JP3035742B2 - Cosmetics - Google Patents

Description

The present invention relates to cosmetics containing stabilized tocopherol. More specifically, it contains an ester or a salt thereof in which the hydroxyl group of tocopherol is phosphorylated,
It mainly relates to skin cosmetics and hair cosmetics (hair growth agents).

[Conventional technology and its problems] Tocopherols, which are known as fat-soluble vitamin E, easily penetrate the skin or scalp, causing skin whitening,
It is known to be effective in strengthening cell membranes, promoting blood circulation, preventing the production of lipid peroxides, etc., and is used in creams, emulsions, lotions, packs as cosmetics for the skin, and hair nourishes as cosmetics for the head hair. Have been. In particular, when used on the scalp, it has attracted attention as a raw material for hair-growing agents because it promotes the activity of hair cells in the scalp due to its blood circulation promoting effect.

Since tocopherols are easily oxidized and unstable when used alone, conventionally, tocopherols are added to cosmetics in the form of organic acid esters such as acetates and succinates to improve stability and solubility in water. It is widely used by adding tocopherol to an aqueous liquid using an emulsifier.

However, conventionally used organic acid esters of tocopherol are insufficient in stability and water solubility,
In order to cause deterioration in quality due to yellowing or foaming with the passage of time, antioxidants have been added or air has been blocked, but this has not been sufficient.

In addition, the method of emulsifying tocopherol using a surfactant did not only ensure the stability of tocopherol, but also did not guarantee uniformity.

Accordingly, an object of the present invention is to improve the stability and water solubility of tocopherol in view of the above-mentioned problems of tocopherol in cosmetics, and to provide a high-quality cosmetic that effectively retains its activity and lasts for a long period of time. is there.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors converted tocopherol into a phosphoric ester and, if desired, converted the phosphoric ester into various salts, thereby obtaining stability and water solubility. Have been found to be significantly improved, and the present invention has been achieved.

That is, the present invention provides: 1) a cosmetic product characterized by containing a tocopherol phosphate monoester or a salt thereof; 2) a salt of the tocopherol phosphate monoester is an alkali metal salt, an alkaline earth metal salt, an amine salt, or 4th
The cosmetic according to the above 1, which is a quaternary ammonium salt; 3) the cosmetic according to the above 1 or 2, which is used for the skin; 4) the cosmetic according to the above 3, which is a cream, an emulsion, a lotion, a lotion or a pack; A hair cosmetic comprising an alkali metal salt or an alkaline earth metal salt of tocopherol phosphate monoester, 6) a hair tonic, a hair lotion, a hair cream, a shampoo or a rinse for the hair according to the above item 5; Cosmetics, and 7) the aforementioned 1 wherein the tocopherol is α-tocopherol
A cosmetic product according to any one of claims 1 to 6.

[Constitution of the Invention] Raw materials of tocopherol phosphate monoester (sometimes simply referred to as tocopherol phosphate) or a salt thereof as an active ingredient of the cosmetic of the present invention are various tocopherols.

Tocopherol (vitamin E) has the formula Α-form (R ₁ , R ₂ , R ₃ = CH ₃ ), β-form (R ₁ , R ₃ = CH ₃ , R ₂ = H) depending on the substituents R ₁ , R ₂ , and R _{3 represented} by , Γ-form (R ₂ , R ₃ = CH ₃ , R ₁ = H), δ-form (R ₃ = CH ₃ , R ₁ , R ₂ = H), ζ ₂ -form (R ₁ , R ₂ = CH ₃ , R ₃ = H) and η-forms (R ₁ , R ₃ = H, R ₂ = CH ₃ ) are known, and carbon atoms adjacent to O atoms in α-form and β-form benzopyran structures A long-chain alkyl group bonded to And zeta ₁ body and also ε- body replaced structures known to both can be used in the cosmetic raw material of the present invention, Particularly preferred among these from the viewpoint of the effect is α- tocopherol.

The phosphate ester of tocopherol is produced according to a conventional method.

That is, a halophosphate esterifying agent such as phosphorus oxychloride or phosphorus oxytribromide is caused to act on tocopherol.

The amount of the halophosphate esterifying agent used varies depending on the type of the solvent used, the reaction temperature, the type of the halophosphate esterifying agent, and the like, but is used in an amount of about 1 to 2 moles per mole of tocopherol as the reaction raw material.

The reaction is carried out using a non-reactive solvent such as benzene as a solvent in the presence of a deoxidizing agent such as pyridine at a temperature of 10 to 30 ° C. for 20 to 30 hours.

The reaction product is extracted with ether and then the ether is distilled off to obtain free tocopherol phosphate. If the pH of the ether extract is adjusted to 7 using various alkalis (alkali metal salts, alkaline earth metal salts, amine salts, quaternary ammonium salts, etc.), the corresponding salts of tocopherol phosphate can be obtained. Can be.

As the salts used as a raw material of the cosmetic of the present invention,
For example, alkali metal salts such as sodium, potassium, calcium, magnesium, etc., alkaline earth metal salts, amine salts such as mono, di, triethanolamine, triisopropanolamine, benzalkonium ion, lauryl trimethyl ammonium ion, stearyl And quaternary ammonium salts such as trimethylammonium ion.

The thus-obtained phosphoric acid esters and salts of tocopherol are much more stable than the conventionally used acetates and succinates. For example, in α-tocopherol phosphate disodium,
It is stable without being decomposed at all even when heated at 100 ° C. for 1 hour or more under slightly alkaline.

Phosphorylated tocopherol and its salts are stable,
It has excellent water solubility, and when applied to the skin, is easily dephosphorylated by phosphatase in the skin (epidermal cells) to form active tocopherol, so skin whitens, strengthens cell membranes, promotes blood circulation, and produces lipid peroxide. It exerts effects such as prevention. Therefore, it can be used as an active ingredient of cosmetics having a beautiful skin effect and a hair-growing effect. That is, the tocopherol phosphate or a salt thereof according to the present invention is blended in various cosmetics, for example, creams, emulsions, lotions, lotions, skin cosmetics such as packs, and hair tonics for hair, hair lotions, hair creams, shampoo,
It is formulated as a hair-growing agent in rinses and the like. For example, an aqueous solution in which a tocopherol phosphate or a salt thereof is dissolved in water in advance is mixed with a separately prepared base material, or is directly added and mixed and dispersed, so as to be appropriately compounded during the production of cosmetics.

Specifically, for example, in the case of skin cosmetics, it is used as a component for a fair skin nutrition cream, fair skin nutrition emulsion, cream for rough skin, lotion, and the like. In each cosmetic,
Phosphorylated tocopherol and its salts are blended together with the normally blended components. The pH of these cosmetics
Is preferably adjusted to neutral to slightly alkaline.

In the case of a cream cosmetic for the skin, liquid paraffin and stearic acid as base materials are added to a surfactant (for example, polyoxyethylene sorbitan triate,
To a solution obtained by heating and uniformly dissolving polyoxyethylene sorbitan monolaurate, etc.) and antioxidants (paraoxybenzoic acid esters, etc.), add a previously prepared aqueous solution mainly containing a phosphorylated tocopherol salt, and stir. It is prepared by mixing and emulsifying, adding an appropriate amount of a fragrance or dye, and cooling.

In the case of milky cosmetics for skin, a solution obtained by heating and dissolving a surfactant or the like in an oily material (such as stearic acid) is added to a heated aqueous solution mainly containing phosphorylated tocopherol salt,
After emulsification, the mixture is prepared by adding a flavor and the like and cooling.

In the case of a lotion, it is prepared by dissolving an appropriate amount of a phosphorylated tocopherol salt, a fragrance, alcohol, glycerin, an antioxidant, a surfactant and the like in water.

In the case of cosmetics for raising hair for hair, among the above-mentioned phosphoric acid esters of tocopherol and various salts, alkali metal salts or alkaline earth salts of tocopherol phosphoric acid ester having high water solubility and good permeability to the skin, especially, are preferred. Metal salts are preferably used because they exhibit remarkable hair-growth and hair-growth effects.

As for the hair growth cosmetics, as long as the action of the alkali metal salt or alkaline earth metal salt of tocopherol phosphate is not impaired, hair growth promoters (for example, N-acetyl-L-methionine) which are blended in conventional hair growth agents are used. ,
L-serine, etc.), vitamins, anti-androgens (eg, progesterone), anti-inflammatory agents (eg, hydrocortisone acetate), vasodilators (eg, nicotinic acid),
Crude drug extract (for example, assembly extract), anti-dandruff agent (for example, hinokitiol), cooling agent (for example, l-menthol), lubricant (for example, glycerin), keratolytic agent (for example, urea, salicylic acid, etc.), antioxidant (For example, dibutyltoluene and the like), a dye (for example, photosensitive dye No. 301 and the like), a fragrance (for example, lavender oil and the like), and the like.

In addition, purified water, monohydric alcohol (eg, ethanol, etc.), oils (eg, olive oil, etc.), surfactants (eg, polyoxyethylene polyoxypropylene copolymer), etc., which are blended in conventional hair tonics Can be blended.

Hair tonic cosmetics containing an alkali metal salt or an alkaline earth metal salt of a tocopherol phosphate of the present invention, hair tonic, hair lotion, hair cream, shampoo, and the like, by appropriately selecting the other components described above, A normal agent such as a rinse is prepared.

EXAMPLES Hereinafter, the present invention will be described with reference to Test Examples and Examples, but the present invention is not limited to the following description. In the following examples, parts and% are based on weight unless otherwise specified.

Test Example 1 (Solubility Test) When the solubility (20 ° C.) of tocopherol, tocopherol acetate and tocopherol phosphate disodium salt in water was measured, tocopherol and tocopherol acetate were not dissolved, but tocopherol phosphate was not dissolved. -The disodium salt dissolved by 0.27%.

Test Example 2 (Stability test) The stability of tocopherol phosphate and tocopherol acetate was examined at a relative humidity of 90% and a temperature of 40 ° C. The purity after 6 months was 98% for tocopherol phosphate, and 98% for tocopherol acetate. 95 esters
%Met.

Test Example 3 (Fostering Hair Test) Approximately 1 head of ddy male mouse (8 weeks old, 1 group, 5 mice)
Hair loss was obtained by spinning over a square area. 3 days after hair removal
A 60% aqueous ethanol solution containing 1% of the test drugs shown in Table 1 below was applied in an amount of 30 μ / day for 18 consecutive days.
After 18 days, dozens of newly grown hairs in the central part were removed, ten were randomly selected, the length was measured, and the average value of the ten hairs was used as the measured value.

The results are as shown in Table 1, and a remarkable hair-growth effect was recognized with the hair-growing agent of the present invention containing an alkali (earth) metal salt of tocopherol phosphate. In addition, the hair-growing agent of the present invention had no irritating effect on the skin.

* 1) α-tocopherol phosphate disodium salt * 2) α-tocopherol phosphate ester magnesium salt Example 1 1 part of polyoxyethylene sorbitan triolate, 2 parts of salami beeswax, 4 parts of lanolin, 15 parts of stearic acid ,
Liquid paraffin 23 parts, propyl paraoxybenzoate 0.15
Heat the part to 75 ° C. Add deionized water to this
41.2 parts of α-tocopherol phosphate / magnesium 3
Part, methyl paraoxybenzoate 0.15 part, sorbitol 1
Add 2.2 parts and heat-dissolve it at 75 ° C, and stir and emulsify. The obtained milky product is gradually cooled, and when the temperature reaches 45 ° C., 0.5 part of flavor is added, and the mixture is further stirred and cooled to obtain a fair-white nutritional cream.

Example 2 5.0 parts of stearic acid, 0.5 parts of cetanol, 0.8 parts of polyoxyethylene sorbitan monolaurate, and 0.1 parts of propyl paraoxybenzoate are heated and dissolved at 80 ° C. To this 78 parts of water in advance 0.3 parts of methyl parahydroxybenzoate,
When 0.4 part of triethanolamine, 5 parts of glycerin, and 3 parts of α-tocopherol phosphate disodium were added and heated and dissolved at 82 ° C., gradually added, stirred and emulsified, and gradually cooled to 45 ° C. , 0.4 part of fragrance is added and stirred to obtain a fair-white nutritional emulsion.

Example 3 Into 65 parts of water, 5 parts of diammonium α-tocopherol phosphate, 1 part of fragrance, 10 parts of ethanol, 7 parts of glycerin, 10 parts of buffer solution (pH = 7.5), 0.1 part of methyl parahydroxybenzoate, polyoxyethylene 1.2 parts of sorbitan monolaurate are dissolved under stirring and filtered to obtain a lotion.

Example 4 α-Tocopherol phosphate disodium 1.
0 parts, estradiol 0.01 parts, carrot extract 1.0 part,
1.0 part of assembly extract, 3.0 parts of polyoxyethylene polyoxypropylene decyl ether, 5.0 parts of urea and 3.0 parts of glycerin were added to and dispersed in 45.6 parts of purified water.
100 parts were obtained.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A61K 7/00 A61K 7/06

Claims (7)

(57) [Claims] 1. A cosmetic comprising a tocopherol phosphate monoester or a salt thereof. 2. The salt of tocopherol phosphate monoester is an alkali metal salt, an alkaline earth metal salt, an amine salt,
The cosmetic according to claim 1, which is a quaternary ammonium salt. 3. The cosmetic according to claim 1, which is for skin. 4. The cosmetic according to claim 3, which is a cream, milky lotion, lotion, lotion or pack. 5. A hair cosmetic comprising an alkali metal salt or alkaline earth metal salt of tocopherol phosphate monoester. 6. The hair cosmetic according to claim 5, which is a hair tonic, a hair lotion, a hair cream, a shampoo or a rinse. 7. The cosmetic according to any one of claims 1 to 6, wherein the tocopherol is α-tocopherol.