JPH0237884B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention provides a hair protection cosmetic composition containing tannins, more specifically, it protects hair that has been damaged by bleaching, perming, hair dye, shampoo, heat from dryers, ultraviolet rays, dust, brushing, etc. , relates to a cosmetic composition for repair. Prior Art Hair is exposed to ultraviolet rays from sunlight, heat from dryers that have become popular in recent years, and treatments such as bleaching, perming, and hair dye, which cause defects in its surface structure, destruction of internal proteins, and release of amino acids. The hair is severely damaged, and the hair's natural moisturizing properties, alkali resistance, elasticity, strength, etc. are reduced. As a result, the hair becomes dry, loses its moisturizing feel and luster, causes split ends and cleft hair, and also becomes difficult to comb. Such protection and repair of hair damage is achieved by using cosmetics containing various hair protectants and by adsorbing the hair protectant to the hair to cover the surface or fill in damaged areas. For example, conventionally,
Cosmetics containing cationic substances such as cationic polymers as hair protectants are used to adsorb the polymers to the hair or polymerize them within the defective areas. Coating with oil to prevent water evaporation is practiced. On the other hand, in recent years, from the perspective of improving the safety of cosmetics, there has been a growing trend to use natural products as ingredients, and as hair protectants, animal and vegetable proteins such as collagen hydrolysates, amino acids, natural oils and fats are being used rather than cationic substances. Natural products or substances derived from natural products are increasingly being used. However, such substances have the disadvantage that they are weakly adsorbed to hair and are less effective than cationic substances. Purpose of the Invention In view of the above circumstances, the present inventor has conducted extensive studies in order to obtain a hair protection cosmetic that uses as a hair protection agent a substance that is a natural product or a substance derived from a natural product and exhibits excellent effects. . As a result, some tannins surprisingly have excellent hair protection effects.
That is, they found that it has an excellent effect on suppressing the release of amino acids due to hair damage, and found that by using this, a hair protection cosmetic that has a satisfactory feeling of use and exhibits excellent effects can be obtained. . Classification and action of tannins Tannins include hydrolyzable tannins, i.e., galloyl groups or derivatives thereof bound to sugars or cyclic polyhydric alcohols, and condensed tannins, i.e., flavan-3-ols such as catechin and epicatechin. etc. are the basis of the structure. It is generally believed that tannins have a non-specific protein adsorption effect and thereby exert a variety of effects. However, it is difficult to clearly classify tannins structurally and to clarify the actions and effects of specific tannins. There are very few examples of this being solved. The present inventor focused on the protein adsorption effect of tannins and investigated the relationship between the types of tannins and the hair protection effect. As a result, tannins or tannin-containing herbal medicines and plants exhibit uniform effects, but
The amount of tannins does not match the strength of the hair protection effect,
Among various tannins, condensed tannins [Okuda et al., Proc. Symp. WAKAN-YAKU, 15, 111
(1982)] was found to have excellent hair protection effects. Structure and Effects of the Invention The present invention was completed based on the above knowledge, and provides a hair protection cosmetic composition characterized by containing condensed tannin as an active ingredient. The cosmetics of the present invention can be used appropriately during daily hair styling, and can also be used as shampoo, shampoo, etc.
By using it before and after bleaching, perming, hair dye, etc., it shows excellent hair protection effect.
It is possible to maintain extremely good moisturizing feeling, texture, and combability of the hair. Next, we will show the results of testing the hair protection effects of various herbal medicines and plant-derived tannins. The protective effect can be evaluated based on the extent to which the test substance suppresses the elution of hair components into an alkaline solution when hair is damaged by bleaching and immersed in the solution. Preparation of samples (a) Preparation of crude extracts: Yahuang, Shinshu rhubarb, Heshudori,
The raw materials are elm, ephedra, black tea, casuarina, as well as gennosyouko for gelinin, yoko for terkevin and chebric acid, and red-eye oak for malotssic acid. 10g of each raw material was mixed with water-acetone (1:
1) Immerse in 100ml of the mixed solution, extract for 15 minutes at room temperature while homogenizing with a mixer, and filter. This operation is repeated three times, and the liquids are combined and concentrated to dryness to prepare a crude extract. (b) Preparation of condensed tannins: Dissolve the crude extract obtained in (a) in water, wash with ethyl ether, extract 10 times with ethyl acetate, and concentrate the entire extract under reduced pressure at 40°C. Dry. Safedex the residue LH
Chromatography was performed on -20°C and low molecular weight polyphenols were eluted with ethanol. Next, continue elution with a mixture of ethanol-water (9:1), gradually increase the ratio of water, and when it reaches ethanol:water=7:3, add ethanol-water-acetone (6:3:1). Continue elution with, gradually increasing the proportion of acetone and gradually decreasing the proportion of ethanol, ethanol:
Continue elution until water:acetone=3:3:4. The tannin quantitative value (RA) of each separated fraction is measured, and the fraction showing a high quantitative value is concentrated to dryness to obtain the desired condensed tannin. (c) Preparation of ellagitannin: The crude extract obtained in (a) is extracted with ethyl acetate in the same manner as in (b). The obtained extract was mixed with n-butanol-acetic acid-water (4:
1:5) The mixed solution is subjected to droplet countercurrent partition chromatography and developed using an ascending method to separate each fraction. The tannin quantitative value (RA) was measured for each fraction, and the fractions that showed a high quantitative value were selected.
Concentrate to dryness under reduced pressure at 40°C to obtain the desired ellagitannin. Tannin quantitative value (RA, specific activity of protein adsorption of each tannin based on pharmacopoeial tannic acid) The amount of adsorbed hemoglobin in each sample was determined according to the method of Okuda et al. (Pharmacological Journal, 96, 1143 (1976)). Measure as follows. Disperse each sample in 0.2M phosphate buffer (PH6.0),
Dissolve to prepare solutions of various concentrations. For each 2 ml of this solution, add 2 ml of hemoglobin solution (fresh human blood added with water to hemolyze it to give an OD ₅₇₈ = 2.5).
and 1 ml of 0.2M phosphate buffer (PH6.0),
Stir and let stand for 1 hour. Then, 12000r.pm
Centrifuge for 10 minutes and measure the absorbance of the supernatant at 578 nm. The amount of adsorbed hemoglobin is determined from the difference from the absorbance when no hemoglobin is added. 50% compared to hemoglobin amount without sample addition
The adsorption concentration (ED ₅₀ ) is calculated, and the ratio to the similarly calculated ED ₅₀ of pharmacopoeial tannic acid is determined, and this is used as the tannin quantitative value (RA). RA = ED ₅₀ of pharmacopoeial tannic acid / ED ₅₀ of the sample Hair protection effect (a) Preparation of sample solution Prepare a 1% solution of the crude extract obtained above and the dried product of each tannin and use it as a sample solution. . (b) Preparation of bleach solution A bleach solution is obtained by mixing 20 parts by weight of 30% hydrogen peroxide solution, 1 part by weight of 28% aqueous ammonia, and 79 parts by weight of purified water. (c) Preparation of hair Approximately 50 mg of unbleached human hair is
% sodium lauryl sulfate aqueous solution, washed with water, dried at 105°C for 3 hours, and weighed accurately. (d) Hair treatment Dry and accurately weighed hair was added to 5 ml of sample solution at 30℃.
After immersing for 30 minutes, rinse thoroughly with water, then immerse in 5 ml of bleach solution at 30°C for 30 minutes, and rinse thoroughly with water (Processing 1). Alternatively, dry and precisely weighed hair is first treated in the same manner with a bleach solution, and then treated in the same manner with a sample solution (treatment 2). (e) Alkali elution Treated hair is treated with 0.1N sodium hydroxide solution.
After soaking in 10ml at 60℃ for 1 hour, wash with water. Furthermore, after washing with 1% acetic acid solution, thoroughly washing with water,
Dry at 105°C for 3 hours and weigh accurately.
The ratio to the weight before treatment is taken as the rate of elution by alkali (A). In addition, the elution ratio (Ac) by alkali is determined for hair (damaged hair) subjected to the same treatment using the same amount of purified water instead of the sample solution. Furthermore, the alkali elution rate (Ab) of hair (undamaged hair) treated using the same amount of purified water instead of bleach solution is determined. From these values, the damage suppression rate ( ) is calculated using the following formula. I (%)=A-Ac/Ab-Ac×100 The results are shown in Table 1. The results of a similar test using pharmacopoeial tannic acid and a 1% aqueous solution of collagen hydrolyzate conventionally used as a hair protection agent as sample solutions are also shown.

【table】

[Table] As shown in Table 1, condensed tannins have a better hair protection effect than hydrolyzable tannins and collagen hydrolysates, and especially in treatment 2 (recovery of damaged hair after bleaching), collagen hydrolyzates Condensed tannins have very good effects, whereas tannins have very little effect. Thus, the cosmetic composition of the present invention contains one or more condensed tannins. Condensed tannins are condensates of flavan-3-ols or derivatives thereof, such as catechin, epicatechin, epicatechin gallate, epigallocatechin, and epigallocatechin gallate, and in the present invention,
The degree of condensation, molecular weight, degree of galoylation, bonding position, etc. are not particularly limited, and in general, a mixture of various condensation types may be used, but those having a molecular weight of 500 to 3,500 are preferred. Condensed tannins can be obtained from various herbal medicines and plants, and for example, herbal medicines and plants containing large amounts of condensed tannins, such as rhubarb, heshouwu, elm, mimosa, chestnut, and tea, can be used as raw materials. The preparation method is not particularly limited, but usually, first,
The raw material is extracted with a solvent such as a 30-70% acetone aqueous solution or an alcohol aqueous solution or alcohol with a concentration of 30% or more. The extraction solvent is 2 to the raw material.
It is sufficient to use a ratio of ~10 times as much and repeat the extraction two to several times at room temperature to 60°C for about 15 minutes to 1 hour. Then, the entire extract is concentrated to dryness at 60° C. or lower to obtain a tannin-containing crude extract. Usually, such a crude extract contains about 20 to 60% (weight %, same hereinafter) of tannins as total tannins. This crude extract is dissolved in water and washed with about an equal volume of ethyl ether.
This aqueous solution was extracted 3 to 20 times with ethyl acetate, and
Below, it is preferably concentrated to dryness under reduced pressure to remove a large amount of tannins (usually about 40 to 70% as total tannins).
%) to obtain a purified extract. This extract is subjected to chromatography to separate the tannin fraction. Although such separation method is not particularly limited, a gel filtration method is preferred. For example, using Sephadex LH-20, elute with ethanol to remove low molecular weight polyphenols, and then elute with a 50-70% acetone aqueous solution to obtain the total tannin fraction. This fraction was concentrated and again subjected to chromatography on Sephadex LH-20.
Elute with acetone mixture. By changing the ratio of ethanol and acetone, condensed tannins having a desired molecular weight can be obtained. The obtained tannins can be used alone or in combination of two or more.
A condensed tannin may be obtained by mixing two or more types of raw materials. In the present invention, the condensed tannin may be used in the form of an extract such as the above-mentioned crude extract, purified extract, or total tannin fraction. The amount of condensed tannin in the cosmetic composition of the present invention can be appropriately selected depending on the actual dosage form, but is generally 0.1 to 10% (as condensed tannin) based on the total amount of the composition, preferably 1%. ~5%
(1 to 10% in the case of crude extract) is sufficient to exhibit the desired effect. The composition of the present invention can be manufactured according to conventional methods, and can be made into conventional dosage forms such as hair treatment, hair conditioner, setting lotion, blushing lotion, shampoo, conditioner, hair spray, etc. Can be done. Other ingredients are not particularly limited and may be any of those normally used in this type of composition, and may also include other protective agents such as soybean lecithin, soybean protein, water and alcohol extracts of beans, etc. It is also possible to use them together. Reference Examples and Examples Next, the present invention will be explained in more detail with reference to Reference Examples and Examples. Reference Example 1 2 kg of commercially available dried roots of Rhubarb (Gahuang) were homogenized in a water-methanol (1:1) mixture for 1 hour using a mixer and filtered. This operation is repeated three times, and all the liquids are combined and concentrated to dryness below 60°C to obtain 340 g of crude extract (total tannins approximately 50%). Dissolve 200 g of this extract in 1 part of water, add 1 part of ethyl ether, shake well, and remove the ethyl ether layer. After repeating this operation three times, add 0.3 ml of ethyl acetate to the remaining aqueous layer, shake well, and extract. After repeating this operation 10 times, the extracts were combined and concentrated to dryness under reduced pressure at 40°C to obtain 70 g of purified extract (about 70% total tannins). Dissolve 50g of this extract in 200ml of ethanol,
Subject to gel chromatography on Sephadex LH-20 (wet volume 1.5) and elute with 10 ml of ethanol. Then, elute with 50% acetone, collect the third fraction, and concentrate to dryness at 40° C. under reduced pressure to obtain 15 g of Yahuang total tannin fraction. 5g of this tannin fraction was added to Cephadex LH-
20 gel chromatography (150ml wet volume)
After eluting with ethanol-water (7:3) mixture 1, ethanol-water-acetone (65:30:
5) and collect the fraction 0.2. This eluate was concentrated to dryness at 40°C under reduced pressure, and the molecular weight
540-890 light brown Yao condensed tannin A0.8g
get. Reference Example 2 1 kg of commercially available dried roots of elm is extracted with 3 parts of a water-acetone (1:1) mixture in the same manner as in Reference Example 1, and a purified extract (40% total tannins) is obtained in the same manner. 50 g of this extract was similarly subjected to gel chromatography, eluted with ethanol and then 70% acetone, and fraction 2 was collected, from which 10 g of total tannin was obtained. Sephadex LH-20 with 5g of total tannins
gel chromatography (wet volume 150ml) and eluted with ethanol-water (7:3) mixture 1, followed by ethanol-water-acetone (65:30:
5) Elute with 0.2 of the mixture, then 0.2 of ethanol-water-acetone (60:30:10), 0.2 of each.
Collect two fractions. Each fraction was concentrated to dryness under reduced pressure at 40°C, and each fraction was a pale brown color with a molecular weight of 1090~1090.
1230 condensed tannin A0.5g and molecular weight
0.6 g of condensed tannin B of 1230-1340 was obtained. Reference Example 3 110 g of purified extract (total tannins approximately 40%) was obtained from 1 kg of commercially available dry root of Heshugarasu in the same manner as in Reference Example 1. 50 g of this purified extract was similarly subjected to gel chromatography, eluted with ethanol and then with 50% acetone aqueous solution, and the two fractions were collected. Further, elute with 70% acetone aqueous solution,
Collect the fraction. Each fraction was concentrated to dryness at 40°C under reduced pressure, and 1.4 g of light brown Heshuwu total tannin fraction I with a molecular weight of 2340 to 3110 and 1.4 g of Heshuwu total tannin fraction I with a molecular weight of 3110 to 3110 were collected.
1.2 g of Heshuu total tannin fraction of 3610 was obtained. Example 1 The hair treatment containing Yahuang condensed tannin A obtained in Reference Example 1 was obtained by the following procedure according to a conventional method. Ingredients % Liquid lanolin 10.0 Liquid paraffin 10.0 Isopropyl myristate 8.0 Cetyl alcohol 5.0 Sorbitan monostearate 1.5 Polyoxyethylene sorbitan monostearate 2.0 Carbopol 940 0.5 Glycerin 5.0 Yahuang condensed tannin A 4.0 Preservatives Appropriate amount of water Adjust to 100% Example 2 A hair treatment containing the condensed tannins A and B obtained in Reference Example 2 was obtained according to the following recipe according to a conventional method. Ingredients % Liquid lanolin 5.0 Liquid paraffin 7.0 Isopropyl myristate 5.0 Cetyl alcohol 2.0 Sorbitan monostearate 1.0 Polyoxyethylene sorbitan monostearate 1.5 Cetyltrimethyl ammonium chloride 1.0 Glycerin 4.0 Diary condensed tannin A 2.0 Diary condensed tannin B 2.0 Preservative Appropriate amount of water Adjusted to 100% Example 3 In the formulation of Example 1, Yahuang condensed tannin
A hair treatment is obtained by using 4.0% of Heshuu total tannin fraction I obtained in Reference Example 3 instead of A4.0%. Example 4 In the formulation of Example 1, Yahuang condensed tannin
A hair treatment was obtained by using 6.0% of the purified extract of Heshuwusu obtained in Reference Example 3 instead of A4.0%. Example 5 In the formulation of Example 2, a hair treatment is obtained using 5.0% of the Yahuang total tannin fraction obtained in Reference Example 1 instead of Diyu condensed tannins A and B. Example 6 In the formulation of Example 2, a hair treatment was obtained by using 8.0% of the Ahuang crude extract obtained in Reference Example 1 in place of the Dhiyu condensed tannins A and B. Using the hair treatments of Examples 1 to 6,
As in Table 1 above (as the sample solution,
Table 2 shows the results of testing the hair protection effect of each hair treatment (using each hair treatment diluted 5 times with water). As a control, the results of a similar test on hair treatments produced using 5% collagen hydrolyzate instead of condensed tannins or tannin extracts in the formulations of each example are also shown.

[Table] Also shown are the results of testing the hair protection effects of the hair treatments of Examples 1 and 2 through sensory evaluation of the use test. 20 girls between the ages of 18 and 24 were divided into two groups. The first group received the hair treatment of Example 1 on the left half of their head for about one month, and the hair treatment of Example 1 on the right half of their heads. The same amount of hair treatment prepared by removing mold tannin was used. Similarly, the second group used the hair treatment of Example 2 and the hair treatment from which the condensed tannins were removed. During this period, the use of other treatments was prohibited, but the subjects were allowed to freely choose the time and number of doses used. Next, the right and left sides of the hair were self-evaluated in terms of dampness, texture, and ease of brushing using the following criteria. -2: Very bad. -1: Bad. 0: Normal. +1: Good. +2: Very good. Average evaluation scores for each group and the left side (the side using the condensed tannin-containing hair treatment) and the right side (the side using the condensed tannin-free hair treatment)
Table 3 shows the difference in the average evaluation scores.

[Table] As shown in Tables 2 and 3, all tannin-containing hair treatments exhibit excellent hair protection effects. Example 7 A hair treatment is obtained using Yahuang condensed tannin A obtained in Reference Example 1 and Diyue condensed tannin A obtained in Reference Example 2 according to the following recipe according to a conventional method. Ingredients % Liquid lanolin 10.0 Liquid paraffin 10.0 Isopropyl myristate 8.0 Cetyl alcohol 5.0 Sorbitan monostearate 1.5 Polyoxyethylene sorbitan monostearate 2.0 Carbopol 940 0.5 Glycerin 5.0 Yahuang condensed tannin A 1.0 Diyu condensed tannin A 1.0 Preservative Agent Appropriate amount of water Adjust to 100% Example 8 According to a conventional method, a settling lotion is obtained using the condensed tannin B obtained in Reference Example 2 according to the following recipe. Ingredients % Sodium polyacrylate 0.5 Ethanol 5.0 Citric acid 0.2 Polyoxyethylene sorbitan monostearate 1.0 Glycerin 2.0 Jiyu condensed tannin B 1.0 Preservative Appropriate amount of water Adjusted to 100% Example 9 In the formulation of Example 8, Jiyu condensed tannin B Instead of condensed tannin B, the Yao purified extract obtained in Reference Example 1
Obtain a settlement using 5.0%. Example 10 A hair rinse is obtained using Yahuang condensed tannin A obtained in Reference Example 1 according to the following recipe according to a conventional method. Ingredients % Glyceryl monostearate 3.0 Glycerin 5.0 Cetyltrimethyl ammonium chloride 1.0 Yahuang condensed tannin A 1.0 Preservative Appropriate amount Coloring agent Appropriate amount Water Adjusted to 100% Example 11 In the formulation of Example 10, Yahuang condensed tannin A Instead, a hair rinse is obtained using 3.0% of the Heshuwusu total tannin fraction I obtained in Reference Example 3.

Claims (1)

[Scope of Claims] 1. A hair protection cosmetic composition characterized by containing condensed tannin as an active ingredient. 2. The composition according to item 1 above, in which the tannin is blended in an amount of 0.1 to 10% by weight based on the total amount of the composition. 3. The tannins are extracted from rhubarb, shucho, ephedra, elm,
The composition according to item 1 or 2 above, which is formulated as an extract from a plant selected from the group consisting of tea, mimosa, and millet.