TW200533383A - External preparation for skin - Google Patents

Abstract

The present invention relates to an external preparation for the skin capable of providing sufficient moisture and turgor to the skin. The external preparation for the skin contains a multi-branched polysaccharide derivative with a multi-branched polysaccharide skeleton comprising sugars as constituent units, wherein at least one of hydroxyl (OH) groups in the multi-branched olysaccharide skeleton is substituted by OR (wherein R represents a hydrogen atom, a 1-30C hydrocarbon or a 1-30C hydrocarbon having a hetero atom). A cosmetic agent comprises the external preparation for the skin.

Description

200533383 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a novel skin external preparation. More specifically, it relates to an external preparation for skin containing a multi-branched polysaccharide derivative having the effect of maintaining moisturizing and elasticity of the skin. [Prior art] • A variety of moisturizers have been used as compounds that can maintain skin moisturizing effects in external preparations for the skin. The moisturizing agent is added to the skin external preparation for the purpose of preventing the evaporation of water, adjusting the moisture on the skin surface, and giving a moisturizing effect while giving a moisturizing feeling. The moisture content of the skin stratum corneum is closely related to the defense function of various stimuli from the outside, and plays an important role in preventing the skin from aging, moisturizing, and smooth feeling. The moisture retention of this stratum corneum is generally controlled by NMF (Natural Moisturizing Factor) and sebum film, but its function is easily reduced due to aging or irritation from the outside #. Therefore, its moisturizing ingredients are added for external use on the skin. Agents, especially for cosmetics. As a moisturizing ingredient that supplements the skin's β moisture, it has been noticed and applied to the same or similar ingredients as the living ingredients. These are amino acids, peptides, proteins, sugars, polysaccharides, lipids, glycoproteins, and the like. For example, cosmetics containing a dipeptide of alanine and glutamic acid (Japanese Laid-Open Patent Publication No. 8-3 2 5 1 3 1) and sugar-based cosmetic materials of vegetable glycogen (Japanese Patent Laying-Open No. 1 1-1 8 0 are known). Bulletin 8 1 8) and mucopolysaccharides can be added to plant glycogen at the same time (Japanese Patent Laid-Open Nos. 2000-1-8 9 3 81). However, amino acids have the disadvantages of 200533383 (2) the burden of use is too heavy, and the control of the skin is poor. Even if the dipeptide has high solubility in low-molecular-weight compounds, there are also skins that can be easily applied to the skin surface. Disadvantages of dissolution of external agents. In addition, polysaccharides such as glycogen or mucopolysaccharides have high moisture retention and are mostly added as raw materials with good permeability on the skin. However, these polysaccharides are generally linear, and the reaction will not affect the skin when dry. The comfortable tightness makes it difficult to use on the ingredients of skin external preparations. In addition, cosmetics containing these compounds cannot achieve the necessary moisture and elasticity to maintain the skin for a long period of time for cold and warm temperatures, dry and humid changes in the air, and skin sweating. In addition, a polysaccharide-derived water-based cosmetic was used (Japanese Patent Application Laid-Open No. 200 2_5 3 426). However, these natural-derived polysaccharides are composed of a plurality of types of monosaccharides, and the composition ratio is not constant, and the structure is not constant. It is difficult to manage each quality. Also, for cosmetic materials, an agglomerative structure may be formed to make the ingredients The homogenization causes gelation or sedimentation, and when applied to the skin, it has the disadvantages of uncomfortable touch. As other moisturizers, there are used polyhydric alcohols such as glycerin, propylene glycol, and butanediol. These not only have a function of retaining moisture, but also have a great influence on the feeling of use. $ 'Animal-derived compounds such as collagen and keratin, their hydrolysates, and placenta extracted from bovine placenta extract J can also be used as moisturizers'. However, animal-derived compounds have reduced reliability due to their safety Therefore, the number of countries banning the use as skin external preparations is increasing, and the development of compounds of safer origin in the industry has proceeded. [Summary of the Invention] -6-200533383 (3)

An object of the present invention is to provide a skin external preparation which can provide sufficient skin moisture and elasticity. Therefore, in the present invention, in order to provide a skin external preparation with less dissolution from the skin external preparation, which can sufficiently maintain the moisture retention amount, and does not produce an uncomfortable tightness to the skin when dry, the structure or ingredients are certain. Quality control is easy, and from the viewpoint of safety, skin external preparations that can be used safely can be used for the purpose. More specifically, the present invention has as one of its problems the provision of a skin external preparation containing a multi-branched polysaccharide and / or a multi-branched polysaccharide derivative of a synthetic polymer derived from anhydrous sugar. The present inventor intends to solve the above-mentioned problems and conducts a detailed review. It is found that the multi-branched polysaccharide derivative and / or the multi-branched polysaccharide derivative in which the saccharide is a constituent unit of the multi-branched polysaccharide as a skeleton is added to the skin external preparation, and can replenish skin moisture, and The adhesion to the skin is significantly improved, and the skin feel when dry is also good, and the present invention has been completed. That is, this invention relates to the following matters. 1. An external preparation for skin, characterized in that it contains a polybranched polysaccharide as a structural unit as a skeleton, and at least one of the hydroxyl groups (OH) of the multibranched polysaccharide is OR (R represents a hydrogen atom and a carbon number of 1 to 30) Multi-branched polysaccharide derivatives, or hydrocarbons having 1 to 30 carbon atoms with hetero atoms). 2. The external skin preparation according to the above 1, wherein the multi-branched polysaccharide as a skeleton is that at least one of the anhydrous sugar and / or anhydrous sugar (0H) is composed of OR (R represents a hydrogen atom, and the number of carbon atoms is 1 to 2). 30 hydrocarbons, or hydrocarbons having 1 to 30 carbon atoms having a hetero atom) are substituted with an anhydrous sugar derivative as a monomer. 3. The external preparation for skin according to the above 2, wherein the anhydrous sugar portion of the anhydrous sugar or the anhydrous sugar derivative is at least one selected from the group consisting of 1,6-anhydrosugar and 1,4-anhydrosugar 200533383 (4), 1, 3- Anhydroose, 1,2 -anhydrosugar, and 5,6-anhydrosugar are clustered. 4. The external preparation for skin as described in 2 above, wherein the polymer is obtained by cationic polymerization or anionic polymerization. 5. The external preparation for skin as described in 1 above, wherein the degree of branching of the multi-branched polysaccharide is 0.05 to 1.00. 6. The external preparation for skin according to any one of 1 to 5 above, wherein the content of the multi-branched polysaccharide derivative is 0.1 to 80% by mass. • 7. A cosmetic comprising a skin external preparation as described in any one of 1 to 6 above. When a multi-branched polysaccharide derivative in which a saccharide is a constituent unit and a multi-branched polysaccharide is used as a skeleton is added to the skin external preparation, it can provide a skin moisture supplement, and has excellent adhesion or affinity to the skin, so it can be used when dry. An excellent skin external preparation that maintains the skin's moisture and elasticity and has a good touch effect. The multi-branched polysaccharide serving as the backbone of the multi-branched polysaccharide derivative of the present invention is not particularly limited as long as it is only a multi-branched polysaccharide, but it is a compound having one or more types of sugars as its constituents. It has a structure in which the same sugar molecule having a plurality of hydroxyl groups has three or more binding sites with adjacent sugar molecules and has a number-shaped pattern of a plurality of branch points. As a general natural substance, many kinds of polysaccharides are straight-chain polysaccharides or branched polysaccharides with fewer branch points, and all have main chains. A multi-branched polysaccharide has a plurality of branch points, so it is a compound in which a main chain is definitely not present. As a method for producing the multi-branched polysaccharide of the present invention, a conventionally known method can be applied. For example, as a manufacturing method by a chemical synthesis method, -8-200533383 (5) A method of producing a multi-branched polyvinegar by polymerizing a monosaccharide derivative as a monomer, and as an example, a method such as Publication No. 2003-252 904 discloses a method for producing a multi-branched polysaccharide by ion polymerization using anhydrous sugar as a monomer. Examples of the anhydrous sugar at this time include derivatives derived from 1,6-anhydrosugar, 1,4-anhydrosugar, 1,3 · anhydrosugar, 1,2-anhydrosugar, and 5,6-anhydrosugar. Specific examples include 1,6-anhydro-/?-〇-glucopyranose, 1,6-p anhydro- / SD-mannan, and 1,6-anhydro- / SD-galactose Pyranose, 1,6-anhydro- / 3-D-alopyranose, 1,6-anhydro- / 3-D-altopyranose, 1,4 · anhydro-Θ-D-ribopyran Mannose, 1,4-anhydro-α-D-xylopyranose, 1,4-anhydro-a-D-arabinopyranose, 1,4-anhydro-a-D-lysopyranose, 1, 3-anhydro-3 / 3-D-glucopyranose, 1,3-anhydro-0-D-mannopyranose, 1,2 · anhydro-α-D-glucopyranose, 1,2-anhydro- / 3-D-mannanose, 5,6-anhydro-a-D-glucopyranose and the like. Examples of the ionic polymerization include cationic polymerization and anionic polymerization. < | It is also possible to use animals, plants, microorganisms, or a method for producing a multi-branched polysaccharide by using methods such as breeding, cultivation, and cultivation. Alternatively, as a method for producing a multi-branched polysaccharide having an increased branching degree, for example, the method disclosed in Japanese Unexamined Patent Publication No. 8-41101 can be used to increase the degree of branching of a branched polysaccharide to a multi-branched polysaccharide. The multi-branched polysaccharide derivative of the present invention has a structure in which a part of the hydroxyl groups of the multi-branched polysaccharide as a skeleton and / or all of them are substituted with a substituent. For example, at least one of the OH groups of the multi-branched polysaccharide is represented by OR (R Represents a hydrogen atom, a hydrocarbon having 1 to 30 carbon atoms, or a hydrocarbon having 1 to 30 carbon atoms having a hetero atom) * 9-200533383 (6) Substituted compounds and the like. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, and 2-methylbutyl. Methyl, 3-methylbutyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethyl Butyl, 2-ethylbutyl, heptyl, methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-hexylhexyl, 1-ethylpentyl, 2-ethyl Pentyl, 3-ethylpentyl, octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6 -Methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, Lauryl, 10-laurenyl, dodecyl, thirteen, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve, twelve Base, isostearyl, cis-9-octadecenyl, 11-octadecenyl, cis, cis-9,12-octadecadienyl, 9,12,15-octadecadienyl Alkenyl, 6,9, 1 2 -octadecanetrienyl, 9, 1 1,1 3 · octadecanetrienyl, undecyl, 2,6,10,14-tetramethylpentadecyl, eicosyl, 8, 11-eicosadienyl, 5,8,11-eicosanetrienyl, 5,8,11,14-eicosatetelenyl, 3,7,11,15 -tetramethylhexadecyl, behenyl, Dodecyl, ethenyl, propionyl, isopropylfluorenyl, butylfluorenyl, 1-methylpropanyl, 2-methylpropanyl, pentyl, 1-methylbutylfluorenyl, 2-methyl Butylmethyl, 3-methylbutylmethyl, ethylpropylmethyl, hexyl, 2-methylvaleryl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl , Heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, octyl, 2-methyl Heptyl-10- 200533383 (7), 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl Methyl, 3-ethylhexyl, 4-ethylhexyl, 2-propylheptyl, nonyl, decyl, 10-decyl, dodecyl, tridecyl Base, tetradecyl fluorenyl, pentadecyl fluorenyl, hexadecyl fluorenyl 9-sixteen stilbene, 17th stilbene, 18s stilbene, isostearyl, cis-9-octadecenyl, 1 1-octadecenyl, cis, cis-9, 12-octadecanedifluorenyl, 9,12,15-octadecanetrifluorenyl, 6,9,12-octadecanetrifluorenyl, 9,11,13-B octadecyltrifluorenyl, ten Jiuyuan Yanji, 2,6,10,14 -Tetramethyl fifteen yuan brewing base, 20 yuan yuan base, 8, 11-20 yuan yuan base, 5,8, 11 · 20 yuan three yuan base Tetramethyl, 5,8,11,14-Eicosyltetramethyl, 3,7,11,15-tetramethylhexadecylfluorenyl, behenylfluorenyl, behenylfluorenyl, phospholipid Base etc. It also contains compounds in which R is bonded with an isocyanate group. The method for synthesizing a multi-branched polysaccharide derivative of the present invention is, for example, a method of obtaining a multi-branched polysaccharide as a skeleton, and modifying a hydroxyl group of a sugar with a desired functional group to synthesize a multi-branched polysaccharide derivative, or a monomer of a multi-branched polysaccharide • A method for synthesizing a polysaccharide derivative of a polybranched polysaccharide by polymerizing an anhydrous sugar with a desired functional group and then polymerizing it. '' Modification of the radical can be carried out using a general esterification reaction of a carboxylic acid derivative, for example. Β ° Specific examples include a method of reacting a carboxylic acid as an acid chloride or a mixed acid, and using a carbodiimide. How to perform the reaction, make use of 1 @method, etc. Further, in the case of a compound having an isocyanate group, a method for modifying a urethane bond by a catalyst such as heat or tin-based or amine-based catalysts, etc. is used. The degree of support is -11-200533383 (8) 0.05 to 10.0, preferably 0.2 to 10, and more preferably 0.4 to 10. Among them, the degree of branching is generally calculated by the following formula of Frechet. Degree of branching two (number of branching units + number of polymer terminals) / (number of branching units + number of polymer terminals + number of linear units) As a preparation method for a skin external preparation of a multi-branched polysaccharide derivative used in the present invention, it can be used as A method for producing a skin external preparation by mixing solid, powder, and semi-solid, a method for producing a skin external preparation by mixing as an aqueous solution, a method of producing an external skin preparation by mixing an alcohol or a solution of an appropriate solvent, and others A method for producing a skin external preparation by mixing or adding it under a known method. The multi-branched polysaccharide derivative used in the present invention can be isolated as a powder, for example, but the aqueous solution obtained in the production step can be directly added to the external preparation for skin. The addition amount of the multi-branched polysaccharide derivative used in the present invention is only required to be added in the form of skin external preparations and cosmetics, and is not particularly limited. It can be added to 0.001 to 100% by mass, preferably 0.1. ~ 80 mass%, more preferably 1 to 50 mass%. When the skin external preparation is added in an amount of less than 0.01% by mass, the adhesion and affinity to the skin may be insufficient, and a touch such as a sufficient moisturizing feeling of the skin may not be obtained. It can be added as a skin external preparation within a range that does not lose its original function. The external preparation for skin as used in the present invention includes a cosmetic, a detergent, a bath agent, a soap, and the like which can directly contact the skin. -12- 200533383 (9) Examples of the skin external preparation of the present invention include, for example, skin care lotion, skin care cream, foundation milk, massage milk, cleansing milk, cleansing cream, cleansing foam, lotion, lotion, Face cream, lipstick, blush, eye shadow, nail polish, soap, bath milk, hand lotion, shampoo, conditioner, shampoo, deep-care hair cream, hair cream, hair spray, hair conditioner, hair conditioner, hair dye Agents, hair conditioners, hair removal agents, antidandruff agents, toothpastes, denture adhesives, mouthwashes, perm agents, hair curlers, styling agents, ointments, patches, tapes, bath agents®, antiperspirants , Sunscreen, etc., a wide range, only any kind that comes into contact with the skin during use. Especially when used as a cosmetic. It has nothing to do with the gender and age of the user. Contains skin contact with animals other than humans. Examples of the shape of the present invention include solids, liquids, semi-solids, and gases, and powders, granules, tablets, gels, Most types such as foam. The skin external preparation of the present invention may contain components other than the multi-branched polysaccharide derivative and / or the multi-branched polysaccharide derivative, and if necessary, components added to the skin external preparation may be added within a range that does not impair the effects of the present invention. ^ Compounds that can be added to cosmetics, compounds that are used as raw materials for pharmaceutical products, pharmaceuticals, pharmaceutical additives, etc. Specific examples of such a component include, for example, Ozocerite, α-olefin oligomer, light isoparaffin, light flowing isoparaffin, triacontene, triacontane, synthetic triacontane, plant-based trisene Decane, ceresin, paraffin, polyethylene powder, polybutane, microcrystalline wax, flowing isoparaffin, flowing paraffin, mineral oil, petroleum jelly and other hydrocarbons; -13- 200533383 (10) Jojoba oil, Carnauba oil, candelilla wax, rice bran wax, shellac, lanolin, mink fat wax, whale wax, sugarcane wax, sperm whale oil, honey wax, montan wax and other natural waxes, avocado oil, almond oil, olives Oil, OLIO EXTRAVERGINE DI Ο LIV A, sesame oil, rice bran oil, rice oil, rice germ oil, corn oil, safflower oil, soybean oil, maize oil, rapeseed oil, apricot kernel oil, palm kernel oil, palm oil,. Castor oil, sunflower oil, high-fat sunflower oil, grape seed oil, cottonseed oil, coconut oil, hydrogenated coconut oil, tallow, B hardened oil, horse oil, mink oil, egg butter, egg yolk fatty oil, rose fruit, Kukui Nuts, Evening Primrose Oil, Wheat Germ Oil, Groundnut Oil, Tsubaki oil,; Camellia oil, cocoa butter, clogs, beef bone fat, tallow oil, lard, horse fat, sheep fat, shea butter, accademianut, medohome oil and other natural oils; lauric acid, nutmeg Acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, r-linolenic acid, isostearic acid, 12-hydroxystearic acid, undecylenic acid, coconut oil fatty acids And other fatty acids; • Isostearyl alcohol, octyldodecanol, hexyldodecanol, cholesterol, phytosterol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol ', behenyl alcohol Higher alcohols such as alcohol and cetylstearyl alcohol; Alkyl glyceryl ethers such as sharkol, cetyl alcohol, shallow alcohol, isostearyl glyceryl ether; isopropyl myristate, butyl myristate, Isopropyl palmitate, Ethyl hard vinegar, Ethyl butyl vinegar, Ethyl oleate, Ethyl linoleate, Isopropyl linoleate, Cetyl caprylate, Hexyl laurate, Nutmeg Isooctyl acid, decyl myristate, myristyl myristate, cetyl myristate, -14- 200533383 (11) nutmeg Octadecyl ester, cetyl palmitate, stearyl stearate, decyl ester, oleic oils and fats, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, myristic acid Isocetyl ester, Isostearic myristate, Octyldodecyl myristate, 2-Ethylhexyl palmitate, Cetyl palmitate, Isostearyl palmitate, 2-Ethylhexyl stearate , Stearyl stearyl, isodecyl oleate, octyldodecyl oleate, octyl ricinoleate, ethyl isostearate, isopropyl isostearate, 2-ethylhexyl ester , Cetyl stearyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, hexyl stearate, ethylene glycol dicaprylate, ethylene glycol dioleate, propyl dicaprylate, di (decanoyl) • Decanoic acid) propylene glycol, decane propylene glycol, dioleyl glycol, neopentyl glycol didecanoate, neopentyl glycol dioctanoate, glyceryl trioctanoate, glyceryl tri-2-ethylhexanoate, tris (decanoyl) • Decanoic acid) Glycerin, Decanoyl • Decanoic acid • Stearic acid) Glycerin, Glyceryl succinic acid, Glyceryl palmitate, Glyceryl triisostearate, Tris 2-ethylhexanoate triylpropane Trimethylol triisostearate Propane, quaternary 2-ethylhexanoate, pentaerythritol tetramyristate, pentaerythritol tetraisostearate, diglyceryl tetraglyceride, octyldodecyl pivalate, isooctanoate Cetyl wax, isostearyl, 2-ethylhexyl isononanoate, hexyldecyl dimethyl octanoate, octyldodecyl methyl octanoate, 2-ethylhexyl isopalmitate, isostearyl cetyl wax Esters, isostearyl isostearate, octyldodecane laurate, lauryl lactate, myristyl lactate, lactate lactate, lactate myristate, cetyl lactate, octyl dodecyl lactate , Triethyl citrate, Ethyl triethyl citrate, Ethyl tributyl citrate, Trioctyl citrate, Triisocetyl citrate, Trioctyl dodecyl citrate, Malate oleic acid Myristyl acid isoisanodecanoate cetyl isostearate propyl trioleate (triisomethylpentanetetraisosuccinate), myristyl lemon ester, diiso-15-200533383 (12) hard Fatty ester, 2-ethylhexyl hydroxystearate, di2-ethylhexyl succinate, diisopropyl adipate, diisobutyl adipate, dioctyl adipate, adipic acid Heptyl undecyl ester, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, cholesterate stearate, cholester isostearate, choline hydroxystearate Esters, cholester oleate, dihydroxy cholester oleate, phytosteryl isostearate, phytosteryl oleate, 1 2-stearylhydroxystearate isostearate, 12-stearate Ethyl hydroxystearate, 12-stearyl hydroxystearate isostearyl stearate, polyethylene oxide acetate (3), polypropylene oxide (1) cetyl ether, polyacetate acetate Ethane (3) polypropylene oxide (1) isocetyl ether, isononyl isononanoate, octyl isononanoate, tridecyl isononanoate, isotridecyl isononanoate, etc .; Methyl polysiloxane, methyl phenyl polysiloxane, methyl hydrogen polysiloxane, methyl cyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Dodecylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecylhexasiloxane, highly polymerized methylpolysiloxane, dimethylφsiloxane • Methyl (polyethylene oxide) Siloxane • Methyl (polypropylene oxide) Oxyalkylene copolymer, dimethylsiloxane • methyl (polyethylene oxide) silicon-oxyalkylene copolymer, dimethylsiloxane • methyl (polypropylene oxide) siloxane copolymer, two Methylsiloxane • Methylcetyloxysiloxane copolymer, dimethylsiloxane • methylstearyloxysiloxane copolymer, polyether modified polysiloxane, alcohol modified polysiloxane Siloxane, alkyl-modified polysiloxane, amine-modified polysiloxane and other polysiloxane oils; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polysiloxane Propylene glycol, pentyl glycol, glycerin, diglycerin, polyglycerin, -16-

200533383 (13) isoprene ethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol butanediol, 1,2-pentanediol, 1,2-hexanediene Polyols such as alcohols; mannitol, sorbitol, xylitol, maltitol, erythritol, glucose, sucrose, fructose, lactose, maltose, trehalose and other sugars; sodium arginine, carrageenan, agar , Dictyostelium polysaccharide preparation, Guan, PYRUS CYDONIA SEED, inulin mannose, tamarind gum, tung gum, dextrin, starch, locust bean gum, acacia gum, Gum gum, arabinogalactin, pectin, Papaya, chitosan, gelatine, gellan, cyclodextrin, dextran, amylopectin, microboxin, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, Propyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose powder, cationized cellulose, phosphate powder, cationized gum, carboxymethyl · hydroxypropylated guanhua bean gum, Hydroxypropylated II gum, albumin, casein, gelatin, sodium polyacrylate, polyacrylic acid, carboxy vinyl polymer, Polyethyleneimine, high-polymer polyethylene_vinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, polypropylene amidamine, acid copolymer, methacrylic acid copolymer, maleic acid copolymer, acetamidine copolymer, ethylene / Acrylic acid copolymer, vinylpyrrolidone, vinyl alcohol / vinylpyrrolidone copolymer, nitrogen-substituted propylene-based polymer, amine-modified silicone, cationized polymer, dimethenyl ammonia Based polymers, acrylic anionic polymers, methyl propylene welded anionic polymers, modified siloxanes, acrylic methacrylic acid (ClOOO) copolymers, polyethylene oxide / polypropylene oxide copolymers, etc .: 1,3- ^ alcohol, sugar, dung bean gum, sugar, 7 sugar, crystalline cellulose, hydroxyl, carboxyl, 3 Chinese bean, Chinese bean, amine, polypropylene, propylpyridine: polymerized, amine, 3 propyl carboxylic acid Department: Base (1 inning • 17- 200533383 (14) subclass; ethanol, isopropanol, 1-butanol coconut oil fatty acid potassium, coconut ethanolamine, potassium laurate, lauric acid < potassium acid, sodium myristate , Nutmeg. Sodium, isopropanolamine palmitate, stearylamine, potassium oleate, Sodium, zinc, zinc laurate, zinc myristate, zinc stearate, calcium stearate, magnesium myristate stearate, aluminum myristate dilaurate, polyethylene oxide lauryl acetate, poly Cyclotridecyl ether sodium stearyl lactate, lauryl acid, coconut fatty acid sodium sarcosinate, lauryl sarcosinate, laurel 醯 triethanolamine, oleyl sarcosinate, glutamine Sodium, coconut oil fatty acid potassium potassium glutamate, coconut oil fatty acid glutamyl triethanolamine, potassium lauryl glutamate, potassium lauryl glutamyl triethanolamine, potassium myristyl glutamate, meat Alcohols such as cardamomyl gluten, stearyl glutamyl glutamate, sodium tallow fatty acid glutamyl glutamate, 2 • butanol, benzyl alcohol, etc .; oil fatty acid sodium, coconut oil fatty acid trisodium, laurel Triethanolamine, isopropylamine myristate, potassium palmitate, potassium palmitate, sodium stearate, sodium triricinoleate fatty acid, undecylenic acid, magnesium myristate, zinc palmitate, Magnesium stearate, aluminum stearate, calcium myristate, aluminum isostearate, polyepoxide Sodium Alkyl Ether Acetate, Sodium Polyethylene Oxide Tridecane Acetate, Sodium Stearoyl Lactate, Sodium Isosinate, Coconut Oil Fatty Acid Inosamine, Coconut Oil Fatty Acid Inosine Ethylamine Inosinate Potassium, Laurel Sarcosinate sodium myristate sarcosinate, stearyl glutamate, coconut oil fatty acid glutamate sodium, coconut oil fatty acid glutamyl glutamate, lauryl glutamate Sodium, lauryl fluorenyl glutamic acid, sodium myristyl fluorenyl glutamic acid, sodium stearyl fluorenyl glutamic acid disodium stearyl glutamic acid, hard, coconut Oil fatty acid • hardened tallow 18- 200533383 (15) Sodium fatty acid glutamate, coconut oil fatty acid sodium methionine, lauryl methionine, lauryl methionine sodium, lauric acid Trimethylamine, trimethylamine, sodium myristylmethylpropionate, sodium laurylmethyltaurine, potassium coconut fatty acid potassium potassium taurine, coconut fatty acid sodium methyltaurate, coconut oil Fatty acid methylmagnesium taurine, myristyl methyl sodium taurate, palmitate Sodium taurate, sodium stearyl methyltaurate, sodium oleylmethyltaurine, sodium chain sulfonate, sodium tetradecene sulfonate, sodium dioctyl sulfosuccinate , Disodium lauryl sulfosuccinate, sodium sodium succinate of coconut oil fatty acid, sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, triethanolamine alkyl (1, 13, 15, 15) sulfate , Alkyl (12,1 3) sodium sulfate, courtyard (12, 1 3) triethanolamine sulfate, courtyard (12, 1, 4, 16) ammonium sulfate, alkyl (12 to 1 3) Diethanolamine sulfate, alkyl (12 to 14) triethanolamine sulfate, alkyl (12 to 1 5) triethanolamine sulfate, coconut oil alkyl magnesium sulfate triethanolamine, ammonium lauryl sulfate, potassium lauryl sulfate, Magnesium lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, sodium myristyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, triethanolamine oleyl sulfate, polyethylene lauryl sulfate sodium sulfate, Polyethylene oxide lauryl ether triethanolamine, polyethylene oxide (1) alkyl (1, 1 3, 15) sodium sulfate, polyepoxide Alkane (1) alkyl (1 1, 1 3, .1 5) -etherethanolamine, polyethylene oxide (3) alkyl (1 1 to 1 5) sodium sulfate ether, polyethylene oxide (2) Alkyl (12,1 3) sodium ether sulfate, polyethylene oxide. (3) Alkyl (1 2 to 1 4) sodium ether sulfate, polyethylene (3) alkyl (1 2 to 1 5) sodium ether sulfate, polyethylene oxide (2) sodium lauryl ether sulfate, polyethylene oxide (3) sodium myristyl ether sulfate, higher fatty acid alkanolamine sulfide-19-200533383 (16) Sodium, Lauryl Phosphate, Sodium Lauryl Phosphate, Potassium Cetyl Phosphate, Diethanolamine Cetyl Phosphate, Poly (ethylene oxide oleyl ether phosphate), Poly (ethylene oxide lauryl ether phosphate), Poly (ethylene oxide lauryl ether sodium), Poly Ethylene oxide cetyl ether phosphate, polyethylene oxide cetyl ether sodium phosphate, polyethylene oxide stearyl ether phosphate, polyethylene oxide oleyl ether phosphate, polyethylene oxide oleyl ether phosphate , Polyethylene oxide alkyl phenyl ether phosphate, polyethylene oxide alkyl phenyl ether sodium phosphate, polyethylene oxide alkyl phenyl ether phosphate triethanolamine, polyethylene oxide octyl ether phosphate, poly Ethylene oxide (10) alkyl (12,13) ether phosphorus Polyethylene oxide alkyl (12 ~ 15) ether phosphoric acid, Polyethylene oxide alkyl (12 ~ 16) ether phosphoric acid, Polyethylene oxide lauryl ether phosphate triethanolamine, Polyethylene oxide oleyl ether Anionic surfactants such as diethanolamine phosphate; dioctylamine, dimethylstearylamine, trilaurylamine, diethylamine ethyl stearate, lauryl trimethylammonium chloride, cetyl chloride Methylammonium, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, stearyl trimethylammonium chloride, alkyl (20 ~ 22) trimethylammonium chloride, lauryl bromide Methylammonium, alkyl (16,18) trimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, chloride Di (polyethylene oxide) oleyl methyl ammonium (2EO), dipolyethylene oxide stearyl methyl ammonium chloride, polyethylene oxide (1) polypropylene oxide (25) Diethyl methyl ammonium, tris (polyethylene oxide) stearyl ammonium (5 EO), distearyl dimethyl ammonium chloride, dialkyl (12 ~ 15) dimethyl Ammonium, dialkyl chloride (12 ~ 18) dimethyl ammonium, dialkyl chloride ( 14 ~ 18) Dimethylcopper, monococoyl monomethylcopper chloride, dipicolinyl dimethyl ammonium chloride, isostearyl lauryl dimethyl ammonium chloride, benzyl ammonium chloride,- 20- 200533383 (17) Myristyl dimethyl benzyl ammonium chloride, lauryl dimethyl (ethyl benzyl) ammonium chloride, stearyl dimethyl benzyl ammonium chloride, lauryl chloride Pyridyl motif, lauryl cholylmethanemethylpyridine methylpyridine gun, stearyl chloromethylene cholinemethanemethylpyridine iron pyridinium chloride, alkyl bromide isoquinoline gun, methyl benzyl chloride Cationic surfactants such as chlorinated benzyl chloride; 2-alkyl-N-carboxymethylhydroxyethylimidazolium betaine, hydrochloric acid

Alkyldiaminoethylglycine, sodium lauryldiaminoethylglycine, undecylhydroxyethylimidazolium betaine sodium, undecyl-N-carboxymethylimidazole iron betaine , Coconut oil fatty acid fluorenyl-N-carboxyethyl-N-hydroxyethyl ethylenediamine disodium, coconut oil fatty acid fluorenyl-N-carboxyethyloxyethyl-N-carboxyethyl ethylenediamine disodium, Coconut oil fatty acid fluorenyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine disodium, sodium laurylaminopropionate, sodium laurylaminodipropionate, laurylaminopropionate Ethanolamine, palm oil fatty acid fluorenyl-N-carboxyethyl-N-hydroxyethyl ethylenediamine, lauryldimethylaminoacetic acid betaine, coconut oil alkyldimethylamine betaine, stearyl Dimethylaminoacetic acid betaine, stearyl dimethylbetaine sodium, coconut oil fatty acid aminopropyl betaine, palm oil fatty acid aminopropyl betaine, lauric acid aminopropyl betaine, castor Amphoteric surfactants such as ammonium aminopropyl betaine, stearyl dihydroxyethyl betaine, lauryl hydroxysulfobetaine; polyepoxide Ethane (10) alkyl 12,13) ether, polyethylene oxide lauryl ether, polyethylene oxide cetyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, polycyclic Ethylene oxide (3,7,12) alkyl (12-14) ether, polyethylene oxide tridecyl ether, polyethylene oxide myristyl ether, polyethylene oxide _ -21-200533383 (18 ) Second alkyl (1 4) ether, polyethylene oxide isocetyl ether, water ethylene oxide cetyl stearyl ether, polyethylene oxide (2,1G, 2〇) isohardenary ether , Polyethylene oxide oil-based cetyl ether, polyethylene oxide (20) alkyl ether, polyethylene oxide octyl dodecyl ether, polyethylene oxide behenyl ether, polyethylene oxide Alkyl octylphenyl charm, polyethylene oxide nonylphenyl ether, polyethylene oxide dinonylphenyl ether, polyethylene oxide (1) polypropylene oxide (丨, 2, 4, 8 ) Contact hunting brewing, polyethylene oxide (5) propylene oxide (1,2,4,8) whale brewing, polyethylene oxide 10) polypropylene oxide (1,2,4,8) Cetyl ether, polyethylene oxide (20), polypropylene oxide (1,2,4,8) cetyl ether, polyethylene oxide polypropylene oxide lauryl ether, polyethylene oxide (3) Polypropylene oxide (3 4) Stearin, Polyethylene oxide (4) Polypropylene oxide (30) Stearyl ether, Polyethylene oxide Polypropylene oxide (23) Stearyl ether, Polyethylene oxide Polypropylene oxide building Waxy acid, polyethylene oxide polypropylene oxide decyl tetradecyl ether, polyethylene monolaurate ~ alcohol, ethylene glycol monostearate, polyethylene glycol monostearate, polyethylene glycol monooleate Alcohols, glycol fatty acid esters, self-emulsifying ethylene glycol monostearate, lauric acid diethylene glycol, myristic acid polyethylene glycol, palmitic acid polyethylene glycol, diethylene glycol stearate, Self-emulsifying polyethylene glycol monostearate (2) isostearic acid polyethylene glycol, dioctanoic acid ethylene glycol, dilauric acid diethylene glycol, dilauric acid polyethylene glycol, dipalmitic acid polyethylene Diol (15 0), ethylene glycol distearate, diethylene glycol distearate, polyethylene glycol distearate, ethylene glycol dioleate, polyethylene glycol dioleate, castor Acid polyethylene glycol, monolauric acid polyethylene oxide (20) sorbitan anhydride, monopalmitic acid polyethylene oxide (20) sorbitan anhydride, monostearic acid polyethylene oxide (6) Sorbitol anhydride, polyethylene monostearate (20) Sugar alcohol anhydride, polyethylene glycol tristearate (20) Sorbose-22- 200533383 (19) Alcohol anhydride, polyethylene glycol monooleate (6) Sorbitol anhydride, polyethylene glycol monooleate Ethane (20) sorbitol anhydride, trioleic polyethylene oxide (20) sorbitol anhydride, polyethylene oxide (20) coconut oil fatty acid sorbitan anhydride, monolauric polyethylene oxide (1〇 ~ 80) Sorbitol anhydride, tristearic acid polycyclic ring 'oxyethane sorbitan, isostearic acid polyethylene oxide (20) sorbitol. Anhydride, tristearic acid polycyclic ring Ethylene oxide (150) sorbitan, polyethylene oxide castor oil, polyethylene oxide hardened castor oil, polyethylene oxide (10) hard φ castor oil, polyethylene oxide (2 0) hardened castor oil, polyethylene oxide (40) hardened castor oil, polyethylene oxide (50) hardened castor oil, polyethylene oxide (60) hardened castor oil, lipophilic monostearate, Lipophilic monoolein, glycerol monostearate, coconut oil fatty acid glycerin, glyceryl laurate, glyceryl myristate, glyceryl isostearate, glyceryl ricinoleate, monohydroxystearate Glyceride, Glyceryl oleate, Glyceryl linoleate, Glyceryl erucate, Glyceryl behenate, Glycerol fatty acid in wheat germ oil, Glyceryl fatty acid in safflower oil, Glyceride in hydrogenated soybean fatty acid, Saturated glyceride , Cottonseed oil fatty acid glyceride, monoisostearic acid monomyristic acid glyceride, mono-tallow fatty acid glyceride, mono-water wool fatty acid glycerol ester, glyceryl semi-oleate, glyceryl distearate, Glyceryl isostearate, Glyceryl diarachidate, Sorbitan monolaurate, Sorbitan monopalmitate, Sorbitan monostearate, Sorbitan monoisostearate, Monooleate Sorbitan, sorbitan sesquistearate, sorbitan sesquioleate, sorbitan tristearate, sorbitan trioleate, sorbitan coconut fatty acid, Sorbitan isostearate, Sorbitan sesquiisostearate, Sorbitan distearate, Di palmitate di-23- 200533383 (20) Glyceryl ester, polylaurate (4 ~ 10) Glyceride, monomyristic acid poly (1 0) glyceride, monohard Poly (2 ~ 1 0) glyceryl fatty acid, Poly (2 ~ 1 0) glyceryl monoisostearate, Poly (2 ~ 1 0) glyceryl monooleate, Diglyceryl sesquioleate, Diiso Poly (2 ~ 10) stearic acid glyceride, Poly (6 ~ 10) glyceryl distearate, diglyceryl triisostearate, poly (1 0) glyceryl tristearate, tri-oil Acid poly (10) glyceride, tetraisostearic acid poly (2) glyceride, decaglyceryl pentastearate, poly (6 ~ 10) glyceryl pentaoleate, poly (10) heptastearate Glyceryl esters, Decaglyceryl decatearate, Poly (10) glyceryl oleate, Poly (6) glyceryl ricinoleate, Sucrose fatty acid esters, Coconut oil fatty acid sucrose esters, Alkyl glucosides, Coconut oil Alkyl dimethyl amination oxygen, lauryl dimethyl amination oxygen, dihydroxyethyl lauryl dimethyl amination oxygen, stearyl dimethyl amination oxygen, oleyl dimethyl amination oxygen, Polyethylene oxide coconut oil alkyl dimethyl aminated oxygen and other non-ionic surfactants; saponin, lecithin, soybean phosphate, hydrogenated soybean phospholipid, ugly Ugly Lipid, Yolk Phosphatidylcholine, yolk-soluble phospholipids, choline, phospholipids, choline, phospholipids, ethanolamine, phospholipids, serine, sphingomyelin, sphingomyelin, bile acid, bile acid, deoxycholic acid, sodium cholate, deoxygenate Sodium cholate, penicillium sporinic acid, rhamnolipid, trehalolipid, rosettolipid, mannitol erythritol and other natural surfactants; p-amine benzoic acid, p-amine benzoic acid ethyl ester, p-amine benzoic acid Glyceryl ester, amyl p-dihexylamine benzoate, 2-ethylhexyl p-dimethylamine benzoate, p-amine benzoic acid derivatives, benzyl cinnamate, di-p-methoxycinnamic acid mono-2 -Ethylhexanoic acid glyceride, 2,4-diisopropyl cinnamate methyl-24.200533383 (21) ester, ethyl 2,4-diisopropyl laurate, sodium p-methoxycinnamate , Cinnamic acid derivatives such as isopropyl p-methoxycinnamate, p-ethylhexyl, ethyl 2-ethoxyethyl p-methoxycinnamate, uric acid, urinary derivatives, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-, 2-hydroxy-4-methoxy-5-sulfobis.benzophenone sodium ,: benzophenone-5 -Sulfonic acid, 2-hydroxy-4-methoxy Benzophenone derivatives such as sodium diphenyl_4,4'-dimethoxybenzophenone, 2,2'-dihydroxy 5-sulfobenzophenone sodium, and 2-ethylsalicylic acid Salicylic acid derivatives such as methylhexyl ester, phenyl salicylate, benzene tertiary butyl salicylate, salicylic acid memthyl, salicylcyclohexyl ester, 2- (2 '· hydroxy-5'- Benzotriazole, 4-tert-butyl-4'-methoxybenzidine-based absorbent; clay, silicic anhydride, aluminum magnesium silicate, sericite, mica, montmorillonite, hemp fiber powder, wheat starch , Starch, nitro-based pigments, azo-based pigments, nitrosomethane-based pigments, tonone dichloride-based pigments, quinoline pigments, Yuqing-based pigments, garden-based pigments, cyanine-based chromones, porphyrin, water-soluble Natural rouge orange red, squid ink powder Ruoyun, gardenia blue pigment, gardenia yellow pigment, cochineal copper chlorophyll sodium, red pepper pigment, safflower pigment, safflower, riboflavin butyrate and other natural pigments, carbon black, yellow oxygen , Red iron, turquoise, ultramarine, zinc oxide, chromium oxide, potassium percutaneous acid, p-methoxymethoxycinnamic acid 2 _, ethyl p-ethoxycinnamic acid, tetrahydroxydi Methyl_ 2-hydroxy-en-methoxymethoxy ketone, 2,2'-Dijing-4,4'-dimethoxy_ ethylene glycol, salicylic acid, salicylic acid para-3,3 , 5-trimethylmethoxyphenyl) benzenemethane and other ultraviolet talc, boron nitride, silk powder, corn-based pigment, diphenyl-based pigment, anthraquinone, flavonoid, benzene powder, caramel , Ancient red pigment, purple root, yellow pigment, shellac iron, black iron oxide titanium oxide, black oxide -25- 200533383 (22) 钹, oxide pin, chromium hydroxide, magnesium oxide, vanadium sulfate, hydroxide, Powders such as calcium carbonate, lithium cobalt titanate, manganese violet, pearl white pigment, and white peony; Mingyue leaf extract, Axen extract, avocado extract, sweet tea extract, Gynostemma pentaphyllum extract, Hollyhock Extract, Arnica Extract, Oil-soluble Arnica Extract, Almond Extract, Aloe Vera Extract, Benzoin Extract, Ginkgo Extract, Biting Cat Extract, Pansy Root Extract, Fennel Extract, Turmeric Extract, Campsis Extract, Echinacea Extract, Golden Flower Extract, Cork Extract, Pistacia Extract , Large extract, okra extract, dichotomy extract, oil-soluble dichotomy extract, prickly thorn flower extract, dutch mustard extract, orange extract, orange flower water, seaweed extract, persimmon tannin, kudzu root extract , Devil's extract, chamomile extract, chamomile extract, oil-soluble chamomile extract, chamomile water, wild oat extract, carrot extract, oil-soluble carrot extract, carrot oil, wormwood extract, licorice extract , Licorice extract powder, oil-soluble licorice, canola iodine, raspberry extract, kiwi fruit extract, quinine extract, gherkin extract, almond extract, PYRUS CYDONIA SEED extract, gardenia extract, coriander Extract, Sophora flavescens extract, walnut shell extract, grapefruit extract, licorice extract, black sugar extract, green algae extract, mulberry extract, cinnamon extract, gentian extract, bovine flat extract , Black tea extract, lotus flower extract, burdock extract, oil-soluble burdock extract, wheat germ extract, hydrolyzed wheat powder, Bran extract, rice bran fermentation extract, fin glass extract, asarum extract, saffron extract, yellow eye extract, oil-soluble wickerwort extract, hawthorn seed extract, mountain pepper extract, shiitake mushroom extract Extract, fragrant -26- 200533383 (23) mushroom extract powder, rehmannia extract, purple root extract, oil-soluble purple root extract, perilla extract, alder extract, oil-soluble alder extract, lower wild grass extract Peony extract, peony extract, ginger extract, oil-soluble ginger extract, ginger tincture, calamus root extract, birch extract, '' oil-soluble birch extract, birch sap, suction kudzu extract, cedar extract Extracts, oil-soluble heliotrope extract, garlic extract, stevia extract, western wood clam extract, western hawthorn seed extract, western elderberry extract, western juniper extract φ extract, western sawgrass extract, oil-soluble western Sawgrass Extract, Western Mint Extract, Mountain Artemisia Extract, Oil Soluble Mountain Artemisia Extract, Mountain Artemisia Water, Golden Sunflower Extract, Celery Extract, Chuanxiong Extract, Chuanxiong Water, Fangs Extract, Soy Extract, Jujube Extract, Thyme Extract, Tea Extract, Tea Distillate, Tea Seed Extract, Clove Extract, Citrus Root Extract, Tsubaki Extract, Tripterygium Root Extract, Oil Soluble Hand Walnut Extract, Duke extract, mangrove extract, capsicum tincture, angelica extract, oil-soluble angelica extract, angelica water, tang marigold extract, oil-soluble tang marigold extractφ extract, soybean milk wood, peach kernel extract, Scallion extract, Houttuynia cordata extract, tomato extract, silver plum extract, natto extract, carrot extract * extract, oil-soluble carrot extract, garlic extract, rose extract, oil, soluble rose Extract, malt extract, malt root extract, malt extract, celery extract, rye leaf juice concentrate, distilled mint water, witch hazel water, witch hazel extract, rose extract, Zinnia chrysanthemum extract, sassafras tea extract, coriander leaf extract, oil-soluble coriander leaf extract, taraxacum extract, Poria cocos extract, fake leaf tree extract, fake leaf tree extract Powder, grape extract, grape leaf extract, grape water, wood grass extract -27-

200533383 (24) extract, loofah extract, loofah water, safflower extract, lime tree water, peony extract, hop extract, pine tree extract, milk thistle extract, soluble horse chestnut extract, wood seed extract , Bee extract, peach leaf extract, oil-soluble peach leaf extract, turquoise hibiscus extract, turquoise hibiscus water, eucalyptus extract, lily extract, coix kernel extract, oil-soluble wormwood extract, variegated wormwood water, Lavender extract fruit extract, lychee extract, lettuce extract, grass extract, rose water, rosemary extract, oil, chamomile extract, myocardial extract and other plants such as glycine, alanine, valine, Leucine, threonine, phenylalanine, tyrosine, tryptophan, methionine, proline, hydroxyproline, glutamine, glutamine, glutamine , R-aminobutyric acid, DL-pyrrolidone carboxylic acid, ε-sexin, water-soluble elastin, hydrolyzed collagen, water-soluble glutathione, wheat peptide, soybean peptide and other amino acid rosin oil, rosin aldehyde, rosin acid, Vitamins such as pine oil Class A, α-carotene, β-carotene, δ-carotene, lycopene, zearalenone, chlorococcus and other carotene, vitamin B2 such as thiamine and riboflavin, vitamin B6 and other vitamins Β6, cobalamin B 1 2 and other vitamins, oil-soluble lime tree extract, oil-soluble hops extract, oil leaf extract, alfalfa, bean sprout extract, extract, saxifraga extract garlic Extract, variegated leaf, lavender water, apple lemon extract, lotus flower soluble rosemary extract extract;, isoamidine acid, serine tamine, cystine, half :, aspartic acid , Aspartic acid, lysine, aminocaproic acid, hydrolyzed bomb: sex collagen, casein, and peptides;-sesame oil, palmitic rosin;-carotene, r-lutein, cryptoxanthin, Sea-based vitamins B-1, acetaldehyde, acetamide B12, folic acid, -28- 200533383 (25) Nicotinic acid, nicotinamide, vitamin B5 acids, biotins, L-ascorbic acid, L-sodium ascorbate, L stearic acid L · ascorbate, palmitate L-ascorbate, dipalmitate L- Ascorbate, tetraisopalmitic acid L-ascorbate, L-ascorbyl sulfate disodium, L-ascorbate, phosphoric acid L-ascorbate, L-ascorbate-2-glucoside, L-ascorbate-2- Vitamins such as magnesium phosphate, keratocalciferol, vitamin D3 and other vitamins D, d-α-tocopherol, DL-α-tocopheryl alcohol, dl-α · tocopheryl acetate, succinic acid (dl-α -Tocopherol, 0-tocopherol, r-tocopherol, d-δ-tocopherol and other vitamins E, enzymes, vitamins K, carnitine, ferulic acid, T-olicosate, α-lipoic acid Vitamins such as lactate and lactate, and factors that act like vitamins; · Benzoic acid, sodium benzoate, undecylenic acid, salicylic acid, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, Isobutyl benzoate, isopropyl p-benzoate, ethyl p-benzoate, butyl p-benzoate, propyl p-benzoate, hexyl p-benzoate, p-methyl benzoate , Methyl sodium paraben, phenoxyethanol, photosensitizer 101, photosensitizer 201, photosensitizer 401, etc. Antioxidants such as butylhydroxyhydroxyanisole, butylhydroxytoluene, propyl gallate, sorbic acid, sodium sorbate, p-hydroxyanisole, octyl gallate, etc .; ethylenediamine hydroxyethyl triacetate, Metal ion blocking agents such as edetic acid, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, gluconic acid, phytic acid, sodium polyphosphate, and sodium methyl phosphate; hyaluronic acid , Sodium hyaluronate, sodium chondroitin sulfate, sodium lactate, mouth ratio -29- 200533383 (26) sodium rolidone carboxylate, betaine, lactic acid bacteria culture solution, yeast extract, neural crestamine and other humectants; glycyrrhizic acid Anti-inflammatory agents such as trisodium glycyrrhizinate, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, / 3-glycyrrhizinic acid, glyceryl glycyrrhizinate, stearyl glycyrrhizinate, chlorinated lysozyme, Hydrocortisone, allantoin, etc. PH adjusters such as sodium, potassium hydroxide, triethanolamine; salts such as sodium chloride, potassium chloride, magnesium chloride, sodium sulfate; α-hydroxy acids such as citric acid, oxalic acid, tartaric acid, and lactic acid; 'arbutin , Α-arbutin, placenta and other whitening agents; White coriander oil, perfume tree oil, olive oil, orange oil, dayflower oil, romania oil, safflower oil, calamus oil, white rosin oil, camphor oil, carrot seed oil, sage oil, grapefruit oil, willow oil , Cinnamon oil, emu oil, cypress oil, sandalwood oil, Atlantic cedar oil, citronella oil, ceylon cinnamon oil, jasmine oil, jenny bar oil, ginger extract, spearmint oil, sage oil, cedar oil, Geranium oil, thyme oil, tea tree oil, nutmeg oil, sage oil, pure essential oil of neroli, paen oil, basil oil, peppermint oil, patchouli oil, rose grass oil, cumin oil, bitter orange leaf oil , Black pepper oil, frankincense oil, vetivene oil, peppermint oil, bee peppermint oil, benzoin essential oil, rosewood oil, marjoram oil, citrus oil, myrrh oil, balsam leaf oil, eucalyptus oil, grapefruit oil, lime Essential oils such as oil, rossandra oil, provence lavender oil, lavender oil, linden oil, lemon oil, lemon glass oil, rose oil, rosewood oil, rosemary oil, angelica oil, etc .; lemon olein, pine leaf oil, pine Oleyl alcohol Fragrant resins, myrcene, longifealene etc. Terpene type; -30-200533383 (27) Perfume, water and the like. In addition, the skin external preparation of the present invention can be added with a known concentration of a known cosmetic raw material, for example, a comment on the second edition of the Cosmetic Raw Material Standard, the Japanese Official Book of the Church, 1984 (Pharmacy Daily), and a cosmetic raw material can be used. Standards for external ingredient specifications, Inspection and Supervision of the Pharmaceutical Affairs Bureau of the Ministry of Health and Welfare, 1 993 (Pharmaceutical Daily News Agency), Supplementary Standards for External Ingredient Specifications for Cosmetics Raw Materials, Inspection and Supervision of the Inspection Division of the Pharmaceutical Affairs Bureau of the Ministry of Health, 193 (Pharmaceutical Daily News Agency), Cosmetics Criteria for species approval, Supervision of the Inspection Division of the Pharmaceutical Affairs Bureau of the Ministry of Health and Welfare, 1 993 (Pharmaceutical Daily News Agency), Specifications of ingredients for cosmetic types, Inspection of the Inspection Division of the Pharmaceutical Affairs Bureau of the Ministry of Health and Welfare, 197 9 (Pharmaceutics Daily News Agency), Cosmetic Raw Materials Dictionary · All cosmetic raw materials listed in Heisei 3 (Nikko Chemicals) and New Cosmetic Functional Materials 300, 2002 (published by CMC). Best Mode for Carrying Out the Invention The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. [Embodiment] Example 1 In a nitrogen atmosphere, a fully dried Schlenk tube was put into a 1,6-dehydration-factory_D-grape pyranose (manufactured by Tokyo Chemical Industry Co., Ltd., 13.0 g), Dry propylene carbonate (manufactured by Aludoliki, 1 2 · 5 m 1) and 66% by mass of 2-butenyl tetramethylsulfonyl hexafluoroantimonate (Asahi Chemical Industry Co., Ltd.) System, 6 5 · 8 // 1). The Schlenk tube was immersed in an oil bath, and the oil-31-200533383 (28) bath was heated to 1 ο 0 ° C 'to fully dissolve the 1,6-dehydrated-yS-D-glucopyranose, and then heated up. To 130 ° C, polymerization was started with sufficient stirring. After 30 minutes of reaction, the polymerization solution was poured into methanol to stop the polymerization. After distilling off the solvent, it was repeatedly reprecipitated with water and methanol, and purified by dialysis. After freeze-drying, a multi-branched polysaccharide A (5.3 g) was obtained as a white powder. The yield was 41%. The structure of this multi-branched polysaccharide A was confirmed by 1H-NHR and 13C-NMR. The weight average molecular weight was 20,000 (astigmatism method), and the degree of branching was 0.38. Example 2 A lotion as shown in Table 1 was produced by a conventional method. This was used by 10 women aged 20 to 30. Table 2 shows the impression after 1 hour of application and humidity of 20%. As a result, when the sample 1 -1 containing the multi-branched polysaccharide A obtained in Example 1 was used, a moisturizing feeling was maintained after coating and after drying, and a tight feeling was not generated after drying. -32- 200533383 (29)

Sample 1-1 1-2 1-3 Multi-branched polysaccharide A 0.50%--Glycogen-0.50% 1,3-butanediol 5.00% 5.00% 5.00% ethanol 5.00% 5.00% 5.00% citric acid 0.01% 0.01% 0.01 % Sodium citrate 1.00% 1.00% 1.00% Methyl Paraben 0.20% 0.20% 0.20% Pure water 8 8.29% 8 8.29% 8 8.79% 1 0 0.00% 1 0 0.00% 1 0 0.00%

Sample 1 -1 1-2 1-3 Moisturizing feeling after coating 9 8 2 Moisturizing feeling after drying 8 4 0 Tightness after coating 0 0 0 Tightness after drying 1 6 9 Example 3 The lotion shown in Table 1 was applied to the elbows of three women aged 30 to 40 two times in the morning and evening over 7 days. Table 3 shows the results of the comparison of the horny -33- 200533383 (30) moisture content on the morning of the 8th day using an impedance meter (SKICON-200, manufactured by IBS Corporation) and the conductivity measurement using the high-frequency impedance method. It was found that when the sample 1-1 containing the multi-branched polysaccharide A obtained in Example 1 was used, the conductivity could be increased, indicating that the moisture content of the horny keratin was increased and the skin moisturizing property was improved. Table 3 Before coating 1 -1 coating 1-2 coating 1-3 coating Conductivity 100 1 83 175 118

Example 4 The lotion shown in Table 4 was produced by a conventional method. This was applied in the same manner as in Example 3. The horny moisture content on the morning of the 8th day was measured by using an impedance meter and high frequency impedance method with conductivity measurement 値 as the index. The results are shown in Table 3 below. It was found that when the sample 2-1 containing the multi-branched polysaccharide A obtained in Example 1 was used, the conductivity could be improved, which indicates that the moisture content of the keratin was increased and the skin moisturizing property was improved. -34- 200533383 (31) Table 4

Sample 2-1 2-2 2-3 Multibranched Polysaccharide A 0.5%--Glycine-0.5%-1,3-Butanediol 9.5% 9.5% 9.5% Ethanol 3 9.6% 3 9.6% 3 9.6% Hemp oil 4.9% 4.9% 4.9% methyl paraben 0.2% 0.2% 0.2% pure water 4 5.3% 4 5.3% 4 5.8% 1 0 0.00% 1 0 0.00% 1 0 0.00% 2-1 coating 2-2 coating Cloth 2-3 Coating Conductivity 100 189 145 125

Example 5 An emulsion shown in Table 6 was prepared by a conventional method. Table 7 shows the results after 10 hours of use from 10 to 30 years of age, after application, and after 1 hour at 20% humidity. As a result, when the sample 3_ 丨 containing the multi-branched polysaccharide A obtained in Example 1 was used, the moisturizing feeling was maintained after coating and after drying, and no tight feeling was generated after drying. -35- 200533383 (32) Table 6 Sample 3-1 3-2 3-3 Multi-branched polysaccharide A 1.0%--Hydroxyethyl cellulose-0.5%-Sanxian gum-0.5%-Glycerin 8.0% 8.0% 8.0% 1,3-butanediol 2.0% 2.0% 2.0% sodium citrate 1.0% 1.0% 1.0% polyethylene glycol-5 0 0.5% 0.5% 0.5% methyl P araben 0.2% 0.2% 0.2% pure water 8 7.3% 8 7.3% 8 8.3% 1 0 0.00% 1 0 0.00% 1 0 0.00%

Sample 3-1 3-2 3-3 Moisturizing feeling after coating 9 8 5 Moisturizing feeling after drying 7 5 0 Tightness after coating 0 0 1 Tightness after drying 1 7 6 Example 6 Basis The lotion shown in Table 6 was produced by a conventional method. This was applied in the same manner as in Example 3 -36- 200533383 (33). Table 8 shows the comparison of the amount of horny water on the morning of the 8th day using an impedance meter and a conductivity measurement method using the high frequency impedance method as an indicator. It was found that when Sample 3 -1 containing the multi-branched polysaccharide A obtained in Example 1 was used, the conductivity r was increased, indicating that the amount of horny water was increased and the skin was moisturized. Table 8 Before coating 3 -1 coating 3-2 coating 3-3 coating Conductivity 100 192 178 125

Example 7 Under a nitrogen atmosphere, a multi-branched polysaccharide A (1.0 g) and dried pyridine were placed in a conical flask under sufficient drying. Ethyl leucine isocyanate (11.5 g) was slowly added dropwise thereto, and reacted at 100 t for 24 hours. After the reaction, methanol was poured into the reaction solution, and the solvent was distilled off. The residue was repeatedly reprecipitated with water and methanol, and purified by dialysis. After freeze-drying, a branched polysaccharide B (1.96 g) was obtained as a white powder. Elemental analysis revealed a degree of substitution of 2.9. Example 8 An emulsion shown in Table 9 was prepared by a conventional method. Table 10 was used for 10 women aged 20 to 30, and the feeling after 1 hour after application and 20% humidity was shown. As a result, when the sample 4-1 containing the multi-branched polysaccharide derivative B obtained in Example 7 was used, the moisturizing feeling was maintained after coating and after drying -37- 200533383 (34), and no tightness was generated after drying. Tense feeling. Table 9

Sample 4-1 4-2 4-3 Multi-branched polysaccharide derivative B 1.0%--hydroxyethyl cellulose-0.5%-Sanxan gum-0.5% _ glycerol 8.0% 8.0% 8.0% 1,3-butanediol 2.0% 2.0% 2.0% Sodium citrate 1.0% 1.0% 1.0% Polyethylene glycol-50 0.5% 0.5% 0.5% Methyl Paraben 0.2% 0.2% 0.2% Pure water 8 7.3% 8 7.3% 8 8.3% 1 0 0.00 % 1 0 0.00% 1 0 0.00% Table 10 Sample 4-1 4-2 4-3 Moisturizing feeling after coating 9 8 5 Moisturizing feeling after drying 7 5 0 Tightness after coating 0 0 1 After drying Tightness 1 7 6 -38- 200533383 (35) Example 9

Under a nitrogen atmosphere, 1,6-dehydrated- / 9-D-mannanose (1.7 g) and dried propylene carbonate (3.5 ml) were placed in a fully dried Schlenk tube. The Schlenk tube was immersed in an oil bath, and the oil bath was heated to 90 ° C to fully dissolve 1,6-anhydro- / 3-D-glucopyranose, and then 66% by weight of 3-formaldehyde was added. The polymerization of the 2--2-butenyltetramethylenesulfohexafluoroantimonate (11.4 // 1) began. After 20 minutes of reaction, the polymerization solution was poured into methanol to stop the polymerization. After distilling off the solvent, it was repeatedly reprecipitated with water and methanol, and purified by dialysis. After freeze-drying, a multi-branched polysaccharide C (1.1 lg) was obtained as a white powder. The yield was 64%. The structure of this multi-branched polysaccharide C was confirmed by 1H-NHR and 13C-NMR. The weight average molecular weight was 80,000 (astigmatism method) and the degree of branching was 0.43. Example 10 A lotion shown in Table 11 was prepared by a conventional method. This was used by 10 females aged 20 to 30 years old. After coating, the feeling after 1 hour at 20% humidity is shown in Table 2. As a result, when the sample 5-1 containing the multi-branched polysaccharide C obtained in Example 9 was used, it maintained a moisturized feeling after coating and after drying, and did not produce a tight feeling after drying. -39- 200533383 (36) Table 1 1 Sample 5-1 5-2 5-3 Multibranched Polysaccharide A 0.50%--Glycogen-0.50%-1,3-Butanediol 5.00% 5.00% 5.00% Ethanol 5.00% 5.00% 5.00% Citric acid 0.01% 0.01% 0.01% Sodium citrate 1.00% 1.00% 1.00% Methyl Paraben 0.20% 0.20% 0.20% Pure water 8 8.29% 8 8.29% 8 8.79% 1 0 0.00% 10 0.00% 1 0 0.00%

Table 12 Sample 5-1 5-2 5-3 Moisturizing feeling after coating 10 8 2 Moisturizing feeling after drying 8 4 0 Tightness after coating 0 0 0 Tightness after drying 0 6 9

The industrial applicability is as described above. The present invention which only adds a small amount of multi-branched polysaccharides and / or multi-branched polysaccharide derivatives to the external preparation for skin can impart sufficient moisture to the skin. An excellent external preparation for skin that has the effect of causing an uncomfortable tightness.

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Claims (1)

200533383 (1) X. Patent application scope * 1. A skin external preparation characterized by containing a multi-branched polysaccharide as a structural unit as a skeleton, and at least one of the hydroxyl groups (OH) of the multi-branched polysaccharide is OR ( R represents a multi-branched polysaccharide derivative substituted with a hydrogen atom, a hydrocarbon having 1 to 30 carbons, or a hydrocarbon having 1 to 30 carbons having a hetero atom. '2 · The external skin preparation according to item 1 of the scope of the patent application, wherein the multi-branched polysaccharide as the skeleton is one of the anhydrous sugar and / or the hydroxyl group (OH) of the anhydrous sugar. • At least one is represented by OR (R represents a hydrogen atom, A polymer having as its monomer a smoke having a carbon number of 1 to 30 or a hydrocarbon having a carbon number of 1 to 30 having a hetero atom). 3. The external skin preparation according to item 2 of the patent application scope, wherein the anhydrous sugar portion of the anhydrous sugar or the anhydrous sugar derivative is at least one selected from the group consisting of 丨, 6_anhydrosugar, 1,4-anhydrosugar, 1,3- Anhydrosugar, 1,2-anhydrosugar, and 5,6-anhydrosugar are clustered. 4. The skin external preparation as described in § 2 of the patent scope, wherein the polymer ^ is obtained by cationic polymerization or anionic polymerization. 5. The external preparation for skin according to item 1 of the application, wherein the degree of branching of the multi-branched polysaccharide is 0.05 to 1.00. 6. The skin external preparation according to any one of claims 1 to 5 in the scope of the patent application, wherein the content of the multi-branched polysaccharide derivative is 0.1 to 80% by mass. 7. A cosmetic material characterized by containing an external preparation for skin according to any one of claims 1 to 6 of the scope of patent application. -42- 200533383 VII. Designated Representative Map (I) The designated representative map in this case is: None (II) The component representative symbols of this representative map are simply explained: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: -4-