufactured by AJINOMOTO OMNICHE SA (NV) (crude tannic acid average molecular weight of about 1800, derived from pentaploid)

[Extract of A-2]
10 g of “TANAL 02” (crude tannic acid average molecular weight of about 900, derived from pentaploid) manufactured by Ajinomoto Omnichem SA. NV is dissolved in 40 mL of methanol and 40 mL of 0.25 M sodium acetate buffer solution (pH 5), and 15 times at 50 degrees. Time, methanolysis was performed. A 0.25M aqueous sodium hydroxide solution was added to adjust the pH to 6, and then methanol was removed under reduced pressure. 10 mL water and 50 mL diethyl ether were added and the diethyl ether layer was removed. 10 mL of ethyl acetate was added, sonication was performed for 30 minutes, and the ethyl acetate layer was taken. This was repeated 5 times, and the ethyl acetate layers were combined and removed under reduced pressure to obtain a solid.

[Extract of A-3]
The extract of A-2 was dissolved in 10 mL of ethyl acetate and 10 mL of isopropyl acetate, 10 mL of water was further added, the organic solvent layer was taken, and the organic solvent was removed under reduced pressure to obtain a solid.

[Extracts of A-4, A-5 and A-6]
The extract of A-3 was repeatedly recrystallized using a 2% aqueous methanol solution, and extracts of Production Examples 4, 5, and 6 were obtained in this order.

(A) Preparation of a plant extract containing gallotannin and (B) ethylenediamine disuccinic acid or a salt thereof 5.0 g of each of the extracts as a solid was taken as 1,3-butylene. Glycol / water = 30/70 (wt / wt) dissolved in 95.0 g while heating, and further 10 mg of ethylenediamine disuccinate trisodium (manufactured by Kyrest Co.) was added, and the composition of Table 2 Examples 1-4 I got a thing. Similarly, 5.0 g of the extract was used as a solid and prepared at the ratios shown in Tables 3 to 4, and compositions of Examples 5 to 9 and Comparative Examples 1 to 12 were obtained.

In addition, the material used in Comparative Examples 7-12 is as follows.
Sodium ethylenediaminetetraacetate: Wako Pure Chemical Industries, Ltd. Ascorbic acid: Wako Pure Chemical Industries, Ltd. Succinic acid: Nacalai Tesque, Inc. Gluconic acid: Junsei Chemical Co., Ltd. Metaphosphoric acid: Kanto Chemical Co., Ltd. 1-hydroxyethane-1,1- Diphosphonic acid: manufactured by Lion

[Coloring evaluation]
These compositions were stored at 40 ° C. for 1 month and then evaluated for coloration at 25 ° C. The degree of coloring was evaluated as an AHPA value and evaluated according to the following criteria.
Less than 50: ◎
50 or more and less than 100: ○
100 or more and less than 200
200 or more: ×

  When Examples 1-4 and Comparative Examples 1-4 were contrasted, it was shown that ethylenediamine disuccinate markedly prevents coloring of plant extracts containing gallotannins. Moreover, the composition of Examples 2-4 using the extract of A-2, A-3, and A-5 whose 50 to 90 weight% is pentagalloyl glucose among the total gallotannins contained in a composition. The product is not colored compared to the composition of Example 1 using an extract of A-1 in which 4.3% by weight of the total gallotannin contained in the composition is pentagalloyl glucose. It was done.

  The compositions of Examples 5 to 9 in which 0.1 parts by weight or more of ethylenediamine disuccinate was added to 100 parts by weight of a plant extract containing gallotannin were comparative examples in which ethylenediamine disuccinate was not added. Compared to 5 and 6, it was shown not to be colored. Moreover, the composition of Examples 5-7 and 9 which added 0.2 weight part or more of ethylenediamine disuccinate with respect to 100 weight part of plant extracts containing gallotannin was carried out in which 0.1 weight part was added. Compared to the composition of Example 8, it was shown not to be colored.

  By contrasting Example 9 and Comparative Examples 7 to 12, it was shown that only ethylenediamine disuccinate prevents coloring of plant extracts containing gallotannins. Even if it is a compound known to have chelating ability, not all compounds can prevent coloring of a plant extract containing gallotannin, and it is an effect peculiar to ethylenediamine disuccinate I understood.

  Take 5.0 g of the A-4 extract as a solid, dissolve it with heating to 95.0 g of 1,3-butylene glycol / water = 30/70 (wt / wt), and then add ethylenediamine. After adding 25 mg of disodium disuccinate (manufactured by Kirest Co., Ltd.) and stirring, a composition obtained by removing ethylenediamine disuccinate 3Na by a liquid-liquid phase extraction method was evaluated in the same manner as described above. The result was ◎.

[Black melanin production inhibition test]
The whitening action of the extract of A-1 and the extract of A-5 was evaluated using the ability to suppress melanin as an index.

  B16 melanoma was cultured in DMEM (Dulbecco's Modified Eagle Medium) (high glucose, containing 10% serum). Confluent cells were detached with trypsin and seeded in a 96-well plate. On the next day, after the cells adhere to the plate, DMEM to which a control (no extract added), an A-1 extract, and an A-5 extract were added at a predetermined evaluation concentration (0.00286 wt% to 2-fold dilution) The medium was changed and cultured for 3 days. The 96-well plate was shaken for 5 minutes with a plate shaker, and the absorbance at 450 nm was measured with a microplate reader (Benchmark microplate reader, manufactured by BIORAD), and the amount of melanin in the medium of each well was compared. When the measured value (absorbance) of the control (no sample addition) was defined as 100%, the absorbance after 3 days after the addition of each sample at a predetermined concentration was shown as a relative%. The results are shown in FIG.

  It was revealed that all the extracts used in the present invention have a whitening effect. Furthermore, the extract of A-5 in which the content of pentagalloylglucose was increased to 85% was observed to have a higher melanin production inhibition rate than the extract of A-1 having a low content of the component. Therefore, it has been clarified that the present invention provides a composition containing a plant-derived gallotannin and free from coloring problems.

  According to the present invention, a composition containing a plant-derived gallotannin and having no coloring problem can be provided.

Claims (8)

(A) A plant extract containing gallotannin, and (B) a composition containing ethylenediamine disuccinic acid or a salt thereof.   The composition according to claim 1, wherein gallotannin is a compound in which 4 to 12 gallic acids are bonded to a hydroxyl group of glucose.   The composition according to claim 1 or 2, wherein the plant is one or more selected from the group consisting of pentaploid, gallic, glaze and large yellow.   The composition according to claim 1, wherein 50% to 90% by weight of all gallotannins contained in the composition is pentagalloylglucose.   The composition according to claims 1 to 4, comprising 0.01 to 100 parts by weight of ethylenediamine disuccinic acid or a salt thereof with respect to 100 parts by weight of gallotannin.   A cosmetic comprising the composition according to claim 1.   A method for preventing coloration of a plant extract containing gallotannin, which comprises adding ethylenediamine disuccinic acid or a salt thereof to a plant extract containing gallotannin.   The method according to claim 7, further comprising removing the added ethylenediamine disuccinic acid or a salt thereof.

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