JPH1077209A - Cosmetic and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic capable of reducing tacky feeling which occurs when used for hair and skin while keeping moisture retention of keratin hydrolyzate and having good compatibility with sebum on the surface of hair or skin, capable of permeating to hair or skin and excellent in moisture retention, antioxidative property and safety. SOLUTION: This cosmetic is obtained by compounding a keratin hydrolyzate forming a tertiary structure which is characteristic to a protein molecule such as keratose having 5,500 to 30,000 average molecular weight. In this case, the keratin hydrolyzate has hydrophilic substituent groups more than hydrophobic substituent groups in the interior and has hydrophobic substituent group more than the hydrophilic substituent groups on the outside.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic product having low stickiness to hair and skin and having high affinity for a sebum film on the surface of hair and skin, and a method for producing the same.

[0002]

2. Description of the Related Art As humectants used in cosmetics, there are many hydrolysis products of animal proteins such as collagen, silk, keratin and milk, and hydrolysis products of vegetable proteins such as soybean and wheat. It's being used. JP-B-60-27680 and JP-A-5-22210
No. 0 discloses that the peptide bonds of these proteins are cleaved under severe conditions using a strong acid or the like, so that protein degradation products mainly composed of low-molecular-weight peptides to which only a few amino acids are linked can be obtained. Moisturizers have been proposed. These humectants are known to have good hydrophilicity and a high moisturizing effect because they have many hydrophilic functional groups such as amino acids and carboxyl groups per peptide molecule (Maichi Kitayama, Komaki Yasuyuki: FRAGRANCE JOURNAL 19
95-1, P99-103).

[0003]

However, the above-mentioned low molecular weight peptide has a high affinity for water due to the large number of hydrophilic functional groups on the surface, and is used in a large amount in cosmetics, and is washed away to the hair and skin. There is a problem that the sticky feeling remains on the hair or the skin when used in a state without the adhesive. In addition, since the surface of hair and skin is coated with sebum, etc., highly hydrophilic low molecular weight peptides are poorly compatible with the sebum film of hair and skin, so it is difficult to penetrate into hair and skin and easily with water There was a problem that was easily washed away.

[0004] It is an object of the present invention to reduce the sticky feeling produced when used on hair and skin while maintaining the moisturizing properties of the keratin hydrolysis product, and to improve the compatibility with sebum on the surface of hair and skin. Another object of the present invention is to provide a cosmetic product that easily penetrates hair and skin and a method for producing the same. Another object of the present invention is to provide a cosmetic having excellent moisture retention, antioxidant properties and safety, and a method for producing the same.

[0005]

The invention according to claim 1 is
A cosmetic product containing a keratin hydrolysis product that forms a tertiary structure specific to a protein molecule, wherein the keratin hydrolysis product has more hydrophilic substituents than hydrophobic substituents inside, A cosmetic product characterized by having more hydrophobic substituents than hydrophilic substituents.
The invention according to claim 2 is the invention according to claim 1,
Keratin hydrolysis product has an average molecular weight of 5500 to 300
00 is a cosmetic which is a γ-keratose. Unlike amino acids and low molecular weight peptides, γ-keratose is a high molecular weight protein having a tertiary structure, and is therefore preferable for achieving the object of the present invention.

The invention according to claim 3 has an average molecular weight of 550.
By placing a keratin hydrolysis product consisting of γ-keratose forming a tertiary structure of 0 to 30,000 in a state of low hydrophilicity, a hydrophilic substituent is converted from a hydrophobic substituent into a keratin hydrolysis product. This is a method for producing cosmetics in which a large amount of the keratin hydrolysis product is present outside the keratin hydrolysis product, and more hydrophobic substituents are present than hydrophilic substituents. The invention according to claim 4 is the invention according to claim 3, wherein the keratin hydrolysis product is dissolved in a mixture of alcohols and water, and the keratin hydrolysis product is placed in a state of low hydrophilicity. It is a manufacturing method of. The invention according to claim 5 is the invention according to claim 3, wherein the keratin hydrolysis product is dissolved in a mixed solution of oil, alcohols and water to convert the keratin hydrolysis product to a state having low hydrophilicity. Is a method of manufacturing cosmetics.

[0007] Proteins are macromolecules (polypeptides) in which 50 or more amino acids are linked, and their molecular structures are known from primary to tertiary structures. The primary structure indicates an amino acid sequence in which several types of amino acids constituting a protein are linked by peptide bonds, and the arrangement of these amino acids basically has a great effect on the function and structure of the protein. The secondary structure is the spatial arrangement of consecutive adjacent amino acid residues in a polypeptide chain, i.e.,
Refers to the conformation. Tertiary structure is the most stable three-dimensional conformation that the polypeptide chain can take,
It is not rigidly fixed, but is known to change in the course of biological function. Keratin hydrolysis products typified by high molecular weight γ-keratose, in which cleavage of polypeptide chains is reduced when keratin is hydrolyzed, are proteins that form a tertiary structure. When this is placed in an aqueous solution, the number of hydrophilic substituents is greater than the number of hydrophobic substituents outside the tertiary structure as shown in FIG. 2, and vice versa. On the other hand, when this is placed in a state of low hydrophilicity, as shown in FIG. 1, the number of hydrophilic substituents is larger than the number of hydrophobic substituents inside the tertiary structure, and vice versa outside the tertiary structure. When the number of hydrophilic groups on the surface of the protein molecule is reduced, the sticky feeling at the time of use of cosmetics is reduced, resulting in a dry feeling. On the other hand, protein molecules have moisture inside because of many hydrophilic substituents. Also, when the number of hydrophobic groups on the surface of the protein molecule increases, the affinity of the surface of the hair and skin with the sebum membrane increases, and as a result, the protein easily penetrates into the hair and skin, thereby improving the antioxidant effect possessed by hydrolyzed keratin. be able to.

In general, the skin is a place that is easily exposed to the outside air, ultraviolet rays, etc., and the sebum film on the surface is constantly oxidized to generate lipid peroxide, which causes the aging of the skin. Keratin hydrolysis products represented by γ-keratose have antioxidant properties that inhibit the oxidation of unsaturated fatty acids and have an affinity for sebum film on the surface of hair and skin. In addition to coating the surface of the membrane, it can penetrate the sebum membrane to decompose lipid peroxides inside the skin and suppress its generation.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The keratin raw material used in the present invention is not limited as long as it contains keratin as a main component. Examples include animal hair such as human hair, wool, and alpaca; feathers of birds represented by Aigamo and chickens; and hooves such as cows and horses. Of these, wool is preferred because it is easily available as a raw material. The keratin hydrolysis product of the present invention is not particularly limited as long as it has an average molecular weight of 5500 to 30000, but examples include γ-keratose, reduced hydrolyzed keratin, and the like.
From the viewpoint of stability in an aqueous solution, γ-keratose is preferred. To produce this keratin hydrolysis product, keratin is hydrolyzed by a weak reaction. As a method for producing γ-keratose, for example, the following method can be mentioned.

A acetic acid solution is prepared by mixing glacial acetic acid and hydrogen peroxide (35%) in a weight ratio of 8: 2 to 9: 1. The weight ratio of this peracetic acid solution and keratin raw material is 3
Mix so as to be 0: 1 to 10: 1, and 40 to 60 ° C.
And hydrolyze for 2 to 5 hours. The keratin hydrolysis product thus obtained is recovered, washed with water,
Dissolve in 0.5 molar aqueous ammonia, then adjust the pH to 4 or less with acid, remove the precipitate by centrifugation, and obtain a clear supernatant. This is removed with a dialysis membrane having a molecular weight fraction of 5000 to remove low molecular weight peptides and impurities to prepare a γ-keratose solution. This solution is freeze-dried or spray-dried to have an average molecular weight of 5500 to
30,000 powdery gamma-keratose are obtained. In this method, the yield is 20-40%. Table 1 shows examples of the amino acid composition of γ-keratose. Since γ-keratose has cysteine converted to cysteic acid, it has a relatively high molecular weight but is stably dissolved in water even under acidic conditions, has high moisture retention, and is stable against salts. is there.

[0011]

[Table 1]

A feature of the present invention is that the average molecular weight is 55%.
A tertiary structure that is a keratin hydrolysis product, such as γ-keratose prepared to a molecular weight of 100 to 30,000, is converted into a tertiary structure such that the surface has more hydrophobic substituents and the inner portion has more hydrophilic substituents. It is about transforming the formation. As the conversion method, a method of converting the tertiary structure of the keratin hydrolysis product in advance and then blending it into cosmetics, or a method of converting the tertiary structure of the keratin hydrolysis product after blending it into cosmetics, are considered. Can be Whichever method is adopted, the object of the present invention is achieved if the tertiary structure is converted into the cosmetic as a result.

In order to convert the tertiary structure of the keratin hydrolysis product so that the surface thereof has more hydrophobic substituents and the inside thereof has more hydrophilic substituents, alcohols such as methanol and ethanol can be used. Acetone, DMSO
(Dimetyl sulfoxide), DMF (NN-dimethylfolmami
A water-miscible solvent such as de) is prepared, and a mixed solution of the solvent and water is prepared, and the keratin hydrolysis product is dissolved therein. As the solvent, alcohols such as ethanol, butylene glycol, and propylene glycol, which are used as cosmetic base materials, are most suitable. At this time, the keratin hydrolysis product needs to be dissolved in the mixture. For example, in the case of ethanol water, ethanol is mixed with water at a ratio of 20 to 50% by volume to prepare ethanol water, and the keratin hydrolysis product is dissolved therein. By simply dissolving the keratin hydrolysis product in this ethanol-water mixture, the conformation is converted to increase the number of hydrophobic substituents on the surface and increase the number of hydrophilic substituents inside. .

The cosmetic of the present invention is characterized in that the solution obtained by dissolving the keratin hydrolysis product in the above-mentioned mixed solution is blended with a cosmetic containing alcohols or oils and alcohols or with alcohols or oils. It is produced by adding a solution of a keratin hydrolysis product simultaneously with the preparation of a cosmetic containing alcohols. The same effect can be obtained by any of the methods, but the former method is preferable because the steric structure cannot be converted in the interaction with other cosmetic raw materials. The keratin hydrolysis product of the present invention is incorporated in an amount of 0.1 to 10% by weight based on the total weight of the cosmetic. In order to effectively provide antioxidant properties and moisturizing properties, 0.5 to 2% by weight
Is appropriate.

The cosmetic of the present invention has various forms such as liquid and gel. The cosmetic must contain either alcohol or oil or both. For example, hair tonics, hair lotions, hair creams, hair treatments, set lotions, hair repair products and other hair cosmetics, packs, lotions, emulsions, acne lotions, hand creams, after shave lotions, shaving creams, cold creams , Skin creams such as moisture cream, antiperspirant, body lotion, and other cosmetics such as nail enamel and lipstick. The cosmetics of the present invention include keratin hydrolysis products, alcohols, oils and various cosmetic bases used in ordinary cosmetics in addition to oils, and do not impair the functions of the present invention such as antioxidant properties or moisturizing properties. It is possible to mix in a range. Examples of such cosmetic base materials include gels, surfactants, polyhydric alcohols, fragrances, dyes, pigments, preservatives, antioxidants, ultraviolet absorbents, ultraviolet scattering agents, humectants, purified water, cosmetic ingredients, and the like. No.

[0016]

EXAMPLES Next, examples of the present invention will be described together with comparative examples, but these do not limit the technical scope of the present invention. <Example 1> First, glacial acetic acid was prepared, and the glacial acetic acid and a hydrogen peroxide solution (concentration: 35%) were collected at a weight ratio of 8: 2.
These are uniformly mixed to prepare 100 g of a peracetic acid solution. 10 g of well washed defatted wool in this peracetic acid solution
The wool keratin was hydrolyzed at 60 ° C. for 3 hours with stirring. Next, the hydrolyzed wool keratin was taken out, washed with water, and dissolved in 100 g of 0.5 molar ammonia water kept at 50 ° C. with good stirring.
From the aqueous ammonia solution, a filter cloth was used to remove those not dissolved in the aqueous ammonia solution, and the filtrate was adjusted to pH 4 with sulfuric acid.
Adjusted below. This was centrifuged, and the clear γ-
A keratose solution was obtained. After concentrating this with an evaporator,
Purified by dialysis and powdered with a spray drier.
The average molecular weight of the obtained γ-keratose measured by high performance liquid chromatography was 9,800. The amino acid composition of this γ-keratose was examined. The results are shown in Table 1 (supra). From this, it was found that cysteine was changed to cysteic acid. Example 1 was prepared by dissolving 1 g of the untreated γ-keratose in 50% ethanol water, adjusting the pH to 12 with 1N caustic soda, and dissolving the total amount in 100 ml.

<Comparative Example 1> Untreated γ in Example 1
-Dissolve 1 g of keratose in water and p with 1 N caustic soda
The aqueous solution of γ-keratose adjusted to H12 and dissolved in 100 ml in total amount was used as Comparative Example 1. <Comparative Example 2> Comparative Example 2 was prepared by dissolving 1 g of sodium glutamate, which is one kind of amino acid, in water, adjusting the pH to 12 with 1N sodium hydroxide, and dissolving the total amount in 100 ml. <Comparative Example 3> Sodium glutamate / ethanol aqueous solution in which 1 g of sodium glutamate, one of the amino acids, was dissolved in 50% ethanol water and adjusted to pH 12 with 1N caustic soda, and the total amount was dissolved in 100 ml was used as Comparative Example 3.

An acid titration test was conducted by dropping 2.5N hydrochloric acid into the four types of ethanol water or the aqueous solution of Example 1 and Comparative Examples 1 to 3. The result is shown in FIG. As is clear from FIG. 3, in Comparative Example 1, the pH slowly decreased from 12 to 10 until the amount of hydrochloric acid dropped to 0.6 ml, and then sharply decreased. On the other hand, in Example 1, the buffering action against the addition of the acid did not work at all, and the tendency for the pH to drop sharply appeared. This is because when γ-keratose is placed in the environment of Example 1 of an alcohol aqueous solution having a higher hydrophobicity than Comparative Example 1 of an aqueous solution, a large number of hydrophilic groups on the surface migrate to the inside of the three-dimensional structure, and the hydrophobic group becomes It is considered that the tertiary structure shown in FIG. 1 which changes to a large amount changed, and the apparent hydrophilic groups on the surface decreased. On the other hand, in the case of sodium glutamate, which is a low molecular weight amino acid, the titration curve did not change between the aqueous solution (Comparative Example 2) and the alcohol aqueous solution (Comparative Example 3). This was thought to be because a low molecular weight could not take a three-dimensional structure like a protein.

Example 2 1 mg of the untreated γ-keratose obtained in Example 1 was added to a 25% aqueous 40% ethanol solution.
Example 2 was γ-keratose / ethanol aqueous solution dissolved in l. The antioxidant performance of this solution on linoleic acid was examined. Vitamin E was used as an antioxidant control. First, 0.13 ml of linoleic acid was made 10 ml with 99% ethanol, and 10 ml of 50 mM phosphate buffer (pH 7) was added thereto. Next, vitamin E and γ-keratose, whose antioxidant properties were examined for the linoleic acid solution, were collected in the amounts shown in Table 2, dissolved in 0.1 ml of water, added to each, and distilled water was added to the total amount. To 25 ml.

The two kinds of linoleic acid solutions as test subjects were
It was left at 0 ° C. for 5 days. The linoleic acid solution to which no sample was added was stored at 40 ° C. for 5 days and in a refrigerator kept at 5 ° C. The thiocyanate method was used for the measurement of antioxidant properties. Take 0.1 ml of each of the four linoleic acid solutions left for 5 days, and add 75% ethanol and 30
% Rodinammon was added and stirred well. First chloride reagent (10 mM of 20 mM FeCl ₂ , 3.5% HCl solution)
l) was added, and exactly 3 minutes later, the absorbance at 500 nm was measured. The degree of oxidation was [(40 ° C on day 5)
Sample) − (4 ° C. control on day 5)] /
[(Linoleic acid only sample at 40 ° C for 5 days)-
(Control at 4 ° C. on day 5)]. Table 2 shows the results. The smaller the value of the degree of oxidation, the higher the antioxidant property. As is clear from Table 2, it was found that the γ-keratose solution of Example 2 exhibited excellent antioxidant properties, although it was inferior to vitamin E. In this example, since γ-keratose shows an effect in a very small amount (0.004%) in a 40% aqueous ethanol solution, when it is blended in cosmetics, it is considered that the γ-keratose may serve as a moisturizing agent. Antioxidant performance is sufficient at a content of about weight%.

[0021]

[Table 2]

Example 3 An aqueous solution of γ-keratose / ethanol obtained by dissolving 5 g of the untreated γ-keratose obtained in Example 1 in 100 ml of 50% ethanol water was used.
And <Comparative Example 4> An aqueous solution of γ-keratose obtained by dissolving 5 g of the untreated γ-keratose obtained in Example 1 in 100 ml of water was used as Comparative Example 4.

Each of the solutions of Example 3 and Comparative Example 4 was spread on the skin and dried. As a result, the aqueous solution of Comparative Example 4 remained sticky, and felt the skin was pulled after drying. In contrast, the alcohol aqueous solution of Example 3 had almost no stickiness, and did not have a feeling of being pulled after drying. The feeling of being pulled is comparative example 4.
Was dried on the skin, and the skin was pulled with the shrinkage of the film due to the drying. On the other hand, in Example 3, it was considered that such a phenomenon did not occur because the skin penetrated the skin. . The stickiness was considered to be due to the difference in hydrophilic substituents on the surface discussed in Example 1 and Comparative Example 1.

<Evaluation Test for Cosmetics> (1) Lotion 20 g of untreated γ-keratose obtained in Example 1 was added to 5 g
Γ dissolved in 0% ethanol water to make the total amount 100 ml
A lotion having the following composition was prepared using an aqueous solution of keratose / ethanol, and this was designated as Example 1. Unit is% by weight
It is. -Γ-keratose (Example 1) 5.0-Propylene glycol 5.0-Glycerin 5.0-Polyethylene glycol 1500 2.0-Polyoxyethylene oleyl ether (15EO) 2.0-Ethanol 15.0 -Potassium hydroxide 0.03-Appropriate amount of preservative-Purified water 65.97 A lotion containing no ethanol in the above composition was prepared, and this was designated as Comparative product 1. The lotions of the product 1 and the comparative product 1 were applied to the faces of 10 monitors, respectively, and the monitor was used to evaluate the product 1 and the comparative product 1. Table 3 shows the results.

[0025]

[Table 3]

As is clear from Table 3, it was found that the lotion of Example 1 containing γ-keratose together with ethanol was superior to the lotion of Comparative Example 1 containing no ethanol.

[0027]

As described above, conventional hydrolysis products of keratin have problems such as "stickiness" and "penetration into hair and skin due to affinity for sebum membrane". On the other hand, according to the present invention, the keratin hydrolysis product is converted into a protein having a tertiary structure, and the keratin hydrolysis product is placed in a state of low hydrophilicity, whereby the keratin hydrolysis product is converted into a protein molecule which is a keratin hydrolysis product. The unique tertiary structure is converted so that many hydrophilic substituents are present inside and many hydrophobic substituents are present outside, increasing the affinity for the sebum film of hair and skin, resulting in a sticky feeling when using cosmetics. It has an excellent effect of reducing and having a smooth feeling of use. Further, the cosmetic of the present invention easily penetrates the skin and can improve the antioxidant effect possessed by the keratin hydrolysis product.

[Brief description of the drawings]

FIG. 1 is a schematic view showing the arrangement of substituents in an alcohol solution of a protein molecule which is a keratin hydrolysis product of the present invention.

FIG. 2 is a schematic diagram showing the arrangement of substituents in an aqueous solution of a protein molecule that is a keratin hydrolysis product.

FIG. 3 is a graph showing a change in pH when an aqueous solution of four kinds of γ-keratose having pH 12 of Example 1 and Comparative Examples 1 to 3 was subjected to acid titration.

Claims (5)

[Claims] 1. A cosmetic product containing a keratin hydrolyzate that forms a tertiary structure specific to a protein molecule, wherein the keratin hydrolyzate has a hydrophilic substituent inside a hydrophobic substituent. Cosmetics characterized by having more and having more hydrophobic substituents on the outside than hydrophilic substituents. 2. The keratin hydrolysis product has an average molecular weight of 5
The cosmetic according to claim 1, which is 500 to 30,000 γ-keratose. 3. A keratin hydrolysis product consisting of γ-keratose which forms a tertiary structure having an average molecular weight of 5500 to 30000 is placed in a state of low hydrophilicity, whereby a hydrophilic substitution occurs inside the keratin hydrolysis product. A method for producing cosmetics, wherein a group is present more than a hydrophobic substituent, and a hydrophobic substituent is present more than a hydrophilic substituent outside the keratin hydrolysis product. 4. The method for producing cosmetics according to claim 3, wherein the keratin hydrolysis product is dissolved in a mixture of alcohols and water to place the keratin hydrolysis product in a state of low hydrophilicity. 5. The method for producing cosmetics according to claim 3, wherein the keratin hydrolysis product is dissolved in a mixture of oil, alcohols and water to place the keratin hydrolysis product in a state of low hydrophilicity.