JP2559678B2 - Hair nourishing cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to low molecular weight acidic mucopolysaccharides and salts thereof which are hyaluronic acid having an average molecular weight of 1000 to 9000, chondroitin sulfate having an average molecular weight of 2000 to 9000, dermatan sulfate and heparan sulfate. The present invention relates to a hair nourishing cosmetic composition containing at least one kind and calcium hopanthenate. For more details,
The present invention relates to a hair nourishing cosmetic composition which is directly applied to hair to activate hair mother cells and is excellent in effects such as hair growth, hair nourishment, hair loss prevention, and dandruff prevention.

(Prior Art) Conventionally, various hair nourishing cosmetics containing a component having a hair mother cell activating action or a blood circulation promoting action have been proposed, but any of these proposed hair nourishing cosmetics is positive. It has been difficult to obtain a hair nourishing agent that is excellent in expecting a hair-growth effect or a hair-growth effect.

Certainly, in order to expect hair growth, hair nourishment, and even a hair growth effect, it is an appropriate technical condition to incorporate a component having a hair mother cell activating action or a blood circulation promoting action into a hair nourishing agent. However, such technical factors alone do not produce the expected hair growth effect.

That is, the hair matrix cells present in the hair follicle epithelium are surrounded by the dermis, and the hair matrix activating components and the nutrients of the hair matrix cells exuding from the peripheral capillaries existing in the scalp are Dermal components existing around the bladder epithelium, especially structural glycoproteins, and acidic mucopolysaccharides, which are substrate components of the scalp filling the gaps between fibrous proteins, such as hyaluronic acid, dermatan sulfate, chondroitin sulfate, and heparan. By migrating a substrate component layer such as sulfuric acid, reaching the hair matrix cells and being incorporated into the hair matrix cells, expected hair growth, hair nourishment, and further hair growth effects are exhibited.

However, if there is some trouble in the abundance and the composition ratio of the above-mentioned components of the acidic mucopolysaccharide that is the substrate component, naturally, the migration of hair matrix activating components and nutrients in the substrate component layer is also affected. However, effects such as hair growth, hair nourishment, and hair growth are not sufficiently expressed.

In particular, it is known that the scalp of male alopecia areata is generally thinned in both the epidermis and the dermis.Also, although the affected skin of alopecia areata has a tendency to relax at the time of onset, it is accompanied by healing. The elasticity gradually restores to the affected skin, and hair growth becomes visible.

A nutrient prepared by normalizing the matrix component intervening between the peripheral capillaries in the scalp and dermis and the hair matrix cell, and incorporating a composition that allows the hair matrix cell activating component and nutrients to be smoothly incorporated into the hair matrix cell. There is still no proposal for hair cosmetics.

DISCLOSURE OF THE INVENTION Therefore, the present inventor has conducted extensive studies on acidic mucopolysaccharides that contribute to the normalization of the substrate component of the scalp, and as a result, acidic mucopolysaccharides or salts thereof usually contained in cosmetics are
It is a polymer having an average molecular weight of tens of thousands to one million, and therefore it is hardly percutaneously absorbed, and the effects of hair growth, hair nourishment, hair growth and the like aimed at by the present invention were not obtained. At least one of low molecular weight acidic mucopolysaccharides and salts thereof,
The hair nourishing cosmetic composition that is used in combination with calcium hopanthenate is effective for hair growth (mouse hair growth promoting effect, human hair growth promoting effect), hair nourishment, hair loss prevention, dandruff prevention, etc., which is the object of the present invention. They have found that they are even better, and have completed the present invention.

(Object of the invention) That is, an object of the present invention is to provide a hair nourishing cosmetic excellent in effects such as hair growth, hair nourishment, hair loss prevention, and dandruff prevention.

(Structure of the Invention) The present invention is hyaluronic acid having an average molecular weight of 1000 to 9000, chondroitin sulfate having an average molecular weight of 2000 to 9000, at least one of low molecular weight acidic mucopolysaccharides and salts thereof which are dermatan sulfate and heparan sulfate, and fopanthenic acid. A hair nourishing cosmetic characterized by being mixed with calcium.

(Specific Description of Structure) Acidic mucopolysaccharide used in the present invention, namely hyaluronic acid,
Dermatan sulfate, chondroitin sulfate, heparan sulfate and the like are known substances, and are widely distributed in the animal body by forming a matrix component in cartilage, joints, eyes, skin and other connective tissues, binding to proteins.

The low molecular weight acidic mucopolysaccharides and salts thereof used in the present invention can be obtained as follows.

(1) Low molecular weight hyaluronic acid and its salt 5 g of commercially available hyaluronic acid with an average molecular weight of 1 million
Is dispersed and dissolved in 100 ml of 0.02N hydrochloric acid aqueous solution, and the pH is 2 to 2.
It was adjusted to 3 and heated to 65 ° C. in a warm bath with sufficient stirring. By changing the heating treatment time from 10 minutes to 120 minutes, low molecular weight hyaluronic acid having an average molecular weight of 1000 to 9000 can be obtained.

Next, after neutralizing with N-caustic soda, the solution was cooled to room temperature, 3 times volume of ethanol was added, the precipitate obtained was washed with ethanol, and then dried to obtain low-molecular weight sodium hyaluronate powder. It was In addition, this low molecular weight hyaluronic acid sodium salt is treated with an acid to give free hyaluronic acid, which is then treated with another basic substance, for example, potassium salt, triethanolamino salt, L-arginine salt, etc. Was prepared.

(2) Low molecular weight chondroitin sulfate and its salt, etc. 5 g of commercially available sodium chondroitin sulfate having an average molecular weight of 50,000 was dissolved in 50 ml of water, and Amberlite IR
The effluent obtained by passing through a -120 (H type) resin column was heated to 75 ° C in a warm bath while being sufficiently stirred. By changing the heating treatment time from 10 minutes to 120 minutes, low molecular weight chondroitin sulfate having an average molecular weight of 2000 to 9000 can be obtained. Next, it is neutralized with N-caustic soda. After the solution was cooled to room temperature, 3 times volume of ethanol was added, the resulting precipitate was centrifuged, washed with ethanol, and dried to obtain a powder of chondroitin sulfate sodium salt. Next, this chondroitin sulfate sodium salt is treated with an acid to give free chondroitin sulfate, and then this is treated with another basic substance, for example, potassium salt, triethanolamine salt, L-arginine salt and the like. Salts were prepared.

Also, low molecular weight dermatan sulfate, low molecular weight heparan sulfate, etc. were prepared in free form or their respective salts by the same treatment as in the above example of chondroitin sulfate.

The method for measuring the average molecular weight of the acidic mucopolysaccharide obtained by each treatment time was Somogyi-Nelson (Somogyi-Ne
lson) method was used.

Furthermore, in order to further exert the effects of hair growth, hair nourishment, hair loss prevention, dandruff prevention, etc., which are the objectives of the present invention, a blood circulation promoting agent to be used in combination was screened, and calcium hopanthenate was most expected as the object of the present invention. Showed the effect.

Calcium hopantenate used in the present invention is a known substance, and its pharmacological effect has an action of promoting glucose uptake into the brain and its metabolism, and hyperactivity associated with aftereffects of encephalitis, cerebral palsy, etc. It is known to be a drug that is effective in treating depression and speech disorders and has few side effects.

The chemical properties and the like of calcium hopantenate are as follows.

(1) Structure (In the above structural formula, R ₁ is a HOCH ₂ group and R ₂ is NHCH ₂ CH ₂ CH ₂ COOH.
Represents a group. (2) Chemical name Calcium D-(+)-4- (2,4-dihydroxy-)
3,3-Dimethyl Butyroamide) Butyrate Hemihydrate Calcium D-(+)-4- (2,4-dihydroxy-3,3-dimeth
yl buthyroamid) butyrate hemihydrat (3) General name: Hopanten calcium (Calcium hopantenate) (4) Molecular _{formula: C 20 H 36 CaNO 5 ·} 1 / 2H 2 O (5) Molecular weight: 513.60 (6) mp: 155-165 ° C. The calcium hopatate to be blended in the hair nourishing cosmetic of the present invention was prepared by adding 400 mg of metallic sodium to 40 ml of methanol and heating to obtain a suspension solution, and 1.2 g of γ-aminobutyric acid was added and dissolved. Then 1.3 g of pantolactone was added and stirred for 2 hours, then left overnight, the solvent was distilled off, water was added to the precipitated white crystals to remove insoluble substances, the water was evaporated, and the crystals were dried to give white crystals. To obtain calcium hopantenoate.

The calcium fopanthenate obtained by the above synthetic method was used in the tests of the present invention. In addition, the calcium fopanthenate used in the present invention has an appropriate percutaneous absorbability, and therefore, maintains an effective concentration of the drug in the epidermis, has weak skin irritation, and has a continuous blood circulation promoting action. Activates hair mother cells to produce excellent hair growth and hair loss prevention effects,
Furthermore, it is presumed that the scalp metabolic function is normalized to enhance the antidandruff effect.

The compounding amount of calcium hopanthenate is 0.05 to 2.0% by weight (hereinafter referred to as w) based on the total weight of the composition of the hair nourishing cosmetic composition of the present invention.
abbreviated as t%), preferably 0.1 to 1.5 wt.
%. If the blending amount is less than 0.05 wt%, the effect aimed at by the present invention is not sufficient. On the other hand, if it exceeds 2.0 wt%, improvement in the effect commensurate with the increase cannot be expected.

Further, the present inventor has variously sought about the blending ratio that maximizes the synergistic effect of the above-mentioned constituents to be blended in the hair nourishing cosmetic, and as a result, (1) low molecular weight acidic mucopolysaccharides and salts thereof. , (2) The ratio (weight ratio) of the respective compounding amounts of calcium hopanthenate is (1) :( 2) = 1: 0.
It is preferably from 01 to 1: 1 and the excellent effect aimed at by the present invention was observed.

That is, the blood circulation accelerating agent of (2) promotes blood circulation of peripheral capillaries in the dermis adjacent to the hair follicle epithelium, and dermal tissue of hair matrix activating components and hair matrix nutrients contained in blood. Infiltration of substances such as hair matrix activating components of hair matrix cells is facilitated by activating the exudation into the body and further improving the composition ratio of the matrix components surrounding the hair follicle epithelium in (1). In addition to promoting hair growth, the excellent water-holding ability of (1) contributes to the appropriate application and retention of water to the scalp, and can also prevent dandruff.

In addition, the proportion of the low-molecular-weight acidic mucopolysaccharide and its salt to be used in combination with calcium hopanthenate in the hair nourishing cosmetic may be 0.01 to 2.0 wt% of (1) based on the total amount. If the amount is less than the lower limit, the effect aimed at by the present invention is not sufficient. On the other hand, if the amount exceeds the upper limit, it is impossible to expect a corresponding improvement in the effect.

In the hair nourishing cosmetic of the present invention, in addition to the above, various oils, polyhydric alcohols, ultraviolet absorbers, dyes, fragrances, preservatives, surfactants, pigments, antioxidants, etc. are achieved to achieve the object of the present invention. It can be appropriately blended within the range.

The hair nourishing cosmetic composition of the present invention is applied to oily hair art nicks, scalp treatments, hair nourishing hair lotions, hair nourishing hair creams and the like.

(Example) Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples.

The mouse hair growth promotion test, human hair growth promotion test and practical test are shown below.

(1) Mouse Hair Growth Promotion Test After cutting the back skin from the tail of a ddy white mouse (male, 6 weeks old, average weight: 35 g) with an electric clipper, the hair was completely removed with a hair removal cream, and the test was carried out from the next day. Each sample of Comparative Example was applied to the skin of the test site twice a day in the morning and in the evening at 0.1 ml per animal. For each sample, 10 animals were used per group.

The hair-growth effect was evaluated by comparing the evaluation points of the macroscopic evaluation according to the following evaluation criteria with the hair length and hair weight of the control group.

On the 15th day after the start of the hair experiment, the animals were sacrificed and visually evaluated according to the criteria, and the evaluation points were totaled to obtain an average evaluation point per animal. Furthermore, after the skin of the test site was punched out and dried, the hair weight was measured, and the length of 20 hairs therein was also measured, and shown as the average value of each.

Criteria for evaluation of hair-growth effect Evaluation point 5 Boundary with surrounding non-pulling area is unknown 〃 4 Hair growth intensity 〃 3 Hair growth moderate 〃 2 Hair growth mild 〃 1 Hair growth extremely light 〃 0 Hair growth not recognized (2) Human hair growth promotion test 10 subjects with male pattern baldness 5c on ear of head
About 3 ml of the sample of Example or Comparative Example was applied twice daily in the morning and evening to the test site where the head at the position of m was shaved in a circular shape with a diameter of 1 cm at two places on the left and right, and compared with the untreated right side. did. On the 28th day after the start of the test, 20 hairs on each of the left and right test sites were shaved and the average value of the lengths of 20 hairs on the left side (applied Example or Comparative Example) was measured (B). Was divided by the average value (A) of the lengths of 20 hairs on the right side (untreated) to evaluate.

The result of the judgment is (B) / (A) for each of the 10 test subjects.
The average value is shown.

(3) Practical test The effect was evaluated after applying the sample to 20 heads of male pattern baldness test subjects for 6 consecutive months twice daily in the morning and evening. The test results show that “hairy hair became bristle or increased virgin hair”, “less hair loss”, “less dandruff” for each item of hair nourishing effect, hair loss preventing effect, and dandruff preventing effect. The number of people who answered

Comparative Examples 1 to 9 and Examples 1 to 4 [Oily Hearth Nickel] In the following raw material compositions, as shown in Table 1, hyaluronic acid (hereinafter abbreviated as HA. The same applies hereinafter) and sodium hyaluronate (HA- Na), chondroitin sulfate (Ch
s), heparan sulfate (Hps), potassium chondroitin sulfate (Chs-K), triethanolamine chondroitin sulfate (Chs-T), dermatan sulfate (Ds), dermatan sulfate L-arginine (Ds-A) and calcium fopanthenate. Each oily hair nick was prepared by blending, and the above-mentioned various tests were carried out.

(1) Composition (2) Preparation Method (A) The component (A) is added to the solution in which the component (A) is mixed with the component (A), the component (A), and the component (D), such as hyaluronic acid, is dissolved in the component (C). ) The components are uniformly mixed and dispersed with stirring and then filled in a container.

When using any of these oily hair tonics, the contents should be evenly dispersed by shaking before use.

(3) Characteristics Table 1 shows the results of various tests of each oily hair art.

Hair makeup of Examples 1 to 4 of the present invention, as compared with Oily Hair Artic which does not contain calcium mupanate in combination with one of the acidic mucopolysaccharides such as hyaluronic acid and salts thereof in Comparative Examples 1 to 9. The test material clearly showed a good effect in various tests.

It is clear that the hair nourishing cosmetic composition in which the acidic mucopolysaccharide and the salt thereof and calcium hopanthenate are used in combination has an excellent action for promoting skin function.

Comparative Examples 10 to 13 and Examples 5 to 8 [Sculp Treatment] Each scalp treatment was prepared and various tests were carried out in the same manner as in Example 1, and the results are shown in Table 2.

(1) Composition (2) Preparation Method (D)
The components are mixed and dissolved in the component (C) in advance, and
After the component (B) is mixed in the component (A), the component (A) and the component (C) are respectively heated and melted at 80 ° C., the aqueous phase component is added to the oil phase component while stirring, and the mixture is emulsified and mixed. Then, the mixture was further cooled to 30 ° C. with stirring to prepare a scalp treatment.

(3) Properties As shown in Table 2, the sculptolithmen of Examples 5-8, which are the hair nourishing cosmetics of the present invention, are excellent in all of the properties as compared with Comparative Examples 10-13. It was clear that there were no abnormalities in the compounding characteristics.

(Effects of the Invention) As described above, the present invention provides hair growth, hair growth, hair loss prevention,
It is obvious to provide a hair nourishing cosmetic excellent in the effect of preventing dandruff.

Claims (1)

(57) [Claims] 1. A compound of at least one of low-molecular-weight acidic mucopolysaccharides or salts thereof, which are hyaluronic acid having an average molecular weight of 1000 to 9000, chondroitin sulfate having an average molecular weight of 2000 to 9000, dermatan sulfate and heparan sulfate, and calcium hopanthenate. Hair nourishing cosmetics characterized by doing.