JP5657902B2 - Polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative, and external preparation composition containing the same - Google Patents

Description

  The present invention relates to an ionic polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative, and an external preparation composition containing the same. More specifically, an ionic polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative having a novel structure having an effect of repairing rough skin and an effect of repairing damaged hair, which can be used as an emulsifier, a solubilizer, and a dispersant. , And pharmaceutical external preparations and cosmetics containing the same.

  Cholesterol is a constituent component of cells and intercellular lipids, and has been used as a component for healthy skin and hair because it enhances the skin barrier function. Sterols are well-familiar with hair and are expected to provide rough skin repairing effect and hair repairing effect when supplied in molecular size to hair and skin. For example, the melting point of cholesterol, which is a typical sterol, is 130. It was difficult to blend into an external composition for skin or hair because it exceeded the temperature of C, and had high crystallinity and low compatibility with oily components used in cosmetics and pharmaceuticals.

  In order to solve such problems, methods for supplying sterols to the skin and hair and various sterol derivatives have been studied.

  In order to supply sterols to the skin and hair, there are formulation methods such as solubilization, emulsion, nanoemulsion, vesicle, etc., in which sterol is blended. However, since sterols have a melting point of around 130 ° C. and are easily crystallized, it is very difficult to produce a product that does not precipitate crystals easily or for a long period of time. In addition, although a very small amount of cholesterol and phytosterol are used as liposome constituents in liposomes used in cosmetics and pharmaceuticals, the production thereof is very troublesome and made by a high-cost process. For example, sterols and lecithins are dissolved in an organic solvent to make it uniform, and then a thin film or a solvent is blown away by spray drying to form a complex. This complex is used with a large mechanical force such as a high-pressure homogenizer. Then, it is a general method to finely disperse in water. Therefore, there is a demand for a method for easily preparing liposomes without a solvent.

  As sterol derivatives, cholesterol, phytosterol, and the like, and esters such as fatty acids and organic acids are used as oily components for skin and hair. Specific examples include cholesterol 12-hydroxystearate, phytosterol 12-hydroxystearate, cholesterol oleate, and cholesterol isostearate (Patent Documents 1 and 2).

  Further, polyoxyethylene adducts are used as emulsion solubilizers based on sterols as lipophilic groups. Specific emulsifying solubilizers derived from sterols include polyoxyethylene adducts as emulsifying solubilizers for pharmaceutical cosmetics (BPS series, DHC series, manufactured by Nikko Chemicals), and polyoxyethylene addition of lanolin alcohol containing lanosterol. The body (BWA series, manufactured by Nikko Chemicals Co., Ltd.) is known, and we have also found that compounds synthesized by adding polyoxypropylene and polyoxyethylene to phytosterol can reduce the stickiness of polyhydric alcohol. It has been reported (Patent Document 3).

  By the way, some ionic sterol derivatives have been reported. For example, sterol sulfate ester salt is a biological component and is expected to be applied in cosmetics and pharmaceuticals. However, it is not used because it is difficult to synthesize, and even if it can be synthesized, purification is difficult and expensive.

  By the way, the present inventors have already found that the melting point of polyoxyalkylene sterol ether is low. For example, the melting point of polyoxypropylene (5) phytosterol ether is 28 ° C.

  In view of the above-mentioned circumstances, the present inventors have assumed that the above-mentioned problems can be solved if the ionic derivative is made from a suitable polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether. As a result of intensive studies on ionic polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives, polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether sulfates and / or salts thereof, phosphate esters Or a salt thereof, an alkyl carboxylic acid and / or a salt thereof, a carboxylic acid ester and / or a salt thereof, a quaternary ammonium and / or a salt thereof has an effect of improving skin roughness and an effect of repairing hair, which acts efficiently on the skin and hair. Found to be significantly better It was.

  In addition, as an ionic polyoxyalkylene sterol ether derivative, a polyoxyethylene sterol ether oxalic acid derivative (Patent Document 4) is known, and this is intended for a polyoxyethylene addition mole number of 10 mol or more. This is a report. Further, a polyoxyethylene sterol ether phosphate derivative (Patent Document 5) is known, but this is for providing a transparent lotion, and the added mole number of polyoxyethylene having high water solubility is 10 This is a report covering more than 1 mol, and the efficacy of ionic polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives having a polyoxyalkylene addition mole number of less than 1 to 10 is sufficiently clear in an external composition. Not been.

JP 52-79030 A JP 05-017317 A JP 2008-31074 A JP 58-223436 A JP 2006-306729 A

  The present invention relates to an ionic polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether having a novel structure having an excellent effect of repairing rough skin by effectively acting on the skin and hair, and a repair effect of damaged hair. An object of the present invention is to provide a derivative and a composition for external use such as pharmaceuticals and cosmetics containing the derivative.

  In response to this problem, an ionic polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol having a novel structure having an excellent effect of repairing rough skin by effectively acting on the skin and hair, and a repair effect of damaged hair As a result of diligent research to find an ether derivative, polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether sulfate and / or salt thereof, phosphate ester or salt thereof, alkylcarboxylic acid and / or salt thereof It has been found that carboxylic acid esters and / or salts thereof, quaternary ammonium and / or salts thereof are remarkably excellent in their effects.

  By using the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention, it has an excellent rough skin repair effect by effectively acting on the skin and hair, and has a damaged hair repair effect, An external composition for skin such as pharmaceuticals and cosmetics can be easily produced. Moreover, since the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention is dissolved in water alone (dispersed in water with a molecular size), it is convenient for external preparation compositions such as pharmaceuticals and cosmetics. Available to: Furthermore, the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention can be used not only as an emulsifier, a solubilizer, and a dispersant, but also in the absence of a solvent and easily prepare liposomes. In addition, the use of the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention together with sterols, and more preferably lecithins, suppresses crystallization of sterols. Since sterols can be efficiently adsorbed to the skin and hair, their effects are further improved.

The present invention relates to a polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative represented by the chemical formula (1).
RO- (AO) n-B (1)
[Wherein, R represents a sterol skeleton selected from cholesterol, phytosterol, lanosterol, ergosterol and hydrogenated products thereof, cholestanol, phytostanol, lanostanol, and ergostanol, and A represents ethylene oxide, propylene oxide, butylene oxide. 1 represents a polyoxyalkylene group obtained by copolymerization, block polymerization or random polymerization of at least one selected from n, and n represents an integer of less than 1-10. B represents a sulfate ester group or a salt thereof, a phosphate ester group or a salt thereof, an alkylcarboxylic acid group or a salt thereof, a carboxylic acid ester group or a salt thereof, a quaternary ammonium group or a salt thereof. ]

  Sterols which are constituents of the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, that is, R in the chemical formula (1) is cholesterol, phytosterol, lanosterol, and hydrogenated cholestanol, Phystanol, lanostanol and so on.

  The polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether, which is an intermediate product of the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention, is an optional addition of the above-mentioned alkylene oxide to the sterols. A unit, that is, one containing AO of the chemical formula (1), specifically, polyethylene glycol, polypropylene glycol, polybutylene glycol, which is a lower alkylene glycol, is added to the sterols, or ethylene oxide, propylene oxide or butylene. A polyoxyalkylene group obtained by copolymerization, block polymerization or random polymerization of two or more selected from oxides is added by a usual method. This intermediate product is preferably synthesized using a special metal catalyst and desirably has a narrow distribution of polyoxyalkylene chains. The number of moles of polyoxyalkylene oxide added, that is, n in the chemical formula (1) is less than 10 moles, preferably 5 moles or less.

  The polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention is a functional group that imparts ionicity to the polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether that is an intermediate product (that is, B) of the chemical formula (1), specifically, a compound imparted anionicity or cationicity by a sulfate ester group, a phosphate ester group, an alkylcarboxylic acid group, a carboxylic acid ester group, or a quaternary ammonium group.

  The polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention can be easily synthesized by a known method.

  The sulfuric acid ester of polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether and / or its salt of the present invention is a raw material polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether, an anhydrous sulfuric acid complex such as pyridine, or sulfamine. Although it can be obtained by adding an acid or chlorosulfonic acid, the production method is not limited to this.

  The alkyl carboxylic acid of polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether of the present invention and / or a salt thereof, sodium hydride or the like acts on the raw material polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether, It can be obtained by generating alcoholate and adding monochlorosodium acetate to it, or by reacting with oxidizing agents such as chromic anhydride and potassium permanganate, or after TEMPO or AZADO oxidation, hypochlorous acid Although it can be obtained by further oxidation with sodium or sodium chlorite, the production method is not limited to this.

  The polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether carboxylic acid ester and / or salt thereof according to the present invention is a raw material polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether, succinic anhydride or maleic anhydride. It can be obtained by reacting dibasic acid anhydrides such as phthalic anhydride and alkylphthalic acid, but the production method is not limited to this.

  The phosphoric acid ester of polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether and / or a salt thereof of the present invention is prepared by adding raw material polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether to phosphorus oxychloride or diphosphorus pentoxide. However, the production method is not limited to this.

  The salt of the above-mentioned polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether sulfate, phosphate ester, alkyl carboxylic acid, carboxylic acid ester is not particularly limited, and sodium, potassium, magnesium, ethanolamine , Diethanolamine, triethanolamine, isopropanolamine, arginine, lysine, and the like, which are composed of one or a combination of two or more.

［式中、Ｒ２、Ｒ３、Ｒ４は水素、炭素数１〜２２のアルキル基、アルケニル基、置換基を有してもよいアリール基を示す。また、Ｒ２、Ｒ３、Ｒ４はそれぞれ同一であっても異なっていてもよく、環構造を形成してもよい。Ｒ５は水素、置換基を有してもよい炭素数１〜２２のアルキル基、アルコキシ基、シアノ基、ニトロ基、ベンゾイル基、アセチル基、ヒドロキシ基又はハロゲンを示す。Ｒ１は置換基を有してもよい炭素数１〜２２のアルキル基、アルケニル基、アリーレン基を示す。］ The quaternary ammonium group of the polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether of the present invention is not particularly limited, but preferably has a structure represented by the following chemical formula (2).

[Wherein, R2, R3, and R4 each represent hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group, or an aryl group that may have a substituent. R2, R3 and R4 may be the same or different and may form a ring structure. R5 represents hydrogen, an alkyl group having 1 to 22 carbon atoms which may have a substituent, an alkoxy group, a cyano group, a nitro group, a benzoyl group, an acetyl group, a hydroxy group or a halogen. R1 represents a C1-C22 alkyl group, alkenyl group or arylene group which may have a substituent. ]

  Examples of the method for synthesizing the quaternary ammonium compound of the polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether of the present invention include, for example, raw material polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether such as glycidyl trimethyl ammonium chloride. It can be obtained by the action of a cationizing agent, or esterified with monochloroacetic acid under an acidic catalyst, and then a tertiary amine can be added to obtain a quaternized cationized product, but the production method is not limited to this. Absent.

  The salt of the quaternary ammonium compound of the polyoxyalkylene sterol ether and / or polyoxyalkylene stanol ether is not particularly limited, and may be a halogen, an organic acid, an amino acid, a fatty acid, an alkyl group having 1 to 22 carbon atoms, or Examples thereof include one or a combination of two or more selected from the anion residues of phosphoric acid ester, phosphonic acid ester, sulfonic acid ester and sulfuric acid ester having an alkenyl group, and halogen, organic acid and amino acid are particularly preferable.

  A general hydrophilic surfactant has slight skin irritation, but the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention is excellent in that no skin irritation is confirmed as described later. Shows skin dryness and hair repair effect. By using the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention, it has an excellent rough skin repair effect by effectively acting on the skin and hair, and has a damaged hair repair effect, An external composition for skin such as pharmaceuticals and cosmetics can be easily produced.

  When the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention is blended in an external preparation composition such as pharmaceuticals and cosmetics, the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether of the present invention. The amount of the derivative varies depending on the application and form of the external preparation for skin, and is not limited, but is usually 0.01 to 40% by mass, preferably 0.1 to 10% by mass, and more preferably. It is 0.1-5 mass%. If it is this range, the effect of this invention can be exhibited more.

  In an external preparation composition containing the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, various components usually used in pharmaceuticals, quasi drugs, cosmetics, such as liquid paraffin, etc. Hydrocarbons, vegetable oils and fats, waxes, synthetic ester oils, silicone-based oil phase components, higher alcohols, alkyl glyceryl ethers, fatty acids, surfactants, moisturizers, physiologically active ingredients, UV absorbers, powders, polymer compounds , Solvents, pH adjusters, neutralizers, antioxidants, preservatives, antibacterial agents, fragrances, pigments and the like can be blended. Illustrative examples of the oily raw materials include hydrocarbons such as squalane and liquid paraffin, vegetable oils such as olive oil, macadamian nut oil and jojoba oil, animal oils such as beef tallow, glyceryl triisooctanoate, tri (caprylic acid / capric acid ) Esters such as glyceryl and isooctyl palmitate, and silicones such as dimethyl silicone, phenylmethyl silicone, and cyclomethicone. Examples of higher alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol. Examples of the alkyl glyceryl ether include batyl alcohol, chimyl alcohol, cerachiral coal and fatty acid esters thereof. Examples of fatty acids include palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, and isostearic acid. As the surfactant, POE sorbitan fatty acid esters such as POE sorbitan monooleate and POE sorbitan monostearate, POE sorbite fatty acid esters such as POE sorbite monolaurate and POE sorbite monooleate, POE glycerin monostearate, POE glycerin POE glycerin fatty acid esters such as monoisostearate, POE fatty acid esters such as POE monooleate and POE monoisostearate, POE alkyl ethers such as POE oleyl ether, POE isostearyl ether and POE stearyl ether, POE / POP cetyl Ether, POE / POP alkyl ethers such as POE / POP decyl tetradecyl ether, sucrose fatty acid esters, glycerin fat Nonionic surfactants such as esters and polyglycerol fatty acid esters, fatty acid soaps such as sodium laurate and sodium palmitate, sulfates such as sodium lauryl sulfate and sodium POE lauryl sulfate, sodium lauroyl sarcosine, cocoyl-N-methyltaurine Acylated amino acid salts such as sodium and sodium lauryl glutamate, anionic surfactants such as phosphate ester salts such as sodium monolauryl phosphate, and cationic surfactants such as quaternary ammonium salts. Moisturizing components include polyethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, sorbitol, xylitol, maltitol, chondroitin sulfate, hyaluronic acid, sodium pyrrolidone carboxylate, amino acids and other NMF components, water-soluble Collagen, elastin, etc. Bioactive ingredients include ascorbic acid, magnesium ascorbate phosphate ester, ascorbyl palmitate, ascorbyl stearate, ascorbyl tetraisopalmitate, ascorbyl glucoside, arbutin, ellagic acid, lucinol and other whitening agents, glycyrrhizic acid, glycyrrhetic acid , Anti-aging agents such as ceramides, anti-aging agents such as retinol and derivatives thereof, vitamin A acid and derivatives thereof, and various vitamins and derivatives thereof. Examples of ultraviolet absorbers include dibenzoylmethane compounds, benzophenone compounds, benzoic acid compounds, salicylic acid compounds, and methoxycinnamic acid compounds. Examples of powders include titanium oxide, zinc oxide, talc, and mica. Examples of pH adjusters and neutralizers include lactic acid, citric acid, and sodium edetate. Antioxidants include α-tocopherol and gallic acid. Examples of antiseptics and antibacterial agents include paraoxybenzoic acid esters, phenoxyethanol, and sorbic acid.

  The dosage form of the external preparation composition containing the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention is arbitrary, and lotion, emulsion, cream, pack, ointment, dispersion, solid, mousse Any dosage form such as can be used. In addition to cosmetics, it can be suitably used for skin external preparations, pharmaceutical ointments and the like.

  Since the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention is dissolved in water alone (dispersed in water with a molecular size), it can be easily used for external preparation compositions such as pharmaceuticals and cosmetics. it can. Furthermore, the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention can be used not only as an emulsifier, a solubilizer, and a dispersant, but also in the absence of a solvent and easily prepare liposomes. can do.

  For the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention (hereinafter referred to as component (A)), (B) sterols other than (A) and / or a liquid crystal forming component, and more Preferably, (C) lecithins are used in combination, so that crystallization of sterols can be suppressed and sterols can be efficiently adsorbed to the skin or hair. Therefore, rather than using a polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative alone, their effects are further improved by using them together with the above components.

  The combined use of the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, sterols, and more preferably lecithins will be described in detail.

(A) polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, (B) sterols and / or liquid crystal forming components other than (A), and more preferably (C) lecithins The composition for external use in combination with can be provided as an aqueous dispersion.
As an aqueous dispersion, the (A) polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention and (B) a sterol other than (A) and / or a liquid crystal forming component can be blended. Examples include solubilization, microemulsions, nanoemulsions, emulsions in which sterol crystals do not precipitate, vesicles, and liposomes.

  (A) Polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, and (B) sterols other than (A) and / or a liquid crystal forming component in combination Although there is no particular limitation, (A) a polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative and (B) a sterol other than (A) and / or a liquid crystal forming component are slightly present. A transparent aqueous dispersion can be obtained by dissolving in a suitable solvent or dipropylene glycol and dispersing it in water.

  It should be noted that the oil component, (A) polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative, and (B) sterols other than the above (A) and / or liquid crystal forming component are generally stirred well. When an aqueous phase is added by an emulsification method, an emulsion is formed, and crystallization of sterols hardly occurs.

  Further, (A) a polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative and (B) a sterol and / or a liquid crystal forming component other than the above (A), and (C) a lecithin is converted into dipropylene glycol or the like. When a solvent is used and finely dispersed by mechanical force, stable liposomes can be formed.

  Such an aqueous dispersion can be made for the first time using the (A) polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention.

  The ratio (mass ratio) of the aqueous dispersion is not particularly specified, but (A) the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention and (B) other than the above (A) The mass ratio (A) / (B) of the sterols is 100/1 to 1/10, preferably 10/1 to 1/10. When lecithins are used in combination, the mass ratio of sterols / lecithins is 1/10 to 10/1, preferably 3/10 to 10/10.

  (B) Sterols other than (A) used in the present aqueous dispersion include plant sterols (phytosterols) such as β-sitosterol, stigmasterol, campesterol, ergosterol, cholesterol, lanosterol, ergosterol, Mycostolol, timosterol and their hydrogenated products, cholestanol, phytostanol, lanostanol, ergostanol, or their lipophilic polyoxyalkylene adducts, polyoxyalkylene-added cholesterol, polyoxyalkylene-added phytosterol, polyoxy Alkylene-added lanosterol, polyoxyalkylene-added ergosterol and their hydrogenated polyoxyalkylene-added cholestanol, with polyoxyalkylene Phytostanols, polyoxyalkylene addition Ranosutanoru, such as polyoxyalkylene addition ergo stanol and the like. These 1 type (s) or 2 or more types can be used in combination. Among these, cholesterol, cholestanol, plant sterol, plant stanol, polyoxyethylene-added phytosterol, and polyoxypropylene-added phytosterol are particularly preferable. Liquid crystal forming components include higher alcohols such as cetanol, ethylene oxide adducts of higher alcohols such as POE (10) oleyl alcohol, alkyl glyceryl ethers such as ceralkyl alcohol, chimyl alcohol, and batyl alcohol, and glyceryl monostearate. , Non-ionic surfactants such as glyceryl monoisostearate, glyceryl monooleate, diglyceryl monosterate, diglyceryl monoisostearate, diglyceryl monooleate, triglyceryl diisostearate, the above polyoxyethylene-added phytosterols and polyoxyls Although propylene addition phytosterol etc. can be mentioned, it is not limited to these. These 1 type (s) or 2 or more types can be used in combination. Of these, ceralkyl alcohol, chimyl alcohol, batyl alcohol, alkyl glyceryl ethers such as glyceryl monostearate, fatty acid monoglycerides such as diglyceryl monooleate, and polyoxypropylene-added phytosterols are particularly preferable.

  The (C) lecithins used in the aqueous dispersion include lecithins such as soybean lecithin, egg yolk lecithin, hydrogenated soybean lecithin, hydrogenated egg yolk lecithin, lysolecithin obtained by converting these lecithins into monoacyl by enzymatic treatment, and Or hydrogenated lysolecithin, hydroxylated hydroxy lecithin, etc. can be mentioned. In addition, phospholipid fractions in lecithin such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidic acid, and phosphatidylserine can be used individually or in combination. Of these, soybean lecithin and hydrogenated soybean lecithin are particularly preferable.

  (A) Polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives, and B) In addition to sterols and / or liquid crystal forming components other than (A), (C) lecithins are used in combination. Thus, due to the synergistic effect, crystal precipitation of sterols is suppressed, and the effect of efficiently adsorbing sterols to the skin and hair is further improved.

  In the present water dispersion, components blended in the above-mentioned cosmetics, quasi-drugs, pharmaceuticals, etc., for example, hydrocarbons such as liquid paraffin, vegetable oils and fats, and waxes, as long as the effects of the present invention are not impaired. , Synthetic ester oil, silicone-based oil phase component, fluorine-based oil phase component, higher alcohols, fatty acids, surfactant, moisturizer, physiologically active component, ultraviolet absorber, powder, polymer compound, solvent, A pH adjuster, a neutralizer, an antioxidant, an antiseptic, an antibacterial agent, a fragrance, a pigment, and the like can be blended.

  In addition, as a polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative, amino acid type (glycine type, aminopropionic acid type), betaine type (aminoacetic acid betaine type, sulfobetaine type), etc. The effects and uses of the present invention can also be expected for polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives and phosphorylcholineated polyoxyalkylene sterol ethers and / or polyoxyalkylene stanol ethers.

  Further, the composition for external use of the present invention exhibits an effect of preventing and relieving rough skin, and preventing and relieving pigmentation, stains, freckles, liver spots, etc. due to sunburn, but is effective in improving and / or preventing hair damage. Can also be expected.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. A compounding quantity is the mass%.

(Production Example 1) Synthesis of POP (5) sodium phytosterol ether sulfate 17.5 g of POP (5) phytosterol ether (manufactured by Nikko Chemicals Co., Ltd.) was dissolved in 150 g of toluene and 12.3 g of pyridine. 0g was charged. The mixture was reacted at room temperature for 18 hours and neutralized with a 10% aqueous sodium hydroxide solution. After washing with water, toluene was distilled off under reduced pressure to obtain 8.94 g of sodium POP (5) phytosterol ether sulfate. IR analysis (2964.5 cm ⁻¹ , 2958.2 cm ⁻¹ , 2875 cm ⁻¹ , 1463.7 cm ⁻¹ , 1380.1 cm ⁻¹ , 1244.3 cm ⁻¹ , 1106.8 cm ⁻¹ ).

(Production Example 2) Synthesis of POE (1) sodium phytosterol ether methylcarboxylate POE (2) phytosterol ether (manufactured by Nikko Chemicals Co., Ltd.) 10.0 g, AZADO (Nissan Chemical Co., Ltd., 2-Azaadamantane N-Oxyl) 002 g, 50 g of toluene, and 50 g of 0.1 M phosphate buffer (pH 6.7) were charged. 11.87 g of NaOCl (0.3%) was added followed by 11.54 g of NaO ₂ Cl (25%). The reaction was carried out at 30 ° C. for 15 hours. 100 mL of pure water was added, and the pH was adjusted to 8.5 with an aqueous sodium hydroxide solution. 3.37 g of sodium hydrogen sulfite was added and stirred for 1 hour. Extract with ethyl acetate, acidify the aqueous phase (pH 3), extract with ethyl acetate again, neutralize the ethyl acetate phase with 10% aqueous sodium hydroxide, concentrate under reduced pressure, and POE (1) phytosterol ether methylcarboxylic acid. 9.4 g of sodium was obtained. IR analysis ^{(3405.8cm -1, 2967.8cm -1, 2850.5cm} -1, 2661.3cm -1, 1758.9cm -1, 1380.9cm -1, 1107.3cm -1).

(Production Example 3) Synthesis of POE (1) POP (5) sodium phytosterol ether maleate POE (1) POP (5) phytosterol ether synthesized according to a conventional method 7.49 g, maleic anhydride 0.98 g and tetrahydrofuran 50 g were charged. It is. Reflux at 70 ° C. for 4 hours. After cooling, 10 g of 10% aqueous sodium hydroxide solution was added, and after stirring for 30 minutes, tetrahydrofuran and excess water were distilled off under reduced pressure, and 8.57 g of POE (1) POP (5) sodium phytosterol ether maleate was added. Obtained. IR analysis (3397.8 cm ⁻¹ , 2970.3 cm ⁻¹ , 2965.3 cm ⁻¹ , 2865.0 cm ⁻¹ , 1761.2 cm ⁻¹ , 1377.3 cm ⁻¹ , 1110.7 cm ⁻¹ ).

(Production Example 4) Synthesis of POE (5) phytosterol ether sodium phosphate POE (5) phytosterol ether (manufactured by Nikko Chemicals Co., Ltd.) 10.0 g was dissolved in toluene 50 g and 1.15 g of diphosphorus pentoxide in a nitrogen atmosphere. Was added and stirred at 90 ° C. for 1 hour. Next, 12.6 g of a 10% aqueous sodium hydroxide solution was added, and after stirring for 30 minutes, toluene and excess water were distilled off under reduced pressure to obtain 11.7 g of sodium POE (5) phytosterol ether phosphate. IR analysis (2933.2 cm ⁻¹ , 2867.6 cm ⁻¹ , 1460.8 cm ⁻¹ , 1377.9 cm ⁻¹ , 1243.9 cm ⁻¹ , 1101.2 cm ⁻¹ , 1017.3 cm ⁻¹ ).

(Production Example 5) Synthesis of POP (5) phytosterol ether trimethylammonium chloride 14.1 g of POP (5) phytosterol ether (manufactured by Nikko Chemicals Co., Ltd.) and 1.1 g of potassium hydroxide were charged and heated to 95 ° C. and stirred. . Under a nitrogen atmosphere, 3.8 g of glycidyltrimethylammonium chloride was added and stirred at 140 ° C. for 2 hours. The water was distilled off under reduced pressure to obtain 15.8 g of POP (5) phytosterol ether trimethylammonium chloride. IR analysis (2964.1 cm ⁻¹ , 2928.6 cm ⁻¹ , 2867.6 cm ⁻¹ , 1460.8 cm ⁻¹ , 1377.9 cm ⁻¹ , 1105.2 cm ⁻¹ )

(Production Example 6) Synthesis of POP (5) sodium phytostanol ether sulfate POP (5) phytosterol ether of Example 1 was replaced with POP (5) phytostanol ether and synthesized in the same manner as in Example 1 to obtain POP (5 ) 8.80 g of sodium phytostanol ether sulfate was obtained. IR analysis (2964.5 cm ⁻¹ , 2958.2 cm ⁻¹ , 2875 cm ⁻¹ , 1463.7 cm ⁻¹ , 1380.1 cm ⁻¹ , 1244.3 cm ⁻¹ , 1106.8 cm ⁻¹ ).

(Production Example 7) Synthesis of POE (1) sodium phytostanol ether methylcarboxylate POE (2) phytosterol ether of Example 2 was replaced with POP (2) phytostanol ether and synthesized in the same manner as in Example 2. (1) 9.0 g of sodium phytostanol ether methylcarboxylate was obtained. IR analysis ^{(3405.8cm -1, 2967.8cm -1, 2850.5cm} -1, 2661.3cm -1, 1758.9cm -1, 1380.9cm -1, 1107.3cm -1).

(Production Example 8) Synthesis of POE (1) POP (5) Sodium Phytostanol Ether Maleate POE (1) POP (5) phytosterol ether of Example 3 was changed to POE (1) POP (5) phytostanol ether In the same manner as in Example 3, 8.4 g of POE (1) POP (5) sodium phytostanol ether maleate was obtained. IR analysis (3397.8 cm ⁻¹ , 2970.3 cm ⁻¹ , 2965.3 cm ⁻¹ , 2865.0 cm ⁻¹ , 1761.2 cm ⁻¹ , 1377.3 cm ⁻¹ , 1110.7 cm ⁻¹ ).

(Production Example 9) Synthesis of POE (5) sodium phytostanol ether phosphate POE (5) phytosterol ether of Example 4 was changed to POE (5) phytostanol ether, and synthesized in the same manner as in Example 4. 5) 12.0 g of sodium phytostanol ether phosphate was obtained. IR analysis (2933.2 cm ⁻¹ , 2867.6 cm ⁻¹ , 1460.8 cm ⁻¹ , 1377.9 cm ⁻¹ , 1243.9 cm ⁻¹ , 1101.2 cm ⁻¹ , 1017.3 cm ⁻¹ ).

(Production Example 10) Synthesis of POP chloride (5) phytostanol ether trimethylammonium chloride POP (5) phytosterol ether of Example 5 was changed to POP (5) phytostanol ether and synthesized in the same manner as in Example 5, and POP chloride (5) 14.0 g of phytostanol ether trimethylammonium was obtained. IR analysis (2964.1 cm ⁻¹ , 2928.6 cm ⁻¹ , 2867.6 cm ⁻¹ , 1460.8 cm ⁻¹ , 1377.9 cm ⁻¹ , 1105.2 cm ⁻¹ )

(Rough skin improvement effect of aqueous solution of polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative)
As shown in Table 1, the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention was synthesized and evaluated for the rough skin repair effect.
Using a 0.1% aqueous solution of the following sample or an aqueous solution obtained by adding 0.01% of phytosterol to 0.01% of the following sample, the measurement of keratin moisture transpiration (TWEL) was performed using a 2-channel moisture transpiration monitor AS-TW2 ( ASAHI BIOMED). Twelve male volunteers (26-51 years old) evaluated the TEWL reduction effect by long-term continuous use (4 weeks). The application site of the sample was the inside of the thigh, and the application frequency was 2 times / day. TWEL of the application site was measured before the start of application and after the start of application 2, and after 4 weeks, and the effect of repairing rough skin was evaluated from the rate of change. The measurement was performed in a constant temperature / humidity chamber adjusted to 22 ° C. and a relative humidity of 45%.

(result)
As shown in Table 1, the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention was significantly reduced compared to the comparative product after 2 weeks and 4 weeks of use, and the skin of the product of the present invention was reduced. The improvement effect was confirmed. Moreover, it became clear from the change rate by using 0.01 mass% of phytosterol together with the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention.

  (Rough skin improvement effect of cream containing polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative)

  Polyoxypropylene (5) sodium phytosterol ether sulfate (phytoste 5PO / SU · Na: manufactured product (SU-2)) or polyoxypropylene (3) arginine ethylcarboxylate (phytosta 3PO / CM · Na) of the present invention : Preparation product (AC-2)) was prepared and a cream having the formulation shown in Table 2 was prepared, and a skin surface moisture measurement test was performed by continuous use (2 weeks) using 10 male volunteers in their 30s. The application site of the sample was a calf, and the application frequency was 2 times / day. Changes in the skin conductance at the application site after 1 week from the start of application were measured using a skin surface moisture measuring device SKICON200.

（調整方法）
Ａ相を８０℃に加温して均一に溶解し、攪拌しながら、同温度に加温したＢ相を加えて、乳化した。４０℃まで攪拌しながら冷却して試料とした。

(result)
As shown in Table 3, the cream containing the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention increases skin conductance relative to the comparative example in continuous use for 1 week and 2 weeks. confirmed. Therefore, the moisturizing effect of the cream containing the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention product was confirmed.

(Adjustment method)
Phase A was heated to 80 ° C. to dissolve uniformly, and while stirring, Phase B heated to the same temperature was added and emulsified. The sample was cooled to 40 ° C. with stirring.

  (Hair restoration effect by hair mist blended with polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives)

Polyoxyethylene (7) sodium phytosterol ether sulfate of the present invention (phytoste 7EO / SU · Na: manufactured product (SU-1)), polyoxypropylene (3) sodium phytosterol ether phosphate (phytoste 5EO / P · Na: manufactured) Product (P-2)), POE (5) phytosterol ether sodium citrate (phytoste 3EO / CA.Na: manufactured product (CE-1)) or chlorinated POE (6) phytostanol ether trimethylammonium (phytosta 6EO / TMA. Cl: A moisturizing mist for hair shown in Table 4 blended with manufactured product (CA-1)) was prepared, and an evaluation test of hair repair effect using 10 female volunteers of 20 to 50 and a hair bundle were used. A hair moisture content measurement test was performed.
In the hair restoration effect evaluation test, after using the moisturizing mist for hair for 10 days, the hair is gathered, the feeling of restoration, and the glossy feeling are interviewed and evaluated according to the following criteria, and the average value of the evaluation values is calculated. And evaluated.
In the moisture measurement test for hair using a hair bundle, 2 g of moisturizing mist for hair was applied to 2 g of the hair bundle and naturally dried. After storing for 24 hours in an atmosphere of 25 ° C. and a relative humidity of 40%, the moisture content was measured by the Karl Fischer method, and the change rate relative to untreated hair was evaluated.
(Evaluation of feeling of hair unity, repair, and gloss)
3: Remarkably improved.
2: Improved.
1: The skin was slightly improved.
0: No effect is felt.

(result)
As shown in Table 5, the hair mist containing the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative of the present invention in the hair repair effect evaluation test has an evaluation that the hair has a feeling of repair and gloss. was gotten. Moreover, it was shown from the moisture content measurement test of hair that it is excellent in the moisture retention ability of the mist hair for hair containing the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of this invention. Furthermore, by using POE (30) phytosterol in combination with the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, the hair restoration effect and the water retention capacity of the hair are improved, and a synergistic effect is achieved. It became clear to show.

  (Nanoemulsion 1 using polyoxyalkylene sterol ether derivative)

  Polyoxyethylene (4) polyoxybutylene (1) phytosterol ether phosphate arginine (4EO · 1BO / P · Arg: manufactured product (P-4)) or chlorinated POP (3) phytosterol ether trimethylammonium (phytoste 3PO) / TMA · Cl: manufactured product (CA-2)) and POE (10) phytosterol were combined at the ratios shown in Table 6, and the emulsification performance was evaluated. About the obtained emulsion, a particle size and stability (40 degreeC, three-month preservation | save) were measured.

(result)
As shown in Table 6, it was confirmed that the polyoxyalkylene sterol ether derivative of the present invention has sufficient emulsification performance even when used alone, and a fine emulsion can be obtained. Further, it was confirmed that a transparent to translucent emulsion was obtained when the polyoxyalkylene sterol ether derivative of the present invention and POE (10) phytosterol were combined in the same amount. That is, when the polyoxyalkylene sterol ether derivative of the present invention is combined with POE-added phytostearyl ether, synergistically excellent expression of emulsifying power is observed, and a nanoemulsion can be easily prepared with a homomixer without using a high-pressure homogenizer. It was shown that can be prepared.
All the emulsions obtained in this test were stable when left at 40 ° C. for 3 months.

(Prescription)
Phase A emulsifier * 2.0 (%)
Soybean oil 10.0
B phase Purified water Residual polyoxyalkylene sterol ether derivative and / or POE (10) phytosterol of the present invention (Preparation method)
Phase A was heated and dissolved uniformly. While stirring the A phase with a homomixer, the B phase was added and emulsified.

  (Nanoemulsion 2 using polyoxyalkylene sterol ether derivative)

  The polyoxyalkylene sterol ether derivative used in Example 14 and various liquid crystal forming components were combined as shown in Table 7 to evaluate the emulsification performance.

(result)
As shown in Table 7, the polyoxyalkylene sterol ether derivative of the present invention is synergistically excellent in emulsifying ability when combined with a liquid crystal forming component, and can easily prepare a nanoemulsion with a homomixer. It has been shown.

(Prescription)
Phase A polyoxyalkylene sterol ether derivative 0.8 (%)
Liquid crystal forming component 1.2
Soybean oil 10.0
Phase B purified water residue (Preparation method)
Phase A was heated and dissolved uniformly. While stirring the A phase with a homomixer, the B phase was added and emulsified.

  (Translucent emulsion using polyoxyalkylene sterol ether derivative)

  Make lotion with the following formulation in combination with POE (2) POB (1) Cholesterol ether methyl carboxylic acid isopropanolamine of the present invention (choleste 2EO · 1BO / CM · IPA: manufactured product (AC-3)) and batyl alcohol did.

(result)
The lotion was a translucent emulsion. When it was allowed to stand at 40 ° C. for 3 months, there was no change in the appearance, and even when observed with a microscope, no precipitation of ceramide crystals contained in the lotion was observed, indicating that it could be blended stably.

(Prescription)
Phase A Choleste 2EO ・ 1BO / CM ・ IPA
(Manufactured product (AC-3)) 0.5 (%)
Glyceryl monoisostearate 0.5
Batyl alcohol 0.5
Isooctanoic acid triglyceride 10.0
Ceramide 3 0.1
Phase B Preservative Appropriate amount Purified water Residue (Preparation method)
Phase A was heated and dissolved uniformly. While stirring with a homomixer, Phase B was added and emulsified. After emulsification, the mixture was cooled with stirring and allowed to stand at room temperature.

  (Liposomes using polyoxyalkylene sterol ether derivatives and / or polyoxyalkylene stanol ether derivatives)

  Polyoxyethylene (7) sodium phytostanol ether sulfate of the present invention (phytosta 7EO / SU · Na: manufactured product (SU-1)), polyoxypropylene (3) by the same preparation method as in Examples 14 and 15 Sodium phytosterol ether phosphate (phytoste 5PO / P · Na: manufactured product (P-2)), POE (1) POP (5) sodium cholestanol ether maleate (cholesta 1EO · 5PO / MA · Na: manufactured product (CE) -3)) or liposomes using POP chloride (3) phytosterol ether trimethylammonium (phytoste 3PO / TMA · Cl: manufactured product (CA-2)). About the obtained liposome, the particle size and stability (40 degreeC, 6-month preservation | save) were measured.

(result)
As shown in Table 8, by using the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention, stable liposomes could be produced without using an organic solvent. The liposomes obtained in this test were all stable for 6 months.

(Prescription)
Phase A Purified lecithin (PC content 80%) 2.0 (%)
Polyoxyalkylene sterol ether derivatives and / or
Polyoxyalkylene stanol ether derivative 2.0
Ethylene glycol 10.0
Purified water 1.0
Phase B purified water residue (Preparation method)
Phase A was heated to 70 ° C. and mixed uniformly. While stirring the A phase, the B phase heated to the same temperature or higher was added, and the mixture was treated with a homomixer at 3000 rpm for 10 minutes, and then rapidly cooled.

  (Solubilized product using polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative)

  By the same preparation method as in Examples 14 and 15, a lotion containing vitamin E using the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative used in Example 17 as a solubilizer was prepared. About the obtained lotion, the residual rate (%) of the vitamin E contained in this lotion when preserve | saved at 40 degreeC was measured.

(result)
As shown in Table 9, a lotion in which vitamin E was stably solubilized could be obtained. Vitamin E contained in this lotion was stable for a long time.

(Prescription)
Phase A Seraquil alcohol 1.0 (%)
Polyoxyalkylene sterol ether derivatives and / or
Polyoxyalkylene stanol ether derivative 0.5
Vitamin E 0.1
Squalane 2.0
Phase B purified water residue

  Next, the composition for external use of skin containing the polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of the present invention will be specifically described with reference to examples, but the present invention is limited to these examples. Is not to be done.

(Lotion 1 <Solubilization>)
POE (3) Cholesterol ether sodium phosphate 0.1 (%)
Cholesterol 0.1
DPG 10.0
Purified water residue (preparation method)
Prepared according to a conventional method.
(result)
Phytosterol was stably solubilized and a transparent lotion was obtained.

(Lotion 2 <Nanoemulsion>)
Phytosterol 0.1 (%)
Macadamia nut oil 5.0
POB (3) sodium phytosterol ether sulfate (manufactured product (SU-3)) 0.5
Purified water residue (preparation method)
Prepared according to a conventional method.
(result)
Phytosterol was stably emulsified, and a translucent lotion was obtained.

(Lotion 3 <Liposome>)
Phytosterol 0.05
Hydrogenated soybean lecithin (PC content 80%) 0.2
POP (5) Cholesterol ether sodium citrate
0.05
DPG 7.0
Natural vitamin E 0.02
Purified water residue (preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the hair repair effect of Example 13 was implemented, the hair was excellent in restoration feeling and glossiness.

(Lotion)
Ethyl alcohol 5.0 (%)
Glycerin 1.0
1,3-butylene glycol 5.0
POE (4) POB (2) Phytosterol ether arginine sulfate (Product (SU-5)) 1.0
Phytosterol 0.1
POP (5) Phytosterol 0.1
Sodium hexametaphosphate 0.03
Trimethylglycine 1.0
Sodium polyaspartate 0.1
Ascorbyl tetrahexyldecanoate 0.1
Tocopherol acetate 0.1
EDTA-2Na 0.1
Carboxyvinyl polymer 0.05
Potassium hydroxide 0.02
Preservative Appropriate amount Purified water Residue (Preparation method)
Prepared according to a conventional method.
(result)
Ascorbyl tetrahexyldecanoate and tocopherol acetate were stably solubilized, and a transparent lotion was obtained.

(Milky lotion)
Squalane 5.0 (%)
Cetyl 2-ethylhexanoate 5.0
Dimethylpolysiloxane 0.5
Cetyl palmitate 0.5
Behenyl alcohol 1.5
Stearic acid 0.5
Ceramide 2 0.1
Hydrogenated tocopherol 0.1
Kimyl alcohol 0.1
Lipophilic glyceryl monostearate 1.0
Monostearic acid POE (20) sorbitan
1.0
Tetraoleic acid POE (40) sorbitan
1.5
POE (2) POP (2) Sodium phytosterol ether phosphate (Product (P-3)) 0.2
POE (30) phytosterol 0.1
Propylene glycol 7.0
Xanthan gum 0.1
Preservative Appropriate amount Purified water The remainder (preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

(Moisturizing cream)
3-O-hexadecyl-L-ascorbic acid
0.3 (%)
Trihexyldecanoic acid pyridoxine 0.5
dl-α-tocopherol 0.2
Retinol palmitate 0.1
Hydrogenated retinol 0.1
Squalane 10.0
Isocetyl myristate 6.0
Glyceryl tri-2-ethylhexanoate 3.0
Macadamia nut oil 1.0
Dimethylpolysiloxane 0.2
Cetanol 5.0
POE (20) cetyl ether 1.0
Tetraoleic acid POE (40) Sorbit
0.5
Glyceryl monostearate 1.0
Hydrogenated soybean lecithin 0.2
POE (1) POP (3) Phytosterol ether sulfate sodium (Product (SU-4))
0.2
1,3-butylene glycol 5.0
Xanthan gum 0.1
Sodium hyaluronate 0.01
Citric acid appropriate amount Sodium citrate appropriate amount Preservative appropriate amount Purified water The remainder (preparation method)
Prepared according to conventional methods.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

(Sunscreen cream)
Liquid paraffin 7.0 (%)
Decamethylcyclopentasiloxane 3.0
Cetyl alcohol 4.0
Condensed ricinoleic acid hexaglyceryl 0.5
POE (20) cetyl ether 1.0
Octyl paramethoxycinnamate 7.0
Titanium oxide 3.0
POP (5) Phytosterol ether sodium sulfate (Product (SU-2)) 0.5
dl-α-tocopherol 0.2
1,3-butylene glycol 5.0
Xanthan gum 0.3
Sodium pyrrolidonecarboxylate 0.1
Mulberry extract 0.1
Preservative Appropriate amount Purified water The remainder (preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

(Foundation cream)
Ethylhexyl methoxycinnamate 7.5 (%)
Ethylhexyl salicylate 5.0
Titanium oxide 8.0
Zinc oxide 5.0
Dimethicone 6mm ² / s 4.0
Phenylmethyl silicone 3.0
Trimethylolpropane triethylhexanoate 2.0
Ethylhexyl palmitate 5.0
Polyglyceryl monostearate-2 0.8
Stearyl alcohol 1.4
Behenyl alcohol 1.6
POP (3) sodium phytostanol ether ethyl carbonate (manufactured product (AC-2)) 0.3
POE (5) sodium phytosterol ether methyl carbonate (Product (AC-1)) 0.2
1,3-butylene glycol 7.0
Glycerin 5.0
Hydroxyethyl cellulose 0.2
Xanthan gum 0.3
EDTA-2Na Appropriate amount Arginine Appropriate amount Preservative Appropriate amount Purified water Residue (Preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

(Cleansing cream)
Stearyl glycyrrhetinate 0.1 (%)
Cetanol 1.0
Stearyl alcohol 2.0
Tocopherol acetate 0.3
Olive Squalane 5.0
Glyceryl tri-2-ethylhexanoate 10.0
Hydrogenated polydecene 15.0
Cyclomethicone 25.0
1,3-butylene glycol 4.0
Glycerin 2.0
POE (5) Phytosterol ether potassium phosphate (Product (P-1)) 1.0
POP (3) Phytosterol 0.2
Preservative Suitable amount Purified water Residue (Preparation method)
Prepared according to a conventional method.
(result)
When sensory evaluation was carried out using the panel, it was difficult for the skin to become rough and the condition of the washed-up skin was good. The emulsified state was also good.

(Scrubbing facial cleansing cream)
Lauric acid 3.0
Myristic acid 15.0
Palmitic acid 3.0
Stearic acid 3.0
POE (80) hydrogenated castor oil 2.0
Glyceryl monostearate 2.0
PEG-3 distearate 2.0
Hardened castor oil 1.0
Cocoyl methyl taurine sodium (30% aqueous solution)
4.0
POE (3) alkyl (12,13) ether sodium sulfate (27% aqueous solution) 10.0
Cocamidotopyrbetaine (30% aqueous solution) 9.0
Palm oil fatty acid diethanolamide 1.0
Glycerin 30.0
Potassium hydroxide 5.4
Purified water 8.25
POE (5) sodium phytosterol ether methyl carbonate (manufactured product (AC-1)) 1.0
EDTA-4Na 0.05
Scrub agent 8.0
Preservative appropriate amount (preparation method)
Prepared according to a conventional method.
(result)
When sensory evaluation was carried out using the panel, it was difficult for the skin to become rough and the condition of the washed-up skin was good.

(Conditioning shampoo)
POE (2) sodium lauryl ether sulfate (27% aqueous solution) 30.0 (%)
Carboxylated POE (4.5) Lauryl ether sodium (25% aqueous solution) 25.0
Lauryldimethylaminoacetic acid betaine (30%)
10.0
Stearic acid dimethylaminopropylamide 1.0
POE (1) POP (2) Cholesterol ether trimethylammonium chloride (Product (CA-4))
1.0
Polyethylene glycol distearate 2.0
Squalane 2.0
Cholesterol 0.1
Lecithin hydroxide 0.5
Soy protein hydrolyzate 0.2
Phosphoric acid 0.4
Preservative Appropriate amount Purified water Residue (Preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the hair repair effect of Example 8 was implemented, the moisturizing effect was excellent and the emulsified state was also good.

(Hair conditioner)
POB (5) phytosterol ether monocetyl dimethylammonium chloride 2.0 (%)
POP (3) phytosterol ether trimethyl ammonium chloride (Product (CA-2)) 2.0
POE (10) Cholestanol 1.0
Hydrogenated soybean lecithin 1.0
Lysolecithin 0.1
Stearic acid 2.0
Behenyl alcohol 8.0
Dimethicone 6mm ² / s 8.0
Isostearyl alcohol 2.0
Dimethylpolysiloxane (silicone rubber) 1.0
Liquid paraffin 1.0
Polyglyceryl stearate 2.0
1,3-butylene glycol 5.0
Hydroxyethyl cellulose 0.5
Glutamic acid 0.8
Preservative Appropriate amount Purified water Residue (Preparation method)
Prepared according to a conventional method.
(result)
When the evaluation test of the hair repair effect of Example 8 was implemented, the moisturizing effect was remarkably excellent and the emulsified state was also favorable.

(Bath additive)
Tetraoleic acid POE (30) sorbitan 7.0 (%)
POE (2) oleyl ether 2.0
Sorbitan sesquioleate 2.0
Lecithin hydroxide 0.5
Glycerin 0.5
Mixed plant extract 1.4
Jojoba oil 1.0
POE (3) phytosterol ether sodium citrate (Product (CE-1)) 1.0
POE (3) Phytosterol 0.3
dl-α-tocopherol 0.1
Preservative appropriate amount Liquid paraffin (# 70) Remainder
Prepared according to a conventional method.
(result)
When sensory evaluation was carried out using the panel, the skin was not easily roughened after bathing, and the skin condition was good.

External preparation (ointment formulation)
POP (5) Sodium phytosterol ether sulfate (Product (SU-2)) 5.0 (%)
POE (30) cetyl ether 2.0
Glyceryl monostearate 10.0
Liquid paraffin 10.0
White petrolatum 5.0
Cetanol 6.0
Propylene glycol 10.0
Preservative Appropriate amount Purified water The remainder (preparation method)
An emulsified composition was prepared according to a conventional method for producing an ointment composition.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

External preparation (emulsion)
POB (3) sodium phytosterol ether propyl carbonate 1.0 (%)
Phosphorylated glyceryl ether 1.0
White petrolatum 1.0
Microcrystalline wax 3.0
Phytosterol 0.2
Lanolin 10.0
Sorbitan monooleate 4.75
Monooleic acid POE (20) sorbitan 0.25
Glycerin 5.0
Preservative Appropriate amount Purified water The remainder (preparation method)
An emulsion composition was prepared according to a conventional method for producing an emulsion composition.
(result)
When the evaluation test of the rough skin improvement effect of Example 12 was implemented, the moisturizing effect was excellent and the emulsified state was also favorable.

Claims (9)

A polyoxyalkylene sterol ether derivative and / or a polyoxyalkylene stanol ether derivative represented by the chemical formula (1).
RO- (AO) n-B (1)
[Wherein, R represents a sterol skeleton selected from cholesterol, phytosterol, lanosterol, ergosterol and hydrogenated products thereof, cholestanol, phytostanol, lanostanol, and ergostanol, and A represents ethylene oxide, propylene oxide, butylene oxide. 1 represents a polyoxyalkylene group obtained by copolymerization, block polymerization or random polymerization of at least one selected from n, and n represents an integer of less than 1-10. B represents a sulfate ester group or a salt thereof, a phosphate ester group or a salt thereof . ]   The said n is an integer of 1-5, The polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative of Claim 1 characterized by the above-mentioned.   An external preparation composition comprising the polyoxyalkylene sterol ether derivative and / or the polyoxyalkylene stanol ether derivative according to claim 1 or 2. An external preparation composition containing the following components (A) and (B).
(A) Polyoxyalkylene sterol ether derivative and / or polyoxyalkylene stanol ether derivative according to claim 1 or 2 (B) Sterols other than component (A)   The component (B) sterols are cholesterol, phytosterol, lanosterol, ergosterol and their hydrogenated cholestanol, phytostanol, lanostanol, ergostanol, or polyoxyalkylene adducts thereof. Addition cholesterol, polyoxyalkylene addition phytosterol, polyoxyalkylene addition lanosterol, polyoxyalkylene addition ergosterol and their hydrogenated polyoxyalkylene addition cholestanol, polyoxyalkylene addition phytostanol, polyoxyalkylene addition lanostanol, poly 5. One or more selected from the group consisting of oxyalkylene-added ergostanols are included. The external preparation composition according.   Furthermore, the external preparation composition of any one of Claims 3-5 which contains lecithin as a component (C).   The lecithin of the said component (C) contains the 1 type (s) or 2 or more types selected from the group which consists of plant-derived lecithin, those hydrogenated substances, and those hydroxides. Topical preparation composition.   The external preparation composition according to any one of claims 3 to 7, wherein the external preparation composition is a skin cosmetic.   The external preparation composition according to any one of claims 3 to 7, wherein the external preparation composition is a cosmetic for hair.