JPH0696510B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by containing an ascorbic acid-tannin conjugate as an active ingredient, which has a skin-beautifying effect, a whitening effect,
The present invention relates to cosmetics having excellent moisturizing effect.

Since ancient times, many basic cosmetics have been proposed for the purpose of smoothing skin, beautiful skin, and whitening, and some effects were obtained.

From the viewpoint of wound healing action and cell activating action, the present inventor conducted extensive research into the natural product active ingredient, and as a result, an ascorbic acid-tannin conjugate having a structure in which ascorbic acid and tannins are bound to the skin has a preferable action. That is, the present invention has been completed by discovering that it has effects such as beautiful skin, whitening, and moisturizing.

That is, the present invention relates to a cosmetic composition containing an ascorbic acid-tannin conjugate as an active ingredient.

The present invention will be described in detail below.

The ascorbic acid-tannin conjugate applied to the present invention is usually obtained by binding ascorbic acid and tannins by a chemical reaction or a microbial technique, and is obtained by extraction from a plant such as Ganoderma lucidum. It is also possible. The above-mentioned ascorbic acid-tannin conjugate is generally a white or pale yellow to yellow powder, is easily dissolved in water, and is safe when eaten or applied to the skin. Ascorbic acid described above - In the production of tannin conjugates, ascorbic acid, a raw material used will generally be those known as vitamin C, chemical name L- ascorbic acid _{(C 6 H 8 O 6:} 176.1
3). Known tannins can be used as the other raw material, and examples of such tannins include, for example, licorice, akamegashiwa, sardine, ginger ginger, waremoko, assenyaku, swordbird, mokumaou,
Extracts such as Gobaishi, green tea, black tea, mao huang, etc., telkevin, quebric acid, quebrag acid, malotsic acid, punicalagin, geraniin, arnushiin, catechin, epicatechin, gallocatechin, epigallocatechin and the like in the tannin used in the present invention. It is included. Among the above-mentioned tannins, geraniin extracted from Gensho ginger and Asenyaku tannin extracted from Asenyaku have excellent properties and are preferably used in the present invention.
Incidentally, the composition obtained by reacting the powder or the like of the crude drug directly or together with other raw materials or solvents with ascorbic acid, as long as the tannins contained in the crude drug are bound to the ascorbic acid. Needless to say, it is included in the present invention.

Next, the method for producing the ascorbic acid-tannin conjugate of the present invention will be described in detail.

The aforementioned ascorbic acid-tannin conjugate is made by known methods. For example, 1 to 2 moles of tannins and 2 to 10 moles of ascorbic acid are added to a water-alcohol mixed solvent and mixed and stirred to uniformly dissolve or disperse, or as it is, or an acid or a buffer solution is added to a temperature of 40 ° C or lower. Warm and leave to react for several hours with stirring. Next, a method for obtaining an ascorbic acid-tannin conjugate by isolating the ascorbic acid-tannin conjugate from the obtained reaction solution using column chromatography or the like, distilling off the solvent under reduced pressure, and further drying under reduced pressure or freeze-drying. And so on. Here, what is important is that the reaction temperature is not too high, and when heated to a temperature of 60 ° C. or higher, the tannins are classified, so that the intended product cannot be obtained. Of course, the ascorbic acid-tannin conjugate of the present invention is not particularly limited as long as it exists as long as ascorbic acid and tannins are bound by a chemical bond, and is limited to the above production method. is not.

Next, in order to explain the present invention in more detail, the ascorbic acid-tannin conjugate provided by the present invention will be described in detail below taking an ascorbic acid-geraniin conjugate as an example.

First, a production example of an ascorbic acid-geraniin conjugate is shown below.

Production Example-1 Production of ascorbic acid-geraniin conjugate Geraniin 200 g was uniformly dissolved in 30 l of a water-methanol 9: 1 weight mixture, and 200 g of ascorbic acid was dissolved in 20 l of the solution, and the mixture was stirred. It should be uniform. Next, the pH is adjusted to about 4 using a citric acid-dibasic sodium phosphate buffer, heated to 37 ° C., and left to react for 18 hours while slowly mixing and stirring. Next, this reaction solution was concentrated under reduced pressure, and the ascorbic acid-geraniin conjugate was isolated from the resulting concentrated solution by using resin column chromatography (Toyopearl HW-40F), and the solvent was distilled off under reduced pressure and further coarsely pulverized. After drying under reduced pressure, 80 g of an ascorbic acid-geraniin conjugate was obtained. (Yield about 34%) The ascorbic acid-geraniin conjugate thus obtained is a white-white amorphous powder and has the following characteristic values.

Solubility Easily soluble in water, methanol, ethanol and alcohols.

Hardly soluble in ethyl acetate.

Insoluble in ether and non-polar solvents.

Melting point 360 ° C or more Specific rotation [α] ¹⁵ D + 26 ° (C = 1, MeOH) Ultraviolet absorption spectrum λmax, MeOH, nm 223 (4.89), (logε) 282 (4.50) Infrared absorption spectrum λmax (KBr) cm ^-1 3430, 1800, 1750-1730, 1625 Thin layer chromatography (Cellulose TLC) Developing solvent 7% acetic acid aqueous solution Rf value 0.25 1 spot Confirmation of spots Gray ferric chloride and orange yellow with sodium nitrite-acetic acid After that, it becomes grayish blue and then becomes yellowish brown.

The structural formula of the ascorbic acid-geraniin conjugate estimated from the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the like is represented by the following formula (1).

Another manufacturing example is shown below.

Production Example-2 Production of Ascorbic Acid-Genoshocotannin Conjugate 200 g of geraniin of Production Example-1 was extracted from Genoshoco extract 20
What is 0g. 64 g of an ascorbic acid-genoshokotanin conjugate was obtained. (The extract of Geno ginger was extracted from the powder of Japanese Pharmacopoeia Geno Ginger) with methanol. Production Example-3 Production of ascorbic acid-acene yak tannin conjugate Dissolve it uniformly and add 500 g of ascorbic acid to it.
Is added to 20 liters of water, mixed and stirred to make uniform. Next, the pH is adjusted to 4 using a citric acid-dibasic sodium phosphate buffer solution, heated to 37 ° C., and allowed to react for 18 hours while slowly mixing and stirring. Next, this reaction solution was concentrated under reduced pressure, and the ascorbic acid-acene yak tannin conjugate was isolated from the obtained concentrated solution using polyamide column chromatography, and the solvent was distilled off under reduced pressure and further coarsely pulverized and dried under reduced pressure. , 54 g of ascorbic acid-acene yak tannin conjugate was obtained. (Acenyak was obtained by extracting methanol from Acenyak powder of the Japanese Pharmacopoeia.) (Yield about 10%) Production Example-4 Ascorbic acid from ginger-
Extraction production of geraniin conjugate To 2 liters of acetone-water (7: 3 V / V) mixed solution was added to 500 g of dried aerial parts of Geno-shokusho, thoroughly mixed with a mixer and filtered. This operation is repeated twice, and the filtrate is collected, concentrated under reduced pressure at a temperature of 40 ° C. or lower, and water is added to make 500 ml. This solution is washed twice with 100 ml of ethyl ether to remove ether-soluble matter. Then use 150-200 ml of ethyl acetate each time from this solution
Extraction is performed 20 times, and ethyl acetate is distilled off from the obtained extract under reduced pressure to obtain 40 g of an extract. Next, this extract was dissolved in 400 ml of a water-methanol (7: 3V / V) mixed solution and allowed to stand for 2 to 3 days, the precipitated geraniin crystals were filtered off, and the filtrate was concentrated and then centrifuged. The target fraction was obtained using countercurrent partition chromatography, and further purified using resin column chromatography (Sephadex LH20) to obtain 0.25 g of ascorbic acid-geraniin conjugate. (Yield about 0.05%) Production Example-5 Ascorbic acid from ginger ginger-
Extraction production of geraniin conjugate To 2 liters of acetone-water (7: 3 V / V) mixed solution was added to 500 g of dried aerial parts of Geno-shokusho, thoroughly mixed with a mixer and filtered. This operation is repeated twice, and the filtrate is collected, concentrated under reduced pressure at a temperature of 40 ° C. or lower, and water is added to make 500 ml. This solution is washed twice with 100 ml of ethyl ether to remove ether-soluble matter. Next, n-butanol (saturated with water) was added to this solution for 200 m each time.
It is extracted 5 times using 1 and n-butanol is distilled off from the obtained extract under reduced pressure to obtain 30 g of an extract. Next, the extract was dissolved in 300 ml of a water-methanol (7: 3 V / V) mixture,
After standing for 2-3 days, the precipitated geraniin crystals are filtered off, the filtrate is concentrated, and the target fraction is obtained using centrifugal countercurrent partition chromatography. Further, resin column chromatography (Sephadex LH20) is used. ) Was used to obtain 0.30 g of an ascorbic acid-geraniin conjugate.
(Yield about 0.06%) In addition, a cosmetic composition containing a water-soluble polymer substance in addition to the ascorbic acid-tannin conjugate has a more desirable skin-conditioning action. This is probably because on the skin, the water-soluble polymeric substance becomes a vehicle, which effectively transfers the ascorbic acid-tannin conjugate, which is the active ingredient, to the stratum corneum, increasing transdermal absorption. Be done. Such a water-soluble polymer substance has a molecular weight of 20.
00 or more, for example, polypeptides, water-soluble collagen, mucopolysaccharides, hyaluronic acid, gum, casein, dextrin, gelatin, pectin and the like,
One or more of these are used.

Next, the cosmetics provided by the present invention include creams, emulsions, lotions, essence lotions, packs, body lotions, suncare cosmetics, powder cosmetics, whitening cosmetics, lip balms, lip colors, and undermake-up. A lot of things such as makeup, foundation, soap, hair treatment, rinse, etc. can be mentioned, and the compounding amount of the ascorbic acid-tannin conjugate is arbitrarily selected according to the properties of the cosmetic, but usually about 10% to the total weight. 0.001-1
0% by weight, preferably 0.1 to 5% by weight. The amount of the water-soluble polymer substance is about 0.001 to 1% by weight based on the total weight.

Next, the compounding method may be ascorbic acid-tannin conjugate as it is or dissolved in water, alcohol, polyhydric alcohol or the like, and may be compounded in the cosmetic composition by the same method as in the case of compounding conventional medicinal ingredients and the like. it can.

Further, the cosmetics according to the present invention include the above-mentioned ascorbic acid-
In addition to tannin conjugates and water-soluble polymer substances, additives usually used in cosmetics, for example, hydrocarbons, silicone oils, esters, triglycerides, lanolin, waxes, waxes, fatty acids, higher alcohols, animal oils, Vegetable oils, metal soaps, fats and oils such as phospholipids, anionic surfactants, cationic surfactants, zwitterionic surfactants, surfactants such as nonionic surfactants, antioxidants, and fragrances , Dyes, pigments, alcohols, polyhydric alcohols, sugars, preservatives, sunscreen agents, water, humectants and the like can be added.

Next, with respect to the ascorbic acid-tannin conjugate used in the present invention, in order to confirm the skin conditioning effect, a wound healing test was conducted using rats, and the results are shown in Table 2. The test method is as follows.

<Sample> Oil-in-water cream containing no ascorbic acid-tannin conjugate (a) <Comparative example-1>, 0.5% blended (b) <Example-1>, 2% blended (c) )
<Example-2> The above three specimens are prepared as shown in Table 1 below.

Wound healing test As experimental animals, SD rats of 5 weeks old were preliminarily bred for 7 days after purchase, and 40 rats were divided into groups IV to 10 and used. First, the backs of the rats in each group are shaved using an electric clipper, and cleaned with water-ethanol 3: 7 disinfectant impregnated with absorbent cotton. After that, using circular chisel (φ11mm), make four symmetrical cutaneous lesions along the median line. Next, the group I was set as a non-treatment group, and the group II was applied once daily with the cream of Comparative Example-1 to give III and IV.
Similarly, the groups are the creams of Example-1 and Example-2, respectively.
Of cream was applied. All samples were applied once a day at 0.1 g per damaged site. The observation was performed once a day by measuring the wound area and observing with the naked eye. The wound area (mm ² ) in each group was the average value of 10 animals (rounded to the second decimal place), and the healing rate was calculated by the following formula.

As described above, the cosmetic containing the ascorbic acid-tannin conjugate has an excellent wound healing effect, has a fast wound healing, and has no treatment of the skin condition after the complete healing (20th day). It was more beautiful than the group and Comparative Example-1 group.

Next, the cosmetics applied to the invention were subjected to sensory evaluation after 30 days of continuous clinical test, and the results are shown in Table 3. At this time, the milky lotion of Example-4 and the lotion of Example-5 described below were used as the products of the present invention, and Example-as the control product.
The emulsion of 4 and the lotion of Example-5 from which the ascorbic acid-tannin conjugate was removed were used.

The test method is as follows.

Clinical test: A total of 20 men and women were panelists, the control product was used on the inside of the left upper arm, the product of the present invention was used on the inside of the right upper arm, and the product of the present invention or the control product was used on the face. It is applied twice a day in the same manner as in normal use, and this is continued for 30 days. After that, the sensory evaluation items such as skin adhesion, gloss, smoothness, and dullness are evaluated according to the following criteria.
The average value of the names was used as the evaluation score.

As described above, by continuously applying the cosmetics applied to the present invention to the skin, it exerts a favorable effect on the skin's acuity, gloss, smoothness, dullness, etc., and particularly, it maintains good skin acuity and It has a remarkable effect on the improvement of dullness. Further, it was confirmed by visual observation that the improvement of the dullness of the skin has not only the whitening effect on the entire skin but also the effect of lightening the color of the local stain.

Next, examples of the present invention will be described. Hereinafter, the blending amount is part by weight.

Example-3 Emollient cream (A) Cetanol 2 Geyrow 5 Liquid paraffin 7 Olive oil 18 Stearic acid 7 Sorbitan monostearate 4 Polyoxyethylene sorbitan monostearate (20EO) 4 (B) Ascorbic acid-Acenyak of Production Example-3 Tannin conjugate 5.5 Propylene glycol 10 Ethylparaben 0.1 Purified water 36 (C) Perfume Suitable amount The above formulation (A) is mixed and heated to 80 ° C. The above-mentioned formulation (B) is mixed and heated in the same manner as above, and what is heated to 80 ° C. is added, and the mixture is uniformly emulsified by a homomixer, and the above-mentioned (C) is added and cooled to obtain a product.

Example-4 Emulsion (A) Beeswax 1 Cetanol 1 Lanolin 3 Stearic acid 2 Liquid paraffin 7 Olive oil 3 Polyoxyethylene monooleate (10
EO) 2 Perfume Suitable amount (B) Ascorbic acid-genoshocotannin conjugate of Production Example-2 1.6 Hyaluronic acid 0.7 Glycerin 4 Propylene glycol 4 Triethanolamine 1 Methylparaben 0.3 Purified water 69 The formulation (B) is mixed and heated 70 ℃. The above-mentioned formulation (A) is mixed and heated in the same manner as above, and a mixture at 70 ° C. is added thereto.

Example-5 Stain removal lotion (A) 95% ethanol 30 1,3 Butylene glycol 4 Ethyl adipate 2 Jojoba oil 1 Polyoxyethylene hydrogenated castor oil (50E.O.) 1 Perfume 0.2 (B) Production Example-1 Ascorbic acid-geraniin conjugate 0.2 Citric acid 0.1 Sodium citrate 0.1 Purified water 60.6 The above formulation (A) is dissolved with stirring, and the above formulation (B) is added and mixed to obtain a clear liquid stain remover lotion. Obtained.

Example-6 Lotion (A) Ethanol 12.3 Glycerin 2 1-Menthol 0.02 Polyoxyethylene hydrogenated castor oil (50 E.O.) 0.5 Perfume Suitable amount (B) Ascorbic acid-geraniin conjugate of Production Example-5 0.02 Hydrolyzed collagen 0.05 Citric acid 0.1 Sodium citrate 0.2 Methylparaben 0.1 Allantoin 0.1 Purified water 84.5 The above formulations (A) and (B) are dissolved by heating, and (A) is added to the above formulation (B) to solubilize the product. .

Example-7 Whitening powder D-mannite 63 Squalene 1 Vitamin C dipalmitate 1 Ascorbic acid-geraniin conjugate of Production-1 35 Fragrance Appropriate amount The above formulation is mixed and stirred to obtain a product.

 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-58-38208 (JP, A) JP-A-59-216810 (JP, A) JP-A-62-207289 (JP, A) JP-A-59- 148712 (JP, A) JP 58-38209 (JP, A) JP 58-35962 (JP, B2)

Claims (8)

[Claims] 1. A cosmetic comprising an ascorbic acid-tannin conjugate as an active ingredient. 2. The cosmetic according to claim 1, wherein the ascorbic acid-tannin conjugate is obtained by binding ascorbic acid and tannins. 3. The cosmetic according to claim 1, which is obtained by extracting the ascorbic acid-tannin conjugate from a plant. 4. The cosmetics according to claim (1) or (3), wherein the ascorbic acid-tannin conjugate is obtained by extraction from Ganoderma lucidum. 5. The cosmetic material according to claim (1) or (3), wherein the ascorbic acid-tannin conjugate is obtained by extraction from Asenyaku. 6. The cosmetic composition according to claim (2), wherein the tannins are ginger-pepper extract or geraniin. 7. The cosmetic according to claim (2), wherein the tannins are Assen drug extracts. 8. The cosmetic according to claim 1 or 6, wherein a water-soluble polymer substance is added to the cosmetic.