JP2005281135A - Skin care preparation for external use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent drying, inflammation and chapped skin by controlling skin exfoliation by excessive acceleration of epidermis turnover in a skin care preparation for external use that comprises an α-hydroxy acid, salicylic acid, trichloroacetic acid and/or phenol in large formulation amounts. <P>SOLUTION: This skin care preparation for external use comprises 10-70 mass %, based on the total of the skin care preparation for external use, of (a) one or more kinds selected from the group consisting of an α-hydroxy acid, salicylic acid, trichloroacetic acid and phenol and (b) an alkylene oxide derivative represented by the formula (I) R<SP>1</SP>O-[(AO)<SB>m</SB>(EO)<SB>n</SB>]-R<SP>2</SP>(1) (AO is a 3-4C oxyalkylene group; EO is oxyethylene group; (m) and (n) are average addition molar numbers of the 3-4C oxyalkylene group and the oxyethylene group, respectively; 1≤m and n≤ 70). A polyoxyethylene (10 mols) polyoxypropylene (10 mols) dimethyl ether may be cited as the concrete example of the alkylene oxide derivative. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an external preparation for skin, and more particularly, to an external preparation for skin for improving skin, preventing aging, preventing or improving wrinkles, etc. with reduced dryness, inflammation and rough skin. .

  In recent years, it has the effect of exfoliating the old stratum corneum on the skin surface and regenerating a new stratum corneum to promote epidermis turnover (metabolism). Hydroxy acid, salicylic acid, trichloroacetic acid, phenol and the like are blended in skin external preparations typified by cosmetics as agents for improving skin texture, dullness, roughness and the like. In addition, these compounds are various pigmentations such as fine wrinkles, blotches, freckles, liver spots, senile pigment spots, acne, dermatitis scars, burns, burns, wounds and their scars It is used for chemical peeling for removal (for example, Patent Documents 1 and 2). Improvement of skin texture, dullness, acne, etc. with these drugs improves as the amount increases, but as the amount increases, skin irritation occurs, and excessive skin turnover promotes skin desquamation. . As a result, there has been a problem that application of an external preparation containing α-hydroxy acid or the like in a high blending amount causes dryness, rough skin, inflammation or the like.

For example, a medicinal component having a rough skin preventing action or rough skin improving action such as an amino acid, polysaccharide, lipid, animal or plant extract, tranexamic acid, L-ascorbic acid or the like having anti-inflammatory action or moisturizing effect, α-hydroxy acid, etc. Attempts have been made to blend with (see, for example, Patent Documents 1 to 4). However, these attempts have been effective to some extent for external preparations containing a low concentration of a drug such as α-hydroxy acid, but in external preparations containing a high concentration of α-hydroxy acid, dryness, inflammation, rough skin, etc. Could not be prevented sufficiently.
JP-A-8-259443 JP-A-8-283138 Japanese Patent Laid-Open No. 10-114642 JP 2000-186036 A

  In view of the circumstances as described above, the present invention suppresses skin desquamation due to excessive acceleration of the epidermis turnover in a skin external preparation containing α-hydroxy acid, salicylic acid, trichloroacetic acid and / or phenol in a high blending amount. Therefore, it is an object of the present invention to provide an external preparation for skin with little dryness, inflammation, and rough skin.

  The inventor of the present invention (a) blends a specific alkylene oxide derivative with (a) α-hydroxy acid, salicylic acid, trichloroacetic acid and / or phenol, thereby adding (a) to a high blending amount of 10 to 70% by mass. In the topical skin preparation included in the above, it is possible to suppress skin desquamation due to excessive acceleration of the epidermis turnover, and such a topical skin preparation is very excellent in improving skin texture, dullness, acne, etc. As a result, the present invention has been completed.

The skin external preparation of the present invention comprises (a) one or more selected from the group consisting of α-hydroxy acid, salicylic acid, trichloroacetic acid and phenol, and (b) an alkylene represented by the following general formula (I) It contains an oxide derivative, and the blending amount of (a) is 10 to 70% by mass with respect to the total amount of the external preparation:
R ¹ O — [(AO) _m (EO) _n ] —R ² (I)
In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyalkylene group and the oxyethylene group is 20 to 80% by mass. The oxyalkylene group and the oxyethylene group may be added in a block form or randomly. R ¹ and R ² are the same or different hydrocarbon groups having 1 to 4 carbon atoms or hydrogen atoms, and the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less. .

  The alkylene oxide derivative (b) is preferably one in which an oxyalkylene group and an oxyethylene group are randomly added. The use feeling of the external preparation for skin is more excellent when a random addition is added than a block addition.

  The external preparation for skin of the present invention preferably contains one or more α-hydroxy acids selected from the group consisting of glycolic acid, lactic acid, malic acid and tartaric acid. In the case of containing such an α-hydroxy acid, the effect of the present invention is remarkable, since skin desquamation due to excessive acceleration of turnover of the epidermis is particularly problematic.

  The external preparation for skin of the present invention preferably further contains a thickener. By blending a thickener, the viscosity can be stably maintained, and usability and stability can be improved.

  The external preparation for skin of the present invention preferably further contains a neutralizing agent. By mix | blending a neutralizing agent, pH can be adjusted appropriately and skin irritation can be reduced.

  The external preparation for skin of the present invention is preferably a chemical peeling composition. In the present specification, the chemical peeling composition means a composition for use in chemical peeling in which a chemical substance is applied to the skin and the surface layer portion is peeled off at a certain depth by its action.

  Since the external preparation for skin of the present invention contains the above (a) at a high blending amount of 10 to 70% by mass, it is excellent in the improvement effect of skin texture, dullness, acne and the like, and further, the alkylene oxide of (b) Since the derivative is contained, it is possible to suppress the desquamation of the skin caused by excessive turnover acceleration of the epidermis, and to prevent dryness, inflammation, rough skin and the like.

  The external preparation for skin of the present invention contains (a) one or more selected from the group consisting of α-hydroxy acid, salicylic acid, trichloroacetic acid and phenol as an essential component.

  The α-hydroxy acid used in the external preparation for skin of the present invention has been conventionally used as a buffer or neutralizing agent for cosmetics and cleaning agents, and for the purpose of softening the keratin or activating cells. It is blended in various cosmetics. Although it does not specifically limit as alpha-hydroxy acid mix | blended with the skin external preparation of this invention, For example, glycolic acid, lactic acid, malic acid, tartaric acid, a citric acid, glyceric acid, pyruvic acid, mandelic acid etc. are mentioned. Among these, glycolic acid, lactic acid, malic acid, or tartaric acid is excellent in the effect of promoting the turnover of the epidermis, and is particularly preferably blended in the skin external preparation of the present invention. In the skin external preparation of this invention, these alpha-hydroxy acids may be mix | blended independently or may be mix | blended in combination of 2 or more type as needed.

  The salicylic acid used in the external preparation for skin of the present invention has been conventionally used as an antibacterial agent in various external preparations, and has recently been used as a chemical peeling agent for improving wrinkles and stains. Trichloroacetic acid and phenol are also used as chemical peeling agents, particularly in Europe and America.

  The blending amount of the above (a) in the external preparation for skin of the present invention is 10 to 70% by mass, preferably 20 to 60% by mass, more preferably 30 to 50% by mass, based on the total amount of the external preparation for skin. It is. If it is less than 10% by mass, it may not be possible to provide sufficient improvement effects such as wrinkles and stains. If it exceeds 70% by mass, skin irritation will be large and it will be difficult to adjust the viscosity.

  Furthermore, the skin external preparation of this invention contains (b) the specific alkylene oxide derivative shown by the said general formula (I) as an essential component.

  In the alkylene oxide derivative (b) to be blended in the skin external preparation of the present invention, AO is an oxyalkylene group having 3 to 4 carbon atoms, and specifically includes, for example, an oxypropylene group, an oxybutylene group, and an oxyisobutylene. Group, oxytrimethylene group, oxytetramethylene group and the like. Preferably, AO is an oxypropylene group or an oxybutylene group.

  m is the average number of added moles of the oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ m ≦ 70, preferably 2 ≦ m ≦ 20. n is the average number of added moles of oxyethylene groups, and 1 ≦ n ≦ 70, preferably 2 ≦ n ≦ 20. When the oxyalkylene group or oxyethylene group having 3 to 4 carbon atoms is 0, the moist feeling is lowered, and when it exceeds 70, a sticky feeling tends to appear.

  Moreover, the ratio of the oxyethylene group with respect to the sum total of a C3-C4 oxyalkylene group and an oxyethylene group is 20-80 mass%. When the proportion of the oxyethylene group is less than 20% by mass, the moist feeling tends to be inferior, and when it exceeds 80% by mass, the smooth feeling tends to be inferior.

  The order of adding ethylene oxide and alkylene oxide having 3 to 4 carbon atoms is not particularly specified. Moreover, the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block shape or randomly, and the block shape may include not only a two-stage block but also a three-stage block or more. included. In addition, in the external preparation for skin of the present invention, the one added in a random form is superior to the one added in a block form because it is superior in use feeling, and therefore is added in a random form. Is preferred.

R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include a tert-butyl group. A methyl group and an ethyl group are preferred. Hydrocarbon groups having 5 or more carbon atoms are less hydrophilic and less moist. R ¹ and R ² may be the same or different.

R ¹ and R ² may be the same type, or a mixture of a hydrocarbon group having 1 to 4 carbon atoms and a hydrogen atom, or a mixture of different hydrocarbon groups having 1 to 4 carbon atoms. Good. However, among the hydrocarbon groups of R ¹ and R ^2, the proportion of hydrocarbon groups and hydrogen atoms is such that the ratio Y / X of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X) is 0.15. Or less, more preferably 0.06 or less. When the ratio of Y / X exceeds 0.15, a sticky feeling tends to appear.

  Although it does not specifically limit as an alkylene oxide derivative of said (b) mix | blended with the skin external preparation of this invention, For example, POE (14) POP (7) dimethyl ether, POE (10) POP (10) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (27) POP (13) dimethyl ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (14) POB (7) dimethyl ether, POE (10) POP (10) diethyl ether, POE (10) POP (10) dipropyl ether, POE (10) POP (10) dibutyl ether, etc. , POB is polyoxy Ethylene, polyoxypropylene, which is an abbreviation of polyoxybutylene).

  The alkylene oxide derivative (b) to be blended in the external preparation for skin of the present invention can be produced by a known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

  The blending amount of the (b) alkylene oxide derivative in the skin external preparation of the present invention is not particularly limited, but is preferably 0.01 to 60% by mass, more preferably 1.0%, based on the total amount of the skin external preparation. -30 mass%. If it is less than 0.01% by mass, there may be cases where skin desquamation due to excessive acceleration of turnover of the epidermis cannot be effectively suppressed, and if it exceeds 60% by mass, a sticky feeling may occur.

  Furthermore, the thickener to be blended is not particularly limited, but gellan gum, native gelam gum, carrageenan, caraya gum, tragacanth gum, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate , Methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropylcellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarint gum, dialkyldimethylammonium sulfate cellulose, xanthan gum, agar, bentonite, hector Examples thereof include light, silicate AlMg (beegum), and laponite. In particular, hydroxypropylcellulose, hydroxyethylcellulose, and sodium carboxymethylcellulose are preferable. In the skin external preparation of this invention, these thickeners may be mix | blended independently or may be mix | blended in combination of 2 or more type as needed.

  The blending amount of the thickener in the external preparation for skin of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the external preparation for skin.

  The viscosity of the external preparation for skin of the present invention is not particularly limited, but the viscosity at room temperature (25 ° C.) is preferably 500 to 5000 mPa · s, and more preferably 1000 to 3000 mPa · s. When it is in such a viscosity range, it does not easily fall off during use and is excellent in usability.

  Further, the neutralizing agent to be blended is not particularly limited, and examples thereof include caustic potash, caustic soda, sodium citrate, sodium carbonate, sodium hydrogen carbonate, ammonia, triethanolamine, L-arginine, and L-lysine. In particular, sodium citrate and caustic soda are preferable. In the skin external preparation of this invention, these neutralizing agents may be mix | blended independently or may be mix | blended in combination of 2 or more type as needed.

  The blending amount of the neutralizing agent in the external preparation for skin of the present invention is preferably from 0.1 to 25 mass%, more preferably from 0.5 to 10 mass%, based on the total amount of the external preparation for skin.

  The pH of the external preparation for skin of the present invention is not particularly limited, but is usually 0.5 to 3.5, and more preferably pH 1 to 3 from the viewpoint of irritation to the skin.

  In the external preparation for skin of the present invention, a humectant may be further blended, and the humectant to be blended is not particularly limited, but glycerin, diglycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, Examples include sorbitol, fructose, mannose, erythritol, trehalose, xylitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, and caronic acid. In particular, 1,3-butylene glycol or diglycerin is preferable. In the external preparation for skin of this invention, these moisturizing agents may be blended alone or in combination of two or more as required.

  The blending amount of these moisturizers in the external preparation for skin of the present invention is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the external preparation for skin.

  In the present specification, the “skin external preparation” is not particularly limited as long as it is applied to the outer skin, and includes cosmetics, pharmaceuticals, quasi drugs and the like. Moreover, the dosage form is also arbitrary such as aqueous solution system, solubilization system, emulsification system, oil liquid system, gel system, paste system, ointment system, aerosol system, water-oil two-layer system, water-oil-powder three-layer, etc. Including dosage forms. Moreover, what was carry | supported by the sheet-like base is also included.

  Moreover, the usage form is also arbitrary, For example, it can be used in arbitrary forms, such as a lotion, a milky lotion, a cream, a pack, a cosmetic liquid, and a face-wash.

  The external preparation for skin of the present invention contains, in addition to the above components, other optional components that are usually used in external preparations for skin, such as cosmetics and pharmaceuticals, as appropriate, and is a conventional method depending on the intended dosage form. Can be manufactured. For example, the external preparation for skin of the present invention can be prepared by blending the above components with one or more of the following components.

  Examples of the ultraviolet absorber include paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, Benzoic acid UV absorbers such as N, N-dimethyl PABA butyl ester and N, N-dimethyl PABA methyl ester, anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate, amyl salicylate, menthyl salicylate, homo Salicylic acid UV absorbers such as menthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, octyl cinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2 , 4-Diisopropylcin Mate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p- Methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, Cinnamic acid UV absorbers such as glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, methyl bis (trimethylsiloxane) silylisopentyl trimethoxycinnamate, 3- (4'-methylbenzylidene) -d, 1-camphor , 3-benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5- Methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methyl Phenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, dimorpholinopyrida Dinone etc. are mentioned, Arbitrary 1 type, or 2 or more types can be used.

  Examples of the ultraviolet scattering agent include powders of titanium oxide, fine particle titanium oxide, zinc oxide, fine particle zinc oxide, iron oxide, fine particle iron oxide, cerium oxide, and the like.

  As these ultraviolet scattering agents, needle-like, spindle-like, spherical and granular powders are usually used. A fine particle powder having a particle size of 0.1 μm or less is preferred.

  Silicone treatment such as methyl hydrogen polysiloxane and silane coupling agent; metal soap treatment; UV scattering agent that has been hydrophobized by fluorine treatment such as perfluoroalkyl phosphate diethanolamine salt and perfluoroalkyl silane, dextrin fatty acid ester treatment, etc. Is also preferable.

  Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

  Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin. , Jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.

  Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and the like. Is mentioned.

  Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, octyldodecanol and the like.

  Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylo Propane, tetra-2-ethylhexanoate pentaerythritol, glycerol tri-2-ethylhexanoate, glycerol trioctanoate, glycerol triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmi Tate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2 -Octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate Le, 2-ethylhexyl succinate, triethyl citrate, polyoxyethylene-polyoxypropylene random polymer methyl ether.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.

  Others include lower alcohols such as ethanol; antioxidants such as butylhydroxytoluene, tocopherol and phytin; antibacterial agents such as benzoic acid, sorbic acid, alkyl alkyl parabenzoate, and hexachlorophene; acyl sarcosine acid (eg, lauroyl sarcosine sodium) ), Organic acids such as glutathione; vitamin B and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbine Vitamin C such as acid, ascorbic acid sulfate (salt), ascorbic acid phosphate (salt), ascorbyl dipalmitate, α-tocopherol, β-tocopherol, δ-tocophero Vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, etc .; nicotinic acid amide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and Derivatives such as hinokitiol, bisabolol, eucarptone, thymol, inositol, psychosaponin, carrot saponin, hechimasaponin, muclodisaponin, pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, cephalanthin, placenta extract, etc. Various drugs, borage, clara, corn, orange, sage, yarrow, mallow, thyme, thyme, suki, spruce, birch, sugina, loofah, maronie, yukinoshi , Arnica, Lily, Mugwort, Peonies, Aloe, Gardenia, Sawara, Hawthorn extract, Hypericum perforatum extract, Iris in extract, Acacia yak extract, Ginkgo biloba extract, Ibuki extract, Oyster extract, Oolong tea extract, Water lily extract , Ages extract, Enmezo extract, Ogon extract, Oat extract, Odori extract, Licorice extract, Gardenia extract, Tea extract, Seika ryu extract, Tormentilla extract, Rose extract, Loofah extract, Peppermint extract, Rosemary extract, Royal jelly extract, etc. Plant extracts, pigments, sorbitan monolaurate, sorbitan monopalmitate, sorbitan sesquioleate, sorbitan trioleate, polylaurate monolaurate Xylethylene sorbitan, polyoxylene sorbitan monostearate, polyethylene glycol monooleate, polyoxyethylene alkyl ether, polyglycol diether, lauroyl diethanol amide, fatty acid isopropanol amide, maltitol hydroxy fatty acid ether, alkylated polysaccharide, alkyl glucoside, sugar Nonionic activators such as esters, cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide, sodium palmitate, sodium laurate, sodium laurate, potassium lauryl sulfate, triethanol alkyl sulfate Amine ether, funnel oil, linear dodecyl benzene sulfate, polyoxyethylene hydrogenated castor oil male Acid, anionic surfactants such as acyl methyl taurine, amphoteric surfactants, .delta.-tocopherol, antioxidant such as butylhydroxytoluene, phenoxyethanol, preservatives such as paraben and the like.

  Furthermore, the external preparation for skin of the present invention includes, for example, N, N, N-trimethylglycine (TMG), L-serine, malonic acid, or succinic acid in addition to α-hydroxy acid, salicylic acid, trichloroacetic acid or phenol. In addition, any other exfoliating agent may be further contained. By further blending such a keratin remover, a higher skin beautifying effect can be brought about.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, EO represents an oxyethylene group, PO represents an oxypropylene group, and [(EO) / (PO)] represents a random bond.

  First, a method for synthesizing an alkylene oxide derivative is illustrated.

Synthesis Example 1 Synthesis <br/> Polyoxyethylene (10 moles) polyoxypropylene (10 mol) of the block polymer ether _{CH 3 O (EO) 5 (} PO) 10 (EO) 5 CH 3
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 440 g of ethylene oxide was dropped by a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and the above alkylene oxide derivative (block polymer) was obtained.

  Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 110, compound 9 had a hydroxyl value of 0.3, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.003. It has been converted to a methyl group.

Synthesis Example 1 Synthesis <br/> Polyoxyethylene (10 moles) random polymers polyoxypropylene (10 mol) dimethyl ether _{CH 3 O [(EO) 10} / (PO) 10] CH 3
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 440 g of ethylene oxide and 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and the above alkylene oxide derivative (random polymer) was obtained.

  Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 107, compound 2 had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.004. It has been converted to a methyl group.

  Next, the evaluation method performed about each Example and the comparative example is demonstrated below.

Drying and desquamation evaluation test 10 panelists in each group applied each external preparation using a cotton swab to an area of 1.0 × 1.0 cm at the center of the human eye, and washed with soap 10 minutes later. The skin condition after 96 hours was evaluated according to the following evaluation criteria. The results were expressed as the average of 10 evaluation points:
0 ... Dry, no desquamation 1 ... Slightly dry 2 ... Berky, white-looking 3 ... Clear horny turn 4 ... Big turn with flakes

According to the synthesis method described above, each alkylene oxide derivative shown in Table 1 was synthesized, and in the formulation shown in Table 2, an external preparation containing α-hydroxy acid (glycolic acid) and each alkylene oxide derivative (Examples 1 to 6, And Comparative Examples 1-4) were prepared. All compounding amounts are expressed as mass% with respect to the total amount of the external preparation. About the obtained external preparation, drying and desquamation evaluation were performed by the evaluation method mentioned above. The results are also shown in Table 2.

The α-hydroxy acid (glycolic acid) of the present invention and a specific alkylene oxide derivative (the ratio of oxyethylene groups to the total of oxyalkylene groups and oxyethylene groups (EO mass ratio (%)) is 20 to 80% by mass, External preparations (Examples 1 to 6) containing a ratio of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X) of R ¹ and R ² (Y / X) is 0.15 or less) Compared with external preparations that do not contain oxide derivatives (Comparative Example 1) and external preparations that contain other alkylene oxide derivatives (Comparative Examples 2 to 4), dryness and desquamation are significantly less, and rough skin is effectively prevented. It was suggested that it could be.

  Below, the formulation example of the skin external preparation of this invention is shown as an Example. In addition, all compounding quantities are represented by the mass% with respect to the external preparation whole quantity.

Example 7
Lactic acid 30.0% by mass
CH ₃ O (EO) ₁₀ (PO) ₁₀ (EO) ₁₀ CH ₃ 5.0
Dynamite Glycerin 1.0
Hydroxyethyl cellulose 1.5
Sodium citrate 3.0
Purified water The remainder (production method) All components were dissolved in purified water and filtered.

Example 8
Trichloroacetic acid 10.0% by mass
_{CH 3 O [(EO) 20} / (PO) 20] CH 3 10.0
1,3-butylene glycol 1.0
Xanthan gum 0.4
Purified water The remainder (production method) All components were dissolved in purified water and filtered.

Example 9
Glycolic acid 40.0% by mass
_{CH 3 O [(EO) 20} / (PO) 10] CH 3 3.0
Dynamite Glycerin 1.0
Gellan gum 0.3
Sodium citrate 5.0
Caustic soda 2.0
Purified water The remainder (production method) All components were dissolved in purified water and filtered.

  All of the external preparations of the present invention of Examples 7 to 9 have less drying and desquamation in the drying / desquamation evaluation test.

Claims (6)

(A) one or more selected from the group consisting of α-hydroxy acid, salicylic acid, trichloroacetic acid and phenol, and (b) an alkylene oxide derivative represented by the following general formula (I), A skin external preparation characterized in that the blending amount of a) is 10 to 70 mass% with respect to the total amount of the external preparation.
R ¹ O — [(AO) _m (EO) _n ] —R ² (I)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyalkylene group and the oxyethylene group is 20 to 80% by mass.The oxyalkylene group and the oxyethylene group are added in a block shape. R ¹ and R ² may be the same or different and each is a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and hydrogen relative to the number of hydrocarbon groups in R ¹ and R ² (The ratio of the number of atoms is 0.15 or less.) 2. The external preparation for skin according to claim 1, wherein the alkylene oxide derivative (b) has an oxyalkylene group and an oxyethylene group added randomly. The skin external preparation according to claim 1 or 2, comprising at least one α-hydroxy acid selected from the group consisting of glycolic acid, lactic acid, malic acid, and tartaric acid. The skin external preparation according to any one of claims 1 to 3, further comprising a thickener. The skin external preparation according to any one of claims 1 to 4, further comprising a neutralizing agent. It is a chemical peeling composition, The skin external preparation of any one of Claim 1 to 5 characterized by the above-mentioned.