JP3107583B2 - Skin and hair cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to skin and hair cosmetics containing a component mainly composed of an antioxidant active substance present in a green leaf juice of a green plant.

[0002] Conventionally, skin and hair cosmetics have been formulated with drugs for various purposes. In particular, antioxidants have been added to enhance the preservability thereof and to suppress the production of lipid peroxide in the skin epidermis. Compounding is also performed, but no compound suitable for compounding with excellent effects as an antioxidant and excellent safety has not been found so far.

Conventional antioxidants include tocopherols, BHA, BHT, vitamin C (kojic acid) and the like.
Tocopherols are limited to oils, BHA and BHT are not always satisfactory in terms of safety, and vitamin C has limited applications.

[0004] The present inventors have found that wheat plants and others, which have been shown to contain a large number of physiologically active components such as antitumor, antihyperlipidemic, hypoglycemic, and antiviral activities. Focusing on the green leaves of green plants (including seaweeds, the same applies hereinafter), the components were examined from the standpoint of antioxidant properties.

As a result, grasses such as wheat plants,
Among the green leaf components of other green plants, a component having a strong antioxidant activity equal to or higher than that of α-tocopherol is contained, which is used for prevention of spots, freckles, rough skin, ultraviolet sunburn (sunburn) and the like. It was found to be extremely effective and safe, and completed the present invention.

Thus, the present invention provides a skin and hair cosmetic containing an antioxidant active substance extracted from green leaves of green plants.

Hereinafter, the antioxidant substance extracted from the green leaves of the green plant, which is incorporated in the cosmetic of the present invention, will be described in more detail. In addition, the water content% of the water-containing alcohol in this specification is based on v / v%.

As a green plant to be used as a raw material, a wheat plant is preferred, but in addition, clover, alfalfa, kale, spinach, lettuce, parsley, celery, cabbage, Chinese cabbage, mizuna, green pepper, carrot green leaf, radish Pastures, vegetables, and wild plants such as green leaves, sasa, and ashitaba; freshwater or marine green algae such as spirulina, chlorella, wakame, and blue seaweed can also be used.

Barley is the most suitable wheat plant for use in the present invention.
Barley, oats, oats, corn, millet, Italian diegrass and the like can also be used.

In the present invention, fresh stems and / or leaves of these green plants, particularly young plants harvested before the maturity stage among the wheat plants (these are collectively referred to as "green leaves" in this specification) ) Are particularly suitable.

The green leaves of a green plant, for example, a wheat plant,
The juice is squeezed by a mechanical crushing means such as a mixer, a juicer, etc., and, if necessary, the squeezed liquid (hereinafter referred to as "green juice") is removed by removing coarse solids by means such as sieving and filtration. Prepare.

Next, the green juice obtained by drying the green juice as it is or by a suitable drying means such as freeze-drying or spray-drying is extracted with a sufficient amount of water or n-hexane. This extraction treatment can be usually performed at room temperature, and may be repeated twice or more depending on the case, whereby the water-soluble component or n-
The component substantially insoluble in hexane is separated and recovered. At this stage, the recovered extract can be dried and solidified in the same manner as described above.

The water-soluble component or n-hexane-insoluble component thus obtained is then treated with a water-containing ethanol having a water content of 0 to 80%, preferably 10 to 70%, more preferably 15 to 50%, for example, a water-containing ethanol having a water content of 20%. An extraction treatment is performed with ethanol, and components soluble in the aqueous ethanol are separated and collected.

The extraction treatment with aqueous ethanol is carried out by using a green juice prepared as described above, or a water-soluble component of green leaves from which water-insoluble components have been completely removed, or a suitable drying means such as freeze-drying or spray-drying. And drying can be carried out directly on the powder obtained.

The aqueous ethanol-soluble component thus recovered can be used as the antioxidant active substance of the present invention as it is or by concentrating or distilling off the solvent.

Further, according to the present invention, if necessary, the above-mentioned aqueous ethanol-soluble component can be added to a suitable adsorbent such as St.
yrene-DVB resin adsorbent (e.g., Rohm & Haas, Amberlite ^R adsorbent XSD-2)
Etc. and a water content of 0 to 80%, preferably 20 to 7
By performing the elution treatment with 0%, more preferably 30 to 60% aqueous methanol, a component soluble in the aqueous methanol can be recovered. As a result, a fraction having more excellent antioxidant activity can be obtained.

The aqueous methanol-soluble component thus recovered can be used as the antioxidant active substance of the present invention as it is or by concentrating or removing the solvent.

Further, the water-soluble methanol-soluble component thus recovered from barley is purified by recrystallization using, for example, water-containing methanol having a water content of 30 to 70%, preferably 40 to 60%. The body of the antioxidant active substance can be obtained as slightly yellow crystals. The body of the antioxidant active substance thus isolated is NM
R, the result of analysis such as mass spectrometry, the following formula

[0019]

Embedded image 2′-O-glycosyl-isovitexin having the structure represented by the following formula (see Reference Example 1 described later). The antioxidant active substance thus isolated can be blended with a cosmetic base.

The antioxidant active substance having the above structural formula or a structure similar thereto is contained in the green leaves of green plants such as wheat plants, which is the active ingredient of the antioxidant active substance of the present invention. It is presumed that they do.

The antioxidant active substance prepared as described above is pale yellow to colorless, water-soluble and alcohol-soluble, and has excellent absorbability in living bodies. Cosmetics, for example, water, alcohol,
It can be easily incorporated into alcohol aqueous solutions, lotions, creams, cream emulsions, hair tonics, hair restorers, bath preparations, soaps, ointments, etc. without substantially affecting their composition or appearance. it can.

The amount of the above-mentioned antioxidant active substance can be varied in a wide range depending on the kind and use of the cosmetic, but generally, it is 0.01 to 10% by weight based on the cosmetic base. Preferably, it is suitable to be blended in the range of 0.1 to 5% by weight.

The cosmetic base that can be used in the cosmetic of the present invention is not limited at all. For example, water, alcohol,
Those conventionally used in skin and hair cosmetics, such as propylene glycol, stearic acid, glycerin, cetyl alcohol, and liquid paraffin, can also be used. In addition, the cosmetics of the present invention, as usual, if necessary, pitamines, crude drug extract extract, hormones,
Other externally usable chemicals and the like can be added.

The skin and hair cosmetic composition of the present invention is effective in preventing spots, freckles, rough skin, ultraviolet rays (sunburn), etc., and is of cosmetic value.

Hereinafter, the present invention will be described in more detail with reference to Reference Examples and Examples. Reference Example 1 (fractionation and preparation method of active ingredient) 500 g of n-hexane was added to 20 g of frozen feeling powder of barley green juice before the fruiting period. After stirring well for about 5 minutes at room temperature,
The insoluble component was separated by centrifugation (8000 rpm, 10 min), and the separated insoluble component was added to n-hexane 5
The same operation was repeated to obtain a component insoluble in n-hexane.

To this insoluble component, 500 ml of ethyl alcohol having a water content of 20 v / v% is added, and the mixture is thoroughly stirred at room temperature for about 5 minutes, and then the insoluble component is filtered off. The filtered insoluble matter is again treated similarly with 500 ml of ethyl alcohol having a water content of 20 v / v%, and the obtained filtrates are combined and the solvent is distilled off under reduced pressure. This gives the ethyl alcohol extract13.
0 g was obtained.

After the ethyl alcohol-soluble matter was adsorbed on an Amberlite XAD-2 column, it was sequentially separated with distilled water, water-containing methanol having a water content of 80, 60, 40, 20 and 0 v / v%, and acetone, respectively. After dissolution, an eluate was obtained.

The solvent was distilled off from each eluate by distillation under reduced pressure. As a result, 4.77 g of an aqueous extract, 180 mg of a 20% methanol extract, 131 mg of a 40% methanol extract, 60 mg of a 60% methanol extract were obtained.
% Methanol extract (199 mg), 80% methanol extract (32 mg), 100% methanol extract (165 mg) and acetone extract (0.87 mg) (where% of methanol is the methanol concentration v / v% in aqueous methanol). ).

The 60% methanol extract obtained as described above is further recrystallized using 60% methanol,
180 mg of slightly yellow crystals were obtained. The structure of this crystal was determined by mass spectrometry and NMR.

Mass spectrometry was performed using FAB-MS: VG ZAB-
2F, using a (Xenon Gun) (Jon Tech) type mass spectrometer, and the results shown in FIG. 1 were obtained. From this mass spectrum, [M + H] at m / z = 595
⁺ ] Was observed, the molecular weight was determined to be 594, and when considered in conjunction with the results of elemental analysis, the molecular formula of the substance was determined to be C ₂₇ H ₃₀ O ₁₅ .

The ultraviolet absorption spectrum of this substance was measured in H ₂ O and methanol, as shown in FIGS. 2 and 3, respectively, showing the absorption of flavonoid glucoside.

The infrared absorption spectrum was measured by JASCO FT
FIG. 4 shows the results obtained by applying the KBr method according to / IR-7000S. The presence of an OH group is shown at 3422 cm ^-1 .

This substance liberated one molecule of glucose when hydrolyzed with hydrochloric acid-methanol in a conventional manner to produce isovitexin.

Further, the ¹³ C NMR spectrum (500 MHz) of the substance was analyzed by using a GE OMEGA 300 type nuclear magnetic resonance spectrum absorption measuring apparatus using 25 mg of the purified antioxidant active substance to obtain tetramethylsilane [TMS, (CH
₃ ) ₄ Si] was used as an internal standard, and the results shown in FIG. 5 were obtained. In FIG. 5, the chemical shift is indicated by δ. Purification Antioxidant active substance in MeOH-d ₄ 27
Giving a signal to carbon atoms, the isovitexin ¹³
Standard values of C-NMR [Ramarathnam, N .; ,
Osawa, T .; , Namiki, M .; and Kaw
akishi, S .; : J. Agric. Food Ch
em. , 37 , 316-319 (1989)].

[0035]

Embedded image This substance is named 2'-O-glucosyl-isovitexin from this structural formula.

Reference Example 2 (Gas Chromatographic Analysis of Lipid Peroxidation Product, MA ¹⁾ 0.25 mg of α-tocopherol or 0.22 mg of 2'-O-glucosyl-isovitexin was added to 7.5 mg of microsomes and arachidonic acid. To this is added a Tris-HCl buffer (0.05 M Trizma HCl, pH 7.4;
0.15M KCl; 0.2% SDS)
Gently shake to suspend, then add Fenton TS (FeC
l ₂ / H ₂ O ₂ ) (200 μl) was added and reacted at 37 ° C. for 16 hours. After stopping the reaction by adding 50 μl of 4% BHT ^2), 40 μl of N-methylhydrazine was added to generate an N-methylhydrazine derivative at room temperature for 1 hour, and 15 ml of saturated saline was added thereto, and dichloromethane was added. Extracted with 5 ml for 3 hours.

The dichloromethane layer was separated, a fixed amount of gas chromatography internal standard station (IS) was added, and the mixture was further adjusted to exactly 10 ml with dichloromethane to obtain a sample for gas chromatography analysis, which was subjected to chromatography under the following conditions. Was.

Capillary column: DB-WAX 25 m × 0.25 mm Column temperature: 35 ° C. (hold 1.0 minute) to 190 ° C. (hold 20 minutes) Temperature rise 40 ° C./min Inlet temperature: 250 ° C. Detector temperature: 300 ° C. Detector: NPD (nitrogenphosphoru)
s detector) Carrier gas: helium The 2'-O-glucosyl-isovitexin represented by the above structural formula can be converted to M as shown in FIGS. 6, 7 and 8.
It has become clear that a remarkable inhibitory effect is exhibited not only on the formation of A but also on the formation of 4HN (4-hydroxynonenal). Further, the 60% methanol-extracted fraction showed the same activity.

Note) 1) MA = malondialdehyde 2) BHT = dibutylhydroxytoluene

[0040]

【Example】

Example 1 After washing green leaves of young barley leaves, 1 kg of green juice obtained by spray-drying green juice obtained by squeezing and powdering was mixed with 20 kg of hexane.
The extraction was repeated twice with L.
L was added and the water-soluble component was spray-dried to obtain 380 g of a spray-dried product. Next, 10 L of aqueous ethanol having a water content of 20% was added to the dried powder to obtain 300 g of a water-soluble ethanol-soluble component having a water content of 20%, and ethanol was distilled off. Further, 1% of water-containing methanol having a water content of 40% was added thereto.
After 0 L was added, a water-soluble methanol-soluble component having a water content of 40% was extracted, and then methanol was distilled off to obtain 250 g of a water-containing methanol-soluble component having a water content of 40%. This component is called substance A.

The obtained water and aqueous alcohol soluble A
A lotion of the following formulation was prepared using the substance.

Extract 5 g 95% ethanol 100 g Methyl parahydroxybenzoate 0.05 g Fragrance 0.5 g Colorant 0.005 g Purified water qs 1,000 g Application Example 1 The lotion obtained in Example 1 is washed daily in the morning after washing the face in the morning. And used before bedtime to test for the improvement of spots and freckles. Table 1 shows the test results of 30 women. The test was conducted for six months. The evaluation was performed according to the following criteria.

About the color of spots and freckles Brown color: invalid Light brown: slightly effective Almost inconspicuous: valid About the border between the stains and freckles and other parts Existence: invalid Unclear: almost indistinguishable :Effectiveness

[0044]

[Table 1] Example 2 The methanol fractionation in Example 1 was accurately performed in a stepwise manner. Substance A, which is a water-containing methanol fraction having a water content of 40%, was collected, and this substance was re-used with water-containing methanol having a water content of 40%. The 2'-O-glucosyl-isovitexin obtained after crystallization is added to the lotion formulation described in Example 1 at a concentration of 0.1% instead of the extract to produce a lotion.

Example 3 Formulation of Cream 10 g of stearic acid 5 g of isopropyl myristate 5 g of cetyl alcohol 5 g of liquid paraffin 7 g of glyceryl monostearate 5 g of polyoxyethylene stearate 5 g of methyl paraoxybenzoate 0.1 g of glycerin was further added thereto. , 1 g of propylene glycol and 50 g of water were mixed and emulsified. When the temperature of the emulsion reached 60 ° C., the 2′-O obtained in Reference Example 1 was obtained.
-Glucosyl-isovitexin (0.3 g) was added and stirred, and a small amount of flavor was added to prepare a cream.

Application Example 2 The cream obtained in Example 3 was used daily after washing the face and before going to bed, and the effect on spots, freckles and rough skin was tested on 30 men and 30 women for 6 months. went. The determination of spots and freckles was performed in accordance with Application Example 1, and the roughness of the skin was evaluated by the following criteria based on the degree of slippage of the cream on the skin.

Ineffective: There is roughness on the skin surface.

Slightly effective: Slight roughness remains, but cream spread is good.

Effective: The cream spreads well on the skin surface.

The results are summarized in Tables 2 and 3.

[0051]

[Table 2]

[0052]

[Table 3] Example 4 A hair restorer having the following formulation was prepared using 2'-O-glucosyl-isovitexin obtained in Reference Example 1.

0.1 g of 2'-O-glucosyl-isovitexin was dissolved in 95 ml of a 66% aqueous ethanol solution.
5 ml of propylene glycol, 0.1 g of flavor and 0.1 g of coloring agent were added to prepare a hair restorer.

Application Example 3 The effect of the hair restorer obtained in Example 4 was evaluated for 20 males and 2 females.
0 persons were examined. The effect of daily use of the hair restorer was determined after 6 months according to the following criteria.

[0055] Table 4 below shows the state before and after application based on the above criteria.

[0056]

[Table 4]

[Brief description of the drawings]

FIG. 1 shows a measurement chart of 2′-O-glucosyl-isovitexin obtained in Reference Example 1 by the FAB-MS method.

FIG. 2 is an ultraviolet absorption spectrum of 2′-O-glucosyl-isovitexin in an H ₂ O system.

FIG. 3 is an ultraviolet absorption spectrum of 2′-O-glucosyl-isovitexin in a MeOH system.

FIG. 4 is an infrared absorption spectrum of 2′-O-glucosyl-isovitexin.

FIG. 5 is a diagram showing the results of ¹³ C-NMR measurement of 2′-O-glucosyl-isovitexin.

FIG. 6 is a continuation of FIG. 5;

FIG. 7 is a continuation of FIG. 6;

FIG. 8 is a gas chromatographic chart (control) of the lipid oxidation products of arachidonic acid, MA and 4HN using the Fenton test.

FIG. 9 is a gas chromatographic chart (α-tocopherol) of lipid peroxidation products of arachidonic acid, MA and 4HN using the Fenton test.

FIG. 10 is a gas chromatographic chart of the lipid peroxidation products of arachidonic acid, MA and 4HN using the Fenton test (2′-O-glucosyl-isovitexy).

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09K 15/08 C09K 15/08 (56) References JP-A-61-51081 (JP, A) JP-A-3-41014 (JP, A) JP-A-5-65480 (JP, A) JP-A-4-13691 (JP, A) JP-A-3-5423 (JP, A) JP-A-60-61513 (JP, A) JP-B-48-15616 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) A61K 7 / CA (STN)

Claims (1)

(57) [Claims] 1. The following formula extracted from green leaves of wheat plants: A skin and hair cosmetic comprising an antioxidant active component mainly composed of 2'-O-glucosyl-isovitexin represented by the formula: