JPH0678214B2 - Hair cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hair cosmetic composition containing a phosphoric acid diester of ascorbic acid and tocopherol represented by the following general formula and / or a salt thereof, and in particular, prevention of dandruff And to prevent split ends hair cosmetics.

The phosphoric acid diester of ascorbic acid and tocopherol according to the present invention has a structure in which two of the three hydroxyl groups of phosphoric acid are esterified with one hydroxyl group of ascorbic acid and one hydroxyl group of tocopherol, respectively.

[Conventional technology]

In general, dandruff is composed of secretions of sebaceous glands, secretions of sweat glands, exfoliated and detached substances of the cortical layer, etc., and is usually caused by increased secretion of sebaceous glands. In particular, when bacteria or yeasts infect the skin, it is said that the occurrence of dandruff is pathologically promoted and causes split ends. Therefore, hair cosmetics to which an antibacterial agent or a bactericidal agent is added have been conventionally used as cosmetics for preventing dandruff or split ends. However, some of the antibacterial agents and bactericides have a problem in safety to the human body in terms of skin irritation, and the cosmetics containing the antibacterial agents and bactericides may cause skin resident bacteria It has been pointed out that it sometimes causes an unfavorable situation from a so-called ecological point of view, such as breaking the delicate balance. For example, zinc pyrithione (ZPT), which has been conventionally recognized as the most effective antidandruff drug, is also included in the category of antibacterial agents, and it is preferable to avoid using it in large amounts as much as possible. Has been.

Therefore, it has been widely desired to prevent the occurrence of dandruff and split ends without using such an antibacterial agent or bactericidal agent, and it has an effective antidandruff effect and further has an antibacterial effect and a bactericidal effect. There has been a search for safe substances.

So far, α-tocopherol / vitamin A acid ester (JP-A-51-73137) and vitamin E have been used as substances having an anti-dandruff action without being based on antibacterial action or bactericidal action.
Nicotinic acid ester (German Patent No. 2301585 and No. 2
301660 each specification) has been reported.

[Problems to be solved by the invention]

However, these conventional tocopherol esters are
It lacks safety on the skin, and a long-lasting effect of dandruff suppression cannot be expected. Further, since the above-mentioned tocopherol esters are insoluble in water, they have a drawback that an oily precipitate is produced depending on the cosmetic form. Further, in order to add the required amount of the substance, a large amount of surfactant is required, and further, the substance has a drawback that the price is high.

The present inventor has extensively investigated the antidandruff action of derivatives of tocopherol in order to solve such conventional drawbacks, and as a result, phosphoric acid diesters of ascorbic acid and tocopherol and / or salts thereof are extremely useful and further safe and stable. The inventors have found that it can also improve the sex, and have completed the present invention.

[Means for solving problems]

That is, the present invention provides a hair cosmetic composition containing a phosphoric acid diester of ascorbic acid and tocopherol represented by the following general formula and / or a salt thereof.

The configuration of the present invention will be described below.

Tocopherol constituting the phosphoric acid diester of ascorbic acid and tocopherol according to the present invention is α, β, γ, δ.
Any type may be used, and the relationship with R ₁ and R _{2 in the} above formula is as follows.

The phosphoric acid diesters of ascorbic acid and tocopherol used in the present invention and salts thereof can be produced, for example, by the method of JP-A-59-219295 (phosphoric acid diester or a salt thereof and a method for producing them) shown below. it can.
That is, a halophosphate esterifying agent is caused to act on tocopherol. The reaction easily proceeds in the presence of a deoxidizing agent in a non-reactive solvent such as benzene. The product thus obtained is reacted with ascorbic acid in which the 5- and 6-position hydroxyl groups are protected. The reaction proceeds in a solvent such as tetrahydrofuran in the presence of a deoxidizer. The protecting group is then removed from the reaction product. Thus, the phosphoric acid diester of ascorbic acid and tocopherol of the present invention is obtained.

The phosphodiester of ascorbic acid and tocopherol of the present invention can be used as a free acid or in the form of a salt. Examples of the salt include organic amine salts and inorganic salts. Examples of the organic amine salt include aminomethyl propanol salt, aminohydroxyl methyl propane diol salt, amino methyl propane diol salt, isopropanol amine salt, monoethanol amine salt, diethanol salt, triethanol amine salt, morpholine salt,
There are glucosamine salts, diisopropanolamine salts, and the like, and inorganic salts include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, and the like.

Among these, for example, sodium salts and potassium salts are well soluble in water, but calcium salts are insoluble. Therefore, the type of salt can be selected according to the purpose.

Phosphoric acid diester of ascorbic acid and tocopherol and / or its salt can be freely dissolved in water or oil by dissolving it in water or in an aqueous alcohol solution as it is, as compared with tocopherol and the like. Wide range of applications.

In the present invention, any one kind or two or more kinds are selected and used from the phosphoric acid diesters of ascorbic acid and tocopherol and salts thereof. The blending amount is 0.01% by weight (hereinafter referred to as%) or more and 10% or less, preferably 0.05% or more and 2% or less based on the total amount of the hair cosmetic composition. If it is less than 0.01%, the antidandruff effect tends to be poor, and conversely 10%.
It is not possible to expect a great increase in the effect even if the amount is exceeded.

The hair cosmetics of the present invention broadly refer to those applied to the hair or scalp, and include, for example, hair tonics, hair liquids, scalp emulsions, hair creams, hair shampoos, hair conditioners and the like.

The hair cosmetic composition of the present invention may further contain other anti-dandruff agents, hair splitting agents, and other conventional agents for hair.

For example, as an antidandruff agent, ZPT, TCC, hinokitiol, α-tocopherol / vitamin A acid ester, vitamin E / nicotinic acid ester, vitamin E / acetic acid ester, selenium sulfide, thioxolone, sulfur, salicylic acid, resorcin, hexachlorophene, Examples thereof include quaternary ammonium salts such as tetrachlorosalicylanilide, benzalkonium chloride, octadecyltrimethylammonium chloride, and hexadecyldimethylbenzylammonium chloride, and any other drug forms are possible. Other commonly used ingredients, for example, talc, kaolin, sericite, muscovite, phlogopite, phlogopite,
Biotite, lithia mica, vermiculite, synthetic mica, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate,
Tungstic acid metal salt, silica, zeolite, boron nitride, barium sulfate, calcined calcium sulfate (calculated gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metallic soap (zinc myristate, calcium palmitate, aluminum stearate, etc.) ) And the like, polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc. Inorganic powders, inorganic white pigments such as titanium dioxide and zinc oxide, iron oxide (red iron oxide), inorganic red pigments such as iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, inorganic matter such as ocher Yellow pigment, black iron oxide, carbon bra Inorganic black pigments such as C, low-order titanium oxide, titanium oxynitride, etc., inorganic purple pigments such as mango violet, cobalt violet, etc., inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate, ultramarine blue, navy blue, etc. Inorganic blue pigment, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, pearl pigment such as fish scale foil, aluminum powder, metal powder pigment such as copper powder , Red No. 201,
Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 22
No. 6, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204,
Organic dyes and pigments such as Yellow 205, Yellow 401, and Blue 404, Red 3, Red 104, Red 106, Red 227
Zirconium, barium or aluminum lakes such as red, red 230, red 401, red 505, orange 205, yellow 4, yellow 5, yellow 202, yellow 203, green 3 and blue 1 Organic pigments, chlorophyll, β-carotene, natural pigments such as calsamine, avocado oil, camellia oil,
Macadamia nut oil, corn oil, olive oil, evening primrose oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, hydrogenated castor oil, linseed oil, safflower oil, sunflower oil, cottonseed oil, soybean oil , Peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, sugar cane wax, cacao butter, coconut oil, hardened coconut oil, turtle oil, mink oil, squalene, squalane, Orange luffy oil, beef tallow, horse fat, mutton fat, pork fat, beef bone fat, beef leg fat, hardened beef tallow, wax, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivorot wax, whale wax, nukarou, kapok wax , Lanolin, lanolin alcohol, hydrogenated lanolin, jojoba wax, shellac wax, POE lanolin alcohol acetate , POE cholesterol ether, lanolin fatty acid polyethylene glycol, oils derived from plants and animals such as POE hydrogenated lanolin alcohol ether, oil derived from a microorganism microorganism Mortierella genus is represented by oil produced, liquid paraffin, ozokerite,
Oils derived from minerals such as pristane, ceresin, vaseline, microcrystalline wax, capryl alcohol,
Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glyceryl ether (batyl alcohol), 2-decyltetradecanol,
2-hexyldecanol, 2-hexyldecanol, 2-octyldodecanol, cholesterol, phytosterols, higher alcohols such as isostearyl alcohol, capric acid, lauric acid, myristic acid, palmitic acid,
Higher fatty acids such as stearic acid, behenic acid (behenic acid), 12-hydroxystearic acid, undecylenic acid, lanolin fatty acid, isostearic acid, linoleic acid, oleic acid, linoleic acid, ricinoleic acid, arachidonic acid, eicosapentaenoic acid, myristic acid Isopropyl, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate,
Hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate,
Isocetyl isostearate, cholesteryl 12-hydroxystearate, di-2-ethylhexanoic acid ethylene glycol ester, dipentaerythritol fatty acid ester, monoisostearic acid-N-alkyl glycol ester, dicapric acid neopentyl glycol ester, diisostearyl malate , Glyceryl di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentane-erythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, Triisostearic acid trimethylolpropane ester, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, triglyceride trioctanoate Ceryl, glyceryl triisopalmitate, glyceryl trioctoate, glyceryl triisopalmitate, glyceryl tri-2-heptylundecanoate, castor oil fatty acid methyl ester, lanolin alcohol acetate ester, lanolin fatty acid isopropyl ester, oleyl oleate, glyceryl triacetate, palmitin acid-
2-heptylundecyl, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyldodecyl, di-2-heptylundecyl adipate, ethyl laurate,
Ester oils such as di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, di-2-hexyldecyl adipate, diisopropyl sebacate, di-2-ethylhexyl succinate, etc. Oil, para-aminobenzoic acid (hereinafter abbreviated as PABA), PA
BA butyl ester, PABA glyceryl ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA amyl ester, N, N-dimethyl PABA PABA-based UV absorbers such as isooctyl ester, homomenthyl-
Anthranilic acid type UV absorbers such as N-acetylanthranilate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, P-isopropanol phenyl salicylate Salicylic acid type UV absorber, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-
2,5-Diisopropylcinnamate, Ethyl-2,4-diisopropylcinnamate, Methyl-2,4-diisopropylcinnamate, Propyl-P-methoxycinnamate, Isopropyl-P-methoxycinnamate, Isoamyl-P-methoxycinnamate Mate, octyl-P-methoxycinnamate (2-ethylhexyl-P-methoxycinnamate), 2-
Ethoxyethyl-P-methoxycinnamate, cyclohexyl-P-methoxycinnamate, ethyl-α-cyano-
Cinnamic acid UV absorbers such as β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, mono-2-ethylhexanoyl-di-P-methoxycinnamoylglycerin, 2,4-dihydroxy Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2 ', 4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-chloro-benzophenone,
2,2'-dihydroxy 4,4'-methoxy-benzophenone-3,
Benzophenone-based UV absorbers such as 3'-disulfonate, 3- (4'-methylbenzylidene) -d, 1-camphor, 3
-Benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2-phenyl-5-methylbenzoxazole,
2-phenyl-benzimidazole-5-sulfonic acid, 2-
(2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoyl Methane, 5-
(3,3-Dimethyl-2-norbornylidene) -3-pentane-
UV absorbers such as 2-one and guanine, polyethylene glycol, polyethylene glycol, dipropylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, mucopolysaccharide and its salts (chondroitin sulfate (salt), hyalurone) Acid (salt), caronine sulfate, heparan sulfate, keratosulfate, etc., proteoglycan (proteokeratosulfate, proteochondroitin sulfate, etc.), (atelo) collagen, soluble collagen, cholesteryl-12-hydroxystearate, lactic acid (salt), bile acid (Salt), pyrrolidonecarboxylic acid (salt), polyglycerin (EO) PO adduct, moisturizer such as glucose EO adduct, gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, Kistrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methylal, polyvinylpyrrolidone, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium. Cellulose sulfate, xanthan gum, hyaluronic acid (salt)
Etc., organic thickeners such as montmorillonite, saponite, hectorite, etc., and organic modified clay minerals obtained by modifying these with quaternary ammonium salt type cationic activators, nonionic activators, silicon activators, etc. Thickeners, such as
Organic solvents such as acetone, toluene, butyl acetate, ethyl acetate, acetyl triethyl citrate, plasticizers such as acetyl tributyl citrate, butyl hydroxytoluene (BHT), butyl hydroxyanisole (BHA), tocopherol, catechin, epigallocatechin, Antioxidants such as epigallocatechin gallate, green tea tannin, propyl gallate, phytic acid, tocopherol ascorbyl phosphate, benzoic acid (salt), salicylic acid (salt), sorbitan acid (salt), dehydroacetic acid (salt), Paraoxybenzoic acid alkyl ester (ethyl paraben,
Butylparaben etc.) Antibacterial preservatives such as hexachlorophene, glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, methionine, proline, hydroxyproline, neutral amino acids such as dopa, Acidic amino acids such as aspartic acid, glutamic acid, asparagine, glutamine, taurine and the like, alkali metal salts thereof, organic amine salts and basic amino acid salts, basic amino acids such as arginine, histidine and lysine and their hydrochlorides, acyl sarcosine salts ( For example, lauroyl sarcosine sodium), acyl amino acid salts (eg sodium lauroyl glutamate, acyl-
β-alanine sodium), glutathione, citric acid,
Organic acids such as malic acid, tartaric acid, lactic acid, vitamin A and its derivatives, vitamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ and its derivatives, vitamin B ₁₂ , vitamin B ₁₅ and Vitamin Bs such as derivatives thereof, ascorbic acid, ascorbate sulfate, ascorbate phosphate, vitamin Cs such as ascorbate dipalmitate, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin E nicotinite. Vitamin Es, vitamin Ds, vitamin H, pantothenic acid, vitamins such as pantethine, nicotinic acid amide, etc.
Benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, phytosterol, thymol,
Inosit, saponins (such as saikosaponin, carrot saponin, hemimasaponin), tannins (gallotannins such as tannic acid, catechins, epigallocatechin, epigallocatechin gallate, catechins such as epicatechin gallate), pantothenylethyl Various drugs such as ether, ethinyl estradiol, placenta extract,
Licorice, Paprika, Hiki-Okoshi, Kurobana Hiki-Okoshi, Oguruma, Rhododendron, Rumex, Clara, Camphor tree, Kouhone, Dokudami, Iris, Honeysuckle, Celery, Geranium, Turmeric, Odorikosou, Cha (green tea,
(Black tea), orange, sage, oleander, swordfish, yarrow, mistletoe, mallow, senkyu, senburi, thyme, clove, chimpi, touki, quince, spruce, carrot, garlic, nobara,
Birch, parsley, gentian, peppermint, fennel, horsetail, saffron, Dutch mustard, savonosa, butcher bloom, grapes, ivy, loofah, nettle,
Bodaiju, hops, salamanders, shiitake mushrooms, horse chestnut, honeywort, swordfish, melissa, peach, eucalyptus, dio, shikon, yukinoshita, arnica, lily, mugwort, perilla, peony, rosemary, lemon, ginger, aget, waremokou, birch , Raspberry, sardine, aloe, cucumber, burdock, gardenia, psyllium, lauren, acacia, acha, turmeric, cinnabar honeywort, sawara, capsicum, succulent, sarcoma moss, choreitake, ganoderma lucidum, oysters, brown algae, red algae, etc. Natural extracts extracted with polyhydric alcohol, water, aqueous alcohol, etc.,
A nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a fragrance, water, alcohol and the like can be added.

〔The invention's effect〕

The hair cosmetic composition of the present invention has the following advantages.

(A) Since the phosphoric acid diester according to the present invention becomes water-soluble or oil-soluble depending on the type of salt and the like, it can be stably incorporated in products of any form.

(B) The compound of the present invention has excellent stability on the skin and high safety.

[Action]

The mechanism by which the hair cosmetic composition according to the present invention has an effective antidandruff and hair loss preventing action is that the metabolic reaction of scalp tissue is appropriately regulated, and the formation of lipid peroxide on the scalp is caused by the phosphodiester of the present invention. It is thought that this is due to inhibition.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
This does not limit the technical scope of the present invention. The blending amount is% by weight.

Production Example 1 L-ascorbic acid / DL-α-tocopherol phosphate potassium 6.12 g of phosphorus oxytrichloride was dissolved in 50 ml of benzene, and 8.6 g (0.02 mol) of DL-α-tocopherol and 9.5 g of pyridine were added to benzene. The mixed solution dissolved in 50 ml is added dropwise with stirring. After the completion of the dropping, the mixture is stirred for 3 hours, the pyridine hydrochloride which has come out is filtered off, and the filtrate is concentrated under reduced pressure.
To this residual oil, add 30 ml of benzene and place.

On the other hand, 5.2 g (0.024 mol) of 5,6-isopropylidene ascorbic acid obtained by acetonizing L-ascorbic acid and 3.2 g of pyridine are dissolved in 120 m of tetrahydrofuran, and the benzene solution is added dropwise with stirring. After completion of the dropping, the stirring is continued for about 1 hour, the pyridine hydrochloride which has come out is filtered off, and the solvent is distilled off from the filtrate under reduced pressure. The obtained oily substance was dissolved in 30 ml of ethyl alcohol, 150 ml of 1N hydrochloric acid was added, and the mixture was heated under reflux for about 20 minutes, cooled, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then added with acetic acid. Distill off the ethyl. The crude free acid is obtained as a residue.

Dissolve this crude free acid in about 100 ml of ethyl alcohol,
When a solution of potassium hydroxide in ethyl alcohol was gradually added dropwise to the solution until the pH of the solution became neutral, white crystals with a faint brown color were deposited. It is filtered off and recrystallized from water-ethyl alcohol-acetone. White powder crystals
7.5 g was obtained. Melting point; gradually begins to carbonize around 210 ° C.
Ultraviolet absorption spectrum (UV); maximum absorption near 257 nm (in water).

Silica gel thin layer chromatography; Rf = 0.81 (ethyl alcohol 10 acetone 4, the ratio of water 1) Elemental analysis; as _{C 35 H 55 O 10 PK 2} · H 2 O, Calculated C; 55.09% H; 7.53% Measured value C; 55.32% H; 7.65% Production Example 2 L-alcorbic acid / DL-α-tocopherol phosphate sodium salt 5 g of L-ascorbic acid and DL-α-tocopherol phosphate potassium salt obtained in Production Example 1 were added. Dissolve in 30 ml of water,
Hydrochloric acid is added to make the mixture acidic, the mixture is extracted with ethyl acetate, and the ethyl acetate is distilled off to give a free acid of L-ascorbic acid / DL-α-tocopherol phosphate (UV285 nm maximum absorption, in water). Dissolve this in ethyl alcohol,
When 30% sodium hydroxide solution is gradually added until the solution becomes neutral, white crystals are obtained. It is filtered off, washed with ethyl alcohol and dried. Get about 4g.

Elemental analysis value; C ₃₅ H ₅₅ O ₁₀ PNa ₂ · H ₂ O, calculated value C; 57.52% H; 7.86% Measured value C; 57.65% H; 7.98% Test Example 1 This example shows the compound of the present invention. It is intended to explain dandruff prevention and hair loss prevention actions.

To 75 g of ethanol, 0.2 g of ascorbic acid / α-tocopherol phosphate sodium salt (Production Example 2), polyoxyethylene (8 mol) oleyl alcohol ether.
A sample hair tonic (referred to as a phosphodiester-containing hair tonic) was prepared by sequentially adding 2 g, 24.6 g of purified water, and a small amount of Yellow No. 1 and a small amount of perfume. Similarly, a hair tonic (referred to as a drug-free hair tonic) that differs only in that it does not contain the phosphodiester (corrected with water) was prepared.

On the other hand, lauroyl polyoxyethylene (3 mol) sulfuric acid ester triethanolamine salt (40% aqueous solution) 25%, carboxyvinyl polymer 1%, glycerin 3%, zinc pyrithione (ZPT) 1%, urea 3%, and the whole 100%
A shampoo consisting of purified water (referred to as ZPT-containing shampoo) was prepared. Furthermore, instead of ZPT of this shampoo, a shampoo containing 1% of ascorbic acid / α-tocopherol phosphate sodium salt (referred to as phosphodiester blend shampoo) and ZPT and ascorbic acid / α-tocopherol phosphate sodium salt are blended. We prepared a similar shampoo (corrected with water) (called a chemical-free shampoo).

Nine men with a relatively high number of dandruff, aged 18 to 55, were selected as test subjects. For the control period, first, the test subject 9
For all names, wash the hair with a chemical-free shampoo and hair with a chemical-free hair tonic, and then wash the hair and collect the dandruff accumulated for two days after washing.
The test was performed twice a week for 1 month (total 8 times). The dandruff was collected by suctioning the head using a suction device. The amount of protein in the collected dandruff was measured by the micro Kjeldahl method, and the average amount of protein Pc per dose was determined for each subject.
Subsequently, 13 test subjects were divided into 3 groups (5, 4 and 4).
Name). About 5 people in the first group, hair was washed with a phosphodiester-containing shampoo and styling with the above-mentioned phosphodiester-containing hair tonic. For the second group, four people were washed with a ZPT-containing shampoo and a phosphodiester-containing hair tonic. Hair styling by the third
Four persons in the group were washed with ZPT-containing shampoo and conditioned with a drug-free hair tonic. In each group, the operation of collecting dandruff accumulated for 2 days after washing and styling hair was performed twice a week for 1 month (total 8 times).
The protein amount in the dandruff collected during this period (sample period) was measured in the same manner as in the control period, and the average protein amount Ps per dose was determined for each subject.

The reduction rate (%) of dandruff in the sample period was calculated by the formula (Pc-Ps) / Pc × 100, and the results are shown in Table 1.

From the above results, the ascorbic acid / α-tocopherol sodium phosphate blended shampoo shows an excellent antidandruff effect as compared with a shampoo containing ZPT, which has been known as an agent for preventing dandruff from the past, and shows ascorbic acid / It was confirmed that the hair tonic containing the sodium α-tocopherol phosphate has a clear antidandruff effect as compared with the hair tonic containing no drug.

Test Example 2 The effect of preventing hair loss was examined by changing the compounding amount of ascorbic acid / α-tocopherol phosphate potassium (Production Example 1) into the hair tonic. Six types of hair tonic samples shown in the composition column of Table 2 were prepared. As test subjects, 30 men aged 25 to 55 were randomly selected, and 5 people were assigned to each sample for the test. Hair tonic will be used once a day, and the number of hairs lost during the control period (using the phosphoric acid diester-free hair tonic) and the sample period (using the phosphate ester-containing hair tonic) within 2 days after washing It was compared with the number of hairs lost in the next two days. When the reduction rate of hair loss is 10% or more, it is determined that there is a hair removal inhibition effect, and when the reduction rate of hair removal is less than 10%, it is determined that there is no hair removal inhibition effect, and the results are shown in Table 2.

The hair tonic (sample No. 1) containing 0.001% by weight of the phosphoric acid diester of the present invention was found to have a hair-pulling preventing effect in 1 out of 5 test subjects, but in sample No. 2 in which the content was increased 10 times. In this case, the results were reversed, and a remarkable effect of preventing hair loss was observed in 3 out of 5 people. When the amount of ascorbic acid / α-tocopherol phosphate potassium was 0.1% by weight (Sample No. 4) or more, a remarkable anti-hair loss effect was observed in all five test subjects.

Test Example 3 This example illustrates the antioxidant properties of the phosphoric acid diesters of ascorbic acid and tocopherol according to the present invention.

Put 1 g of ethyl linoleate in a 50 ml screw tube, add 0.2 mg of each test substance described in Table 3 below, mix well, and irradiate with ultraviolet rays for 3 hours to oxidize air,
The amount of purified ethyl linoleate peroxide was measured by high performance liquid chromatography (HPLC). The amount of lipid peroxide shown in Table 3 below is 100% when the test substance was not added (control).

According to the research conducted by the present inventor, the occurrence of dandruff and the amount of lipid peroxide in dandruff have an extremely high correlation. That is,
It has been found that reducing the amount of lipid peroxide in the scalp can suppress the occurrence of dandruff. Therefore, an antioxidant that reduces the amount of lipid peroxide is originally useful as an antidandruff agent.

As is clear from Table 3 above, the compound according to the present invention was remarkably recognized as having an antioxidant activity as compared with the conventional ester of tocopherol.

Example 1 Polyoxyethylene (40 mol) in 60 g of ethyl alcohol
Add 2 g of oleyl alcohol ether and an appropriate amount of fragrance,
It was dissolved at room temperature to obtain an alcohol phase. Separately purified water 3
To 2.9 g, 5 g of glycerin and 0.1 g of ascorbic acid / α-tocopherol potassium phosphate were added and dissolved by heating.
After cooling, an appropriate amount of Yellow No. 1 was added, and an alcohol phase was added to the aqueous phase portion to solubilize the hair to obtain a hair tonic having an effect of preventing dandruff and hair loss.

Example 2 In an alcohol phase obtained by dissolving 20 g of polyoxypropylene butyl ether and an appropriate amount of perfume in 50.0 g of ethyl alcohol at room temperature, 0.2 g of ascorbic acid / δ-tocopherol phosphate magnesium ester was added to 29.8 g of purified water and dissolved by heating. After cooling, mix the appropriate amount of Blue No. 2 and mix,
A hair liquid having dandruff prevention and hair loss prevention effects was obtained.

Example 3 Stearic acid 2 g, cetyl alcohol 1.5 g, petrolatum 3 g,
Liquid paraffin 13 g, polyoxyethylene (10 mol) monooleate 1 g and a proper amount of perfume are mixed, and 80 ° C
Separately heated to obtain an oil phase propylene glycol 5g, triethanolamine 1g, ascorbic acid / β-tocopherol sodium phosphate 0.05g and purified water 73.45g
Was heated to 80 ° C., the above oil phase was gradually added to this aqueous phase with stirring, and the mixture was cooled after emulsification to obtain a scalp emulsion having dandruff prevention and split ends effect.

Example 4 Stearic acid 2 g, stearic alcohol 7 g, lanolin 2
g, squalane 5 g, octyldodecanol 6 g, polyoxyoctylene (10 mol) cetyl ether 3 g, glyceryl monostearate 2 g, and an appropriate amount of perfume were added, and the mixture was heated to 80 ° C. to obtain an oil phase. Separately, 5 g of propylene glycol, 2 g of ascorbic acid / β-tocopherol phosphate sodium salt and 66.0 g of purified water were gradually added to the water phase heated to 80 ° C while stirring, emulsifying and cooling to prevent dandruff. A hair cream having an effect of preventing hair loss was obtained.

Example 5 To 70.0 g of purified water, triethanolamine 15 of lauryl sulfate was added.
g, coconut oil fatty acid monoethanol amide 5g, ascorbic acid / γ-tocopherol phosphate calcium
10.0 g, and appropriate amounts of Red No. 222 and fragrance were added, and after heating and mixing, the mixture was cooled to obtain a hair shampoo having dandruff prevention and hair loss prevention effects.

Example 6 3.5 g of polyethylene glycol 1500, 1 g of triethanolamine, and 0.01 g of ascorbic acid / δ-tocopherol phosphate potassium salt were dissolved by heating in 74.49 g of purified water.
It was kept at ℃. Stearic acid 2.5 g, cetyl alcohol 1.5
g, vaseline 5 g, squalane 10 g and polyoxyethylene (10 mol) monooleate 2 g are heated and dissolved to 70
It was added to the aqueous phase while maintaining the temperature at 0 ° C. After the preliminary emulsification, the emulsion was uniformly emulsified with a homomixer and gradually cooled to prepare a hair emulsion having dandruff prevention and hair loss prevention effects.

Example 7 18.9 g of purified water and 1 part of sodium lauroylmethyltaurine
0 g, lauroyl propyl amide betaine 5 g, coconut oil fatty acid monoethanol amide 5 g, ascorbic acid / γ-tocopherol phosphate calcium 1.0 g, milk hydrolyzate 1 g, and red 222 and a suitable amount of flavors are added and heated. After mixing, the mixture was cooled to obtain a hair shampoo having dandruff prevention and hair loss prevention effects.

Example 8 To 67.5 g of ethyl alcohol, 0.5 g of polyoxyethylene (40 mol) hydrogenated castor oil and 0.2 g of fragrance were added and dissolved at room temperature to obtain an alcohol phase. Separately, ascorbic acid / γ-tocopherol phosphate potassium was added to 31.1 g of purified water.
0.4 g, pantothenic acid derivative 0.1 g and buffer 0.2 g were dissolved by heating. After cooling, an alcohol phase was added to the aqueous phase portion to solubilize it to obtain a stock solution portion.

A stock solution of 60 g and a propellant (DME / LPG = 8: 2) of 40 g were filled in a can to obtain a spray-type hair tonic having dandruff prevention and hair loss prevention effects.

Claims (1)

[Claims] 1. A hair cosmetic containing a phosphoric acid diester of ascorbic acid and tocopherol represented by the following general formula and / or a salt thereof.