JP3260467B2 - Hair cosmetics for prevention of gray hair and blackening of gray hair - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to dehydrodiconipheryl alcohol-4.beta.-D-glucoside (Dehydro
diconiferyl alcohol-4β-D-
(glucose) as an active ingredient, and a hair cosmetic for preventing and blackening white hair (including quasi-drug cosmeceuticals and medicinal external hair preparations, the same shall apply hereinafter). In more detail, the present invention has been conventionally effective for preventing whitening associated with aging of human hair and the like, for which there is no fundamental treatment or preventive means and no effective drug has been developed. The present invention relates to a hair cosmetic for preventing gray hair and having a blackening effect for gray hair and which can be used safely and for blackening white hair.

[0002]

2. Description of the Related Art Whitening of human hair is recognized as one of the typical phenomena of the physiological aging process. In general, albinism is clinically known as a symptom of many skin diseases, for example, vitiligo vulgaris, albinism, alopecia areata, etc. In some cases, hair growth can be prevented. In addition, whitening due to nutritional disorders and chronic systemic diseases has been reported.

[0003] At present, no fundamental pharmacotherapy for human hair whitening as a physiological aging phenomenon has been established at present, and as a countermeasure, at present, cosmetic treatment is exclusively used. The only means of dyeing gray hair with a hair dye (hair dye) is as a means. For this reason, various types of hair dyes have been developed so far, but the use of these hair dyes is merely a passive means of hiding gray hair, and its effect is also high. In addition to being temporary, there are various difficulties such as frequently causing hair damage and allergic contact dermatitis caused by the use of hair dyes.

Further, melanocyte stimulating hormone [T.
K. Sawyer, et al. , Amer. Zoo
l. , 23, 529 (1986)] and hormonal substances such as β-lipotrophin (Japanese Patent Application Laid-Open No. 1-207226) are said to have an action of preventing the development of white hair. It is not suitable for use in gray hair cosmetics that are presumed to be used widely and safely.

As described above, along with the development of hair dyes,
Although various attempts have been made to develop an active ingredient for preventing human hair from whitening or treating gray hair, it has been widely and safely used so far. In addition, a drug capable of fundamentally preventing the generation of white hair or a drug capable of treating white hair has not yet been developed, and the development has been strongly demanded.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have found that despite the great social demand, there is no fundamental treatment or preventive means, and at present, useful drugs A study has been conducted with the aim of developing a new hair cosmetic which has a preventive effect and / or a blackening effect on gray hair associated with aging of human hair, which has not been developed, and which is safe. As a result, the inventors succeeded in finding a new active ingredient having the preventive effect and the blackening effect of gray hair, and completed the present invention.

[0007] That is, an object of the present invention is to provide a hair cosmetic for preventing gray hair, which has a preventive effect on whitening associated with aging of human hair.

[0008] Another object of the present invention is to provide a hair cosmetic for blackening white hair which has a blackening effect on white hair and is useful for treating white hair.

Further, the present invention provides a novel hair cosmetic for preventing and graying white hair, which has high safety and can be used widely and safely, using an active ingredient derived from natural products. It is the purpose.

[0010]

SUMMARY OF THE INVENTION The gist of the present invention is to provide dehydrodiconiferyl alcohol-4.
β-D-glucoside (Dehydrodiconife)
ryl alcohol-4β-D-glucosid
e) is a highly safe hair cosmetic for preventing and graying white hair, characterized by containing e) as an active ingredient.

The active ingredient of the hair cosmetic composition of the present invention, dehydrodiconipheryl alcohol-4β-D-glucoside (Dehydrodiconiferyl alcohol)
ol-4β-D-glucoside) is a substance obtained as a degradation product of lignin, a natural organic compound contained in wood and almost all other plant tissues. As plants grow, a phenomenon called lignification is observed. This is because lignin is present in the plant.
This phenomenon is characterized by the generation of a special substance called n). Therefore, lignification is also referred to as lignification.

[0012] The division and proliferation of plant cells are observed in living cells that do not turn into wood, and it is thought that wooded cells lose the ability to divide. As a result of lignification, the content of lignin therein is also constant, and grown conifers contain 27 to 29%, broadleaf trees contain 20 to 24%, and plants and plants contain about 15 to 24% lignin. The lignin content is the second largest number after cellulose, which is the largest natural organic substance on earth.

In general, many attempts have been made for industrial use of lignin in various fields. For example, lignin is an important substance as a raw material for synthesis, and crocodile is inexpensive due to oxidation of lignin. It has been obtained and used, and it has also been attempted to use it as a soil amendment.However, these are known as typical methods of using lignin, and others are based on industrial profitability. In some cases, despite the fact that it is not a substance, it is a substance that occurs a lot in the natural world, but its use has not been sufficiently performed, and most of it is burned and consumed.

However, the present inventors have been studying such lignin, and surprisingly, surprisingly, dehydrodiconipheryl alcohol (Dehyd) obtained as a decomposition product of lignin by exploding conifers.
Dehydrodiconipheryl alcohol-4β-D-, which is a glycoside of R. cond.
Glucosides (Dehydrodiconiferyl
alcohol-4β-D-glucoside)
They have been found to have the property of promoting the activity of the oxidase tyrosinase, which produces melanin pigment.

According to Fitzpatrick et al., The mechanism of gray hair development in human hair is attributed to changes in the pigment cell line [Fitzpatrick T. et al. In, "A
dvance in Biology of Ski
n ", Pergamon Press, p35 (196
5)]. In other words, the reduction or disappearance of the activity of tyrosine oxidase (tyrosinase) in the hair matrix pigment cells contributes to gray hair.

According to the findings of the present inventors, dehydrodiconipheryl alcohol-4β-D-glucoside (Deh)
hydriconiconyl alcohol-4
β-D-glucoside) is used as an active ingredient, and by applying a hair cosmetic containing the ingredient to the scalp or the like, the activity of the oxidase tyrosinase, which is greatly involved in melanin formation in hair, is increased, and the melanin pigment is enhanced. It was found that a remarkable effect was obtained on prevention of whitening of hair and blackening of gray hair.

The dehydrodiconiferyl alcohol-
4β-D-glucoside (Dehydrodiconif
eryl alcohol-4β-D-glucosi
The amount of de) depends on the dosage form and the like, and is not particularly limited.
It is 0% by weight, preferably 0.0001 to 10% by weight, and it is found that when the saturation amount is less than 0.0001%, it is difficult to sufficiently obtain the effects of preventing the whitening of the hair and blackening the white hair.

The hair cosmetic composition of the present invention may be in any form of external use such as hair tonic, hair treatment, hair cream, hair shampoo, hair rinse, etc. Ingredients include various components commonly used in cosmetics, quasi-drugs and pharmaceuticals, for example, solvents such as alcohol and solubilizers, surfactants, humectants, fragrances, coloring agents, preservatives, and viscosity control. Agents and the like can be appropriately compounded.

[0019]

The results of tests on the effectiveness and safety of the thus obtained hair cosmetic composition of the present invention are shown below as test examples. The hair cosmetic of the present invention, as apparent from the following test results, prevention of whitening of hair,
And it was confirmed that it was effective in blackening white hair and had high safety. Dehydrodiconipheryl alcohol which is an active ingredient of the hair cosmetic of the present invention
4β-D-glucoside (Dehydrodiconif
eryl alcohol-4β-D-glucosi
As a result of the tyrosinase activity promotion test, it was confirmed that de) has an effect of promoting the activity of tyrosinase, a tyrosine oxidase present in hair matrix pigment cells.

[0020]

[Test example]

Test Example 1: Dehydrodiconipheryl alcohol-4β-
D-glucoside
l alcohol-4β-D-glucoside)
Method for producing dehydrodiconiferyl alcohol (Dehydrod
iconiferylcohol) (Merck)
Reaction solution 5 consisting of 2.5% (w / v), starch 2% (w / v), 10 mM phosphate buffer (pH 6.5), and 100 units / ml of CGTase (from Bacillus macerans).
0 ml was placed in an Erlenmeyer flask (200 ml) and reacted at 37 ° C. for 90 hours.
After stopping the reaction by adding 1 l, the precipitated insolubles were removed by centrifugation.

After the residue was subjected to vacuum concentration and drying treatment using a rotary evaporator, the residue was dissolved in 7 ml of water, the aqueous solution was subjected to column chromatography under the following conditions, and the reaction product was eluted in volume. 480-5
Eluted with 40 ml Column: 2.6 cm id x 91 cm Filler: Biogel p-2 (400 mesh) Eluent: 5% (v / v) aqueous ethanol

The obtained fraction was concentrated to dryness under reduced pressure, and further dried using a vacuum drier to obtain 32 mg of a product as a white powder. The product was single in thin layer chromatography under the following conditions (Rf
Value: 0.60): thin layer: silica gel 60F254 developing solvent: ethyl acetate / acetic acid / water (3: 1: 1) detection: 110-120 ° C. after ultraviolet irradiation or spraying of a sulfuric acid / methanol (1: 2) mixture To form a color. The product (Dehydrodiconiferyl)
(Alcohol-4β-D-glucoside) was confirmed by ¹ H-NMR.

Test Example 2: Test for promoting the activity of tyrosinase (1) Preparation of tyrosinase crude enzyme solution B16 melanoma cells (manufactured by Kurashiki Boseki) were subjected to 10% FCS and penicillin (penicillin).
in), streptomycin (streptomycin)
n), amphotericin
Dulbecco's modified ea medium containing B (Fungizon)
culture medium (φ9)
cultivation (95% air, 5% C) using a culture flask (75 cm ³ ) at 37 ° C.
O ₂ ). The cells grown by culturing for 2 to 3 days were treated with trypsin for 3 minutes to suspend the cells, and the cells were collected by centrifugation (450 × g, 3 minutes).

The obtained cells were washed three times with a phosphate buffer solution (pH 6.8) supplemented with 10 mM physiological saline, and the number of cells was counted. Then, 0.1% trypsin (Triton) X-10 was added.
The suspension was suspended in 0.1 M phosphate buffer (pH 6.8) containing 0. Ultrasonic treatment (15 sec ×
3 times) and centrifuged (11,000 xg, 20 minutes, 4
C) and the supernatant was collected. The obtained supernatant was used as a tyrosinase crude enzyme solution.

(2) Dehydrodiconipheryl alcohol-4β-D-glucoside against tyrosinase activity (Dehydrodiconiferyl alcohol)
The activity of tyrosinase was determined by the method of Akiho et al. (Melanin production inhibitory effect of arbutin, Journal of the Japanese Dermatological Association, 101, 60).
9-613). That is, 0.5 ml of the tyrosinase crude enzyme solution and dehydrodiconipheryl alcohol-4β-D-glucoside (Dehydrodi) were used.
conferyl alcohol-4β-D-gl
ucoside) in 50 mM phosphate buffer (pH 6.
8, hereinafter referred to as a buffer).
0.9 ml of buffer was added, and the mixture was heated at 37 ° C. for 3 minutes.
Buffer containing 0.067% L-dopa.
5 ml was added, and the change in absorbance at 475 nm at 37 ° C. was measured over time.

The tyrosinase activity was calculated from the obtained initial rate of change in absorbance, and the acceleration rate was obtained from the following equation (1). In addition, dehydrodiconiferyl alcohol-4β-D-glucoside (Dehydrodiconiferyla)
lcohol-4β-D-glucoside) was prepared in buffer at 0.1, 1.0, and 10 mg / ml (final concentration 0.005, 0.05, 0.5 mg / ml),
The supernatant obtained by centrifugation (11,000 × g, 20 minutes, 4 ° C.) was added to the reaction system. In Formula 1, dehydrodiconiferyl alcohol-4β-D-glucoside (Dehy
droconiferyl alcohol-4β
-D-glucoside) is abbreviated as DDCAG.

[0027]

(Equation 1)

The results are shown in Table 1, which shows that the active ingredient of the hair cosmetic composition of the present invention, dehydrodiconipheryl alcohol-4β-D-glucoside (Dehydro).
diconiferyl alcohol-4β-D-
glucoside) was found to promote the activity of the enzyme tyrosinase, which produces melanin pigment, and to be effective in preventing whitening and blackening of hair.

[0029]

[Table 1]

Test Example 3: Safety test (patch test) Sample: 10% dehydrodiconipheryl alcohol-4β
-D-glucoside (Dehydrodiconifer
yl alcohol-4β-D-glucosid
e) Aqueous solution Implementation method: 20 men and women 2 ages 20-60
A filter paper for a fin chamber in which a sample and a control solution (physiological saline) were respectively immersed on the upper arm flexion side of a total of 40 subjects was put into the chamber portion of the fin chamber, and affixed, and a closed patch test was performed. The application time was set to 24 hours. After 24 hours, the fin chamber was removed, and 30 minutes after removing the sample, and 24 hours and 48 hours were judged three times.

Judgment criteria: Evaluation was performed based on the following five-step criteria. -: No reaction ±: Slight erythema +: Clear erythema ++: Erythema and pus or papule +++: Blisters observed

As a result of the above patch test, as shown in Table 2, dehydrodiconipheryl alcohol-4β-D-glucoside (De) was used as an active ingredient of the hair cosmetic composition of the present invention.
hydrodiconiferyl alcohol-
4β-D-glucoside) has a very low possibility of inducing a stimulus reaction and an allergic reaction, and has been found to be highly safe.

[0033]

[Table 2]

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments of the present invention. The scope of the present invention is not limited by these. Example 1 <Hair Tonic> A hair tonic for prevention of gray hair and blackening of gray hair was prepared according to the following formulation. Dehydrodiconiferyl alcohol-4β-D-glucoside 0.5 g Polyoxyethylene (9) lauryl ether 1.0 g 1,3 butylene glycol 5.0 g Ethanol 50.0 g Fragrance 3g Purified water suitable amount ─────────────────────────────────── total amount 100.0g

Example 2 Hair Treatment A hair treatment for preventing gray hair and blackening white hair was prepared according to the following formulation. Dehydrodiconiferyl alcohol-4β-D-glucoside 1.0 g Polyoxyethylene (10) behenyl ether 5.0 g Glycerin monostearate 6.0 g Isopropyl myristate 5.0 g Stearic acid 5.0 g Liquid paraffin 5.0 g Lanolin alcohol 3.0 g 1,3-butylene glycol 5.0 g Triethanolamine 1.0 g Methyl paraben 0.1 g Ethyl paraben 0.1 g Flavor 0.3 g Purified water qs ──────────────────────────── Total amount 100.0g

Example 3 <Hair cream> A hair cream for preventing gray hair and for blackening white hair was prepared according to the following formulation. Dehydrodiconiferyl alcohol-4β-D-glucoside (dehydrodiconiferyl alcohol-4β-D-glucoside) 1.0 g Liquid paraffin 30.0 g Dehydrated lanolin 3.0 g Beeswax 2.0 g Cetanol 3.0 g Glycerin 5.0 g Polyoxyethylene 10) Cetyl ether 3.0 g Sorbitan monostearate 0.1 g Methyl paraben 0.1 g Ethyl paraben 0.1 g Fragrance 0.5 g Purified water qs. ─────────────── Total amount 100.0g

Example 4 <Hair Shampoo> A hair shampoo for preventing gray hair and for blackening white hair was prepared according to the following formulation. Dehydrodiconiferyl alcohol-4β-D-glucoside 0.5 g Triethanolamine lauryl sulfate 20.0 g Sodium lauryl sulfate 5.0 g Magnesium stearate 5.0 g Lanolin 1.0 g 1, 3-butylene glycol 5.0 g cetyl alcohol 2.0 g polyvinyl alcohol 1.0 g flavor 0.5 g purified water qs ──────── Total amount 100.0g

Example 5 <Hair rinse> A hair rinse for preventing gray hair and for blackening white hair was prepared according to the following formulation. Dehydrodiconiferyl alcohol-4β-D-glucoside 0.5 g Polyoxyethylene (2) oleyl ether 7.0 g Distearyl dimethyl ammonium chloride 3.0 g Propylene glycol 3.0 g Methyl paraben 0 0.1g Ethylparaben 0.1g Fragrance 0.3g Purified water suitable amount ─────────────────────────────────── total amount 100.0g

[0039]

As described above in detail, the present invention relates to a method for preparing dehydrodiconipheryl alcohol-4β-D as an active ingredient.
-Glucoside (Dehydrodiconiferyl)
The present invention relates to a hair cosmetic characterized by containing (alcohol-4β-D-glucoside), wherein the active ingredient of the hair cosmetic of the present invention has the tyrosinase activity promoting action as described above. Therefore, against whitening of hair due to aging, etc., it has a preventive effect and is effective in blackening white hair, and is also extremely safe, and is expected to have sufficient practical application.
It is of great industrial significance.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masataka Funayama 14-5 Shimogita-cho, Neyagawa-shi, Osaka Kurashiki Textile Co., Ltd. (72) Inventor Hirokuni Arakawa 14-5 Shimogita-cho, Neyagawa-shi, Osaka Kurashiki (56) References JP-A-5-221834 (JP, A) JP-A-6-256145 (JP, A) JP-A-3-120217 (JP, A) JP-A-62-162 223106 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. Dehydrodiconiferyl alcohol-4
β-D-glucoside (Dehydrodiconife)
ryl alcohol-4β-D-glucosid
e) a hair cosmetic for preventing gray hair and blackening white hair, which comprises e) as an active ingredient.