WO2001091702A1

WO2001091702A1 - Cosmetic

Info

Publication number: WO2001091702A1
Application number: PCT/JP2000/003457
Authority: WO
Inventors: Kiyoshi Hirabayashi
Original assignee: Road Nijuuichi Co., Ltd.
Priority date: 2000-05-29
Filing date: 2000-05-29
Publication date: 2001-12-06
Also published as: AU4782800A

Abstract

A cosmetic having an ultraviolet ray prevention effect, excellent in a use property and a use feeling, and not stimulating a skin. The cosmetic contains, as an effective component, water-soluble protein which is a hydrolysis substance of silk protein and contains at least tyrosine.

Description

Light

Cosmetics

TECHNICAL FIELD The present invention relates to a cosmetic that contains a water-soluble protein derived from silk protein, contains an ultraviolet absorbent that does not irritate the skin, and has a good feeling in use.

Rice field

Background Art In recent years, sunburn, especially sunburn due to ultraviolet rays, is considered to cause various disorders such as skin cancer, pigmentation, and aging, and the importance of ultraviolet inhibitors to protect skin from ultraviolet rays has been recognized. I have. In particular, due to the problem of depletion of the ozone layer, the need for cosmetics having an anti-UV effect is increasing. Conventionally, sunscreen cosmetics such as sunscreen creams and sunscreen lotions, and makeup products such as foundations, which contain a substance that scatters or absorbs and blocks ultraviolet rays to protect the skin from ultraviolet rays, have an effect of preventing ultraviolet rays. Many fees are commercially available. The ultraviolet blocking substances contained in these cosmetics include fine particle ultraviolet scattering agents such as titanium dioxide and zinc oxide, P-aminobenzoic acids, hydroxybenzophenones, cinnamic acids, benzofurans, salicylic acids, coumarins. And ultraviolet absorbing compounds such as azoles are well known. However, those that can be used for cosmetics are limited. For example, titanium dioxide, acid Fine particles, such as zinc oxide, have a very high UV scattering effect.However, when the amount is too large, the feeling of use decreases, such as roughness and poor elongation, and the skin becomes whitish and finishes as a cosmetic. There is a problem. It may also act as a photocatalyst on the surface of the skin, generating reactive oxygen radicals that can adversely affect the skin.

In recent years, among the ultraviolet rays contained in the sun's rays, UV-B having a shorter wavelength than 320 nm has a more adverse effect on the skin than UV-A having a longer wavelength than 320 nm. However, the UV-absorbing compound is not necessarily sufficient in terms of UV-B absorption.

In addition, if you have a skin disorder such as atopy, you are often limited in the cosmetics that can be used because they are sensitive to the compounds contained in the cosmetics. Appearance is desired. Disclosure of the invention

The present invention has been made in such a situation, and it is an object of the present invention to provide a cosmetic product that contains an ultraviolet ray Kaizumi absorbent that does not irritate the skin and has a good feeling of use. The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and have found that tyrosine and phenylalanine contained in silk protein are excellent in UV-UV absorption even among ultraviolet rays. The hydrolyzed silk protein can also be used as food, and there is no need to worry about adverse effects on the human body.It is water-soluble and can be suitably used as cosmetics. The present inventors have found that the above problems can be solved at once if a water-soluble protein derived from silk containing tyrosine is included in cosmetics, and have completed the present invention. That is, the present invention is a cosmetic product having an ultraviolet-ray-preventing effect and containing, as an active ingredient, a water-soluble protein containing at least tyrosine, which is a hydrolyzate of silk protein.

The average molecular weight of the water-soluble protein is usually about 150 to 500,000. The water-soluble protein usually further contains phenylalanine.

The water-soluble protein is desirably contained in an amount of 3% by mass or more based on 100% by mass of the cosmetic.

The silk protein is preferably a silk-five mouth in-protein. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing a test material for testing the ultraviolet absorption effect of silk protein.

FIG. 2 is a diagram showing test results of the ultraviolet absorption effect.

FIG. 3 is a diagram showing a UV-B ultraviolet absorption spectrum. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically.

The cosmetic according to the present invention contains, as an active ingredient, a water-soluble protein containing at least tyrosine, which is a hydrolyzate of silk protein.

The hydrolyzate of the silk protein contained in the cosmetic of the present invention is obtained by hydrolyzing, preferably partially hydrolyzing the silk protein so that the amount of free amino acid produced is 1 to 70%. As the silk protein raw material to be subjected to the above hydrolysis, cocoon balls, silk yarn, etc. can be used, and it is preferable to use yarn waste generated in the spinning, weaving process, etc. from the viewpoint of both waste treatment and economy. . Silk is a fibrous protein secreted from the silk glands of silkworms, and fibrous mouth fibers are hardened with sericin.

When fiber-in fiber is used as the silk protein, sericin can be removed by a known refining method to obtain fiber-in fiber.For example, treatment such as dissolution, precipitation, extraction, purification, and culture from cocoons or silk thread can be performed. It is obtained by performing.

Hydrolysis of silk proteins can be performed using acids, alkalis or enzymes. Specifically, for example, the above silk fiber mouth-in fiber is heated and dissolved in a concentrated solution of a mineral acid selected from hydrochloric acid (hereinafter sometimes referred to as a hydrochloric acid method), sulfuric acid, phosphoric acid, and the like, and then hydrolyzed. After neutralization and desalting, a water-soluble protein derived from silk protein can be obtained. In addition, in the case of using an alcohol, for example, the above silk fibroin fiber is mixed with a 45% calcium chloride solution or a 1: 2: 8 (weight ratio) solution of calcium chloride, ethanol and water (these are referred to as calcium chloride method). ), And this solution can be obtained by desalting.

Further, by hydrolyzing with a proteolytic enzyme such as papain, samoase, elastase or bank creatine, a water-soluble protein derived from a silk protein having a small molecular weight can be obtained.

If the water-soluble protein obtained above is dried and powdered by a method such as spray drying or freeze drying, a water-soluble protein powder derived from silk protein can be obtained.

The hydrolysis is preferably partially hydrolyzed so that the average molecular weight of the protein is usually about 150 to 500,000, preferably about 300 to 300.000. If the average molecular weight is larger than 500, 000, it has a gelling ability, so that the processability in preparing the cosmetic composition tends to be inferior.

In the present invention, it is particularly preferable to use a water-soluble protein having an average molecular weight of about 300, and a cosmetic having a good feeling in use can be obtained.

The amount of free amino acids produced after hydrolysis is usually preferably about 1 to 70% (by mass) of the fibroin fiber as a raw material.

The amount of free amino acids generated in the water-soluble protein solution was determined by treating the water-soluble protein solution with a basic protein solution with basic copper carbonate, converting the amino acid and the peptide into a copper complex, and adsorbing this to an anion exchange resin. It can be analyzed by quantifying free amino acids eluted with a 0.05 M borate buffer using an automatic amino acid analyzer. Acidic amino acids that are not released by the borate buffer can be analyzed by using an amino acid analyzer with the water-soluble protein solution as it is.

For example, an example of the amino acid composition of silk fibroin fiber is shown below.

Amino acid number of residues / 1000 number of molecules weight%

L e u 5 131 0.7

I 1 e 7 131 1.0

V a 1 22 117 2.7

L y s 3 146 0.5

Th r 9 119 1.1

Me t 1 149 0.2

C y s 2 240 0.5

P he 6 165 1.1

Ty r 52 181 10.0

T r p 2 204 0.4

G 1 y 445 75 35.5

A 1 a 293 89 27. 8

S e r 121 105 13.5

As 13 133 1.8

G 1 u 10 147 1.6

A r g 5 174 0.9

P ro 3 115 0.4

H is 2 155 0.3

Although silk protein absorbs ultraviolet light, it has been confirmed that tyrosine also absorbs UV-B ultraviolet light among silk proteins, as described in Examples described later. In addition, the UV-B absorption effect of phenylalanine has been confirmed.

In addition, since silk protein is used in surgical threads, there is no concern about adverse effects on the human body, and a skin regeneration effect can be expected.

Therefore, the water-soluble protein used in the present invention contains the amino acid component of the silk protein and at least tyrosine. Further, it is desirable to include fenilalanine.

The cosmetic of the present invention contains a water-soluble protein containing at least tyrosine as described above as an active ingredient.

Specifically, the content of the water-soluble protein varies depending on the form of use of the cosmetic, but is usually 3% by mass or more in the total 100% by mass of the cosmetic.

The cosmetics according to the present invention may be used in the form of a liquid (lotion), an emulsion, an oily liquid, a paste, an oil-in-water emulsion, a water-in-oil emulsion, a cream, a wax, a gel, a solid, It may be in any of a powder form, a powder solid form, an oily solid form, and a multilayer form, and is not particularly limited.

It can be used in a wide range of applications without any particular limitation. For example, sunscreen cosmetics such as sunscreen creams, moisturizing jewels such as lotions, lotions, and serums, white powder, foundations, shampoos Hair care products such as hair care, hair conditioners, hair treatments, hair creams, hair sprays, hair styling agents, stones, liquid stones, cleansing creams, cleansing jewels, etc. It can be widely used as various cosmetics such as creams, massage creams and lipsticks.

The cosmetic of the present invention can optionally contain various additives commonly used in cosmetics as long as the effects of the present invention are not impaired, and optional components are appropriately used according to each use. be able to.

Examples of general components to be added when forming such cosmetics include, more specifically, oil components, aqueous components, humectants, amino acids and their derivatives, anti-fading agents, antioxidants, and surfactants. , Defoamer, beauty and whitening ingredients, other UV absorbers, powder ingredients, preservatives, coloring agents, fragrances, moisturizers, enzymes, anti-inflammatory agents, bactericides, preservatives, antioxidants, chelating agents, Antiperspirants, pigments, inorganic compounds, pH regulators, pearlizing agents, wetting agents, astringents, cosmetics varieties, standardization of quasi-drug ingredients, Japanese Pharmacopoeia, food additives Can be used.

The amounts of these may be appropriately selected according to the application.

The oil component may be any of solid, semi-solid, liquid, volatile oil, etc., and if it can be used for cosmetics, it may be animal, plant, etc. It may be any of synthetic or synthetic, such as hydrocarbons, oils and fats, waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives, Oily gelling agents and the like can be used.

More specifically, liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, mokurou, montank , Oils such as fishtrophs wax, olive oil, coconut oil, castor oil, jojoba oil, mink oil, mala demian nut oil, apogado oil, armando oil, fennel oil, perilla oil, orange oil, Sesame oil, cocoa butter, potato beetle oil, safflower oil, soybean oil, camellia oil, corn oil, nayu oil, persic oil, cottonseed oil, peanut oil, tallow, tallow fatty acid, mink oil, egg yolk oil, lard oil, '' Fats and oils such as milk fats and hydrogenated products thereof, waxes such as beeswax, carnauba wax, candelilla wax, gay wax, cetyl isooctanate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, trio Glyceryl butanoate, polyglyceryl diisostearate, triiso Diglyceryl thearate, glyceryl tribehenate, penyl erythritol ester, rosin acid neopentyldaricol dioctanoate, cholesterol fatty acid ester, N-lauroylu L-glutamate di (cholesteryl-behenyl-octyldodecyl) Esters, stearic acid, lauric acid, myristic acid, behedionic acid, isostearic acid, oleic acid, rosin acid, fatty acids such as 12-hydroxystearic acid, stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol Higher alcohols such as isostearyl alcohol, behenyl alcohol, low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentane Silicones such as oxane, octamethylcyclotetrasiloxane, polyether modified ^ fe polysiloxane, crosslinked organopolysiloxane, fluorine-modified polysiloxane, perfluorodecane, perfluorooctane, perfluoropolyer Fluorinated oils such as tel, lanolin, lanolin acetate, lanolin fatty acid Lanolin derivatives such as isopropyl and lanolin alcohol, dextrin fatty acid esters, sucrose fatty acid esters, starch fatty acid esters, oily gelling agents such as aluminum 12-hydroxystearate, calcium stearate, liquid paraffin, petrolatum, paraffin, ozokeride , Ceresin, microcrystalline wax, squalene, squalane and the like. Two or more of these may be used in combination.

Examples of the aqueous component include water and water-soluble components that can be used for cosmetics. Examples of the water-soluble component include alcohols such as ethyl alcohol and isopropyl alcohol, propylene glycol, 1,3-butylene glycol, and dipropylene glycol. , Polyethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, polyethylene glycol, propylene oxide, propylene glycol, polypropylene glycol, 1,3-butylene Glycols, glycerin, phenol, polyhydric alcohols and derivatives such as sorbitol, mannitol, glycerin, diglycerin, polyg Glycerols such as Lyserine, Esters, Aloe Vera, P. tihazel, Hamamelis, Cucumber, Lemon, Lavender, Rose, etc., plant extracts, Gua Gum, Chondroitin Sulfate, Hyaluronic Acid, Arabia Gum, Sodium Alginate, Natural water-soluble polymers such as carrageenan; semi-synthetic water-soluble polymers such as methylcellulose, hydroxyethylcellulose and carboxymethylcellulose; lipoxyvinyl polymer; alkyl-adding lipoxyvinyl polymer; polyvinyl alcohol; polyvinylpyrrolidone; polyacryl acid Synthetic water-soluble polymers such as sodium and the like can be mentioned.

As the surfactant, those which can be used for cosmetics can be widely used. For example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like can be used.

Nonionic surfactants include, for example, dariserin fatty acid esters and their alkylene dalicol adducts, polyglycerin fatty acid esters and their alkylene glycol adducts, propylene glycol fatty acid esters and their alkylene glycol adducts, sorbitan fatty acid esters and their Alkylene glycol adducts, fatty acid esters of sorbitol and their alkylene diglycol adducts, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyalkylene alkyl ethers, glycerin alkyl ethers, polyoxyethylene alkyl phenyl ethers, poly Oxyethylene hydrogenated castor oil, adduct of lanolin with alkylenedaricol, polyoxyalkylene-modified silicone, polyether And modified silicone.

Examples of anionic surfactants include inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfates, alkyl sulfonates, monoolefin sulfonates, dialkyl sulfosuccinates, α-sulfonates Fatty acid salts, acyl methyl taurine salts, polymethyl mono-alkyl taurine salts, polyoxetylene alkyl ether sulfates, polyoxetylene alkyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ethers Phosphate, polyoxyethylene alkyl phenyl ether phosphate, Ν-amino acid salt, Ν-amino acid salt, 0-alkyl-substituted malate, alkyls And rufosuccinate. Examples of the cationic surfactant include an alkylamine salt, a polyamine and an alkanolamine fatty acid derivative, an alkyl quaternary ammonium salt, and a cyclic quaternary ammonium salt. Examples of amphoteric surfactants include phospholipid-containing components such as lecithin and lysolecithin and their hydrogenated products, carboxylic acid type, amino acid type, and bayone type, sulfate ester type, sulfonate type, and phosphate ester type. There are things that can be used for humans. For example, N, N-dimethyl-1-N-alkyl-1-N-hydroxypropylammonium betaine, N, N-dialkylaminoalkylenecarbonic acid, N, N, N-trialkyl-1-N-sulfoalkyleneammonium betaine Tyne, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1 lipoxymethylimidazolinium betaine, etc. .

As long as the object of the present invention is not impaired, other known ultraviolet absorbers for cosmetics may be used. For example, para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, para-dimethylamino PABAs such as amyl benzoate, paradimethylamino-1-ethylhexyl benzoate, para-dihydroxypropyl ethyl benzoate, etc., p-methoxy cinnamate 1-2-ethyl hexyl, 4-methoxy cinnamate-2-ethoxyxetil, etc. Salicylic acids such as citric acid, 2-ethylhexyl salicylate, phenyl salicylate, homomenthyl salicylate, 2-hydroxy-14-methoxybenzophenone, 2-hydroxy-14-methoxybenzophenone-15-sulfonic acid, 2-Hydroxy-1-methoxybenzofenone 5-Sulfo Sodium acid, 2, 2 '- dihydroxy - 4, 4' - Dimethoxybenzophenone, 2,2'-dihydroxy-1,4'-dimethoxybenzophenone-15-sodium sulfonate, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzo Benzophenone-based compounds such as phenone, 2_ (2-hydroxy_5-methylphenyl) benzotriazole, 4_tert-butyl-4'-methoxydibenzoylmethane, oxybenzone and the like can be mentioned.

In addition, amino acid derivatives such as sodium pyrrolidonecarboxylate, other proteins, moisturizing agents such as mucopolysaccharide, collagen, elastin, and keratin; antioxidants such as tocopherol, ascorbic acid and esters or salts thereof; , Anti-inflammatory agents, herbal medicines and other beauty and whitening ingredients, paraoxybenzoic acid esters, phenoxyethanol and other preservatives, magnesium silicate, aluminum magnesium silicate, talc, kaolin, bentonite, my power, potato black, Examples include inorganic pigments such as calamine, astringents such as lactic acid, tartaric acid, succinic acid, cunic acid, and allantoin, and anti-inflammatory agents such as guaiazulene and methyl salicylate. Example

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Test Example 1)

A test material as shown in Fig. 1 was prepared, and the UV absorption test of the hydrolyzate of silk protein Was done.

Each test sample cream was prepared by adding 10% (mass ratio) of each powder of silk, wool, chitin and chitosan to cold cream (commercially available product).

The silk here is a powder obtained by drying a relatively high molecular weight water-soluble silk protein obtained by hydrolyzing silk fibroin by a calcium chloride method.

A silk cloth (Habuta) was fixed on cardboard, and the above-mentioned test sample cream of the same mass was applied to each area of 3 cm x 3 cm.

The test material was irradiated with ultraviolet light (1.5 kW) of 254 nm from the upper lcm for 24 hours. After irradiation, the cream on the silk cloth was washed off, and the yellowing degree was measured using a measuring instrument (manufactured by Tokyo Kogaku).

The result is shown in figure 2. Silk powder had the lowest yellowing index.

In addition, when the same test as above was performed on human skin by irradiating sunlight for 1 hour, the same effect as above was confirmed.

After the ultraviolet irradiation, the yellowed silk cloth was hydrolyzed with hydrochloric acid to obtain amino acids. After standing, a tan precipitate was separated from the clear, colorless supernatant and dried. Amino acid analysis revealed that 70% or more was tyrosine. In addition, feniralanine was also confirmed.

From the above, it was confirmed that the ultraviolet absorption effect of silk (hydrolysate) was at least due to tyrosine. It is particularly effective in absorbing ultraviolet rays B (below 300 nm), which are harmful to the skin.

K absorption spectrum> In addition, the ultraviolet absorption spectrum of silk and tyrosine was measured, and the effect of ultraviolet absorption below 300 nm was confirmed. Figure 3 shows.

In FIG. 3, the solid line is the ultraviolet absorption spectrum of silk, and the dotted line is the ultraviolet absorption spectrum of tyrosine.

(Example 1)

After dissolving 100 g of silk thread (water content 10%) in concentrated hydrochloric acid, water was added to make up to about 2 liters, and hydrolysis was performed at 50 ° C for 4 hours 30 minutes while adjusting the hydrochloric acid concentration to 2N. Next, it was neutralized with caustic soda, desalted by electrodialysis, concentrated to about 200 ml by vacuum concentration, and freeze-dried.

82 g of a powder having an average molecular weight of 300 and a free amino acid value of 28% by mass was obtained. This powder dissolves easily in water.

Preparation of lotion>

30 g of the obtained powder (partially hydrolyzed product) was dissolved in 100 ml of water to prepare a 30% aqueous solution.

Using this 30% aqueous solution, a lotion having the composition (% by mass) shown in Table 1 below was prepared by a conventional method. table 1

In a sensory evaluation by ten panelists, the usability and feeling of use of the lotion obtained above were evaluated to be good in terms of elongation, stickiness, smoothness, conformability, and moisturizing property (moist feeling).

(Example 2)

Using the above 30% aqueous solution, a jewel having the composition shown in Table 2 was prepared by a conventional method. Table 2

In a sensory evaluation by 10 panelists, the usability and feeling of use of the moisturizing jewel was evaluated as being good in all of elongation, stickiness, smoothness, conformability, and moisturizing (moist feeling). Industrial applicability

As described above, according to the present invention, it is possible to provide a cosmetic product having an ultraviolet ray preventing effect, excellent usability and a feeling of use, and having no skin irritation.

Claims

The scope of the claims

1. A cosmetic product having an ultraviolet-ray-preventing effect, comprising a hydrolyzate of a silk protein and a water-soluble protein containing at least tyrosine as an active ingredient.

2. The cosmetic according to claim 1, wherein the water-soluble protein has an average molecular weight of 150 to 50,000.

3. The cosmetic product according to claim 1, wherein the water-soluble protein further contains phenylalanine.

4. The cosmetic according to any one of claims 1 to 3, wherein the water-soluble protein is contained in an amount of 3% by mass or more based on 100% by mass of the total amount of the cosmetic.

5. The cosmetic according to any one of claims 1 to 4, wherein the silk protein is a silk-five mouth in-protein.