JPH09208448A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic containing a specific amount of an ester derivative of a specific fatty acid and lactic acid or glycolic acid or a salt of the derivative, effective for improving the moisture-keeping performance of the cuticle layer of the skin and useful for keeping the skin in blooming and healthy state. SOLUTION: This cosmetic contains 0.05-5wt.% of an ester derivative of (A) a fatty acid containing >=85% cis-9-octadecenoic acid and (B) lactic acid or glycolic acid or a salt of the derivative. The cosmetic contains an α- hydroxyacid octadecenate composed of the components A and B as an essential component and is optionally compounded with a surfactant, an additive, water, etc., and applied to the skin in the form of cream, emulsion, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic useful for improving the moisturizing property of the stratum corneum of the skin and keeping the skin youthful and healthy.

[0002]

2. Description of the Related Art Various functional substances have been proposed and used so far from the viewpoints of preventing the skin from drying and preventing the generation and increase of wrinkles to keep the skin youthful and healthy. Examples of these are hyaluronic acid (skin, Vo
l.27, P.276 (1984)), sphingolipids (Journal of the Japanese Dermatological Association, Vol.96, P.617 (1986), ISFCCYokohama (1992),
Proceedings, A101), Cholesterol ester (Fragrance Journal, Vol.18, No.7, P.111 (1990)) or NMF (Natura such as amino acids and pyrrolidonecarboxylic acid)
l Moisturing Factor (Fragrance Journal, No.2
2, P.6 (1977)), α-hydroxy acids such as glycolic acid and lactic acid (Archives of Dermatology, Vol.110, P.586
(1974), Jounal of the Society of Cosmetic Chemis
ts, Vol.25, P.519 (1974)). Especially α
-Hydroxy acid has attracted attention for its remarkable effect and has recently been often used in creams, emulsions, lotions and the like (Household and Personal Products).
Industry, No. 5, P. 49 (1993)).

Α-Hydroxy acids such as glycolic acid and lactic acid have a moisturizing action, and are said to act as a keratin exfoliating or desquamation promoting agent. By exfoliating aged keratin, the skin becomes fresh and young. Keeps you cool. However, in many cases, these α-hydroxy acids are contained in products such as creams and emulsions in an amount of several wt% to several tens wt%, which is relatively large amount as a functional substance of this kind. This is because the α-hydroxy acid is water-soluble and its permeability to the epidermis is not as high as that of the fat-soluble compound, and it must be blended in large amounts in order to exert a sufficient effect on the skin. On the other hand, when a large amount of α-hydroxy acid is used, it may cause irritation to the skin, and it is feared that use of a large amount in a formulation has a problem. It is desirable to minimize its use to the extent that it can be expected to be effective.

On the other hand, it has been reported that α-hydroxy acid is chemically modified into a highly lipophilic compound. For example, in U.S. Pat. No. 4,946,832, fatty acid esters of lactic acid, especially glycolic acid stearate, are described in 3-4.
Cosmetics containing 5% by weight of reduced skin dryness are disclosed. However, even in this formulation, in order to fully develop the moisturizing effect, in order to increase the compounding amount to several wt% or more,
May cause skin irritation. Further, US Pat. No. 3,728,447 discloses a hair cleaner containing glycolic acid and lactic acid and an ester of a fatty acid having 6 to 22 carbon atoms. JP-A-5-29203 discloses a detergent composition containing glycolic acid and lactic acid and an ester of a fatty acid having 6 to 22 carbon atoms, and JP-A-2-2-2.
No. 5412 discloses a shaving cream containing a fatty acid ester of lactic acid, and JP-A-6-40850 discloses a cleansing composition of lactic acid and a fatty acid ester having 6 to 16 carbon atoms. However, these fatty acid esters of α-hydroxy acid must be blended in a range of several wt% to a few dozen wt% in order to actually apply a cream or lotion containing them to the skin to sufficiently exert a moisturizing effect. , May cause skin irritation.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide α-
By increasing the permeability of hydroxy acids into the skin, the moisturizing and desquamation effects inherent in α-hydroxy acids can be fully exerted with a relatively small amount of use, keeping the skin youthful and healthy, and the skin with a large amount of use An object of the present invention is to provide a cosmetic which can avoid the problem of irritation to the skin.

[0006]

Means for Solving the Problems As a result of studying the induction of α-hydroxy acid into various fatty acid esters to improve skin permeability, the present inventors have found that specific fatty acid groups, specifically Has a cis-9-octadecenoic acid content of 85%
It has been found that by introducing a fatty acid group having a content (measured by gas chromatography) or more, a sufficient action can be specifically expressed with a small amount of use, and the present invention has been completed. That is, the present invention provides an ester of a fatty acid having a cis-9-octadecenoic acid content of 85% or more with lactic acid or glycolic acid, or a salt thereof (hereinafter referred to as α-
Hydroxy acid octadecenate) 0.05-5
It is a cosmetic material characterized in that it is contained in a weight percentage.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Cis-in fatty acids used in the present invention
The content of 9-octadecenoic acid is 85% or more, more preferably 90% or more, and the higher the content, the higher the moisturizing action of α-hydroxy acid. When the content is less than 85%, the permeability is deteriorated and the moisturizing property to the skin is deteriorated, which is not preferable. The ester of α-hydroxy acid and fatty acid is a fatty acid whose content of cis-9-octadecenoic acid has been increased to 85% or more by a precision distillation method or a recrystallization method, for example EXTRA OLEIC-90 (manufactured by NOF Corporation). Or EXTRA OLEIC-99 (manufactured by NOF CORPORATION)
Is used as a raw material and is produced, for example, by the following esterification method. The fatty acid is mixed with a solvent such as N, N-dimethylformamide, and phosphorus oxychloride is gradually added dropwise within a temperature range of 50 to 60 ° C to form a fatty acid chloride. N, N-
Α-Hydroxy acid is dissolved in a solvent such as dimethylformamide, and this fatty acid chloride is gradually added dropwise to react (Sc
hotten-Bauman reaction) to produce α-hydroxy acid ester. This is separated and purified from the unreacted material using preparative liquid chromatography or the like. In addition to the desired α-hydroxy acid ester, the compound obtained by such a production method can also obtain a compound represented by the following formula (1) by intermolecular condensation of α-hydroxy acid itself as a by-product.

[0008]

Embedded image

(However, n: 1 to 7. R: Acyl group of fatty acid having a content of cis-9-octadecenoic acid of 85% or more. A: Hydrogen or methyl group M: Hydrogen, alkali metal, alkaline earth Metal, ammonium, or alkanolamine.)

The α-hydroxy acid octadecenate used in the product of the present invention may contain a compound in which n is 2 to 7 in the above formula (1). Further, in the above formula (1), the alkali metal of M is sodium, potassium or lithium, the alkaline earth metal is magnesium or calcium, and the alkanolamine is triethanolamine, diethanolamine, monoethanolamine and isopropanolamine. Indicates.

The cosmetic of the present invention contains the above-mentioned α-hydroxy acid octadecenate as an essential component, and if necessary combined with a surfactant, an additive, water and the like, it is applied to the skin in the form of a cream or an emulsion. It is a thing. Other surfactants and additives are not particularly limited, and those usually used for cosmetics can be used, but in the case of a fatty acid derivative, the higher the content of cis-9-octadecenoic acid, the higher the content. preferable. The blending amount of the α-hydroxy acid octadecenate in the cosmetic of the present invention is kept to a necessary minimum within a range where a sufficient effect is exhibited from the viewpoint of avoiding the skin irritation of the α-hydroxy acid as described above. Therefore, it is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on the total composition. If the blending amount of α-hydroxy acid octadecenate is less than 0.05% by weight, it is difficult to obtain the effect as a cosmetic and it is 5% by weight.
It is not preferable that the amount is larger than that because the skin irritation is increased.

[0012]

EFFECTS OF THE INVENTION The cosmetic composition of the present invention enhances the permeability of α-hydroxy acid into the skin, thereby sufficiently exhibiting the moisturizing and desquaming properties inherent to α-hydroxy acid even when used in a relatively small amount. It is useful for keeping the skin youthful and healthy and avoiding skin irritation problems due to heavy use.

[0013]

EXAMPLES The present invention will be specifically described with reference to examples. <Measurement of fatty acid composition> EXTRA OLEIC-99 (NOF CORPORATION)
Made) 10mg to boron trifluoride / methanol reagent 5ml
Was added and heated on a water bath for 15 minutes. After cooling, 5 ml of n-hexane and 15 ml of saturated saline were added and shaken. After standing, gas chromatography analysis of the n-hexane phase was performed, and the cis-9-octadecenoic acid content was measured by the area ratio of each peak. . The results are shown below. Cis-9-octadecenoic acid 99% Other components 1% (Other components are the sum of peak values less than 1% by gas chromatography)

<Measurement Conditions of Gas Chromatography> The measurement conditions of gas chromatography are as follows. Column: SP-2560 (capillary column, Supelco) Column temperature: 210 ° C Injection temperature: 225 ° C Split ratio: 1/100 Carrier gas and flow rate: Nitrogen, 30 ml / min Detector: FID Sample amount: 2.0 μl ( Sample 1% in n-hexane)

The content of each raw material fatty acid was measured by the same method as described above. EXTRA OLEIC-90 (manufactured by NOF CORPORATION) cis-9-octadecenoic acid 91% hexadecanoic acid 3% octadecanoic acid 2% cis-9, cis-12 octadecadienoic acid 2% octadecadienoic acid isomer 1% other Ingredients 1% NAA-34 (manufactured by NOF CORPORATION) cis-9-octadecenoic acid 63% tetradecanoic acid 3% hexadecanoic acid 5% cis-9-hexadecenoic acid 9% octadecanoic acid 2% octadecenoic acid isomer 6% octa Decadienoic acid 2% Other ingredients 10% NAA-180 (manufactured by NOF Corporation) Octadecanoic acid 98% Hexadecanoic acid 1% Other ingredients 1%

<Synthesis Example of Glycolic Acid Octadecenate-91> EXTRA OLEIC-90 (fatty acid having a cis-9-octadecenoic acid content of 91%, manufactured by NOF CORPORATION) and dimethylformamide (special grade reagent) in a molar ratio of 1 The mixture was stirred at /1.2, and phosphorus oxychloride (special grade) with a molar ratio of 1 / 0.9 to the fatty acid was gradually added dropwise in an ice-water bath, taking care not to raise the temperature above 50 ° C. 50 after completion of dropping
Aged at ℃ for 1 hour. Separate the layers by standing, remove the lower dimethylformamide layer, and blow about 30 while blowing nitrogen gas.
Degassing was performed at 50 to 55 ° C. for 1 hour under reduced pressure of Torr. This is a thin film distiller (type 2-03, Shinko Pantech Co., Ltd.)
The product was obtained by distillation under reduced pressure of about 1 Torr at 180 to 190 ° C. to obtain a pale yellow liquid product. The infrared absorption spectrum of this product showed absorption of an acid chloride at 1805 cm ^-1 , the total chlorine content was 11.7% (vs. the theoretical value 99.2%), and the free fatty acid was 0.8%. , And confirmed that it was a fatty acid chloride. Glycolic acid (special grade reagent) was dissolved in N, N-dimethylformamide (special grade reagent), which was 1.5 times the weight of glycolic acid, and heated to 80 to 85 ° C. under a nitrogen gas stream and stirred. Where the molar ratio is 0.3
A fatty acid chloride of 3/1 (weight ratio of 1.32 / 1 (to glycolic acid)) was added dropwise over about 20 minutes, and further about 120
It was aged by stirring at 80 to 85 ° C for a minute. After acetic acid was added to the reaction product to make it acidic, n-hexane was added by 1.5 times the weight of N, N-dimethylformamide for extraction, and then the solvent was distilled off under reduced pressure. When gas chromatography analysis was performed under the following conditions, the content of glycolic acid octadecenate was 91.3%. The glycolic acid octadecenate was purified by preparative liquid chromatography under the following conditions. The product has an absorption of an ester bond at 1740 cm ^-1 and an infrared absorption spectrum of 1710 cm ^-1.
The absorption of carboxyl group was confirmed. The content of glycolic acid octadecenate by the above-mentioned gas chromatographic analysis was 99.4%. This was designated as glycolic acid octadecenate-91.

<Synthesis Example of Glycolic Acid Octadecenate-99> EXTRA OLEIC-99 (cis-9) was prepared by the same method as described above.
-Glycolic acid octadecenate using fatty acid having 99% octadecenoic acid content, manufactured by NOF CORPORATION
99 was prepared to be the product of the present invention. The ester purity of glycolic acid octadecenate as determined by gas chromatography was 99.2%. This was designated as glycolic acid octadecenate-99.

<Measurement Conditions of Gas Chromatography> The measurement conditions of gas chromatography are as follows. Column: OV-1 (3%, GL Science Co., Ltd.), 3 m
m × 50 cm packed column Column temperature: 80 → 200 ° C., heating rate 4 ° C./min Injection temperature: 300 ° C. Carrier gas and flow rate: nitrogen, 30 ml / min Detector: FID Sample amount: 2.0 μl (sample 5% , In pyridine)

<Measurement Conditions for Preparative Liquid Chromatography> The measurement conditions for gas chromatography are as follows. Column: ODS, 5 cm × 50 cm, 15/30 μm Mobile phase solvent: Methanol / water (80/20) Flow rate: 80 ml / min Detector: RI Sample injection amount: 5 ml

<Synthesis Example of Lactic Acid Octadecenate-91>
Lactic acid octadecenate-91 was prepared in the same manner as above except that lactic acid was used instead of glycolic acid. The ester purity of lactic acid octadecenate as determined by gas chromatography was 99.1%.

<Synthesis Example of Lactic Acid Octadecenate-99>
Lactic acid octadecenate-99 was prepared in the same manner as above except that lactic acid was used instead of glycolic acid. The ester purity of lactic acid octadecenate as determined by gas chromatography was 99.2%.

<Synthesis Example of Glycolic Acid Octadecenate-63> Glycolic acid octadecenate-using a fatty acid having a cis-9-octadecenoic acid content of 63% (NAA-34, manufactured by NOF CORPORATION) in the same manner as described above. 63 (ester purity 99.0%) was prepared.

<Synthesis Example of Lactic Acid Octadecenate-63>
Fatty acid with a cis-9-octadecenoic acid content of 63% (NAA-
34, manufactured by NOF CORPORATION, and lactic acid octadecenate-63 (ester purity 99.2)
%)made.

<Synthesis Example of Glycolic Acid Stearate> Using stearic acid (NAA-180, manufactured by NOF CORPORATION) having an octadecanoic acid content of 98%, glycolic acid stearate (ester purity: 99) was obtained in the same manner as above. 0.0%).

<Synthesis Example of Lactic Acid Stearate> Lactic acid stearate (ester purity is 99.1) was prepared in the same manner as above using stearic acid (NAA-180, manufactured by NOF CORPORATION) having an octadecanoic acid content of 98%. %)made.

Example 1 The cosmetics of the present invention having the formulations shown in Table 1 were obtained as samples and evaluated by the following methods. About 0.1 g of the prepared sample was applied to the inner part of the upper arm of the subject (about 9 cm ² ), gently rubbed for 15 seconds, and then wiped off. The same application was performed 24 and 48 hours later, and 72 hours later, the conductance (μS
(Siemens) Skin Surface Hygrometer (SKICON-
200, manufactured by IBS Co., Ltd., and compared with the conductance of the same site measured before coating the sample. Before measuring the conductance, the subject waited for about 30 minutes under the conditions of 20 ° C. and 50% relative humidity and then measured.
The conductance was measured three times at different places and the average value was taken. The test subjects were 20 men and women aged 24 to 35, and were randomly divided into 4 groups, one for each group.
The sample was tested and this test was performed three times. The test result was evaluated by the average value within the group. The results are shown in Table 1.

[0027]

[Table 1]

1) NOFABLE SO-902, NOFABLE ESO-9020, NOFABLE ESO-9020, NOFABLE ESO-9020, NOFABLE SO-902, NOFABLE SO-902 ) Made

Examples 2 to 10 Using the formulations shown in Table 1, cosmetics were prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Examples 1 to 10 Cosmetics were prepared in the same manner as in Example 1 with the formulations shown in Table 2 and evaluated in the same manner. The results are shown in Table 2.

[0031]

[Table 2]

1) 2) Special grade reagent 3) Nippon Oil & Fats Co., Ltd. 4) Daicel Chemical Industries, Ltd. 5) Nippon Oil & Fats Co., Ltd. 6) Nikko Chemicals Ltd. 7) Squatech Co., Ltd. 8) NOFABLE SO-902, made by NOF Corporation 9) NOFABLE ESO-9020, made by NOF Corporation

From Tables 1 and 2, the cosmetics in which the content of cis-9-octadecenoic acid in the raw material fatty acid is 85% or more have high skin conductance and high moisturizing property, whereas cis-9 in the raw material fatty acid is high. -85% octadecenoic acid content
It can be seen that lower cosmetics and cosmetics containing other fatty acids in the raw material fatty acids have low skin conductance. Further, it can be seen that the skin conductance is high and the moisturizing property is excellent even if the content of α-hydroxy acid octadecenate in the cosmetic is low.

Claims (1)

[Claims] 1. The content of cis-9-octadecenoic acid is 85.
% Or more of an ester derivative of a fatty acid and lactic acid or glycolic acid or a salt thereof in an amount of 0.05 to 5% by weight.