JPH10158290A - Retional glycoside and cosmetic obtained by formulating the same glycoside - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new glycoside comprising a specific retinol glycoside and useful as a skin cosmetic, capable of imparting tenseness and gloss to skin and remarkably improved in preventing and improving effect on formula of wrinkles and slackness caused together with aging of skin. SOLUTION: This new retinal glycoside is represented by the formula [R is glucosyl residue such as glucose or galactose; (n) is an integer of 1-3] and useful as a component for skin cosmetic, etc., capable of imparting tenseness and gloss to skin and remarkably improved in preventing and improving effect on formation of wrinkles and slackness caused together with aging of skin. The compound is obtained by adding retinol, glucose pentaacetate and anhydrous iron (III) chloride to dichloromethane, mixing these components overnight at ambient temperature, cleaning dichloromethane solution of the product with a saturated aqueous solution of sodium hydrogencarbonate, washing the solution with water, adding sodium methoxide and ethanol to the concentrate, refluxing the solution for 6hr and concentrating the solution and purifying the concentrate with column chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cosmetic composition having significantly improved effects of preventing and improving skin aging.
More specifically, the present invention relates to a skin cosmetic excellent in the effect of improving wrinkles, rough and dry skin caused by aging of the skin.

[0002]

2. Description of the Related Art Skin is in a special environment where cells are directly exposed to the outside air, and is more susceptible to external factors than the aging phenomenon of internal organs. Skin aging includes biological aging due to aging and photoaging due to sunlight, which is the most influential of external factors, and it is thought that both proceed in combination. In general, it is said that qualitative and quantitative changes in components in the dermis tissue of the skin have a major effect as a main cause of formation of wrinkles and sagging of the skin, which is a measure of skin aging. That is,
The strength, flexibility and elasticity of the skin are determined mainly by fibrous protein components such as collagen fibers and elastin fibers, which are present in the dermal tissue, and these are protein denatured by various external or internal factors. It is thought that the elasticity is reduced and wrinkles and sagging are caused as a result. Various types of cosmetics are provided for the purpose of preventing skin aging and improving wrinkles by giving the skin shine and gloss to such aging phenomena and preventing or improving the occurrence of wrinkles and sagging. Products have been proposed.

[0003] As typical examples, polyhydric alcohols (glycerin, propylene glycol, sorbitol, etc.), natural moisturizing factors:
Amino acids, lactates, sodium pyrrolidone carboxylate, urea), acidic mucopolysaccharides (hyaluronic acid, chondroitin sulfate, etc.), vegetable polysaccharides (pectin, carrageenan, trehalose, etc.), animal polysaccharides (chitin derivatives, chitosan derivatives, etc.), Fibrous protein (collagen, elastin, placenta, etc.), intercellular lipid (phospholipid, sphingolipid,
There are cosmetics containing moisturizing ingredients such as sterols and sebum-like substances (olive oil, jojoba oil, squalane, etc.). These are used to maintain and enhance the moisturizing function of the horny layer of the epidermis as protection against an external factor of drying, and are used for the purpose of preventing and improving wrinkles generated in the epidermis. The effects of preventing and improving wrinkles generated in the dermal tissue are not generally recognized.

[0004] Various protective agents have been developed for ultraviolet rays, which is the largest external factor relating to skin aging, and photochemically absorbing absorbers and scattering agents that physically scatter and reflect are used. Blended cosmetics are used. UV absorbers are classified into benzophenones, paraaminobenzoic acids, methoxycinnamic acids, salicylic acids, etc., but may have problems such as irritation and sensitization.
The development of highly safe absorbents is desired. Most of these UV absorbers are medium wavelength ultraviolet (UVB)
There is a need for the development of better long wavelength ultraviolet (UVA) absorbers, where the region has a maximum absorption wavelength. As an ultraviolet scattering agent, there are inorganic pigments such as titanium oxide and zinc oxide, which are highly safe and can cope with a wide range of ultraviolet rays. There are disadvantages subject to restrictions.

[0005] An important internal factor affecting skin aging is a decrease in the activity of fibroblasts that produce fibrous proteins such as collagen and elastin that constitute the dermis. It is considered that the decrease in the activity of fibroblasts leads to a decrease in the amount of collagen and elastin in the dermis, and the thinning of the skin results in a lack of elasticity and easy wrinkling. Substances used for the purpose of bringing the activity of such cells with reduced activity close to the activity before aging are cell activators and occupy an important position as an active ingredient of anti-aging cosmetics. Cell activators include vitamins, plant and animal extracts, α-hydroxy acids, and the like. However, at present, no effective component has been found that performs a sufficient function as a wrinkle improving cosmetic. For example, there are reports that α-hydroxy acids such as glycolic acid, lactic acid, malic acid and citric acid stimulate fibroblasts, promote biosynthesis of intercellular matrix, and improve dermal wrinkles, Effective concentration is 6
Due to the restrictions on the formulation, it is expected to develop α-hydroxy acids having higher efficacies so that the intended use can be achieved at lower concentrations. In addition, it has been reported that retinoic acid, which has sebaceous gland atrophy and has been developed as a therapeutic agent for acne, promotes collagen renewal and significantly improves wrinkles, and is used in the United States for anti-aging cosmetics. I have. However, retinoic acid has been pointed out with various side effects and safety problems such as malformation, and it is difficult to incorporate it into cosmetics in Japan. As described above, as a measure to improve wrinkles at the dermis level, the use of a cell activator that activates fibroblasts is expected, but there are components that function sufficiently in terms of efficacy and safety. At present it has not been found.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cosmetic which has a markedly improved effect of giving skin a shine and luster and preventing and improving the formation of wrinkles and sagging caused by aging of the skin. To provide a fee.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that a specific retinol glycoside has a remarkable cell activating effect, and that a cosmetic containing the same has a retinol glycoside. It has been found that the application can prevent and improve the formation of wrinkles and sagging, and have completed the present invention. That is, the gist of the present invention is represented by the following structural formula (1)

[0008]

Embedded image

(In the formula (1), R represents one or more glycosyl residues selected from the group consisting of glucose and galactose, and n represents any one of integers from 1 to 3.) Retinol glycosides and cosmetics comprising the same, further comprising a humectant together with the retinol glycoside, more preferably a polyhydric alcohol and / or a natural moisturizing factor, an acidic mucopolysaccharide, a vegetable polysaccharide, It is a cosmetic that is formulated by combining animal polysaccharides, fibrous proteins, intercellular lipids, sebum-like substances, and the like. Hereinafter, the present invention will be described in detail. First, when the retinol glycoside used as an essential component in the present invention is represented by a general chemical structural formula, it is represented by the general formula (1). That is, the retinol glycoside according to the present invention has a β-cyclohexynyl ring as a hydrocarbon, a retinoid (retinol) moiety having a side chain having isoprene and a terminal hydroxyl group, and glucose at the hydroxyl group. One or two or more sugar residues selected from the group consisting of galactose are composed of a sugar moiety having 1 to 3 molecules bonded thereto.

The retinol glycoside targeted by the present invention is:
Preferably, the sugar residue in the formula (1) is a glycoside retinol, which is a monoglycoside residue and / or a diglycoside residue, and still more preferably, the sugar residue is mainly composed of glucose. Such a retinol glycoside may be prepared by a chemical synthesis method in which retinol and a saccharide are mixed, heated and etherified, but are enzymatically synthesized in consideration of the quality of the product, such as color and odor. It is more preferable to use the method of As the enzyme, a glycoside hydrolase such as glycosidase can be used.

Next, a method for measuring a cell activating effect, which is a characteristic property of the retinol glycoside according to the present invention, will be described below. The cell activating effect is measured by MTT (3- (4,5-dimethyl-2-thiazonyl), which is one of the cytotoxicity evaluation methods.
(2,5-diphenyltetrazolium bromide) reduction method. That is, MT is added to human fibroblasts.
The amount of formazan formed by adding T is measured by absorbance. When MTT is taken into living cells, it undergoes reductive cleavage by NADH present in mitochondria and is converted to blue formazan. Therefore, the amount of formazan obtained by this MTT reduction method corresponds to the amount of NADH and can be considered to reflect the metabolic activity of mitochondria, that is, the energy metabolic activity of cells. The retinol glycoside according to the present invention exhibits a high formazan production amount even at a minute concentration, and has extremely high activity as an active ingredient having a cell activating action.

For this reason, the use of the above-mentioned retinol glycoside according to the present invention in various skin-applied products such as cosmetics, toiletry products, and quasi-drugs prevents skin aging and activates the skin. It is considered to be extremely useful in improving skin aging. The gist of the present invention based on this idea relates to a cosmetic comprising the retinol glycoside represented by the structural formula (1) as an essential component. The type of the cosmetic of the present invention is not particularly limited, but it is particularly desirable to target various known cosmetics used for the skin, such as cold cream, burnishing cream, emollient cream, and sunscreen. Examples include various creams such as creams, milky lotions, lotions, foundations, facial cleansers, serums, packs, and the like. Although there is no limitation on toiletry products as well, soaps, bath additives and the like can be preferably exemplified. The amount of such a retinol glycoside blended in the cosmetic is 0.001% by weight or more, and the upper limit of the blending is not particularly limited. However, when blended in an extremely large amount, the effect of the present invention is not impaired. However, the quality as a cosmetic may not be maintained due to precipitation of crystals and the like. It is preferably at most 10% by weight.

The cosmetic of the present invention can be prepared by a conventional method using the above-mentioned retinol glycoside and other known components. That is, if known oil components, surfactants, humectants, thickeners, preservatives, pigments, powders, pH adjusters, antioxidants, ultraviolet absorbers, fragrances, dyes, purified water, etc. are appropriately blended. Good. In the cosmetic of the present invention, by combining the retinol glycoside according to the present invention with the humectant, the effects of the present invention, i.e., the formation of wrinkles and sagging are prevented, and the skin becomes firm and shiny. The effect to be imparted is more remarkably exhibited. As such humectants, known cosmetic raw materials such as polyhydric alcohols (glycerin, propylene glycol, sorbitol, etc.), natural moisturizing factors (Na
tural Moisturizing Factor: amino acids, lactates, sodium pyrrolidonecarboxylate, urea, etc., acidic mucopolysaccharides (hyaluronic acid, chondroitin sulfate, etc.), vegetable polysaccharides (pectin, carrageenan, trehalose, etc.), animal polysaccharides (chitin derivatives, chitosan) Derivatives, etc., fibrous proteins (collagen, elastin, placenta, etc.), intercellular lipids (phospholipids, sphingolipids, sterols, etc.), sebum analogues (olive oil, jojoba oil, squalane, etc.) and the like are preferred. These humectants can be used alone or in combination of two or more. The combination ratio of the retinol glycoside and the humectant is preferably the retinol glycoside / humectant according to the present invention = 1/100 to 100/1 (weight ratio).

[0014]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples and Examples. Production Example 1 Retinol (Sigma Co., Ltd.) in 100 ml of dichloromethane
5.8 g), 8.0 g of glucose pentaacetate (manufactured by Sigma) and 3.3 g of anhydrous iron (III) chloride.
Add g. Stir at room temperature overnight and wash the dichloromethane solution with saturated aqueous sodium hydrocarbon solution. This was further washed with water, and the concentrate was added with 18 g of sodium methoxide and 100 ml of ethanol, refluxed for 6 hours, and then concentrated. The concentrate was washed with water and dried, and then 2 g of purified retinol glucoside was obtained by column chromatography.

Production Example 2 Retinol (Sigma Co., Ltd.) was added to 100 ml of dichloromethane.
5.8 g), 8.0 g of galactose pentaacetate (manufactured by Sigma) and 3.3 g of anhydrous iron (III) chloride.
Add g. Hereinafter, the same procedure as in Production Example 1 was performed to obtain 2 g of purified retinol galactoside.

Example 1 (Cream) A cream was prepared according to the formulation shown in Table 1 and the following production method. Also prepare a cream for comparison in the same way,
The properties of both creams were evaluated. Table 2 shows the results.
The cream of the present invention has a large effect of giving a skin a shine and luster, and has an effect of preventing the formation of wrinkles and sagging.

[0017]

[Table 1] * 1 Purified retinol glucoside obtained in Production Example 1 * 2 Purified retinol galactoside obtained in Production Example 2

[Manufacturing method] (1) to (4), (7), (8) and (10) are mixed while heating and maintained at 70 to 80 ° C. (5), (6), (9) and (11) are added to (12), mixed while heating, and kept at 70 to 80 ° C. Stir while gradually adding the mixture to the above mixture, and uniformly emulsify. In a water bath and continue to stir to room temperature to obtain a cream.

[Evaluation Method] An appropriate amount of each of the cream of the present invention and the comparative cream was applied to the face twice a day after washing the face in the morning and evening for 10 months, using 10 women in their 20s to 50s as panels. The evaluation of each cream was based on the following criteria. Judgment contents ────────────────────────────────── ○ (effect was recognized): Affix to skin , Gloss is given, wrinkles and sagging are improved. △ (Effect was recognized slightly): Slightly applied to the skin and gloss, wrinkles and sagging were improved. × (No effect was observed): Same as before use

[0020]

[Table 2]

Example 2 (Emulsion) An emulsion was prepared according to the formulation shown in Table 3 and the following production method. In addition, an emulsion for comparison was prepared in the same manner, and the properties of both emulsions were evaluated (the evaluation method and criteria were the same as in Example 1). Table 4 shows the results. The emulsion of the present invention has a great effect of giving a shine and gloss to the skin, and an effect of preventing the formation of wrinkles and sagging was recognized.

[0022]

[Table 3] * 1 Purified retinol glucoside obtained in Production Example 1 * 2 Purified retinol galactoside obtained in Production Example 2

[Manufacturing method] (1) to (3), (6), (7) and (9) are mixed while heating, and kept at 70 to 80 ° C. (4), (5), (8) and (10) are added to (11), mixed while heating, and maintained at 70 to 80 ° C. Stir while gradually adding the mixture to the above mixture, and uniformly emulsify. In a water bath and continue stirring until it reaches room temperature to obtain an emulsion.

[0024]

[Table 4] Note) Evaluation criteria are the same as in Example 1.

Example 3 (Lotion) A lotion was prepared according to the formulation shown in Table 5 and evaluated in the same manner as in Example 1. As a result, the products of the present invention (3-1 to 3-2) were all skin In particular, the effect of 3-2 (combination of sodium pyrrolidonecarboxylate and retinol glucoside) was remarkable (Table 6).
reference). From this, it was clarified that the product of the present invention has an effect of preventing the formation of skin wrinkles and sagging.

[0026]

[Table 5] * Purified retinol glucoside obtained in Production Example 1

[0027]

[Table 6] Note) Evaluation criteria are the same as in Example 1.

Example 4 (Essence) A serum was prepared according to the formulation shown in Table 7, and evaluated in the same manner as in Example 1. The products of the present invention (4-1 to 4-3) were all skin 4-2 and 4-3 (in combination of hyaluronic acid and retinol glucoside) showed a remarkable effect (see Table 8). From this, it was clarified that the product of the present invention has an effect of preventing the formation of skin wrinkles and sagging.

[0029]

[Table 7] * Purified retinol glucoside obtained in Production Example 1

[0030]

[Table 8] Note) Evaluation criteria are the same as in Example 1.

[0031]

According to the present invention, there is provided a retinol glycoside represented by the structural formula (1) having a cell activating effect and a cosmetic comprising the same. The present cosmetic has an effect of giving a skin a luster and gloss, preventing the formation of wrinkles and sagging of the skin, and further improving it. The effect is further remarkably exhibited by using a humectant in combination with the cosmetic.

Claims (5)

[Claims] 1. A retinol glycoside represented by the following general formula (1). Embedded image (In the formula (1), R represents one or more glucosyl residues selected from the group consisting of glucose and galactose, and n represents any one of integers from 1 to 3.) 2. A cosmetic comprising a retinol glycoside represented by the following general formula (1). Embedded image (In the formula (1), R represents one or more glucosyl residues selected from the group consisting of glucose and galactose, and n represents any one of integers from 1 to 3.) 3. The cosmetic according to claim 2, wherein the cosmetic further comprises a humectant. 4. The method according to claim 2, wherein the humectant is a polyhydric alcohol, a natural humectant, an acidic mucopolysaccharide, a vegetable polysaccharide, an animal polysaccharide, a fibrous protein, an intercellular lipid, a sebum-like substance, or the like. 3. The cosmetic according to 3. 5. The humectant is one or more of glycerin, sodium pyrrolidonecarboxylate, hyaluronic acid, trehalose, chitin derivative, collagen, phospholipid, sphingolipid, and jojoba oil.
The cosmetic according to any one of the above.