JP2999829B2 - External preparation for skin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a skin external preparation, and more particularly to a skin external preparation containing a water-soluble sugar cinnamate derivative having an ultraviolet absorbing property.

[0002]

2. Description of the Related Art Ultraviolet rays contained in sunlight are 400 nm.
Long wavelength ultraviolet (UV-A) up to 320 nm, 320 nm to 2
It is classified into 80 nm middle wavelength ultraviolet (UV-B) and 280 nm or shorter short wavelength ultraviolet (UV-C). Of these, 29
Ultraviolet light having a wavelength of 0 nm or less is absorbed by the ozone layer and does not reach the surface of the earth.

[0003] Ultraviolet rays reaching the ground surface have various effects on human skin. UV-A also causes a problem of primary blackening, but the effect of UV-B is particularly serious. When a certain amount or more of light is irradiated on the skin, erythema and blisters are formed, and melanin is formed. It causes problems such as accelerated formation and pigmentation, and further promotes skin aging in the long term, causing skin cancer and the like.

[0004] Therefore, in order to remove the influence of ultraviolet rays, various ultraviolet absorbers have been developed. As existing UV absorbers, PABA derivatives, cinnamic acid derivatives, salicylic acid derivatives, benzophenone derivatives, urocanic acid derivatives, camphor derivatives, heterocyclic derivatives and the like are known.

[0005] These UV-B absorbers are usually blended into skin external preparations such as cosmetics and quasi-drugs, and low-molecular-weight dimethylsiloxane-based bases are widely used as external bases. It is used.

That is, since sunscreens are most frequently used in summer, oil-soluble ones have been used as ultraviolet absorbers from the viewpoint of sweat resistance and water resistance. .

[0007]

However, recently, the influence of ultraviolet rays in daily life has become a problem, and sunscreen is desired even in ordinary skin care.
For this reason, it is better to be able to mix a large amount of UV absorbers into the entire system even when formulating an external preparation having a higher UV absorption effect. In addition, there has been a strong demand for the development of a skin external preparation containing a water-soluble ultraviolet absorber from the viewpoint that it is desirable to incorporate an ultraviolet absorber also into the aqueous phase.

However, most of the conventional UV-B absorbers are oil-soluble and have low water-solubility as described above, and the formulation is limited. As a water-soluble UV-B absorber, only 2
-Hydroxy-4-methoxy-5-sulfoxonium benzophenone sodium salt is only known, and since it is a salt, there is a problem that it affects the pH of the formulation system.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide an external preparation for skin using a sugar cinnamate derivative having excellent UV-B absorption and being water-soluble. To provide.

[0010]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, it has been found that a sugar-cinnamic acid derivative in which a sugar is bound to cinnamic acid has excellent UV-B absorption and water solubility. The inventors have found that the present invention has been completed.

That is, the external preparation for skin according to claim 1 of the present application is characterized in that one or more sugar cinnamic acid derivatives represented by the following general formula 2 are blended.

Embedded image (In the formula, A is a residue obtained by removing one hydroxyl group from a sugar, and R is preferably an —O-bonded aliphatic chain having a total of 1 to 4 carbon atoms.)

Hereinafter, the configuration of the present invention will be described in more detail. In the general formula 2, specific examples of the sugar of A include glucose, galactose, xylose, fructose, altrose, talose, mannose, arabinose, idose, lyxose, ribose, monosaccharides such as allose, and mixtures thereof, or Maltose, isomaltose, lactose, xylobiose, kentiobiose, kojiobiose, cellobiose, sophorose, nigerose, sucrose, melibiose, disaccharides such as laminaribiose, rutinose and mixtures thereof, and further polysaccharides can be used. is there. In addition, a mixture of monosaccharides, disaccharides, and higher polysaccharides may be used.

R is preferably an -O-bonded aliphatic chain, and is preferably a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group, an unsaturated hydrocarbon group, a cycloalkyl group or the like. Specific examples of R include a methyl group (—OCH ₃ ), an ethyl group (—OC ₂ H ₅ ), an acetylenyl group, a propyl group, an isopropyl group, a propenyl group, a butyl group bonded via oxygen (O). Examples include an isobutyl group, a t-butyl group, and a butenyl group. In any case, there is no significant difference in the UV-B absorption wavelength, but a methyl group and an ethyl group are particularly preferable from the industrial viewpoint. Further, R represents —NH ₂ , —NHCH ₃ , —NHC ₂
H _{5 and the} like can be bonded.

The orientation of the anomers of the glycosidic bond is not particularly limited, and α and β may be used alone or in a mixture thereof.

Since the above cinnamic acid derivatives are solid and extremely excellent in safety and stability, they can be blended as components of pharmaceuticals, quasi-drugs, cosmetics and skin cleansing agents.

The sugar cinnamic acid derivative of the present invention can be synthesized using, for example, an acid catalyst for modifying sugars described in JP-A-63-84637, and in addition to the reactions generally used for glycosylation (König-Knoll reaction, Hellereich method). Or other ether exchange methods).

For example, it can be synthesized as follows. The acetylated saccharide is dissolved in a non-polar solvent such as dibutyl cellosolve, toluene, or the like.

Embedded image (Wherein R is the same as in the above formula 2), and a compound represented by the formula
Stir at 130 ° C. At this time, the reaction is performed under reduced pressure,
The compounds represented by Formula 2 may be used alone or in combination of two or more.

The catalyst used herein includes acid catalysts such as p-toluenesulfonic acid, sulfuric acid, methylsulfonic acid, and heteropolyphosphoric acid, zinc acetate, zinc chloride, and the like.
These may be used as a mixture.

After the reaction, the reaction solvent is distilled off under reduced pressure, and the product is extracted with toluene and washed with water. The obtained extract is concentrated under reduced pressure and then deacetylated as it is, or purified by silica gel column chromatography or the like and then deacetylated.

The reaction product thus obtained includes:
In addition to the sugar cinnamic acid derivative represented by the general formula 2, salts and sugars at the time of neutralization coexist. Therefore, for example, when removing sugar and salt, methyl alcohol, ethyl alcohol, butyl alcohol, extraction with a solvent that does not dissolve the sugar such as isopropyl alcohol, or water containing a large amount of salt and methyl ethyl ketone, partition with n-butanol, It can be purified by separating the organic solvent layer. Also removes sugar and salt,
When the compound is separated, the reaction product is suspended in water or a mixture of water and an alcohol, and is first separated by a reverse-phase partitioning column such as a hyperporous polymer (eg, a porous resin manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) or octadecyl silica. Through water, and then through a mixture of water and an alcohol such as methanol or ethanol, or a polar organic solvent such as acetonitrile, and then fractionate and purify the solution.

The sugar cinnamic acid derivative synthesized as described above is
The extraction solvent may be distilled off or purified by a column before use, or may be used as it is.

The sugar cinnamic acid thus obtained has excellent chemical stability and oxidative stability, is water-soluble, has an absorption in the UV-B region, and has a function of being excellent in moisture retention.

[0023] In addition to the present invention, other commonly used cosmetic and pharmaceutical ingredients can be appropriately compounded. For example, liquid paraffin, squalane, petrolatum, cetyl alcohol, isostearyl alcohol, cetyl 2-ethylhexanoate, 2-octyldodecyl alcohol, glycerin triisostearate, macadamian nut oil, various hydrocarbons such as lanolin, oils and fats, wax Oily components, silicones, surfactants, thickeners, neutralizers, preservatives, bactericides, antioxidants, powder components, pigments, fragrances, other ultraviolet absorbers, medicinal agents, metal sequestration Agents, pH adjusters and the like.

When the sugar cinnamic acid derivative according to the present invention is used as an external preparation for skin, the dosage form is arbitrary, for example, a solubilizing system such as a lotion, an emulsifying system such as an emulsion or a cream,
Alternatively, it may be in the form of an ointment or a powder such as a foundation.

[0025]

The external preparation for skin according to the present invention comprises
Because it contains one or more sugarcinnamic acid derivatives, it is possible to formulate an aqueous base that has a sufficient UV protection effect, and it is stable and safe without any interaction with base components have.

[0026]

Next, the present invention will be described in more detail with reference to Test Examples and Examples. Note that the present invention is not limited by this.

First, a method for producing sugar cinnamic acid according to the present invention will be described. Production Example 1 (p-glycosyloxycinnamic acid methyl ester) 4 g of p-hydroxycinnamic acid was added to an HCl-MeOH solution 8
The solution was dissolved in 0 ml, heated under reflux for 1 hour, and concentrated under reduced pressure. Extract with 200 ml of ethyl acetate and 200 ml of purified water
After washing 5 times with, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.

Subsequently, this was mixed with dibutyl cellosolve 20
dissolved in 1 ml of pentaacetylglucose,
After adding 220 mg of molybdophosphoric acid, the pressure was reduced under an argon atmosphere, and the mixture was heated and stirred at 100 ° C. for 30 minutes. The reaction system was air-cooled to room temperature, extracted with toluene, washed once with purified water and four times with saturated saline, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 100 ml of acetic anhydride and 100 ml of pyridine were added to the residue, and the mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the unreacted methyl p-hydroxycinnamate and their decomposition products were removed from the residue by silica gel column chromatography. Was.

The obtained acetylated product of p-glucosyloxycinnamic acid methyl ester and unreacted pentaacetylglucose are dissolved in 8 ml of methanol, 1 ml of sodium methylate is added, and the mixture is stirred at room temperature for 30 minutes and then formed. The coming glucose is filtered off and the reaction system is MeOH-HC
Neutralized with 1 solution. The reaction solution was concentrated under reduced pressure, and
The mixture was extracted with 0 ml, washed with 20 ml of purified water 5 times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
Further, the product was extracted with 50 ml of purified water, and hexane 2
After washing with 0 ml, the aqueous layer was concentrated.

The residue was analyzed by HPLC using a capsule pack (ODS column, 5 cmφ × 50 c, manufactured by Shiseido Co., Ltd.).
m) using methyl alcohol: purified water =
The sample was collected using 28:72 (flow rate: 80 ml / min). The eluted portions having a retention time of 35.5 minutes and a retention time of 37.7 minutes were concentrated to give p-β glycosyloxycinnamate methyl ester,
-Α-Glycosiloxycinnamic acid methyl ester was obtained.

The yield of p-β-glycosyloxycinnamate methyl ester and p-α-glycosyloxycinnamate methyl ester was 2.8 g (27.8% yield). The obtained p
-Β-glycosyloxycinnamic acid methyl ester, p-α-
Glucosyloxycinnamic acid methyl ester was analyzed by the following methods (1) to (5), respectively. The thus obtained p-glucosyloxycinnamic acid methyl ester was used as a sample 1
And

P-β-glycosyloxycinnamate methyl ester
Le (1) using the infrared absorption spectrum measurement method JASCO IRA-1 infrared absorption spectrum measurement device of Industry Co., Ltd., it was measured with a neat method, 33
Hydroxyl stretching vibration in 50 cm ^-1, 2900 cm ^- 1 on the stretching vibration of Gurukoshirokishi group, absorption by stretching vibration of the carbonyl group in 1690 cm ^-1 were observed. The results are shown in FIG.

(2) ¹³ C-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, 1
69 ppm, 161 ppm, 146 ppm, 131 pp
m, 130 ppm, 118 ppm, 117 ppm (1 to
7) The signal derived from the carbon of the cinnamic acid ester is 1
01 ppm, 78 ppm, 74 ppm, 71 ppm, 6
A signal derived from carbon in the glucose portion was observed at 2 ppm (8 to 12), and a signal derived from carbon of the methyl group was observed at 52.6 ppm (13). The results are shown in FIG.

(3) ¹ H-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, δ
7.67 (1H, J = 16 Hz), 7.58 (2H,
d, J = 8.8 Hz), 7.15 (2H, d, J = 8.
8 Hz) and 6.43 (1H, d, J = 16.1 Hz), the signal derived from hydrogen of cinnamic acid was δ5.01 (1
(H, d, J = 6.8 Hz), a signal derived from anomeric hydrogen of glucose was observed, and δ3.93 to 3.33, a signal derived from hydrogen in the glucose portion and hydrogen derived from a methyl group were observed. The results are shown in FIG.

(4) Ultraviolet Absorption Spectroscopy Method Using a UVIDEC 61OC ultraviolet absorption spectrometer (manufactured by JASCO Corporation) with a solvent methanol, it showed a maximum absorption at 223.8 nm and 295.6 nm. FIG. 4 shows the results.

(5) Melting Point Measuring Method Using a capillary melting point measuring device manufactured by ARTHUR H. THOMS COMPANY, the melting point was measured at 166 to 168 ° C.

Methyl p-α-glycosyloxycinnamate
Tell (1) Infrared absorption spectrum measuring method Using an IRA-1 infrared absorption spectrum measuring device manufactured by JASCO Corporation, it was measured by the neat method.
Hydroxyl stretching vibration in 50 cm ^-1, 2900 cm ^- 1 on the stretching vibration of Gurukoshirokishi group, absorption by stretching vibration of the carbonyl group in 1690 cm ^-1 were observed. FIG. 5 shows the results.

(2) ¹³ C-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, 1
69 ppm, 161 ppm, 146 ppm, 131 pp
m, 130 ppm, 118 ppm, 117 ppm (1 to
7) The signal derived from the carbon of the cinnamic acid ester is 1
01 ppm, 78 ppm, 74 ppm, 71 ppm, 6
A signal derived from carbon in the glucose portion was observed at 2 ppm (8 to 12), and a signal derived from carbon of the methyl group was observed at 52.6 ppm (13). FIG. 6 shows the results.

(3) ¹ H-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, δ
7.67 (1H, J = 16 Hz), 7.58 (2H,
d, J = 8.8 Hz), 7.15 (2H, d, J = 8.
8 Hz) and 6.43 (1H, d, J = 16.1 Hz), the signal derived from hydrogen of cinnamic acid was δ5.62 (1
(H, d, J = 3.4 Hz), a signal derived from anomeric hydrogen of glucose was observed, and a signal derived from δ3.93 to 3.36 derived from hydrogen of the glucose portion and hydrogen of the methyl group was observed. FIG. 7 shows the results.

(4) Ultraviolet Absorption Spectrum Measurement Method Using a UVIDEC 61OC ultraviolet absorption spectrum measurement apparatus manufactured by JASCO Corporation, the maximum absorption was observed at 223.8 nm and 295.6 nm when measured with methanol in a solvent. FIG. 8 shows the results.

(5) Melting Point Measuring Method Using a capillary-type melting point measuring device manufactured by ARTHUR H. THOMAS COMPANY, the melting point was measured at 188 to 192 ° C.

Production Example 2 (p-glycosyloxycinnamic acid
11.3 g of p-hydroxycinnamic acid was added to 12 ml of ethanol.
And 12.0 g of DCC and 0.6 g of 4-pyridinopyridine were added thereto, followed by stirring at room temperature for 2 hours. After the reaction, the mixture was concentrated under reduced pressure, extracted with 300 ml of chloroform, and 200 ml of purified water.
, Washed with water 5 times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

The residue was subjected to silica gel column chromatography,
The solvent was purified by using hexane: ethyl acetate as a developing solvent to obtain 8.46 g of p-hydroxycinnamic acid ethyl ester (yield: 64%).

Subsequently, 3.2 g of this ethyl ester of p-hydroxycinnamic acid was dissolved in 20 ml of dibutyl cellosolve, and 5.42 g of pentaacetylglucose and 600 mg of molybdophosphoric acid were added.
The mixture was heated and stirred at 100 ° C. for 30 minutes. The reaction system is air-cooled to room temperature, extracted with toluene, and washed once with purified water and four times with saturated saline. Then, the organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Acetic anhydride 50
After adding 1 ml of pyridine and 50 ml of pyridine, the mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the unreacted ethyl p-hydroxycinnamate and their decomposed products were removed from the residue by silica gel column chromatography.

The obtained acetylated product of ethyl p-glucosyloxycinnamate and unreacted pentaacetylglucose were dissolved in 8 ml of ethanol, 1 ml of sodium ethylate was added, and the mixture was stirred at room temperature for 30 minutes and then formed. The coming glucose was filtered off and the reaction was neutralized with 0.1 M HCl solution. The reaction solution was concentrated under reduced pressure, and 25 ml of butanol was added.
, And washed 5 times with 10 ml of purified water. The organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. further,
The product was extracted with 30 ml of purified water, washed with 20 ml of hexane and the aqueous phase was concentrated.

The obtained residue was subjected to column chromatography using a hyperporous polymer (a high-porous resin manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), and purified water was first used as a developing solvent, then ethyl alcohol: purified water = 4: 6, and the eluted portion of ethyl alcohol: purified water 4: 6 was concentrated to obtain glucosylcinnamic acid ethyl ester. The yield was 1.7 g (35% yield).

The obtained glucosyloxycinnamic acid ethyl ester was analyzed by the following methods (1) to (5). Physical data of p-glycosyloxycinnamic acid ethyl ester (1) Infrared absorption spectrum measurement method Using an IRA-1 infrared absorption spectrum measurement apparatus manufactured by JASCO Corporation, the measurement was performed by the neat method.
Hydroxyl stretching vibration in 50 cm ^-1, 2900 cm ^- 1 on the stretching vibration of Gurukoshirokishi group, absorption by stretching vibration of the carbonyl group in 1690 cm ^-1 were observed.

(2) ¹³ C-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, 1
69 ppm, 161 ppm, 146 ppm, 131 pp
m, 118 ppm, 117 ppm, the signal derived from the carbon of the cinnamic acid ester is 101 ppm, 78 ppm,
At 74 ppm, 71 ppm, and 62 ppm, signals derived from carbon in the glucose portion were 52.6 ppm, 15 p
In pm, a signal derived from the carbon of the ethyl group was observed.

(3) ¹ H-NMR measurement method JOEL GX-400 manufactured by JEOL Ltd.
When measured at room temperature using CD ₃ OD as a solvent, δ
7.67 (1H, d, J = 16 Hz), 7.58 (2
H, d, J = 8.8 Hz), 7.15 (2H, d, J =
8.8 Hz), 6.43 (1H, d, J = 16.1H)
In z), the signal derived from hydrogen of cinnamic acid has δ5.62.
(1H, d, J = 3.4 Hz), the signal derived from the anomeric hydrogen of glucose was δ3.93 to 3.36.
In addition, a signal derived from hydrogen in the glucose portion and hydrogen in the ethyl group was observed, and a signal derived from hydrogen in the ethyl group was observed at δ 1.28 (3H, t, 7.2 Hz).

(4) Method of measuring ultraviolet absorption spectrum Using a UVIDEC 61OC ultraviolet absorption spectrum measuring apparatus manufactured by JASCO Corporation, the maximum absorption was shown at 223.8 nm and 295.6 nm when measured with a solvent methanol. Next, a skin external preparation containing the sugar cinnamic acid derivative obtained as described above will be described.

First, a test was carried out on the sunscreen effect of the external preparation for skin according to the present invention. Test Example In the formulation shown in Table 1 below, a serum containing a cinnamic acid derivative and a serum containing 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone as a control were produced.

[0052]

[Table 1] ----------------------------------------------------------------------------------------- Component Ingredient Example 1 Comparative Example 1 ----------------------------- -------------------------------------------------------------------------- A. (Alcohol phase) Ethanol 5.0% 5.0% POE oleyl alcohol ether 2.0 2.0 Fragrance 0.05 0.05 B. (Aqueous phase) 1,3-butylene glycol 5.0 5.0 p-glycosyloxycinnamic acid methyl ester 7.0-2-human peroxy-4-methoxy-5-sulfoxonium benzophenone-7.0 triethanolamine 0.1 0.1 Carboxyvinyl polymer 0.15 0.15 Purified water Residue Residual ------------------------------------------------ --- Production method: The alcohol phase of A was added to the aqueous phase of B, and the fragrance was solubilized to obtain a serum.

Appearance State In Example 1, a colorless, transparent and viscous good serum was obtained, whereas the control example had a strong yellowish color and no viscosity. Sunscreen effect In a practical use test on the beach, two samples were applied to each of 10 panels, half of the body, and a questionnaire survey on the degree of sunburn and a skin trouble were conducted. Table 2 shows the results.

[0054]

Table 2---------------------------------------------------------------------------------------------------------------- Part Sample application part --------------------------------------- Panel A ○ △ B △ × C △ ×------------------------------------- D ○ × E △ △ F ○ △ G ○ × H ○ △ I △ △ J ○ ○ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−− Number of skin troubles None None 3 itches 5 rashes 2 rashes −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−− Evaluation criteria for degree of sunburn Strong erythema was observed… × Slight erythema was observed… △ Erythema was not observed… ○

From these results, the external preparation for skin containing a sugar cinnamic acid derivative has a higher ultraviolet protection effect and a higher safety without skin troubles than the conventional external preparation for skin containing a water-soluble ultraviolet absorber. Was.

Hereinafter, examples of the formulation of the external preparation for skin according to the present invention will be described. In addition, each skin external preparation showed an excellent ultraviolet protection effect.

Example 2 Cream A. Oil phase Stearic acid 10.0% Stearyl alcohol 4.0 Stearic acid monoglycerin ester 8.0 Vitamin E acetate 0.5 Fragrance 0.4 Ethyl paraben 0.1 Butyl paraben 0.1 Propyl paraben 0.1 B. Water phase Propylene glycol 8.0 Glycerin 2.0 p-Glucosyloxycinnamic acid methyl ester 5.0 Potassium hydroxide 0.4 Trisodium edetate 0.05 Purified water Residue <Production method> The aqueous phases are each heated to 70 ° C. and completely dissolved. Add phase A to phase B and emulsify with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

Example 3 Cream A. Oil phase Cetanol 4.0 Vaseline 7.0 Isopropyl myristate 8.0 Squalane 12.0 Dimethyl polysiloxane 3.0 Monoglycerin stearate 2.2 POE (20) Sorbitan monostearate 2.8 Glycyrrhetinate stearate BHT 0.02 ethyl paraben 0.1 butyl paraben 0.1 B. Aqueous phase 1.3 Butylene glycol 7.0 Disodium edetate 0.07 Phenoxyethanol 0.2 Magnesium L-ascorbic acid phosphate ester 3.0 Alkyl polyacrylate 1.0 Ethyl p-glucosyloxycinnamate 7 0.0 Purified water residue <Production method> A cream was obtained according to Example 2.

Example 4 Emulsion A. Oil phase Squalane 5.0 Oleyl oleate 3.0 Vaseline 2.0 Sorbitan sesquioleate 0.8 Polyoxyethylene oleyl ether (20E.O.) 1.2 2-Ethylhexyl-p-methoxycinnamate 3.0 Methyl paraben 0.15 fragrance 0.12 B. Aqueous phase Dipropylene glycol 5.0 Ethanol 3.0 Carboxyvinyl polymer 0.17 Sodium hyaluronate 0.1 Methyl p-glucosyloxycinnamate 4.0 Potassium hydroxide 0.08 Sodium hexametaphosphate 0.05 Purified water residue <Production method> An emulsion was obtained according to Example 2.

Example 5 Cream A. Oil phase Behenyl alcohol 0.5% Cholestanol ester of 12-hydroxystearate 2.0 Squalane 7.0 Jojoba oil 5.0 Self-emulsifying glyceryl monostearate 2.5 Polyoxyethylene sorbitan monostearate (20EO) 5 2-hydroxy-4-methoxybenzophenone 3.0 ethyl paraben 0.2 butyl paraben 0.1 fragrance 0.1 B. Water phase Propylene glycol 5.0 Glycerin 5.0 Vegum (montmorillonite) 3.0 Potassium hydroxide 0.3 Ethyl p-glucosyloxycinnamate 6.0 Trisodium edetate 0.08 <Production method> According to Example 2 I got a cream.

Example 6 Toner containing powder A. Oil phase ethanol 8.0 POE (60) glyceryl monoisostearate 2.0 L-menthol 0.1 camphor 0.1 methyl paraben 0.1 fragrance 0.03 B. Aqueous phase Glycerin 3.5 p-Glucosyloxycinnamic acid methyl ester 2.0 Zinc 1.5 Kaolin 0.5 Bentonite 0.3 Sodium hexametaphosphate 0.03 Purified water residue <Production method> By the production method according to Example 1. A powdered lotion was obtained.

[Brief description of the drawings]

FIG. 1 shows p-β compounded in the external preparation for skin according to the present invention.
FIG. 3 is an infrared absorption spectrum of glycosyloxycinnamic acid methyl ester.

FIG. 2 p-β compounded in the external preparation for skin according to the present invention
FIG. 3 is a ¹³ C-NMR diagram of glycosyloxycinnamic acid methyl ester.

FIG. 3 p-β formulated in the external preparation for skin according to the present invention
FIG. 3 is a ¹ H-NMR diagram of glycosyloxycinnamic acid methyl ester.

FIG. 4 p-β formulated in the external preparation for skin according to the present invention
FIG. 3 is an ultraviolet absorption spectrum of glycosyloxycinnamic acid methyl ester.

FIG. 5: p-α blended in the external preparation for skin according to the present invention
FIG. 3 is an infrared absorption spectrum of glycosyloxycinnamic acid methyl ester.

FIG. 6: p-α formulated in the external preparation for skin according to the present invention
FIG. 3 is a ¹³ C-NMR diagram of glycosyloxycinnamic acid methyl ester.

FIG. 7: p-α formulated in the external preparation for skin according to the present invention
FIG. 3 is a ¹ H-NMR diagram of glycosyloxycinnamic acid methyl ester.

FIG. 8: p-α formulated in the external preparation for skin according to the present invention
FIG. 3 is an ultraviolet absorption spectrum of glycosyloxycinnamic acid methyl ester.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keiichi Uehara 1050 Nippa-cho, Kohoku-ku, Yokohama City, Kanagawa Prefecture Inside Shiseido Research Laboratories Co., Ltd. (56) References JP-A-4-305592 (JP, A) JP-A-4 -270298 (JP, A) JP-A-4-183773 (JP, A) JP-A-64-13017 (JP, A) JP-A-63-201116 (JP, A) JP-A-57-58644 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/42 A61K 7/00

Claims (1)

(57) [Claims] A skin external preparation comprising one or more sugar cinnamic acid derivatives represented by the following general formula (1). Embedded image (In the formula, A is a residue obtained by removing one hydroxyl group from a sugar, and R is preferably an —O-bonded aliphatic chain having a total of 1 to 4 carbon atoms.)