JP2003321337A - Cosmetic for protection against active oxygen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic with no offensive smell having a high protecting ability against active oxygen which inhibits aging such as appearance of wrinkled or saggy skins caused by lowering in the resistance to active oxygen with age. <P>SOLUTION: The cosmetic is compounded with an extract obtained by removing essential oil components from an extract which is extracted from cloves with a lower alcohol and/or water, or an extract extracted from cloves, of which the essential oil components are previously eliminated, with the lower alcohol or water. <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly active oxygen protective effect for suppressing aging and disorders such as wrinkles and sagging of the skin caused by deterioration of active oxygen tolerance with aging. The present invention relates to an active oxygen protective cosmetic composition having no odor and having an unpleasant odor. [0002] Aerobic organisms such as human beings use oxygen to obtain energy necessary for life activities, but are also constantly exposed to the toxicity of active oxygen generated from oxygen. As active oxygen, superoxide, hydroxyl radical, hydrogen peroxide, singlet oxygen and the like are known, and these also generate various free radicals. It is thought that active oxygen and free radicals attack lipids, sugars, proteins, DNA, and the like, and as a result, induce or promote aging such as wrinkles and sagging in various diseases and skin. Active oxygen is also generated inside living cells, but active oxygen generated by irradiation with solar ultraviolet rays is particularly important. Originally, in living organisms, SOD (superoxide dismutase), which makes superoxide non-uniform into hydrogen peroxide and oxygen, catalase, peroxidase, which decomposes hydrogen peroxide, and free radicals generated from active oxygen, are trapped to form a radical chain reaction. Although it has a defense mechanism against active oxygen and free radicals such as radical scavengers such as vitamin C and vitamin E which stop, but with the aging, SO
It is said that skin aging occurs due to a decrease in the expression level of enzymes such as D and catalase and a decrease in enzyme activity. Also, in recent years, the amount of ultraviolet rays reaching the ground surface due to the expansion of the ozone hole has increased, and the amount of active oxygen generated has also increased, and the importance of protection against active oxygen has increased. [0003] For this reason, conventionally, for the purpose of protection against active oxygen, enzymes such as SOD and catalase, ascorbic acid, tocopherol, oryzanol, plant extracts (hamamelis, melissa, enmeisou, birch, sage, rosemary, age, basil, The use of ginkgo, psycho, peonies, hanger, calyx, lysium, gougon, carrot, licorice, ginger, linden, shobu, tsuldokudami, clove) and the like has been proposed. [0004] However, SOD
Enzymes such as and catalase have extremely low stability in cosmetics, and ascorbic acid, tocopherol, and oryzanol have radical scavenging effects, but not enough to scavenge active oxygen. It is not sufficient, and the odor of the cosmetic may be impaired due to the strong odor derived from plants, and it has not been satisfactory as a cosmetic aiming at an active oxygen protective effect. Particularly, cloves contain a large amount of essential oil components such as eugenol which is a strong odor component, and the clove extract used so far contains an essential oil component such as eugenol, which is unique to eugenol and the like. The strong odor was unsuitable for basic cosmetics. In addition, the confirmation test of the `` clove extract '' of the compounding component standard according to cosmetic varieties is only for the qualitative confirmation of eugenol, that is, the essential oil obtained by steam distillation of the clove extract has a odor peculiar to clove, that is, the eugenol odor, Only shows the coloration of the phenolic hydroxyl groups of eugenol. In addition, in the name column of “clove extract” (also known as “clove extract”) in the list of items on the list of existing additives of food additives, “eugenol obtained from clove buds, leaves or flowers, and Do ". As described above, the clove extract used in cosmetics and foods contains eugenol, and there is no interest in components other than eugenol. It was thought to be due to eugenol. It has not been known that a clove extract mainly containing tannins from which essential oil components such as eugenol have been removed has a high active oxygen protective effect. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a cosmetic that has a high active oxygen protective effect and has no unpleasant odor. Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have high safety and have a strong erasing effect of superoxide which is initially generated by ultraviolet irradiation, and As a result of searching for a substance having a high action of suppressing superoxide damage to fibroblasts, which are cells of the dermis, the present inventors have reached the present invention. That is, the present invention relates to a clove (Diptera,
An active oxygen blended with an extract obtained by removing essential oil components from an extract obtained by extracting a flower bud of a Japanese crested cypress) with lower alcohol and / or water, or an extract obtained by extracting a clove whose essential oil components have been previously removed with lower alcohol and / or water. It is a protective cosmetic. Hereinafter, the present invention will be described in detail. The clove used in the present invention is also called clove, and is a member of the family Myrtaceae (scientific name: Eugenia carryop).
(Hylata ) flower bud, which is used as a spice and a herbal medicine, and can be easily obtained. In order to obtain the clove extract used in the present invention, it may contain leaves and stems in addition to the flower buds, but it is preferable to use only the flower buds. As an extraction solvent for obtaining a clove extract, one or more selected from lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol and water can be used. If the proportion of water in the extraction solvent is high, a large amount of the pigment component is extracted and the appearance of the added cosmetic may be impaired. Therefore, as the extraction solvent, an ethyl alcohol aqueous solution having an ethyl alcohol concentration of 50% by weight or more and / or A methyl alcohol aqueous solution having a methyl alcohol concentration of 50% by weight or more is preferable,
More preferably, the concentration of ethyl alcohol is 70% by weight or more. The amount of the above-mentioned extraction solvent is not particularly limited,
It is equivalent to 20 times, preferably equivalent to 5 times by weight relative to the clove. Also, the extraction temperature is not particularly limited, and the extraction can be performed at low temperature, normal temperature or by heating. The clove extract used in the present invention needs to remove essential oil components such as eugenol. It is not preferable that essential oil components such as eugenol remain contained since the fragrance of the added cosmetic is impaired. Examples of the method for removing essential oil components such as eugenol include a method of removing the same by steam distillation before extraction of a clove, and a method of adding water or blowing steam after the extraction and azeotropically removing water. And either method may be used. The thus-obtained clove extract from which essential oil components have been removed may be used as it is, may be used after being concentrated, or may be used after being completely or appropriately concentrated and then dissolved in a solvent. . The solvent that dissolves after the concentration is not particularly limited, but is preferably one commonly used in cosmetics, such as water, ethyl alcohol, isopropyl alcohol, glycerin, propylene glycol, and 1,3-butylene glycol. And the like. [0013] These clove extract from which essential oil components have been removed, a concentrate obtained by concentrating the extract, or an extract dissolved in a solvent after concentration may be added to cosmetics as they are, but in aqueous cosmetics such as lotion. Since the water-insoluble component precipitates or separates, it is preferable to remove the water-insoluble component before use. The water-insoluble component can be removed by adding water to the extract or the concentrate to dissolve the water-soluble component, and then performing filtration or the like. The step of removing the water-insoluble component may be before or after the step of removing the essential oil component.
When the water-insoluble component is removed after removing the essential oil component, it can be used as it is, after concentrating it into a concentrate, or dissolving it in the above-mentioned solvent after concentration to obtain an extract, and then using it in cosmetics. . When removing the essential oil component after removing the water-insoluble component, after removing the essential oil component, similarly, after concentrating this to a concentrate, or dissolving in the above-mentioned solvent after concentration to obtain an extract, Can be used for cosmetics. The above-mentioned clove extract can be used by separating or concentrating tannins in order to enhance the active oxygen defense activity. Examples of the method include solvent extraction with ethyl acetate or the like, and separation and purification by column chromatography using silica gel or a synthetic adsorbent as a carrier. [0015] The thus-obtained clove extract has a solid content of 0.0001 to
2% by weight, preferably 0.001 to 1% by weight.
If the content is 0.0001% or less, a sufficient active oxygen protective effect cannot be obtained, and if the content is 2% or more, the effect does not change much and the color of the cosmetic is adversely affected, which is not preferable. The cosmetic containing the active oxygen protective agent of the present invention is not particularly limited, and creams, emulsions, lotions, serums, packs, sunscreens, foundations, hair tonics, hair stylings, etc. Can be exemplified. Various components used in cosmetics, quasi-drugs, pharmaceuticals and the like can be arbitrarily added to the cosmetics containing the active oxygen protective agent of the present invention. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The units of numerical values in the following examples are% by weight unless otherwise specified. [Preparation Example 1] 200 g of ethyl alcohol was added to 100 g of dried clove, and the mixture was refluxed for 1 hour and filtered to obtain an extract. Ethyl alcohol (200 g) was added to the residue again, and the mixture was refluxed for 1 hour and filtered to obtain an extract. The two extracts were combined, concentrated under reduced pressure, 400 g of purified water was added to remove the precipitated water-insoluble component by filtration, concentrated under reduced pressure, and 400 g of purified water was added again to filter and concentrate. Do
Essential oil components such as eugenol were completely removed by azeotropic distillation with water to obtain a solid content of 4.0 g. Production Example 2 The procedure of Comparative Example 1 was repeated except that an 85% aqueous ethyl alcohol solution was used, to obtain 8.3 g of a solid content. Production Example 3 Purified water 100% was added to 5.0 g of the solid content of Production Example 2.
g was added and dissolved, and 100 g of ethyl acetate was added thereto. After sufficiently stirring, the ethyl acetate phase was recovered. Perform this operation a total of 5
This was repeated twice, and the obtained ethyl acetate extract was concentrated under reduced pressure to obtain 1.2 g of a solid content rich in tannins. still,
The tannin content measured by the Folin-Denis method using gallic acid as a reference substance was as follows.
The solid content of Production Example 3 was 72.3%. Comparative Production Example 1 200 g of ethyl alcohol was added to 100 g of dried clove, and the mixture was refluxed for 1 hour and filtered.
An extract was obtained. Ethyl alcohol (200 g) was added to the residue again, and the mixture was refluxed for 1 hour and filtered to obtain an extract. The two extracts were combined and concentrated under reduced pressure to obtain 6.7 g of a solid containing essential oil components such as eugenol. [Superoxide erasing activity] The superoxide erasing activity of the clove extract and the like of Production Examples and Comparative Production Examples was measured by the following method. Take 0.5 mL of 0.05 M sodium carbonate buffer (pH 10.2), and add 3 mM Hypo.
xantine (HPX) 0.1 mL, 3 mM E
DTA 0.1mL, 0.15% Bovine Se
rum Albumin 0.1 mL, 0.19 mM
Nitro Blue Tetrazorium
Add 0.1 mL, 0.3 mL of each sample aqueous solution of a predetermined concentration, and 1.7 mL of distilled water. This is kept at 25 ° C. for 10 minutes, and 0.2 unit / mL Xanthine Oxi
0.1 ml of Dase (XOD)
After holding for 1 minute, the reaction is stopped by adding 0.1 mL of 6 mM copper chloride, and the absorbance (At) is measured at 560 nm. At the same time, as a blank test, a sample to which distilled water was added instead of the sample solution was similarly operated, and the absorbance (Ab), Xanthin
The absorbance (Ao) is measured in the same manner as above except that distilled water is added instead of the oxidase solution, and the superoxide elimination ratio is calculated by the following equation. Erasure rate (%) =
{Ab− (At−Ao)} / Ab × 100 The results are shown in Table 1. From this result, the clove extract of the present invention was 10 p
It can be seen that the superoxide scavenging activity is higher than that of the pentagon extract, rosemary extract and ascorbic acid at any concentration of pm and 1 ppm. Further, it can be seen that the clove extract containing a large amount of tannins of Production Example 3 has higher superoxide erasing activity than those of Production Examples 1 and 2. [Table 1] [Effects of Reducing Human Fibroblasts by Active Oxygen]
The effect of suppressing the damage of human fibroblasts by active oxygen was measured by the following method for the clove extract and the like of Production Examples. 5% fetal bovine serum (F
BS) and 0.1 mM L-glutamine
cco's modified Eagle media
Human fibroblasts precultured with um (DMEM) are seeded at 3 × 10 ⁴ cells per well in a 96-well microplate, and cultured at 37 ° C., 5% CO ₂ for 1 day. 5% F
The medium is exchanged with DMEM containing BS, 0.1 mM L-glutamine and a predetermined amount of a sample, and cultured at 37 ° C. for 24 hours. The cells were washed with Hank's buffer (HBS) to remove the sample, 4.5 mM HPX, 1500 uni.
t / mL catalase, 300 uint / mL XOD
33 μL of each HBS solution is added to generate superoxide, and incubated at 37 ° C. for 2.5 hours. Cells were grown with 1.26 mM calcium chloride and 0.8
After washing with HBS containing 1 mM magnesium sulfate, MT
The cell viability is determined by the T method. 5% FBS, 0.
1 mM L-glutamine and 1 mM 3- [4,5-di
methylthiazol-2-yl] -2,5-d
iphenyltetrazolium bromide
e) Add DMEM containing (MTT) to the cells and incubate at 37 ° C for 2 hours. During this time, mitochondria of living cells reduce MTT to blue formatazan.
And live cells are stained. 2-propanol 100
Extract blue formatazan with μL, 560n
m and the absorbance at 650 nm.
Determine the amount of formatan. At the same time, the sample without addition was subjected to the same operation to obtain a survival rate of 0%, and the sample without addition of the HBS solution of catalase and XOD and instead of the same amount of HBS was operated similarly. Then, the survival rate is set to 100%, and the survival rate of each sample is calculated. The results are shown in FIG. From these results, the clove extract of the present invention, at any concentration tested, has a significantly higher fibroblast survival rate than the gougy extract, rosemary extract and ascorbic acid,
The clove extract maintained a high survival rate even at a low concentration of 1 ppm, indicating that the clove extract was extremely effective as an active oxygen protective agent. In addition, since there is no large difference in the survival rate between 10 ppm and 1 ppm in the clove extract, the clove extract has a function of increasing the expression level of SOD in fibroblasts or increasing the SOD enzyme activity. It is suggested that the compound has an effect of improving oxide resistance. Furthermore, the clove extract containing a large amount of tannins obtained in Production Example 3 has a significantly higher fibroblast survival rate at any concentration than those obtained in Production Examples 1 and 2; It was suggested to be the main component of the activity. FIG. 1 Formulation Example 1 Lotion A lotion having the following formulation was prepared. The lotion containing the clove extract of Production Examples 1 to 3 had no problem in appearance and odor, but the lotion containing the clove extract containing eugenol of Comparative Production Example 1 had a peculiar smell. However, it was unsuitable for use as a lotion. (1) 1,3-butylene glycol 6.00% (2) concentrated glycerin 4.00% (3) polyethylene glycol 1000 1.00% (4) sodium lactate solution (50%) 0.05% (5) butterfly Extract 0.10% (Production Examples 1 to 3, Comparative Production Example 1) (6) Preservatives Appropriate (7) Purified Water Residue [Formulation Example 2] Emollient Cream (1) Squalane 23.00% (2 ) Stearyl alcohol 6.00% (3) Polyoxyethylene (25) cetyl alcohol ether 1.00% (4) Stearic acid 2.00% (5) Glycerin monostearate 2.00% (6) 1,3- Butylene glycol 6.00% (7) Polyethylene glycol 1000 4.00% (8) Concentrated glycerin 2.00% (9) Clove extract (Production Example 1) 0 10% (10) Preservative Appropriate amount (10) Purified water Residue [Formulation Example 3] Foundation (1) Stearic acid 2.4% (2) Propylene glycol monostearate 2.0% (3) Cetostearyl alcohol 0.2% (4) Liquid lanolin 2.0% (5) Liquid paraffin 3.0% (6) Isopropyl myristate 8.5% (7) Sodium carboxymethyl cellulose 0.2% (8) Bentonite 0.5% (9) Propylene glycol 4.0% (10) Triethanolamine 1.1% (11) Titanium oxide 8.0% (12) Talc 4.0% (13) Bengala 3.0% (14) Yellow iron oxide 2.5% (15) Black iron oxide 0.5% (16) Clove extract (Production Example 2) 0.1% (17) Fragrance 0.1% (18) Preservative proper amount (1) As described above in detail, the extract of clove has a high superoxide scavenging activity and, even at a low concentration, greatly suppresses the damage of fibroblasts caused by superoxide. It is extremely useful as an active oxygen protective agent. In addition, the extract of the present invention containing no essential oil components such as eugenol can be blended in cosmetics without impairing the odor of the cosmetics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61P 17/16 A61P 17/16 43/00 111 43/00 111 (72) Inventor Atsuyuki Miyamoto Izumiotsu, Osaka Rinkaicho 1-chome No.20, Sakamoto Yakuhin Kogyo Co., Ltd.F-term (reference) 4C083 AA111 AA112 AB232 AB242 AB432 AB442 AC022 AC072 AC092 AC122 AC182 AC242 AC302 AC352 AC392 AC422 AC542 AD042 AD272 AD512 CC02 CC04 CC05 CC12 DD23 DD27 DD31 EE12 EE13 4C88 AB57 AC03 BA09 BA10 CA05 CA06 MA63 NA14 ZA89 ZC02

Claims (1)

[Claim 1] An extract obtained by removing an essential oil component from an extract obtained by extracting a clove (Myrtaceae, flower bud) with lower alcohol and / or water, or a clove having an essential oil component removed in advance. An active oxygen protective cosmetic comprising an extract extracted with lower alcohol and / or water.