JPH10236943A - Skin-whitening cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin-whitening cosmetic that has excellent skin-whitening action and tyrosinase inhibitory activity by using a condensation type tannin substance as an active ingredient. SOLUTION: This cosmetic contains, as active ingredient, a substance represented by the formula (n is 1 or more). The substance of the formula dissolves in a hydrophilic solvent and is included in the extract of jatoba, a plant in Hymenaea courbaril. The extract is obtained by defatting the fruits or peels of the plant with a non-aqueous solvent as petroleum ether or n-hexane, extracting them with a mixed solvent of water and acetone, followed by fractionation. A part of tannin has been used in cosmetics, but the condensation type tannin substance has not yet been utilized in cosmetics. The substance, trimer or more oligomers of the formula, obtained from the extract of jatoba, can be safely applied to skin and has high skin-whitening action and is effective for skin roughening.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a whitening cosmetic.

[0002]

2. Description of the Related Art Although various substances are known as substances which can be used as raw materials for whitening cosmetics, the use of synthetic products is not guaranteed because there is no guarantee of safety when applied to human skin for a long time. It is getting. On the other hand, many natural products have a weak whitening effect. However, from the viewpoint of safety for human skin, it is a natural product that is guaranteed by humans to eat for many years and also has other effects such as anti-aging on the skin. I was Jatob (JATOB)
A) is a tree belonging to the genus Cucumber in the legume family, and is referred to as the Japanese name Cucumber, Scientific name Hymenaea courbaril.
Distributed in tropical America, height 15-40 m, trunk diameter 100
~ 200 cm, bark is light gray to gray. The wood is used as wood for furniture, etc., the bark, resin, endothelium are deworming, stomach,
It is used for bronchitis, cystitis, urination, prostatitis, gonorrhea and the like. Beans are considered edible. It has already been disclosed that the extract obtained by extracting Jatoba nuts and bark with water, ethanol or the like is used for whitening cosmetics (Japanese Patent Application Laid-Open No.
-12441 publication).

[0003]

However, there is a problem that the relationship between the extraction method of Jatoba and the extracted substance and the chemical structure of the extracted substance involved in the whitening action have not been clarified. That is, some tannins are used in cosmetics, but condensed tannin-based substances are not used in cosmetics, and trimeric or higher condensed tannins obtained by fractionating Jatoba extract No whitening effect of the system was known.

[0004] The present invention has been made to address such a problem, and by elucidating the chemical structure of Jatoba extract, it is safe to apply to the skin and has a large whitening effect. An object of the present invention is to provide a whitening cosmetic containing a substance effective for rough skin and the like.

[0005]

Means for Solving the Problems The whitening cosmetic of the present invention comprises:
A substance that can be represented by Chemical Formula 1, and is dissolved in a hydrophilic solvent,
And n is 1 or more.

[0006]

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Another whitening cosmetic of the present invention is a whitening cosmetic containing an extract of Jatoba, which is obtained by treating Jatoba with a non-aqueous solvent and then extracting it with a hydrophilic solvent. It is an extract and a substance represented by Chemical Formula 1.

[0008]

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Here, n is 1-14.

[0010] Further, the extract obtained by extraction with a hydrophilic solvent is fractionated with water and ethanol in that order and then further extracted with at least an aqueous solution of methanol and acetone.
It is an extract obtained by fractionation with one hydrophilic solvent.

The present inventors have screened plants which have been used for food for many years and have been confirmed to be safe for the human body, and have studied those which have utility as whitening cosmetics and whitening cosmetics. As a result, they have found that the above-mentioned substance, which is an extract of Jatoba, is effective as a whitening cosmetic raw material or as a quasi-drug.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The substance represented by the chemical formula 1 is a kind of condensed tannin-based substance and is contained in jatoba, cedar, hinoki and the like. Taking Jatoba as an example, the method of solvent extraction and fractionation will be described. After degreasing the skin of Jatoba with a non-aqueous solvent, extract with a hydrophilic organic solvent,
Further fractionation gives the condensed tannin-based substance according to the present invention.

The non-aqueous solvent according to the present invention does not show an affinity for water, and any non-aqueous organic solvent which can effectively defatting oils and fats such as the skin of Jatoba can be used. Specifically, petroleum ether, aliphatic hydrocarbons such as n-hexane, benzene, diethyl ether and the like are preferable. Among these, petroleum ether and n-hexane are suitable for degreasing the skin of Jatoba, especially for removing terpenes.

The hydrophilic solvent according to the present invention is a solvent having an affinity for water, for example, a hydrophilic organic solvent having a hydrophilic group such as a hydroxyl group, a carboxyl group and a carbonyl group in the molecule. Examples include ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, acetone and the like. Water is also included in the hydrophilic solvent.

Among these hydrophilic solvents, in order to extract the peel of Jatoba after the degreasing treatment to obtain the condensed tannin-based material of the present invention, a mixed solvent of water and acetone, Alternatively, methanol is preferred, and a mixed solvent of water and acetone is particularly preferred for obtaining more condensed tannin-based substances. The mixing ratio of water and acetone is 50
An aqueous solution of 100% by weight of acetone is preferred, more preferably 60 to 90% by weight, even more preferably 65 to 75% by weight, most preferably 70% by weight of acetone. Within this range, a trimer or higher condensed tannin-based substance can be obtained from the skin of Jatoba after degreasing by subsequent fractionation means.

As the fractionation means, liquid-liquid distribution, reversed-phase column chromatography, high-performance liquid chromatography, gel filtration, ion exchange resin, adsorption distribution and the like can be used alone or in combination.

The extract of Jatoba peel extracted with 70% by weight acetone aqueous solution is adsorbed and distributed by Sephadex LH.
A method for fractionation by column chromatography using -20 will be described. The fractionation can be performed by sequentially flowing a hydrophilic solvent through Sephadex LH-20 to which the pericarp extract has been applied, and thereby fractionating as a substance eluted in the order of dissolution in each solvent. As the order of the hydrophilic solvent, water,
Examples include ethanol, methanol, and a 70% by weight aqueous solution of acetone. For the Jatoba peel extract, water and ethanol were fractionated in this order, followed by methanol, 7
Fractionation in the order of 0% by weight acetone aqueous solution is preferable in order to obtain a condensed tannin-based substance of trimer or more in Chemical Formula 1.

In addition, the upper limit of n in Chemical Formula 1 can be suitably used as a whitening cosmetic material as long as it is within the range of dissolving in a hydrophilic solvent. More specifically, n is 1 to 1
4 is preferable, and n is more preferably in the range of 1 to 10. Note that the purity of the obtained substance can be selected depending on the cost required for the separation and the application. Further, it can be used as a solution of a hydrophilic solvent or as a powder after freeze-drying.

After degreasing with a non-aqueous solvent, the substance obtained by extraction and fractionation with a hydrophilic organic solvent is used to determine the degree of polymerization by gel permeation chromatography or the like, and the chemical structure of the substance by nuclear exchange or methylation nucleation. It can be determined by an exchange method or the like. The nuclear exchange method and the methylated nuclear exchange method are described, for example, in the journal of the Japan Wood Science Society (vol.33, No. 7, p582-588).
(1987)).

The obtained substance and other cosmetic ingredients such as liquid oils such as squalane and jojoba oil, solid oils such as beeswax and cetyl alcohol, various activators, glycerin, 1,3-
By adding a humectant such as butylene glycol or various chemicals, it is possible to prepare whitening cosmetics of various dosage forms. For example, lotions, creams, emulsions, packs and the like can be used according to the purpose.

Since the substance represented by the chemical formula 1 exhibits strong tyrosinase activity inhibition, cosmetics containing this substance are:
Has an excellent whitening effect.

[0022]

EXAMPLE A production example of the substance represented by the chemical formula 1 used for the whitening cosmetic of the present invention and determination of its structure will be described. Production Example 1 and Production Example 2 1) Preparation of sample by degreasing, extraction and fractionation 108 g of Jatoba peel (dried product) was pulverized, and petroleum ether
12 hours with 500 ml, then 12 times with 500 ml of n-hexane
It was degreased for hours. After defatting Jatoba peel
Extraction was performed for 10 hours with 500 ml of a weight-% acetone aqueous solution. The extract was filtered using filter paper (No. 5C). The residue was further extracted with 500 ml of 70% by weight acetone aqueous solution for 10 hours,
The extract was filtered using filter paper (No. 5C). The two filtrates were collected, evaporated and lyophilized. as a result,
19.2 g of a solid was obtained. This solid is separated by Sephadex L
The fraction was fractionated on a 3.5 cmφ × 45 cm column packed with 100 g of H-20. The eluate is water, ethanol, methanol, 70
A 1% by weight aqueous solution of acetone was flowed in order. The methanol fraction was evaporated and lyophilized to prepare Preparation Example 1, and the 70% by weight acetone aqueous solution fraction was evaporated and lyophilized to Preparation Example 2. The fraction eluted with water was named Comparative Production Example 1, and the fraction eluted with ethanol was named Comparative Production Example 2.

2) Structure determination of sample by nuclear exchange method and methylated nuclear exchange method 20 mg of Production Example 1 was sampled, and a nuclear exchange reagent (xylene: phenol: BF ₃ -phenol complex salt = 19: 10: 10: 3)
(V / V)), and reacted at 80 ° C. for 4 hours. The reaction product was analyzed by gas chromatography. The analysis conditions were as follows: the column was a methyl silicon capillary column QU
ADREX-S2006 (0.25mmφ, 25m, 0.25μm fil
The initial temperature is 130 ° C, the heating rate is 3 ° C / min., the final temperature is 190 ° C, the detector is FID, and the injection temperature is 230 ° C. As a result of the analysis, phloroglucinol was detected. Also, set the reaction conditions at 150 ° C.
After 4 hours, the same reaction was carried out and analyzed by gas chromatography under the same conditions. As a result, catechol was detected. When the same reaction and analysis were performed on Production Example 2, phloroglucinol and catechol were detected as in Production Example 1. The results of the above nuclear exchange method show that phloroglucinol was released from ring A and catechol was released from ring B, and that Production Examples 1 and 2 were procyanidin types.

Next, the presence or absence of ring opening of the heterocycle was examined by the methylation nuclear exchange method. The preparation 1 15mg collected K ₂ CO
₃ Add 0.5g, acetone 5ml, dimethyl sulfate 0.5ml
The reaction was performed at 65 ° C. for 3 hours. Using this, a nuclear exchange method was carried out and reacted at 80 ° C. for 2 hours and analyzed by gas chromatography. The analysis conditions were as follows: the column was a methyl silicon capillary column QUADREX-S2006 (0.25
mmφ, 25m, 0.25μm film thickness), Column temperature is initial temperature 70 ℃, heating rate 7.5 ℃ / min., final temperature 250
° C, detector FID, injection temperature 230 ° C. As a result of the analysis, phloroglucinol dimethyl ether was detected. When the same reaction and analysis were performed on Production Example 2, phloroglucinol dimethyl ether was detected. If the heterocycle is open, phloroglucinol trimethyl ether will be detected, and the result of the above methylated nuclear exchange method indicates that the heterocycle is closed.

3) Measurement of molecular weight The molecular weights of Production Examples 1 and 2 were measured by gel permeation chromatography. The analysis conditions were as follows: Shodex kf804-kf802 column, THF in which the eluate was rectified, flow rate 0.1 ml / min.
nm. The average molecular weight is (+)-catechin, synthetic procyanidin dimer, polystyrene 2200, 90
It was calculated by a regression equation using a calibration curve using 00 and 25000.

The measurement results show that the average molecular weight of Production Example 1 was 145.
3, and the average degree of polymerization in Chemical Formula 1 was estimated to be 5.0. In this case, n in Chemical Formula 1 is 3. The average molecular weight of Production Example 2 was 3461, and the average degree of polymerization in Chemical Formula 1 was estimated to be 11.9 (n = about 10). As a result of measuring the average molecular weights of Comparative Production Example 1 and Comparative Production Example 2 by the same method as Production Example 1 and Production Example 2, they were 435 and 439, respectively, and the average degree of polymerization was estimated to be 1.5.

4) Evaluation of Production Example 1 and Production Example 2 (a) B16 melanoma cell test A specimen (for example, Production Example 1) was prepared so as to have a predetermined concentration.
After adding to the Eagle MEM medium and filtering through a sterilization filter,
Add 10% fetal calf serum and adjust the pH to 7.6 soil 0.1
Adjusted with sodium bicarbonate to be, dispensed 6ml content in Shiyare, B16 melanoma cell suspension (1 × 10 ⁶
cell / ml), 5% CO ₂ , 95% air
And cultured at 37 ° C for 3 days. Further, medium exchange (Eagle M containing 10% fetal bovine serum containing the above sample)
EM medium) and cultured for 3 days (at this time, cell proliferation was determined). Thereafter, the cells were detached, centrifuged to collect the cells, and the degree of whiteness was visually determined. Table 1 shows the results. Kojic acid, which is known as a whitening agent, was used for comparison. The blank is a case where no sample is added.

[0028]

[Table 1]

As shown in Table 1, Production Examples 1 and 2 exhibited good whiteness.

(B) Tyrosinase activity inhibition test 0.9 ml of a phosphate buffer solution (pH 6.8, 30 mM), 1.0 ml of a 1.66 mM tyrosine solution, and a 0.1% by weight aqueous solution of a sample (for example, Production Example 1). 1.0 ml was placed in a screw vial and heated in a constant temperature water bath at 37 ° C. for 5 minutes or more. Tyrosinase solution (Si
gma, mushroom-derived, 914 units / ml)
Add 0.1 ml, and keep it warm in a constant temperature water bath at 37 ° C.
The absorbance was measured at 75 nm, and the tyrosinase activity inhibition rate was determined by the following formula. As a blank, pure water was added instead of the sample, and the measurement was performed in the same manner. In this test, the final concentration of the sample is 0.033%. Table 2 shows the results.

Tyrosinase activity inhibition rate (%) = [ΔB−
(A−P)｝ / B] × 100 where A: absorbance of sample, B: absorbance of blank,
P: Absorbance due to coloring of sample (3 times dilution)

[0032]

[Table 2]

As shown in Table 2, Production Examples 1 and 2 showed strong inhibition of tyrosinase activity.

Embodiment 1 An example of a lotion will be described. The components and amounts (% by weight) are shown below. Olive oil 0.5 Production example 1 0.5 Polyoxyethylene (20E.0) sorbitan monostearate 2.0 Polyoxyethylene (60E.0) hydrogenated castor oil 2.0 Ethanol 10.0 Sodium hyaluronate aqueous solution ( 1.0% by weight) 5.0 Purified water 80.0

The purified water and an aqueous solution of sodium hyaluronate are added, and the temperature is adjusted to 70 ° C. by heating. Add polyoxyethylene (20E.0) sorbitan monostearate and polyoxyethylene (60E.0) hydrogenated castor oil to olive oil and heat to 70 ° C. The oil phase was added to the previously prepared aqueous phase, pre-emulsified, and the extract of Production Example 1 and ethanol were added to homogenize the emulsified particles with a homomixer, followed by degassing, filtration, and cooling. 1 lotion was obtained.

Example 2 An example of a cream will be described. The components and amounts (% by weight) are shown below. A component Squalane 20.0 Olive oil 2.0 Mink oil 1.0 Jojoba oil 5.0 Beeswax 5.0 Cetostearyl alcohol 2.0 Glycerin monostearate 1.0 Sorbitan monostearate 2.0 B component Purified water 47. 9. Polyoxyethylene (20E.0) sorbitan monostearate O Polyoxyethylene (60E.0) hydrogenated castor oil 1.0 Glycerin 5.0 Production Example 2 1.0 Aqueous sodium hyaluronate (1.0% by weight) 5.0 Methyl paraoxybenzoate 0.1

The components A and B were each weighed and heated to 70 ° C., and the component A was gradually added to the component B with stirring, and then cooled to 30 ° C. while stirring slowly. I got a cream.

The cosmetics obtained in Examples 1 and 2 were subjected to the following use tests. Use test The face of 6 women was divided into left and right. One face was used as an example, and the other face was used as a comparative example. The lotion of Example 1 and the cream of Example 2 were used at least once every day. A month later, a questionnaire was conducted based on the following criteria. Note that Comparative Examples 1 and 2 were the same as Examples except for Production Example 1 and Production Example 2 except that water was used.

The judgment criteria were represented by the following scores, and the results were totaled. Example is very good 3 points Example is considerably better 2 points Example is slightly better 1 point No difference between example and comparative example 0 point Comparative example is slightly better -1 point Comparative example is much better -2 points Comparative example is much better -3 points

The questionnaire totaling results of the six subjects were 12 points. As a result, a cosmetic product having an excellent whitening effect was obtained by blending the substances of Production Examples 1 and 2.

[0041]

Industrial Applicability The present invention contains a substance represented by the chemical formula 1, which is dissolved in a hydrophilic solvent and has n of 1 or more, so that the substance has an excellent whitening effect by a B16 melanoma cell test. And tyrosinase activity inhibitory effect,
A whitening cosmetic product having an excellent whitening effect can be obtained.

Further, since Jatoba is treated with a non-aqueous solvent and then extracted with a hydrophilic solvent, it contains a substance represented by the chemical formula 1, so that a whitening cosmetic product excellent in safety and whitening effect can be obtained. .

Further, after treating Jatoba with a non-aqueous solvent, an extract obtained by extraction with a hydrophilic solvent is fractionated with water and ethanol in that order, and then at least one hydrophilic solution selected from methanol and acetone aqueous solution. Since it contains an extract fractionated with a neutralizing solvent, a whitening cosmetic product excellent in safety and whitening effect can be obtained.

Claims (3)

[Claims] 1. A whitening cosmetic containing the substance represented by the chemical formula 1, wherein the substance is dissolved in a hydrophilic solvent and n is 1 or more. 2. A whitening cosmetic containing an extract of Jatoba, wherein the extract is an extract obtained by treating the Jatoba with a non-aqueous solvent and then extracting the same with a hydrophilic solvent,
And a whitening cosmetic characterized by being a substance represented by Chemical Formula 1 Here, n is 1-14. 3. The extract obtained by extraction with the hydrophilic solvent is fractionated with water and ethanol in that order and then further extracted with at least one selected from methanol and acetone aqueous solution.
3. The whitening cosmetic according to claim 2, which is an extract fractionated with one hydrophilic solvent.